Volume I

OBJECTIVE CHEM STRY

Volume I

NEET
FOR

OBJECTIVE CHEM STRY

NEET
FOR
(National Eligibility Cum Entrance Test)

and Other Medical

Entrance Examinations
K Rama Rao
The first edition of Objective Chemistry for NEET Vol. I is the first of a two-part series written for aspiring
doctors who seek to crack the medical entrance test. Designed as a one-stop solution to revise topics in
chemistry pertinent to popular medical entrance examinations, the book provides a comprehensive and (National Eligibility Cum Entrance Test)
systematic coverage of the subject supported by numerous practice questions in every chapter. It covers all

and Other Medical

key topics, beginning with the first principles before delving progressively into the subject’s finer aspects.

Also Available

Volume II OBJECTIVE PHYS CS OBJECTIVE BIOLOGY

Entrance Examinations
NEET NEET
OBJECTIVE CHEM STRY FOR FOR

NEET
FOR w Chapter-wise practice questions for better understanding of concepts
w Topic-wise summary points for quick and effective study
(National Eligibility Cum Entrance Test) (National Eligibility Cum Entrance Test)

(National Eligibility Cum Entrance Test) es

Includ e I
and Other Medical es
Includ e I
Phas
and Other Medical es
Includ e I
w Over 7000 Class-tested problems for hands-on guidance
NEET 6
Phas
Entrance Examinations
NEET 6
201 Paper Entrance Examinations NEET
Phas

and Other Medical 201 Paper

tion
tion
Ques Answers
2016Paper
tion
Ques Answers
Ques Answers with
Entrance Examinations with w 4000+ Multiple Choice Questions with answers
w Over 350 'assertion and reason' based questions for the benefit of
with
w Written in accordance with NCERT syllabus for classes XI and XII
w Over 450 'assertion and reason' based questions for the
w Chapter-wise practice questions for better understanding of concepts AIIMS and JIPMER aspirants benefit of AIIMS and JIPMER aspirants
w Topic-wise summary points for quick and effective study w Chapter-wise summary of key concepts along with hints and w Comprehensive pedagogy designed to maximize score
w Over 3900 Class-tested problems for hands-on guidance solutions for better understanding w Solved question papers of the past 6 years arranged
w Solutions to questions from previous years NEET, AIPMT

K Rama Rao
chapter-wise
and AIIMS examinations w Six sample test papers for practice

K Rama Rao w Board-Text Drills section based on NCERT syllabus

w Three model question papers for practice
Dr Rajiv Vijay
Abhay Kumar

www.pearson.co.in

Vol. I

Rao

Size: 8”x10”mm Spine: 23mm ISBN: 9789332575424 Title Sub Title Edition Authors / Editors Name With CD Red Band Territory line URL Price mQuest
 for

(National Eligibility Cum Entrance Test)

and Other Medical
Entrance Examinations

K. Rama Rao
Copyright (©) 2016 Pearson India Education Services Pvt. Ltd
Published by Pearson India Education Services Pvt. Ltd, CIN: U72200TN2005PTC057128,
formerly known as TutorVista Global Pvt. Ltd, licensee of Pearson Education in South Asia.

No part of this eBook may be used or reproduced in any manner whatsoever without the
publisher’s prior written consent.

This eBook may or may not include all assets that were part of the print version. The publisher
reserves the right to remove any material in this eBook at any time.

ISBN: 978-93-325-7542-4
eISBN 978-93-325-7825- 8

Head Office: A-8 (A), 7th Floor, Knowledge Boulevard, Sector 62, Noida 201 309,
Uttar Pradesh, India.
Registered Office: 4th Floor, Software Block, Elnet Software City, TS-140, Block 2 & 9,
Rajiv Gandhi Salai, Taramani, Chennai 600 113, Tamil Nadu, India.
Fax:  080-30461003, Phone: 080-30461060
www.pearson.co.in, Email: [email protected]

This page is intentionally left blank.
This page is intentionally left blank.
 1

Chapter
Basic Concepts of Chemistry

Matter • Mixtures which contain different phases each with its

own set of properties are referred to as heterogeneous.
• Anything which has mass and occupies space is matter.
• Conversion of one substance into another is called a
• On the basis of state, the matter is classified into solid, chemical change, e.g., rusting of iron.
liquid and gaseous substances; e.g., water in the form
of ice is solid, water is liquid and water vapour is gas.
• If a substance changes from one state to another state
without any chemical change, it is referred to as a
• Solids have high density, rigid shape, slight compres­ physical change, e.g., conversion of water into ice or
sibility, only slight expansion at atmospheric pressure water vapour.
with rise in temperature.
• In a chemical change, the substances that are present
• Liquids are characterised by high density, lack of defi­ initially (the reactants) disappear.
nite shape, slight compressibility and slight expansion • One or several new substances (the products) appear
at atmospheric pressure when heated.
as the reaction proceeds.
• Gaseous state is characterised by low density, indefi­ • The properties of products are different from those of
nite shape and volume, high compressibility and con­ the reactants.
siderable expansion when heated at constant pressure.
• Energy in the form of heat, light or electricity is re­
• A substance which cannot be broken down into yet leased or absorbed in the course of a chemical change.
simpler substances by any means is known as an
element.
• The mass of an object is a measure of the amount of mat­
ter it contains, while the weight is a measure of the force
• An element consists of only one kind of atom. with which the object is attracted to the earth by gravita­
• A compound is a pure substance composed of two or tional force. Weight is always proportional to mass.
more elements joined in chemical combination into a • Mass and weight of a substance are numerically equal
definite proportion by weight. at the sea level. If the object is moved away from earth
• Molecules are identifiable units of matter consisting of the gravitational attraction decreases and therefore the
two or more atoms of the same element or of different weight diminishes, but the mass remains constant.
elements combined in a definite ratio.
• Atomicity is the number of atoms in a molecule. Physical Quantities and their Measurement
• Pure substances contain only a single substance. • Properties of matter like mass, length, time, tem­
• Mixture is a material obtained as a result of mixing perature, which can be quantified and expressed in
two or more substances (elements or compounds) in numerals with suitable units are called as physical
any proportion so that the compounds do not lose their quantities.
identity, e.g., air, gasoline, etc. • Mass of any matter can be determined by measuring
• A mixture that is uniform throughout is referred resistance to movement.
to as homogeneous if it has the same composition • The size of the object is measured in terms of length,
throughout. area and volume.

Chapter_01.indd 1 3/26/2014 2:39:09 PM

 1.2  Objective Chemistry - Vol. I

• Length refers to one dimension, area to two ­dimensions the same number of decimal places as that of the
and volume to three dimensions of space. term with the least number of decimal places.
• Time is another term of measurement used to know (ii) In the calculation involving multiplication or divi­
how long it takes a process or a chemical transforma­ sion, the number of significant figures in the final
tion to take place. answer should not be greater than the number of
significant figures in the least precision factor.
• Temperature is a physical quantity used for measuring (iii) The number that comes from direct count of
the degree of hotness and coldness. ­objects or those results from definitions is called
• Temperature determines the heat flow from a body at a an exact number and is considered to possess an
higher temperature to a body at lower temperature. ­infinite number of significant figures.
• The physical quantities which are derived with the • Rounding up is the procedure of dropping non-
help of two or more physical quantities are called significant digits in a calculation result and adjusting
derived physical quantities. the last digit reported. The general procedure is listed
e.g., density is a derived physical quantity, derived hereunder:
from mass and volume. (i) If the digit is 5 or greater add 1 to the last digit to
• The three aspects of the numerical result of measure­ be retained and drop all digits farther to the right.
ment are (i) numerical magnitude, (ii) precision and (ii) If the digit is less than 5, simply drop it and all
(iii) indicator scale. digits farther to the right.
• The physical quantities which depend on the size of
the sample like mass, weight, volume, pressure, etc.
are called extensive properties.   Objective Questions
• The physical quantities which do not depend on the
size of the sample like temperature, density, refractive 1. SI unit of time is
index, surface tension viscosity, etc. are called inten- (1) second (2)  minute
sive properties. (3) hour (4)  day
2. Which of the following statements is incorrect?
Measurement and Significant Figure
(1) All elements are homogeneous
• Precision is the closeness of the set of values obtained (2) Compounds made up of a number of elements are
from identical measurements of a quantity. heterogeneous
(3) A mixture is not always heterogeneous
• Accuracy is the closeness of single measurement to its
(4) Air is an heterogeneous mixture
true value.
• The digits in a properly recorded measurement are known 3. Which of the following is not an element?
as significant figures or significant figures are the mean­ (1) Diamond (2)  Graphite
ingful digits in a measured or calculated quantity. (3) Silica (4)  Ozone
• The greater the number of significant figures in a re­ 4. Which one is a physical change?
ported result, the smaller is the uncertainty and the (1) Burning of S in air
greater the precision. (2) Burning of C in air
• Rules for reporting the number of significant figures: (3) Conversion of white phosphorous to red
(i) All non-zero digits are significant, starting with ­phosphorous
the first digit that is not zero. (4) Corrosion of metals
(ii) Zeros between non-zero digits are significant. 5. A pure substance can only be
(iii) Zeros to the right of significant figures are signifi­
(1) a compound
cant for a number less than that.
(2) an element
 (iv) When a number ends in zeros that are not to the
(3) an element or a compound
right of a decimal point, the zeros may not be
(4) a heterogeneous mixture
s­ignificant.
6. A pure substance which contains only one type of
Calculation Involving Significant Figures atoms is called
(i) W
 hile carrying out addition or subtraction of a (1) an element (2)  a compound
number of terms the result should be reported to (3) a solid (4)  a liquid

Chapter_01.indd 2 3/26/2014 2:39:09 PM

 Basic Concepts of Chemistry  1.3

7. The number of significant figures in 0.0500 is • Law of definite proportions: Proposed by Proust,
(1)  one (2)  three verified by Strass and Richards. When two elements
(3)  two (4)  four combine to form a compound they combine in definite
proportion by weight (or) a chemical compound has
8. The correctly reported answer of the addition of
same composition by whatever method it is prepared.
29.4406, 3.2 and 2.25 will have significant figures
(1) three (2)  four
• Law of multiple proportions: Proposed by Dalton,
proved by Berzelius and Strass. When two elements
(3) two (4)  five
combine to form more than one compound the different
9. The correctly reported answers of the addition of weight of one of the elements combining with a fixed
294.406, 280.208 and 24 will be weight of the other are in proportions of whole number.
(1) 598.61 (2)  599 • Law of reciprocal proportions: Proposed by Ritcher.
(3) 598.6 (4)  598.614 The weight of two or more substances which sepa­
10. Two students, X and Y, reported the mass of the same rately react chemically with identical weights of third
substance as 7.0 g and 7.00 g, respectively. Which of element are also the weights in which they combine
the following statement is correct? with each other or multiples of them.
(1) Both are equally accurate • Gay Lussac’s law of gaseous volumes: Volumes of
(2) X is more accurate than Y gases used and produced in a chemical reaction stand
(3) Y is more accurate than X in a simple integral ratio when these volumes are
(4) Both are inaccurate scientifically measured under the same conditions of temperature
and pressure.
11. The number of significant figures in p is
• Berzelius Hypothesis: Equal volumes of all gases un­
(1)  one (2)  two
der the same conditions of temperature and pressure
(3)  three (4)  infinite
contain equal number of atoms.
12. Given the numbers 786, 0.786 and 0.0786 the number • Avogadro’s Hypothesis: Equal volumes of all gases
of significant figures for the three numbers is under the same conditions of temperature and pressure
(1) 3, 4 and 5, respectively contain equal number of molecules (or) the volume of
(2) 3, 3 and 3, respectively a gas at fixed pressure and temperature is proportional
(3) 3, 3 and 4, respectively to the number of moles (or molecules of a gas present).
(4) 3, 4 and 4, respectively Mathematically, Avogadro’s law is V a n.
13. In which of the following numbers all zeros are • Dalton’s atomic Theory: The observations of law of
significant? multiple proportions led to the formation of atomic
(1) 0.0005 (2)  0.0500 theory.
(3) 50.000 (4)  0.0050 • An atom is the smallest indivisible particle of an ele­
ment that can take part in a chemical change.
Answers • All atoms of a given element are identical both in mass
and chemical properties.
  (1) 1   (2) 2   (3) 3 (4)  3   (5) 3
• Atoms of different elements have different masses and
  (6) 1   (7) 2   (8) 1 (9)  2 (10) 3
different chemical properties.
(11) 4 (12) 2 (13) 3
• Compounds are formed by the combination of differ­
ent atoms in the ratio of small whole numbers.
• Chemical reactions involve only combination, separa­
Laws of chemical combination tion and rearrangement of atoms.
• Laws of conservation of mass: It was proposed by • Atoms are neither created nor destroyed in the course
Lavoiser. Total amount of matter in the universe of an ordinary chemical reaction.
is ­unaltered whatever the change take place in its • The two modifications made in the hypothesis of John
­distribution (or) the sum of the weights of reacting Dalton are
substances are equal to the sum of the weights of prod­ (i) an atom is divisible and destructive
ucts (or) matter can neither be created nor destroyed. (ii) all atoms of an element are not identical in mass

Chapter_01.indd 3 3/26/2014 2:39:10 PM

 1.4  Objective Chemistry - Vol. I

21. Law of reciprocal proportions can be used to determine

  Objective Questions (1) Atomic weight of a gas
(2) Equivalent weight of a gas
14. Element A reacts with oxygen to form a compound (3) Molecular weight of a gas
A2O3. If 0.359 gram of a compound contains 0.128 g
(4) None of these
of oxygen, atomic weight of A will be
(1) 51 amu (2)  43.08 amu 22. SO2 gas was prepared by (i) burning sulphur in ­oxygen,
(3) 49.7 amu (4)  47.9 amu (ii) reacting sodium sulphite with dilute H2SO4 and
(iii) heating copper with conc. H2SO4. It was found
15. Oxygen combines with two isotopes of carbon, 12C that in each case sulphur and oxygen combined in the
and 14C, to form two samples of carbon dioxide. The ratio of 1:1. The data illustrate the law of
data illustrates
(1) Conservation of mass
(1) Law of conservation of mass (2) Multiple proportions
(2) Law of multiple proportions (3) Constant proportions
(3) Law of reciprocal proportions (4) Reciprocal proportions
(4) None of these
23. H2S contain 5.88% hydrogen, H2O contain 11.11%
16. Suppose that A and B are two elements which form hydrogen while SO2 contains 50% sulphur. The data
compounds B2A3 and B2A, respectively. If 0.05 mole illustrate the law of
of B2A3 weighs 9.0 g and 0.10 mole of B2A weighs
(1) Conservation of mass
10 g, then the atomic weight of A and B, respectively is
(2) Constant proportions
(1) 30 and 40 (2)  40 and 30
(3) Multiple proportions
(3) 20 and 5 (4)  15 and 20
(4) Reciprocal proportions
17. In the reaction, N2 + 3H2 → 2NH3, ratio by volume of
24. 6 g of carbon combines with 32 g of sulphur to form
N2, H2 and NH3 is 1:3:2. This illustrates
CS2. 12 g of C also combine with 32 g of oxygen to
(1) definite proportions form carbon dioxide. 10 g of sulphur combines with
(2) multiple proportions 10 g of oxygen to form sulphur dioxide. Which law is
(3) reciprocal proportions illustrated by them?
(4) gaseous volumes
(1) Law of multiple proportions
18. One part of an element X combines with two parts of (2) Law of constant composition
another element Y. Six parts of the element Z com­ (3) Law of reciprocal proportions
bines with four parts of element Y. If X and Y combine (4) Gay Lussac’s law
together, the ratio of their weights will be governed by
25. Two elements X (at mass 16) and Y (at mass 14) com­
(1) Law of multiple proportions
bine to form compounds A, B and C. The ratio of dif­
(2) Law of definite proportions
ferent masses of Y which combine with a fixed mass
(3) Law of reciprocal proportions
of X in A, B and C is 1:3:5. If 32 parts by mass of X
(4) Law of conservation of mass
combines with 84 parts by mass of Y and B, then in C
19. Two samples of lead oxide were separately reduced to 16 parts by mass of X will combine with
metallic lead by heating in a current of hydrogen. The (1) 14 parts by mass of Y
weight of lead was obtained from the other oxide. The (2) 42 parts by mass of Y
data illustrates (3) 70 parts by mass of Y
(1) Law of reciprocal proportions (4) 84 parts by mass of Y
(2) Law of constant proportions
(3) Law of multiple proportions
(4) Law of equivalent proportions
Answers
20. Chemical equation is balanced according to the law of
(1) Multiple proportions (14) 2 (15) 4 (16) 2 (17) 4 (18) 3
(2) Reciprocal proportions (19) 3 (20) 3 (21) 2 (22) 3 (23) 4
(3) Conservation proportions (24) 3 (25) 3
(4) Definite proportions

Chapter_01.indd 4 3/26/2014 2:39:10 PM

 Basic Concepts of Chemistry  1.5

Mole concept • Reciprocal of Avogadro’s number is known as

Avogram.
• Atomic weight scale is a table that lists the weights of
all the elements relative to the same common standard. 1 1
Avogram = = = 1.67 × 10–23
• The mass of C-12 is taken as standard and its mass is N 6.022 × 10 23
assigned exactly 12. Atomic mass unit (amu) and mass­ • The number of molecules present in 1 cc of a gas at
es of all other atoms are given relative to this standard.
STP is known as Loschmidt number. Its value is
• One amu is defined as a mass exactly equal to one- 2.617 × 1019.
twelfth the mass of one C-12 atom. 1 amu = 1.66056 × • The mole is the amount of substance containing the
10–24 g. same number of atoms in exactly 12 grams of C-12
• Many naturally occurring elements consist of more isotope.
than one isotope. For such elements, the atomic weights • Number of moles “n” ’
determined are the average atomic weights of isotopes.
Weight in grams W
• = =
Molecular weight or molecular mass of a molecule
Gram molecular weight M
of a substance is the sum of the atomic weights or
atomic masses of atoms present in the molecule. • Weight of a substance containing a definite number of
• For ionic compounds which do not contain molecules, moles = Number of moles × Gram molecular weight
formula weights are calculated as indicated in the for­ (W = n × MW)
mula of an ionic compound. • No. of molecules present in a given substance.
• The atomic weight expressed in grams is known as Weight
= × Avogadro number
gram atomic weight. Gram molecular weight
• Molecular weight expressed in grams is known as W
gram molecular weight or gram mole. = ×N
MW
• At STP, one gram mole of any gas occupies 22.414
litres or 22414 cc of volume. It is known as gram
• No. of atoms present in a given element
­molar volume. Weight
= × Avogadro number
• One gram mole of any substance will contain Gram molecular weight
6.022 × 1023 molecules.
• The number of atoms in one gram atom of an element
or the number of molecules present in one gram mole
of substance, i.e., 6.022 × 1023 is known as Avogadro’s   Objective Questions
number or Avogadro’s constant denoted by N.
26. One mole of CO2 contains
• The mass of 1 mole of a substance in grams is known
as molar mass. (1) 6.02 × 1023 atoms of C
Gram molecular weight = weight of molecule in (2) 6.02 × 1023 atoms of O
g × 6.022 × 1023. (3) 18.1 × 1023 atoms of CO2
(4) 3 grams of carbon
• Wt. of one molecule in grams
27. How many water molecules will be lost on dehydrating
Molecular Wt. Molecular Wt. 0.684 g of sucrose?
= =
N 6.022 × 10 23 (1) 1.3244 × 1022
Wt. of one atom in grams (2) 6.622 × 1021

(3) 6.02 × 1020
Atomic weight Atomic weight (4) 7.224 × 1021
= =
N 6.023 × 10 23 28. Which one of the following gas contains the same
• The gaseous substances at NTP will have 6.022 × 1023 number of molecules as 16 g of oxygen?
molecules in 22.4 litres or 22400 cc whose weight is (1) 16 g of O3 (2)  16 g of SO2
equal to their molecular weight. (3) 32 g of SO2 (4)  All the above

Chapter_01.indd 5 3/26/2014 2:39:14 PM

 1.6  Objective Chemistry - Vol. I

29. 18 g of water contains

(1) 19.089 × 109 years
(1) 1 g atom of hydrogen atom
(2) 18.089 × 109 years
(2) 2 g atom of hydrogen atom
(3) 19.089 × 1010 years
(3) 3 g atom of hydrogen atom
(4) 19.089 × 1011 years
(4) None of these 38. 4.6 × 1022 atoms of an element weigh 13.8 g. The
30. Volume at NTP of 0.44 g of CO2 is the same as that of atomic mass of the element is
(1) 0.02 g of H2 (1) 290   (2)  180   (3)  13.4    (4)  10.4
(2) 0.085 g of NH3 39. The number of moles of SO2Cl2 in 13.5 g is
(3) 320 mg of gaseous SO2
(1) 0.1   (2)  0.2   (3)  0.3   (4)  0.4
(4) All the above 
31. 4.4 g of an unknown gas occupies 2.24 litres of volume 40. The total number of protons in 10 g of calcium
at STP. The gas may be ­carbonate is
(1) carbon dioxide (2)  carbon monoxide (1)  3.0115 × 1024
(3) oxygen (4)  sulphur dioxide

(2)  1.5057 × 1024
(3)  2.0478 × 1024
32. Which of the following has the smallest number of
(4)  4.0956 × 1024
molecules?
41. Which of the following is wrong?
(1) 0.1 mole of CO2 gas
(1) One mole of hydrogen weighs less than one mole
(2) 11.2 litres of CO2 gas
of glucose
(3) 22 g of CO2 gas
(2) Two moles of hydrogen and one mole of helium
(4) 22.4 × 103 ml of CO2 gas
weigh the same
33. Choose the wrong statement. (3) 0.1 mole of oxygen weighs more than one mole of
(1) 1 mole means 6.023 × 1023 particles hydrogen
(2) Molar mass is mass of 1 molecule (4) One mole of nitrogen and half a mole of oxygen
(3) Mole is mass of 1 mole of substance weigh the same
(4) Molar mass is molecular mass expressed in 42. Avogadro’s law finds application in the determination of
grams
(1) Atomicity of gases
34. Which of the following pairs contain equal number of (2) Molecular weight of gases
atoms? (3) Molecular formula of certain gaseous compounds
(1) 11.2 cc of the N2 and 0.015 g of nitric oxide (4) All the above
(2) 22.4 litres of nitrous oxide and 22.4 litres of nitric 43. Assuming the density of water is 1g/ml, the volume
oxide occupied by one molecule of water is
(3) 1 milli mole of HCl and and 0.5 milli mole of H2S
(1) 3 × 10–23 cc (2)  1.5 × 10–23 cc
(4) 1 mole of H2O2 and 1 mole of N2O4
(3) 6 × 10 cc
–23
(4)  3 × 10– 22 cc
35. A piece of copper weighs 0.635 g. How many atoms of
44. Molecular weight of haemoglobin is 67200. If haemo­
copper does it contain?
globin contains 0.33% of iron atoms, the number of
(1) 6.02 × 1022 electrons iron atoms that are present in one molecule of haemo­
(2) 6.02 × 1021 electrons globin is (At. wt. of iron = 56)
(3) 6.023 × 1023 electrons
(1) 2   (2)  4   (3)  6   (4)  8
(4) 6.012 × 1024 electrons
45. How many moles of atoms are present in one mole of
36. How many electrons are present in 1.6 g of methane? CH3COOH molecule?
(1) 6.02 × 1023 electrons (1) 2 moles of C atoms, 4 moles of H atoms, 2 moles
(2) 6.02 × 1022 electrons of O atoms
(3) 6.02 × 1024 electrons (2) 1 mole of C atoms, 2 moles of H atoms, 1 mole of
(4) 6.02 × 1025 electrons O atoms
37. How many years would it take to spend one Avogadro (3) 2 moles of C atoms, 3 moles of H atoms, 2 moles
number of rupees at a rate of 10 lakh of rupees per of O atoms
second? (4) None

Chapter_01.indd 6 3/26/2014 2:39:15 PM

 Basic Concepts of Chemistry  1.7

46. Which contains the greatest number of oxygen atoms? Answers

(1) 1 g of O2
(2) 1 g of O2 (26) 1 (27) 1 (28) 3 (29) 2 (30) 1
(3) 1 g of O3 (31) 1 (32) 1 (33) 2 (34) 1 (35) 2
(4) All have the same number of atoms (36) 1 (37) 1 (38) 2 (39) 1 (40) 1
(41) 4 (42) 4 (43) 1 (44) 2 (45) 1
47. Which of the following pairs of gases contain the same
(46) 4 (47) 1 (48) 1 (49) 1 (50) 4
number of molecules?
(51) 2 (52) 2 (53) 2 (54) 1 (55) 3
(1) 16 g of O2, 14 g of N2
(2) 8 g of O2, 22 g of CO2
(3) 28 g of N2, 22 g of CO2
(4) 32 g of O2, 32 g of N2
cALCULATION OF eMPIRICAL FoRMULA
48. A glass of juice contains 9 g of glucose. The number of AND mOLECULAR FORMULA
carbon atoms in the glass of juice is
(1) 1.8069 × 1023 (2)  1.5012 × 1023 • Empirical formula of a compound gives the simplest
(3) 2.5012 × 10 23
(4)  None ratio of the number of atoms of different elements pre­
sent in one molecule of a compound.
49. Weight of 6.023 × 1021 atoms of zinc (At. wt. of Zn =
• Empirical formula will not give the actual number of
65.4) is
atoms of different elements present in one molecule of
(1) 0.645 g (2)  0.0654 g the compound.
(3) 6.54 g (4)  0.00654 g
• Calculation of the empirical formula involves the
50. The number of ions produced by 0.1 mole of ­following steps.
AlCl3 . 6H2O in a litre solution is 1. Percentage composition by weight of each ­element
(1) 5 × 6023 × 1022 (2)  4 × 6.023 × 1023 in the compound should be determined.
(3) 4 × 6.023 × 10
–22
(4)  4 × 6.023 × 1022 2. The percentage of each element should be divided
by its atomic weight to get the relative number of
51. Two containers have equal weights of NO2 and N2O. atoms of each element.
The one containing more number of moles is 3. The numbers obtained in the above step (2)  should
(1) NO2 be divided to get the simplest ratio.
(2) N2O 4. If the numbers obtained in the above step (3)  are
(3) both have same number of moles not whole numbers; for, they should be multiplied
(4) cannot be determined by a suitable integer to get the whole number ratio.
5. The ratio obtained in the above step (4)  gives the
52. Which of the following mixtures contain less number
empirical formula.
of ions?
(1) 2M K2SO4; 3M Na2CO3
• Molecular formula represents the actual number of
atoms of different elements present in one molecule of
(2) 2M NaCl; 2M KCl
the compound.
(3) 2M MnSO4; 2M K2SO4
(4) 2M K2SO4; 2M (NH4)2SO4 • For certain compounds, the empirical formulae and
molecular formula may be same.
53. Caffeine (molecular weight = 194) contains 28.9% Molecular formula = Empirical formula × n
nitrogen. The number of nitrogen atoms in caffeine
molecule is Molecular weight
n=
(1) 2    (2)  4    (3)  7    (4)  8 Empirical formula weight
54. Sugar costs Rs. 10/kg. The cost of one mole of sugar is
• Molecular weight of a substance can be determined by
(1) Rs. 3 ps 42 (2)  Rs. 6 ps 84 different methods such as (i) vapour density method
(3) Rs. 1 ps 80 (4)  None and (ii) methods based on colligative properties.
55. The number of gram atoms of sulphur that represents 2 × vapour density = Molecular weight
0.5 mole of sulphuric acid is • The molecular weights of volatile compounds are
(1) 0.2    (2)  0.4    (3)  0.5    (4)  0.9 ­determined by Victor Mayer’s method.

Chapter_01.indd 7 3/26/2014 2:39:16 PM

 1.8  Objective Chemistry - Vol. I

Stoichiometry and stoichiometric

  Objective Questions Calculations
56. The vapour density of gas A is four times that of B. • Stoichiometric calculations help in calculating
If the molecular mass of B is M then the molecular ­whether the production of a particular substance is
mass of A is e­ conomically cheap or not.
(1) M   (2)  2M   (3)  M/4   (4)  4M • Stoichiometric calculations are of four types:
57. Vapour density of a volatile substance is 4 (CH4 = 1). (i) Calculations based on weight–weight relationships
Its molecular weight would be (ii) Calculations based on weight–volume relationships
(iii) Calculations based on volume–volume relationships
(1)  8   (2)  2   (3)  64   (4)  128
(iv) Calculations based on weight–volume–energy
58. An oxide of metal (M) has 40% by mass of oxygen.  relationships
Metal M has a relative atomic mass of 24. The empiri­ • If the amount of reactant in a particular reaction is
cal formula of oxide is known, then the amount of the other substance re­
(1) M2O   (2)  M2O3   (3)  MO   (4)  M3O4 quired in the reaction or the amount of the product
59. A compound (60 g) on analysis gave C = 24 g, H = 4 g, formed in the reaction can be calculated.
O = 32 g. Its empirical formula is • For stoichiometric calculations, the following steps
(1) C2H4O2 (2)  C2H2O2 should be considered.
(3) CH2O2 (4)  CH2O (a) a balanced chemical equation using chemical for­
mulae of reactants and products must be written.
60. A compound contains 38.8% C, 16.0% H and 45.2% N.
(b) The coefficients of a balanced chemical equation
The formula of the compound would be
give the mole ratio of the reactants and products.
(1) CH3NH2 (2)  CH3CN (c) The mole ratio can be converted into weight-
(3) C2H5CN (4)  CH2 (NH2)2 weight ratio, weight-volume ratio or volume-
61. An organic compound on analysis was found to con­ volume ratio.
tain 0.032% sulphur. The molecular mass of the com­ • Limiting reactant or limiting reagent is the reactant
pound, if its molecule contains two sulphur atoms is that is entirely consumed when a reaction proceeds to
(1) 200 (2)  2000 completion. The reactant that is not completely con­
(3) 20,000 (4)  2,00,000 sumed in a reaction is called as an excess reactant.
62. 15 ml of a gaseous hydrocarbon requires 45 ml of
oxygen for complete combustion and 30 ml of CO2 is Methods for expressing the
formed. The formula of the hydrocarbon is concentration of solutions
(1) C3H6   (2)  C2H6   (3)  C4H10   (4)  C2H4 Mass per cent
63. Insulin contains 3.4% of sulphur. The minimum Mass of solute
­molecular mass of insulin is • Mass per cent = × 100
Mass of solution
(1) 940   (2)  560   (3)  470   (4)  350 • Mole fraction is the ratio of the number of moles of
64. The concentration of C = 85.45% and H = 14.55% is one component to the total number of moles (solute
not obeyed by the formula and solvent) in a binary solution.
(1) CH2   (2)  C2H4   (3)  C2H6   (4)  C4H8 n2
• Mole fraction of solute cA =
–1 n1 + n2
65. The density of air is 0.001293 gm L . Its vapour
density is where n1 and n2 are the number of moles of solvent and
solute, respectively.
(1) 143   (2)  14.3   (3)  1.43   (4)  0.143 W
• The number of moles of a substance =
M
• Mole fraction of a substance A in a solvent B is given by
Answers WA
(56) 4 (57) 3 (58) 3 (59) 4 (60) 1 MA
cA =
(61) 4 (62) 4 (63) 1 (64) 3 (65) 4 WA W
+ B
MA MB

Chapter_01.indd 8 3/26/2014 2:39:18 PM

 Basic Concepts of Chemistry  1.9

• For a dilute solution, the number of moles of a solute • Number of moles present in a solution = Molarity ×
in the denominator can be neglected. Then Vol. in litres.
WA M • Number of milli moles present in a solution =
cA = × B
M A WB Molarity × Vol. in cc.
• In a solution, the sum of mole fractions of all compo­ • Molarity of a mixture of solutions of different concen­
trations of the same substance can be calculated by
nents = 1.
V M + V M + ...... + Vn M n
M= 1 1 2 2
Molarity Total Volume
• Molarity is temperature dependent.
• Molarity: M is the number of moles of a solute pre­
sent in one litre of a solution.
• Units of molarity are moles litre–1
Molarity is represented by M.
Normality
Number of moles of solute
M=
Volume of solution in litres • Normality is the number of gram equivalents of a sol­
ute present in one litre of a solution. It is denoted by N.
Weight of the solute (W )
M=
Molecular ( MW ) × volume in litres (V ) Normality N =
Number of gram equivalents of solute
Volume of solution in litres
W
or M =
M .W . × V in lit Weight of the solute (W )
N=
W × 1000 Equivalent weight ( EW ) × volume in litres (V )
M=
M .W . × V in cc W
or N =

• If one gram molecular weight of the substance is present EW × V in litres
in one litre of the solution it is said to be 1M (one molar). W × 1000
or N =

• If 0.1 g molecular weight of the substance is present EW × V in cc
in one litre of the solution, it is said to be 0.1M or
decimolar or M/10 of the solution.
• If one gram equivalent weight of a substance is pre­
sent in one litre of a solution, it is said to be 1 N (one
• Weight of the substance present in one litre = normal).
Molarity × Mol. wt. If the solution of M1 of volume V1
is diluted to valency V2, its molarity M2 can be calcu­
• If 0.1 gram equivalent weight of a substance is present
in one litre of a solution, it is said to be 0.1 N or deci­
lated by V1M1 = V2M2.
normal or N/10 of the solution.
• The volume to be added to dilute a solution of volume
V1 of molarity M1 to a concentration of M2 is given by
• Weight of the substance present in one litre =
Normality × Equivalent weight.
volume of water to be added =
Volume after dilution – Volume before dilution or V2 – V1 W = VNE
V1 M1 • If the solution of N1 of volume V1 is diluted to a vol­

Volume of water to be added = − V1 ume V2 then its normality N2 can be calculated by
M2
V1N1 = V2N2
• When the solutions of two different substances react
V1 M1 V M • The volume of water to be added =
together, then = 2 2
n1 n2 Volume after dilution – Volume before dilution or
where V, M and n are volume, molarity and number of V2 – V1.
VN
molecules participating in the reaction of a substance, Volume of water to be added = 1 1 - V1
N2
respectively.
• When the solutions of two different substances react
• If density (d) and per cent by weight of a substance in with each other, then V1N1 = V2N2 where V1 and N1
a solution are known, then its molarity are the volume and normality of one substance while
10 V2 and N2 are volume and normality of the other
M = d × per cent ×
M.W. substance.

Chapter_01.indd 9 3/26/2014 2:39:21 PM

 1.10  Objective Chemistry - Vol. I

• The weight of a substance that can react with a par­ • For bases
ticular volume (V) of a solution of another substance Equivalent weight of base =
having normality (N) and equivalent weight (E) can be Molecular weight or formula weight of the base
calculated by
Acidity of the base
W = VNE
• If the density (d) and per cent by weight of a substance • Acidity of a base is the number of replaceable hydrox­
in a solution are known, then its normality can be yl (–OH) groups in the molecule of a base.
calculated by Formula weight of NaOH
10 E. Wt. for NaOH =
N = d × per cent × 1
EW Formula weight of KOH
• Number of gram equivalents present in solution = E. Wt. for KOH =

1
Normality × Volume in litres (N × V in litres). Number
of milli equivalents present in a solution = Normality × Formula weight of Ba ( OH )2
E. Wt. for Ba(OH)2 =

Volume in CC (N × V in CC). 2
• Normality of a mixture of solutions of different con­ • For Salts
centrations of the same substance Equivalent weight
V N + V2 N 2 + ........... + Vn N n Formula weight of the salt
N= 1 1 =
Total volume Total charge on the cation or the anion of thhe salt
• In acid–base neutralisation reactions, the excess sub­ • For oxidants and reductants
stance is given by Equivalent weight
V N −V N Formula weight
N= 1 1 2 2 =
Total Volume Number of electrons transfered in the reaction per moole
• Relation between molarity (M) and normality (N) of • Equivalent weight of certain compounds.
any solution is
Molecular weight
Molarity × = normality Substance Equivalent weight in g
Equivalent weight
Acids
Normality × Equivalent weight HCl 36.5
Molarity =
Molecular weight HNO3 63
H2SO4 49
C2H2O4 . 2H2O 63 (oxalic acid)
Equivalent Weights
H3PO4 32.7
Bases
• For acids: Equivalent weight of an acid = NaOH 40
Molecular weight or formula weight of the acid KOH 56

Basicity of the acid Ba(OH)2 85.67
• Basicity of an acid is the number of replaceable hydro­ Fe(OH)3 35.7
gen (by metal ions) in a molecule of the acid. Salts
NaCl 58.5
Formula weight of HCl
E. Wt. for HCl = Na2CO3 53
1 AgNO3 170
Formula weight of HNO3 Oxidants
E. Wt. for HNO3 =
KMnO4 31.6 (acid medium)
1
K2Cr2O7 49 (acid medium)
Formula weight of H 2SO 4
E. Wt. for H2SO4 =
2 • Molality is the number of moles of a solute present in
Formula weight of H 3 PO 4 1 kg (100 g) of a solvent.
E. Wt. for H3PO4 =
3 • Molality is represented by “m”. Its units are mole kg–1.

Chapter_01.indd 10 3/26/2014 2:39:24 PM

 Basic Concepts of Chemistry  1.11

Number of moles of solute 71. 1.0 g of pure calcium carbonate was found to react with
• Molality = 50 ml of dilute HCl for completion of the ­reaction.
Weight of solvent in kg
The strength of the HCl solution is
W (1) 4M   (2)  2M   (3)  0.4M   (4)  0.2M
or m =
MW × Wt of solvent in kg
72. 12 g of magnesium (At. Wt. = 24) will react complete­
W × 1000 ly with an acid to give
or m =
MW × Wt of solvent in gram (1) one mole of H2 (2)  one-half mole of H2
• Temperature has no effect on molality and mole (3) one mole of O2 (4)  none of these
­fractions since the quantities of solute and solvent are
73. What volume of CO2 measured at STP can be obtained
­expressed by weights.
by reacting 50 g of CaCO3 with excess hydrochloric acid?
• Molarity and normality changes with temperature CaCO3 + 2HCl  → CaCl2 + H2O + CO2
since the volume of solvent changes with temperature.

(1) 22.4 litres (2)  11.2 litres

(3) 1.12 litres (4)  44.8 litres
74. In the hydrogenation of phenyl ethylene C6H5CH = CH2
  Objective Questions using a platinum catalyst the volume of hydrogen
(measured at STP) that reacts with one mole of phenyl
66. In a clinical laboratory, a sample of urine containing
ethylene could be
0.120 g of urea NH2CONH2 (M. Wt. 60) was treated
with excess of nitrous acid. The urea reacted according (1)  11.2 litres (2)  22.4 litres
to the following equation (3)  44.8 litres (4)  1 litre
NH2CONH2 + 2HNO2  → CO2 + 2N2 + 3H2O 75. What is the volume of oxygen required for complete
The gas formed was passed through aqueous sodium combustion of a mixture of 5 cc of CH4 and 5 cc of C2H4?
hydroxide and final volume is measured at STP. What (1) 25 cc    (2)  5 cc   (3)  50 cc   (4)  10 cc
was the volume? 76. A certain sample of coal contains 1% sulphur by
(1) 89.6 cc (2)  179.2 cc weight. What is the weight of sulphur dioxide pro­
(3) 44.8 cc (4)  22.4 cc duced when 2 × 106 kg of this coal is burnt?
67. How many grams of water are produced by the com­ (1) 2 × 104 kg (2)  4 × 104 kg
plete combustion of 1.00 litre at STP of methane? (3) 4 × 10 kg
5
(4)  2 × 105 kg
1.00 1.00 77. A certain grade coal contains 1.6 per cent sulphur.

(1) ×2 (2)  × 2 × 18
22.4 22.4 Assuming that on burning the coal, S in it is oxidised
1.00 1.00 × 2 to SO2, how many moles of SO2 would be formed on

(3) × 18 (4)  burning 1 metric ton (1000 kg) of coal?
2.24 × 2 22.4 × 18
2
68. The weight of Na2CO3 that would be needed to react
(1) 16 (2)  16000 ×
64
with 0.1 mole of HCl according to the equation is
Na2CO3 + 2HCl  → 2NaCl + H2O + CO2 2 16000
(3) 16000 ×
(4) 
(1) 5.3 g (2)  53 g 32 64
(3) 0.53 g (4)  0.053 g 78. The amount of a given product calculated to be ob­
69. The amount of silver chloride formed on mixing tained in a chemical reaction that goes to completion is
250 ml of 0.1M AgNO3 with 400 ml of 0.1M NaCl is (1) The per cent efficiency of the reaction
(1) 0.10M (2)  0.05M (2) The yield of the reaction
(3) 0.025M (4)  0.2M (3) The theoretical yield of the reaction
(4) None of the above
70. How much of 0.1M of HCl must be added to
0.55 litre of 0.1M Na2CO3 if all of this is to be 79. 5.6 g of carbon monoxide is heated with excess of O2
­converted to CO2? to form carbon dioxide. What is the theoretical yield in
(1) 0.55 litre (2)  1.1 litre grams of carbon dioxide (2CO + O2  → 2CO2)?
(3) 0.275 litre (4)  100 ml
(1) 44 g   (2)  88 g   (3)  4.4 g   (4)  8.8 g

Chapter_01.indd 11 3/26/2014 2:39:27 PM

 1.12  Objective Chemistry - Vol. I

80. Lactose commonly used as a binder in tablets has a 88. A mixture of 20 ml of methane and 20 ml of O2 is
molecular weight 342. What weight of CO2 would be ­exploded and cooled to room temperature. If the
formed when 1/12 mole of this compound is burnt ­reaction between the two substances is written as
completely? CH4 + 2O2  → CO2 + 2H2O
(C12H22O11 + 12O2  → 12CO2 + 11H2O) then the final volume of the gaseous mixture is
(1) 12 g (2)  44 g (1) 10 ml (2)  20 ml
(3)  4.4 g (4)  440 g (3) 30 ml (4)  60 ml
81. What mole ratio of molecular chlorine (Cl2) to molec­ 89. Find the number of moles of KClO3 required to com­
ular oxygen (O2) would result from the breakup of the plete the reaction
compound Cl2O7? KClO3 + C12H22O11  → KCl + CO2 + H2O
(1) 1:1   (2)  7:2   (3)  1:3.5   (4)  2:4
(1) 8   (2)  7   (3)  4   (4)  2
82. When 100 g of ethylene polymerises to polyethylene
90. The weight of magnesium that will be required to
according to the equation nCH2 = CH2  → ........
produce just sufficient hydrogen, from an acid to
(..... CH2–CH2 ...)n ..... the weight of polyethylene pro­
combine with all the oxygen that can be obtained by
duced will be
the complete decomposition of 24.5 g of potassium
n chlorate is
(1) gm (2)  100 g
2 (1) 10.4 g (2)  14.4 g
100 (3) 9.32 g (4)  12.4 g
(3)  g (4)  100 ng
n
91. 10 g of carbon burns giving 11.2 litres of CO2 at NTP.
83. How many moles of Fe2+ ions are formed when excess
After combustion, the amount of unburnt carbon is
of iron is treated with 50 ml of 4.0 M HCl under inert
atmosphere? Assume no change in volume. (1) 2.5 g   (2)  4 g   (3)  3 g   (4)  1 g
(1) 0.4   (2)  0.1   (3)  0.2   (4)  0.8 92. The weight of MnO2 required to produce 1.78 litres of
chlorine gas at STP according to the reaction
84. The reaction 2C + O2  → 2CO is carried out by
taking 24 g of carbon and 96 g of O2. Which one is the MnO2 + 4HCl → MnCl2 + 2H2O + Cl2 is
limiting reagent?
(1) 6.905 g (2)  5.905 g
(1) C   (2)  O2   (3)  CO2   (4)  None
(3) 6.509 g (4)  6.059 g
93. 100 g potassium hydrogen carbonate on strong heat­
85. For the reaction A + 2B  → C, 5 moles of A and 8
ing gives 69 g of a solid residue. The equation which
moles of B will produce
represents the reaction is
(1) 5 moles of C (2)  4 moles of C
(1) KHCO3  → K2CO3 + H2O + CO2
(3) 8 moles of C (4)  13 moles of C
(2) 2KHCO3  → K2CO3 + H2
3 1 1 1
86. The equation 2Al(s) + O2(g) → Al2O3(s) shows that (3) KHCO3  → K2CO3 + H2O + CO2
2 2 2 2

(1) 2 moles of Al react with 3/2 mole of O2 to produce (4) 2KHCO3  → 2KOH + 2CO2
7/2 mole of Al2O3

(2) 2 g of Al react with 3/2 mole of O2 to produce 94. Chlorophyll contains 2.68% of magnesium. The num­
1 mole of Al2O3 ber of magnesium atoms present in 2 g of chlorophyll is

(3) 2 g mole of Al react with 3/2 litre of O2 to produce (1) 1.34 × 1021 (2)  6 × 1020
1 mole of Al2O3 (3) 5.34 × 10
22
(4)  5.34 × 1023

(4) 2 moles of Al react with 3/2 mole of O2 to produce 95. 100 ml of 0.2M K2SO4 is diluted with 100 ml of water.
1 mole of Al2O3 The K+ ion in the solution
87. Element A (atomic weight 12.01) and element B (1)  0.4M (2)  0.1M (3)  0.2M (4)  0.8M
(atomic weight 16) combine to form a new substance
X. If two moles of B combines with one mole of A, Answers
then the weight of one mole of X is
(1) 28.01 g (2)  44.01 g (66) 1 (67) 2 (68) 1 (69) 3 (70) 2
(3) 40.02 g (4)  56.02 g (71) 3 (72) 2 (73) 2 (74) 2 (75) 1

Chapter_01.indd 12 3/26/2014 2:39:29 PM

 Basic Concepts of Chemistry  1.13

(76) 2 (77) 2 (78) 3 (79) 4 (80) 2

(1) C6H6 (2)  C8H8
(81) 3 (82) 2 (83) 2 (84) 1 (85) 2
(3) C2H2 (4)  Any one of these
(86) 4 (87) 2 (88) 2 (89) 1 (90) 2 10. If an iodised salt contains 1% of KI and a person takes
(91) 2 (92) 1 (93) 3 (94) 1 (95) 3 2.5 g of the salt every day, the iodide ions going into
his or her body every day would be approximately
(1) 7.2 × 1021 (2)  7.2 × 1019
(3) 3.6 × 10
21
(4)  9.03 × 1019
  Practice Exercise Level-1
11. A mixture of magnesium chloride and magnesium sul­
1. In a sample of pure compound, Na = 0.0887 mole, phate is known to contain 0.6 moles of chlorides ions
O = 0.132 mole and C = 2.65 1022 atoms. The empiri­ and 0.2 moles of sulphate ions. The number of moles
cal formula of the compound is of magnesium ions present is
(1) Na2CO3 (1) 0.4    (2)  0.5    (3)  0.8   (4)  1.0
(2) Na3O2C5 12. A sample of ammonium phosphate contains 3.18
(3) Na0.0887 O0.132 C2.65 ×1022 moles of hydrogen atoms. The number of moles of
(4) NaCO oxygen atoms in the sample is
2. The numbers of atoms of Cr and O are 4.8 × 1010 and (1) 0.265    (2)  0.795   (3)  1.06   (4)  3.18
9.6 × 1010, respectively. The empirical formula is 13. Which of the following statements about Avagodro’s
(1) Cr2O3 (2)  CrO2 constant is true?
(3) Cr2O4 (4)  None of these (1) It is the number of electrons required to deposit
3. One atom of an element A weighs 6.644 × 10–23 g. The one mole of atoms of any metallic element from a
gram atoms of the same element in 40 kg will be solution of one of its salts.
(2) It is the number of atoms contained in one mole of
(1) 40 (2)  400
atoms of any monoatomic element.
(3) 4000 (4)  1000
(3) It is the number of grams of any element which
4. Atomicity of oleum is contains 6.02 × 1023 atoms of the element.
(1) 11   (2)  8   (3)  7   (4)  18 (4) It is the number of particles (ions, atoms and
molecules) required to make one gram of the sub­
5. When water is electrolysed, hydrogen and oxygen were
stance under consideration.
obtained which were collected and found to be 16.8
litres at STP. Then, the weight of water electrolysed is 14. The number of moles of oxygen in 1 litre of air contain­
(1) 18 g   (2)  36 g   (3)  9 g   (4)  45 g ing 21% oxygen by volume in standard conditions is
(1) 0.186 mol (2)  0.21 mol
6. 3.2 g of a hydrated salt lost 1.8 g of H2O on heating.
(3) 2.1 moles (4)  0.0093 mol
Molecular weight of the anhydrous salt is 160. The
number of moles of water of crystallisation is 15. On mixing equal volumes of 0.08 M Pb(NO3)2 and
(1) 2   (2)  3   (3)  5   (4)  10 0.1 M KIO3, a white Pb(IO3)2 precipitates. Assum­
ing the reaction goes to completion, the ratio of the
7. 0.3 mole of hydrocarbon on combustion gave 26.4 g ­
number of moles of Pb(IO3)2 to the number of moles
of CO2. If that hydrocarbon decolourises Bayer’s rea­ of the reactant left unreacted is
gent and gave a precipitate with Tollen’s reagent, the
(1) 10/3   (2)  5/3   (3)  2/3   (4)  3/10
molecular weight of hydrocarbon is
(1) 28   (2)  26   (3)  30   (4)  14 16. The number of moles of H2O formed when 0.1 mole of
Ba(OH)2 is treated with 0.25 mole of HClO3 according
8. A compound has 50% of A (at. wt. 20) and 50% B to the equation
(at. wt. 30). If the molecule of the compound contains
Ba(OH)2 + 2HClO3  → Ba(ClO3)2 + 2H2O is
6 atoms of A, then the molecular formula is
(1) A4B6   (2)  A6B4   (3)  A3B8   (4)  A6B2
(1) 0.05   (2)  0.2   (3)  0.15   (4)  0.3

9. A vessel contains 0.32 g of O2 and under similar con­ 17. The reaction between aluminium metal and dilute
ditions another vessel contains 0.26 g of compound ­hydrochloric acid produced H2 and Al3+ ions. The
X. If X contains C and H in 1:1, then the molecular ­molar ratio of aluminium used to produce hydrogen is
­formula of X is (1) 1:2   (2)  2:1   (3)  3:2   (4)  2:3

Chapter_01.indd 13 3/26/2014 2:39:30 PM

 1.14  Objective Chemistry - Vol. I

18. Equal volumes of 0.2M HCl and 0.4M KOH are 26. 10 grams of CaCO3 is completely decomposed to X
mixed. The concentrations of the principal ions in the and CaO. X is passed into an aqueous solution contain­
resulting solutions are ing one mole of sodium carbonate. What is the number
(1) [K+] = 0.4M; [Cl–] = 0.2M; [H+] = 0.2M of moles of sodium bicarbonate formed (Mol. Wts.:
(2) [K+] = 0.2M; [Cl–] = 0.1M; [OH–] = 0.1M CaCO3 = 100; Na2CO3 = 106 and NaHCO3 = 84)?
(3) [H+] = 0.1M; [Cl–] = 0.1M; [OH–] = 0.1M (1) 0.2   (2)  0.1   (3)  0.01   (4)  10
(4) [H+] = 0.2M; [Cl–] = 0.1M; [H+] = 0.1M
27. Study the following table
19. Zinc reacts with CuSO4 according to the equation Zn +
CuSO4  → ZnSO4 + Cu. If excess zinc is added Compound Weight of compound
to 100 ml of 0.05 M CuSO4 solution, the amount of Mol. Wt. Taken (in g)
copper formed is I CO2 (44) 4.4
1 1 II NO2 (46) 2.3
(1) moles (2)  moles
200 250
III H2O2 (34) 6.8
200 7
(3)  moles (4)  moles IV SO2 (64) 1.6
7 200
20. 2.79 g of iron is completely converted into rust (Fe2O3). Which two compounds have the least weight of oxy­
The weight of oxygen in the rust (At. Wt. of Fe = 55.8) is gen? (Molecular weights of compounds are given in
(1) 2 g   (2)  1.2 g   (3)  3 g   (4)  1.8 g brackets.)

(1) II and IV (2)  I and III
21. A compound contains 69.5% oxygen and 30.5% nitro­

(3) I and II (4)  III and IV
gen and its molecular weight is 92. The formula of the
compound is 28. In the decomposition of 10 g of MgCO3, 0.1 mol of
(1) N2O (2)  N2O3 CO2 and 4.0 g of MgO are obtained. Hence, the per­
(3)  N2O4 (4)  N2O5 centage purity of MgCO3 is
(1) 50%   (2)  60%   (3)  40%   (4)  84%
22. One mole mixture of CO and CO2 requires exactly
20 g of NaOH to convert all the CO2 into Na2CO3. 29. In which case the purity of a substance is 100%?
How many more grams of NaOH would it require for (1) 1 mole of CaCO3 gave 11.2 L of CO2 (at STP)
conversion into Na2CO3, if the mixture is completely (2) 1 mole of MgCO3 gave 40.0 g of MgO
­oxidised to CO2? (3) 1 mole of NaHCO3 gave 4 g of H2O
(1) 80 g   (2)  60 g   (3)  40 g   (4)  20 g (4) 1 mole of Ca(HCO3)2 gave 1 mole of CO2
23. The correct arrangement of the following in order of 30. X+, Y2+ and Z– are isoelectronic of CO2. Increasing
increasing mass is order of protons in X+, Y2+ and Z– is
I. Nitrogen molecule (1) X+ = Y2+ = Z–
(2)  X– < Y2+ < Z–
 II. Oxygen atom (3) Z < X < Y
– + 2+
(4)  Y2+ < X+ < Z–
III. 1 Avogram 31. Per cent yield of NH3 in the following reaction is 80%:
IV. 1 × 10–10 g atoms of copper NH2CONH2 + 2NaOH ∆ → Na2CO3 + 2NH3. If
(1) I > II > III > IV (2)  I < II < III < IV 6 g of NH2CONH2 react with 8 g of NaOH the NH3
(3) III < II < I < IV (4)  II < III < I < IV formed is
(1)  3.4 g (2)  2.72 g (3)  4.25 g (4)  11.2 g
24. C-12 and C-14 isotopes are found as 98% and 2%,
respectively in any sample. Then the number of C-14 32. Cortisone is a molecular substance containing 21
atoms in 12 g of the sample will be ­atoms of carbon per molecule. The mass percentage of
(1) 1.5 mole atoms (2)  1.032 × 1022 atoms carbon in cortisone is 69.98%. Its molar mass is
(3) 2.06 of × 10 atoms
21
(4)  2 g atom (1)  176.5 (2)  252.2 (3)  287.6 (4)  360.1

25. A sample of copper sulphate pentahydrate 33. One mole of BaF2 is treated with 2 moles of H2SO4. To
(CuSO4 . 5H2O) contains 3.2 g of Cu (Atomic weight make the resulting mixture neutral, NaOH is added. The
= 64). How many grams of O2 are in this sample? number of moles of NaOH required in this process is
(1) 7.2 g   (2)  3.2 g   (3)  14.4 g   (4)  0.8 g (1) 4   (2)  2   (3)  3   (4)  1

Chapter_01.indd 14 3/26/2014 2:39:31 PM

 Basic Concepts of Chemistry  1.15

34. If m gram of a metal A displaces m2 gram of another

(1) 224 mL (2)  112 mL
metal B from its salt solution and if the equivalent
(3) 336 mL (4)  none of these
weights are E1 and E2, respectively then the equivalent
42. Which among MnO2, Mn2O3, MnO3 and Mn2O7 con­
weight of A can be expressed by
tains the maximum percentage by weight of combined
m m × E2 oxygen?
(1) E1 = 1 × E2 (2)  E1 = 2
m2 m1 (1) MnO2 (2)  Mn2O3
m1 × m2 m1 (3) MnO3 (4)  Mn2O7
(3)  E1 =
(4)  E1 = × E2
E2 m2 43. Three samples of iron of equal weights are used to
form FeO, Fe2O3 and Fe3O4 independently. Then, the
35. If Al, Zn and Fe scraps has the same rate per Kg then amount (in grams) of O2 required is
for the production of H2 by the action of dilute H2SO4
(1) maximum for the formation of Fe3O4
(1) Fe will be cheapest and Al will be costliest (2) maximum for the formation of Fe2O3
(2) Al will be cheapest and zinc will be costliest (3) minimum for the formation of Fe2O3
(3) Fe will be cheapest and zinc will be costliest (4) the same for the formation of all the three
(4) Zn will be cheapest and Al will be costliest
44. On analysis, a certain compound was found to con­
36. Choose the correct statement: tain iodine and oxygen in the ratio 254 g of iodine and
The use of 12C scale has superseded the older scale 80 g of oxygen. The atomic mass of iodine is 127 and
of atomic mass based on 16O isotope, one important that of oxygen is 16. Which is the formula of the com­
advantage of the former being pound?
 he atomic masses on 12C scale became whole
(1) T (1) IO   (2)  I2O   (3)  I5O2   (4)  I2O5
numbers.
(2) 12C is more abundant in the earth’s crust than 16O.
45. A metal M forms a chloride MCl2, the formula of

(3) The difference between physical and chemical phosphoric acid is H3PO4. The formula of phosphate
atomic masses got narrowed down significantly. of the metal is
(4) 12
 C is situated midway between metals and non­ (1) MPO4 (2)  M2PO4
metals in the periodic table. (3) M3(PO4)2 (4)  M(PO4)2
37. 2.2 g of compounds of phosphorous and sulphur con­ 46. A compound of carbon, hydrogen and nitrogen con­
tain 1.24 g of phosphorous. The empirical formula of tains three elements in the respective ratio of 9:1:3.5.
the compound is Its empirical formula is
(1)  P4S3 (2)  P3S4 (3)  P3S2 (4)  P2S3 (1) C3H4N (2)  C2H4N
(3) CH2N (4)  C3H6N
38. 0.1 mole of a compound containing sulphur and
chlorine is subjected to a number of chemical reac­ 47. In a gaseous reaction of the type
tions which resulted in the precipitation of 0.1 mole aA + bB  → cC + dD
of PbCl2 and 0.2 mole of BaSO4. The formula of the which is wrong?
original compound is (1) a litre of A combines with b litre of B to give
(1)  SCl2 (2)  S2Cl2 C and D
(3)  SCl4 (4)  S2Cl (2) a mole of A combines with b mole of B to give
C and D
39. Under the same conditions of temperature and pres­
(3) a gram of A combines with b gram of B to give
sure, equal volumes of oxygen and hydrocarbon
C and D
weights are 0.32 g and 0.26 g, respectively. The for­
(4) a molecules of A combine with b molecules of
mula of hydrocarbon is
B to give C and D
(1)  C2H4   (2)  C2H6   (3)  C2H2   (4)  CH4
48. Which of the following about chemical equation is false?
40. Comparing CO, CO2, HCHO and CH4 the per cent
(1) It generally describes only the overall change, that
composition of carbon is maximum in
is the number of atoms, molecules or ions before
(1) CO   (2)  CO2   (3)  HCHO   (4)  CH4 and after a reaction.
41. 0.01 mole of iodoform (CHI3) reacts with Ag powder (2) It indicates nothing about how products are
to produce a gas whose volume at STP is formed from reactants.

Chapter_01.indd 15 3/26/2014 2:39:32 PM

 1.16  Objective Chemistry - Vol. I

(3) I t does not show how long it will take for the reac­ 4. A 1.04 g sample of a metal carbonates of A and B on
tion to occur. heating gave 0.6 g of mixture of oxides A and B. Given

(4) It cannot indicate the actual mole ratio in which that A is 80% by weight and B is 60% weight in their
reactants react. oxides, then the composition obtained and final mix­
tures of compounds of A and B, respectively are
49. Sodium combines with 35Cl and 37Cl to give two sam­
ples of NaCl. Their formation follows the law of (1) 0.62 g, 0.42 g, 0.4 g and 0.2 g
(2) 0.42 g, 0.62 g, 0.4 g and 0.2 g
(1) Definite proportions
(3) 0.31 g, 0.73 g, 0.2 g and 0.4 g
(2) Multiple proportions
(4) None of these
(3) Reciprocal proportions
(4) None of these 5. If the percentage of water of crystallisation in MgSO4.
50. Gay Lussac’s law is not applicable for those gases xH2O is 13%, what is the value of x (relative atomic
which on mixing masses H = 1, O = 16, Mg = 24 and S = 32)?
(1) do not react (1) 1   (2)  4   (3)  5   (4)  7
(2) diffuse 6. Sodium salt of an acid dye contains 7% of sodium.
(3) react with each other What is the minimum molar mass of the dye?
(4) all are wrong (1) 336.5 (2)  286.5
(3)  300.6 (4)  306.5
Answers 7. An element X is found to combine with oxygen to form
X4O6. If 8.4 g of this element combine with 6.50 g of
  (1) 1   (2) 2   (3) 5   (4) 1   (5) 3 oxygen, then the atomic weight of the element in grams is
  (6) 3   (7) 2   (8) 2   (9) 3 (10) 4 (1) 24.0   (2)  31.0   (3)  50.4   (4)  118.7
(11) 2 (12) 3 (13) 2 (14) 4 (15) 2
(16) 2 (17) 4 (18) 2 (19) 1 (20) 2 8. Using scientific notation 1000 metre in centimetres up
(21) 3 (22) 2 (23) 3 (24) 2 (25) 1 to two significant figures is expressed as
(26) 1 (27) 1 (28) 4 (29) 2 (30) 3 (1) 1.0 × 104 (2)  1 × 105
(31) 2 (32) 4 (33) 1 (34) 1 (35) 2 (3) 1.0 × 10
5
(4)  1.00 × 103
(36) 3 (37) 1 (38) 2 (39) 3 (40) 4
(41) 2 (42) 4 (43) 2 (44) 4 (45) 3 9. Which of the following has three significant figures?
(46) 1 (47) 3 (48) 4 (49) 1 (50) 3 (1) 0.52 (2)  543.00
(3) 126 (4)  0.0600
10. Among the following pairs, law of multiple proportion
is illustrated by
  Practice Exercise Level-II (1) H2S and SO2 (2)  BeO and BeCl2
(3) NH3 and NO2 (4)  N2O and NO
1. The vapour density of completely dissociated NH4Cl
would be 11. Which of the following statements is true regarding
(1) Half that of NH4Cl rounding off the digits?
(2) less than half that of NH4Cl (1) If the digit coming after the desired number of
(3) more than half that of NH4Cl significant figures is more than 5, the preceding
(4) depends on the amount of NH4Cl taken at start digit is increased by one.
(2) If the digit coming after the desired number of
2. A sample of clay was partially dried. It contains 50% significant figure is less than 5, the preceding digit
silica and 10% water. The original clay contained 19% is not changed.
water. The percentage of silica present in the sample is (3) If the digit coming after the desired number of sig­
(1) 45%   (2)  47.3%   (3)  52%   (4)  59.1% nificant figure is 5, the preceding digit is increased
3. The number of C2O42– ions in 100 ml of 0.2M aqeous by one if it is odd and not changed if it is even.
Na2C2O4 is (assume complete ionisation) (4) All of these.
(1) 0.62 × 1022 (2)  1.204 × 1022 12. Four one-litre flasks are separately filled with the gases,
(3) 1.86 × 10
22
(4)  18.6 × 1022 hydrogen, helium, oxygen and ozone at the same room

Chapter_01.indd 16 3/26/2014 2:39:33 PM

 Basic Concepts of Chemistry  1.17

temperature and pressure. The ratio of total number

(3) T he mass of a piece of Pt is the same before and
of atoms of these gases present in the different flasks after heating.
would be
(4) A sample of air increases in volume when heated at

(1) 1:1: 1:1 (2)  1:2:2:3 constant pressure but the mass remains unchanged.

(3) 2:1:2:3 (4)  3:2:2:1 19. Law of definite proportions does not apply to nitrogen
13. If two compounds have the same empirical formula oxide because
but different molecular formulae, they must have (1) Mass number of nitrogen is not constant.
(1) different per cent compositions (2) Atomic weight of oxygen is variable.
(2) different molecular weights (3) Equivalent weight of nitrogen is variable.
(3) same viscosity (4) Molecular weight of nitrogen is not fixed.
(4) same vapour density 20. Gay Lussac’s law of gaseous volume is derived from
14. If 1021 molecules are removed from 200 mg of CO2, (1) Law of definite proportions
then the number of moles of CO2 left is (2) Law of multiple proportions
(1) 2.88 × 10–3 (2)  4.54 × 10–3 (3) Law of reciprocal proportions
(3) 1.66 × 10
–3
(4)  1.66 × 10–2 (4) Experimental observations

15. The percentage composition of four hydrocarbons is as 21. The composition of compound A is 40% x and 60% y.
follows The composition of compound B is 25% x and 75% y.
According to the law of multiple proportions, the ratio
(i) (ii) (iii) (iv) of the weight of element y in compounds A and B is
% of C 75 80 85.79 1.3 91.3 (1) 1:2   (2)  2:1   (3)  2:3   (4)  3:4
% of H 25 20 14.3 8.7   8.7 22. Equal masses of oxygen, hydrogen and methane are
kept under identical conditions. The ratio of the vol­
The data illustrate the law of umes of the gases will be

(1) constant proportions
(1) 2:16:2 (2)  2:16:1

(2) reciprocal proportions
(3) 1:16:2 (4)  1:1:1

(3) multiple proportions

(4) conservation of energy 23. H2 combines with O2 to form H2O in which 16 g of
oxygen combines with 2 g of hydrogen. H2 also com­
16. The following data are available bines with carbon to form CH4 in which 2 g of hydro­
(a) % of Mg in MgO and in MgCl2 gen combine with 6 g of carbon. If C and O2 combine
(b) % of C in CO and CO2 together then they will do so in the ratio
(c) % of K2Cr2O7 in K2CrO4 (1) 6:18   (2)  6:16   (3)  1:2   (4)  12:24
(d) % of Cu isotopes in copper metal
The law of multiple proportions may be illustrated by 24. The mass of nitrogen per gram in the compound hydra­
the data zine is exactly one and half the mass of nitrogen in the
(1) a and b (2)  b only compound ammonia. The fact illustrates
(3) a, b and d (4)  c only (1) Law of conservation of mass
(2) Multiple valency of nitrogen
17. Zinc sulphate contains 22.65% of Zn and 43.9% of
(3) Law of multiple proportions
H2O. If the law of definite proportions is true, then
(4) Law of definite proportions
the mass of zinc required to give 20 g of the crystals
will be 25. A sample of AlF3 contains 3.0 × 1024 F- ions. The
(1) 0.453 g (2)  4.53 g number of formula units in this sample is
(3) 45.3 g (4)  453 g (1) 9.0 × 1024 (2)  3.0 × 1024
(3) 0.75 × 10
24
(4)  1 × 1024
18. Which of the following is a best example of law of
conservation of mass? 26. 400 mg of capsule contains 100 mg of ferrous fuma­
(1) 12 g of C combines with 32 g of O2 to form 44 g rate. The percentage of iron present in the capsule is
of CO2. approximately
(2) 12 g of C is heated in vacuum there is no change (1) 8.2% (2)  25%
in mass. (3) 16% (4)  unpredictable

Chapter_01.indd 17 3/26/2014 2:39:33 PM

 1.18  Objective Chemistry - Vol. I

27. Assume that the nucleus of the fluorine atom is a 3.15 g of the oxide has yielded 1.05 g of the metal.
sphere of radius 5 × 10–13 cm. What is the density of We may deduce that
matter in the nucleus?
(1) the atomic weight of the metal is 8
(1) 6.02 × 1023 g mL–1  (2)  6.02 × 1013 g mL–1
(2) the atomic weight of the metal is 4
(3) 12.02 × 1023 g mL–1  (4)  12.02 × 1013 g mL–1
(3) the atomic weight of the metal is 4
28. In a mole of water vapour at STP, the volume actually
(4) the atomic weight of the metal is 8
occupied or taken by the molecules (i.e., Avogadro’s 36. When KClO3 is heated to its melting point, it dispro­
No. × volume of one molecule) is portionates into KCl and KClO4. How many of KClO4
(1) zero are formed on heating 0.1 mole of KClO3?
(2) less than 1% of 22.4 litres (1) 01   (2)  0.05   (3)  0.75   (4)  0.075
(3) 1% to 2% of 22.4 litres
37. 10 litres of polluted air is passed through lime water so
(4) between 2% and 5% of 22.4 litres
that all the CO2 is precipitated as CaCO3. The weight
29. 2.59 g of a mixture of calcium carbonate and magnesi­ of CaCO3 formed is 0.05 g. What is the percentage of
um carbonate is strongly heated to a constant weight of CO2 in the air sample? (1 mole of gas under experi­
1.3 g. The atomic weights of calcium and magnesium mental conditions has a volume of 24 litres.)
are 40 and 24, respectively. State which of the follow­ (1) 0.12   (2)  1.2   (3)  0.03   (4)  0.6
ing weights expresses the weight of calcium carbonate
in the original mixture. 38. For complete oxidation of 1 mole of an organic com­
(1) 980 mg (2)  400 mg pound, 3 moles of oxygen gas are required. Hence, the
(3) 1.75 mg (4)  0.84 g compound is likely to be
(1) ethyne (2)  ethanol
30. Which of the following is a characteristic of both mix­
(3) ethane (4)  methanol
ture and compounds?
(1) They contain components in fixed proportions. 39. Which of the following fertilizers is the richest nitro­
(2) Their properties are the same as those of their gen source on a mass percentage basis?
components. (1) NH4NO3 (2)  (NH2)2CO
(3) Their weights equal the sum of weights of their (3) NH3 (4)  (NH4)2SO4
components.
40. The drug nicotine has the molecular formula C10H14N2.
(4) Energy is given out when they are made.
If 0.1 mole of this is combusted, what would be the
31. 100 mL of PH3 when decomposes produces phospho­ weight of CO2 obtained?
rous and hydrogen. The change in volume is (1)  440 g (2)  4.4 g (3)  44 g (4)  100 g
(1) 50 mL (2)  500 mL
(3) 100 mL (4)  150 mL
Answers
32. Rydberg’s constant is 1.097373157 × 107 m–1. It can be
expressed to three significant figures as   (1) 1   (2) 1   (3) 2   (4) 1   (5) 1
(1) 1.0974 × 107 m–1 (2)  1.09 × 107 m–1   (6) 4   (7) 2   (8) 2   (9) 4 (10) 4
(3) 1.10 × 107 m–1 (4)  1.10 × 10–1 (11) 4 (12) 3 (13) 2 (14) 1 (15) 3
33. The mass of a piece of paper is 0.02 g and the mass of (16) 2 (17) 1 (18) 1 (19) 3 (20) 4
a solid substance along with the same piece of paper (21) 1 (22) 3 (23) 2 (24) 3 (25) 4
is 20.036 g. If the volume of the solid is 2.16 cm3, its (26) 1 (27) 2 (28) 2 (29) 4 (30) 3
density to the proper number of significant digits will be (31) 1 (32) 3 (33) 1 (34) 2 (35) 3
(36) 4 (37) 1 (38) 2 (39) 3 (40) 3
(1) 9.27 g cm–3 (2)  9.3 g cm–3
–3
(3) 9.267 g cm (4)  43.24 g cm–3
34. On reduction with hydrogen 3.6 g of an oxide of metal
left 3.2 g of the metal. If the atomic weight of the metal
is 64, the simplest formula of the oxide would be   Statement-Type Questions
(1)  M2O3 (2)  M2O (3)  MO (4)  MO2 In each of the following questions, a statement-I is given
35. A metal oxide is reduced by heating it in a stream of followed by corresponding statement-II just below. Mark
hydrogen. It is found that after complete reduction the correct answer as indicated.

Chapter_01.indd 18 3/26/2014 2:39:34 PM

 Basic Concepts of Chemistry  1.19

1. If both statement-I and statement-II are true and the Answers

statement-II is the correct explanation of statement-I.
2. If both statement-I and statement-II are true but state­   (1) 1   (2) 1   (3) 2   (4) 3   (5) 4
ment-II is not the correct explanation of statement-I.   (6) 4   (7) 2   (8) 3   (9) 4 (10) 1
3. If statement-I is true but statement-II is false.
4. If statement-I is false but statement-II is correct.
1. Statement-I: The number of O atoms in 16 g of
oxygen and 16 g of ozone is same. Hints
Statement-II: Each of the species represent 1 g atom Multiple Choice Questions with Only One
of oxygen.
Answer
2. Statement-I: The atomic masses of most of the
­elements are in fractions. 2. Compounds are homogeneous though made up with
Statement-II: The atomic mass represents the ratio of different elements.
the average mass of the atom to one avogram. 3. Silica is a compound (SiO2).
3. Statement-I: Molarity of pure water is 55.5 M. 4. Conversion of one allotrope into another is a physical
change.
Statement-II: Molarity is a temperature-dependent 14. 0.128 g of a combines with 0.231 g of A.
parameter.
48 g ................. ?
4. Statement-I: The ratio by volume of H2:Cl2:HCl in a
reaction H2 + Cl2  → 2HCl is 1:1:2. 16. M. Wt. = B2A3 = 180 M. Wt. of B2A = 100.
180 − 100
Statement-II: Substances always react in such a way \ At. Wt. of = = 40
that the volume ratio is a simple whole number. 2
5. Statement-I: 1 Avogram is equal to 10 amu. 25. In B, 32 parts of x combines with y = 84 parts.
16 parts of x will combine with y = 42 parts.
Statement-II: 1 amu is equal to x gram where x is the Now, the number of parts of x in both B and c is of
reciprocal of Avogadro number. equal different masses of y which combine with a
6. Statement-I: 1 g atom of iron represents the number fixed mass of x in B and C in the ratio 3:5.
of iron atoms present in 1 g of it. Mass of y in B 3
=
Statement-II: 1 g atom of element weight is equal to Mass of y in C 5
gram atomic weight of element.
42 parts 3
7. Statement-I: The formula of calcium carbide is CaC2. =
Mass of y in C 5

 tatement-II: 1 mole of calcium carbide contains 2
S
moles of carbon atoms. 5
Mass of y in C = × 42 = 70 parts
3
8. Statement-I: 1 mole of sulphuric acid represents 98 g
of the species. 27. M. Wt. of sucrose = 342
Statement-II: 1 mole of sulphuric acid contains 32 g C12H22O11 ∆ → 12C + 11H2O
each of sulphur and oxygen elements. No. of molecules lost on heating 0.684 =
9. Statement-I: Equal volumes of the gases contain 0.684 × 11× 6 ×10 23
equal number of atoms. = 1.32 × 1022
342
Statement-II: Atom is the smallest particle which
35. Gram atomic mass of Cu = 63.5
takes part in chemical reactions.
0.635
10. Statement-I: Both 12 g of carbon and 27 g of alu­ No. of moles of 0.635 of Cu = = 0.01
63.5
minium will have 6.02 × 1023 atoms.
No. of Cu atoms in one mole = 6.02 × 1023
Statement-II: Gram atomic mass of an element con­ No. of Cu atoms in 0.01 mole = 0.01 × 6.02 × 1023
tains Avogadro number of atoms.          
= 6.02 × 1021

Chapter_01.indd 19 3/26/2014 2:39:40 PM

 1.20  Objective Chemistry - Vol. I

36. Mol. Wt. of CH4 = 16 44

No. of moles in 1.6 g = 0.1 Number of moles of N2O = = 1 mole
44
No. of molecules in 1.6 g = 0.1 × 6 × 1023 So, N2O contains more number of molecules
Each molecule contains 6 + 4 = 10 electrons
No. of electrons present in 1.6 g = 0.1 × 6 × 1023 × 10 2M K2SO4 gives 6M ions (2M K+ and 1M SO42–)
52. (1)
= 6 × 1023 3M Na2CO3 gives 9M ions (6M K+ and 3M CO32–)
37. No. of rupees spent in one second = 106 Total 15M
No. of spent in 1 year = 106 × 60 × 60 × 24 × 365 2M NaCl gives 4M ions (2M Na+ 2MCl–) and
(2)
Avogadro number rupees will be spent in 2M KCl also gives 4M ions (2M K+ 2MCl–).
Total 3M.
6.02 × 10 23 (3) 2M MnSO4 gives 2M Mn2+ and 2M SO42– ions

= 19.089 × 109 years
10 × 60 × 60 × 24 × 365
6
and 3M K2SO4 gives 6M K+ and 3M SO42– ions.
Total 10M.
43. The volume of 6 × 1023 molecules of water is 18 cc.
18 (4) 2M K2SO4 gives 4M K+ ions 2M SO42– ions and

The volume of 1 molecule = = 3 × 10 −23 cc 2M (NH4)SO4 gives 4M NH4+ and 2M SO42– ions.
6.023 × 10 23
Total 12N.
44. 100 g of haemoglobin contains 0.33 g of iron and 2M NaCl and 2M KCl mixture contains less
67200 g of haemoglobin contains ­number of ions.
67200 1 53. 100 g of caffeine contains 28.9 g of N2.
× = 224
100 3
194 × 28.9
194 g of caffeine contains = 56 g
224 100
No. of iron atoms = =4
56
56
No. of nitrogen atoms in caffeine = =4
45. Each molecule of CH3COOH contains two atoms of C, 14
2 atoms of O2 and 4 atoms of H2. 54. The cost of 1000 g of sugar is Rs. 10.
So, one mole of CH3COOH contains 2 moles of C 342 × 10
atoms, 4 moles of H atoms and 2 moles of O atoms. The cost of 1 mole or 342 g of sugar is = 3.42
1000
47. (1) 16 g of O2 is 0.5 mole and 14 g of N2 is 0.5 mole
(2) 8 g of 0.25 mole and 22 g of CO2 is 0.5 mole 55. Each molecule of sulphuric acid (H2SO4) contains
(3) 28 g of N2 is 1 mole and 22 g of CO2 is 0.5 mole 1 sulphur atom. So, 0.5 mole of sulphuric acid con­
(4) 32 g of is 1 mole and 32 g of N2 is 1.143 mole tains 0.5 gram atom of sulphur.
So, 16 g of O2 and 14 g of N2 contain the same 342 × 10
number of molecules. = 3.42
1000
48. Each molecule of glucose (C6H12O6) contains 6 carbon 56. \ Vapour density of A is 4 times that of B. Hence, the
atoms and 9 g of glucose contain molecular weight of A must be 4 times that of B.
9
× 6.023 × 10 23 57. Since VD of the substance is 4 times that of methane, the
180 M.W. of the substance must also be 4 times that of CH4.
= 3.0115 × 1022 glucose molecules or
6 × 3.0115 × 1022 58. Ratio of the elements
= 1.8069 × 1023 carbon atoms 40 60 5 5
: or : \ The empirical formula = MO
49. The weight of 6.023 × 10 23 atoms of zinc is 65.49 16 24 2 2
The weight of 6.023 × 10 21 atoms of zinc is 0.654 g 24 4 32
59. : : = 2 : 4 : 2 \ The empirical formula = CH2O
50. AlCl3 ionises giving 4 ions (AlCl3  → Al3+ + 3Cl-) 12 1 16
So, 0.1 mole of AlCl3 gives 4 × 6.023 × 10 22 ions
38.8 16 45.2
51. Let the weight of NO2 and N2O is 44 gm. 60. = : : 3=
.23 : 16 : 3.22 1 : 5 : 1
12 1 14
44 The empirical formula of the compound is CH5N. The
Number of moles of NO2 = = 0.9565 mole
46 compound is CH3NH2.

Chapter_01.indd 20 3/26/2014 2:39:43 PM

 Basic Concepts of Chemistry  1.21

61. 0.032 g of S present in 100 70. Na2CO3 + 2HCl 

→ 2NaCl + H2O + CO2
2 × 32 × 100 V1 M1 V2 M 2 0.55 × 0.1 V2 × 0.1
232 g of S present in = 2, 00, 000 Applying = = =
0.032 n1 n2 1 2
63. Minimum molecular mass must contain at least one
      V2 = 1.1 litre
S atom.
32 × 100 71. CaCO3  → CaO + CO2
= 941
0.34 100 g 56 g  44 g
85.45 14.55 56 g of CaO is obtained from 100 g of CaCO3 and
64. : = 7.12 : 14.55 or 1 : 2 56 kg of CaO will be obtained from 100 kg of CaCO3.
12 1
So, the empirical formula is CH2. 72. Mg + 2HCl  → MgCl2 + H2
For C2H6, the empirical formula should be CH3. 1 g atom of Mg liberates 1 mole of H2 from acid and
65. VD of air is weight of 11200 cc or 11.2 litres 12 g of Mg or 0.5 g atom of Mg liberates 0.5 mole
of H2.
0.001293 × 11.2 = 0.143
62. Let the formula of hydrocarbon is CxHy. 73. CaCO3 + 2HCl  → CaCl2 + H2O + CO2
 y y 100 g of CaCO3 gives 22.4 litres of CO2 at STP
CxHy +  x +  O2  → xCO2 + H2O 50 g of CaCO3 gives 11.2 litres of CO2 at STP
 4 2
y 74. C6H5CH = CH2 + H2 Pt → C6H5CH2CH3
1 mole x + moles x moles
4 one mole of phenyl ethylene combines with 1 mole of
15 ml 45 moles 30 ml H2, i.e., 22.4 litres of H2 at STP
13 2
75. CH4 + 2O2  → CO2 + 2H2O
y y
∴x = 2x + = 3 = 3 − 2 (∴ x = 2) or y = 4 1 vol 2 vol
4 4 5 cc of methane requires 10 cc of O2
Hence, the formula of hydrocarbon = C2H4 C2H4 + 3O2  → 2CO2 + 2H2O
66. According to the reaction 1 vol  3 vol
NH2CONH2 + 2HNO2  → CO2 + N2 + 3H2O 5 cc of C2H4 requires 15 cc of O2
60 g of urea gives 222,400 cc of N2 at STP \ Total volume of O2 required is 10 + 15 = 25 cc
0.120 g of urea gives 76. 100 g of coal contain 1 g of sulphur.
0.12 × 22400 × 2
= 89.6 cc 2 × 106 × 1000 g of coal contains
60
67. CH4 + 2O2  → CO2 + 2H2O 2 × 106 × 1000
= 2 × 10 7 g of sulphur
22.4 litres of methane at STP on burning give 218 g 100
of water.
Sulphur on burning gives SO2 according to the equation
1 litre of methane at STP on burning gives
S + O2  → SO2
1.0 × 2 × 18 32 g of sulphur gives 64 g of SO2
g of water
22.4 2 × 10 7 g of sulphur gives
2 × 10 7 × 64
68. Na2CO3 + 2HCl  → 2NaCl + H2O + CO2 = 4 × 10 7 g
32
2 moles of HCl react with 1 mole of Na2CO3
0.1 mole of HCl reacts with 0.05 mole of Na2CO3 or 4 × 10 4 kgSO2
\ 0.05 mole of Na2CO3 = 0.05 106 = 5.3 g
77. Follow the above question (76)
69. NaCl + AgNO3  → AgCl + NaNO3 2
1 mole of NaCl reacts with 1 mole of AgNO3. 16000 ×
64
250 ml of 0.1 M AgNO3 = 0.025 mole
400 ml of 0.1 M NaCl = 0.04 mole 78. The amount of product to be obtained according to
\ 0.025 mole of AgNO3 can react with 0.025 mole of a chemical reaction is called theoretical yield of the
NaCl forming 0.025 mole of AgNO3. ­reaction.

Chapter_01.indd 21 3/26/2014 2:39:48 PM

 1.22  Objective Chemistry - Vol. I

79. 2CO + O2  → 2CO2 2H2 + O2  → 2H2O

According to the equation, 56 g of CO gives 88 g 32 g of O2 can combine with 4 g of H2
of CO2. 9.6 g of O2 can combine with 1.2 g of H2
So, 5.6 g of CO gives 8.8 g of CO2. Mg + 2HCl  → MgCl2 + H2
2 g of H2 can be liberated by 24 g of Mg
80. C12H22O11 + 12O2  → 12CO2 + 11H2O 1.2 g of H2 can be liberated by 14.4 g of Mg
1 mole of lactose gives 12 moles of CO2.
91. C + O2  → CO2
1
\ mole of lactose gives 1 mole of 44 g of CO2. 12 g of carbon gives 22.4 litres of CO2
12
\ 11.2 litres of CO2 is given by 6 g of C
81. Cl2O7 decomposes according to the equation: The unburnt carbon is 10 – 6 = 4 g
2Cl2O7  → 2Cl2 + 7O2
The ratio of Cl2:O2 is 2:7 or 1:3.5. 92. MnO2 + 4HCl  → MnCl2 + 2H2O + Cl2
22.4 litres of Cl2 at STP can be produced by 87 g of
82. Since all the ethylene molecules in 100 g polymerises,
MnO2
the polyethylene formed will be 100 g.
1.78 litres of Cl2 at STP can be produced by
83. Fe + 2HCl  → FeCl2 + H2 1.78 × 87
= 6.905 g
2 moles of HCl will produce 1 mole of Fe2+ ions. 22.4
50 93. 2KHCO3  → K2CO3 + H2O + CO2
Numbers of moles present in HCl = × 4 = 0.2 mole
1000 200 g of KHCO3 gives residue of 138 g of K2CO3
\ No. of Fe2+ ions formed is 0.1 mole. 1 1 1
∴ KHCO3 → K 2 CO3 + H 2 O + CO2
84. 2C + O2  → 2CO 2 2 2
24 32 94. In 100 g of chlorophyll, the quantitiy of Mg is 2.68 g.
Since 24 g of carbon can react only with 32 g of oxy­ In 2 g of chlorophyll, the quantity of
gen, the excess oxygen will be left over. Thus, carbon 2 × 2.68
Mg = = 0.0536 g
is the limiting reagent. 100
85. A + 2B  → C 24 g of Mg contain 6 × 1023 atoms
\ 0.0536 g of Mg contains =
1 mole of A reacts with 2 moles of B to produce
1 mole of C. 0.0536 × 6 × 10 23
= 1.34 × 10 21 atoms
\ 8 moles of B can react with 4 moles of A to produce 24
4 moles of C. 95. K2SO4  → 2K+ + SO42–
86. The reaction shows that 2 moles of Al react with moles Since 1 mole of K2SO4 gives 2 moles of K+ ions on
of O2 to produce 1 mole of Al2O3. diluting 100 ml of 0.2 M K2SO4 with 100 ml of water, the
87. Mol. wt. of x = 12.01 + (2 × 16) = 44.01 g concentration of K+ ions in the solution becomes 0.2 M.

88. CH4 + 2O2  → CO2 + 2H2O

20 mL of O2 can oxidise only 10 mL of CH4 to pro­ Practice Exercise Level-I
duce 10 mL of CO2 and 20mL of H2O(g). But when
cooled to room temperature, H2O(g) becomes H2O (l) 2.65 × 10 22
1. = 0.0442 mole
and its volume is negligible. So, after explosion the 6 × 10 23
reaction mixture contains 10 mL of CH4 and 10 mL of 0.0887 0.0442 0.132
CO2 (a total of 20 mL). Mole ratio = : :   = 2:1:3
0.0442 0.0442 0.0442
89. 2KClO3  → 2KCl + 3O2 \ The empirical formula = Na2CO3
C12H22O11 + 12O2  → 12CO2 + 11H2O 2. Ratio of the atoms is 1:2. So, the empirical formula
\ moles of KClO3 required = 8 is CrO2.
90. 2KClO3  → 2KCl + 3O2 3. Gram at. Wt. = 6.644 × 10 −23 × 6 × 10 23 = 40
245 g of KClO3 gives 96 g of O2 40 × 1000
No. of gram atoms = = 40
24.5 g of KClO3 can give 9.6 g of O2 40

Chapter_01.indd 22 3/26/2014 2:39:52 PM

 Basic Concepts of Chemistry  1.23

4. Oleum is H2S2O7. Atomicity =11. 17. 2Al + 6HCl 

→ 2AlCl3 + 3H2
2 moles
5. 2H2O  → 2H2 + O2
36 g of water gives 67.2 litres of H2 and O2 mixture 18. HCl + KOH  → KCl + H2O
and 16.8 litres of H2 and O2 mixture is obtained from 0.2M  0.4M  0.2M
16.8 × 36 HCl completely reacts 0.2M KOH left, 0.2M KCl are
= 9 gm of H 2O formed. Since the volume is doubled the solution con­
67
tains 0.2M K+, 0.1M OH– and 0.1 MCl–.
6. 3.2 of salt lost 1.8 g of H2O
19. 0.05 M Cu is present in 100 mL.
160 g loses 90 g of H2O and 5 moles of H2O
0.05 × 100 1
7. 0.3 mole gives 26.4 g of CO2 No. of moles = =
1000 200
1 mole gives 88 g of CO2
So, the hydrocarbon contains 2 carbon atoms. 20. 111 g of iron combines with 48 g of O2 in Fe2O3 and
Since it decolourises Bayer’s reagent and gives 2.79 g of iron combines with 1.2 g.
­precipitate (with Tollen’s reagent it should be alkyne.
69.5 30.5
Hence, the hydrocarbon is C2H2. 21. = =
16 14
50 50 4.34:2.17 ⇒ 4:2
8. Ratio of atoms : = 3:2
20 30 The formula is N2O4.
Since the compound contains 6 atoms of A, the
22. 2NaOH + CO2  → Na2CO3 + H2O
formula is A6B4.
80 1 mole
0.32 The No. of moles of CO2 in the mixture is 0.25.
9. Moles of O2 = = 0.01
32 Since it reacts with only 20 g of NaOH. So, the No.
Therefore, the moles of compound x is also 0.1 Mol. of moles of CO is 0.75. It is converted into CO2 and
Wt. of x = 26. Molecular formula = C2H2. requires 60 g of NaOH for the same.
10. Iodine present in 2.5 is 0.025 gm. 25. CuSO4 . 5H2O contains 64 g of Cu and 144 g of oxygen.
167 g of KI contain 6 × 1023 iodide ions \ The CuSO4 ⋅ 5H2O containing 3.2 g of Cu have 7.2 g
0.025 g of KI ---- ? of oxygen.
0.025 × 6 × 10 23
= 9.03 × 1019 26. CaCO3 
→ CaO + CO2
167
1 mole of CaCO3 gives 1 mole of CO2
11. 0.6 mole of chloride ion = 0.3 mole of MgCl2 10 g of CaCO3 = 0.1 mole of CaCO3
0.2 mole of sulphate ion = 0.2 mole of MgSO4 0.1 mole of CaCO3 gives 0.1 mole of CO2
12. (NH4)3PO4 contains 12 moles of H atoms and 4 moles Na2CO3 + H2O + CO2  → 2NaHCO3
of O atoms. So, 1 mole of CO2 gives 2 moles of NaHCO3
3.18 moles of H atoms is equal to 1.06 atom of O. \ 0.1 mole of CO2 gives 0.2 moles of NaHCO3.
14. The oxygen present in 1 litre of air is 0.21 litre of O2. 27. All the molecules contain the same number of oxygen
0.21 atoms. The more the molecular weight, the lesser the
\ No. of moles of O2 = = 0.0093 mole
22.4 weight of oxygen.
15. Pb(NO3)2 + 2KIO3  → Pb(IO3)2 + 2KNO3 28. MgCO3  → MgO + CO2
1 mole   2 moles
84 g = 1 mole
0. M of KIO3 reacts with 0.5 mole of Pb(NO3)2. So
\ 10 g of MgCO3 contain 8.4 g
0.3 mol of Pb(NO3)2 left behind and 0.5 mol of
Hence, per cent purity of MgCO3 = 84.
Pb(IO3)2 is formed. Hence the ratio is 5/3.
29. Follow the above question (28).
16. Limiting reagent is Ba(OH)2. For one mole of Ba(OH)2
two moles of water are formed. So, from 0.1 mole of 30. CO2 contains 22 protons. So, z– contains 21, x+ con­
Ba(OH)2, 0.2 mole of water is formed. tains 25 and y2+ contains 24 electrons.

Chapter_01.indd 23 3/26/2014 2:39:55 PM

 1.24  Objective Chemistry - Vol. I

31. According to the equation, 60 g of urea react with 80 g 46. The ratio of C, H and N is 9:1:3.5
of NaOH giving 34 g of ammonia. So, 6 g of urea can 9 1 3.5
give 3.4 g of NH3. But the per cent yield is only 80%. : : or 0.75 :1 : 0.25 or 3 : 4 : 1
12 1 14
3.4 × 80 \ The empirical formula is C3H4N.
= 2.72 g
100
32. No. of carbon atoms in cortisone = 21 Practice Exercise Level-II
Wt. of 21 C atoms = 21 × 12 = 252 1. NH4Cl ∆ → NH3 + HCl
69.98 g of carbon in 100 g of cortisone Since one mole of NH4Cl is giving two moles of gase­
252 g of carbon contain in ous NH3 and HCl, vapour density becomes half.
252 × 100
= 360.1 2. Clay contains x% silica, 81 – ­­­­x% impurities, 19% H2O.
69.98
After partial drying 50% silica, 40% impurities and
33. BaF2 + H2SO4 
→ BaSO4 + 2HF 10% H2O are obtained.
x 81 − x
2NaOH + H2SO4  → Na2SO4 + 2H2O So, =
50 40
1 mole of H2SO4 reacts with BaF2 and produces 2
moles of HF. To react with 2 moles of HF the NaOH x = 45%
required is 2 moles and to react with 1 mole of H2SO4 3. Moles of C2O42– = 0.02
left required 2 moles of NaOH. Thus, a total of 4 moles No. of ions = 0.02 × 6.02 × 1023 = 1.204 × 1022
of NaOH is required.
35. Since the gram atomic weight of Al is less, more 4. A2(CO3)x 
→ A2Ox + XCO2
amounts can be obtained for the same rate. B2(CO3)y 
→ B2Oy + yCO2
1.24
Moles of P = = 0.04 5. 120 g MgSO4 contains 18x g of H2O
31
87 g of MgSO4 contains 13 g of H2O
0.96
Moles of S = = 0.03 120 18 x
32 =
Ratio of moles of P:S = 0.04:0.03 = 4:3. 87 13
\ Empirical formula = P4S3. \  x = 1.
38. For precipitating 0.2 moles of BaSO4, 0.2 moles of 6. 7 g of sodium combines with 93 g of anion present in
H2SO4 and to precipitate 0.1 mole of PbCl2, 0.2 mole the sodium salt of dye.
of HCl are required. These can be obtained from 23 × 93
23 g of sodium react with g of anion
0.1 mole of S2Cl2. 7
Mol. wt. of acid dye = 1 + 305.5 = 306.5
41. 2HCI3 + 6Ag  → C2H2 + 6AgI
2 moles of CHI3 gives 1 mole of C2H2 7. 8.4 g of x combines with 6.5 g of oxygen.
0.01 mole of CHI3 gives 0.005 mole of C2H5 that 96 × 8.4
occupies. 96 g of oxygen combines with = 124 g of
6.5
42. The mole ratio of oxygen that combines with 1 mole x g of x
of manganese in MnO2, Mn2O3, MnO3 and Mn2O7 is 124
\ At. Wt. = = 31.
2:1.5:3:3.5. So, Mn2O7 contains maximum percentage 4
by weight of combined oxygen. 14. Initial no. of moles of CO2
43. The mole ratio of oxygen that combines with 1 mole of 200 × 10 −3
= = 4.545 × 10 −3
iron in FeO, Fe2O3 and Fe3O4 is 1:1.5:1.33, respective­ 44
ly. Therefore, the amount of O2 required is maximum No. of moles of CO2 removed = 1.66 × 10 −3
for the formation of Fe2O3.
No. of CO2 moles remained = 2.88 × 10 −3
254 80
44. : = 2 : 5. So, the compound is I2O5.
127 16 17. 100 g of crystals contain zinc = 22.65 g
45. Since the metal ion is M2+ and phosphate is PO43– the 22.65
20 g of crystals contain zinc = × 20 = 4.53 g
formula of metal phosphate would be M3(PO4)2. 100

Chapter_01.indd 24 3/26/2014 2:39:59 PM

 Basic Concepts of Chemistry  1.25

21. Compound Composition 29. Let the weight of CaCO3 = xg

A 40% x; 60% y CaCO3  → CaO + CO2
B 25% x; 75% x MgCO3  → Mgo + CO2
In compound A, 40 g of x combine with 60 g of y. Weight of CaO + MgO = 1.3 g
In compound B, 25 g of x combine with y = 75 g 56 40
75 ∴ × x + (259 − x ) = 1.3 g
40 g of x combine with y = × 40 = 120 g 100 84
25 x = 0.84 g.
Ratio between the weight of y which combine with the
fixed weight of x (40 g) = 60:120 =1:2. 31. 2PH3  → 2P + 3H2
2 moles 3 moles
22. Let the mass of each substance is 32 a.
100 mL 150 mL
Then. mole ratio is Increase in volume = 150 ­ 100 = 50 mL.
32 32 32
O2 = ; H 2 = and CH 4 = 33. Mass = 20.036 – 0.02 = 20.016 g = 20.02 g
32 2 2
Reported to two decimal places.
\ The volume ratio is also 1:16:2
20.02
25. 3F–; 1 Formula unit AlF3 Density = = 9= .268 9.27
2.16
3.0 × 10 24 F − = 1× 10 24 formula units. as it should contain three significant figures.
26. Mol. mass of Fe(HCOO)2 = 170
34. Weight of metal oxide = 3.6 g
Fe in 100 mg of Fe(HCOO)2
Weight of metal = 3.2 g
56 × 100
= = 32.9 mg Weight of oxygen = 0.4 g
170
Element Relative No. of atoms Simple ratio
Total Fe in 400 mg capsule = 32.9 mg
Metal    3.2/64 = 1/20    2
32.9 × 100
\ % of Fe in capsule = = 8.2 Oxygen      0.4/16 = 1/40    1
400 \ Formula of the compound = MnO
27. Since almost whole the mass of an atom is in the nucleus 36. 4KClO3  → (3KClO4 + KCl)
Mass of F nucleus = Mass of F atom 4 moles 3 moles
19 0.1 mole 0.75 mole
   = g
6.02 × 10 23
37. Ca(OH)2 + CO2  → CaCO3 + H2O
   = 3.15 × 10 −23 g 1 mole 1 mole
(At. mass of F = 19) 100 g of CaCO3 = 1 mole
4 0.05 g of CaCO3 = 0.0005 mole
Volume of nucleus = π r 3 \ 0.0005 mole of CO2 = 0.012 litre
3
0.012 litre of CO2 is present in 10 litres of air
4 22 Per cent of CO2 in air = 1.12.
= × × (5 × 10 −13 )3 cm3
3 7 5
38. C2H2 + O2  → 2CO2 + H2O
= 5.24 × 10 −37 cm3 2
Mass 3.15 × 10 −23 g 7
Density = = C2H6 + O2  → 2CO2 + 3H2O
Volume 5.24 × 10 −37 cm3 2
3
= 6.02 × 1013 g cm − 3 = 6.02 × 1013 g / mL. CH3OH + 
→ O2CO2 + 2H2O
2
28. We suppose that at 4°C (when it has maximum den­ C2H5OH + 2CO2  → 2CO2 + 2H2O
sity) there is no empty space between the molecules of
Wt.of nitrogen
water = 18 mL 39. % of N = ×100 \ NH3 has maxi­
M.W.of fertiliser
Vol. of 1 mole of water vapour at STP = 22400 mL
mum per cent of N.
Percentage  of  Volume occupied = 18 × 100 = 0.08%
22400 40. One mole of nicotine gives 10 moles of CO2
The volume actually occupied is less than 1%. 0.1 mole of nicotine gives 1 mole of CO2 = 44 g

Chapter_01.indd 25 3/26/2014 2:40:04 PM

 This page is intentionally left blank.

Chapter_01.indd 26 3/26/2014 2:40:04 PM

 2

Chapter
Structure of Atom

Sub-atomic particles • The charge on a proton is equal to 4.8 × 10−10 esu or

1.602 × 10−19 coulombs.
• The fundamental particles of every atom are (i) e­ lectron,
(ii) proton and (iii) neutron.
• The smallest +ve charged particle is proton. Proton
is H+ ion.
• The only element whose atoms do not contain a funda-
mental particle (neutron) is hydrogen.
Neutron
Electron • Neutron was discovered by Chadwick.
• Discovered by J.J. Thomson in 1897. • Neutron is emitted when lighter elements like beryllium
and boron are bombarded with α-particle.
• Experiments in a discharge tube show that cathode
rays are formed in a discharge tube at high voltage
• Neutron has no charge.
(10,000 V) and low pressure. • Mass of neutron is 1.00866 amu or 1.675 × 10−24 g or
• Electron is the lightest fundamental particle. 1.675 × 10−27 kg.
• Charge on electron is equal to − 4.8 × 10−10 esu or
• Neutron is the heaviest fundamental particle of the atom.
−1.602 × 10−19 coulombs.
• Mass of one electron is equal to 11837 of hydrogen Atomic models
atom or 9.109 × 10 −28
g or 9.109 × 10−31
kg. Rutherford’s atomic model
• Mass of one mole of electrons is equal to 0.55 mg.
• Energy of electron is not influenced by any magnetic • Rutherford’s experiment proved the presence of
nucleus.
field.
• • The total mass of the atom is concentrated at the centre
Specific charge decreases with increase in velocity of
of the spherical atom known as nucleus.
electron due to the increase in mass.
• • The positive charge of the nucleus is counter balanced
e/m ratio is constant for the cathode ray.
by the negatively charged electrons revolving round
the nucleus.
Proton
• Rutherford model is also known as the planetary
• Discovered by Goldstein in canal rays experiment. model.
• Properties of the canal rays are characteristic of the • As per the laws of electrodynamics a moving electron
gas taken in the discharge tube. (charged particle) should continuously loose energy
• The canal rays contain positively charged ions of gas by emission of radiation. Consequently, it should fall
present in the discharge tube. into the nucleus.
• The smallest +ve charged particle is proton. • If the electron loses energy continuously, the atomic
spectrum should be band spectrum but the atomic
• The mass of proton is 1.008 amu or 1.672 × 10−24 g or spectra are line spectra.
1.672 × 10−27 kg.

Chapter_02.indd 1 3/26/2014 2:47:04 PM

 2.2  Objective Chemistry - Vol. I

Atomic Number
(3) If S1 is the e/m of cathode rays and S2 is the e/m of
positive rays then S1 > S2.
• The number of electrons or protons in an atom is equal
(4) The specific charge of positive rays is much less
to its atomic number. than the specific charge for cathode rays because
• Moseley discovered the relation between the frequen- charge in positive rays is less.
cies of the characteristic X-rays (υ) of an element and
its atomic number (Z). 4. Among the following the correct statements are
u = a(Z - b), where a and b are constants.  I. Neutrons are not deflected by any magnetic field.
• II. Cathode rays can be deflected by both magnetic
Sum of the numbers of protons and neutrons in an
and electric fields.
atom is called its mass number.
III. Atomic weight of an element is not necessarily be a
• Mass number is the corrected atomic weight to a whole
whole number because it is average isotopic weight.
number.
IV. The constancy of e/m ratio for electron shows that
• Mass number A = Z + N where Z is the atomic number electron mass is 1/1837th of proton.
and N is the no. of neutrons. (1) I, II, III and IV (2)  I, II and III
• Atoms of an element which differ in their mass but (3) II, III and IV (4)  I, III and IV
have the same atomic number are called isotopes.
• Isotopes have the same number of protons but differ in 5. An atom has net charge of –1. It has 18 electrons and
the number of neutrons present in them. 20 neutrons. Its mass number is
• Different atoms having the same mass numbers but (1) 37 (2) 35 (3) 38 (4) 20
with different atomic numbers are called isobars. 6. The incorrect statement among the following is
• Atoms of different elements containing the same num- (1) The mass of one mole of electron is 0.55 mg.
ber of neutrons are called isotones. (2) Positive charge in an atom is concentrated in the
• Isotones differ in both atomic numbers and mass num- nucleus.
bers but difference in the atomic number and mass (3) Combination of a α-particle with a nuclide results
number is the same. in the formation of a new nuclide that has higher
atomic number.
(4) Atoms of all elements should contain equal num-
 Objective Questions ber of protons and neutrons.
7. Which of the following statements is wrong?
1. Among the following the false statement is
(1) Compared to mass of lightest nucleus the mass of (1) α-rays, β-rays and cathode rays consist of parti-
electron is only about 1/1836. cles of matter.
(2) The ratio of e/m, i.e., specific charge for a cathode (2) The addition of a neutron to the nucleus of an
ray is constant. atom do not affects its chemical properties.
(3) Among He2+, H+, He+ and H the species having (3) When the speed of electron increases its specific
the highest e/m ratio is He2+. charge decreases.

(4) The e/m for positive rays in comparison to ­cathode (4) The fundamental particle with highest specific
rays is very low. charge is proton.
2. The wrong statement among the following is 8. Which of the following statements are correct?
(1) The mass of neutron is of the order 10−27 kg.  I. The fundamental particle that can be removed
(2) Mass of neutron is 1840 times the mass of electron. from a stable neutral atom with least energy
(3) The minimum real charge on any particle which change is electron.
can exist is 4.8 × 10−10 coulomb. II. Since neutron is chargeless its discovery became
(4) Proton is ionised hydrogen atom. very late.
3. Which do not explains correctly about the e/m (­specific III. Atoms and ions of the same element differ in their
charge)? relative sizes, configuration and charge.
(1) The e/m is not constant for positive rays. IV. A proton is similar to hydrogen nucleus.
(2) The ratio of the e/m of an electron to that of a (1) I, III and IV (2)  I, II, III and IV
hydrogen ion is 1840:1. (3) I and V (4)  II, III and IV

Chapter_02.indd 2 3/26/2014 2:47:05 PM

 Structure of Atom  2.3

9. Atoms consist of electrons, protons and neutrons. 17. The atomic mass of lead is 208 and its atomic num-
If the mass attributed to neutrons were halved and that ber is 82. The atomic mass of bismuth is 209 and its
attributed to the electrons were doubled, the atomic atomic number is 83. The ratio of neutrons/protons in
mass would be approximately the atom
(1) same (2)  doubled (1) higher of Pb (2) higher of Bi
(3) halved (4)  reduced by 25% (3) same of both (4) none of these

10. The ratio between the neutrons present in carbon and 18. When β-particles are sent through a tin metal foil most
silicon with respect to atomic masses of 12 and 28 is of them go straight through the foil because
(1) 3:7 (2)  7:3 (1) β-Particles are much heavier than electrons.
(3) 3:4 (4)  6:28 (2) β-Particles are positively charged.
(3) Most of the atom is empty space.
11. A transition element X has the configuration [Ar] 3d5 (4) β-Particles are slow moving electrons.
in its +3 oxidation state. Its atomic number is 235
19. If three neutrons are added to the nuclei U, the new
(1) 22 (2) 25 (3) 26 (4) 19 92
particle have an atomic number
12. Which one of the following statements about atomic (1) 89 (2) 95 (3) 90 (4) 92
number is false? +
20. The HD ion contains
(1) It is equal to the number of protons present in the
nucleus. (1) 1 proton, 1 neutron, 1 electron
(2) It is a more fundamental property of the atom than (2) 2 protons, 1 neutron, 2 electrons
the atomic weight. (3) 2 protons, 1 neutron, 0 electron
(3) No two elements can have the same atomic number. (4) 2 protons, 1 neutron, 1 electron
(4) The atomic number of an element decides its
­stability. Answers
13. The nucleus of an atom contains “n” number of pro- (1) 3 (2) 3 (3) 4 (4) 1 (5) 2
tons. Therefore (6) 4 (7) 4 (8) 2 (9) 4 (10) 1
(1) The atom should be unstable (11) 3 (12) 3 (13) 3 (14) 4 (15) 2
(2) There should be n number of neutrons in it (16) 1 (17) 1 (18)  3 (19)  4 (20)  4
(3) There should be n number of extra nuclear
­electrons in the atom.
(4) There should exist n number of isotopes for that
atom.
developments leading to the
14. The electrons of Rutherford’s model of the atom are bohr’s model of atom
expected to lose energy because they
Nature of Electromagnetic Radiation
(1) are attracted by the nucleus
(2) strike each other • All radiant energy propagates in the form of waves.
(3) are accelerated • The radiant energy is in the form of electromagnetic
(4) are in motion waves.
15. X-rays are produced when a stream of elections in an • The radiations are associated with electric and magnetic
X-ray tube field perpendicular to one another.
(1) Hit the glass wall of the tube • On the propagation of an electromagnetic ­radiation
(2) Strike the metal target there is only propagation of wave but not that of
(3) Pass through a strong magnetic field medium.
(4) Pass through a strong electric field • Wavelength (λ) is the distance between two successive
16. The electronic configuration of a dispositive metal in crests or between two successive troughs of waves.
M2+ is 2, 8, 14 and its atomic weight is 56 amu. The • Wavelength is measured in Å (Angstroms) or nm
number of neutrons in its nucleus would be (nanometers)
(1) 
30 (2) 32 (3) 34 (4) 42 1 Å = 10−8 cm or 1 nm = 10−9 m

Chapter_02.indd 3 3/26/2014 2:47:05 PM

 2.4  Objective Chemistry - Vol. I

• Frequency is the number of waves per second passing • The emission of electrons from metal surface when
at a given point. It is denoted by υ. Units of frequency exposed to radiation of suitable wavelength is known
are Hertz or Cycles s−1. as photoelectric effect.
• Velocity of light c = 3 × 108 ms−1 • The photoelectric effect is readily exhibited by alkali
• Wavelength is inversely proportional to the frequency metals like K and Cs.
of the wave. • When photon strikes the metal, its energy is absorbed
• Velocity of light = Frequency × Wavelength or c = υλ. by the electron of an atom in the surface of metal and
emission of electron takes place.
• Wave number is the number of waves spread in one
centimetre, denoted by u. • A part of the energy of the photon is used up to escape
the electron from the attractive forces and the remaining
• Wave number u is the reciprocal of wave length.
energy is used in increasing the kinetic energy of the
1 c electron.
υ = ; υ = ∴ υ = cυ
λ λ hν = W + KE
• Units of wave number are cm−1 or m−1
hν is the energy of photon, W = energy required to over-
come the attractive forces on an electron in the metal
Quantum Theory of Radiation atom and KE is the energy of the emitted electron.
• A photon exists independently until it is absorbed by
• Corpuscular theory of light was proposed by Newton. another body.
• According to corpuscular theory of Newton, light is • A body can absorb light energy in the form of photons
propagated in the form of small invisible particles. and goes to the excited state E2 from the ground state E1.
• Quantum theory was proposed by Max Planck and was • Emission of energy takes place during the transition
extended by Einstein. from excited state to ground state
• A hot vibrating body does not emit or absorb energy E2 − E1 = ∆E = hν
continuously but emits or absorbs energy discontinu-
ously in the form of small energy packets called quanta.
• The energy of radiation (E) is proportional to its
­frequency (n).  Objective Questions
E ∝ ν (or) E = hν
21. Which is not characteristic of Planck’s quantum theory

h is a constant known as Planck’s constant. Its value of radiation?
is 6.6256 × 10−34 Js or kg m2 s−1 or 3.6253 × 10−27 erg (1) Radiation is associated with energy.
second or g cm2.
(2) Energy is neither absorbed nor emitted in whole
• A hallow sphere coated with platinum black inside and number or multiples of quanta.
having a small hole in its wall acts as a near-black (3) The magnitude of energy associated with quanta
body. is proportional to the frequency.
• Black body is a perfect absorber and perfect emitter of (4) Radiation energy is neither emitted nor absorbed
radiant energy. continuously but in small packets called quanta.
• At a given temperature the intensity of radiation 22. Find out the false statement among the following.
­increases with wavelength, reaches a maximum and
(1) The ejection of electrons when surface of a metal
then decreases.
is irradiated by light is known as Compton effect.
• As the temperature increases, the intensity of the (2) Light, a well-known form of energy, is treated as
­radiation will be more towards the lower wavelengths. a form of matter by saying that it consists of pho-
• Planck’s quantum theory explains only the black body tons or bundles of energy.
radiations. (3) Einstein’s theory of photoelectric effect is based
• Einstein extended the quantum theory to all types of on Planck’s quantum theory.
electromagnetic radiations. (4) In photoelectric effect, the photocurrent does not
• Einstein called the energy packets of electromagnetic depend on the frequency of photon but depends
radiations as photons. on the intensity of incident light.

Chapter_02.indd 4 3/26/2014 2:47:06 PM

 Structure of Atom  2.5

23. Among the following the correct statement(s) is/are 28. A surface ejects electrons when hit by violet light but
(1) Increase in the frequency of the incident radiation not when hit by yellow light. Will electrons be ejected
increases the kinetic energy of photoelectrons. if the surface is hit by red light?
(2) Threshold wavelength depends upon work function.
(1) Yes
(3) The study of photoelectric effect is useful in
(2)  No
­understanding quantisation of energy.
(3) Yes, if the red beam is quite intense
(4) To cross the threshold energy intensity of the light
(4) Yes, if the red beam continues to fall upon the sur-
must be increased. face for some time
(1) I, II and III (2)  II, III and IV
29. If l1 and l2 are wavelengths of characteristic X-rays
(3) I, III and IV (4)  I, II, III and IV and gamma rays, respectively then the relation be-
24. The incorrect statement among the following is tween them is
(1) Dimensions of Planck’s constant are force × time. (1) l1 = 1/l2 (2)  l1 = l2
(2) A photon is a quantum of matter. (3) l1 > l2 (4)  l1 < l2
(3) Photoelectric effect shows particle-like behaviour
30. When the frequency of light incident on a m ­ etallic
of light.
plate is doubled, the kinetic energy of the emitted
(4) The best metal to be used for photoemission is
­photoelectrons will be
caesium.
(1) Doubled
25. Among the following the wrong statement is (2) Halved
(1) A quanta will have more energy if the frequency (3) Increased but more than double of the previous KE
is higher. (4) Unchanged
(2) The minimum energy required to eject an electron 31. A light beam irradiates simultaneously the surfaces
from an atom is called work function. of two metals A and B. At wave length l1 electrons
(3) The photoelectric effect occurs only when the are ejected only from metal A. At wavelength l2 both
incident light has more frequency than a certain metals A and B eject equal number of electrons. Then,
minimum wavelength. which one of the following is false?
(4) The Planck’s constant has a unit of angular
(1) l1 = l2
­momentum.
(2) Electrons need more energy to escape from B
26. Which of the following statement is correct? (3) With l2 the kinetic energy of electrons emitted
(1) The kinetic energy of photoelectrons increases from A is less than that of electrons from B
linearly with wavelength of the light. (4) Electrons emitted from A have the greater kinetic
(2) Photoelectric effect can be explained based on energy when produced by l2 light
corpuscular nature of light. 32. The ratio of the energy of photon 2000 Å wavelength
(3) Einstein was awarded Nobel Prize in physics in radiation to that of 4000 Å radiation is
1921 for his theory of relativity. (1) 1/4 (2) 1/2 (3) 2 (4) 4
(4) The ratio of energy to frequency of electromag-
33. What is the energy in joule of a photon of light with
netic radiation is called Rydberg’s constant.
wavelength 4 × 103 nm?
27. Photoelectric effect is the phenomenon in which (1) 7.5 × 10−20 (2) 5 × 10−20
(1) Photons come out of the metal when it is hit by a (3) 2 × 10−10 (4) 2.5 × 10−10
beam of electrons.
34. The work function for a metal is 4 eV. To emit a photo-
(2) Photons come out of the nucleus of an atom under electron of zero velocity from the surface of the metal
the action of an electric field. the wavelength of incident light should be
(3) Electrons come out of the metal with a constant
(1) 2700 Å (2)  1700 Å
velocity which depends on the frequency and
(3) 5900 Å (4)  3100 Å
­intensity of incident light wave.
(4)  Electrons come out of a metal with different 35. The energy per mole of photon of electromagnetic
­velocities not greater than a certain value which ­radiation of wavelength 4000 Å
depends only on the frequency of the incident (1) 3 × 1012 erg (2)  4 × 1012 erg
light wave and not on its intensity. (3) 5 × 10 erg
12
(4)  6 × 1012 erg

Chapter_02.indd 5 3/26/2014 2:47:06 PM

 2.6  Objective Chemistry - Vol. I

36. The wavelength of an electromagnetic radiation with • The spectrum formed by the absorption of energy
energy 3.3 × 10−12 erg is in the form of light radiation is called absorption
(1) 8000 Å (2)  6000 Å spectrum.
(3) 4000 Å (4)  5000 Å • Absorption spectrum consists of dark lines or bands
on a bright background.
37. Find the frequency of light that corresponds to photons
having energy 5 × 10−5 erg • Absorption spectrum is just opposite to emission
spectrum.
(1) 2.2 × 10-11 erg (2)  7.5 × 1021 s-1
(3) 4.0 × 10-5 cm (4)  4.0 × 104 cm • The dark lines in the absorption spectrum and bright
lines in the emission spectrum of a particular ­substance
38. What is the energy of photons that corresponds to a appear at the same place (wavelength).
wave number of 3.33 × 10−5 cm−1? • The apparatus used to record the spectrum is called
(1) 2.5 × 10-20 erg (2)  5.1 × 10-23 erg spectrometer or spectrograph.
(3) 5.0 × 10 erg
-22
(4)  6.62 × 10-21 erg • Emission spectrum is due to the emission of light by
39. An atom is known to absorb energy of 5.0 × 10 erg. −11 the excited atoms or molecules.
In the spectrum of this atom the missing wavelength is • Absorption spectrum is due to the excitation of atoms
(1) 3.975 × 10-6 cm or molecules by absorbing energy.
(2) 3.975 × 106 cm • Each element has its own characteristic line spectrum
(3) 3.975 × 10-8 cm by which they can be identified.
(4) 3.975 × 108 cm • Line spectra are given by atoms so known as atomic
40. If the wavelength of certain wave of light is 2 × 10 cm,
3 spectra and band spectra are given by molecules, so
what is the frequency of this wave? known as molecular spectra.
(1) 3 × 10-10 cm/s (2)  1.5 × 107/s
(3) 5000 Å (4)  3 × 104 cm Hydrogen Spectrum
• Of all the atomic spectra, the hydrogen spectrum is the
simplest spectrum.
Answers • Hydrogen spectrum consists of groups of lines classi-
fied into various series.
(21) 
2 (22) 1 (23) 1 (24) 1 (25) 3 • Only Balmer series is the visible series in the hydrogen
(26) 
2 (27) 4 (28) 2 (29) 3 (30) 3 spectrum.
(31) 
3 (32) 3 (33) 2 (34) 4 (35) 1 • Wavelength of a spectral line in the hydrogen spectrum
(36) 
2 (37) 2 (38) 4 (39) 1 (40) 2 can be calculated by using Rydberg’s equation.
1 1 1
• υ= RH  2 − 2 
λ  n1 n2 
types of spectra • R is the Rydberg constant and its value is 109677 cm−1
for hydrogen atom.
• The arrangement obtained by splitting of electromag-
• In Balmer series, the first line is called Hα, second line
netic radiation into its component wavelengths when
as Hβ, third line as Hγ, fourth line as Hδ and so on.
passed through a prism is called spectrum.
• • The wavelengths of Hα, Hβ, Hγ and Hδ are obtained by
When white light is passed through a prism, it gives a
substituting n1 = 2 and n2 = 3, 4, 5 or 6.
continuous spectrum of seven colours (VIBGYOR).
• • The different series in hydrogen spectrum are
In a continuous spectrum each colour fades into the
next colour as in rainbow. Name of series n1 n2 spectral
• The spectrum of incandescent white light obtained by region
heating a solid to very high temperature is a c­ ontinuous Lyman series 1 2, 3, 4, 5... U.V.
spectrum. Balmer series 2 3, 4, 5, 6... Visible
• Emission spectrum consists of bright lines or bands
Paschen series 3 4, 5, 6, 7 Near IR
on a dark background.

Chapter_02.indd 6 3/26/2014 2:47:07 PM

 Structure of Atom  2.7

Name of series n1 n2 spectral 44. Which are in ascending order of wavelength?

region (1) Hα, Hβ, Hγ ......... line in Balmer series of hydro-
gen atom
Bracket series 4 5, 6, 7... IR
(2) Lyman limit, Balmer limit and Paschen limit in
Pfund series 5 6, 7... Far IR the hydrogen spectrum
(3) Blue, violet, yellow, red colours in solar spectrum
• The spectral lines get closer and closer as we move (4) None
from n2 = 3 to 4 to 5 to 6, etc. 45. The frequency of first line in Balmer series in h­ ydrogen
• If n2 is taken as ∝, the limiting wavelength of the lines atom is n0. The frequency of corresponding line emit-
in any series can be obtained. ted by singly ionised lithium atom is
• From Lyman series to Pfund series, wavelength i­ ncreases (1) 2n0 (2) 4n0 (3)  n0/2 (4)  n0/4
but frequency and energy decreases. 46. Which of the following statements is correct?
• Maximum difference in energy for hydrogen atom is (1) Rydberg constant is same for all elements.
found when n1 = 1 and n2 = 2 or higher value. (2) Line spectra is characteristic of molecules.
(3) Transition of electron from n = 3 to n = 1 level
• RH value of 109677 cm−1 is valid only for the lines in
results in band spectrum.
the hydrogen spectrum.
(4) The continuum of atomic spectrum is due to ioni-
• For a spectral line of any one electron species like He+ sation of atom.
or Li2+ the value of R is equal to 109677 × Z 2 cm−1
47. Which of the following statements is wrong?
where Z is the atomic number.
(1) In the hydrogen spectrum least energetic series is
• Number of spectral lines when an electron is coming Pfund series.
to ground state or to the orbit n1 from excited state in (2) The lines of longest wavelength in the Balmer
orbit n2 can be calculated by ­series correspond to the transition between n = 3
• n ( n + 1) where n = (n − n ) and n = 2 levels.
2 1
2 (3) The dark lines in a spectrum are produced by
­existing gases to very high energy levels.
(4) The wave number of infinity line in Lyman series
of hydrogen spectrum is 9R/3.
 Objective Questions 48. The first emission lines of hydrogen atomic spectrum
in the Balmer series appears at (R = Rydberg constant)
41. Which best describes the emission spectra of atomic
3R
hydrogen? (1) 5 R cm−1 (2)  cm−1
(1) A series of only four lines. 36 4
9R
(2) A discrete series of lines of equal intensity and
(3) 7 R cm−1 (4)  cm−1
equally spaced with respect to wavelength. 144 400
(3) Several discrete series of lines with both intensity 49. If the series limit of wavelength of the Lyman series for
and spacing between decreasing as the wave number the hydrogen atom is 912 Å then the series limit of wave-
increases within each series. length for the Balmer series of the hydrogen atom is
(4) A continuous emission of radiation of all fre­quencies. (1) 912 Å (2)  912 × 2 Å
42. Consider the spectral lines resulting from the ­transition (3) 912 × 4 Å (4)  912/2 Å
n = 2 to n = 1, in the atoms and ions given below, the 50. The shortest λ for the Lyman series is ..... (given
shortest wavelength is produced by RH = 109 678 cm−1)
(1) Hydrogen atom (1) 912 Å (2)  700 Å
(2) Deuterium atom (3) 600 Å (4)  811 Å
(3) Singly ionised lithium
[Hint:  For shortest wavelength n1 = 1 and n2 = ∝]

(4) Doubly ionised lithium
43. Of the following transitions in hydrogen atom the one 51. The longest λ for the Lyman series is ...... (given
which gives an absorption line of lowest frequency is RH = 109 678 cm−1)
n = 1 to n = 2
(1)  (2)  n = 3 to n = 8 (1) 1215 (2)  1315 (3)  1415 (4)  1515
n = 2 to n = 1
(3)  (4)  n = 8 to n = 3 [Hint:  For longest wavelength, n1 = 1 and n2 = 2]

Chapter_02.indd 7 3/26/2014 2:47:08 PM

 2.8  Objective Chemistry - Vol. I

52. The wave number of the first line in Balmer series of • Bohr’s equation to calculate the radius of an orbit r
hydrogen is 15200 cm−1. The wave number of the first n2 h2
line in the Balmer series of Li2+ is =
4π 2 Ze 2 m
(1) 15,200 cm-1 (2)  60,800 cm-1 • For hydrogen since z is 1 the radius of an orbit is equal
-1
(3) 76,000 cm (4)  1,36,800 cm-1 to 0.529 × n2 Å.
53. The wavelength of radiation emitted by hydrogen • Radius of 1st orbit = 0.529 Å
when compared to He+ is
Radius of 2nd orbit = 2.11 Å

(1) 2 times that of He+ ion
(2) 3 times that of He+ ion • Kinetic energy of the electron due to motion = 1 mv2
(3) 4 times that of He+ ion 2 e2
Potential energy of the electron due to position = −
(4) Same as that of He+ ion r
• Total energy of the electron E = kinetic energy +
Answers ­potential energy.
1 e2 e2 e2
(41) 3 (42)  3 (43)  2 (44)  2 (45)  2 = mv2 − = −
2 r 2r r
(46) 4 (47)  2 (48)  1 (49)  3 (50)  1
(51) 1 (52)  4 (53)  3  e2 2 e2
∵
 r = mv  = −
2r
• Bohr’s equation for calculating the energy of an orbit:
Bohr’s theory of atom 2π 2 me 4 Z 2
En = −
n2 h2
• The basis for the Bohr’s model of atom is the Planck’s • The energy of an electron in an atom is negative and
quantum theory and hydrogen spectrum. inversely proportional to the square of the n value (n is
• Electrons revolve round the nucleus in concentric circu- the number of orbit).
lar orbits which are represented by K, L, M, N, O, P... etc. • As the electron moves away from the nucleus the k­ inetic
or 1, 2, 3, 4, 5, 6,.... etc. energy decreases and potential energy increases.
• Each orbit is associated with some definite energy. • The potential energy of an electron is zero when the
So, they are known as energy levels or stationary orbits. electron is at infinite distance from the nucleus.
• Energy of the orbit increases with increase in the • The kinetic energy of an electron (positive value) is
­distance from the nucleus. greater than the potential energy (negative value).
• The energy of an electron moving in an orbit remains • The energy of an electron in the hydrogen atom:
constant.
• The electrons can move from one orbit to another orbit En = − 313.6 k cal mole−1
only when they lose or gain the energy difference of n2
the orbits. = −1312 kJ mole−1
∆E = E2 − E1 = hυ n2
−11
• An electron while moving from higher energy level to
= 2.18 × 10 ergs atom−1
the lower energy level emits energy in the form of light. n2
• The angular momentum (mvr) is quantised. It is an = −13.6 = eV atom−1
integral multiple of h/2π where h is Planck’s constant. n2
nh • Bohr’s equation to calculate the velocity of an electron
mvr = in hydrogen atom:
2π
Vn = nh = 2πe × Z
2
• The force of attraction between the nucleus and the
e2 2πmr h n
electron = − 2 • The velocity of electron in the first orbit of hydrogen is
r
• The centrifugal force gained by the electron due to 2.188 × 106 ms−1.
mv 2 • The energy emitted or absorbed when an electron moves
­revolving round the nucleus = −
r from one orbit to another orbit can be calculated from

Chapter_02.indd 8 3/26/2014 2:47:10 PM

 Structure of Atom  2.9

 56. Which of the following concerning Bohr’s model is

∆E = hυ = hc u can be calculated by using Rydberg’s
not true?
Ritz equation.
(1) It predicts that probability of an electron near ­nucleus
 1 1 is more.
υ = RH  2 − 2 
 n1 n2  (2) Angular momentum of electron in nth orbit is
2π 2 mer given by nh/2π.
The RH value =
= 109699 cm-1 n2
ch3 (3) The radius of an orbit is proportional to .
Z
• Bohr’s theory could explain the spectra of atom and
(4) When an electron jump from N to K shell, energy
ions like He+, Li2+ and Be3+ having one electron only.
is released.
• Bohr’s theory correlates velocity of light, electronic
mass, Planck’s constant and electronic charge. 57. If the mass of the electron is reduced to half, the
­Rydberg constant
• The energy of orbit, radius of orbit and the value of
Rydberg constant RH calculated from Bohr’s theory (1) Remains unchanged (2)  Becomes half
are in good agreement with experimental value. (3) Becomes double (4)  Becomes one-fourth
• Bohr’s theory could not explain the spectra of atoms  2π2 me 4 
having electrons more than one.  Hint : RH = 
ch3 

• Bohr’s theory could not explain the wave nature of
electron established later by de Broglie. 58. The ratio of the difference in energy of electron be-
• It could not explain Zeeman effect and Stark effect. tween the first and second Bohr’s orbits to that between
• Splitting of spectral lines in a strong magnetic field is second and third Bohr’s orbits is
called Zeeman effect. (1) 1/3 (2) 27/5 (3) 9/4 (4) 4/9
• Splitting of spectral lines in a strong electric field is 59. The binding energy of the electron in the lowest orbit
called as Stark effect. of the hydrogen atom is 13.6 eV. The energies required
• The further splitting of ordinary spectrum when taken in eV to remove an electron from three lowest orbits of
by a super spectrometer is called fine spectrum. the hydrogen atom are
(1) 13.6, 6.8, 8.4 eV (2)  13.6, 10.2, 3.4 eV
(3) 13.6, 27.2, 40.8 eV (4)  13.6, 3.4, 1.5 eV
 Objective Questions
60. Bohr’s model violates the rules of classical physics
54. Which of the following statements is wrong? ­because it assumes that
(1) Bohr’s model can explain spectrum of any atom or (1) All electrons have same charge.
ion having one electron only. (2) The nucleus has same charge.
(2) The wavelength of spectral line for electronic (3) Electrons can revolve around the nucleus.
transition is inversely related to the difference in (4) A charged particle can accelerate without ­emitting
the energy levels involved in transition. radiant energy.
(3) Outer orbits have greater energy than inner orbits. 61. According to Bohr’s postulates which quantity can
(4) Splitting of spectral lines when atoms are subjected take up only discrete values?
to a strong electronic field is called Zeeman effect.
(1) Kinetic energy (2) Angular momentum
55. Among the following the wrong statement is (3) Momentum (4) Potential energy
(1) As the number of orbit increases from the ­nucleus, 62. If the speed of electron in the Bohr’s first orbit of
the difference between the adjacent energy levels ­hydrogen atom is X, the speed of the electron in the
decreases. third Bohr’s orbit is
(2) The angular velocity of the electron in the nth (1) X/9 (2)  X/3 (3) 3X (4) 9X
­orbit of Bohr’s hydrogen atom is inversely pro­
portional to n3. 63. Ionisation potential of hydrogen atom is 13.6 eV. The
ionisation potential of He+ will be
(3) According to Bohr’s model of hydrogen atom, the
angular momentum of the electron is quantised. (1) 54.4 eV (2)  6.8 eV
(4) The total energy of an atomic electron is more (3) 13.6 eV (4)  24.5 eV
than zero. [Hint: E1He+ = E1H × Z2]

Chapter_02.indd 9 3/26/2014 2:47:15 PM

 2.10  Objective Chemistry - Vol. I

64. If the hydrogen atom is excited by giving 8.4 eV of en- Answers

ergy, then the number of spectral lines emitted is equal to
(1) None (2) Two (3) Three (4) Four (54) 4 (55)  4 (56)  1 (57)  2 (58)  2
65. Which of the following statements is wrong? (59) 4 (60)  4 (61)  2 (62)  2 (63)  1
(64) 1 (65)  3 (66)  3 (67)  4 (68)  1
(1) The energy of the electron at infinite distance
from the nucleus in Bohr’s model is taken as zero.
(2) If an electron is brought from an infinite distance
close to the nucleus of the atom, the energy of the Quantum numbers
electron nucleus system decreases to a greater
negative value. • To explain the line spectrum, each electron in an atom
(3) As the electron moves away from the nucleus its is assigned with a set of four quantum numbers.
velocity increases. • Quantum numbers explain the orbital concept of
(4) As the electron moves away from the nucleus its atomic model, i.e., size, shape, orientation and spin of
kinetic energy decreases while potential energy the electron.
increases.
66. The incorrect statement among the following is Principal Quantum Number
(1) If the energy of an electron in the first Bohr orbit • It was proposed by Bohr and denoted by n.
of hydrogen atom is −313.6 k cal/mol, then the
energy of the electron in the second orbit will be • It will have any integer value except zero.
−78.4 kJ cal/mol. • It gives the size of the orbit and hence energy of the orbit.
(2) If the velocity of an electron in the first Bohr orbit • As the value of n is increasing, the size and energy of
of hydrogen is v1 then the velocity in the second the orbit increases.
will be v1/2.
(3) The angular momentum of an electron in He+ is • It also represents the distance of the electron from the
h/2π when it is present in the second orbit. nucleus.
(4) When an excited atom returns to the ground state, • The number of electrons that can present in an orbit is
it emits photons. equal to 2n2.
67. When electronic transition occurs from an higher ­energy
to a lower energy state with energy difference equal to Azimuthal Quantum Number
expressed in electron volts the wavelength of line emit-
ted is approximately equal to • It was proposed by Sommerfeld and denoted by l.
• It gives the shape of the orbital.
12375 Å
(1)  (2)  12375 × 10−8 cm • l values depend upon the values of “n” and are equal to
∆E ∆E “n−1” i.e., l = 0, 1, 2, 3, .......
12375 × 10−10 m • Depending upon “l” values the subshell in which the

(3)  (4)  Either of these
∆E electron is present can be known.
 12375  If l = 0, the electron belongs to s-subshell.

Hint : ∆ (eV ) =

 λ 
If l = 1, the electron belongs to p-subshell.

68. Considering the three electronic transitions n = 2 →
n = 1, n = 3 → n = 2 and n = 4 → n = 3 for the hydrogen If l = 2, the electron belongs to d-subshell.

at which one of the following is true. If l = 3, the electron belongs to f-subshell.

(1) The photon emitted in the transition n = 4 to n = 3 • The number of electrons that can present in a subshell
would have the longest wavelength.
is equal to 2(2l + 1) or (4l + 2).
(2) The photon emitted in the transition n = 2 to n = 1
would have the longest wavelength.
• The number of subshells present in an orbit is equal to
the value of principal quantum number “n” value.
(3) The transition from n = 3 to n = 1 is forbidden.
(4) The electron does not experience any change in • No. of subshells in K shell (n = 1) = 1 (1s)
orbit radius for any of these transitions. • No. of subshells in L shell (n = 2) = 2 (2s, 2p)

Chapter_02.indd 10 3/26/2014 2:47:16 PM

 Structure of Atom  2.11

• No. of subshells in M shell (n = 3) = 3 (3s, 3p, 3d) [Hint: No. of spectral lines = n(n + 1) /2

• No. of subshells in N shell (n = 4) = 4 (4s, 4p, 4d, 4b) where n = n2 − n1, n1 is the lowest energy level and n2

• s-orbital is spherically symmetrical in shape. is the highest energy level.

p-orbital is dumb-bell shaped. or ΣDn (Dn = n2 − n1)]


d-orbital is double dumb-bell shaped.
70. Which of the following is false about electron?

f-orbital is fourfold dumb-bell shaped. (1) The negatively charged electrons in an atom are
attracted by the positively charged nucleus by
Magnetic Quantum Number electrostatic attractive force.
(2) An electron near the nucleus is strongly attracted
• It was proposed by Lande to account for Zeeman effect. by the nucleus and has low potential energy.
• It is denoted by “ml”. (3) An electron distant from the nucleus is less firmly
• It gives the orientation of the orbital. held and has high potential energy.
• The values of ml depend upon “l” and are equal to (4) On heating an atom, all of its electrons are ejected.
(2l + 1) ranging from −1 passing through “0” to +l. 71. From the line spectrum of hydrogen it is possible to
• s-subshell will have only one value of “0” so contain calculate the ionisation energy of hydrogen by meas-
only one orbital, i.e., s-orbital. urement of the frequency of the
• p-subshell will have three orbitals having ml values (1) Line of the longest wavelength
−2, −1, 0, + 1. They are Px, Py and Pz. (2) Line of the shortest wavelength
• d-subshell will have five orbitals having ml values (3) Line of the smallest frequency
−2, −1, 0, +1, +2. (4) Line of the greatest intensity
• f-subshell will have seven orbitals having ml values 72. The ratio of the radius of the first Bohr orbit for the
−3, −2, −1, 0, +1, +2, +3. electron orbiting around the hydrogen nucleus that of
• The + and - signs indicate only change in direction but the electron orbiting around the deuterium nucleus is
the magnetic quantum number ml as such is neither approximately
positive nor negative. (1) 1:1   (2) 1:2   (3) 2:1 (4)  1:4
73. The velocity of an electron in the M shell of hydrogen
Spin Quantum Number
is X. So, its velocity in the L shell is
• It was proposed by Uhlenbeck and Goudsmit. 2x 9x 3x
(1)  (2)  (3)  (4) 3x
• It is denoted by “s”. 3 2 2
• Electron moving in an orbital can spin on its own axis. 74. In the hydrogen atom the magnitude of total energy (E)
• and potential energy (u) is given by the relation
The spin of the electron may be clockwise or
anticlockwise. (1) E = u (2)  E = 1/2u
• The clockwise spin is denoted by +1/2 or ↑ and (3) E = 2u (4)  E = 4u
­anticlockwise spin is denoted by −1/2 or ↓. 75. The electron in a hydrogen atom in the first excited
• The difference between the two spin quantum numbers state when the electron acquires an additional 2.36 eV
is 1, which is equal to the difference between succes- of energy, the electron now moves in a state whose
sive other quantum numbers. quantum number is
(1) 3 (2) 4 (3) 5 (4) 6
76. Photons of 2.55 eV are produced from certain tran-
sitions in hydrogen atoms. The ionisation energy of
 Objective Questions ­hydrogen atom is 13.6 ev. The transitions are
69. How many lines are possible in the emission spectrum (1) n = 2 to n = 1
of hydrogen by all possible transitions among the five (2) n = 3 to n = 2
levels of lowest energy within the atom? (3) n = 4 to n = 3
(1) 5 (2) 10 (3) 8 (4) 6 (4) n = 4 to n = 2

Chapter_02.indd 11 3/26/2014 2:47:17 PM

 2.12  Objective Chemistry - Vol. I

77. A gas of monoatomic hydrogen is excited by an energy 83. In a certain Bohr orbit the total energy is -4.9 eV, for
of 12.75 eV. Which spectral lines should be emitted? this orbit, the kinetic energy and potential energy are
(1) 3 Lyman, 2 Balmer and 1 Paschen lines respectively
(2) 2 Lyman, 3 Balmer and 1 Paschen lines (1) 9.8 eV, - 4.9 eV (2)  4.9 eV, - 9.8 eV
(3) 1 Lyman, 2 Balmer and 2 Paschen lines (3) 4.9 eV, - 4.9 eV (4)  9.8 eV, - 9.8 eV
(4) 1 Lyman, 2 Balmer and 1 Paschen lines 84. To move an electron in a hydrogen atom from the
78. The amount of energy required to remove the elec- ground state to the second excited state, 12.084 eV is
tron from a Li2+ ion in ground state is how many times required. How much energy is required to cause one
greater than the amount of energy needed to remove mole of hydrogen atoms to undergo this transition?
the electron from an hydrogen atom in its ground state? (1) 984 kJ (2)  1036 kJ
(1) 3 (2) 4 (3) 6 (4) 9 (3) 1166 kJ (4)  1312 kJ

79. Energy levels A, B and C of a certain atom corre- 85. Which of the following statements is false?
spond to increasing values of energy, i.e., EA < EB < (1) For azimuthal quantum number l = 3, the ­maximum
EC. If l1, l2 and l3 are the wavelengths of radiations number of electrons will be 14.
corresponding to the transitions C to B, B to A and C (2) The concept of electron spin was introduced by
to A, respectively, which of the following statement is Uhlenbeck and Goudsmit.
correct? (3) The principal quantum number of an atom rep-
resents size of the orbit and distance of electron
(1) λ3 = λ1 + λ2 (2)  λ3 = λ1λ 2 from nucleus.
λ1 + λ 2
(4) The shape of an orbital is governed by magnetic
λ1 = λ2 + λ3 = 0
(3)  (4)  λ 32 = λ12 + λ 22 quantum number.

 hc hc hc  86. Which one represents an impossible arrangement?

 Hint: E3 = E1 + E2 or = +        n   l   m   s
 λ3 λ1 λ 2 
(1) 3 2 -2 +1/2
80. If the energy difference between two electronic states (2) 4 0  0 +1/2
is 46.12 k cal/mole, what will be the frequency of the (3) 3 2 -3 +1/2
light emitted when an electron drops from a higher to (4) 5 3  0 +1/2
a lower state (nh = 9.52 × 10-14 kcal sec/mole)? 87. Which of the following is wrong?
(1) 25 × 1037 s−1
(2)  48 × 1014 s−1 (1) The correct orbital designation for the electrons
(3) 5 × 1024 s−1 (4)  50 × 1020 s−1
with quantum number n = 4, l = 3, m = 2 and
s = 1/2 is 4f.

[Hint: ∆E = nhu]
(2) Correct set of four quantum numbers of valency
81. The wave number of first line in the Balmer series of (outermost) electron of rubidium (Z = 37) is 5, 0,
hydrogen is 15200 cm-1. The wave number of the first 0, +1/2.
line in the Balmer series of Be3+ is (3) The four quantum numbers of the fourth electron
(1) 2.43 × 105 cm-1 (2) 3.43 × 105 cm-1 in beryllium are n = 2, l = 0, m = 0, s = 1/2.
(3) 4.43 × 10 cm
5 -1
(4) 5.43 × 105 cm-1 (4) The correct set of four quantum numbers of a 4d
electron is 4, 3, 2, +1/2.
 1 
 Hint: υ H / υ Be3+ = Z 2 ∴ υ Be3+ = Z υ H 
2

88. The false statement among the following is

(1) In the absence of magnetic field p-orbitals are
82. What minimum energy should electrons have for the known as threefold degenerate.
hydrogen spectrum to consist of three spectral lines
(2) Three electrons in p-subshell must have the
when hydrogen atoms are excited?
­quantum number s = +1/2 or -1/2.
(1) 10.1 eV (2)  12.1 eV (3) The magnetic quantum number for valency electron
(3) 12.75 eV (4)  13.6 eV of sodium is zero.

[Hint: The electron has to be excited to third orbit to (4) The total values of magnetic quantum number of
give three spectral lines.] an electron when the value of n = 2, is 3.

Chapter_02.indd 12 3/26/2014 2:47:18 PM

 Structure of Atom  2.13

89. An electron that has the quantum number n = 3 and where λ = wavelength of a moving particle; h = Planck’s

m = 2 must constant; m = mass of particle; v = velocity of particle and
(1) have spin value +1/2 p = momentum of the particle.
(2) have l = 1 • The dimensions of Planck’s constant depend upon the
(3) have l = 0, 1 or 2 dimensions of momentum.
(4) have l = 2 • de Broglie derived the wave nature of a moving ­particle
90. Which of the following statements is wrong? from Einstein’s mass energy equation (E = mc2) and
Planck’s quantum theory (E = hν).
(1) The quantum number that does not describe the
distance and the angular disposition of the elec- • While the electron wave is moving in an orbit if the two
tron is spin quantum number. ends meet to give regular series of crests and troughs
(2) Among the various quantum numbers (n, l, m, s) the electron wave is said to be in phase.
describing an electron, the one which has the largest • For an electron to be in phase it is necessary that the
value is principle quantum number. circumference of the Bohr’s orbit (=2πr) must be equal
(3) Each p-orbital and each d-orbital except one has to the whole number of the wavelength (λ) of electron
lobes respectively 2, 4. wave nλ = 2πr.
(4) The value of magnetic quantum number depends
on m value. Heisenberg’s Uncertainty Principle
91. Out of four quantum numbers for an electron only spin
• It is impossible to know exactly both position and
quantum number is fractional because
­ omentum of an electron or any other smaller particle
m
(1) Two consecutive values of any quantum number simultaneously and accurately.
must differ by at least 1.
• Mathematically, the uncertainty principle can be
(2) The electrons complete half revolution during spin.
­expressed as
(3) Fractional values assigned are arbitrary only.
h
(4) None. D x . Dp ≥ (where n = 1, 2, 3, 4 ......)
4π
Answers • For an electron revolving round the nucleus in an atom
the value of n is nearly 4. Hence
(69) 2 (70)  4 (71)  2 (72)  1 (73)  3 h
(74) 2 (75)  3 (76)  4 (77)  1 (78)  4 D x . Dp ≥
4π
(79) 2 (80)  2 (81)  1 (82)  2 (83)  2
(84) 3 (85)  4 (86)  3 (87)  4 (88)  4
(89) 3 (90)  4 (91)  1
 Objective Questions

92. Which of the following statements is false?

modern theory of atomic (1) de Broglie wavelength associated with matter
structure ­particle is inversely proportional to momentum.
• Modern theory of atomic structure was proposed on the (2) de Broglie equation is a relationship between a
basis of quantum mechanics proposed independently moving particle and its momentum.
by de Broglie, Schrodinger and Heisenberg. (3) de Broglie equation suggests that an electron has
particle wave nature.
(4) de Broglie equation is applicable to electrons only.
Wave Theory of Matter
93. The wrong statement among the following is
• de Broglie proposed the wave theory of moving parti- (1) If neutron, proton, electron and helium atom are
cle. Wavelength of a moving particle can be calculated moving with same velocity, the longest wavelength
by the relation: is associated with helium atom.
λ= h = h (2) The momentum of electron is inversely propor-
mv p tional to wavelength.

Chapter_02.indd 13 3/26/2014 2:47:18 PM

 2.14  Objective Chemistry - Vol. I

(3) To observe the wave nature of particles the parti- Answers

cle must have small mass and large velocity.
(4) According to de Broglie concept the circumfer- (92) 4 (93) 1 (94) 3  (95) 2 (96) 2
ence of orbit must be equal to the integral number (97) 1 (98)  1 (99)  2 (100) 
2
of electron wavelength.
  94. Which of the following statement is incorrect?
(1) The permitted orbits for electrons to revolve in an
atom should have an angular momentum equal to schrodinger wave equation
nh/2p. • The consequence of Heisenberg’s uncertainty principle
(2) Wave properties are important for the particles is that since the exact position of an electron in an atom
with very low mass. cannot be predicted, only probability of finding an elec-
(3) If uncertainty in the position of an electron is zero, tron in space around the nucleus can be predicted.
the uncertainty, in its momentum would be zero.
(4) Heisenberg’s principle postulates that the mo- • Schrodinger wave equation gives the probability of
mentum and position of an electron cannot be finding the electron in space around the nucleus.
known simultaneously. • Schrodinger wave equation is
  95. Heisenberg uncertainty principle in terms of uncer- ∂2 ψ ∂2 ψ ∂ 2 ψ 8π 2 m
+ + + (E - u) Ψ = 0
tainty of the momentum Dp and that of position Dx is ∂x 2 ∂y 2 ∂z 2 h2
represented mathematically as
where Ψ is wave function; m is the mass of electron,

(1)  (Dp) (Dx) = h
E is the total energy of electron and u is the potential
(2)  Dp/Dh = h
energy of electron.
(3)  (Dp) (Dx) = h
(4)  (Dp) (Dx) = l • Schrodinger wave equation indicates the variation of
the Ψ value along x-, y- and z-axes.
  96. Wave nature of matter is not experienced in our daily
life because the value of wavelength is • Ψ is the amplitude of the wave function.
(1)  very large • Ψ2 denotes the particle density when applied to particles.
(2)  very small • The space around the nucleus where the probability
(3)  lies in the ultraviolet region of finding an electron is maximum, i.e., 95% is called
(4)  lies in the infrared region atomic orbital.
  97. The wavelength of light is 12 nm. The momentum of • The values of Ψ can be calculated with the help of
that photon is Schrodinger wave equation and if a plot is drawn show-
(1)  5.52 × 10-26 kg m/s ing the relation between Ψ2 and r the shape of atomic
(2)  6.625 × 10-27 kg m/s orbital will be obtained.
(3)  2 × 10-27 kg m/s • The probability of finding an electron within a radial
(4)  1 × 10-27 kg m/s space around the nucleus is called radial probability
  98. The momentum of a photon is p, the corresponding distribution.
wavelength is • Radial probability distribution of an electron can be
(1)  h/p (2)  hp (3)  p/h (4)  h/ p calculated by 4pr2dr Ψ2.
  99. If the uncertainty in the position of an electron is 10–8 • Angular probability of finding an electron within the
cm, the uncertainty in its velocity is radial space around the nucleus is called atomic orbital.
(1)  3 × 108 cm/s (2)  5.8 × 107 cm/s • The probability of finding an electron at the nucleus is
(3)  6.625 × 10 cm/s 9
(4)  7.35 × 10-8 cm/s zero.

100. Dx for hydrogen atom is 10-11 m, so the minimum

• The maximum probability of finding an electron in an
orbital increases with increase in the principal quantum
­uncertainty in velocity is
number. E.g.: The maximum probability for 1s orbital
(1) 1.67 × 104 ms-1 is 0.53 Å , for 2s orbital is at 2.12 Å.

(2) 3.15 × 103 ms-1
  

(3) 5.27 × 10-30 m • The size of the orbital increases in the order 1s < 2s < 3s.
(4)  5.25 × 1028 m • s-orbital is spherical in shape.

Chapter_02.indd 14 3/26/2014 2:47:19 PM

 Structure of Atom  2.15

• p-orbital is dumb-bell in shape. The three p-orbitals 104. Wave mechanical model of the atom depends upon
are oriented along the x-, y- and z-axes which are mu-   (1) de Broglie concept of dual nature of electron
tually perpendicular.   (2) Heisenberg uncertainty principle
• The five d-orbitals are designated as dxy, dyz, d xz , d x - y
2 2
  (3) Schrodinger wave equation
and d z2 .   (4) All the above
• The first four d-orbitals are double dumb-bell in shape 105. Which element possess non-spherical shells?
each having 4 lobes.  (1) He (2) B (3) Be (4) Li
• The d z orbital is dumb-bell in shape containing a
2 106. The region of space where there is maximum prob-
ring called torus or collar or tyre of negative charge ability of finding an electron at any instant is
­surrounding the nucleus in x-y plane.  (1) an orbit
• The surface at which the probability of finding an elec-  (2) an orbital
tron is zero is called node or nodal plane.   (3) a stationary state
• The spherical “s” orbitals do not have nodal planes  (4) subshell
but have nodal regions equal to n - 1 which present 107. The electron density of 3dxy orbital in y-z plane is
between spherical “s” orbitals.  (1) 50%
• p-orbitals have both nodal regions equal to n - 2 and  (2) 95%
nodal plane equal to the “l” value, i.e., 1.  (3) 33.33%
• The nodal planes for px, py and pz orbitals are yz, xz and  (4) zero
xy respectively. 108. The chance of finding an s-electron in any particular
• Each d-orbital has nodal regions equal to n - 3 and direction from the nucleus is
nodal planes are equal to “l”.   (1) proportional to the value of its principal quantum
• For any orbital the total number of nodal regions and number
nodal planes are equal to n - 1.  (2) the same
  (3) dependent on the direction
• The nodal regions are known as radial nodes and the  (4) zero
nodal planes are known as angular nodes.
109. Which of the following statements is correct?
  (1) An orbital describes the path of an electron in an
atom.
 Objective Questions   (2) An orbital is a region where the electron is not
located.
101. The maximum probability of finding an electron in   (3) An orbital is a function which gives the ­probability
the dxy orbital is of finding the electron in a given region.
  (1) Along the x-axis  (4) None
  (2) Along the y-axis 110. Which of the following statement is false?
  (3) At an angle of 45° from the x- and y-axis   (1) The orbit with more number of nodal planes will
  (4) At an angle of 90° from the x- and y-axis be of more energy.
102. In the Schrodinger wave equation Ψ represents   (2) The orbital with two angular nodes (nodal planes)
 (1) orbits is f-orbital.
 (2) wave function  (3) The zero probability of finding the electron in
 (3) amplitude function px-orbital is in y-z plane.
 (4) all  (4) The orbital which do not has angular nodes is
s-orbital.
103. Ψ2, the wave function, represents the probability of
finding an electron. Its value depends Answers
  (1) inside the nucleus
  (2) far from the nucleus (101) 3 (102)  4 (103)  4 (104)  4 (105)  2
  (3) near the nucleus (106)  2 (107)  4 (108)  1 (109)  3 (110)  2
  (4) upon the type of orbital

Chapter_02.indd 15 3/26/2014 2:47:20 PM

 2.16  Objective Chemistry - Vol. I

Rules for filling the electrons • According to Hund’s rule, all the available orbitals are
in orbitals filled first with electrons of parallel spin and then only
pairing of electrons starts.
Pauli’s exclusion principle
• The half-filled and completely filled degenerate
• No two electrons in the same atom can have the same ­orbitals in atoms give stability.
values for all the four quantum numbers. • When two electrons are paired with parallel spin they
• The two electrons present in a given orbital may have the remain farther apart due to Coulombic repulsions.
same value of n, l and m, but they must have o­ pposite • When two electrons are paired with opposite spin
1 1 Coulombic repulsion energy is lowered.
spin, i.e., either + or -
2 2
• Pauli’s principle helps the determination of maximum Stability of Atoms
number of electrons that can be placed in an orbital of
a subshell and a main shell. • On exchanging the position in space of two electrons
• Pauli’s principle is followed only while writing the with parallel spins, if there is no change in the electron-
electronic configurations of atoms in their ground state. ic arrangement, then that leads to decrease in energy.
This pair is called exchange pair.
• The energy decrease per exchange pair of electrons is
Aufbau Principle termed as exchange energy.

• The electronic configurations of successive elements • As the number of exchange pairs increases the stability
of an atom increases by the lowering exchange energy
differ only in the last electron which is known as
E for each pair.
­differentiating electron.
• According to Aufbau principle “the electrons tend to • Chromium with electronic configuration 3d5 4s1 has
five unpaired electrons in d-orbitals and one electron in
occupy orbitals of minimum energy” in the ground
4s orbital having parallel spin, which form 15 exchange
state of atom.
pairs (6C2). So, average lowering energy is -15E.
• The energies of different orbitals can be calculated
from n + l values.
• Chromium with electronic configuration 3d4 4s2 has
only four unpaired electrons in d-orbitals which have
• In case two orbitals have the same n + l values the 10 exchange pairs (5C2). So, average lowering of ­energy
electron goes into the orbital having less n value. is -10E. Further, it requires pairing energy (+ p) for the
• The sequence of filling different orbitals by electrons paired electrons in 4s orbital.
can be known from Moeller diagram. • For chromium, the 3d54s1 configuration rather than
• The energy of 4s orbital is less than that of 3d orbital in 3d44s2 configuration is stable due to above reasons.
elements having atomic number up to 20, but in elements
having atomic number above 20, the energy of 3d orbital Magnetic properties of Atoms
is less than 4s.
• Atoms which contain unpaired electrons exhibit
• The energy of 4f orbital has more energy than 6s in the paramagnetism.
elements having atomic number up to 57, but in the
elements having atomic number around 90, the energy • Paramagnetic substances are attracted by the external
of 4f orbital is less even than 5s orbital. magnetic field.
• Electronic configurations are written in nl x method • Atoms in which all the electrons are paired exhibit
diamagnetism.
where n is the principal quantum number, l is the
­azimuthal quantum number and x is the number of • Diamagnetic substances are repelled by the external
electrons present in it. magnetic field.
• The paramagnetic moments of atoms depend upon the
number of unpaired electrons.
Hund’s Rule • The paramagnetic moment can be calculated by using
• The orbitals in a subshell having equal energy are the formula µ = n ( n + 2) BM where n is the number
called degenerate orbitals. of unpaired electrons.

Chapter_02.indd 16 3/26/2014 2:47:21 PM

 Structure of Atom  2.17

120. The total number of electrons that can be accom-

 Objective Questions modated in all the orbitals having principal quantum
number 2 and azimuthal quantum number 1 is
111. Which of the following statements is wrong?

 (1) 2 (2) 4 (3) 6 (4) 8
 (1) The rule that limits the maximum number of
­electrons in an orbital to two is Pauli’s exclusion 121. The number of vacant orbitals of element with a­ tomic
principle. number 14 is
  (2) Hund’s rule states that in a set of degenerate orbit-  (1) 2 (2) 4 (3) 8 (4) 6
als the electrons distribute with parallel spins. 122. Which atom has as many as s-electrons as p-electrons?
  (3) The order of filling of electrons in the orbitals of
an atom will be 5s, 4p, 3d, 4d, 4s.
 (1) H (2) Mg (3) N (4) Na
 (4)  The number of unpaired electrons in the 123. Suppose a completely filled or half-filled set of p- or
­electronic configuration 1s22s22p4 is 2. d-orbitals is spherically symmetrical. Point out the
species which is spherically symmetrical.
112. How many unpaired electrons are there in Ni2+?

 (1) N (2) C (3) Cl (4) Fe

 (1) 
0 (2) 2 (3) 4 (4) 8
124. The electronic configuration of the element which is
113. The orbital diagram in which Aufbau principle is
just above the element with atomic number 43 in the
­violated is
same group is
 (1)  ↑ ↓    (2)  ↑ ↑↓ ↑ ↑ (1) 1s22s22p63s23p63d104s24p6

(2) 1s22s22p63s23p63d54s2

 (3)  ↑ ↓
↑ ↑ ↑  (4)  ↑ ↓ ↑↓ ↑↓ ↑ (3) 1s22s22p63s23p63d64s1

(4) 1s22s22p63s23p63d104s24p5
114. In the ground state of chromium atom (Z = 24) the 125. The number of vacant d-orbitals in completely
total number of orbitals populated by one or more ­excited chlorine atom is
electrons is
 (1) 2 (2) 3 (3) 1 (4) 4
 (1) 15 (2) 16 (3) 20 (4) 14
126. Which set of quantum numbers represent the electron
115. An improbable configuration is of the lowest energy?
 (1) [Ar] 3d44s2 (2)  [Ar] 3d54s1 1
(1) n = 2, l = 0, m = 0, s = -
 (3) [Ar] 3d64s2 (4)  [Ar] 3d104s1 2
116. Which has the highest number of unpaired electrons? (2) n = 2, l = 1, m = 0, s = + 1
2

 (1) Mn (2)  Mn5+ (3)  Mn3+ (4) Mn4+
(3) n = 4, l = 1, m = 0, s = + 1
117. Predict the total spin in Ni2+ ion 2
5 3 1
 (1)  ± (2) ± (4) n = 4, l = 0, m = 0, s = -
2 2 2
1 127. n and l values of an orbital “A” are 3 and 2 and of
 (3)  ± (4)  ±1
2 ­another orbital “B” are 5 and 0. The energy of
118. An atom has 2 electrons in K-shell, 8 electrons in (1) B is more than A
L-shell and 6 electrons in M-shell. The number of (2) A is more than B
s-electrons present in the element is (3) A and B are of same energy

 (1) 10 (2) 7 (3) 6 (4) 4 (4) None

119. Atom containing odd number of electron is 128. The correct set of quantum number for the unpaired
electron of chlorine atom is

 (1) Ferromagnetic
 (1) n = 2, l = 1, m = 0

 (2) Ferrimagnetic  (2) n = 2, l = 1, n = 1

 (3) Paramagnetic  (3) n = 3, l = 1, m = 1

 (4) Diamagnetic  (4) n = 3, l = 0, m = 0

Chapter_02.indd 17 3/26/2014 2:47:23 PM

 2.18  Objective Chemistry - Vol. I

129. Which electronic configuration does not follow Pau-

(3) In silver atom, 23 electrons have a spin of one type
li’s exclusion principle? and 24 of the opposite type (At. No. of Ag = 47).
 (1) 1s22s22p4 (2)  1s22s22p44s2
(4) All
2 4
 (3) 1s 2p (4) 1s22s22p63s3 139. The electron identified by quantum numbers n and l
7
130. The total spin resulting from a d configuration is (i)  n = 4, l = 1  (ii)  n = 4, l = 0
1 3
 (1) ± (2)  ±2 (3)  ±1 (4)  ± (iii)  n = 3, l = 0
(iv)  n = 3, l = 1
2 2
131. The electronic configuration 1s22s22p63s13p1 correct-
 can be placed in the order of increasing energy from
ly describes the lowest to highest
(1) ground state of Na (1) (iv) < (ii) < (iii) < (i)  (2) (ii) < (iv) < (i) < (ii)
(2) ground state of Si+ (3) (i) < (iii) < (ii) < (iv)   (4)  (iii) < (iv) < (ii) < (i)
(3) excited state of Mg
140. Generally half-filled or completely filled degenerate
(4) excited state of Al3+
orbitals have lower energy because
132. Which orbital is nearest to the nucleus after filling (1) of their symmetry and possible larger exchanges
with electrons? (2) they cannot participate in bonding
 (1) 5d (2) 6s (3) 6p (4) 4f (3) such orbitals have only paired electrons
(4) such orbitals have only unpaired electrons
133. The number of unpaired electrons in the trivalent ion
of atom of atomic number 24 will be 141. Which of the following about the electron orbital is
(1) 1 (2) 3 (3) 2 (4) 7 false?
(1) No orbital can contain more than two electrons.
134. Which set has the same number of s-electrons?
(2) If two electrons occupy the same orbital, they
(1) C, Cu2+, Zn (2)  Cu2+, Fe2+, Ni2+ must have different spins.
2- 2+
(3) S , Ni , Zn (4)  None (3) No two orbitals in an atom can have the same
135. Which set has the same number of unpaired electrons energy.
in their ground state? (4) The number of orbitals in different subshells is
(1) N, P, V (2)  Na, P, Cl not the same.
(3) Na+, Mg2+, Al (4)  Cl-, Fe3+, Cr3+ 142. An electron in the lithium atom is in the third energy
1 36. For the energy levels in an atom, the correct statement is level. Then, which of the following is false?
(1) There are seven principal electron energy levels. (1) The electron is in the excited state.
(2) The second principal energy level can have four (2) The atom can emit light.
subenergy levels and contains a maximum of (3) The atom will decay due to radioactivity.
eight electrons. (4) This implies no change in its nucleus.
(3) The M-energy level can have a maximum of 32 143. A completely filled d-orbital (d10)
electrons. (1) has spherical symmetry
(4) The 4s subenergy level is at a higher energy than (2) has octahedral symmetry
the 3d sub-energy level. (3) has tetrahedral symmetry
137. An electron that will have the highest energy in the set is (4) depends upon the atom
1 1 144. Which of the following statement is wrong?

(1) 3, 2, 1, (2)  4, 2, -1,
2 2 (1) An electron revolving in the level n = 1 has less
1 energy than that revolving in the level n = 2.
(3) 4, 1, 0, -
(4)  5, 0, 0, 1 (2) The energy of electrons in the s, p, d and f
2 2
sublevels in the same shell varies in the order
138. Which of the following statements is correct? s > p > d > f.
(1) The electronic configuration of Cr is [Ar] 3d54s1 (3) Any electron can jump from an inner level to an
(At. No. of Cr = 24). outer level by absorbing energy.
(2) The magnetic quantum number may have a (4) An atom is stable in ground state than in one of
­negative value. its excited state.

Chapter_02.indd 18 3/26/2014 2:47:25 PM

 Structure of Atom  2.19

145. Which of the ions has the same number of unpaired

(3) 
Y will be halved and Z will remain the same
electrons as that of V3+ ion?
(4) 
Y will remain the same and Z will be halved
Cr3+
 (1)  (2) Mn2+ (3) Ni2+ (4)  Te+ 5. The ionisation potential of hydrogen atom is 13.6 eV.
The wavelength of the energy radiation required for
Answers the ionisation of hydrogen atom is
(1) 1911 nm (2)  912 nm
(111) 3 (112)  2 (113)  2 (114)  1 (115)  1
(3) 68 nm (4)  91.2 nm
(116) 1 (117)  4 (118)  3 (119)  3 (120)  3
(121) 4 (122)  2 (123)  1 (124)  2 (125)  1 6. The wave number (υ) of the limiting line of Lyman
(126) 1 (127)  1 (128)  3 (129)  4 (130)  4 series multiplied by (x) gives the wave number of that
(131) 3 (132)  4 (133)  2 (134)  2 (135)  1 of the limiting line of Balmer series. Then, x is
(136) 2 (137)  2 (138)  4 (139)  4 (140)  1 (1) 2 (2) 1/2 (3) 1/4 (4) 4
(141) 3 (142)  3 (143)  1 (144)  2 (145)  3
7. Which of the following lines will have a wave number
equal in magnitude with the value of R in H-spectral
series?
 Practice Exercise Level-I (1) limiting line of Balmer series
(2) limiting line of Lyman series
1. Ca has atomic number 20 and atomic weight 40. (3) first line of Balmer series
Which of the following statements is not correct about (4) first line of Lyman series
Ca atom?
(1) The number of electrons is same as the number of 8. According to Bohr’s model of the atom, electron in the
neutrons. ground state
(2) The number of nucleons is double of the number (1) radiates electromagnetic radiation continuously
of electrons. (2) forms spectral lines
(3) The number of protons is half the number of (3) remains there
­neutrons. (4) can jump to higher orbit when enough energy is
(4) The number of nucleons is double the atomic given
number.
9. Angular momentum of the electron present in the
2. According to quantum theory, heat, light, electricity or ­M-shell of hydrogen atom is
any other form of energy (1) 2h/π (2)  h/π (3) 3h/2π (4) h/4π
(1) is continuous
(2) exists in discrete bundles 10. Which of the following statements is correct?
(3) can be of any size (1) The ratio of KE and PE of electron in Bohr orbit
(4) is transferred in a small amount as one could of H atom is +1/2.
­imagine (2) The ratio of KE and total energy of the electron in
Bohr orbit of H atom is -1.
3. Which of the following statements is false in the (3) The ratio of PE and the total energy of the e­ lectron
­context of photoelectric effect? in Bohr orbit of H atom is -2.
(1) The kinetic energy of ejected electrons is inde- (4) The energy of electrons present in Bohr’s second
pendent of the intensity of radiation. orbit of H atom is -328 J mol-1.
(2) The threshold frequency is the same for all metals.
(3) The number of photoelectrons ejected depends 11. In Bohr’s model of the atom when an electron jumps
upon the intensity of the incident radiation. from n = 1 to n = 3, how much energy will be emitted
(4) The kinetic energy of the emitted electrons depends or absorbed?
on the frequency of the incident radiation. (1) 2.15 × 10-11 ergs (2)  0.1911 × 10-10 ergs
(3) 2.389 × 10 ergs
-12
(4)  0.239 × 10-10 ergs
4. Light of wavelength λ strikes a metal surface with inten-
sity X and the metal emits Y electrons per second of aver- 12. The maximum number of electrons with spin value
age energy Z. What will happen to Y and Z if X is halved? +1/2 in the orbitals with azimuthal quantum number
(1) Y will be halved and Z will be doubled value l = 4 is
(2) Y will be doubled and Z will be halved (1) 3 (2) 5 (3) 7 (4) 9

Chapter_02.indd 19 3/26/2014 2:47:25 PM

 2.20  Objective Chemistry - Vol. I

13. The minimum angular momentum of an electron with

(3) Number of angular nodes (nodal planes) in an
the magnetic quantum numbers -1, 0, +1 is orbital = l.
(1)  3 / 2 h/π
(2) h/π
(4) All are correct.
3 h 21. Bohr’s model of atom is not in agreement with
(3) 2h/π (4) 
2 π (1) line spectra of hydrogen atom
14. Which of the following statements is not correct for an (2) Planck’s theory
electron that has the quantum numbers n = 4 and m = 2? (3) Pauli’s principle
1 (4) Heisenberg’s principle
(1) The electron may have the quantum number s = +
2
(2) The electron may have the quantum number l = 2. 22. The orbital diagram in which both the Pauli’s exclu-
(3) The electron may have the quantum number l = 3. sion principle and Hund’s rules are violated is
(4) The electron may have the quantum number l = 0, (1) ↓↑ ↑ ↑ ↑ (2) 
↓↑ ↑↓ ↑↓
1, 2, 3.

(3) ↓↑ ↓ ↓ ↓ (4) 
↓↑ ↑↓ ↑↓ ↑
15. At 473 K, hydrogen molecules have velocity 2.4 × 105
cm s-1. The de Broglie wavelength in this case approxi- 23. Consider the electronic configuration for neutral atoms.
mately is (A) 1s22s22p63s1
(B) 1s22s22p64s1
(1) 1 Å (2)  10 Å
(3) 100 Å (4)  1000 Å Which of the following statements is not true?
(1) Energy is required to change A to B.
16. Eigenfunction of an electron is
(2) A represents sodium atom.
(1) de Broglie concept
(3) A and B represents same elements.
(2) Schrodinger concept
(4) More energy is required to remove one electron
(3) Sommerfeld concept
from B than from A.
(4) Heisenberg concept
24. For a particular value of azimuthal quantum number
17. The number of electrons in the p-sublevels of an atom
(l) the total number of magnetic quantum number (m)
is three. This implies that
is given by
(1) spin of electron will be paired m +1 m −1
(2) p-orbital will have one electron each (1)  l= (2) l =
2 2
(3) one orbital will have two electrons with paired
2m + 1 2l + 1
spin and one electron will be unpaired (3)  l= (4)  l =
2 2
(4) All the three electrons will be in the same
orbital. 25. Which of the following statements concerning Px
­orbital is false?
18. An atom has the electronic configuration of 1s22s2
(1) The electron density has two regions of high mag-
2p63s23p63d104s24p5. Its atomic weight is 80. Its atom-
nitude pointed in the +x and -x directions.
ic number and the number of neutrons in its nucleus
(2) These two high probability regions are separated
shall be
by a node passing through the nucleus.
(1) 35 and 45 (2)  45 and 35 (3) The electrons stay half the time in one of these
(3) 40 and 50 (4)  30 and 50 ­regions and the remaining time in the other region.
19. If n + l value of an orbital is 5, its shape may be (4) Its l value is equal to one.
(1) spherical 26. Which of the following statement is false?
(2) dumb-bell (1) Wave function describes the probability distribu-
(3) double dumb-bell tion of the electrons in space.
(4) Any one of these (2) Pauli’s exclusion principle can be derived from
quantum numbers.
20. Among the following statements, which is correct?
(3) Planetary model is not the correct picture of the
(1) Number of total nodes in an orbital = n - l. atom.
(2) Number of radial nodes (nodal regions) in an (4) The position and velocity of the electron cannot
orbital = n - l - 1. be defined precisely simultaneously.

Chapter_02.indd 20 3/26/2014 2:47:28 PM

 Structure of Atom  2.21

27. An electron that has quantum numbers n = 3 and m = 2 35. The threshold frequency for photoelectric effect on so-
(1) must have spin value = 1/2 dium corresponds to wavelength of 5000 Å. Its work
(2) must have l value 1 function is
(3) must have l = 0, 1 or 2 (1) 1 J (2)  4 × 10-19 J
(4) must have l = 2 (3) 3 × 10 J
-19
(4)  2 × 10-19 J
28. Five valence electrons of 15P are labelled as 36. In photoelectric emission, the energy of emitted
ab xyz ­electron is
3s 3p (1) smaller than that of incident light
(2) larger than that of incident light
If the spin quantum of B and Z is +1/2, the group of elec-
(3) same as that of incident light
trons with three of the same quantum numbers are (4) proportional to the intensity of incident light

(1) AX, XYZ, BY (2)  AY 37. The energy of an orbital in hydrogen atom is given

(3) XYZ, AZ (4)  AB, XYZ by the relation E = -Constant/n2 (kJ mol-1). Which of
29. Number of electrons that F (Z = 9) has in p-orbitals is the following properties represent the constant in this
equal to ­relation?
(1) number of electrons in d-orbital in Fe3+ (23e) (1) Bond energy (2)  Electronegativity
(2) number of electrons in d-orbital in Mn (25e) (3) Electron affinity (4)  Ionisation energy
(3) number of electrons in s-orbital in Na (11e) 38. The wavelengths of light emitted by the excited atoms of
(4) all are correct a particular element that makes up its bright line spectrum
30. The value of the magnetic quantum number, m for the (1) are different from the wavelengths in its dark-line
electron most easily removed from a gaseous atom of spectrum
an alkaline earth metal is (2) are characteristic of the element involved
(1) same as the maximum value of  “n” for the ­element (3) come from the nuclei of the atoms
(2) any number from -(n - 1) to +(n - 1) (4) are evenly distributed throughout the entire ­visible
(3) any positive number from 1 to (n - 1) spectrum
(4) zero 39. Which of the following pairs have identical values
31. When an element is bombarded with high energy of e/m?
­electrons it emits X-rays, the frequency of which is (1) A proton and neutron
­related to its (2) A proton and deuterium
(1) atomic number (3) Deuterium and an α-particle
(2) relative atomic mass (4) An electron and γ-rays
(3) mass number 40. Choose the incorrect statement among the following.
(4) ionisation energy (1) Every object emits radiation whose predominant
32. When the electron moves from the higher orbit to the frequency depends on its temperature.
lower orbit, which of the following is not possible? (2) The quantum energy of wave is proportional to its
(1) Its velocity decreases frequency.
(2) Its mass increases (3) Photons are quanta of light.
(3) Its wavelength decreases (4) The value of Planck’s constant is energy dependent.
(4) Its kinetic energy increases 41. If Ee, Eα and Ep represents the kinetic energies of elec-
33. X 3- is isoelectronic with argon. It has electrons and tron, alpha particle and a proton, respectively each
neutrons in 1:1 ratio. The mass number of X is moving with the same de Broglie wavelength then
(1) 30 (2) 32 (3) 33 (4) 35 (1) Ee = Eα = Ep (2)  Ee > Eα > Ep
(3) Eα > Ep > Ee (4)  Ee > Ep > Eα
34. In hydrogen atom energy of the first excited state is
-3.4 eV. Then, find out the KE of the same orbit of 42. The particle nature and wave nature of electrons in an
hydrogen atom. atom are
+3.4 eV
(1)  (2)  +6.8 eV (1) directly related
-13.6 eV
(3)  (4)  +13.6 eV (2) inversely related

Chapter_02.indd 21 3/26/2014 2:47:29 PM

 2.22  Objective Chemistry - Vol. I

(3) not related to each other
(4) the difference in the energies for the ground state and

(4) may be related or not related depending on excited state energy levels of the excited e­ lectron
­experimental conditions 50. The boundary surface diagram of an orbital outlines
43. The radiation is emitted when hydrogen atom goes (1) the regions in which there is a certain probability
from an higher energy state to a lower energy state. (<100%) of finding the electron it describes
The wavelength of one line in visible region of atomic (2) the regions in which there is a 100% probability
spectrum of hydrogen is 6.63 × 10-7m. The energy dif- of finding the electron it describes
ference between the two states is (3) the shape of the electron it describes
(1) 3.0 × 10-19 J (2)  1.0 × 10-18 J (4) the orbit followed by the electron it describes
(3) 5.0 × 10 J
-10
(4)  None of these 51. What does the value of ψ2 at a given point in space
44. For a hydrogen atom, what is the orbital degeneracy represents in the wave mechanical model of atom?
hcR α (1) The circumference of the orbit of the electron at
of the level that has energy = − , where R∝ is the
9 that point.
Rydberg constant for the hydrogen atom? (2) The circumference of finding the electron at that
point in space.

(1) 1 (2) 9 (3) 36 (4) 3
(3) The square of the distance of that point from the
45. For an electron the product vn (velocity × principal nucleus.
quantum number) will be independent of the (4) The kinetic energy of the electron at that point.
(1) principal quantum number 52. The mass of an atom is 234. The nucleus of the atom
(2) spin quantum number contains 60% more neutrons than protons. The atomic
(3) energy of the electron number of the atom is
(4) frequency of its revolution
(1) 39 (2) 58 (3) 90 (4) 117
46. The mass of an electron is m, its charge e and it is
53. The quantum mechanical theory of the atom is
­accelerated from rest mass through a potential differ-
ence V. The velocity of electron will be calculated by (1) based upon a mechanical model of the atoms
the formula (2) a theory that restricts itself to physical quantities
that can be measured directly
(1)  V (2)  eV (3)  2eV (4) None of these (3) less accurate than Bohr theory of the atom
m m m
(4) impossible to reconcile with Newton’s laws of
47. Atomic emission spectra of an element cannot be motion
used to
(1) identify the atom 54. An electron can revolve in orbit around an atomic
(2) determine the mass number of the nucleus of the ­nucleus without radiating energy provide that
atom (1) is far enough away from the nucleus
(3) measure the difference in energy between pairs of (2) is less than a de Broglie wavelength in circum­
stationary state of the atom ference.
(4) all of the above (3) is an integral number of de Broglie wavelength in
48. In polar coordinates r and dr, a spherical volume circumference
­element is given by (4) is a perfect circle
(1) 4π2r2dr (2) 4π2dr 55. The angular momentum of an atomic electron
(3) 5π2rdr (4)  πr2dr (1) is not quantised
49. Each line in the spectrum of an element is produced by (2) is quantised in magnitude only
a photon of energy equal to (3) is quantised in direction only
(1) the energy of the ground state energy level of the (4) is quantised in both magnitude and direction
excited electron
(2) the energy of the excited state energy level of the 56. Schrodinger wave equation for the hydrogen atom
excited electron (1) introduces three different quantum numbers one
(3) the sum of the energies for the ground state and of which (principal quantum number) gives total
excited state energy levels of the excited electron energy of the stationary atomic state

Chapter_02.indd 22 3/26/2014 2:47:29 PM

 Structure of Atom  2.23

(2) gives the orbital angular momentum quantum
(3) Zeeman effect is explained by magnetic quantum
number, which depends on the value of the princi- number.
pal quantum number and is equal to positive and
(4) The spin quantum number gives the orientation of
negative integral values electron cloud.

(3) gives the magnetic quantum number which deter-
mines the shape of the orbital 63. According to Bohr’s theory, the energy required for the
(4) when n = 4 the degeneracy would be eightfold
transition of H atom from n = 6 to n = 8 state is
(1) equal to energy required for the transition from
57. The two particles A and B have de Broglie wavelengths n = 5 to n = 7 state
of 1 mm and 5 mm, respectively. If mass of A is four (2) larger than in (1)
times the mass of B, the ratio of kinetic energies of (3) less than in (1)
A and B would be (4) equal to energy for the transition from n = 7 to n = 9
(1) 5:1 (2) 25:4 (3) 20:1 (4) 5:4 state
58. The atomic numbers of elements X, Y and Z are 19, 21 64. In a discharge tube containing only one elementary gas
and 25, respectively. The number of electrons present other than hydrogen, the different anode ray particle
in the “M” shells of these elements follows the order (1) have same e/m value but not equal to unity
(1) Z > X > Y (2)  X > Y > Z (2) have different e/m values which are not related to
(3) Z > Y >X (4) Y > Z > X each other
(3) may have different e/m values which are integral
59. Which one of the following statements is not correct? multiple of lowest possible e/m value
(1) Rydberg constant and wave number have same (4) have e/m value equal to unity
units.
65. Light of wavelength λ shines on a metal surface with
(2) Lyman series of hydrogen spectrum occurs in the
intensity X and the metal emits Y electrons per second
UV region.
of average energy Z. What will happen to Y and Z if λ
(3) The angular momentum of the electron in the
is halved?
ground state hydrogen atom is equal to h . (1) Y will increase and Z will decrease
2π
(2) Z will increase and Y will remain constant
(4) The radius of first Bohr orbit of hydrogen atom is
(3) Z will decrease and Y remains constant
2.116 × 10-8 cm.
(4) Y will decrease and Z will increase
60. Which of the following statement is false? 66. By what factor the velocity of an electron in a Bohr’s

(1) The energy of radiation increase with decrease in orbit for a hydrogen atom will change if the value of
wavelength. principal quantum number is doubled?

(2) The spectrum of H atom is exactly same as that of (1) Velocity is halved
He+ ion. (2) Velocity is doubled
(3) Energy of radiation increases with increase in u.
(3) Velocity is quadrupled

(4) The frequency of radiation is related to wave (4) Velocity remains unchanged
number ν = eu. 67. If we assume 1/6th part instead of 1/12th part of weight
of 12C as one amu, what will be the molecular mass of
61. The amount of energy required to remove the electron water?
from a Li2+ ion in its ground state is how many times
(1) 9 (2) 18 (3) 36 (4) 24
greater than the amount of energy required to remove
the electron from H atom in its ground state? 68. What is the energy emitted when electrons of 1.0 g
atom of hydrogen undergo transition giving the spectral

(1) 
3 (2) 6 (3) 9 (4) 2
lines of lowest energy in the visible region of its atomic
62. Which of the following statement about quantum num- spectra? Given RH = 1.1 × 107 m-1, C = 3 × 108 m s-1
ber is wrong? and h = 6.2 × 10-34 m J S.
(1) If the value of l = 0 the electron distribution is (1) 182.5 kJ
spherical. (2) 18.25 kJ
(2) The shape of the orbital is given by subsidiary (3) 382.5 kJ
quantum number. (4) 1825 kJ

Chapter_02.indd 23 3/26/2014 2:47:30 PM

 2.24  Objective Chemistry - Vol. I

69. Gases begin to conduct electricity at low pressure 1/ 2

  
­because (3)  2hc λ 0 − λ 

 
(1) at low pressure gases turn to plasma  m  λ0λ  
(2) colliding electrons can acquire higher KE due to 
1/ 2
 
increased mean free path leading to ionisation of (4)  2h 1 − 1 

 λ  
atoms  m  λ0
(3) atoms breakup into electrons and protons
1  c c 
(4) the electrons in atoms can move freely at low Hint: mv2 = h(υ - v0) = h  λ − λ 
2 
0

pressure
 1 1   λ0 − λ 
70. Electronic energy is a negative energy because = hc  −  = hc  
(1) Electron carries negative charge.  λ λ0   λ0 λ 
(2) Energy is zero at the nucleus and decreases as the 2 hc  λ 0 − λ 
or v2 =  
distance from the nucleus increases. m  λ0λ 
(3) Energy is zero at infinite distance from the n­ ucleus 1/ 2
2 hc  λ 0 − λ  
and decreases as the electron comes closer to the or v =   λ λ 
nucleus.  m  0 
(4) There are interelectronic repulsions. 74. Choose the incorrect relation on the basis of Bohr’s
71. If the threshold frequency of a metal for photoelectric theory.
1
effect is ν0 then which of the following will not happen? (1) Velocity of electron ∝
n
(1) If the frequency of the incident radiation is ν, the (2) Radius of orbit ∝ n2Z
1
kinetic energy of the electron ejected is zero. (3) Frequency of revolution ∝ 3
(2) If the frequency of the incident radiation is ν, the ki- 1 n
netic energy of the electron ejected will be hν - hν0. (4) Force on electron ∝ 4
n
(3) If the frequency of incident radiation is kept same 75. In Mosely’s equation, υ = a ( Z − b )
as ν but intensity is increased the number of elec- (1) “b” depends on metal and “a” is independent of
trons ejected will increase. metal
(4) If the frequency of incident radiation is further (2) both “a” and “b” are independent of metal
­increased the number of photoelectrons ejected (3) both “a” and “b” are metal dependent
will increase. (4) “a” is metal dependent while “b” is not
72. Which of the following statement is false? 76. A near-UV photon of 300 nm is absorbed by a gas and
(1) Probabilities of electron are found by solving then reemitted as two photons. One photon is red with
Schrodinger wave equation. wavelength 760 nm. Hence, wavelength of the second
(2) Energy of the electron at infinite distance is zero photon is
and yet it is maximum. (1) 460 nm (2)  1060 nm
(3) Some spectral lines of an element may have the (3) 496 nm (4)  300 nm
same wave number. 77. Select the correct statement.
(4) The position and momentum of a moving micro- (1) The ideal body, which emits and absorbs all
particle cannot be measured accurately. ­frequencies, is called a black body.
73. If l0 is the threshold wavelength for photoelectric (2) The exact frequency distribution of the emitted
emission, λ the wavelength of light falling on the sur- radiation from a black body depends upon its
face of a metal and m the mass of electron then the ­temperature.
velocity of ejected electron is given by (3) The radiation emitted goes from a lower ­frequency
to a higher frequency as the temperature i­ ncreases.
1/ 2
 2h

(1)  (λ 0 − λ ) (4) All the above are correct statements.
 m  78. An electron in H atom in its ground state absorbs 1.5
1/ 2 times as much as energy as the minimum required for
 2hc
(2)  (λ 0 − λ ) its escape (13.6 eV) from the atom. Thus, KE given to
 m  emitted electron is

Chapter_02.indd 24 3/26/2014 2:47:33 PM

 Structure of Atom  2.25

(1) 13.6 eV (2)  20.4 eV
(2) inversely proportional to the magnitude of applied

(3) 34.0 eV (4)  6.8 eV magnetic field

(3) inversely proportional to the velocity of electron
79. Consider the following statements.

(4) directly proportional to the e/m value
I. The spin angular momentum of the electron is
constant and cannot be changed. 85. Suggest two transitions in the atomic spectrum of
1
II. For spin = +1/2, spin angular momentum is . ­hydrogen for which the wave number ratio is 108:7.
2
III. Spin angular momentum is a vector quantity and can (1) First Lyman and first Bracket transitions
have only two orientations relative to a chosen axis. (2) First and second Lyman series transitions
(3) First Lyman and first Balmer transitions

Of these, the correct statements are
(4) First Lyman and first Paschen transitions

(1) I, II (2)  II, III

(3)  I, III (4)  I, II, III 1 1
Hint : υ = R  2 − 2 
n
 1 n2 
80. I.  n = 3, l = 2, ml = -2
II.  n = 3, l = 1, ml = 0 1 1 3

For first Lyman series υ = R  2 − 2  = R
 1 2  4
III.  n = 3, l = 0, ml = -1

1 1 5
 IV.  n = 3, l = 2, ml = 0

For first Balmer series υ = R  2 − 2  = R
2 3  56
V. n = 3, l = 1, ml = -2
1 1 7

For first Paschen series υ = R  2 − 2  = R

Of these, quantum state designations which does not 3 4  144
describe an allowed state for an electron in an atom are

(1) I and IV (2)  III and V 1 1 9

For first Bracket series υ = R  2 − 2  = R

(3) II and V (4)  IV and V 4 5  400
81. The energy levels for z A (+z −1) can be given by 3 7 7

Lyman: Paschen = := 3=: 108 : 7
(1) En for zA(+z–1)
= Z × En for H
2
4 144 36
(2) En for zA(+z–1) = Z × En for H
1
(3) En for zA(+z–1) = 2 × En for H
Z Answers
1
(4) En for zA(+z–1) = × En for H (1) 3 (2) 2 (3) 2 (4) 3 (5) 4
Z
82. The specific charge for positive rays is much less than (6) 3 (7) 2 (8) 4 (9) 3 (10) 2
the specific charge for cathode rays. This is because (11) 2 (12) 4 (13) 2 (14) 4 (15) 1
(1) Possible rays are positively charged. (16) 2 (17) 2 (18) 1 (19) 4 (20) 4
(2) Charge on positive rays is less. (21) 4 (22) 1 (23) 4 (24) 2 (25) 3
(3) Positive rays comprises ionised atoms whose (26) 2 (27) 4 (28) 4 (29) 4 (30) 4
mass is much higher. (31) 1 (32) 1 (33) 3 (34) 1 (35) 2
(4) Experimental method for determination is wrong. (36) 1 (37) 4 (38) 2 (39) 3 (40) 4
83. Wavelength of an electron is equal to distance travelled (41) 4 (42) 2 (43) 1 (44) 2 (45) 2
by it in 1s, then correct relation is (46) 3 (47) 2 (48) 4 (49) 4 (50) 1
h h (51) 2 (52) 3 (53) 2 (54) 3 (55) 4
(1) λ = (2)  λ = (56) 1 (57) 2 (58) 3 (59) 4 (60) 2
p p
(61) 3 (62) 4 (63) 3 (64) 3 (65) 2
h h (66) 1 (67) 1 (68) 1 (69) 2 (70) 3
(3)  λ = (4)  λ =
m m (71) 4 (72) 3 (73) 3 (74) 2 (75) 4
84. The radius of deflection of an electron beam is (76) 3 (77) 4 (78) 4 (79) 4 (80) 2
(1) 
directly proportional to magnitude of applied (81) 1 (82) 3 (83) 4 (84) 2 (85) 4
magnetic field

Chapter_02.indd 25 3/26/2014 2:47:36 PM

 2.26  Objective Chemistry - Vol. I

7. During the excitation of an electron, it travels at a

 Practice Exercise Level-II ­distance of nearly 0.7935 nm in the hydrogen atom.
The maximum number of spectral lines formed during
1. Identify the correct statement(s)
the deexcitation is
I. The radial probability distribution curves for 1s,
(1) 1 (2) 2.3 (3) 3.6 (4)  10
2s, 2p and 3d are identical.
II. The number of nodal planes for 2p, 3p and 4p orbit- 8. When an excited state of H atom emits a photon of
als is the same. wavelength λ and returns to the ground state, the prin-
III. Theoretically calculated spin only magnetic moment cipal quantum number of the excited state is given by
is same for Ti 2+ and Ni 2+.
IV. A p-orbital can accommodate a maximum of six
(1) 
(λ R − 1) (2)  λR ( λR − 1)
electrons. λR
(1) I and II are correct λR
(2)  II and III are correct
(3)  (4)  λR ( λR + 1)
λR −1
(3) III and IV are correct
(4)  only IV is correct 9. Which of the following statements in relation to the
hydrogen atom is correct?
2. The magnetic moment of two ions Mx+ and My+ of the
(1) 3s, 3p and 3d orbitals all have the same energy.
element M (Z = 26) is found to be 5.916 BM. If x > y,
(2) 3s and 3p orbitals are of lower energy than the 3d
then which of the following statements is correct?
orbital.
(1) My+ is more stable than Mx+ (3) 3p orbital is lower in energy than the 3d orbital.
(2) My+ is less stable than Mx+ (4) 3s orbital is lower in energy than the 3p orbital.
(3) Both are equally stable
(4) Cannot be predicted exactly 10. If electrons were to fill up progressively with orbit satu-
ration (neglecting Aufbau rule) and each orbital were to
3. From the following observations of Mr. Rao,
accommodate the three electrons, instead of two, which
Mr. Ramesh and Mr. Kumar predict the type of orbital.
of the following would NOT hold correct for the new

Mr. Rao: The angular function of the orbital intersects electronic arrangement in zirconium atom (Z = 40)?
the three axes at the origin only. (1) The number of p-electrons would be double the

Mr. Ramesh: X-Y plane acts as a nodal plane. number of s-electrons.

Mr. Kumar: The graph of radial probability Vs “r” (2) Spin quantum number would become super flows.
intersects the radial axis at three separate regions
­ (3) Zirconium would continue to belong to the 4th
­including origin. ­period (in new periodic table).
(4) Zirconium would show retention of block.
(1) 5dyz (2)  4pz (3) 6dyz (4) 6dxy
11. If the following radial probability curve indicates 2s
4. The angular momentum of an electron changes from
orbital, the distance between the peak points x, y is
2h h
to during a transition in a hydrogen atom, thus
π π
it results in the formation of spectral lines in
Radial probability (D)

(1) UV region (2)  Visible region

(3) IR region (4)  Far-IR region
5. The uncertainty in position is of the order of 1 Å. The
uncertainty in velocity of a cricket ball (0.1505 kg) is
(1) 1.7 × 10-23 m/s (2)  1.7 × 10-24 m/s
(3) 3.4 × 10 m/s
-23
(4)  3.4 × 10-24 m/s
6. When an electron is transited from 2E to E energy ­level,
the wavelength of photon produced is λ1. If electronic x y
transition involves 4/3E to E level, the wavelength Distance from the nucleus
of resultant photon is λ2. Which of the following is a
­correct relation?
(1) 2.07 Å (2)  1.59 Å
(1) λ2 = λ1 (2)  λ2 = 3λ1 (3) λ2 = λ1 (4) λ2 = λ1
(3) 0.53 Å (4)  2.12 Å

Chapter_02.indd 26 3/26/2014 2:47:38 PM

 Structure of Atom  2.27

12. An electron is continuously accelerated in a v­ acuum

tube by applying a potential difference. If the de
­Broglie’s wavelength is decreased by 10% the change
in the kinetic energy of the electron is nearly
(1) decreased by 11%
(2) increased by 23.4%
(3) increased by 10%
(4) increased by 11.1%
13. The velocity of an electron in nth orbit of hydrogen (1) 6.5 × 1015
(2)  2 × 1014
atom bears the ratio 1:411 to the velocity of light. The (3) 2 × 1013
(4) 1.01 × 1014
number of coloured lines formed when electron jumps
from n + 3 state to ground state is 20. Pick out the correct option where T stands for True and
F for false.
(1) 4 (2) 3 (3) 5 (4) 6
(I) The energy of the 3rd orbital is high compared to
14. Maximum value (n + l + m) for unpaired electrons in the 4s orbital in hydrogen atom.
second excited state of chlorine (17Cl) is (II) The electron density in x-y plane in d x2 - y2 orbital
(1) 
28 (2) 25 (3) 20 (4) None of these is zero.
(III) 24th electron in Cr go to 3d orbital.
15. In Mosely’s equation given constants a = b = 1 then the
(IV) The three quantum numbers were clearly explained
frequency is 100 s-1. The element will be
in terms of Schrodinger wave equation.
(1) K (2) Na (3) Rb (4) Cs
(1) T T F F (2)  TF TT
16. Consider the following statements concerning the (3)  TF TF (4)  F F T T
­subshells
21. The velocity of electron in a certain Bohr orbit of
(I) The maximum value of m for g subshell is 4. ­hydrogen atom bears the ratio 1:275 to the velocity of
(II) The maximum number of unpaired electrons in g light. So, the number of orbits is
subshell is 9. (1) 1 (2) 2 (3) 3 (4) 4
(III) The lowest value for the shell having of g sub-­
shell is 5. 22. Consider the following plots for 2s-orbitals.

Select correct statements. x
y

(1) I, II only

(2) II, III only

(3) I, III only

(4) I, II, III
17. The photoelectric emission requires a threshold r
­frequency ν0 for a certain metal λ1 = 2000 Å and r
I II
λ2 = 1660 Å, produce electrons with kinetic energy KE1
and KE2. If KE2 = 2KE1. The threshold frequency ν0 is
z
(1) 1.15 × 1015 s-1

(2) 1.15 × 1014 s-1
(3) 1.19 × 1015 s-1

(4) 1.19 × 1014 s-1
18. The bond dissociation energy of H-H bond is 400 kJ/ r
mol. The energy required to excite 0.04 mole of hydro- III
gen gas to the first excited state of hydrogen atom is
(1) 94.6 kJ (2)  47.3 kJ
X, Y and Z are respectively
(3)  70.9 kJ (4)  80.4 kJ
(1) Ψ, Ψ2 and 4πr2Ψ2
19. In hydrogen atom the electronic motion is represented
(2) Ψ2Ψ and 4πr2Ψ2
as follows. The number of revolutions made by that (3) 4πr2Ψ2 and Ψ2 and Ψ
electron in 1 s is equal to (4) Ψ2, 4πr2 Ψ2 and Ψ

Chapter_02.indd 27 3/26/2014 2:47:39 PM

 2.28  Objective Chemistry - Vol. I

23. For a hypothetical H-like atom which follows Bohr’s 1. If both statement I and statement II are true and state-
model, some spectral lines were observed as shown. ment II is the correct explanation of statement I.
If it is known that line “E” belongs to the visible region, 2. If both statement I and statement II are true but state-
then the lines possibly belonging to ultraviolet region ment II is not the correct explanation for statement I.
will be (n1 is not necessarily ground state) [Assume for 3. If statement I is true but statement II is false.
this atom, no spectral series shows overlaps with other
series in the emission spectrum.] 4. If statement I is false but statement II is true.
1. Statement I: In the third energy level, there is no
n5
f-subshell.
n4
Statement II: For n = 3, the possible values of l are 0,
B 1 and 2.
C n3
2. Statement I: The angular momentum of an electron in
an atom is quantised.
D A
n2 Statement II: In an atom only those orbits are permit-
ted in which angular momentum of the electron is the
h
E whole number multiple of
n1 2π
3. Statement I: The principal quantum number n can

(1) B and D (2)  D only
have whole number values 1, 2, 3, .... etc.

(3) C only (4)  A only
24. Given the wave function of an orbital of hydrogen Statement II: The angular momentum of quantum
 1  number l can never be numerically equal to n.
atom; Ψ1,0 =   e − r / a0, the most probable
4. Statement I: The two electrons in an orbital can have
 π a 3/2 
 0 
opposite spin.
distance of the electron present in the given orbital
Statement II: No two electrons in an atom can have
same set of all the four quantum numbers.
from the nucleus is
(1) a0e−2r
(2)  a0 (3) (3/2)a0 (4) 2a0 5. Statement I: Zn2+ is diamagnetic.

25. The difference of nth and (n + 1)th Bohr’s radius of Statement II: Zn2+ ion has unpaired electrons.
H atom is equal to (n - 1)th Bohr’s radius. Hence, the 6. Statement I: s-orbital cannot accommodate more than
value of “n” is two electrons.
(1) 
1 (2) 2 (3) 3 (4) 4
Statement II: s-orbitals are extremely poor shielders.
7. Statement I: The fully filled configuration is more
Answers ­stable as compared to the half-filled configuration.
(1) 2 (2) 2 (3) 1 (4) 2 (5) 4 Statement II: More exchange energy causes greater
(6) 2 (7) 3 (8) 3 (9) 1 (10) 3 stability.
(11) 1 (12) 2 (13) 1 (14) 2 (15) 2
8. Statement I: Pairing of electrons in the degenerate
(16) 4 (17) 3 (18) 1 (19) 4 (20) 4
­orbitals decreases the energy of the system.
(21) 2 (22) 2 (23) 4 (24) 2 (25) 4
Statement II: Spinning directions of the two paired
electrons are different.
9. Statement I: Kinetic energy of photoelectrons is
  Statement-Type Questions ­directly proportional to the intensity of the incident
In the following questions, a statement I is given and a radiation.
­corresponding statement II is given below it. Mark the Statement II: Each photon of light causes the e­ mission
­correct answer as of only one photoelectron.

Chapter_02.indd 28 3/26/2014 2:47:40 PM

 Structure of Atom  2.29

10. Statement I: Bohr’s theory gave reasonably correct 19. Statement I: Orbitals form the basis of the electronic
spectroscopic results for hydrogenic species even though structure of atoms.
it is used in classical mechanics for its derivation.
Statement II: An atomic orbital is the wave function
Statement II: The semiclassical approach is valid to Ψ for electron in an atom.
some extent for spectroscopic derivations in the context
of hydrogenic species. 20. Statement I: Spin quantum number can have the value
+1 / 2 or -1/2.
11. Statement I: Spectral wave numbers bear a linear
­relationship with the square of the principal quantum Statement II: + Sign here signifies the wave function.
number.
21. Statement I: Orbit and orbitals are synonymous.
Statement II: There is direct consequence of Bohr’s
energy condition. Statement II: Orbits represent a circular path around
the nucleus in which electron revolves.
12. Statement I: Zeeman effect could not be predicted by
Bohr model. 22. Statement I: Electrons are ejected from a certain metal
when either blue or violet light strikes the metal surface.
Statement II: Zeeman effect is the result of the inter-
However, only violet light causes electron ejection from
action of the magnetic field B and the quantised angu-
a second metal.
lar momentum l.
13. Statement I: The electronic configurations in which Statement II: The electrons in the first metal require
all the orbitals of the same subshell are either com- less energy for ejection.
pletely filled or are exactly half-filled are more stable. 23. Statement I: A spectral line will be seen for 2px - 2py.
Statement II: The completely filled or exactly half-
Statement II: Energy released in the form of wave of
filled shells possess a symmetrical distribution of elec-
light when an electron drops from 2px to 2py orbital.
trons and allow their maximum number of exchanges.
14. Statement I: The configuration of B atom cannot be 24. Statement I: Electrons may be considered as particles
1s2, 2s3. and waves.

Statement II: Hund’s rule demands that the configura- Statement II: An electron in an atom may be described
tion should display maximum multiplicity. as occupying an atomic orbital or by a wave function Ψ
which is a solution to Schrodinger wave equation.
15. Statement I: Fe3+ is more stable than Fe2+ ion.
25. Statement I: The energy of an electron is largely
Statement II: Fe3+ has more number of unpaired
­determined by its principal quantum number.
­electrons than Fe2+.
16. Statement I: The kinetic energy of the photoelectron Statement II: The principal quantum number “n” is a
ejected increases with increase in intensity of light. measure of most probable distance of finding the electron
around the nucleus.
Statement II: Increase in intensity of incident light
increases the rate of emission.
17. Statement I: Threshold frequency is characteristic for
a metal. Answers
Statement II: Threshold frequency is maximum (1) 1 (2) 1 (3) 2 (4) 1 (5) 3
­frequency required for the ejection of e- from the
(6) 3 (7) 1 (8) 4 (9) 4 (10) 3
­metal surface.
(11) 4 (12) 2 (13) 1 (14) 2 (15) 2
18. Statement I: Ten distinct set of four quantum numbers (16) 4 (17) 3 (18) 2 (19) 1 (20) 3
are possible for d-subshell.
(21) 4 (22) 1 (23) 4 (24) 2 (25) 1
Statement II: d-subshell splits into five d-orbitals.

Chapter_02.indd 29 3/26/2014 2:47:41 PM

 2.30  Objective Chemistry - Vol. I

The correct matching is
 Match the Following Type
Questions S.No. A B C D
1. iv ii i iii
1. Match the following. 2. i ii iii iv
List-I List-II 3. iv iii i ii
4. ii i ii iv
(A) Energy of electron in nth orbit  (i) ∝ n2
1
(B) Wavelength of electron in nth orbit    (ii) ∝ −
n2
Answers
(C) Velocity of electron in nth orbit (iii) ∝ n
1 (1) 4 (2) 2 (3) 3
(D) Radius of electron in nth orbit  (iv) ∝
n

The correct matching is
S.No. A B C D Hints to Practice Exercise Level-II
1. i ii iii iv
1. I. The no. of peaks in a radial probability curve is equal
2. iv iii ii i to n - 1. So, no. of peaks in 1s and 2s are not equal.
3. i ii iv iii
  II. No. of nodal planes equals to l. So, it is same for
4. ii iii iv i 2p, 3p and 4p orbitals.

2. Match the following. III. Ti2+ and Ni2+ both have same no. of unpaired e-

and have the same magnetic moments.
List-I List-II

 IV. 
Any orbital of any subshell can accommodate
(A) P
 rincipal quantum (i) Shape of orbital only two e-.
number
2. M+x and M+y both have same magnetic moment 5.916
(B) M
 agnetic quantum (ii) Orientation of orbital which means that both have same no. (5) of u­ npaired
number e-. It is possible only if x and y are +3 and +1.
(C) Azimuthal quantum (iii) Spinning of electron ­Electronic configuration corresponding to these two
number oxidation states is
(D) S
 pin quantum number (iv) Size of orbital M+x → 3s23p63d5


The correct matching is M+y → 3d64s1

S.No. A B C D So, M+x is more stable due to half-filled configuration.

1. iv i ii iii 3. From the observations for that orbital n - l - 1 = 2 and

2. iv ii i iii it must be not in x-y plane so that orbital is 5dyz.

3. i ii iii iv nh
4. Angular momentum of
2π
4. iii i ii iv
So, the transition occurs from 4 → 2; that means the

3. Match the following transition lies in Balmer series and will be observed in
the visible region.
List-I List-II
h
(A) Number of electrons present in an orbit (i) 2 5. Dx. Dv =
4πm
(B) Number of orbitals in an orbit (ii) n 6.625 × 10 − 34 1
∴ ∆ν = × −10
(C) Number of electrons in an orbital (iii) n2   4 × 3.142 × 0.1505 10
(D) Number of subshells in an orbit (iv) 2n2 ≈ 3.4 × 10 −24 m / s

Chapter_02.indd 30 3/26/2014 2:47:42 PM

 Structure of Atom  2.31

2.17 × 106
6. Energy involved in transition 13. Velocity of an e- in nth orbit = m/s.
n
hc
E1 = 2E - E = E =
From the data 2.17 × 10 3 × 108
6

λ =
4E E n 4
Energy involved in transition E1 = − E = =1
3 3 ⇒ n = 3.

E E hc / λ1 λ No. of lines in Balmer series is 6 - 2 = 4.

∴ 1 = = ⇒ 2 =3
E2 E / 3 hc / λ 2 λ1
14. Electronic configuration in the second excited state
7. From the data the differences between radii of ground = 1s22s22p63s23p33d2

state and excited state orbit radius.
So, max (n + l + m) value for this configuration

⇒ rn - r1 = 0.7935 × 10-9 m

= [(3 + 1 (-1)] + (3 + 1+ 0) + (3 + 1 + 1)

⇒ rn - (0.0529 × 10-9 m) = 0.7935 × 10-9 m

15. Mosley’s equation is u = a (Z - b)
⇒ rn = 0.8464 × 10-9 mg = 0.0529 × 10-9 xn2


So, from the data
⇒ n = 4.

100 = 1 (Z - 1) Z = 11.

So, the maximum spectral lines formed:
16. l value for g subshell is 4

(n − n ) (n2 − n1 + 1) = 6
= 2 1 I. Maximum no. of m values = 2l + 1,
2 So, for g = 9
8. From Rydberg’s equation II. Maximum no. of unpaired = 2l + 1.
1 1 1 So, for g = 9.
= R 2 − 2  III. The minimum principal quantum no. of = 5 g shell.
λ  n n2 

hc
1 1 λR 17. From the data, = hυ0 + E1
⇒ 2 = 1− ⇒ n2 = λ1
n λR λR −1
hc
= hυ0 + 2 E1
λ1
9. In case of unielectron systems energy can be deter-
mined only from n values, i.e., orbital of same shell

By substituting and on solving.
have same energy.
⇒ u0 = 1.19 × 1015 s-1.

10. According to the given rules Zr (40) has electronic
configuration as 18. Before the excitation the molecule should undergo the
homolytic cleavage. So, energy required for association
1s32s32p93s33p93d13

Ed = 0.04 × 400 = 16 kJ. On association the sample

12. l1 is the wavelength corresponding to initial kinetic consists of 0.08 moles of H gas atoms.
energy E1.

Energy required for excitation:
l2 is the wavelength corresponding to final kinetic

energy E2 and l2 = 0.9 l1  13.6  −13.6  
= 0.08 × 6.023 × 1023  − − 
hc hc  4  1 
λ1 = : λ2 =
2mE1 2mE2 = 4. 914768 × 1023 eV

4.914768 × 10 23 × 1.602 × 10 −19 kJ
λ 1 E2 =
⇒ 1 = = 103
λ2 0.9 E1
= 78.734 kJ

⇒ E2 = 1.23456 E1

So, total energy required

So, E2 is 23.456% is more than that of E1. = 16 + 78.734 = 94.7345 kJ

Chapter_02.indd 31 3/26/2014 2:47:45 PM

 2.32  Objective Chemistry - Vol. I

19. We know that the no. of waves made by an e- in an velocity of e − 1

orbit equals to its principal quantum number “n”. 21. From the data = =
velocity of light 275
So, from the figure n = 4.
⇒ V = 1090909 m/s

No. of revolutions made by an e- per second (or) Velocity of e- in nth orbit:

2.18 × 106
Z2 Vn =
m/s, n = 2
Frequency =
× 6.66 × 1015 s −1 n
n3
1 23. For the line in the UV region, the energy must be more
= × 6.66 × 1015 = 1 ×1014 s −1 than that corresponding to E.
(4)
3

Energy of A > Energy of E.
20. 1. In H-like systems energy of electron in an orbital 24. To find the distance at which finding probability of
increases with increase in “n”. So, energy of 3d is d 2ψ
less than the energy of 4s. e- is maximum, we have to count =0
− r / a0
dr 2
2. In d x2 − y2 orbitals electron cloud is along x and y
⇒e = 0 - ln (r/a0) = -ln 1
⇒ r = a0
axes. So, it lies in x-y plane.
25. From the data, r(n + 1) - rn = r(n - 1)
Electronic configuration of Cr is 1s22s22p63s2
3. 
3p63d54s1 [(0.529) (n + 1)2] - [0.529 (n2)]

= (0.529) (n - 1)2

4. Except the spin quantum number, the remaining
quantum numbers are obtained from Schrodinger’s ⇒ n2 + 2n + 1 - n2 = n2 - 2n + 1

equation. ⇒ n2 = 4n, n = 4.

Chapter_02.indd 32 3/26/2014 2:47:46 PM

 3

Chapter
Classification of Elements and
Periodicity in Properties

• Classification of elements into different groups which (b) the discovery of elements like scandium, gallium,
makes the study of physical and chemical properties germanium, etc.
of the elements and their compounds is known as • Defects in the Mendeleev’s table are
periodic classification. (a) Elements like lanthanides (rare earths) having dif-
• The scientists to be remembered who worked on the ferent atomic weights are kept in the same group.
periodic classification are William Prout, Dobereiner, (b) Isotopes have no place in the periodic table.
Newlands, Lother Mayer, Dimitri Mendeleev, Moseley,
etc. (c) Anomalous pairs in which the arrangement of el-
ements inverted with respect to their increasing
• Dobereiner proposed that particular groups of three
order of atomic weights. They are potassium and
elements with similar chemical properties (triads as he
argon, tellurium and iodine and cobalt and nickel.
called them) has atomic weight of the middle member
of the triad was approximately the arithmetic mean of • Moseley discovered the atomic numbers from X-ray
the other two. spectra of elements.
• Some Dobereiner’s triads • Moseley’s periodic law states that the physical and
Li 7 Ca 40 S 32 Cl 35.5 chemical properties of the elements are periodic func-
Na 23 Sr 87.5 Se 79 Br 80 tions of their atomic numbers.
K 39 Ba 137.5 Te 127.5 I 127 • Modern periodic law states that the physical and
• Newlands law of octaves states that if known elements chemical properties of the elements are periodic func-
are arranged in ascending order of atomic weight tions of their electronic configuration.
similar properties recurred in every eight element, like
notes in a musical scale. long form periodic table
• Lother Meyer proposed that when the properties of
the elements are plotted as a function of their atomic • Long form periodic table is known as Bohr’s Table.
weight the elements with similar properties occupied • Long form periodic table is based on the electronic
almost similar positions. configuration of elements.
• Mendeleev’s periodic law states that the physical and • The vertical columns of the table are called groups
chemical properties of the elements are periodic func- while the horizontal columns are called as periods.
tions of their atomic weight. • Long form periodic table contains 7 periods and 18
• Mendeleev first prepared the short form periodic table groups.
by arranging the elements in the increasing order of • Long form periodic table is the graphical representa-
their atomic weights. tion of Aufbau principle.
• Mendeleev’s periodic table helped in • Every period starts with filling of the s-orbital of a new
(a) the correction of atomic weight of elements like orbit and ends with complete filling of the p-subshell
beryllium and indium of the same orbit.

Chapter_03.indd 1 3/26/2014 2:46:10 PM

 3.2  Objective Chemistry - Vol. I

• The first period contains only two elements in which 3. Which of the following statement is false?
the first orbit (K-shell) is filled with two electrons. It is (1) In modern periodic table the elements are ar-
known as the shortest period. ranged in increasing order of atomic number.
• The second period starts with the filling of differentiat- (2) The number of periods in the long form periodic
ing electron into 2s orbital of second orbit (L-shell) table is 7.
and ends with the complete filling of 2p orbital of the (3) The long form periodic table is nothing but just a
same orbit in neon. graphical representation of Pauli’s principle.
(4) Elements of III period are called typical elements.
• The second and third periods contain eight elements
each and are known as short periods. 4. In Mendeleev’s periodic table Fe, Co, Ni are placed in
• The sixth period contains 32 elements and is known as (1) same period (2)  same group
the longest period. (3) both (4)  none

• The seventh period is the incomplete period. 5. What is the atomic number of the element, which is in
the same group of periodic table in which the element
• Every period starts with an alkali metal and ends with with atomic number 15 is present?
an inert gas.
(1) 5 (2)  7 (3)  11 (4)  17
• The number of periods of which an element belongs is
equal to the number of orbits filled in the atom of that 6. Which of the following statement is false?
element or to the value of principal quantum number. (1) The group in which all the elements do not have
same number of valence electrons is zero.
• The number of groups to which an element belongs is
(2) Elements of II period elements are collectively
equal to the number of electrons present in its outer-
called as bridge elements.
most orbit.
(3) The cause of periodicity of properties is reoccur-
• Elements of III period are known as typical elements rence of similar outer electronic configuration.
because they represent the properties of the elements (4) The most reactive gaseous element in the second
in that group. period is oxygen.
• III period elements are known as bridge elements be- 7. The statement that is true for the long form periodic
cause they act as bridge between A and B subgroups. table is
• The elements in a group will have similarities in the (1) It reflects the sequence of filling the electrons in
chemical properties due to the similar outer electron the order of sub energy levels s, p, d and f.
configuration but shows gradation in their physical (2) It helps in predicting the valence states of the
properties. elements.
(3) It reflects trends in physical and chemical proper-
ties of the elements.
(4) All
 Objective Questions 8. The statement that is not correct for the periodic clas-
1. Increasing order of atomic weights was violated sification of elements is
(anomalous pairs) in the case of (1) The properties of elements are the periodic func-
(1) Te, I (2)  Ar, K tions of their outer electronic configurations.
(3)  Co, Ni (4)  All (2) Non-metallic elements are lesser in number than
metallic elements.
2. The wrong statement among the following is (3) For transition elements the d-subshells are filled
(1) Mendeleev arranged the elements in a tabular with electrons monotonically with increase in
form according to increasing atomic weight. atomic number.
(2) One of the defects in Mendeleev’s periodic table (4) In the periodic table metallic elements appear in
is position of lanthanides. the right-hand columns.
(3) Maximum number of groups in Bohr’s periodic
table is 18. 9. Which of the following statement is wrong?
(4) Elements with similar chemical properties occur (1) In the sixth period the orbitals being filled are 6s,
only within the same period. 4f, 5d, and 6p.

Chapter_03.indd 2 3/26/2014 2:46:10 PM

 Classification of Elements and Periodicity in Properties   3.3

(2) All the elements in a group in the periodic table (1) IV period, VIB group
have the same number of electrons in the outer (2)  III period, VIA group
most shell of their atoms. (3) IV period, IVB group
(3) Periodicity in the properties of elements when (4)  III period, IVB group
elements are arranged in increasing order of
17. The element with atomic number 21 may belong to
their atomic weights is that elements with similar
nature repeat after certain fixed interval. (1) IIIA group; IV period
(4) The last member in each period of the periodic (2)  IIIA group; III period
table is an inert gas. (3) IIIB group; IV period
(4)  IIIA group; II period
10. The false statement among the following is
18. The element with atomic number 84 belongs to
(1) Modern periodic table is based on the atomic
number of elements which is mainly due to (1) VI group, VI period
Moseley’s work on X-ray spectra. (2)  I group, VI period
(2) The element with atomic number 33 will be (3) V group, VI period
placed in fifth group and 4th period of periodic (4)  VI group V period
table.
(3) The starting element in any period in the periodic
table is an alkali metal. Answers
(4) The group in which all the elements are gases is
VIIA. (1) 4 (2) 4 (3) 3 (4) 3 (5) 2
(6) 4 (7) 4 (8) 4 (9) 3 (10) 4
11. An element having the electronic configuration of its (11) 2 (12) 3 (13) 2 (14) 2 (15) 3
atom as ns2np2 should have similar properties to those (16) 2 (17) 1 (18) 1
of
(1) Sodium (2)  Carbon
(3) Magnesium (4)  Oxygen
Classification of Elements into
12. Which pair of elements belong to the same group? s-, p-, d- and f-Block Elements
(1) Elements with atomic number 17 and 38
(2) Elements with atomic number 20 and 40 • Depending on the type of orbital in which the differen-
(3) Elements with atomic number 17 and 53 tiating electron enters, the elements are classified into
(4) Elements with atomic number 11 and 53 s-, p-, d- and f-block elements.

13. Which pair has both members from the same period s-Block Elements
of periodic table?
(1) Mg, Ba (2)  Mg, Na (i) Differentiating electron enters into s-orbital
(3) Mg, Cu (4)  K, Cl (ii) Their general electronic configuration is ns1 or ns2

(iii) Since the maximum capacity of s-orbital is 2, the
14. Each period in the periodic table starts with a s-block contain only two groups
s-subshell of the new shell and ends with filling of (iv) The first two groups of the periodic table are
(1) Same subshell s-block elements
(2) p-subshell of the same shell (v) I Group contain hydrogen and alkali metals with
(3) p-subshell of the next shell outer electronic configuration ns1
(4) d-subshell of the same shell (vi) II Group contain alkaline earth metals with outer
electronic configuration ns2
15. The electronic configuration of two elements A and
(vii) Except hydrogen, all the s-block elements are
B are respectively 1s22s22p6 and 1s22s22p63s23p6.
metals
Therefore, their positions in the periodic table are
(viii) All the s-block metals are soft with low m.pts and
(1) A after B (2)  A before B b.pts.
(3) A above B (4)  A below B (ix) All the s-block elements exhibit a fixed valency
16. The position of the element in the periodic table with (x) All the s-block elements form colourless com-
its outer electronic configuration 3s23p4 is pounds which are diamagnetic

Chapter_03.indd 3 3/26/2014 2:46:10 PM

 3.4  Objective Chemistry - Vol. I

p-Block Elements Classification of Elements

(i) T
 he last six groups of the periodic table are p-block Depending on Properties and
elements. Electronic Configuration
(ii) In these elements, the differentiating electron en- • Depending on the chemical properties and electronic
ters into p-orbital. configurations the elements are classified into four
(iii) Their general outer electronic configuration is types: (a) inert gases, (b) representative elements, (c)
ns2np1-6. transition elements and (d) inner transition elements.
(iv) p-block contain metals, non-metals and metalloids.
(v) The only p-block element in which the differentiat-
Inert Gases
ing electron does not enter into p-orbital is He.
(vi) p-block elements exhibit variable valence. (i) These are zero group elements.
(vii) p-block elements form colourless compounds (ii) There are six elements He, Ne, Ar, Kr, Xe and Rn.
which are diamagnetic. (iii) Except in He (1s2) all the other elements have
ns2np6 outer electronic configuration.
d-Block Elements (iv) All these elements are gases.
(v) All are chemically inert due to the presence of
(i) T he middle 10 groups of elements in long form stable electronic configuration (ns2np6) in their
periodic table are d-block elements. outermost shell.
(ii) In these elements the differentiating electron enters (vi) All are monoatomic gases.
into (n - 1) d orbital.
(iii) Their general outer electronic configuration is Normal (or) Representative Elements
(n -1) d1-10 ns1 or 2.
(iv) The d-block elements are placed in between the (i) E xcept “0” group all the remaining s- and p-block
s- and p-block elements. elements of the periodic table are called represent-
(v) All the d-block elements are metals. ative elements.
(ii) Their general outer electronic configuration is
ns1-2np0-5.
f-Block Elements
(iii) Their outermost orbit is incomplete.
(i) T
 he lanthanides and actinides which are placed (iv) Metals, non-metals and metalloids are present in
below the periodic table are known as f-block representative elements.
elements. (v) All are chemically reactive and to get stable inert
(ii) The differentiating electron enters into the f-orbital gas configuration (ns2np6), they lose or gain or
of antipenultimate shell. share electrons.
(iii) Their general outer electronic configuration is
(n -2) f1-14 (n - 1)d 0 or 1 ns2. Transition Elements
(iv) In the elements after lanthanum starting from ceri- (i) T hese are d-block elements.
um (Z = 58) to lutetium (Z = 71) the differentiating (ii) Their general outer electronic configuration is
electron enters into 4f orbital. So, they are known (n - 1)d1-10ns1 or 2.
as 4f series.
(iii) In these elements the outer most and penultimate
(v) Since the properties of 4f series elements are simi- shells (two orbits) are incompletely filled.
lar to lanthanum they are known as lanthanides or (iv) Differentiating electron enters into the d-orbital of
lanthanons or lanthanoids. the penultimate shell.
(vi) In the elements after actinium starting from (v) There are four series each containing 10 elements.
thorium (Z = 90) to lawrentium (Z = 103) the (vi) The first transition series is from scandium
differentiating electron enters into 5f orbital. So, (Z = 21) to zinc (Z = 30) in which differentiating
they are known as 5f series. electron enters into 3d-orbital and hence known as
(vii) Since the properties of 5f series elements are 3d series.
similar to actinium they are known as actinides or (vii) In the second series of 10 elements (39Y to 48Cd)
actinons or actinoids. the differentiating electron enters into 4d orbital
(viii) Each series of f-block contain 14 elements. and hence known as 4d series.

Chapter_03.indd 4 3/26/2014 2:46:11 PM

 Classification of Elements and Periodicity in Properties   3.5

(viii) I n the third series of 10 elements (57La to 80Hg) the Classification of Elements into
differentiating electron enters into 5d orbital and Metals, Non-Metals and Metalloids
hence known as 5d series.
(ix) The fourth transition series is an incomplete series. • Elements are classified into metals, non-metals and
(x) Due to the small size, high effective nuclear charge metalloids basing on their properties.
and unpaired d-electrons, transition elements • 78% of the known elements are metals and appear on
exhibit characteristic properties. the left side of the periodic table.
(xi) All the transition elements are hard and heavy metals. • Metals usually have high melting points and boiling
(xii) The transition elements have high m.pt, b.pt and points.
densities.
(xiii) They exhibit variable valency.
• Mercury is a liquid, gallium and caesium have very
(xiv) Due to d-d transition, their compounds are coloured. low melting points.
(xv) Transition elements and their compounds act as • All metals are good conductors of heat and electricity.
catalysts. For example, nickel in the hydrogena- • All metals are on the left-hand side of the periodic table.
tion of oils, iron powder mixed with molybdenum • Non-metals are on the right-hand side of the periodic
powder as promoter in the manufacture of ammo- table.
nia is used as catalysts.
(xvi) Due to the presence of unpaired electrons in
• Non-metals are usually solids or gases. Only bromine
d-orbitals, the transition elements and their com- is a liquid non-metal.
pounds are paramagnetic. • Generally nonmetals have low m.pts and b.pts.
(xvii) Transition elements form alloys like brass, bronze, • Non-metals are poor conductors of heat and electricity.
german silver, etc. • All metals are malleable and ductile.
• Most non-metallic solids are brittle and are neither
Inner Transition Elements malleable nor ductile.
(i) T hese are f-block elements. • In a group as we move down, metallic character in-
(ii) Their outermost three orbits are incompletely creases and non-metallic character decreases.
filled. • In a period from left to right along a period metallic cha­
(iii) Their general outer electronic configuration is racter decreases and non-metallic character increases.
(n - 2) f1-14 (n - 1) d0 or 1 ns2.
• If a diagonal line is drawn starting from boron to as-
(iv) In these elements the differentiating electron enters
tatine in the p-block elements, the elements along this
into an antipenultimate shell.
line are metalloids showing the properties of both met-
(v) Since the electronic configuration in the outermost
als and non-metals. The elements above the line are
two orbits is similar, in these elements the simi-
nonmetals and the elements below the line are metals.
larities are very much with respect to their physical
and chemical properties.
(vi) These are two series, 4f and 5f series or lanthanides
and actinides.  Objective Questions
(vii) Lanthanides are also known as rare earths because
of their rare occurrence. 19. Cerium (Z = 58) is a member of
(viii) The common stable oxidation state of lanthanides
(1) s-block elements
is +3.
(2) p-block elements
(ix) The elements after uranium in actinides or 5f-
(3) d-block elements
series are called transuranium elements.
(4) f-block elements
(x) All the transuranium elements are man-made,
synthetic and radioactive. 20. Which electronic configuration represents a transi-
(xi) The lanthanides and actinides are present in the 3rd tion element?
group and 6 and 7 periods of long form periodic (1) 1s22s22p63s23p63d104s24p6
table. (2) 1s22s22p63s23p63d104s24p1
(xii) In these elements the outermost three orbits are (3) 1s22s22p63s23p63d24s2
incomplete. (4) 1s22s22p63s23p64s2

Chapter_03.indd 5 3/26/2014 2:46:13 PM

 3.6  Objective Chemistry - Vol. I

21. Which statement is false? periodic properties

(1) Elements of VA group are transition elements.
(2) Elements of I and II groups are normal elements.
• Periodicity means that when elements are arranged
(3) Elements of zero group are monoatomic gases. according to their electronic configuration the proper-
(4) All transition elements are metals. ties of elements in the periodic table reoccur at regular
intervals. Such properties which reoccur are called as
22. Among the following pairs of atomic numbers, the periodic properties.
pair which belongs to p-block is • Only the outer electrons are responsible for the chemi-
(1) 8, 16 (2)  4, 8 (3)  6, 12 (4)  12, 24 cal properties but not the electrons in the inner orbits.
23. In the transition elements, the incoming electron • As the electronic configuration in the outermost orbit
occupies (n - 1)d sublevel in preference to changes the chemical properties of the elements also
(1) np (2)  ns changes.
(3) (n - 1) d (4)  (n + 1) s • The elements having similar outer electronic configu-
ration will have the same chemical properties.
24. The most common oxidation state of lanthanides in
their compounds is • The periodicity occurs at regular intervals after every
(1) +2 (2)  +3 (3)  +4 (4)  +1 2, 8, 8, 18, 18 and 32 elements. These are called magic
numbers.
25. The false statement regarding transition elements is
(1) they exhibit variable valence
(2) they form coloured compounds or ions which are shielding effect: effective
paramagnetic nuclear charge
(3) the elements and their compounds are diamagnetic
(4) the elements and their compounds act as catalysts • The decrease in the force of attraction exerted by the
nucleus on the valence electrons due to the presence of
26. Which of the following statement is wrong?
electrons in the inner shells is called screening effect
(1) Transition elements lie between III and IV groups or shielding effect.
in the periodic table.
• The actual attractive power of the nucleus reaching the
(2) Transition elements are those which contain
valence electrons after shielded by the inner electrons is
­incomplete d-orbital.
called effective nuclear charge and represented by Z*.
(3) The 14 elements placed in the 3rd group and 6th
period of the periodic table are known as rare earths. • Z* is always less than Z (actual nuclear charge) and
(4) The element californium belongs to actinide series. can be calculated by
Z* = Z - S where S is the screening constant.
27. About transuranic elements the wrong statement is,
they • The screening constant S can be calculated by the fol-
(1) are of higher atomic number than uranium lowing Slater rules.
(2) belong to actinide series (i) The electronic configurations of the elements
(3) are radioactive and decay into other elements should be written in the following order and group-
(4) occur naturally ings.
(2s2p); (3s3p); (3d); (4s4p); (4d); (4f); (5s,5p), etc.
28. The false statement among the following is (ii) Electrons in any group which are right to the
(1) Inert gases belong to p-block. (ns, np) group do not contribute anything to the
(2) f-block elements are called inner transition shielding effect.
elements. (iii) All the electrons in the (ns, np) group (valence
(3) Lanthanum is a member of f-block element. shell or outermost orbit) shield the valence elec-
(4) The element with Z = 106 belong to d-block. tron to an extent of 0.35 each.
(iv) All the electrons in the (n - 1) shell (penultimate
Answers shell) shield to an extent of 0.85 each.
(v) All the electrons in (n - 2) shell or lower, shield
(19) 4 (20) 3 (21) 1 (22) 1 (23) 1 completely, i.e., their contribution is 1.00 each.
(24) 2 (25) 3 (26) 1 (27) 4 (28) 3 (vi) All the electrons in groups lying to the left of nd or
nf contribute a shielding effect of 1.00.

Chapter_03.indd 6 3/26/2014 2:46:13 PM

 Classification of Elements and Periodicity in Properties   3.7

atomic radii and Ionic radii • In a period from left to right the atomic radius
d­ ecreases due to the increase in the effective nuclear
• The distance from the nucleus to the outer most shell charge.
is called as atomic radius. • In every period the alkali metal has the maximum
• Atomic radius cannot be determined directly because atomic size while the halogens have the minimum size.
according to wave mechanical picture, the electron • In a period atomic radius decreases up to halogen but
cloud is more diffused. suddenly increases in inert gases, because the atomic
• Atomic radius of atom is affected by (i) the type of radius of inert gases is Van der Waal’s radius.
bonding, (ii) its oxidation state, (iii) its coordination • The decrease in atomic size in a period is more when
number (iv) number of bonds between atoms and the differentiating electron enters into s-orbital or
(v) type of hybridisation of the atom. p-orbital.
• Metallic or crystal radius is half the internuclear dis- • In transition elements the atomic radius decreases
tance of the two adjacent atoms in a metal crystal. slowly in the beginning, remains almost constant in
• The internuclear distance in sodium metal crystal is the middle and then increases a little at the end.
372 pm, so the atomic radius of sodium atom is 186 pm. • The initial decrease in atomic radius of transition
• Van der Waal’s radius is half the internuclear distance elements is due to the increase in effective nuclear
of the two atoms of different molecules when they charge.
come close due to Van der Waal’s attractive forces. • The constant atomic radii in the middle and a little
• Van der Waal’s radius is 40% greater than the radius increase at the end in a transition series is due to repul-
measured when the atoms are in chemical bond. sion between paired electrons.
• Covalent radius is half the internuclear distance of the • In lanthanides the atomic radii decreases with increase
two atoms of same element in a covalent bond. in the atomic number in a regular manner due to the
poor shielding capacity of f-electrons. This is known
• In heteroatomic molecules the covalent radius of one as lanthanide contraction.
atom can be calculated, if the covalent radius of other
• The lanthanide contraction is more pronounced in
atom and the bond length in that molecule is known.
their trivalent ions than in lanthanides.
e.g., The C-H bond length is 110 pm and the covalent
radius of carbon is 0.77 pm. So, the covalent radius of • Because of lanthanide contraction the crystal struc-
hydrogen atom is 110 - 77 = 33 pm. tures and their properties are very similar which makes
their separation difficult.
• The bond length in a covalent molecule is equal to
the sum of the covalent radii of the two atoms in that • Due to lanthanide contraction the atomic sizes of 4d
molecule. and 5d series transition elements become almost equal
due to which their properties are very close.
• Covalent radius is affected by (i) the number of bonds
between two atoms, (ii) the oxidation number and
• In p-block elements the atomic radius in a group
(iii) coordination number. ­increases largely between first and second element, but
the atomic sizes of second and third elements are near-
• As the number of covalent bonds between the atoms ly equal due to the poor shielding effect of d-electrons
increases the covalent radius decreases, e.g., the co- in the 3rd element which is followed by the 3d series
valent radius of carbon decreases with increase in the elements.
number of bonds between carbon atoms.
• There is slight increase in the atomic size between
third and fourth element but the atomic sizes of fourth
Type of bond Bond length Covalent radius
and fifth elements are almost equal. This is again be-
C-C 154 pm 77 pm cause of the poor shielding effect of 4f electrons and
C=C 134 pm 67 pm lanthanide contraction.
C≡C 120 pm 60 pm • Ionic radius is the effective distance from the nucleus
of an ion up to which it has its influence on its electron
• As the oxidation number of atom increases the cova- cloud.
lent radius decreases, e.g., Fe3+ is smaller than Fe2+. • Positive ion is always smaller than the parent atom
• In a group from top to bottom the atomic radius increas- because of the contraction of orbits by the increased
es gradually due to the increase in the number of orbits. effective nuclear charge.

Chapter_03.indd 7 3/26/2014 2:46:13 PM

 3.8  Objective Chemistry - Vol. I

• The size of the negative ion is always greater than the 36. Which one of the following is the smallest in size?
parent atom because of the decrease in the effective (1) N3- (2)  O2- (3)  F- (4)  Na+
nuclear charge.
37. In which pair the first atom or ion is not larger than
• Ions having the same number of electrons but with the second?
different nuclear charge are known as isoelectronic
(1) N, F (2)  Cl, Cl
species.
(3) O, S (4)  Fe2+, Fe3+
• In isoelectronic species the size of the ion increases
with increase in the number of negative charges and 38. Na+ is smaller than Na atom because
decreases with increase in the number of positive (1) Nucleus in each case contains different nucleons.
charges. (2) Sodium atom has an electron lesser than sodium ion.
(3) Sodium atom has 11 electrons and sodium ion
has 10 electrons.
(4) The force of attraction is less in Na+ than in Na
 Objective Questions atoms.
29. The ionic radii of N3-, O2- and F- are respectively 39. Which is correct among the following statements?
(1) 1.36, 1.40, 1.70 (2)  1.36, 1.71, 1.40 (1) Radius of Cl atom is 0.99 Å while that of Cl+ ion
(3) 1.71, 1.40, 1.36 (4)  1.71, 1.36, 1.40 is 1.54 Å.
30. The maximum atomic radius exists for (2) Radius of Cl atom is 0.99 Å while that of Na
(1) Mg (2)  N (3)  Si (4)  P atom is 1.54 Å.
(3) Radius of Cl atom is 0.95 Å while that of Cl- ion
31. As we move along the periodic table from left to right is 0.81 Å.
the atomic size decreases. However, noble gases have (4) Radius of Na atom is 0.95 Å while that of Na+ ion
the largest size because of is 1.54 Å.
(1) covalent radii
(2) ionic radii 40. The correct ionic radii order is
(3) Van der Wall’s radii (1) N3- > O2- > F- > Na+
(4) stable octet (2) N3- > Na+ > O2- > F-
(3) Na+ > O2- > N3- > F-
32. Which relation represent the correct relationship of
(4) O2- > F- > Na+ > N3-
the radius of an atom, its cation and its anion?
(1) atom = cation = anion 41. The size of ionic species is correctly given in the
(2) atom > cation > anion order.
(3) atom > cation < anion (1) Cl7+ > Si4+ > Mg2+ > Na+
(4) atom < cation > anion (2) Na+ > Mg2+ > Si4+ > Cl7+
33. Which statement is correct? (3) Na+ > Mg2+ > Cl7+ > Si4+
(1) X+ ion is larger than X- ion (4) Cl7+ > Na+ > Mg2+ > Si4+
(2) X– ion is larger than X atom 42. If the ionic radii of K+ and F- are about 1.34 Å each,
(3) X+ ion and X have same size then the expected values of atomic radii of K and F
(4) X+ ion is larger in size than X atom should be respectively
34. Atomic radii of fluorine and neon in angstrom units (1) 1.34 and 1.34 Å
are respectively given by (2) 2.31 and 0.61 Å
(1) 0.72; 1.60 (2)  1.60; 1.60 (3) 0.64 and 2.31 Å
(3) 1.60; 0.72 (4)  0.72; 0.72 (4) 2.31 and 1.34 Å
35. Na+, Mg2+, Al3+, Si4+ are isoelectronic. Their ionic 43. Which of the series of elements listed below would
size follows the order: have nearly same atomic radii
(1) Na+ < Mg2+ < Al3+ < Si4+ (1) F, Cl, Br, I
(2) Na+ > Mg2+ < Al3+ < Si4+ (2)  Na, K, Rb, Cs
(3) Na+ < Mg2+ > Al3+ > Si4+ (3) Li, Be, B, C
(4) Na+ > Mg2+ > Al3+ > Si4+ (4)  Fe, Co, Ni, Cu

Chapter_03.indd 8 3/26/2014 2:46:14 PM

 Classification of Elements and Periodicity in Properties   3.9

44. Which one of the following indicates the correct nuclear charge will be more. Hence, ionisation
order of atomic size? enthalpy decreases.
(1) Be > F > C > Ne • With increase in the number of positive charges on an
(2) Be < C < F < Ne ion ionisation enthalpy increases.
(3) Be > C > F < Ne
• If the valence electrons are more penetrated into inner
(4) F < Ne < Be < C
shells ionisation enthalpy increases.
45. In isoelectronic cations, ion having more nuclear • Penetration power of different orbitals is in the order
charge has the size
s>p>d>f
(1) higher (2)  smaller
(3) equal (4)  cannot be determined • If the outermost electronic configuration is stable, i.e.,
either exactly half-filled or completely filled ionisation
46. The element with the following atomic number may enthalpy is more.
be bigger than aluminium atom.
• The element with highest ionisation enthalpy is helium.
(1) 12 (2)  14 (3)  16 (4)  17
• In the graph showing relation between ionisation en-
47. Correct increasing order of size in the following is thalpy and atomic number, the inert gases appear at the
(1)  Mg2+ < Na+ < F- < Al peaks and alkali metals appear at the bottoms.
(2)  F- < Al < Na+ < Mg2+ • The number of ionisation enthalpies that an element
(3) Al < Mg < F- < Na+
possesses is equal to the atomic number of atom or
(4) Na+ < Al < F- Mg2+
electrons possessed by that species.
48. O2- and Si4+ are isoelectronic ions. If the ionic radius • Ionisation enthalpies are measured in discharge tubes.
of O2- is 1.4 Å units, the ionic radius of Si4+ is
• If the ionisation enthalpy of an element is less, it is
(1) 1.4 Å (2)  0.41 Å
more reactive and acts as a strong reducing agent.
(3) 2.8 Å (4)  1.5 Å
• In a group from top to bottom ionisation enthalpy
decreases due to the increase in atomic size and
Answers
increase in the screening effect of inner electrons.
(29) 3 (30) 1 (31) 3 (32) 3 (33) 2 • In a period from left to right ionisation enthalpy
(34) 1 (35) 4 (36) 4 (37) 3 (38) 3 increases due to the increase in the effective nuclear
(39) 2 (40) 1 (41) 2 (42) 2 (43) 4 charge.
(44) 3 (45) 2 (46) 1 (47) 1 (48) 2 • Ionisation enthalpy of Be is greater than B because the
electron to be removed in B is from 2p orbital which is
at a slightly higher energy level than the 2s electron in
Ionisation potential beryllium. The 2p electron in boron is well shielded by
two orbitals 1s and 2s where the 2s electron in beryl-
• The amount of energy required to remove the most lium is shielded by only one orbital 1s and is nearer to
loosely bound electron from an isolated, gaseous, neutral the nucleus.
atom in a ground state is known as ionisation enthalpy. • Due to similar reasons as explained above the
• The ionisation enthalpy is expressed either in terms of first ionisation enthalpy of aluminium is less than
eV atom-1 or Kcal mol-1 or KJ mol-1. magnesium.
1 eV atom-1 = 23.06 Kcal mol-1 = 96.45 KJ mol-1. • The first ionisation enthalpy of nitrogen is greater than
• With increase in the atomic size ionisation enthalpy oxygen because in nitrogen the electron to be removed
decrease due to the decrease in attractive power of nu- is from stable exactly half-filled 2p orbital. Due to sim-
cleus on electrons of the outermost orbit. ilar reasons, first ionisation enthalpy of phosphorous is
• With increase in the effective nuclear charge ionisa- greater than sulphur.
tion enthalpy increases. • In any period the alkali metal has lowest ionisation
• If the number of electrons in the inner shells are enthalpy and inert gas will have the highest ionisation
more, shielding capacity of the inner electrons on the enthalpy.

Chapter_03.indd 9 3/26/2014 2:46:14 PM

 3.10  Objective Chemistry - Vol. I

(1) 1s22s22p63s1 (2) 1s22s22p63s23p1

 Objective Questions (3) 1s22s22p63s23p2 (4) 1s22s22p63s2

49. A neutral atom will have the lowest ionisation poten- 58. The first ionisation potential of Na, Mg, Al and Si
tial when electronic configuration is (1) Na < Mg > Al < Si (2)  Na > Mg > Al > Si
(1) 1s1 (2)  1s22s22p6 (3) Na > Mg < Al > Si (4)  Na > Mg > Al > Si
2 2 6 1
(3) 1s 2s 2p 3s (4)  1s22s22p2 59. The decreasing order of second ionisation potential
50. The ionisation energy of nitrogen is more than oxy- of K, Ca and Ba is
gen because (1) K > Ca > Ba (2)  Ca > Ba > K
(1) more attraction of electrons by the nucleus (3) Ba > K > Ca (4)  K > Ba > Ca
(2) the extra stability of half-filled p-orbitals 60. IP1 and IP2 of Mg are 178 and 348 K cal mol-1. The
(3) the size of nitrogen atom is smaller energy required for the reaction Mg → Mg2+ + 2e- is
(4) more penetrating effect
(1) +170 Kcal (2)  +526 Kcal
51. The correct order of second ionisation potential of (3) -170 Kcal (4)  -526 Kcal
C, N, O and F is
61. The IP1, IP2, IP3, IP4 and IP5 of an element are 7.1,
(1) C > N > O > F (2)  O > N > F > C
14.3, 34.5, 46.8, 162.2 eV, respectively. The element
(3) O > F > N > C (4)  F > O > N > C
is likely to be
52. The first ionisation energy of sodium is 500 KJ mol-1. (1) Na (2)  Si (3)  F (4)  Ca
This denotes the energy
62. IP2 for an element is invariably higher than IP1
(1) Given out when 1 mole of sodium atoms dissolve
because
in water to form sodium ions
(2) Required to remove one electron to infinity from (1) The size of cation is smaller than its atom.
one atom of sodium (2) It is difficult to remove electron from cation.
(3) Required to raise the electron in one mole of gas- (3) Effective nuclear charge is more for cation.
eous sodium atoms to a higher energy level (4) All
(4) Required to change one mole of gaseous sodium 63. The ionisation potential order for which set is correct?
atoms into gaseous ions (Na+) (1) Li < K < Cs (2)  B > Li > K
53. Among the following elements the configuration (3) Au < Ag < Cu (4)  Cs < Rb < K
having highest ionisation energy is 64. One among the following is the incorrect order of
(1) [Ne] 3s23p1 (2)  [Ne] 3s23p3 increasing ionisation energy.
2 2
(3) [Ne] 3s 3p (4)  [Ar] 3d104s24p3 (1) Cl- < Ar < K+ (2)  K < Ca < Sc
54. The first ionisation potential in electron volts of nitro- (3) Au < Ag < Cu (4)  Cs < Rb < K
gen and oxygen atoms are respectively given as 65. Which of the following process requires greatest
(1) 14.61; 13.67 (2)  13.61; 14.6 amount of energy?
(3) 13.6; 13.6 (4)  14.6; 14.6
(1) Na ( g ) 
→ Na + ( g ) + e −
55. The correct order of decreasing first ionisation
(2) Al3+ ( g ) 
→ Al3+ ( g ) + e +
potential is
(1) C > B > Be > Li (2)  C > Be > B > Li (3) Al 2 + ( g ) 
→ Al 4 + ( g ) + e −
(3) B > C > Be > Li (4)  Be > Li > B > C
(4) Na + ( g ) 
→ Na 2 + ( g ) + e −
56. Which transition involves maximum amount of
energy? 66. Which of the following isoelectronic ions has lower
(1) M–(g) → M(g) + e- (2)  M(g) → M2+(g) +2e- first IP value?

(3) M+(g) → M2+(g) + e- (4)  M2+(g) → M3+(g) + e- (1) K+ (2)  Ca2+ (3)  S2- (4)  Cl-

57. A sudden jump between the values of second and 67. Successive ionisation energies of an element (M) are
third ionisation energies of an element would be 176.0, 346.0 and 1850 Kcal. Formula of its chloride
associated with the electronic configuration. (1) MCl (2)  MCl2 (3)  MCl4 (4)  MCl5

Chapter_03.indd 10 3/26/2014 2:46:15 PM

 Classification of Elements and Periodicity in Properties   3.11

68. Which one of the following relation is correct with • Electron affinities of Be and Mg (2nd group) are also
respect to first (I) and second (II) ionisation poten- positive.
tials of sodium and magnesium? • The electron affinity in a period increases from left
(1) INa > I Mg (2)  I Mg = II Na to right due to the increase in the effective nuclear
(3) II Mg > II Na (4)  II Na > II Mg charge.
69. Which of the following has highest ionisation • The electron affinity in a group from top to bottom
potential? decreases due to the increase in size.
(1) Li+ (2)  Mg+ (3)  Al+ (4)  Ne+ • The electron affinity of chlorine is greater than fluo-
rine because of the repulsion between the extra elec-
70. If the number of electrons in the inner shells increases
tron added and the electrons already present in small
then
second orbit.
(1) Ionisation potential increases
(2) Screening effect increases
• Due to similar reasons the electron affinity of oxygen
(3) Shielding effect decreases is less than sulphur and that of nitrogen is less than
(4) Nuclear attraction on outer electrons increases phosphorous.
• The electron affinities of Group-VB elements, i.e.,
71. Successive ionisation energies of an element M are nitrogen family are very low because of stable exactly
176, 346 and 1850 Kcal. Formula of its sulphate is half-filled np3 configuration.
(1) M2SO4 (2)  M3(SO4)2
• In metals, gold has maximum electron affinity.
(3) MSO4 (4)  M(SO4)2
• The electron affinity of neutral atom (X) is equal to the
ionisation enthalpy of its negative ion (X-).
Answers
• The ionisation enthalpy of neutral atom (M) is equal to
(49) 3 (50) 2 (51) 3 (52) 4 (53) 2 the electron gain enthalpy of its cation (M+).
(54) 1 (55) 2 (56) 4 (57) 4 (58) 1 • The second electron gain enthalpy of any element is
(59) 2 (60) 2 (61) 2 (62) 4 (63) 2 endothermic (energy will be absorbed in the addition
(64) 3 (65) 3 (66) 3 (67) 2 (68) 4 of second electron to a uninegative ion).
(69) 1 (70) 2 (71) 3 • Of all the elements, chlorine has the maximum electron
gain enthalpy.

electron gain enthalpy

 Objective Questions
• The energy released when an electron is added to a
neutral gaseous isolated atom to convert into anion is 72. The false statement among the following is
called electron gain enthalpy or electron affinity. (1) Electron affinity of noble gases is almost zero.
• Electron gain enthalpy is represented as negative value (2) The halogen with highest electron affinity is
while electron affinity is represented as positive value fluorine.
and are related as DegH = -Ae - 5/2 RT because at dif- (3) Electron affinity values are obtained indirectly by
ferent temperatures heat capacities of the reactants and Born-Haber Cycle.
the products have to be taken into account. (4) Ionisation potential of Na would be numerically
• Electron gain enthalpies are expressed in electron the same as electron affinity of Na+.
volts per atom or kilojoules per mole of atoms. 73. Electron affinity of
• Electron gain enthalpies can be calculated from Born- (1) Carbon is greater than oxygen
Haber Cycle. (2) Sulphur is lesser than oxygen
• Electron affinity depends on size, effective nuclear (3) Iodine is higher than bromine
charge and electronic configuration of an element. (4) Bromine is lesser than chlorine

• The electron affinities of inert gases are positive be- 74. The process requiring absorption of energy is
cause they have no tendency to gain electron due to (1) F → F- (2)  H → H-
stable ns2np6 configuration. (3) Cl → Cl -
(4)  O → O2-

Chapter_03.indd 11 3/26/2014 2:46:16 PM

 3.12  Objective Chemistry - Vol. I

75. Arrange O, S and Se in the increasing order of their • According to Mulliken’s scale the electronegativity is
electron affinity. the average of ionisation enthalpy and electron gain
(1) Se < S < O (2)  O < Se < S enthalpy.
(3) S < O < Se (4)  S < Se < O IE1 + Ae1
Electronegativity =
76. Electron affinity of  V group → VI group is maximum 2
respectively for • Mulliken’s electronegativity values are approximately
(1) P, O (2)  N, O (3)  P, S (4)  None 2.3 times greater than Pauling’s electronegativity
values.
77. The correct statement among the following is
• Mulliken scale is applicable only to univalent elements.
(1) Electron affinity of X- ion is equal to ionisation
energy of X atom. • The electronegativities of inert gases are almost zero.
(2) The second electron gain enthalpy is more than • The nearest actual values of electronegativities in
the first electron gain enthalpy. Mulliken scale can be obtained by
(3) Among the metals gold has maximum electron IE + Ae IE + Ae
affinity. Thus, χM = =
2 × 2.8 5.6
(4) Electron affinity of fluorine is more than that of
chlorine due to lower size. • If IE and Ae are measured in KJ mol-1 then the above
equation becomes
IE1 + Ae 1
Answers χM =
5.6 × 96.48
(72) 2 (73) 4 (74) 4 (75) 2 (76) 3 • According to Alred and Rochow electronegativity of
(77) 3 an atom can be calculated as
0.359 Z *
χM =
r2

electronegativity where χM is the electronegativity of atom M, Z* is the

effective nuclear charge of M and r is the radius of the
• The tendency of an atom in a compound to attract the atom of M.
shared pair of electrons in a covalent bond towards • In a group from top to bottom electronegativities
itself is known as electronegativity. increases due to the increase in the atomic size and
• Though both electron gain enthalpy and electron- increase in effective nuclear charge.
egativity refers to the measure of electron attracting • Smaller atoms will have more electronegativities than
power, the electron affinity refers to individual atom bigger atoms. Elements of whose atoms have electronic
while electronegativity refers to bonded atom. configuration nearest to inert gas configuration will
• Pauling scale is the most widely used scale. have more electronegativity values.
• Pauling scale is based on bond energies. • Next to fluorine, the most electronegative element is
oxygen.
• Pauling assigned arbitrary values of electronegativities
• Metals which acquire inert gas configuration by losing
4.0 for most electronegative element fluorine and 2.1
electron have less electronegativity values.
for hydrogen. Pauling calculated the electronegativi-
ties of other elements by using the formula χA - χB = • The least electronegative element is caesium.
0.208 ∆ if bond energies are measured in Kcals or • Electronegativity values are useful in predicting the na-
χA - χB = 0.1017 ∆ if bond energies are measured ture of bond between two atoms of different elements.
in KJ where χA and χB are electronegativities of A and • If the electronegativity difference between two ele-
B and ∆ is the difference in the actual bond energy ments is more than 1.7 the bond formed between their
and calculated bond energy. atoms will be ionic.
1 • Electronegative values are useful in assigning +ve or
∆ = actual bond energy EA-B - (EA - A + EB - B)
2 -ve sign to the oxidation numbers of elements in a
• ∆ indicates the bond polarity. compound.

Chapter_03.indd 12 3/26/2014 2:46:17 PM

 Classification of Elements and Periodicity in Properties   3.13

• The oxidation number for more electronegative ele- (3) dipole moment of molecules
ment is given -ve sign and for less electronegative (4) polarity of bond
element is given +ve sign.
81. Electronegativity of beryllium is approximately equal
• While writing the formulae of inorganic compounds
to that of
the least electronegative element is written first and the
most electronegative element is written last. (1) Aluminium (2)  Boron
(3) Magnesium (4)  Sodium
• The greater the electronegativity of an element the
greater the tendency to gain electron and hence it acts 82. The electronegativity of elements arranged in the
as a strong oxidising agent and will be a nonmetal. periodic table
• The percent ionic character of a bond between (1) increases from right to left in a period
two atoms can be calculated from difference in (2) decreases from right to left in a period
electronegativities. (3) remains constant in going from left to right in a
% ionic character period
(4) increases in going down the group
= 16 [ χ A − χ B ] + 3.5 [ χ A − χ B ]
2

where χA and χB are the electronegativities of more 83. The electronegativity of the following elements
electronegative and less electronegative elements increases in the order
A and B. (1) C, N, Si, P
• Increase in the difference in electronegativities makes (2)  N, Si, C, P
the bond more stronger, e.g., in the nitrogen trihalides (3) Si, P, C, N
the order of the strength of N-X bond is (4)  P, Si, N, C
N-F > NCl > N-Br > N-I 84. According to Mulliken, the electronegativity of an
• Increase in the s-character of hybrid orbital of an atom element is the
participating in the bond, the electronegativity of that (1) Product of electron affinity and ionisation poten-
atom increases. Electronegativity of sp3C < sp2C < spC. tial values
(2) Difference of electron affinity and ionisation
potential values
(3) Sum of the electron affinity and ionisation poten-
 Objective Questions
tial values
78. Which among the following statements is false? (4) Average of the electron affinity and ionisation
potential values
(1) Pauling electronegativity scale is based on the
experimental value of bond energies. 85. Which set has strongest tendency to form anions?
(2) Electronegativity is a measure of the capacity of (1) Ga, In, Te (2)  Na, Mg, Al
an atom to attract shared pair of electrons. (3) N, O, F (4)  V, Cr, Mn
(3) The atom with high electronegativity generally
86. Highest covalent character is found in which of the
has high ionisation potential.
following?
(4) The electronegativity difference between the
atoms gives an idea about bond length. (1) CaF2 (2)  CaCl2
(3) CaI2 (4)  CaBr2
79. The wrong statement among the following is
(1) The element with outer electronic configuration Answers
ns2np5 is more electronegative.
(2) The units of electronegativity are eV. (78) 4 (79) 2 (80) 4 (81) 1 (82) 2
(3) The element with higher electronegativity value (83) 3 (84) 4 (85) 3 (86) 3
may act as an oxidising agent.
(4) The atom of an electronegative element becomes
an ion by gaining electrons.
valence or oxidation states
80. Pauling scale of electronegativity of elements helps
to determine • Valence of an element is the number of hydrogen at-
(1) covalent nature of an element oms or double the number of oxygen atoms that can
(2) position of an element in EMF series combine with one atom of that element.

Chapter_03.indd 13 3/26/2014 2:46:18 PM

 3.14  Objective Chemistry - Vol. I

• The valence of an element is not always constant. • In the first transition series, manganese exhibits maxi-
• If the same element exhibits more than one valence mum oxidation state of +7.
it is known as variable valence. • Of all the elements, Os and Ru exhibit maximum oxi-
• The maximum valence that can be exhibited by atom dation state of +8 in OsO4, RuO4.
of an element is equal to the number of electrons pre-
sent in the outermost orbit of an atom.
• The number of possible charges that can present on an electropositive character
atom of an element is known as oxidation number or • The tendency to loose electrons by an element is called
oxidation state. electropositive character.
• The oxidation states of elements may be positive or • Electropositive character is opposite to electro-
negative or zero or fractional. negativity.
• The oxidation numbers of s-block elements is equal to • Generally metals exhibit electropositive character.
their group number, i.e., 1st group elements exhibit +1
and II group elements exhibit +2 oxidation state.
• If the tendency to lose the electrons is more the elec-
tropositive character is also more.
• p-block elements exhibit variable valence to some extent.
• Electropositive character can be measured in terms of
• The different oxidation states of one element of ionisation potential.
p-block changes by two units.
• With increase in the electropositive character the
• III group elements exhibit two oxidation states +1 tendency to form ionic compounds, reactivity with
and +3. water and acids, the tendency to form basic oxides and
• IV group elements exhibit two types of oxidation hydroxides increases.
states: +2 and +4. • More electropositive metals dissolve in water giving
• V group elements exhibit -3, +3 and +5 oxidation states. hydroxide ions.
• VI group elements exhibit -2, +2, +4 and +6 oxidation • More electropositive metal ions do not hydrolyse in
states. water but are hydrated.
• The VIIth group elements exhibit -1, +1, +3, +5 and • Electropositive character can be explained in terms of
+7 oxidation states. electronic potentials.
• The most electronegative element fluorine always • In a group from top to bottom the electropositive char-
exhibit only -1 oxidation state. acter increases due to increase in atomic size.
• The elements in I to IV groups always exhibit oxida- • In a period from left to right electropositive character
tion number equal to group number. decreases due to the decrease in atomic size, the elec-
• The elements in IV to VII groups exhibit an oxida- trons are more attracted by the nucleus.
tion number either equal to group number or (8-group • In every period the more electropositive element will
number). be called an alkali metal.
• In a period valence increases from 1 to 7 with respect
to oxygen but with respect to hydrogen increases from
1 to 4 up to fourth group and then decreases to I up to metallic and non-metallic nature
VII group.
• If the electronegativity of an element is more it will be
• Though there is a pair of ns2 electrons in the valence
a non metal.
shell but are reluctant to participate in the bond, then
that pair of electrons is called an inert pair and the • The elements in VI and VII groups of periodic table
effect is called the inert pair effect. are mostly non metallic.
• d-block elements exhibit variable valence due to the • The elements with less electronegativity will be
participation of ns and (n - 1)d electrons. metallic.
• The different oxidation states of a transition element • The elements in I and II groups are mostly metallic.
changes by one unit. • In a group from top to bottom the electronegativity
• All the d-block elements exhibit common oxidation decreases, so metallic character increases and non-
state +2 due to the presence of ns2 electrons. metallic character decreases.

Chapter_03.indd 14 3/26/2014 2:46:18 PM

 Classification of Elements and Periodicity in Properties   3.15

• In a period from left to right the electronegativity (3) The element R that can form the highest oxide
increases, so metallic character decreases and non- R2O5 belongs to the V group.
metallic character increases. (4) On moving from left to right in the 3rd period the
valence with respect to hydrogen increases from
Diagonal Relationship 1 to 4 and then decreases.
• The second period elements show some similarities 91. Transition element exhibits variable oxidation states
with the third period elements which are diagonal to because they release electrons from the following
them. This is known as diagonal relationship. orbitals.
I II III IV V VI VII (1) ns and np orbitals
Li Be B C N O F (2) (n - 1)d and ns orbitals
Na Mg Al Si P S Cl (3) (n - 1)d orbital
• Diagonal relationship does not exist after IV group. (4) ns orbital
• The reason for the diagonal relationship is due to the 92. Maximum group valence of halogens with respect to
similar ionic sizes and electronegativities. oxygen is
• BeO and Al2O3 are amphoteric oxides. (1) one (2)  five (3)  six (4)  seven
• Carbides of beryllium and aluminium on hydrolysis 93. Among the following group of elements the one
give methane gas. whose elements can have positive as well as negative
Al4C3 + 12H2O → 4Al(OH)3 + 3CH4 oxidation states.
Be2C + 2H2O → 2BeO + CH4 (1) H, F, O (2)  Na, Mg, Al
• In modern concept diagonal relationship is due to (3) He, Li, Be (4)  H, Cl, Br
similar polarising power of the ions. 94. The elements in the same period in the periodic table
ionic charge show increase in
• Polarising power =
( ionic radius )
2 (1) Metallic nature with increase in atomic number
(2) Electronegativity with increase in metallic
character
(3) Electronegativity with increase in atomic number
 Objective Questions (4) Electropositivity with increase in atomic number

87. The element with electronic configuration 1s22s22p6 95. The valency shell of an element A contains 3 elec-
3s2 is trons while the valence shell of another element B
contains 6 electrons. If A combines with B, the prob-
(1) metalloid (2)  metal
able formula of the compound formed will be
(3) noble gas (4)  non-metal
(1) AB2 (2)  A2B (3)  A2B3 (4)  A3B2
88. In the periodic table the metallic character with
increase in atomic number 96. Li and Mg shows similar properties because of
similar
(1) decreases in a period and increases in a group
(2) increases in a period and decreases in a group (1) electric charge
(3) increases both in a period and in the group (2) ionic radii
(4) decreases both in a period and in the group (3) charge/atomic radius
(4) charge/(ionic radius)2
89. The diagonal relationship is not shown by
(1) Li and Mg (2)  Be and Al 97. The strongest acidic oxide among the following is
(3) B and Si (4)  N and S (1) CO2 (2)  N2O5 (3)  P2O5 (4)  SiO2

90. Which of the following statement is false? 98. Which of the following is true?
(1) An element having electronic configuration (1) Halogens are metals.
1s22s22p63s23p64s1 forms basic oxide. (2) ZnO is more basic than CO.
(2) Chloride of an element A gave a neutral solution (3) A nonmetal is more electropositive than a metal.
in water. In the periodic table the element A be- (4) A metal is more electronegative than a non-
longs to III group. metal.

Chapter_03.indd 15 3/26/2014 2:46:18 PM

 3.16  Objective Chemistry - Vol. I

99. The element that can exhibit highest oxidation state 6. Exactly half-filled and completely filled sub-shells
among the following is give stability to the atoms. Then, which of the follow-
(1) V (2)  Mn (3)  Ni (4)  Co ing is the correct order of stability?
(1) p3 < d5 < d10 < p6
100. The highest oxidation state that can be exhibited by
(2)  p3 < d10 < d5 < p6
transition metal is
(3) d5 > p3 > d10 > p6
(1) +7 (2)  +8 (3)  +6 (4) +5
(4)  d5 < d10 > p3 < p6
101. A common trend to both groups I and VII elements in 7. An element having the electronic configuration
the periodic table as the atomic number increases is 1s22s22p63s23p1 is
(1) oxidising power increases (1) An inert gas
(2) atomic radius increases (2) A transition element
(3) maximum valence increases (3) A representative element
(4) reactivity with water increases (4) An inner transition element
8. If the quantum numbers of the highest energy in an
Answers atom are n = 4, l = 3, m = +3, the element belongs to
(1) p-block (2)  d-block
(87) 2 (88) 1 (89) 4 (90)  4 (91)  2
(3) f-block (4)  s-block
(92) 2 (93) 4 (94) 3 (95)  3 (96)  4
(97) 2 (98) 2 (99) 2 (100)  2 (101)  2 9. The element with electronic configuration
1s22s22p63s2 in the periodic table is
(1) on the left side
(2) on the extreme right side
(3) at the centre
 Practice Exercise
(4) at the bottom
1. The electronic configuration of an atom A is 1s22s22p6
10. Which of the following represents pseudo inert gas
3s23p63d104s24p3. The chemistry of A is therefore
configuration?
likely to be similar that of
(1) (n - 2) f14 (n - 1) d10ns2
(1) boron (2)  oxygen
(2) (n - 1) s2p6d10ns2np6
(3) nitrogen (4)  chlorine
(3) (n - 1) s2p6d10
2. In which of the following, the elements belong to the (4) (n - 2) f14 (n - 1) s2p6d10ns2p6
same period?
11. Which two ions (or atoms) of the following are iso-
(1) Li, N, K (2)  Cu, Cr, Zn electronic with one another: Na+, K+, Ne and O?
(3) Cr, Sn, Pb (4)  H, He, F
(1) Na+ and K+
3. The 10th element in the periodic table resembles (2)  Na+ and O
with the (3) Na+and Ne
(1) First element (2)  Second element (4)  Ne and O
(3) Fourth element (4)  Ninth element 12. Which one of the following is an example of a positive
4. The electronic configuration of an element is ion and a negative ion that is isoelectronic with F- ?
1s22s22p63s23p3. What is the atomic number of the (1) S2- and Mg2+ or Na+
element which is just below this element in the peri- (2) O2- and Mg2+ or Li+
odic table?
(3) O2- and Ca2+ or K+
(1) 33 (2)  34 (3)  37 (4)  49
(4) O2- and Mg2+ or Na+
5. Which of the elements have the following set of 13. Which one of the following is an example of positive
atomic number belong to the same group? ion and a negative ion that is isoelectronic with argon?
(1) At. Nos. = 12, 20, 4, 88 (1) K+ and Cl- or Ca2+ and S2-
(2) At. Nos. = 9, 16, 35, 3 (2) Na+ and Cl- or Mg2+ and O2-
(3) At. Nos. = 11, 19, 27, 5 (3) K+ and F - or Mg2+ and O2-
(4) At. Nos. = 24, 47, 42, 55 (4) K+ and Br- or Ca2+ and O2-

Chapter_03.indd 16 3/26/2014 2:46:19 PM

 Classification of Elements and Periodicity in Properties   3.17

14. Ionic radii of M3+ lanthanide ions gradually decrease.       (I) Is22s22p63s23p5
This is called     (II) 1s22s22p3

(1) Lanthanide contraction  (III) 1s22s22p5
(2) III group contraction (IV) 1s22s22p63s1
(3) s-block contraction
(1) II, IV, III, I (2)  I, II, III, IV
(4) p-block contraction (3) I, III, II, IV (4)  IV, III, II, I
15. Which electronic configuration represents the largest 23. If the difference in electronegativities of two ele-
atom? ments is very large, then
(1) 1s22s2 (2)  1s22s22p1 (1) the bond is 50% ionic
2 1
(3) 1s 2s (4)  1s22s22p2 (2) the bond is 100% ionic
16. Ions of which have the same electronic configuration (3) the bond is more covalent than ionic
are those of (4) the bond is more ionic than covalent
(1) Lithium and sodium
24. The experimental bond energy of HY differs from its
(2) Sodium and potassium
calculated value by 2.0 kCal. mol-1. The electronega-
(3) Potassium and calcium
tivity of Y is equal to
(4) Oxygen and chlorine
(1) 1.5 (2)  1.8 (3)  1.6 (4)  1.9
17. Which has the highest second ionisation potential?
25. Which of the following statements is false?
(1) Nitrogen (2)  Carbon
(3) Oxygen (4)  Fluorine (1) F is the most electronegative and Cs is the most
electropositive element.
18. The atoms with high value of first ionisation potential (2) The electronegativity of halogen decreases from
will always have F to I.
(1) Large atomic size (3) The electron affinity of Cl is higher than that of
(2) Small atomic size F though their electronegativity values are in the
(3) Strongly bound valence electrons reverse order.
(4) None (4) The electron affinity of noble gases is zero.
19. An increase in principal quantum number as well as 26. Which of the following statement is incorrect for an
shielding effect of electrons in an atom will result in atom having electronic configuration 2, 8, 7?
an increase of (1) It forms diatomic molecule
(1) Electronegativity (2) It is a non-metal element
(2) Electron affinity (3) Its valency is 7
(3) Atomic size (4) It forms an amphoteric oxide
(4) Physical properties
27. An element “X” of the short period has the valency
20. The order of the second IP of elements A, B and C shell configuration of s2p1. Its oxide is acidic then the
with their atomic numbers 19, 20, 56 respectively is element is
(1) A > B > C (2)  A > C > B (1) B (2)  Al
(3) B > C > A (4)  C > A > B (3)  Ca (4)  Any of these
21. The first ionisation potential and first electron affinity 28. Which of the following pairs of atomic numbers can
of silicon are 785 KJ mole-1 and 135.0 KJ mole-1, have diagonal relationship?
respectively. Then, the electronegativity of silicon is
(1) 3,11 (2)  3, 12
785 + 135 785 + 135 (3)  6, 15 (4)  11, 15
(1)  (2) 
125 2
29. An element X which occurs in the first short period
785 + 135 785 + 135 has an outer electronic structure s2p1. What is the for-
(3)  (4) 
544 2 mula and acid-base character of its oxide?
22. The order of increasing electron affinity of the (1) XO3, basic (2)  XO3, acidic
­following electronic configurations is (3) X2O3, acidic (4)  X2O3 basic

Chapter_03.indd 17 3/26/2014 2:46:19 PM

 3.18  Objective Chemistry - Vol. I

30. X, Y and Z are elements in the same short period. The (3) The second IE of S is greater than that of Cl.
oxide of X is a giant molecule, the oxide of Z is ionic, (4) The second IE of B is greater than that of C.
and Y is a gas. The arrangement of the elements in 38. Which one is incorrect about ionisation energy?
order of increasing atomic number would be
(1) IE1 of N > IE1 of O
(1) X, Y, Z (2)  X, Z, Y (2)  IE2 of N > IE2 of O
(3) Z, X, Y (4)  Y, Z, X (3) IE2 of Li > IE2 of Ne
31. Oxide of an element is a gas and gives an acid when (4)  IE of Al = IE of Ga
dissolved in water. It belongs to the .... group in the 39. The true statement about electronegativity and elec-
periodic table. tron affinity is as
(1) I (2)  II (3)  III (4)  IV (1) both represents the same quantity
32. Which of the following statements is false? (2) Ae is a characteristic of simple atom while elec-
(1) Reducing power of elements decrease along a tronegativity is the characteristic of bonded atom
period. (3) Ae is always lesser than electronegativity
(2) Oxidising power of elements increase along a (4) both of them release or absorb energies during
period. the process
(3) Basic nature of oxides increase along a period. 40. The correct statement regarding BOH is (χ is
(4) Electronegativity of elements increase along a ­electronegativity)
period. (1) If χO - χB > χO - χH, BOH will be basic.
33. Reason not seen for diagonal relationship is (2) If χO - χB > χO - χH, BOH will be acidic.
(3) If χO - χB < χO - χH, BOH will be basic.
(1) same size
(4) None of the above
(2) same electronegativity
(3) same electron affinity 41. Choose the incorrect statement.
(4) same polarisability (1) Van der Waal’s radius of I is more than its cova-
lent radius.
34. The incorrect statement among the following is
(2) All isoelectronic ions belong to same period of
(1) The properties of elements are periodic function the periodic table.
of their atomic numbers. (3) IE of N is higher than that of O while IE2 of O is
(2) Among the isoelectronic species Na+, Mg2+ and higher than that of N.
Al3+, the ion having smallest radius is Al3+. (4) The electron affinity of N is zero while that of
(3) The outermost electronic configuration of group P is 74.3 KJ mole-1.
15 elements is ns2np5.
(4) Electronegativity of an element depends upon its 42. The correct IE (in KJ mole-1) of Si, P, Cl and S,
atomic size. respectively.
(1) 786, 1012, 999, 1256
35. The statement incorrect for f-block elements is
(2) 1012, 786, 999, 1256
(1) they belong to group 3rd (III B) of periodic table (3) 786, 1012, 1256, 999
(2) their outermost three shells are incomplete. (4) 786, 999, 1012, 1256
(3) they are collectively known as transuranic elements
(4) 4f elements are called rare earths or lanthanons 43. The incorrect statement out of the following is
(1) Isoelectronic ions may be obtained from ele-
36. Which of the following statements is incorrect? ments belonging to different periods of the
(1) Ae of 15th (VB) group elements is more than that periodic table.
of corresponding elements of 16th group. (2) Electron affinity of noble gases is zero.
(2) Electronegativity of halogens decreases from F to I. (3) Van der Wall’s radii of iodine is more than its
(3) Ae of Cl is higher than that of F though their covalent radius.
electronegativities are reverse in order. (4) X- ion is formed with more ease in chlorine than
(4) Ae of noble gases is positive. in fluorine.
37. Choose the incorrect statement. 44. Which of the following statements is correct?
(1) The third IE of P is greater than that of Al. (1) Ionic radius of a metal is generally less than its
(2) The first IE of Al is same as that of Ga. atomic radius.

Chapter_03.indd 18 3/26/2014 2:46:20 PM

 Classification of Elements and Periodicity in Properties   3.19

(2) Ionic radius of nonmetal is generally less than (3) On moving across a period polarising power
their atomic radii. generally decreases.
(3) Ionic radius of a metal is almost same as its (4) On moving down a group polarising power
­atomic radius. generally remains constant.
(4) Ionic radius of a metal is greater than its atomic
51. Actinides are those having atoms with
radius.
(1) complete outermost shell
45. Which of the following statements is correct? (2) incomplete three outermost shells
(1) Ionisation energies are always endothermic. (3) incomplete two outermost shells
(2) Ionisation energy is inversely related to reducing (4) incomplete outermost shell
nature.
(3) Electron affinity is directly related to oxidising 52. Which of the following statements is correct for
power. s-block elements?
(4) All are correct (1) They are strong reducing agents.
(2) Their hydroxides are strong bases.
46. Electron affinity depends to some extent upon the (3) s-block elements are most reactive of all the
type of orbital that the added electron enters. It fol- metals.
lows the order (4) All are correct
(1) s > p > d > f (2)  s < p < d < b
(3) s > d > p > f (4)  s < p < f < d 53. Which of the following statements is incorrect for
d-block elements?
47. The second IP of an element M is the energy required to
(1) They are more electropositive than s-block
(1) remove 2 moles of electrons from one mole of elements.
gaseous atoms (2) They are all metals and good conductors of heat
(2) remove one mole of electron from one mole of and electricity.
gaseous anion (3) They show variable valence and oxidation state.
(3) remove one mole of electron from one mole of (4) The ionisation energies are larger than those
gaseous cation of the element of s-block elements but smaller than p-block
(4) remove one mole of electrons from one mole of elements.
unipositive gaseous ion of the element
54. Identify the correct order for the covalent radius of
48. Periodicity in the properties of elements is due to the following elements.
(1) a regular increase in atomic weights of elements (I) Ti (II) Ca (III) Sc
(2) successive increase in the atomic number of
elements (1) I, II, III (2)  III, II, I
(3) periodicity in the electron configuration of atoms (3) II, I, III (4)  I, III, II
of elements
55. The first ionisation potentials of four consecutive ele-
(4) existence of families of elements
ments, present in the second period of the periodic
49. The first ionisation energy of Ar is less than that of table are 8.3. 11.3, 14.5 and 13.6 eV, respectively.
Ne. An explanation of this fact is that Which one of the following is the first ionisation
(1) The effective nuclear charge experienced by a potential (in eV) of nitrogen?
valence electron in Ar is much more than in Ne. (1) 13.6 (2)  11.2 (3)  8.3 (4)  14.5
(2) The atomic radius of Ar is larger than that of Ne. -1
(3) The atomic radius of Ar is smaller than that 56. The electron affinity values (in KJ mol ) of three
of Ne. halogens X, Y and Z are respectively, -349, -333 and
(4) The number of protons in the Ar nucleus is larger -325. Then X, Y and Z respectively are
than the number of protons in the Ne nucleus. (1) F, Cl and Br (2)  Cl, F and Br
(3) Cl, Br and F (4)  Br, Cl and F
50. Which of the following statements are correct?
(1) On moving across a period polarising power 57. The correct order of the size of C, N, P and S follows
generally increases. the order
(2) On moving down a group polarising power (1) N < C < P < S (2)  C < N < S < P
generally increases. (3) C < N < P < S (4)  N < C < S < P

Chapter_03.indd 19 3/26/2014 2:46:20 PM

 3.20  Objective Chemistry - Vol. I

58. Which atomic number out of the following cannot 66. The order of screening effect of electrons of s, p, d
be accommodated by the present set up of long form and f orbitals of a given shell of an atom on its outer
periodic table? electrons
(1) 107 (2)  118 (3)  126 (4)  120 (1) f   > d > p > s (2)  s > p > d > f
(3) p < d < s < f (4)  f   > p > s > d
59. The correct order to electron affinity of B, C, N and O is
(1) O > C > N > B (2)  B > N > C > O 67. Which of the following statements is correct?
(3) O > C > B > N (4)  O > B > C > N (1) The magnitude of the second electron affinity of
60. Which of the following ions are isoelectronic with sulphur is greater than that of oxygen.
krypton? (2) The magnitude of the second electron affinity of
sulphur is less than that of oxygen.
(1) Cd2+, Sr2+, Zn2+ (2)  Br-, Se2+, Sr2+
(3) The electron affinities of bromine and iodine are
3+ 2-
(3) Sc , Se , Zn 2+
(4)  Ag+, Br-, Cd2+
approximately the same.
61. Choose the correct answer. (4) The first electron affinity of fluorine is greater
(1) Ionisation enthalpy and electron gain enthalpy than that of chlorine.
increases along a period. 68. The two elements discovered in August 2003 with
(2) Ionisation enthalpy increases but electron gain atomic numbers 113 and 115 are to be placed in
enthalpy decreases along a period.
(1) s-block (2)  p-block
(3) Ionisation enthalpy decreases but electron gain
(3) d-block (4)  f-block
enthalpy increases.
(4) Both decrease along a period. 69. The element with atomic number 115 has valence
62. Elements X, Y and Z have atomic numbers 19, 37 and shell electronic configuration
55, respectively. Which of the following statements is (1) ns2np3 (2)  ns2np1
2 5
true about them? (3) ns np (4)  ns2np2
(1) Their ionisation potential would increase with 70. In the process A(g) → A+(g) + e-
increasing atomic number. (1) Energy is gained by the system and the atom
(2) Y would have an ionisation potential between becomes larger.
those of X and Z. (2) Energy is evolved by the system and the atom
(3) Z would have the highest ionisation potential. becomes larger.
(4) Y would have the highest ionisation potential. (3) Energy is gained by the system and the atom
63. Aqueous solutions of two compounds M - O - H becomes smaller.
and M′ - O - H have been prepared in two different (4) Energy is evolved by the system and the atom
beakers. If the electronegativity of M = 3.5, M′ = 1.72, becomes smaller.
O = 3.5 and H = 2.1, then the solutions respectively are 71. Which of the following statement is correct?
(1) acidic, acidic (2)  acidic, basic (1) Oxygen has more negative electron gain enthalpy
(3) basic, basic (4)  basic, acidic than sulphur.
64. Which of the following does not represent the correct (2) Second electron gain enthalpy of oxygen is
order of the property indicated? positive.
(1) Sc3+ > Cr3+ > Fe3+ > Mn3+ - ionic radius (3) Nitrogen has positive electron gain enthalpy.
(2) Sc < Ti < Cr < Mn - density (4) Larger is the tendency of an atom to gain an elec-
(3) Mn2+ > Ni2+ > Co2+ > Fe2+ - ionic radii tron less negative is its electron gain enthalpy.
(4) FeO < CaO < MnO > CuO - basic nature 72. The ions O2-, F-, Na+, Mg2+ and Al3+ are isoelectronic.
-1 Their radii show
65. The ionisation enthalpies of Li and Na are 520 KJ mol
and 495 KJ mol -1, respectively. The energy required (1) an increase from O2- to F-,
to convert all the atoms present in 7 mg of Li vapours Na+, Mg2+ and Al3+
and 23 mg of Na vapours to their respective gaseous (2) a decrease from O2- to F- and then increase from
cations respectively is Na+ to Al3+.
(1) 525, 49.5 J (2)  520 J, 495 J (3) A significant increase from O2- to Al3+.
(3) 49.5J, 525 (4)  495 J, 520 J (4) A significant decrease from O2- to Al3+.

Chapter_03.indd 20 3/26/2014 2:46:21 PM

 Classification of Elements and Periodicity in Properties   3.21

73. Ionic radii are   I. The three elements are metals.
(1) inversely proportional to square of effective II. The electronegativity decreases from X to Y to Z.
nuclear charge III. The atomic radius decreases in the order X, Y and Z.
(2) directly proportional to effective nuclear charge    IV. X, Y and Z could be phosphorous, aluminium and
(3) directly proportional to square of effective sodium, respectively.
nuclear charge (1) I, II and III only correct
(4) inversely proportional to effective nuclear charge (2) I and III only correct
(3) II and IV only correct
74. Five ionisation energy values in KJ mol-1 are E1 = (4) II, III and IV only correct
870, E2 = 830, E3 = 1010, E4 = 1290 and E5 = 376.
These are 79. The first ionisation energy of Ar is less than that of
Ne. An explanation of this fact is that
(1) Successive ionisation energies for the element
with atomic number 5     I. The effective nuclear charge experienced by a va-
(2) The first IE of successive elements in group 15, lence electron in Ar is much larger than that in Ne.
16, 17, 18 and I, respectively.    II. The effective nuclear charge experienced by a va-
(3) The first IE for elements with atomic number 1-5 lence electron in Ar is much smaller than that in Ne.
(4) Successive IE for transition elements with four III. The atomic radius of Ar is larger that of Ne.
electrons in d-subshell.     IV. The atomic radius of Ar is smaller that of Ne.
(1) I and III (2)  I and II
75. Consider the following changes: (3) II and III (4)  III and IV
     I. M(s)→ M(g)
80. The radius of cation is r+, anion is r-, Za is nuclear
  II. M(s)→ + M (2g+) + 2e- charge of anion, Zc is nuclear charge of cationand “S” is
screening constant. Which of the following is correct for
III. M(g)→ M (+g ) + e-
isoelectronic series ?
   IV. M+(g)→ M (2g+) + e- r Z −S r Z −S
(1)  c = a (2)  a = a
ra Zc − S rc Z c − S
      V. M(g)→ M (2g+) + 2e-
rc Za ra Z c
The second ionisation energy of M could be calcu- (3)  = (4)  =
ra Zc rc Z a
lated from the energy values associated with
81. Which of the following process refers to ionisation
(1) I + V (2)  II + IV potential?
(3) V - III (4)  II - I + III
(1) Y(s )  → Y(+g ) + e −
76. Consider the ions (a) Li+ and Na+ and (b) Be2+ and → Y(+g ) + e −
(2) Y( g ) + aq 
Mg2+. Which two are closest to one another in size?
→ Y(+g ) + e −
(3) Y( g ) 
(1) Li+ and Na+ (2)  Be2+ and Mg2+
+
2+
(3) Be and Li (4)  Li+ and Mg2+ (4) Y( g ) + e − 
→ Y(−g )
77. Number of electrons that F(Z = 9) has in p-orbitals, 82. A metal from period 4 is added to water and a vigor-
is equal to ous reaction takes place with the evolution of a gas.
(1) Number of electrons in s-orbitals in Na (11e) Which statements are correct?
(2) Number of electrons in d-orbitals in Fe3+(23e)    I. Oxygen is evolved
(3) Number of electrons in d-orbitals in Mn (25e)    II. Hydrogen is evolved
(4) a, b and c are true III. The resulting solution is acidic
  IV. The resulting solution is basic
78. A, B and C are hydroxy compounds of the elements
(1) I and III only (2)  II and III only
X, Y and Z, respectively. X, Y and Z are in the same
(3) II and IV only (4)  I and IV only
period of the periodic table. A gives an aqueous solu-
tion of pH less than seven. B reacts with both strong 83. If an electron is transferred from A to B forming
acids and strong alkalis. C gives an aqueous solution A+ and B- , then the reaction is possible when
which is strongly alkaline. (1) (EB + IB) > (IA - EA) (2)  (IA + EB) > (IB - EA)
Which of the following statement is/are true? (3) (IB + EB) > (IA + EA) (4)  (IA + EA) > (IB + EB)

Chapter_03.indd 21 3/26/2014 2:46:23 PM

 3.22  Objective Chemistry - Vol. I

Answers 5. Statement I: Properties of atom and its correspond-

ing ions remain same.
(1) 3 (2) 2 (3) 2 (4) 1 (5) 1 Statement II: Electron configuration of atom and ion
(6) 4 (7) 3 (8) 3 (9) 1 (10) 3 are different.
(11) 3 (12) 4 (13) 1 (14) 1 (15) 3 6. Statement I: Isoelectronic species have same radii.
(16) 3 (17) 4 (18) 3 (19) 3 (20) 1
Statement II: They contain same number of elec-
(21) 3 (22) 1 (23) 4 (24) 2 (25) 4
trons.
(26) 4 (27) 1 (28) 2 (29) 3 (30) 3
(31) 4 (32) 3 (33) 3 (34) 3 (35) 3 7. Statement I: Smaller is the size of an atom greater is
(36) 1 (37) 3 (38) 2 (39) 2 (40) 1 the electronegativity.
(41) 2 (42) 3 (43) 4 (44) 1 (45) 4 Statement II: Electronegativity refers to the tenden-
(46) 1 (47) 4 (48) 3 (49) 2 (50) 1 cy of atom to share electrons.
(51) 2 (52) 4 (53) 1 (54) 4 (55) 4 8. Statement I: NO+ ion is isoelectronic with CN- ion.
(56) 2 (57) 4 (58) 3 (59) 3 (60) 2
(61) 1 (62) 2 (63) 2 (64) 1 (65) 2 Statement II: Isoelectronic ions have the same num-
(66) 2 (67) 2 (68) 2 (69) 1 (70) 3 ber of electrons.
(71) 2 (72) 4 (73) 4 (74) 2 (75) 3 9. Statement I: More is the electron affinity, greater is
(76) 4 (77) 4 (78) 3 (79) 3 (80) 1 the oxidising character.
(81) 3 (82) 3 (83) 3 Statement II: Oxidising character depends on elec-
tron affinity.
10. Statement I: The reaction O + 2e- → O2- is endo-
thermic and yet a large number of compounds con-
 Statement-Type Questions taining the oxide ion do exist.
In the following questions, a statement I is given and a Statement II: The reaction is exergonic.
corresponding statement II follows it. Mark the correct 11. Statement I: The first ionisation energy of “Be” is
answer as greater than that of B.
1. If both statement I and statement II are true and Statement II: 2p orbital is lower in energy than 2s.
statement II is the correct explanation of statement I.
12. Statement I: The electron affinity of “O” is less than
2. If both statement I and statement II are true but state- that of “S”.
ment II is not the correct explanation for statement I.
Statement II: Oxygen atom is smaller in size than
3. If statement I is true but statement II is false. the sulphur atom.
4. If statement I is false but statement II is true. 13. Statement I: All the lanthanide elements exhibit a
1. Statement I: Elements in the same vertical column common oxidation state of +3 in their compounds.
have similar properties. Statement II: The atoms of lanthanide elements con-
Statement II: Elements have periodic dependence tain three electrons in their outer shell.
upon the atomic number. 14. Statement I: Electron affinity of oxygen is less than
2. Statement I: Helium is placed in group 18 along nitrogen but larger than fluorine.
with p-block element. Statement II: N, O, F belong to the same period of
Statement II: It shows properties similar to p-block the periodic table.
elements. 15. Statement I: In the periodic table, the elements are
3. Statement I: Ionisation energy is always positive. arranged in order of increasing atomic number, which
Statement II: Energy is always released when elec- is in order of increased nuclear charge.
trons are removed. Statement II: So that each element contains one
4. Statement I: Transition elements exhibit variable more orbital electron than the preceding element.
valency. 16. Statement I: Hydrogen and helium differ from the
Statement II: Transition elements possess unpaired rest of elements.
electrons. Statement II: They have no p-orbital in the first shell.

Chapter_03.indd 22 3/26/2014 2:46:23 PM

 Classification of Elements and Periodicity in Properties   3.23

17. Statement I: On descending the group, the size of (11) 3 (12) 2 (13) 3 (14) 3 (15) 4
atom increases from Li to Cs. (16) 1 (17) 2 (18) 1 (19) 1 (20) 1
Statement II: Due to extra shells of electrons being (21) 1 (22) 1 (23) 1 (24) 1
added which outweighs the effect of increased nu-
clear charge.
18. Statement I: The first IP of Mg is greater than that of
sodium.  Match the Following Type Questions
Statement II: Partly due to the increased nuclear
charge and partly due to the smaller size of Mg. 1. Match the following

19. Statement I: The electron affinity of oxygen accord- List-I List-II

ing to O → O2- is negative, i.e., endothermic. (A) 1s 2s 2p 3s
2 2 6 2
  (i) In
Statement II: Usually only one electron is added (B) 1s22s22p63s23p63d104s1  (ii) Pd
forming a uninegative ion. This repels further (C) 1s22s22p63s23p63d10 (iii) Mg
electrons and energy is required to add on a second 4s24p64d85s2
electron. (D) 1s22s22p63s23p63d10   (iv) Cu
20. Statement I: Metallic character increases as we go 4s24p64d105s25p1
down the group in the periodic table.
The correct matching is
Statement II: It is easier to remove an electron from
a large atom than from a small one. S.No. A B C D
21. Statement I: In the main groups of the periodic table 1. IV III I II
(except some transition elements such as Cr, Mn, Fe, 2. III IV II I
Co and Ni) basic properties increase on descending 3. II I III IV
the group. 4. IV I II III
Statement II: The elements become more electropo-
sitive and more ionic. 2. Match the following atomic number given in List I
22. Statement I: On moving across a period polarising with the type of element given in List II
power generally increases while on moving down a List-I List-II
group polarising power decreases.
(A) 31   (i) Metal
Statement II: On moving across a period the charge (B) 16   (ii) Non-metal
on the ions increases and the size decreases, while (C) 36 (iii) Metalloid
moving down a group the size increases. (D) 55   (iv) Inert gas
23. Statement I: Ionisaion of s-electrons requires more
energy than that for the ionisation of p-electrons from The correct matching is
the same shell.
Statement II: s-electrons are closer to the nucleus S.No. A B C D
than the p-electrons of the same shell and hence are 1. i ii iii iv
more strongly attracted by the nucleus. 2. iii ii iv i
24. Statement I: The greater the tendency to accept elec- 3. ii iii i iv
trons the more non-metallic is the element. 4. ii i iii iv
Statement II: A non-metallic element has a tendency
to gain one or more electrons during chemical reac- 3. Match the following property given in List I with the
tions thereby becoming an anion. element given in List II
List-I List-II
(A) Element with highest electronegativity    (i) I2
Answers
(B) Element with highest electron affinity   (ii) Br2
(1) 2 (2) 3 (3) 3 (4) 2 (5) 4 (C) Liqiuid non-metal (iii) Cl2
(6) 4 (7) 3 (8) 1 (9) 1 (10) 3 (D) solid non-metal    (iv) F2

Chapter_03.indd 23 3/26/2014 2:46:23 PM

 3.24  Objective Chemistry - Vol. I

The correct matching is 5. Match the order given in List I with the property
given in List II
S.No. A B C D
1. i ii iii iv
List-I List-II
2. ii iii iv i (A) Li < Na < K < Rb   (i) Increasing order of ionising
3. iii ii i iv energy
4. iv iii ii i (B) Li < Be > B < C (ii) Decreasing order of metallic
nature
(C) F2 > Cl2 > Br2 > I2 (iii) Increasing order of size
4. Match the element given in List I with the type of
(D) F2 > O2 > Cl2 > S (iv) Increasing order of electron
element given in List II
affinity
List-I List-II
The correct matching is
(A) He   (i) Representative element
(B) Mg   (ii) Noble gas S.No. A B C D
(C) Cu (iii) Inner transition element 1. i ii iii iv
(D) U   (iv) d-block element 2. iii i ii iv
3. iii i iv ii
The correct matching is 4. i iv ii iii

S.No. A B C D
1. ii i iii iv
2. i ii iv iii
Answers
3. ii i iv iii
(1) 2 (2) 4 (3) 4 (4) 3 (5) 2
4. i ii iii iv

Chapter_03.indd 24 3/26/2014 2:46:24 PM

 4

Chapter
Chemical Bonding and
Molecular Structure

• The force of attraction between atoms in a molecule is • Calculate the total number of available electrons by
called chemical bond. summing up the valence electrons present in all atoms
• Energy changes or the rearrangement of electrons are in a molecule.
primarily responsible for the bond formation. • Half the difference in the total number of electrons
• The internal energy of a molecule is less than the sum of required and the total number of available electrons
the internal energy of individual atoms in that molecule gives the number of bond pairs.
and that difference is released outside as bond energy. • Half the difference in the total number of electrons
• In the formation of a chemical bond, there is always available and the total number bonding electrons gives
a decrease in potential energy and is the lowest at the the number of lone pairs.
interatomic distance, i.e., the principle of minimum • While calculating the total number of available
energy. e­ lectrons in an ion, the number of negative charges
must be added to the available electrons and for cation
Kossel–Lewis Theory: Octet Theory the number of positive charges must be subtracted
from the total number of available electrons.
• Kossel proposed the electrovalent bond while Lewis • Write the skeletal structure of the molecule by taking
proposed the covalent bond. least electronegative atom as the central atom.
• Atoms combine to form molecules to decrease their • Hydrogen and oxygen atoms are usually found on the
internal energy and to acquire octet in their valence outside of the molecule.
shell like inert gases. This is known as octet rule.
• If there are single atoms of two elements, the one with
• Atoms acquire stable inert gas configuration in their more atomic number is the central atom of the molecule,
valence shell by losing or by gaining or by sharing e.g., POCl3, SOCl2.
electrons when they combine with one another.
• The carbon family usually has four bonds, the nitrogen
family three bonds, the oxygen family two bonds and
Lewis Dot formulae the halogen usually have one bond in neutral molecules.
• Lewis diagrams provide a picture of bonding in mol- • When oxygen and hydrogen atoms are in the same
ecule and ions in terms of the shared pairs of electrons molecule, they usually form the combination H-O-X
and the octet rule. where X is whatever other atom in the molecule.
• Lewis dot formulae can be written by applying certain • Three-membered rings are unlikely. For most mole-
guidelines as follows. cules larger rings are possible, but still not as common
• as other structures.
First calculate the total number of electrons required for
the stability of all atoms so that each atom has an octet • Single bonds are constructed first with bond pairs.
of electrons except for hydrogen. For each ­hydrogen The remaining bond pairs, if any, should be used for
atom 2 electrons are required for stability. ­multiple bonding.

Chapter_04.indd 1 3/26/2014 2:50:01 PM

 4.2  Objective Chemistry - Vol. I

• The lone pairs obtained by calculation should be used

for the non-bonded pairs so that each atom (except  Objective Questions
­hydrogen) gets an octet of electrons.
1. Which of the following molecules is adequately rep-
• The molecules in which the central atom is having an resented by a single Lewis structure?
octet and if all the electron pairs are bond pairs are
(1) O3 (2)  NOCl
called electron-precise molecules.
(3) SO2 (4)  N2O
• The molecules in which the central atom is having an
octet but some are bond pairs and some are lone pairs 2. In PO3−
4 the formal charge on each oxygen atom and
are called electron-rich molecules. the P-O bond order are respectively
• Molecules whose central atom is having more than an (1) –0.75, 0.5 (2)  –0.75, 1.25
octet of electrons are called hypervalent molecules or (3) –0.75, 1.0 (4)  –3, 1.25
valence shell expansion or expanded octet by utilising
3. The formal charges on the three atoms in O3 molecule
the availability of valence shell d-orbitals for bonding.
are
• The molecules in which if all the atoms (generally cen- (1) 0, 0, 0 (2)  0, 0, –1
tral atom) except hydrogen have not achieved octet are (3) 0, 0, +1 (4)  0, +1, –1
called electron-deficient molecules, e.g., BF3, BeCl2.
• Octet theory could not explain the shape of molecules. 4. The most likely arrangement of atoms in S2Cl2 is
• Octet theory could not explain the relative stability (1) S-S-Cl-Cl (2)  S-Cl-S-Cl
(3) S-Cl-Cl-S (4)  Cl-S-S-Cl
of molecules being totally silent about the energy of
molecules. 5. The way of writing Lewis structure of the cyanate ion
• Octet theory could not explain the formation of elec- OCN– places one double bond between the carbon
tron deficient and hypervalent molecules. atom and the oxygen atom and another double bond
between the carbon atom and nitrogen atom. What
are the formal charges on the oxygen, carbon and ni-
trogen atoms, respectively for those structures?
formal charge (1) 0, 0, –1 (2)  –1, 0, 0
(3) –1 +1, –1 (4)  –2, 1, 0
• Formal charge is the apparent electronic charge of
each atom in a molecule based on Lewis diagrams. 6. Which of the following is the correct and stable elec-
• Formal charge tron dot structure of N2O molecule?
(1) N = N = O: (2)  N ≡ N – O:
 No of valence  (3) N = N = O: (4)  N = N = O:
electrons in a   No. of unshared   No.of 
  − electrons on the  −  bonds to  7. During the bond formation normally all the elements
freeatom of the     
  atom   theatom  in their outermost shell acquire
element
  (1) 2 electrons (2)  4 electrons
(3) 8 electrons (4)  10 electrons
• Charge on the molecule or ion = Sum of all the charges
1 8. Chemical bond formation takes place when
F = [NA – Nlp – Nbp]
2 (1) Energy is absorbed
• Molecules having small formal charges are more stable. (2) Forces of attraction overcome forces of repulsion
• Charges on adjust atoms are usually of opposite sign. (3) Forces of repulsion overcome forces of attraction
(4) Forces of attraction are equal to forces of repulsion
• More electronegative atoms should have negative
charges rather than positive charges. 9. All chemical bonds are the result of
• Structures having formal charges of opposite sign (1) interaction of nuclei
should not be at longer distances. (2) interaction of electrons
• Structures in which there is largest difference in elec- (3) difference in electronegativity
tronegativity between the nearest atoms is more stable. (4) interaction of electrons and nuclei

Chapter_04.indd 2 3/26/2014 2:50:04 PM

 Chemical Bonding and Molecular Structure   4.3

Answers • Cation with an inert gas configuration favours the ion-

ic bond formation while the cation with pseudoinert
(1) 2 (2) 2 (3) 4 (4) 4   (5) 1 gas configuration favours the covalent bond formation.
(6) 2 (7) 3 (8) 3 (9) 4 E.g., CaCl2 is ionic while ZnCl2 is covalent.
• When the ionic bond is formed, the oppositely charged
ion approach an equilibrium distance where the attrac-
Ionic bond
tive forces overcome the repulsive forces.
• The electrostatic attractive force between two oppo-
sitely charged ions formed by transfer of electrons Lattice Energy
from one another is called an ionic bond.
• Ionic bond is formed between an atom of low ­ionisation
• Lattice energy is the amount of energy released when
one mole of solid is formed due to the attraction between
potential and an atom of more electron affinity with an
oppositely charged ions which are at infinite distance.
electronegativity difference of about or greater than 1.7.
• or
An ionic bond having maximum ionic character is
formed between caesium and fluorine. • The amount of energy absorbed when one mole of solid
• Favourable conditions for the formation of cation crystal is broken into ions and the ions are separated to
from an atom are infinite distance.
(i) Its ionisation potential must be low. • If lattice energy is more, the stability of the crystal is
(ii) the ion should have low charge. more and thus the strength of the ionic bond is more.
(iii) the size of the atom should be large.
(iv) the cation should have an octet (e.g., Ca2+) ­rather • Lattice energies are calculated using Born–Haber
than pseudoinert gas configuration (Zn2+). ­cycle and Hess’s law of constant heat of summation.
• Favourable conditions for the formation of anion • Lattice energy may be calculated by using Born–
are Lande equation or Born Mayer equation.
(i) high electronegativity and high electron affinity Born–Lande equation
(ii) small size of the atom
(iii) charge on the anion should be less Z + Z − e2 AN  1
µ= 1 − n 
• Large cation and small anion with less number of 4π ∈ R e
charges favour ionic bond formation with more ionic
character. where Z + and Z – are the number of charges on ion, e
• The bond formed between the atoms of more is the charge on ion, A is called Madelung constant, Re
­electronegative atoms will be due to electron sharing is the distance between the nearest oppositely charged
and it is a covalent bond. ions and N is Avogadro’s number.
• Elements in their lower oxidation state form ionic Born–Mayer equation.
compounds while in the higher oxidation state form
covalent compounds. For example, SnCl2 is ionic but Z + Z − e2 AN  ρ 
U= 1 − 
SnCl4 is covalent. r+ + r−  r+ + r− 

Covalent Character of Ionic Bond Fajan’s • ρ is the constant for ions with inert gas configuration
Rules and is about 0.35 × 10–10 m. r+ and r – are the radii of
cation and anion, respectively.
• Increase in cationic size increases the ionic nature of
the bond. E.g., Li+ < Na+ < K+ < Rb+ < Cs+.
Born–Haber Cycle
• Increase in anionic size favours the formation of
­covalent bond, e.g., CaF2 is ionic while CaI2 is more • Born–Haber cycle is useful for calculating lattice
covalent. ­energy of ionic compounds.
• Highly charged cation or anion or both favour the
• Born–Haber cycle is based on Hess’s law of constant
­covalent bond formation, e.g., NaCl is ionic while
heat of summation.
AlCl3 is covalent.

Chapter_04.indd 3 3/26/2014 2:50:05 PM

 4.4  Objective Chemistry - Vol. I

Coordination Number • Ionic compounds undergo electrolysis in fused state and

in aqueous solution, hence they are called electrolytes.
• Number of oppositely charged ions surrounding a • Ionic bonds are nondirectional, hence they do not
­particular ion in an ionic crystal is called ­coordination
e­ xhibit stereoisomerism.
number.
• Ionic compounds show the reactions of the constituent
• Coordination number of Na+ and Cl– ions in sodium ions and the reactions are very fast.
chloride crystal is 6.
• Coordination number of Cs+ and Cl– ions in caesium Consequences of Lattice Energies
chloride crystal is 8.
• Limiting radius ratio = radius of small ion • The more the number of charges on the ions in an ionic
radius of large ion compound the more is the lattice energy. Thus, they
have more melting points and more stability. E.g., NaF
i.e., radius of cation
radius of anion has low melting point (997° C) while MgO has high
melting point (2800° C) though NaF is more ionic than
Unit Cell MgO.
• Increasing charge on ions resulting in increasing covalent
• Unit cell is the smallest portion of the lattice which character particularly when small cation combines with
has the same structure as lattice and is extended in all large anion due to which their melting point and boiling
directions. point decreases. E.g., silver halides having covalent char-
• Total number of ionic pairs (Na+Cl–) belonging to one acter have low melting point and boiling point than alkali
unit cell of sodium chloride is 4. metal halides.
• Total number of ionic pairs (Cs+Cl–) belonging to one • Ionic compounds having large differences in their
unit cell of caesium chloride is 1. ­ionic radii are more soluble, but the compounds hav-
• An ion at a corner of cube will be shared by eight unit ing ions of equal size are least soluble.
cells and the contribution of that ion to one unit cell • The solubilities of group-II sulphates, carbonates, etc.
is 1/8. (where the size of anion is large) decreases down the
• An ion at the edge centre of cubic cell will be shared by group as the difference between the sizes of ions goes
four unit cells and its contribution to one unit cell is 1/4. on decreasing while the solubilities of hydroxides and
• An ion at the face of a cubic cell is shared by two unit oxides increases from magnesium to barium as the
cells and its contribution to one unit cell is 1/2. ­difference in the sizes of ions increases.
• An ion at the body centre of cubic cell will be shared by • Ionic compounds dissolve in water when the sum of
only one unit cell and its contribution to one unit cell is 1. h­ ydration energies of cation and anion of the ionic com-
• Sodium chloride crystal has face centred cubic lattice pound exceeds the lattice energy of that compound.
structure while caesium chloride crystal has body cen- • Both hydration and lattice energies decreases with in-
tred cubing lattice. crease in sizes of the cation and anion but the decrease
in hydration energy is rapid than the decrease in lat-
Characteristics of Ionic Compounds tice energy with increase in size of cation combined
with large anion. Hence solubility of ionic compounds
• Melting points and boiling points of ionic compounds containing large anion decreases compared with the
are very high because to break the strong electrostatic compounds having small anion.
attractive forces, high amount of energy is required.
• If enthalpy of hydration is greater than the lattice
• Ionic compounds are soluble in polar solvents like energy of an ionic compound, the dissolution is
­water but insoluble in non-polar solvents like benzene. exothermic.
• When the ionic compounds are dissolved in polar
• If enthalpy of solution for ionic compound is more, i.e.,
­solvents the ions get solvated which decreases the
the hydration energy is lesser than the lattice energy,
­interionic forces and thus dissolves.
cooling effect take place during dissolution. This is
• Ionic compounds are nonconductors of electricity in because some work is done to pull apart the ions and
solid state but conducts electricity in fused state or increase in entropy in adiabatic process at the expense
in aqueous solution state due to the free ions. of internal energy.

Chapter_04.indd 4 3/26/2014 2:50:06 PM

 Chemical Bonding and Molecular Structure   4.5

• If the enthalpy of solution is sufficiently positive, 11. The false statement among the following is
f­ avourable entropy may not be able to overcome it and (1) Ionic reactions take place in solution state.
the compound will be insoluble. (2) When elements form compounds they become
• Thermal stability of ionic compounds increases with stable by decreasing the energy content.
increase in lattice energy. (3) An electrovalent compound is made of electri-
cally charged particles.
• Thermal stability of ionic compounds containing (4) Electrovalent compounds exhibit stereoisomerism.
­oxoanions like carbonate, sulphate, nitrate, superoxide,
etc., increases with increase in the size of cation though 12. Many ionic crystals dissolve in water because
lattice energy decreases. (1) water is an amphiprotic solvent
• When the bigger oxoanion decomposes, it gives a (2) water is a high boiling liquid
small anion (O2 –). (3) the process is accompanied by a positive heat of
• This when combined with small cation gives more solution
(4) Water decreases the interionic attraction in the
lattice energy that compensates the decomposition
crystal lattice due to solvation
energy of the compound containing small cation and
large anion, but cannot compensate the decomposition 13. The atomic numbers of three elements A, B, and C are
energy of the compound containing large cation and a, a + 1 and a + 2. C is an alkali metal. In compounds
large anion as the lattice energy of large cation and A and C the nature of bonding is
small anion (O2–) is also small. E.g.,
(1) Coordinate (2)  Covalent
MgCO3(s) ∆→ MgO(s) + CO2(g) (3) Ionic (4)  Metallic
∆
BaCO3(s)  → BaO(s) + CO2(g)
14. The electronic configurations of four elements L, P, Q
• The small Mg2+ ion when combined with small O2– and R are given below.
l­iberate more lattice energy and compensate the energy L = 1s22s22p4; Q = 1s22s22p63s23p5;
required to decompose MgCO3. So, the decomposition
P = 1s22s22p63s1; R = 1s22s22p63s2
temperature of MgCO3 is less but when bigger Ba2+
ion combine with small O2–, the lattice energy liber- The formula of ionic compounds that can be formed
ated is less. Hence, the decomposition temperature of between these elements are
BaCO3 is large. (1) L2P, RL, PQ, R2Q (2)  LP, RL, PQ, RQ
• Smaller anions stabilises the higher oxidation states of (3) P2L, RL, PQ, RQ2 (4)  LP, R2L, P2Q, RQ
cations while bigger anions stabilises the lower oxida- 15. Which among the following is expected to conduct
tion states of cation because smaller non-metal atoms electricity?
have more electronegativities and high electron affini- (1) Diamond (2)  Molten sulphur
ties and liberate more lattice energies. (3) Molten KCl (4)  Crystalline NaCl
• Metal ions in higher oxidation states can oxidise the
16. The false statement among the following when ionic
bigger anions because the bigger anions cannot hold
compounds get dissolved in water is
the electrons strongly and act as reducing agents. E.g.,
I– act as a reducing agent but F– cannot. (1) They involve heat changes.
(2) Interionic attraction is reduced due to solvation.
(3) Ions show dipole-ion attraction with water
molecule.
 Objective Questions (4) The cations are hydrolysed.

10. Which of the following statements is wrong in the 17. Solid NaCl is a bad conductor of electricity because
­reaction of sodium and chlorine? (1) In solid NaCl, there are no ions.
(2) Solid NaCl is covalent.
(1) Energy is released and ionic bond is formed.
(3) In solid NaCl, there is no movement of ions.
(2) In sodium chloride crystal each Na+ ion is sur-
(4) In solid NaCl, there are no electrons.
rounded by eight Cl– ions.
(3) Each unit cell of sodium chloride consists of 18. An atom with atomic number 20 is most likely to com-
4 Na+Cl– ionic pairs. bine chemically with the atom whose atomic number is
(4) Sodium is oxidised and chlorine is reduced. (1) 11 (2)  16 (3)  18 (4)  10

Chapter_04.indd 5 3/26/2014 2:50:07 PM

 4.6  Objective Chemistry - Vol. I

19. Born–Haber cycle is used to determine 28. LiCl is soluble in organic solvents while NaCl is not
(1) lattice energy (2)  electron affinity because
(3) ionisation energy (4)  any of these (1) Lattice energy of NaCl is less than that of LiCl
(2) Li+ has higher value of hydration energy than Na+
20. According to Fajan, covalent character of a com-
(3) LiCl is more covalent than NaCl
pound is more when there are
(4) Li+ has lower value of hydration energy than Na+
(1) small cations and large anion
(2) small cations and small anion 29. Which set has the strongest tendency to form anions?
(3) large cations and large anion (1) Ga, In, Te (2)  Na, Mg, As
(4) large cations and small anion (3) N, O, F (4)  V, Cr, Mn

21. If Na+ ion is larger than Mg2+ ion and S2– ion is ­larger 30. The relation between the magnitudes of lattice energy
than Cl– ion, which of the following will be least of crystal and its formation energy is
soluble in water? (1) Lattice energy > Formation energy
(1)  NaCl (2)  Na2S (3)  MgCl2 (4)  MgS (2) Lattice energy = Formation energy
(3) Lattice energy < Formation energy
22. Among LiCl, BeCl2, BCl3 and CCl4 the covalent bond (4) None
character follows the order
31. Using the following data calculate the electron affin-
(1) LiCl > BeCl2 > BCl3 > CCl4
ity of chlorine.
(2) LiCl < BeCl2 < BCl3 > CCl4
(3) LiCl > BeCl2 > CCl4 > BCl3 Heat of formation of NaCl (∆Hf NaCl)
(4) LiCl < BeCl2 < BCl3 > CCl4 = –98 Kcal mole–1
1 
23. Among NaF, NaCl, NaBr and NaI, the NaF has high- Dissociation energy of Cl2  DCl2 
est melting point because  2 
= +29 kcal mole–1
(1) It has maximum ionic character.
Heat of sublimation of Na(∆HsNa)
(2) It has minimum ionic character.
(3) It has associated molecules. = +26 kcal mole–1
(4) It has least molecular weight.
IP of Na = +118 kcal mole –1
24. Amongst LiCl, RbCl, BeCl2 and MgCl2 the Lattice energy (U) of NaCl(s)
­compounds with the greatest and least ionic character = –184 kcal mole –1
respectively are
(1) 17.14 kcal mole –1 (2)  48 kcal mole –1
(1) LiCl and RbCl
(3) –87 kcal mole –1 (4)  None
(2)  RbCl and BeCl2
(3) RbCl and MgCl2
(4)  MgCl2 and BeCl2 Answers
25. The three-dimensional graph of lattice points which (10) 2 (11) 4 (12) 4 (13) 3 (14) 3
sets the pattern for the whole lattice is called (15) 3 (16) 4 (17) 3 (18) 2 (19) 4
(1) unit cell (2)  crystal lattice (20) 1 (21) 4 (22) 2 (23) 1 (24) 2
(3) simple lattice (4)  space lattice (25) 1 (26) 1 (27) 2 (28) 3 (29) 3
26. Favourable conditions for ionic bond are (30) 1 (31) 3
(1) low charge on ions, large cation and small anion
(2) high charge on ions, small cation and large anion
(3) high charge on ions, large cation and small anion covalent bond
(4) low charge on ions, small cation and large anion • Covalent bond was proposed by Lewis.
+
27. Coordination number of Na ion in NaCl is 6 and that • Covalent bond is formed by mutual sharing of ­electrons
of caesium ion in CsCl is 8. This is because between two atoms.
(1) IP of Cs is less than Na • Pure covalent bond (100%) or pure ionic bond (100%)
(2) Size of Na+ is less than Cs+ is only an ideal situation. Even a covalent bond between
(3) Attraction of Na+ is higher than Cs+ similar atoms like H2, Cl2, etc. has some ionic character
(4) None due to shifting of electrons in a fraction of second.

Chapter_04.indd 6 3/26/2014 2:50:08 PM

 Chemical Bonding and Molecular Structure   4.7

• Covalent bond formed between two atoms having 34. The nature of bonding in CCl4 and CaH2 is
d­ ifferences in their electronegativities has partial (1) electrovalent in both CCl4 and CaH2
ionic character. (2) covalent in CCl4 and electrovalent in CaH2
• A covalent bond formed between two atoms by sharing (3) electrovalent in CCl4 and covalent in CaH2
one electron pair is single bond. E.g., F2, Cl2, HCl, etc. (4) covalent in both CCl4 and CaH2
• If two pairs of electrons are shared between two atoms, 35. CCl4 is insoluble in water because
the covalent bond formed is a double bond. E.g. O2, (1) CCl4 is nonpolar and water is polar
CO2, C2H4, etc. (2) water is nonpolar and CCl4 is polar
• If three electron pairs are shared between two atoms, (3) water and CCl4 are both polar
the covalent bond formed is a triple bond. (4) none
• Covalency is the number of electron pairs shared by 36. Which is not an exception to octet rule?
an atom in the formation of a covalent compound.
(1) BF3 (2)  SnCl4
• The molecules present in a covalent solid are attracted (3)  BeI (4)  ClO2
2
by weak Van der Waal’s forces. So, they have low
­melting points and boiling points. 37. The compound with lowest melting point is
• Most of the covalent compounds are either gases or (1) AlF3 (2)  AlCl3
low melting solids. (3) AlBr3 (4)  AlI3
• Polar covalent compounds such as glucose, sugar, etc. 38. A solid substance is soft, has low melting point and is
dissolve in polar solvents like water, alcohol, etc. poor conductor of electricity. The substance is most
• Non-polar covalent substances such as iodine, camphor likely
dissolve in non-polar solvents like benzene, carbon (1) an ionic solid
tetrachloride. (2)  network solid
• Covalent compounds do not conduct electric current (3) a metallic solid
either in molten state or in their aqueous solutions (4)  a molecular solid
­because of the absence of ions or free electrons. 39. When a solution of silver nitrate is added to pure
• Covalent compounds are nonelectrolytes. ­carbon tetrachloride
• Covalent bonds are directional in nature, hence cova- (1) A white curdy precipitate soluble in ammonia is
lent compounds exhibit stereoisomerism. obtained
• The chemical reactions, in which covalent molecules (2) A curdy precipitate insoluble in ammonia is
participate involves bond breaking and bond making. ­obtained.
Hence, their reactions are slow. (3) A pale yellow precipitate is obtained.
• Lewis theory cannot explain the shapes and bond (4) No precipitate is obtained.
­angles in molecules. 40. The electronic configuration of 4 elements K, L, M
and N are
K = 1s22s22p1
 Objective Questions L = 1s22s22p6
M = 1s22s22p4
32. Octet rule is not valid for the molecule
N = 1s22s22p3
(1) CO2 (2)  H2O (3)  O2 (4)  CO
The element that would form a diatomic molecule
33. Regarding covalency which of the following state- with double bond is
ments is wrong?
(1) K (2)  L (3)  M (4)  N
(1) In covalency, sharing of electrons takes place.
(2) Maximum covalency is restricted to 8.
(3) Covalency is the number of electron pairs shared Answers
by an atom.
(4) Covalency of an atom is equal to the number of (32) 4 (33) 4 (34) 2 (35) 1 (36) 2
electrons contributed by an atom in the formation (37) 4 (38) 4 (39) 4 (40) 3
of covalent bonds.

Chapter_04.indd 7 3/26/2014 2:50:08 PM

 4.8  Objective Chemistry - Vol. I

Valence shell electron • The order of repulsion between various electron pairs
pair repulsion (vsepr) is lp-lp > lp-bp > bp-bp.
theory • Molecules having all bond pairs around the central
atom have regular shapes.
• VSEPR theory was proposed by Sidgwick and Powell
and later developed by Gillespie and Nyholm. • The magnitude of repulsions between bond pairs
of electrons depend on the electronegativity differ-
• VSEPR theory predicts the shapes of molecules ence between the central atom and the other atoms
­without reference to the hybridisation.
bonded to it.
• The shapes of molecules depend on the number of • With increase in the electronegativity of central atom
electron pairs present on central atom including
bond angle increases, but with increase in electro­
lone pairs.
negativity of the bonded atom, bond angle decreases.
• A lone pair (lp) electrons occupy more space around This is because with increase in electronegativity of
the central atom than a bond pair (bp) of electrons the central atom, the bp moves towards central atom
­because the lone pair electrons are attracted by only causing more repulsion, but with increase in electron-
one nucleus while the bond pair electrons are under the egativity of the bonded atom bp moves away from the
attraction of two atoms sharing this electron pair. central atom causing less repulsion.

Shapes of molecules based on VSEPR Theory are summarised in the following table.
No. of electron pairs Type of electron pairs Type of molecule Shape Example
2 2BP AX2 Linear BeCl2, HgCl2
3 3BP AX3 Plane triangular BF3, BCl3, SO3
3 2BP+ 1LP AX2 Angular or
V-shaped SnCl2, SO2
4 4BP AX4 Tetrahedral CH4, CCl4, SiCl4
4 3BP + 1LP AX3 Pyramidal NH3, PH3, PCl3
4 2BP + 2LP AX2 Angular H2O, H2S, SCl2
4 1B + 3LP AX Linear HCl, ICl
5 5BP AX5 Trigonal
bipyramid PF5, PCl5
5 4BP + 1LP AX4 Distorted or irregular
Tetrahedron SF4, SCl4, TeCl4
5 3BP + 2LP AX3 T-shaped ClF3, BrF3
5 2BP + 3LP AX2 Linear XeF2
6 6BP AX6 Octahedral SF6, TeCl6
6 5BP + 1LP AX5 Square pyramid BrF5, IF5
6 4BP + 2LP AX4 Square planar XeF4
7 7BP AX7 Pentagonal
bipyramid IF7
7 6BP + 1LP AX6 Distorted
Octahedron XeF6

• Double bonds cause more repulsion than single bonds • Molecules having 5 or 7 electron pairs around the
­
and triple bonds cause more repulsion than double central atom possess asymmetric structures and
bonds. the electron pairs with largest number of near-
• Repulsions between electron pairs in filled shells are est ­­neighbours will be located at a greater average
greater than those between electron pairs in completed ­distance from the central atom than the other electron
shells. pairs.

Chapter_04.indd 8 3/26/2014 2:50:09 PM

 Chemical Bonding and Molecular Structure   4.9

• As the number of lone pairs on the central atom in-

creases distortion of the molecule also increases.  Objective Questions
• A lone pair causes more repulsion (e.g., NO2–) than
41. The central atom in a molecule has three bond pairs and
an unpaired electron (NO2) and an unpaired electron
one lone pair of electrons. The shape of the molecule is
cause more repulsion than in the molecules having all
bond pairs. For example, the order of bond angles in (1) Triangular
NO2, NO–2, and NO+2 will be NO2– < NO2 < NO2+. (2)  Pyramidal
(3) Linear
• If in a molecule, the central atom is having vacant (4)  Tetrahedral
orbitals and the bonded atom has lone pair or vice
versa delocalisation of electrons from the atom having 42. Which of the following molecules does not have a
lone pair into the atom having vacant orbital causing ­linear arrangement of atoms?
the increase in bond angle and change in shapes of (1) C2H2 (2)  H2O (3)  BeCl2 (4)  CO2
molecules. 43. Two lone pairs of electrons and two bond pairs are
­present in
(1) NH3 (2)  BF3 (3)  CO32– (4)  H2O
SiH3 44. BCl3 is a planar molecule, whereas NCl3 is pyramidal
P P– N
H3Si –N because
+ (1) BCl3 has no lone pair of electrons but NCl3 has a
H H H F F
F H3C CH CH3 SIH3
3 lone pair of electrons.
(2) B-Cl bond is more polar than N-Cl bond.
93.3° 96.3° Pyramidal Planar (3) Nitrogen atom is smaller than boron atom.
(4) N-Cl bond is more covalent than B-Cl bond.
• Molecules having 5 electron pairs adopt asymmetric
45. More the number of lone pairs of electrons on the
trigonal bipyramid (TBP) structure having two long
­central atom
axial bond lengths and three short equatorial bond
lengths. The three equatorial bond angles are 120 while (1) greater is the contraction in the angle between
the axial to equatorial position are 90°. bond pairs
• (2) the smaller is the contraction in the angle be-
In the TBP structure, the lone pair always occupies the
tween BPs
equatorial position only.
(3) no effect on bond angle
• In the TBP structure, always the double-bonded oxygen (4) all
occupies the equatorial positions only.
• 46. The H-O-H bond angle in H2O is 104.5° and not
If there are different types of atoms in the TBP struc-
109°28′ because of
ture, the more electronegative atom occupies the axial
positions (Bent’s rule). (1) high electronegativity of oxygen
• (2) bond pair-bond pair repulsion
In the octahedral structure having 6 electron pairs, if
(3) Lone pair-lone pair repulsion
there are more than one lp they occupy opposite corners
(4) Lone pair-bond pair repulsion
as in XeF4 and if there are double-bonded oxygen atoms,
they also occupy the opposite corners of octahedron as 47. The lone pair of electrons in a molecule spread out
in XeO2F4. (1) more than the bond pair electrons
(2) less than the bond pair electrons
(3) as much as the bond pair electrons
isoelectronic and (4) only when they are present in oxygen atoms
isostructural species
48. The decrease in bond angle to 106°45– from the tetra-
• If Lewis diagrams of different species are identical, hedral angle in NH3 is because of
except for the identity of central atom and having same (1) bond pair-bond pair repulsion
electronic structure are called isoelectronic species. (2) lone pair-lone pair repulsion
• Isoelectronic species have similar structures. E.g, BO33–, (3) bond pair-lone pair repulsion
CO32 − , NO3− are isoelectronic and isostructural. (4) none

Chapter_04.indd 9 3/26/2014 2:50:10 PM

 4.10  Objective Chemistry - Vol. I

–
49. The geometrical arrangement and shape of I3 are
­respectively  Objective Questions
(1) trigonal bipyramidal geometry, linear shape 51. The angle between the overlapping of one s-orbital
(2) hexagonal geometry, T-shape and one p-orbital is
(3) triangular planar geometry, pyramidal shape
(1) 180° (2)  120°
(4) tetrahedral geometry, pyramidal shape
(3)  109° 28′ (4)  120° 50′
50. The bond angles of NH3, NH +4 and NH 2− are in the
52. A covalent bond is formed between the atoms by the
order
overlapping of orbitals containing
(1) NH 2− > NH3 > NH +4
(1) a single electron
(2)  NH +4 > NH3 > NH 2−
(2) paired electron
(3) NH3 > NH2– > NH +4
(3) single electron with parallel spin
(4)  NH3 > NH +4 > NH 2−
(4) single electron with opposite spin
53. How many σ and π bonds are there in the molecule of
Answers tetracyanoethylene (CN)2 C = C (CN)2?
(1) Nine σ and nine π
(41) 2 (42) 2 (43) 4 (44) 1 (45) 1
(2)  Five σ and nine π
(46) 3 (47) 1 (48) 3 (49) 1 (50) 2 (3) Nine σ and seven π
(4)  Five σ and eight π
54. Which statement among the following is correct?
valence bond theory
(1) π-bond always exist with σ-bond
• Valence bond (VB) theory was proposed by Hietler (2) π-bond can exist independently
and London, later extended by Pauling and Slater. (3) σ-bond is weaker than π-bond
• A covalent bond is formed by the overlap of the ­atomic (4) π-bond is less reactive than σ-bond
orbitals of the two atoms. 55. Which is not characteristic of a π bond?
• The greater the extent of overlap the stronger is the (1) A π-bond is formed when a sigma bond is al-
bond formed. ready formed.
• The spin of the two electrons present in the ­overlapping (2) π-bonds are formed by hybrid orbitals.
orbitals must be opposite. (3) π-bonds may be formed by the overlapping of
• atomic orbitals.
The imaginary line joining the nuclei in a molecule is
(4) π-bond results from lateral overlap of atomic
known as inter nuclear axis or molecular axis.
­orbitals.
• The covalent bond formed with the linear overlap of
atomic orbitals along the internuclear axis is known as 56. Which p-orbital overlapping would give the strongest
σ-bond. bond?
• (1) (2)
The covalent bond formed by the lateral overlap or
sidewise overlap of two atomic orbitals perpendicular
to internuclear axis is known as π-bond.
• A σ-bond can exist independently but a π-bond cannot
exist independently.
• A π-bond is formed only after the formation of a (3) (4)
σ-bond.
• π-bond is weaker than σ-bond.
• The shapes of molecules depend only on σ-bond but
not on π-bonds. 57. π-bond
• The order of the strength of covalent bonds formed by (1) shortens the bond length
overlapping of different types of orbitals will be in the (2) increases the bond length
order. (3) distorts the geometry of the molecule
sp-p > ss-p > ss-s > pp-p (4) none

Chapter_04.indd 10 3/26/2014 2:50:12 PM

 Chemical Bonding and Molecular Structure   4.11

58. According to valence bond theory bond angle in wa- Hybridisation

ter should be 90°. But experimental value is 104.5°.
This is due to • The concept of hybridisation was proposed by Linus
(1) repulsion between positively charged hydrogen Pauling.
atoms • The intermixing of atomic orbitals of similar energies
(2) the presence of lone pair of electrons in oxygen and their redistribution into an equal number of identical
(3) repulsion between two bonds is very high orbitals is hybridisation.
(4) None • Orbitals of only one atom can participate in hybridisa-
59. The number of bonds present and the number of tion but orbitals of different atoms cannot participate
­unpaired electrons according to valence bond theory in hybridisation.
in O2 are • The hybrid orbitals are symmetrically arranged
(1) 2, 2 (2)  2, 0 (3)  3,0 (4)  0, 2 around the nucleus so that the repulsion between them
60. Which of the following pairs of orbitals conform a is less.
pi bond? • The angle between any two hybrid orbitals in an atom
(1) py-py (2)  py-pz (3)  s-py (4)  s-s must be equal, except in sp3d and sp3d3.
61. Valence bond theory of Pauling and Slater accounts • Only orbitals undergo hybridisation but not electrons.
for ......... characteristics of covalent bond. • The distribution of electrons in hybrid orbitals follows
(1) strength (2)  directional Pauli’s exclusion principle and Hund’s rule of maxi-
(3) both (4)  none of these mum multiplicity.
62. Which orbital is used by oxygen atom to form a ­sigma • Hybrid orbitals always form σ-bond only.
bond with other oxygen atom in O2 molecule?
(1) sp hybrid orbital (2)  sp2 hybrid orbital role of d-orbitals in Bonding
3
(3) sp hybrid orbital (4)  pure p-orbital
• The valence shell d-orbitals are far higher in energy
63. Iodine monochloride molecule is formed by the and much more diffuse than the s- and p-orbitals and
­overlap of thus cannot contribute much to the bonding.
(1) s-s orbitals (2)  s-p orbitals • When an atom is in bond with more electronegative
(3) p-d orbitals (4)  p-p orbitals
atoms such as fluorine or oxygen, positive charge de-
64. Which of the following is not characteristic of a cova- velops on the central atom resulting in the contraction
lent bonding? of d-orbitals and decrease in energy, which can partici-
(1) s-orbital never participates in π bonding pate in bonding. Because of this reason, elements can
(2) it is effective only at small internuclear distances form compounds in higher oxidation states utilising
(3) it is directional d-orbitals, only with more electronegative elements
(4) it is weaker than Van der Waal’s bonding but not with less electronegative elements. E.g., SF6 is
formed but not SH6.
65. Which of the following about covalent bond is false?
(1) energy is required to break a covalent bond Bent’s Rule
(2) covalent bonds involve overlap of orbitals
(3) covalent bonds are generally stronger than the • sp3d hybrid orbitals may be considered to be combina-
ionic bonds tion of two sets of hybrid orbitals: one set s, px and py
(4) covalent bonds are not formed by small atoms (sp2) and another set pz and dz2 (pd).
• The pd hybrid orbitals make two linear bonds axially
while the sp2 hybrid orbitals form trigonal equatorial
Answers bonds.
• The sp2 hybrid orbitals form stronger bonds and they
(51) 1 (52) 4 (53) 1 (54) 1 (55) 2 are shorter than the weaker axial bonds.
(56) 3 (57) 1 (58) 1 (59) 2 (60) 1 • When different types of atoms are present in a
(61) 3 (62) 4 (63) 4 (64) 4 (65) 4
TBP structure, more electronegative substituents

Chapter_04.indd 11 3/26/2014 2:50:12 PM

 4.12  Objective Chemistry - Vol. I

“prefer” hybrid orbitals having less s-character, i.e., Type of hybridisation Atomic orbitals
axial ­positions and more electropositive ­substituents
­“prefer” hybrid orbitals having more s-character sp s + pz
(Bent’s rule). sp2 s + pz + px or py
sp3 s + pz + px + py
Calculation of Percent dsp2 d x 2 − y 2 + s + px + py
Character of Hybrid Orbitals dsp3 (trigonal bipyramid) d z 2 + s + px + py + pz
dsp3 (square pyramid) d x 2 − y 2 + s + px + py + pz
• There is a relation between hybridisation and bond d2sp3 d x 2 − y 2 + d z 2 +s + px + py + pz
a­ ngles for s-p hybrid orbitals. sp3d3 s + px + py + pz + dxy + dyz + dxz
• For two or more equivalent orbitals, the per cent s-char-
acter or per cent p-character is given by the relationship: • Generally the orbitals directed towards the bond
S P −1 f­ ormation in a particular geometry will participate in
Cos = = hybridisation.
S −1 P
where q is the angle between the equivalent orbitals
and the S and P characters are expressed as decimal Geometry (Shape) of Covalent Molecules
fractions.
• The structure of any covalent molecule can be pre-
• In the case of small atoms like N and O the steric ­effects dicted by knowing the total number of electron pairs
are more prominent, but in larger atoms in the respec- (P), the number of bond pairs (bp) and lone pairs (lp)
tive groups such as P, As, Sb, S, Se and Te these effects around the central atom in a molecule. These can be
are somewhat relaxed, allowing the ­reduced hybridisa- calculated by using the formula
tion energy of more p-character in the ­bonding orbit-
als. Because of this reason only N and O are involved 1
P= (V + M – c + a)
in sp3 hybridisation in NH3 and H2O but almost pure 2
p-orbitals involve in bonding in larger atoms in their “V” is the number of electrons in the valence shell of
respective groups during the formation of hydrides. the central atom, “M” is the number of monovalent
atoms, “c” is the number of positive charges if the
Orbitals Participating in Different given species is cation and “a” is the number of nega-
Types of Hybridisation tive charges if the given species is anion.
• If the molecular axis is selected as z-axis, the orbitals • The number of bp and lp can be known from the relation
participating in different types of hybridisation are as    lp = P – bp

follows:

Shapes of molecules based on VSEPR Theory and hybridisation are summarised in the following table.
Total No. of
electron pairs
Type of P=
( V + M − C + a ) No. of No. of Type of
molecule 2 bp lp hybridisation Shape Bond angle Example
AX2 2 2 — sp Linear 180° BeCl2, C2H2, HgCl2
AX3 3 3 — sp2 Plane triangular 120 BF3, BCl3, C2H2
AX2 3 2 1 sp2 Angular or <120 SnCl2, SO2
V-shape
AX4 4 4 — sp3 Tetrahedral 109°28′ CH4, CCl4, SiH4
SCl4, NH4+, BF4
AX3 4 3 1 sp3 Pyramidal <109°28′ NH3, PH3 PCl3 H3O+
AX2 4 2 2 sp3 Angular or
V-shape <109°28′ H2O, H2S, F2O, Cl2O

Chapter_04.indd 12 3/26/2014 2:50:14 PM

 Chemical Bonding and Molecular Structure   4.13

Total No. of
electron pairs
Type of P=
( V + M − C + a ) No. of No. of Type of
molecules 2 bp lp hybridisation Shape Bond angle Example
3
AX5 5 5 — sp d Trigonal bi 3 angles –120°
pyramid 2 angles –90° PF5 PCl5 SbCl5
AX4 5 4 1 sp3d Distorted or 1 angle < 120°
irregular Tetra-
hedron (or) 2 angles < 90° TeCl4, SF4, SCl4
see-saw
AX3 5 3 2 sp3d T-shape 2 angles < 90° ClF3, BrF3
AX2 5 2 3 sp3d Linear 180° XeF2, I3–
AX6 6 6 — sp3d2 Octahedral 90° SF6, TeF6
AX5 6 5 1 sp3d2 Square pyramid < 90° BrF5, IF5
AX4 6 4 2 sp3d2 Square planar 90° XeF4
AX7 7 7 — sp3d2 Pentagonal 5 angles –72°
bipyramid 2 angles –90° IF7
AX6 7 6 1 sp3d2 Distorted
Octahedron — XeF6

• The bp in a molecule is equal to the number of atoms • For anions like NO3–, NO2–, PO43–, CO32–, SO42–, SO32–,
around the central atom. Knowing the number of lp etc. For example, for NO3–
and bp, the structure of molecules can be written. 1
P = (5 + 0 – 0 + 1) = 3; bp = 3; lp = 3 – 3 = 0
• For molecules containing only monovalent atoms 2
and do not contain multiple bonds. Calculation for Only bp is present, no lp. so NO3– will have the planar
SF6 is as follows: triangular structure.
1
P = (6 + 6 – 0 + 0) = 6 bp
2 • For complex ions like ICl4–, I3–, ClF2–, etc.
lp = 6 – 6 = 0 For example, for ICl4–
Since there are 6 bp without lone pairs, the molecule 1
SF6 is octahedral. Similarly, the structures of BeF2, P = (7 + 4 – 0 + 1) = 6
2
BCl3, CCl4, PCl3, PCl5, NH3, H2O, SF4, ClF3, IF7,
XeF2, etc. can be written. bp = 4, lp = 6 – 4 = 2.
• For molecules containing multiple bonds • Iodine atom in ICl4– contain 2 lp and 4 bp. So, it will
have a square planar structure with two lp occupying
(π-bonds) e.g., COCl2. the opposite corners of the octahedron.
1
P = (4 + 2 – 0 + 0) = 3 • The total number of electron pairs (P) decides the type
2
bp = 3; lp = 3 – 3 = 0 of hybridisation since each electron pair can occupy
one hybrid orbital.
Since oxygen is divalent, there will be double bond
­between carbon and oxygen.
The ClCCl angle is less than 120° while OCCl bond
angle is greater than 120°.  Objective Questions
• For cations like NH4+, CH3+, H3O+, etc. e.g., For H3O+
66. Which has the planar structure?
1
P = (6 + 3 – 1 + 0) = 4 ; bp = 3, lp = 4 – 3 = 1 (1) NH4+ (2)  SCl4 (3)  XeF4 (4)  BF4–
2
H3O+ will have pyramidal shape with one lone pair 67. The molecule/ion which is not planar is
and three bond pairs. (1) BF3 (2)  NO3– (3)  CO32– (4)  NF3

Chapter_04.indd 13 3/26/2014 2:50:15 PM

 4.14  Objective Chemistry - Vol. I

68. Which does not use sp3 hybrid orbitals in its bonding? 79. The pair having similar geometry
(1) BF3 (2)  H3O+ (3)  NH4+ (4)  NF3 (1) BF3, NH3 (2)  BF3, AlCl3
(3) BeF2, H2O (4)  BCl3, PCl3
69. OF2 is
(1) Linear molecule (2)  Tetrahedral molecule 80. CO2 is isostructural with
(3) Angular molecule (4)  None (1) SnCl2 (2)  HgCl2
(3) H3O+ (4)  SCl2
70. The molecule which is not linear is
(1) CO2 (2)  BeCl2 (3)  Cl2O (4)  HgCl2 81. Which has triangular planar shape?
(1) CH3+ (2)  ClO2–
71. Which has the lowest bond angle? (3) H3O +
(4)  ClO3–
(1) BeF2 (2)  H2O (3)  NH3 (4)  CH4
82. Which of the following pairs are nonlinear?
72. The type of hybridisation present in SO2 and SO3 is (1) NH3, CO2 (2)  NH3, H2O
respectively (3) CO2, BeCl2 (4)  BeCl2, NH3
(1) sp, sp2 (2)  sp2, sp2
2 3
83. Which of the following statement is false?
(3) sp , sp (4)  sp, sp3
(1) Octahedral molecular shape exists in sp3d2
73. Which statement is wrong? ­hybridisation.
(1) Hybridisation is the mixing of atomic orbitals (2) XeF2 involves sp3d hybridisation.
prior to their combining into molecular orbitals. (3) The repulsion among four hybrid orbitals is
(2) sp2 hybrid orbitals are formed from two p- and smallest if they point to the corners of a square.
one s-atomic orbitals. (4) Hybridisation can take place only between orbit-
(3) sp3d hybrid orbitals are all at 90° to one another. als of roughly the same energy.
(4) sp3d2 hybrid orbitals are directed towards the 84. A triatomic molecule must be either linear with a
­corners of the regular octahedron. bond angle of 180° or else
74. PCl5 exists but NCl5 does not exist because (1) Pyramidal (2)  Tetrahedral
(3) Bent (4)  L-shaped
(1) Nitrogen has no vacant 2d-orbitals.
(2) NCl5 is unstable. 85. Odd number regarding the shape of the following is
(3) Nitrogen atom is much smaller than p. (1) BCl3 (2)  PCl3
(4) Nitrogen is highly inert. (3) NF3 (4)  H3O+
75. The shape of NO3– is planar. It is formed by the 86. Increasing order of the size of various hybrid orbitals is
­overlapping of oxygen orbitals with which orbitals of (1) sp > sp2 > sp3
nitrogen are
(2)  sp3 > sp2 > sp
(1) sp3 hybridised (3) sp2 > sp > sp3
(2)  sp2 hybridised

(4)  sp > sp3 > sp2
(3) sp hybridised 87. Which one of the following is not a consequence of
(4)  3 pure p-orbitals hybridisation?
76. Which hybridisation results in non-planar orbitals? (1) effective overlapping of orbitals
(1) sp (2)  sp2 (3)  sp3 (4)  dsp2 (2) minimised repulsion between orbital electrons
(3) stronger bonds
77. The hybridisation of carbon in diamond, graphite and (4) enhanced reactivity of the molecule
acetylene is
(1) sp3, sp2, sp (2)  sp3, sp, sp2 88. PCl5 in the solid state exists as PCl4+ and PCl6–
­
2 3
(3) sp , sp , sp (4)  sp, sp2, sp3 because
(1) Solid PCl5 is a conductor.
78. CO2 has the same geometry as (2) PCl4+ and PCl6– have stable symmetrical struc-
(A) HgCl2 (B) NO2 tures unlike PCl5 that has asymmetrical structure.
(C) SnCl4 (D) C2H2 (3) Ion pairs are more stable than neutral molecules.
(1) A
 and C (2)  B and D (4) Phosphorous belongs to V group in the periodic
(3) A and D (4)  C and D table.

Chapter_04.indd 14 3/26/2014 2:50:16 PM

 Chemical Bonding and Molecular Structure   4.15

89. Regarding hybridisation which is incorrect?

(1) BF3, C2H4, C6H6 involves sp2 hybridisation.  Objective Questions
(2) BeF2, C2H2, CO2 involves sp hybridisation.
91. When two species A and B form an electron pair bond
(3) NH3, H2O, CCl4 involves sp3 hybridisation.
and A does not provide its electrons for bonding, the
(4) CH4, C2H4, C2H2 involves sp2 hybridisation.
bond present between A and B must be
90. The % p character in hybrid orbitals of the central (1) ionic (2)  covalent
atom of water molecule is (3) dative (4)  hydrogen
(1) 25%
92. Each of the following pairs of chemical species will
(2)  75%
combine. Which of the following combination is best
(3) Less than 75%
explained by the coordinate covalent bond?
(4)  More than 75%
(1) H2 + I2 (2)  Mg + O2
(3) Cl + Cl (4)  H+ + H2O
93. BF3 forms an adduct with NH3 because
Answers
(1) Nitrogen has high electronegativity.
(66) 3 (67) 4 (68) 1 (69) 3 (70) 3 (2) Boron has high electronegativity.
(71) 2 (72) 2 (73) 3 (74) 1 (75) 2 (3) Boron has an empty p-orbital and nitrogen has
(76) 3 (77) 1 (78) 3 (79) 2 (80) 2 one lone pair of electrons.
(81) 1 (82) 2 (83) 3 (84) 3 (85) 1 (4) Boron has electropositive character.
(86) 2 (87) 4 (88) 2 (89) 4 (90) 4 94. Proton plays an important role in ........bonding.
(1) electrovalent (2)  hydrogen
(3) covalent (4)  coordinate
95. Which of the following compounds contain all three
coordinate covalent types: ionic, covalent and dative bonds?
bond or dative bond (1) CuSO4 . 5H2O (2)  Solid N2O5
(3) (NH4)2SO4 (4)  All
• It was proposed by Sidgwick.
• A bond formed by sharing a pair of electrons, provid- 96. The type of bond formed during the hydration of
ing both electrons by one of the two bonded atoms is cation is
called a dative bond or a coordinate covalent bond. (1) ionic (2)  covalent
(3) electrostatic (4)  dative bond
• The atom providing two electrons to form a dative
bond is called a donor and the atom sharing the pair
of electrons from a donor is known as an acceptor.
Answers
• Dative bond may be represented with an arrow from
the donor to acceptor as A → B or as A+– B– with posi- (91) 3 (92) 4 (93) 3 (94) 4 (95) 4
tive charge on donor and negative charge on acceptor. (96) 4
• Donor should have at least one lone pair of electrons
and acceptor should have a vacant orbital.
• The properties of compounds containing dative bonds molecular orbital theory
are intermediate to ionic and covalent compounds.
• Since the dative bond is directional in nature the com- • Molecular orbital theory was proposed by Hund and
pounds containing dative bonds exhibit stereo­­isomerism. Mulliken.
• Coordinate covalent compounds are nonelectrolytes, • An electron in an atomic orbital is centred about a
do not conduct electricity because they do not ionise single nucleus but an electron in a molecular orbital
in water. (MO) is spread out over all the nuclei in a molecule.
• Coordinate covalent compounds dissolve more in non- • Mathematically, an MO is a linear combination
polar solvents like benzene, carbon tetrachloride, etc. of atomic orbitals (LCAO) of two different atoms
than in polar solvents. a­ pproaching one another.

Chapter_04.indd 15 3/26/2014 2:50:16 PM

 4.16  Objective Chemistry - Vol. I

• The number of MOs formed is equal to the number of Bond Order

atomic orbitals that combined. • Bond order may be defined as half the difference
• Two atomic orbitals can be combined to yield two between the number of bonding and anti-bonding
molecular orbitals: one a bonding and another anti- electrons.
bonding molecular orbitals. Bond order =

• Bonding MO is at lower energy than the original 1  No of electrons in No of electrons in 
 −
atomic orbital. 2  bonding MOs antibonding MOs 
• In the bonding MO, most of the electron density is • Bond order of 1, 2 or 3 corresponds to a single, double
l­ocated in the region between the two nuclei, both or triple bonds, respectively.
­nuclei are attracted to this electron density. • Bond order may be fractional, integer or zero and
• Anti-bonding MO is at higher energy than the original rarely negative.
atomic orbital and represented by an asterisk (*) • Zero and negative bond order indicates that the species
• In the anti-bonding MO, only a small fraction of the exist but unstable.
electron density is in the region between the nuclei. • The bond order of a molecule is directly proportional
• If the overlapping of the two atomic orbitals takes to its bond dissociation energy and stability and in-
versely proportional to bond length.
place along their axes, the resulting MOs are known
as s–MOs. • The addition of an electron in the bonding MO makes
the molecule more stable, whereas that in the anti-
• If the overlapping of the two atomic orbitals takes place bonding MO makes it less stable.
sideways, the resulting MOs are known as π−MOs.
• The removal of an electron from the bonding MO
• π−MOs are formed by the overlapping Px – Px and py – makes the molecule less stable, whereas from the anti-
py orbitals, if z-axis is selected as the molecular axis. bonding MO makes it stable.
• MOs formed by the overlapping of 1s, 2s, 2px, 2py and • Paramagnetism in a substance is due to the presence of
2pz orbitals can be arranged in the order of increasing unpaired electrons in its molecule.
energies as follows. • Molecules or ions having same number of electrons
σ1s < σ*1s < σ2s < σ*2s < π2px = p2py < σ2pz < are called isoelectronic species and they have same
π*2px = π*2py < σ*2pz bond order and same MO electronic configuration.
• The highest occupied MO (HOMO) and the lowest
• This order is valid for Li2 to N2 because of sp mixing unoccupied MO (LUMO) collectively are called fron-
of orbitals in these elements. tier orbitals.
• For O2 and F2 the following sequence for the energies • The electronic configurations and bonding properties
of MOs is observed of certain diatomic species can be seen in Table 4.1.
σ1s < σ*1s < σ2s < σ*2s < σ2pz < p2px = p2py < • Heteronuclear diatomic molecules also follow the
π*2px = π*2py < σ*2pz same general bonding pattern as the homonuclear
molecules, but greater nuclear charge on one of the
Electronic Configuration atoms lowers its atomic energy levels and shifts the
resulting MO levels lower.
• The number of electrons belonging to two atoms are • In heteronuclear atomic molecules due to the difference
counted and these are filled in the various MOs accord- in the electronegativities of the two atoms, the electrons
ing to the following rules. in bonding MO spend more time near the more elec-
(i) The MO in the lowest energy is filled first tronegative atom while the electrons in anti-bonding
(­Aufbau principle). MOs are closer to the less electronegative atom.
(ii) A MO can accommodate a maximum of two • The order of the energies of different MOs follows
electrons with opposite spins (Pauli’s exclusion the order of energies of MOs in more electronega-
principle). tive diatomic molecules, e.g., in CN– both carbon and
(iii) The electrons present in bonding MOs are ­nitrogen are in the set of B, C and N; therefore, the
called bonding electrons (nb) and the electrons order of energies of MO will be as in B, C and N due
in the anti-bonding MOs are called anti-bonding to sp mixing but in NO they will follow O2 molecule.
­electrons (na) • CO molecule is of a special case where HOMO is the
non-bonding orbital of carbon.

Chapter_04.indd 16 3/26/2014 2:50:17 PM

 Chemical Bonding and Molecular Structure   4.17

Table 4.1  Molecular orbital results for selected diatomic molecules and molecular orbital predictions

No. of outer
Electronic electrons Bond Bond length Energy Magnetic
Molecule configuration Bonding Antibonding order pm KJ mol–1 character
H2+ s1s1 1 0 0.5 269.6 1.06 Para
H2 s1s2 2 0 1.0 257 432 Dia
H2– s1s2σ*1s1 2 1 0.5 — — Para
He2+ s1s2 σ*1s1 2 1 0.5 — — Para
He2 s1s2σ*1s2 (KK*) 2 2 0 — — —
Li2 KK* [s2s2] 2 0 1 267 105 Dia
Be2 KK* [s2s2σ*2s2] 2 2 0 — — —
B2 KK* [σ2s 2σ * 2s 2 π2 p1x π2 p1y ] 4 2 1 159 289 Para
C2 KK* [σ2s 2σ * 2s 2 π2 p2x π2 p2y ] 6 2 2 131 627.9 Dia
N2+ KK* [σ2s 2σ * 2s 2 π2 p2x π2 p2y σ2 p1z ] 7 2 2.5 112 841 Para
O2+ KK* [σ2s 2σ * 2s 2σ2 p2z π2p2x π2p2y π * p1x ] 8 3 2.5 112 644 Para
O2 KK* [s2s2σ2s2σ2pz2p2px2 p2py2 π*2px12py1] 8 4 2 121 494.6 Para
O2– KK* [s2s σ*2s
2 2
s2pz2 p2px2 p2py2 π*px2 π* 2py1] 8 5 1.5 128 — Para
O22– KK* [s2s2σ*2s2s2pz2 p2px2 p2py2 π*px2 π* 2py2] 8 6 1.0 149 — Dia
F2 KK* [s2s σ*2s
2 2
s2pz2 p2px2 p2py2 π*px2 π* 2py2] 8 6 1.0 142 155 Dia
NO KK* [s2s2σ*2s2s2pz2 p2px2p2py2 π*2px1] 8 3 2.5 — 667.8 Para
NO+ KK* [s2s2σ*2s2s2pz2 p2px2 p2py2 ] 8 2 3.0 106 Dia

 Objective Questions (1) always has an integer value

(2) can have only fractional value
97. The bond order of a molecule is given by (3) is always equal to one
(1) Half the difference between number of bonding (4) can be zero, integral or fractional
electrons and anti-bonding electrons.
100. Given H2, H2+ and He2+, the correct order of increas-
(2) The difference between the number of bonding
ing bond energy is
electrons and anti-bonding electrons.
(3) Twice the difference between the number of (1) H2 < H2+ < He2+ (2)  He2+ < H2+ < H2
bonding electrons and anti-bonding electrons. (3) H2 < He2 < H2
+ +
(4)  H2 < He2+ < H2+
(4) The total number of bonding electrons. 101. Each one of the following molecule/ion is paramag-
netic except.
98. Which of the following statement is correct?
(1) O2 (2)  O2+
(1) Non-bonding orbitals have the same energy as 2–
(3)  O2 (4)  O2–
the bonding MOs.
(2) Anti-bonding MOs have higher energies than 102. Which of the following molecules do not exist?
highest energy atomic orbitals from which they (1) H2 (2)  Be2 (3)  C2 (4)  N2
are formed.
(3) Bonding orbitals have higher energies than the 103. Which one of the following molecule has the shortest
anti-bonding MOs. bond length?
(4) All are correct. (1) C2 (2)  O2 (3)  F2 (4)  N2

99. Bond order in the MO theory depends on the number 104. Which of the following diatomic species do you
of bonding electrons and anti-bonding electrons. The ­expect to have the longest bond length?
bond order (1) N2 (2)  O2– (3)  O2+ (4)  N2+

Chapter_04.indd 17 3/26/2014 2:50:18 PM

 4.18  Objective Chemistry - Vol. I

105. In which of the following pairs, both the species have 116. In the conversion of O2 to superoxide ion, the electron
the same bond order? is added to
(1) N2, N22+ (2)  O2, F2 (1) σ-orbital (2)  σ*-orbital
(3) C2, O2 (4)  C2, N2 (3) π-orbital (4)  π*-orbital
106. In which set both species are paramagnetic? 117. In an anti-bonding MO the electron density is ­minimum
(1) B2, O2 (2)  N2, F2 (1) around one atom of the molecule
(3)  Be2, O2 (4)  N2, O2 (2) between the nuclei
(3) at a point away from nuclei of the molecule
1 07. The bond order in N2+ is same as in except
(4) at no place
(1) O2+ (2)  N2– (3)  C2– (4)  O22–
118. The paramagnetism of O2 molecule is believed to be
108. Which of the following set have lowest bond order? due to the presence of two electrons in
(1) H2 and He2+ (2)  H2+ and He2+ (1) bonding π-orbitals with parallel spin
(3) Li2 and H2 (4)  H2 and B2 (2) antibonding π-orbitals with parallel spin
109. The MO electron configuration of peroxide ion (3) antibonding π-orbitals with opposite spin
( O2−2 ) is (4) antibonding σ-orbitals with parallel spin
(1) KK* [σ2s2σ*2s2σ 2 p2z π 2 p2x π 2 p2y π∗ 2 p2x π∗ 2 p2y ] 119. Which of the following statements is not correct?
(2) KK*[σ2s σ*2s σ 2 p π 2 p π 2 p π∗ 2 p π∗ 2 p ]
2 2 2
z
2
x
2
y
1
x
1
y (1) He2 molecule cannot exist.
(2) H  2+ ion is less stable than H2 molecule.
(3) KK*[σ2s2σ*2s2σ 2 p2z π 2 p2x π 2 p2y π∗ 2 p2x π∗ 2 p1y]
(3) N 2+ ion is less stable than N2 molecule.
(4) KK*[σ2s2σ*2s2σ 2 p2z π 2 p2x π 2 p2y π∗ 2 p2x ] (4) The O-O bond length in O2 less than that in ion.
110. Which of the following set has highest bond order? 120. Which of the following statements is correct?
(1) N 2+ , O2+ (2)  N2, O2+
2 (1) The peroxide ion has a bond order of 1.5 while
(3) O22− , O22+ (4)  O2, C2 the oxygen molecule has a bond order of 2.
(2) The peroxide ion has a longer and weaker bond
111. A molecular orbital in a polyatomic molecule is
than the oxygen molecule.
(1) monocentric (2)  bicentric (3) The peroxide ion as well as the O2 molecule is
(3) polycentric (4)  none of these paramagnetic.
112. Which of the following sets are isoelectronic? (4) The bond length of peroxide ion is shorter than
(1) N2, O2− (2)  N2, O2+ that of O2 molecule.
2 2

(3) N 2+ , O2+ (4)  N2, O2− 121. Which set of the following species has a bond order
of 2.5?
113. The bond in peroxide ion and fluorine molecule is (1) N2+, NO, O2+ (2)  O2+, NO, CN–
equal because + – +
(3) N2 , CN , O2 (4)  CN–, N2+, N2
(1) these are isoelectronic
(2) their bond energies are nearly equal 122. Which of the following statements is correct?
(3) their bond lengths are nearly equal (1) If bond order is zero or negative the molecule
(4) all of these formed is unstable.
(2) If bond order is positive, the bond formed is ­stable.
114. Which statement of the following is false for isoelec-
(3) Bond dissociation energy is directly proportional
tronic species?
to the bond order.
(1) They have same outer electronic configuration. (4) All are correct.
(2) Their bond orders are same.
(3) Their outer electronic configuration is different. 123. Which of the following statements is not correct for
(4) Their bond energies are nearly same. species O2+, O2, O2– and O22– ?
(1) Bond order decreases in the order:
115. In the conversion of N2 to N2+ ion the electron is
­removed from O2+ > O2 > O2− > O22−
(1) σ orbital (2)  σ* orbital (2) Bond length increases in the order:
(3) π orbital (4)  π* orbital O2+ < O2 > O2− > O22−

Chapter_04.indd 18 3/26/2014 2:50:25 PM

 Chemical Bonding and Molecular Structure   4.19

(3) Bond energy decreases in the order: 129. The energy of 2s is greater than σ∗1s orbital because
O2+ > O2 > O2− > O22− (1) s2s-orbital is bigger than σ1s-orbital.
(4) Stability decreases in the order: (2) s2s is a bonding orbital, whereas σ∗1s an anti-
O2+ < O2 > O2− > O22− bonding orbital.
(3) s2s orbital has a greater value of n that σ*2s-orbital.
124. Only on the basis of bond order which of the follow- (4) s2s orbital is formed only after s1s.
ing statements is not correct for species NO, NO+,
1 30. The bond length of H2+, H2– and H2 are in the order
NO2+, and NO–? − −
(1) H 2+ > H 2 > H 2 (2)  H 2 > H 2+ > H 2
(1) Bond order follows the order: − −
(3) H 2 > H 2 > H 2+ (4)  H 2 > H 2+ > H 2
NO+ > NO = NO+ > NO–
(2) Bond energy follows the order: 131. N2 and O2 are converted into monoanions N2– and
NO+ > NO = NO2+ > NO– O2–, respectively. Which of the following statements
is wrong?
(3) Bond length follows the order:
(1) In N 2−, N-N bond weakens.
NO+ < NO = NO2+ < NO–
(2) In O2−, O-O bond order increases.
(4) Stability decreases in the order:
NO+ < NO = NO2+ < NO– (3) In O2−, O-O bond order decreases.
(4) N 2− becomes paramagnetic.
125. Which of the following statements is not correct?
132. The nodal plane in the π-bond of ethene is located in
(1) The bond order of CN+, CN and CN– follows the
(1) the molecular plane
order CN– > CN > CN+.
(2) a plane perpendicular to the molecular plane
(2) The species H 2− , C2+ and F2+ have a bond order of
which bisects the carbon–carbon sigma bond at
1.5 each.
right angle
(3) The species H 2− , C2+ and F2+ are paramagnetic.
(3) a plane parallel to the molecular plane
(4) The species H 2− , C2+ and F2+ are diamagnetic. (4) a plane perpendicular to the molecular plane
which contains the carbon–carbon σ-bond
126. Which of the following statement is false?
(1) During N2+ formation, one electron each is 133. Anti-bonding MO is formed by
­removed from the bonding MOs. (1) addition of atomic orbitals
(2) During O2+ formation, one electron each is (2) subtraction of atomic orbitals
­removed from the anti-bonding MOs. (3) multiplication of atomic orbitals
(3) During O2– formation one electron each is added (4) none of these
to the bonding MOs.
134. In which of the following pair or pairs is the stronger
(4) During H2– formation one electron each added to
bond found in the first species?
the antibonding MOs.
(I)  O2, O2– (II)  N2, N2+ (III)  NO+, NO–
127. Which of the following statements is not correct (1) I only (2)  II only
­regarding bonding MOs? (3) I and III only (4)  I, II and III
(1) Bonding MOs possess less energy than the ato­
mic orbitals from which they are formed. 135. Which of the following MO has two nodal planes per-
(2) Bonding MOs have low electron densities pendicular to each other?
­between the nuclei. (1) σ2s (2)  p2px
(3) Every electron in bonding MO contributes to the (3) π*2py (4)  σ*2pz
attraction between atoms.
(4) They are formed when the lobes of the combin-
ing atomic orbitals overlap. Answers
128. Which of the following combinations is not allowed   (97)  1   (98)  2   (99)  4 (100)  2 (101)  3
in the LCAO method for the formation of a MO (con- (102)  2 (103)  4 (104)  2 (105)  3 (106)  1
sider the z-axis as the molecular axis)? (107)  4 (108)  2 (109)  1 (110)  2 (111)  3
(1) s + pz (2)  s – px (112)  2 (113)  4 (114)  3 (115)  1 (116)  4
(3)  px – px (4)  pz + pz (117)  2 (118)  2 (119)  4 (120)  2 (121)  3

Chapter_04.indd 19 3/26/2014 2:50:28 PM

 4.20  Objective Chemistry - Vol. I

(122)  4 (123)  4 (124)  4 (125)  4 (126) 3 soluble in water than ethers, aldehydes or ketones
(127)  2 (128)  2 (129)  3 (130)  4 (131) 2 which cannot form hydrogen bonds.
(132)  1 (133)  2 (134)  4 (135)  3 • The solubility of alcohols in water decreases with
increase in the size of alkyl group due to increase in
hydrophobic nature of alkyl group.
• When ammonia is dissolved in water, N-atom in
hydrogen bond ­ammonia form hydrogen bond with H-atom of water
but not H-atom of ammonia with O-atom of water.
• The electrostatic force of attraction between a partially
positive charged hydrogen atom of a molecule and • Due to hydrogen bonding molecules of certain
highly electronegative atom of the same molecule or a ­compounds like perchloric acid, carboxylic acids
different molecule is known as hydrogen bond. ­dimerise and give abnormal molecular weights when
determined by using colligative properties.
• Hydrogen bond is formed when the hydrogen is bonded
to a small highly electronegative atom like F, O, N, etc.
• Primary and secondary amine molecules can associate
due to hydrogen bonding and have more boiling point
• Liquids in which molecules are associated through hy- than tertiary amine which cannot form hydrogen bond
drogen bond are called associated liquids, e.g., H2O, due to the absence of H-atoms.
NH3, HF, alcohol, etc.
• Quaternary bases like [(CH3)4N]OH are stronger than
• Liquids in which hydrogen bonds does not exist be- primary, secondary and tertiary amines due to the ab-
tween their molecules are called normal liquids. sence of H-atoms in quaternary base which can form
• The boiling points of associated liquids are greater hydrogen bonds.
than those of normal liquids. • Due to hydrogen bonding ice has an open structure in
• The energy of hydrogen bond is approximately 40 KJ which O-atom in every water molecule is surrounded
mol–1 (3–10 kcal mol–1) which is relatively small when by 4 Oxygen atoms tetrahedrally and joined by 4 hy-
compared to the 418 KJ mol–1 (100 Kcal mol–1) for a drogen atoms two of which are in covalent bond while
covalent O-H bond. the other two are in hydrogen bonds.
• The bond length of hydrogen bond of 176 pm is higher • In several compounds some water molecules are
than the O-H bond length of 100 pm. ­present as hydrogen bonded water molecules.
E.g., in CuSO4 . 5H2O each Cu2+ ion is surrounded
• Hydrogen bonding is two types:
­octahedrally by six O-atoms four of them being from
(i) intermolecular hydrogen bonding ­water ­molecules and two from two SO42– ions; the
(ii) intramolecular hydrogen bonding ­extra ­water ­molecule is situated between two such
• Intermolecular hydrogen bonding is between two ­octahedral groups linked by hydrogen bonds.
different molecules of the same compound or different • The crystal structure of several compounds is
compounds, e.g., HF, H2O, alcohols, etc. ­dominated by hydrogen bonds. E.g., HF in liquid state
• The compounds containing intermolecular hydrogen has a zig-zag structure due the presence of lone pairs
bonds have high melting points and high boiling points on fluorine atoms.
because more energy is required to break the hydrogen • The strength of hydrogen bond depends on the
bonds. ­magnitude of polarity and size of the atoms and the
• number of hydrogen bonds.
The hydrogen bond in H-F is stronger than in H2O,
yet the boiling point of H2O is higher than HF be- • Though electronegativities of nitrogen and chlorine
cause in HF the hydrogen bond is so strong that it are same (3.0), chlorine has the least tendency to form
can exist in vapour phase also and exist as (HF)6, i.e., hydrogen bonds due to bigger size.
the number of hydrogen bonds broken before it con- • Intramolecular hydrogen bonding is between two
verted into vapour are less. But during the conversion groups of the same molecule. E.g., orthoisomers of
of water into vapour all the hydrogen bonds should nitrophenol, hydroxy benzaldehyde (salicylaldehyde),
be broken. hydroxy benzoic acid (salicylic acid) chlorophenol,
• The solubility of the compounds in water, which can fluorophenol, nitroaniline, etc.
form hydrogen bonds with water is more than those • Due to intramolecular hydrogen bonding, the
which cannot form hydrogen bonds. E.g., alcohol ­molecules of orthoisomers are not associated. So, their
which can form hydrogen bonds with water is more boiling points are less and are steam volatile.

Chapter_04.indd 20 3/26/2014 2:50:29 PM

 Chemical Bonding and Molecular Structure   4.21

• In meta- and para-isomers, intramolecular hydrogen (3) The high heat of vapourisation of water is due to
bonding is not possible due to increase in ring size. hydrogen bonding.
So, molecules of meta- and para-isomers are associ- (4) Acetic acid exists as a dimer in benzene due to
ated with intermolecular hydrogen bonding and hence hydrogen bonding.
have high melting and boiling points. 142. The predominant intermolecular forces in hydrogen
• Molecules of orthoisomers cannot form hydrogen fluoride is due to
bonds with water due to intramolecular hydrogen (1) Dipole-induced dipole interaction
bonding but molecules of meta- and para-isomers (2) Dipole–dipole interaction
can form hydrogen bonds with water molecules. (3) Hydrogen bond formation
So, orthoisomers are less soluble than meta- and (4) Dispersion interaction
para-isomers.
143. Which of the following does not change as a
­consequence of hydrogen bonding in a compound?
(1) colour (2)  boiling point
 Objective Questions (3) density (4)  freezing point
136. Ice has an open structure compared to water due to 144. The hydrogen bonding in oxygen compounds is more
which it floats on water and occupies a greater vol- significant than that in sulphur compounds because
ume of space. The open structure of ice is due to oxygen is
(1) solid state of ice (1) a very small atom compared to the sulphur atom
(2)  its low density (2) more electronegative than sulphur
(3) crystalline nature (3) more reactive than sulphur
(4)  hydrogen bonding (4) a gas whereas sulphur is a solid at room ­temperature
137. Which of the following statement is false? 145. There is no hydrogen bonding in CH4 unlike in H2O
(1) The boiling point of a compound is raised by because
­intermolecular hydrogen bonding. (1) C is not sufficiently electronegative to be linked
(2) o-nitrophenol is more volatile than p-nitrophenol by hydrogen bonds.
because of intramolecular hydrogen bonding. (2) C atom is bigger than O atom.
(3) Lower alcohols such as methanol and ethanol are (3) C in CH4 has no lone pair of electrons.
miscible in water due to hydrogen bonding. (4) CH4 is bigger than H2O.
(4) Intramolecular hydrogen bond enhances the boil- 146. Which one of the following about hydrogen bonding
ing point. is false?
138. The hydrogen bond is strongest in (1) It alters some of the physical properties of the
(1) O–H ....S (2)  S–H .....O compound.
(3) F–H .... F (4)  F–H ....O (2) Not all H-compounds can have hydrogen ­bonding.
(3) The H-atom in a hydrogen bonded pair of atoms
139. The pair likely to form the strongest hydrogen is equidistant from the atoms.
­bonding is (4) Hydrogen bond is a week bond.
(1) H2O2 and H2O
(2) HCOOH and CH3COOH 147. Arrange the following in the decreasing order of
(3) CH3COOH and CH3COOCH3 ­hydrogen bonding CH4, CH3OH, CH3F and CH3NH2.
(4) SiH4 and SiCl4 (1) CH3OH > CH3NH2 > CH3F > CH4
(2) CH3OH > CH3F > CH3NH2 > CH4
140. The maximum possible number of hydrogen bonds in (3) CH3F > CH3OH > CH3NH2 > CH4
which a water molecule can participate is (4) CH4 > CH3F > CH3NH2 > CH3OH
(1) 4 (2)  3
148. The melting point of 2-nitrophenol is lower than that
(3)  2 (4)  6
of 4-nitrophenol and this is because of
141. The false statement among the following is (1) Intramolecular hydrogen bonding in 2-­nitrophenol
(1) Bond energy of covalent O-H bond in water is (2) Intramolecular hydrogen bonding in 4-­nitrophenol
greater than bond energy of hydrogen bond. (3) Intermolecular hydrogen bonding in 2-­nitrophenol
(2) The intermolecular attractive forces vary in the (4) Hydrogen bonding has no relation to the melting
order: water > ether > alcohol. point.

Chapter_04.indd 21 3/26/2014 2:50:29 PM

 4.22  Objective Chemistry - Vol. I

149. The hydrogen bond length is minimum in 157. Pick out the property which is not relevant. In a mol-
(1) HF (2)  H2O ecule, hydrogen bond results in
(3)  H2S (4)  CH3COOH (1) molecule association
(2) abnormal boiling points
150. The relative strength of the hydrogen bond between
(3) high solubility value
the molecules in liquid hydrogen halides can be best
(4) high Van der Waal’s forces
ascertained by a comparison of their
(1) bond dissociation energies
(2) enthalpy changes of vapourisation Answers
(3) freezing points
(4) enthalpy changes of formation (136)  4 (137)  4 (138)  3 (139)  2 (140)  1
151. Although nitrogen and chlorine have the same elec- (141)  2 (142)  3 (143)  1 (144)  2 (145)  1
tronegativity, nitrogen atoms form stronger hydrogen (146)  3 (147)  1 (148)  1 (149)  1 (150)  2
bonds than chlorine atoms. This is due to (151)  2 (152)  3 (153)  3 (154)  1 (155)  3
(156)  3 (157)  4
(1) the basic character of nitrogen
(2) the smaller size of nitrogen
(3) the lesser number of electrons in the nitrogen atom
(4) the inertness of nitrogen atom bond parameters
152. Hydrogen bonding is exhibited by Bond Length
(1) all the molecules containing H-atom
• Bond length is the distance between the nuclei of two
(2) molecules in which two H-atoms are present
covalently bonded atoms.
(3) molecules in which H-atom is covalently bonded
to F, O, N • The magnitude of the bond length between the similar
(4) molecules in which H-atom is bonded to atoms atoms in different molecules is generally same, e.g., O-H
with electronegativity more than 2.1 bond length in H2O or H2O2 or C2H5O-H is the same.
• With increase in the bond order (number of bonds),
153. The normal boiling points of CS2, H2O and CCl4
the bond lengths decreases, e.g., the C-C bond lengths
are 41.3°C, 100°C and 77°C, respectively. In which
in ethane, ethylene and acetylene with single, double
­liquid the intermolecular forces are the weakest?
and triple bonds, respectively are 154 pm, 134 pm and
(1) CCl4 (2)  H2O 120 pm.
(3) CS2 (4)  all are equal
• The bond length also depends on the type of hy-
154. o-nitrophenol is steam volatile, whereas p-­nitrophenol bridisation of the atom with which another atom is in
is not. This is due to bond, e.g., C(sp3)-H(110 pm) > C(sp2)-H(108 pm) >
(1) intramolecular hydrogen bonding present in C(sp)-H(106 pm)
­orthonitrophenol • In diatomic molecules, the bond length is equal to the
(2) intermolecular hydrogen bonding present in sum of the covalent radii of two atoms, if the bond is
­orthonitrophenol purely covalent. But in several cases, the bond length
(3) intermolecular hydrogen bonding present in is less than the sum of the covalent radii of the bonded
paranitrophenol atoms because of partial ionic character and in such
(4) none of these cases the bond length may be calculated as
155. Organic compounds soluble in water contain A – B = rA + rB – 0.09 (χA – χB)
(1) C, H, Cl (2)  C, H where rA and rB are covalent radii of A and B while χA
(3) C, H, O (4)  C, S and χB are electronegativities of A and B.
156. Hydrogen bonds are formed between molecules in • Due to resonance hybridisation, the normal bond
which hydrogen is covalently bonded to an element lengths in several molecules will become less than the
whose atomic radius and electronegativity respec- sum of the covalent radii, e.g., in BF3 the B-F bond
tively are length is shorter than the sum of covalent radii of bo-
(1) large and low (2)  large and high ron and fluorine due to back bonding from fluorine to
(3) small and high (4)  small and low born and resonance hybridisation.

Chapter_04.indd 22 3/26/2014 2:50:29 PM

 Chemical Bonding and Molecular Structure   4.23

• The bond length increases with increase in size of the (3) Bond energy decreases with increase in the lone
atom in similar compounds for the elements in a given pair electrons on bonded atoms.
family. (4) Bond energy of a covalent bond increases with
increase in the difference of electronegativities of
bond energy bonded atoms.

• The energy required to break the bonds in one mole 159. Average bond energy values can be used to calculate
of diatomic molecules or the energy released when a (1) the energy content of the molecule
bond is formed between two atoms to form one mole (2) heat of formation
of substance is known as bond energy. (3) heat of reaction
• The bond energies are expressed as room temperature. (4) all
• The bond energy depends on the type of cleavage. The 160. The term bond energy and dissociation energy
energy required for the heterolytic cleavage of bond is (1) always have the same meaning
higher than required for homolytic cleavage. (2) always have different meaning
• If the bond energy increases, stability of the bond (3) have no correlation with each other
­increases and reactivity of molecule decreases. (4) are same only for diatomic molecules
• σ-bonds are stronger than π-bonds. 161. In the series ethane, ethene and ethyne the C-H bond
• As the number of bonds between two atoms increases, energy is
the bond strength increases. (1) the same in all the three compounds
• The bond energies of similar compounds in a group (2) greatest in ethane
decreases down the group due to increase in bond (3) greatest in ethene
length with increase in atomic size. (4) greatest in ethyne
• With increase in the p-character in the hybrid orbitals
162. The heat of formation of CH4 is 360 k.cal. The heat of
the bond energy decreases sp > sp2 > sp3.
formation of C2H6 is 620 k.cal. The C-C bond energy is
• With increase in the number of lone pairs of electrons
(1) 80 kCal (2)  90 kCal
on bonded atoms, bond energy decreases. e.g.,
(3) 100 kCal (4)  120 kCal
C–C > N–N > O–O
• In multi atom molecules like CH4, the bond energy is 163. The order of relative strengths of bonds formed by sp,
the average value of all bond dissociation energies. sp2 and sp3 hybrid orbitals is
• The heat of a reaction can be estimated from bond (1) sp > sp2 > sp3 (2)  sp < sp2 < sp3
­energy values. (3) sp = sp = sp
2 3
(4)  sp < sp2 > sp3
164. The F-F bond in F2 is weak because of
Bond Angle (1) the high electronegativity of fluorine
(2) the small size of fluorine and the repulsion ­between
• It is the angle between two bonds in a molecule or the the lone pairs of electrons in adjacent ­atoms
angle between the lines joining the nuclei of atoms in
(3) fluorine being the first member of the halogen
a molecule.
family
• It is an average value. (4) the reactivity of fluorine
• It depends on the number and nature of other atoms
165. Energy required to dissociate 4 g of gaseous hydro-
in a molecule and on hybridisation in central atom of
gen into free gaseous atoms is 208 kCal at 25° C. The
a molecule (discussed already in VSEPR theory and
bond energy of H-H is
hybridisation).
(1) 104 kCal (2)  208 kCal
(3) 52 kCal (4)  4 kCal

 Objective Questions 166. The average bond energy of C-C bond is 342 KJ mol–1.
The bond energy of Si-Si bond is
158. Which of the following statement is wrong? (1) = 342 KJ mol–1
(1) Bond length decreases with increase in p-­character.
(2)  <342 KJ mol–1
(2) Bond energy of HF is the highest among ­hydrogen (3) >342 KJ mol–1

halides. (4)  cannot be predicted

Chapter_04.indd 23 3/26/2014 2:50:30 PM

 4.24  Objective Chemistry - Vol. I

167. If the bond distance in H2 is r1 and Cl2 is r2, the bond H2S, SnCl2, SO2, etc.) have any dipole moment greater
distance in HCl is than zero, then they are angular in shape.
(1) r1 + r2 (2)  r1/r2 • AB3 molecules (BF3, BCl3, SO3, CO32–, NO3–, etc.)
r1 r2 having dipole moment zero are planar triangular in
r1 + r2 +
(3)  (4)  2 2 shape but if they have any dipole moment greater than
2 2 zero (NH3, PCl3, NF3, SO32–, etc.), they are pyramidal
168. Bond length decreases with in shape.
(1) increase in size of the atom • AB4 molecules having dipole moment zero (CH4,
(2) increase in the number of bonds between atoms CCl4, SO42–, etc.) have symmetrical tetrahedral struc-
(3) decrease in the number of bonds between atoms ture but if they have any dipole moment greater than
(4) decrease in bond angle zero (CHCl3, CH2Cl2, CH3Cl, etc.) have distorted
169. The correct order of the arrangement of bond length is ­tetrahedral structure.
(1) F2 > N2 > Cl2 > O2 (2) Cl2 > F2 > O2 > N2 • Among geometrical isomers cis-isomers have dipole
(3) O2 > Cl2 > N2 > F2 (3) F2 > Cl2 > N2 > O2 moment greater than zero while trans-isomers have
dipole moment almost equal to zero.
170. The correct order of the O-O bond length in O2, H2O2
and O3 is • Among dichlorobenzenes para-isomers have zero
(1) O2 > O3 > H2 O2 (2)  O3 > H2O2 > O2 d­ ipole moment while orthoisomers have more dipole
(3) H2O2 > O3 > O2 (4)  O2 > H2O2 > O3 moment than metaisomers.
• The dipole moment of a molecule depends on the
­nature of bonds, direction, geometry and bond angles.
Answers
• Because dipole moment is a vector quantity in a
(158)  1 (159)  4 (160)  4 (161)  4 (162)  1 ­molecule it may be polar but the molecule may be
(163)  1 (164)  2 (165)  1 (166)  2 (167)  3 p­ olar or nonpolar.
(168)  2 (169)  2 (170)  3 • Strength of a covalent bond increases with increase in
polarity.
• Dipole moments of NH3, NCl3 and NF3 is in the order
dipole moment NH3 > NCl3 > NF3.
• Whenever atoms with different electronegativities
combine, the resulting molecule has polar bonds with
the bond pair of electrons shifted more towards elec-
tronegative atom.
• Two equal and opposite but separated, electrical N N N
charges in a molecule constitute an electrical dipole
moment. Dipole moment H H Cl Cl F F
µ = charge (Q) × distance between charges (r) H Cl F
• Dipole moment is expressed in terms of coulomb ­metre
(cm units) or Debye unit, D being equal to 3.33564 × • The lone pair moment will be in the outward direction
10–30 cm or 1 Debye = 1 × 10–18 esu cm. from the central atom. In NH3, the bond moments and
• lone pair moment are in the same direction. In NCl3 the
Dipole moment is useful in calculating the per cent
N–Cl bonds are nonpolar as the electronegativities of
ionic character of a polar covalent bond
N and Cl are equal and hence lone pair moment ­exists.
µ
Per cent ionic character = expt × 100 In NF3, the bond moments and lone pair ­moment are
µ ionic acting in opposite direction and hence cancel out. So,
• Dipole moment is an additive vector quantity acting its dipole moment is zero.
in the direction of the chemical bond and so the dipole • The individual bond moments of a triatomic molecule
moment of whole molecule is the vector sum of the such as H2O, H2S, etc. can be calculated from the
constituent dipole moment (such as CO2, BeCl2). d­ ipole moment of the molecule.
• For AB2 type molecules, if dipole moment is zero, the • Observed dipole moment mobs = 2(bond moment)
molecules are linear but if the molecules (such as H2O, (cos q/2) where q is bond angle.

Chapter_04.indd 24 3/26/2014 2:50:31 PM

 Chemical Bonding and Molecular Structure   4.25

177. The bonds between P atoms and Cl atoms in PCl5 are

 Objective Questions likely to be
(1) ionic with no covalent character
171. Which of the following is not correct?
(2) covalent with some ionic character
(1) Among CHCl3, SiCl4, SnCl2 and NH3, the non- (3) covalent with no ionic character
polar molecule is SiCl4. (4) ionic with some metallic character
(2) Among CO2, SO2, H2O and NH3, the one with
zero dipole moment is CO2. 178. Which have zero dipole moment?
(3) Among CH3Cl, CH2Cl2, CHCl3 and CCl4, the one (1) 1,1-dichloroethane
with maximum dipole moment is CHCl3. (2) cis-1,2-dichloroethane
(4) Among Cl-F, F-F, Br-F and Br-Cl, the strongest (3) trans-1,2-dichloroethane
bond is Br-F. (4) none

172. NH3 has a net dipole moment but boron trifluoride 179. Dipole moment is exhibited by
has zero dipole moment because (1) 1,4-dichlorobenzene
(1) B is less electronegative than N (2) 1,2-dichlorobenzene
(2) F is more electronegative than H (3) trans-1,2-dichloroethane
(3) BF3 is pyramidal while NH3 is planar (4) trans-2,3-dichloro 2-butene
(4) BF3 is trigonal planar while NH3 is pyramidal 180. If a molecule of MX3 has zero dipole moment, the
173. Which of the following statements is wrong? sigma bonding orbitals used by M (At. No. < 21) is
(1) pure p (2)  sp hybrid
(1) HCl molecule in the vapour state is an example
(3) sp2 hybrid (4)  sp3 hybrid
of polar covalent bond.
(2) Among CH2Cl2, BF3, NF3 and ClO2, only BF3 181. A molecule containing polar bonds is nonpolar, this is
has zero dipole moment. because of
(3) The dipole moment of NH3 is less than NCl3. (1) small sizes of atoms in the molecule
(4) Anhydrous HCl is a bad conductor of electricity (2) big sizes of atoms in the molecule
but aqueous HCl is a good conductor. (3) the atoms in it being highly electronegative
174. The correct order of decreasing dipole moment is (4) the vector cancellation of the bond moments
(1) HF > SO2 > H2O > NH3 182. H2O has net dipole moment while BeF2 has zero
(2) HF > H2O > SO2 > NH3 ­dipole moment because
(3) HF > NH3 > SO2 > H2O (1) H2O molecule is linear while BeF2 is bent
(4) H2O > NH3 > SO2 > HF (2) BeF2 molecule is linear while H2O is bent
(3) Fluorine is more electronegative than oxygen
175. The electronegativity values of C, H, O, N and S are
(4) Be is more electronegative than oxygen
2.5, 2.1, 3.5, 3.0 and 2.5, respectively. Which of the
following bonds is most polar? 183. Which of the following is wrong?
(1) C-H (2)  N-H (3)  S-H (4)  O-H (1) Among I-F, I-Br, N-H and N-Cl, the nonpolar
176. Which bond angle would result in the maximum dipole one is I-Br.
moment for the triatomic molecule XYZ shown below? (2) The highest polar bond among F-O, C-S, Cl-Br
and N-H is N-H.
Z (3) F2 molecule is nearly 100% covalent.
(4) A triatomic molecule must be either linear with a
bond angle 180° or bent.

θ 184. Which of the following statement is false?

(1) The measurement of dipole moment of a gaseous
Y
X diatomic molecule is a direct indication of bond
polarity.
(1) θ = 90° (2)  θ = 120° (2) For a polyatomic molecule, its dipole moment is
(3) θ = 150° (4)  θ = 180° determined only from bond moments.

Chapter_04.indd 25 3/26/2014 2:50:32 PM

 4.26  Objective Chemistry - Vol. I

(3) SO2 is nonlinear and as a consequence it should • Non-polar resonance structure having more number
have dipole moment. of covalent bonds (without charge separation) is more
(4) Lone pair of electrons present on central atom stable than polar resonance structures (charge separa-
can give rise to dipole moment. tion) having less number of covalent bonds.
185. Which of the following is incorrect? • Increase in the distance between charges in a reso-
(1) The unit of dipole moment is Debye, i.e., 10–18 nance structure decreases the stability due to decrease
esu cm. in attraction between charges.
(2) Dipole moment is a vector quantity. • Resonance structures in which negative charge ­present
(3) Decrease in bond angle of triatomic polar mol- on more electronegative atom and positive charge
ecule decreases the dipole moment. p­ resent on less electronegative atom are more stable
(4) Dipole moment can be used to calculate the mag- than the structures in which negative charge present on
nitude of charge on an atom in a polar molecule. less electronegative atom and positive charge present
on more electronegative atom.
• Resonance gives rise to identical bond lengths in mol-
Answers ecule and extra stability to the molecule.
(171)  3 (172)  4 (173)  3 (174)  2 (175)  4 • More the number of canonical forms having same
(176)  1 (177)  2 (178)  3 (179)  2 (180)  3 energy, more is the resonance energy and more is the
(181)  4 (182)  2 (183)  1 (184)  2 (185)  3 stability of the molecule.
• Bond order in a resonance hybrid structure is
Total number of bonds around the central atom

resonance Total number of atoms aroound the central atom
• If it is possible to write different Lewis diagrams for • For cyclic compounds, the bond order between two
the same molecule or ion, the different Lewis dia- atoms in a ring is
grams are called resonance structures or canonical
Total number of bonds in the ring
structures and the actual structure will be the hybrid
structure of all the resonance structure called reso- Total number of atoms in the ring
nance hybrid structure.
• Resonance structures are only hypothetical and as
such they can never be isolated.
 Objective Questions
• Tautomerism is different from resonance and tau-
tomeric forms exist actually and can be isolated 186. Resonance structures of a molecule should have
sometimes. (1) nearly the same energy contents
• The resonance energy of a substance is the extra sta- (2) same number of paired electrons
bility of the resonance hybrid compared with the most (3) identical arrangement of atoms
stable of the resonating structures. (4) all
187. Which of the following is not characteristic of ­resonance?
rules for writing the resonance (1) The chemical structure shows the constituent
structures ­atoms in the same relative position.
• While writing the resonance structures only the posi- (2) They have nearly the same energy.
tion of electrons must be changed but not the position (3) They have the same number of unpaired ­electrons.
of nuclei of atoms. All resonance structures must be (4) The actual structure can be represented on paper
proper Lewis structures. using conventional symbols.
• All resonance structures must have the same number 188. The different forms of a molecule having different
of unpaired electrons which decide the magnetic char- ­arrangement of atoms are called
acter of the molecule. (1) Tautomers
• More stable resonance structure contributes more to (2)  Isomers
the resonance hybrid and equivalent resonance struc- (3) Canonical forms
tures contribute equally to the hybrid. (4) All

Chapter_04.indd 26 3/26/2014 2:50:33 PM

 Chemical Bonding and Molecular Structure   4.27

189. Resonating forms of a molecule can Answers

(1) be isolated
(2)  cannot be isolated (186)  4 (187)  4 (188)  1 (189)  2 (190)  3
(3) either (1) or (2) (191)  4 (192)  2 (193)  3 (194)  2 (195)  1
(4)  none (196)  3
190. The relatively unimportant contributing structure in
case of H3N is
(1) H − N  = N + = N  − N + ≡ N :
(2)  H − N
 :
 Practice Exercise Level-I
(3) H − N + ≡ N + − N (4)  None
1. Which statement is true?
191. The correct statement about resonating structure is
(1) Absolutely pure water does not contain any ion.
(1) They have no real existence. (2) Some covalent compounds may also give ions in
(2) These are hypothetical structures. aqueous solution.
(3) These structures can never be separated. (3) In aqueous solution only electrovalent com-
(4) All are correct. pounds give ions.
192. A molecule may be represented by three structures (4) Very sparingly soluble substances do not dissoci-
having energies E1, E2 and E3, respectively. The ener- ate in aqueous solution.
gies of these structures follow the order E3 < E2 < E1, 2. Which of the following is correct?
respectively. If the experimental bond energy of the (1) Decrease in bond length means increase in bond
molecule is E0, the resonance energy is strength.
(1) (E1 + E2 + E3) – E0 (2)  E0 – E3 (2) Covalent radius of carbon is less than that of
(3) E0 – E2 (4)  E0 – E1 ­nitrogen.
193. Which of the following conditions is not correct for (3) Single bonds are shorter than double bonds.
resonating structures? (4) Fe (III) chloride cannot exist in the dimeric form,
Fe2Cl6.
(1) The contributing structures must have the same
number of unpaired electrons. 3. Molecules with odd electron bond are
(2) The contributing structures should have similar (1) Paramagnetic
energies. (2) Unstable
(3) The contributing structures should be so written (3) Forms dimers at low temperature
that unlike charges reside on atoms that are far (4) All are correct
apart.
(4) The positive charge should be present on the 4. It is thought that atoms combine with each other such
electropositive element and the negative charge that the outermost orbit acquires a stable configura-
on the electronegative element. tion of eight electrons. If stability were attained with
six electrons rather than with eight, what would be
194. Which is not true for resonance? the formula of the stable fluoride ions?
(1) Canonical forms differ only in electronic (1) F3+ (2)  F+
­arrangement.
(3)  F –
(4)  F2–
(2) Canonical forms differ in atomic as well as elec-
tronic arrangement. 5. In the electronic structure of acetic acid there are
(3) Canonical forms have the same number of un- (1) 16 shared and 16 unshared valence electrons
paired electrons. (2) 16 shared and 8 unshared valence electrons
(4) Cannnical forms are hypothetical. (3) 12 shared and 12 unshared valence electrons
(4) 16 shared and 6 unshared valence electrons
195. Resonance structures can be written for
(1) O3 (2)  NH3 (3)  CH4 (4)  H2O 6. In a crystal, atoms are located at the positions of
(1) maximum potential energy
196. Which of the following do not have resonance (2) minimum potential energy
­structures? (3) zero potential energy
(1) CO32– (2)  NO3– (3)  NH3 (4)  BF3 (4) infinite potential energy

Chapter_04.indd 27 3/26/2014 2:50:34 PM

 4.28  Objective Chemistry - Vol. I

7. Which of the following is false? 13. A bond with maximum covalent character between
(1) The bond formed between two non-metallic two elements is found
­elements is covalent bond. (1) Between atoms of same size
(2) The bond formed between two inert gas atoms is (2) Between identical atoms
Van der Waal’s bond. (3) Between atoms of widely different electronega-
(3) The bond formed between a metal and a ­nonmetal tivities
is electrovalent bond. (4) Between chemically similar atoms
(4) The bond formed between two metallic elements
14. Which of the following involves breaking of covalent
is covalent bond.
bonds?
8. Which of the following compounds is essentially (1) Boiling of H2S (2)  Melting of KCN
­ionic and which is essentially covalent? (3) Melting of SIO2 (4)  Boiling of CF4
  (i)  SiCl4    (ii)  RaO (iii)  KH (iv)  IBr
15. A, B and C are three substances. A does not conduct
(1) All are covalent
electri­city in the solid or liquid state. B conducts
(2) All are ionic
­electri­city both in the fused and solution C conduct
(3) (i) and (iv) are covalent while (ii) and (iii) are
­electricity in aqueous solution but not in liquid state.
ionic
Which of the following statements is false regarding A,
(4) (i) and (iv) are ionic while (ii) and (iii) are covalent
B and C?
9. Covalent compounds are generally soft and have low (1) A has polar covalent linkage.
melting points. However, silica and diamond, though (2) A has nonpolar covalent linkage.
covalent, are hard and have high melting point. This (3) B is ionic in nature.
is because (4) C has polar covalent linkage.
(1) both are made up of small atoms
(2) in both strong forces operate in all directions 16. Molecular shapes of SF4, CF4, and XeF4 are
(3) both occur in nature (1) the same with 2, 0 and 1 lone pairs of electrons,
(4) both have unique crystal structure respectively
(2) the same with 1, 1 and 1 lone pairs of electrons,
10. Comparing HF and KF which one of the following respectively
is true? (3) different with 0, 1 and 2 lone pairs of electrons,
(1) both contain covalent bonds respectively
(2) both contain ionic bonds (4) different with 1, 0 and 2 lone pairs of electrons,
(3) HF is more covalent than ionic, whereas KF is respectively
more ionic than covalent
(4) HF contains ionic bond, whereas KF contains 17. In a change from PCl3 → PCl5 the hybrid state of
­covalent bond phosphorous changes from
11. If the water molecule is linear (1) sp2 to sp3

(2)  sp3 to sp2
(1) it would have a very high boiling point
(2) it would be highly reactive (3) sp3 to sp3d
(3) its dipole moment would be zero (4)  sp3 to dsp2
(4) it would be highly ionic 18. The percentage of ionic character of bond between two
12. Polarisation may be called the distortion of the shape atoms is calculated from the difference between their
of an anion by an adjacently placed cation. Which of (1) ionic radii (2)  electronegativities
the following statements is correct? (3) electron affinities (4) ionisation energies
(1) Minimum polarisation is brought about by a
19. Dipole moment of polar covalent bond is calculated
­cation of low radius.
by the formula µ = d × l in this d is the
(2) A large cation is likely to bring about a large
­degree of polarisation. (1) partial charge formed on the more electronega-
(3) Maximum polarisation is brought about by a tive element
­cation of high charge. (2) partial charge formed on either of the two atoms
(4) A small anion is likely to undergo a large degree (3) sum of the partial charges on the atoms
of polarisation. (4) difference of the partial charges on the atoms

Chapter_04.indd 28 3/26/2014 2:50:34 PM

 Chemical Bonding and Molecular Structure   4.29

20. SnCl4 is a covalent liquid because 25. CaO and NaCl have same crystal structure and
(1) electron cloud of the Cl– ions are weakly polar- ­approximately the same ionic radii. If U is the ­lattice
ised to envelop the cation energy of NaCl, the approximate lattice energy
(2) electron clouds of the Cl– ions are strongly polar- of Ca is
ised to envelop the cation U
(1)  (2)  U (3)  2U (4)  4U
(3) its molecules are attracted to one another by 2
strong Van der Waal’s forces 26. Anhydrous AlCl3 is covalent but AlCl3 . 6H2O is ionic
(4) Sn shows inert pair effect because
21. Which of the following sets of characteristics leads to (1) AlCl3 has a planar triangular structure.
the increase in solubility of ionic substances? (2) The ionisation energy of Al is very low.
(1) high dipole moment, strong attraction by an ion (3) The hydration energy of AlCl3 is very high.
and large solvation energy (4) The hydration energy of AlCl3 compensates for
(2) low dipole moment, weak attraction by an ion the high ionisation energy of aluminium.
and high solvation energy 27. Amongst NO3–, AsO33–, CO32–, ClO3–, SO32– and
(3) high dipole moment, strong attraction by an ion BO33– the non-planar species are
and low solvation energy
(1) CO32–, SO32– and BO33–
(4) High dipole moment, weak attraction between
(2) AsO33–, ClO3– and SO32–
ion and large solvation energy
(3) NO3–, CO32– and BO33–
22. The I 3− ion has (4) SO32–, NO3– and BO33–
(1) 5 equatorial lps on the central I atom and 2 axial 28. A section of the periodic table is given below with
bps in a trigonal bipyramid arrangement elements A, B and X, Y in two groups. Which of the
(2) 5 equatorial lps on the central I atom and 2 axial bonds given below is the least polar?
bps in a pentagonal bipyramid arrangement
A  X
(3) 3 equatorial lps on the central I atom and 2 axial B  Y
bps in a trigonal bipyramid arrangement (1) AX (2)  AY (3)  BX (4)  BY
(4) 2 equatorial lps on the central I atom and 3 axial
bps in a trigonal bipyramidal arrangement 29. Which of the following is not correct for dipole ­moment?
(1) Lone pair of electrons present on central atom
23. The melting point of AlF3 is 1040° C and that of SiF4
can give rise to dipole moment.
is –77°C (it sublimes) because
(2) Dipole moment is a vector quantity.
(1) there is very large difference in the ionic charac- (3) CO2 molecule has no dipole moment since C-O
ter of the Al–F and Si–F bonds. bonds are nonpolar.
(2) in AlF3, Al3+ interacts very strongly with the (4) Difference in electronegativities of combining
neighbouring F– ions to give a three-dimensional atoms can lead to dipole moment.
structure but in SiF4 no interaction is possible
(3) the silicon ion in the tetrahedral SiF4 molecules 30. Total number of electron pairs in PCl5, PCl4+ and
is not shielded effectively from the fluoride ions, PCl6– are respectively
whereas in AlF3, Al3+ ion is shielded on all sides (1) 20, 16, 24 (2)  24, 16, 20
(4) the attractive forces between the SiF4 ­molecules (3) 16, 20, 24 (4)  24, 20, 16
are strong, whereas those between AlF3 ­molecules 31. The shape of PCl5, PCl4+ and PCl6– molecules or spe-
are weak cies are respectively
24. The true statements from the following are (1) Octahedral, tetrahedral and trigonal bipyramidal
  (i)  PH5 and BiCl5 do not exist (2) Tetrahedral, octahedral and square planar
(ii)  pπ-dπ bond is present in SO2 (3) Trigonal bipyramidal, tetrahedral, octahedral
(4) Trigonal bipyramidal, octahedral and square ­planar
(iii)  electrons travel at the speed of light
  (iv)  SeF4 and CH4 have same shape 32. Which of the following is correct?
  (v)  I3+ has bent geometry (1) The number of electrons present in the valence
 (1)  i, iii (2)  i, ii, v shell of S in SF6 is 12.
 (3) i, iii, v (4)  i, ii, iv (2) The rate of ionic reactions is very slow.

Chapter_04.indd 29 3/26/2014 2:50:35 PM

 4.30  Objective Chemistry - Vol. I

(3) According to VSEPR theory SnCl2 is a linear 41. The molecule MLx is planar with six pairs of
molecule. ­electrons around M in the valence shell. The value
(4) The correct order of ability to form ionic com- of x is
pounds among Na+, Mg2+ and Al3+ is Al3+ > (1) 6 (2)  2
Mg2+ > Na+. (3)  4 (4)  3
33. If the boiling point of ethanol (molecular weight = 42. Which of the following statements is not correct for
46) is 78°C what is the boiling point of diethyl ether sigma and pi bonds formed between two carbon ­atoms?
(molecular weight = 74)?
(1) Sigma bond is stronger than pi bond.
(1) 100°C (2)  78°C (2) Bond energies of sigma bond and pi bonds are of
(3) 86°C (4)  34°C the order 264 KJ mol–1 and 347 KJ mol–1.
34. The bond order of the species with orbital configura- (3) Free rotation of atoms about the sigma bond is
tion s(1s)2 s*(1s)2 s(2s)2, s*(2s)2, s(2pz)1 will be allowed but not in case of pi bond.
(1) 0.5 (2)  2 (4) Sigma bond determines the direction between
(3)  3 (4)  0 carbon atoms but a pi bond has no primary effect
in this regard.
35. If the bond length and dipole moment of diatomic
molecule are 1.25 Å and 1.0 D, respectively, what is 43. Which of the following statements is correct?
the per cent ionic character of the bond? (1) All carbon to carbon bonds contain a sigma bond
(1) 10.66 (2)  12.35 and one or more pi bonds.
(3) 16.66 (4)  19.33 (2) All oxygen to hydrogen bonds are hydrogen bonds.
36. Which of the following statements about LiCl and (3) All carbon to hydrogen bonds are sigma bonds.
NaCl is wrong? (4) All carbon to carbon bonds are sigma bonds.
(1) LiCl has lower melting point than NaCl. 44. For two ionic solids CaO and KI, identify the wrong
(2) LiCl dissolves more in organic solvents, whereas statement among the following
NaCl does not. (1) lattice energy of CaO is much larger than of KI
(3) LiCl would ionise in water more than NaCl. (2) KI is soluble in benzene
(4) Fused LiCl would be more conducting than fused (3) CaO has higher melting point
NaCl.
(4) KI has lower melting point
37. In an ionic compound A+X– the degree of covalent
45. A diatomic molecule has dipole moment of 1.2 D. If
bonding is greatest when
its bond distance is 1.0 Å, what fraction of electric
(1) A+ and X– ions are small. charge “e” exist on each atom?
(2) A+ is small and X– is large.
(1) 12% of e (2)  18% of e
(3) A+ and X– ions are approximately of the same size.
(3) 25% of e (4)  30% of e
(4) A+ and X– ions are larger.
46. Consider the following reactions
38. Which of the following statements is correct?
(a) 2K(s) + Cl2(g) → 2KCl(s)
(1) FeCl2 is more covalent than FeCl3.
(2) FeCl3 is more covalent than FeCl2. (b) Ca(s) + Cl2(g) → CaCl2(s)
(3) Both FeCl2 and FeCl3 are equally covalent. Which of the following statements is correct?
(4) FeCl2 and FeCl3 do not have any covalent ­character. (1) Reaction (b) is more exothermic than (a).
(2) Reaction (a) releases more heat per mole of Cl2
39. The hybridisation of phosphorous in POCl3 is the
used.
same as in
(3) Reaction (b) release more heat per mole of Cl2 used.
(1) P in PCl3 (2)  S in SF4
(4) The heat liberated per mole Cl2 in both reactions
(3) Cl in ClF3 (4)  B in BCl3
is same.
40. The correct order of the bond angle is
47. Which reaction involves change in the electron pair
(1) NH3 > H2O > PH3 > H2S geometry for the underlined atom?
(2) NH3 > PH3 > H2O > H2S
(1) BF3 + F– → B F4− (2) NH3 + H+ → NH4+
(3) NH3 > H2S > PH3 > H2O
(4) PH3 > H2S > NH3 > H2O (3) 2SO2 + O2 → 2SO3 (4) H2O + H+ → H3O+

Chapter_04.indd 30 3/26/2014 2:50:35 PM

 Chemical Bonding and Molecular Structure   4.31

48. In solid NH3, each NH3 molecule has 6 other NH3 (3) the carbon atom has four valence electrons
molecules as nearest neighbours. ∆H of sublimation (4) maximum covalency carbon is three
of NH3 at the melting point is 30.8 KJ mole–1 and 55. Which of the following compounds has the elec-
the estimated ∆H of sublimation in the absence of tron pair geometry as trigonal bipyramidal with
­hydrogen bonding is 14.4 KJ per mole. The strength three equatorial positions occupied by lone pairs of
of H bond in solid NH3 is ­electrons?
(1) 5.5 KJ mole–1 (2)  16.4 KJ mole–1 (1) AlCl3 (2)  XeF2
–1
(3) 2.7 KJ mole (4)  –8.7 KJ mole–1 (3) Pt (NH3)2Cl2 (4)  CH3MgBr
49. In BrF3 molecule the lone pairs occupy equatorial 56. Which pair of substances will have the most similar
­position to minimise geometry?
(1) lone pair-bond pair repulsion only (1) SO3, SO32− (2)  SO3, SO2−4
(2) bond pair-bond pair repulsion only (3) SO3, CO3 2−
(4)  SO24− , CO32−
(3) lone pair-lone pair repulsion and lone pair-bond
pair repulsion 57. Consider the species NO3–, NO2+ and NO2– and pick up
(4) lone pair-lone pair repulsion only the correct statement.
(1) The hybrid state of N in all the species is same.
50. In X-H .... Y, X and Y both are electronegative ­elements
(2) The shapes of both NO2+ and NO2– is bent while
(1) electron density of X will increase and on H will NO3– is planar.
decrease (3) The hybrid state of N in NO3– and NO2– is same.
(2) in both electron density will increase (4) The hybrid state of N in NO2+ is sp2.
(3) in both electron density will decrease
(4) on X electron density will decrease and on H will 58. In Lewis formula of chromyl chloride CrO2Cl2
increase    (I)  one O-O bond is present
  (II)  one O-Cl bond is present
51. Polarising action of Cd2+ ion on anions is stronger
(III)  two O-Cl bonds are present
than that of Ca2+ because
(1) I and II are correct
(1) the charge of the ions are same
(2)  I and III are correct
(2) their radii are same (Ca2+ = 0.104 nm, Cd2+ =
(3) Only I is correct
0.0.99 nm)
(4)  All are wrong
(3) the Ca2+ ion has noble gas electron configuration
and the Cd2+ ion, an 18-electron configuration of 59. In a chemical change PCl5 → PCl3 + Cl2
its outer shell    (I)  Chlorine atoms are reduced.
(4) all are correct   (II)  P changes its hybrid state from sp3d to sp3.
52. Select correct statement. (III)  Angle around P also undergoes change.
(1) Cations with 18 electron shell have greater polar- (1) I and II are correct (2)  I and III are correct
ising power than the cations with 8-electron shell. (3) II and III are correct (4)  All are correct
(2) Inner electrons have poor shielding effect on 60. Homolytic fission of C-C bond of ethane (C2H6)
the nucleus and thus electronegativity of the which gives an intermediate in which carbon atom is
18-­electron shell is increased.
(1) sp3 hybridised (2)  sp2 hybridised
(3) CuCl is covalent and NaCl is ionic. (3) sp hybridised (4)  sp3d hybridised
(4) All are correct statements.
61. Calcium carbide gets hydrolysed to form acetylene gas
53. Which pair is not in the correct order of lattice energy?
   (I)  Hybrid state of C does not change.
(1) KCl > MgO (2)  AlN > MgO
  (II) Bonding between the carbon atom does not
(3) AlF3 > AlCl3 (4)  BeCO3 > Mg CO3
change.
54. Covalency of carbon in the CO molecule is three (III) Boiling point of carbon compounds does not
­because change.
(1) an unexcited carbon atom has two unpaired (1) I and II are correct
­electrons (2)  only II is correct
(2) the carbon atom can be an acceptor of an (3) I and III are correct
electron pair (4)  II and III are correct

Chapter_04.indd 31 3/26/2014 2:50:37 PM

 4.32  Objective Chemistry - Vol. I

62. Molecule having maximum number of covalent bonds is (3) Structures II and IV contribute to greater extent
(1) NH4OH (2)  NH4Cl to the resonance hybrid.
(3) (NH2)2CO (4)  CH3OH (4) The B-F bond has been found to possess
p-character.
63. The molecules which contains sp3d2 and p orbitals
overlapping in it is 2. The geometrical shapes of XeF5+ , XeF6 and TaF8
(1) PCl5 (2)  BrF5 (3) ClF3 (4)  IF7 ­respectively are
(1) Trigonal bipyramidal, octahedral and square ­planar
64. On catalytic hydrogenation, ethylene gives ethane. (2) Square-based pyramidal, distorted octahedral
During this reaction and octahedral
(1) Hybridisation of carbon atoms changes from sp2 (3) Planar pentagonal, octahedral and square anti-
to sp3. prismatic
(2) Bond angle decreases from 120° to 109.5°. (4) Square-based pyramidal, distorted octahedral
(3) C-C bond length increases from 1.34 Å to 1.54 Å. and square antiprismatic
(4) All of these.
3. Which of the following statements is/are true regard-
ing ICl2– ion?
Answers (1) I atom is sp3d hybridised.
(2) The three lone pairs occupy equatorial positions
  (1) 2   (2) 1   (3) 4   (4) 2   (5) 2
and two bond pairs the axial positions giving rise
  (6) 2   (7) 4   (8) 3   (9) 2 (10) 3
to linear shape.
(11) 3 (12) 3 (13) 2 (14) 3 (15) 1
(3) ICl acts as Lewis acid and Cl– ion acts as Lewis
(16) 4 (17) 3 (18) 2 (19) 2 (20) 2
base.
(21) 4 (22) 3 (23) 2 (24) 2 (25) 4
(4) All of the above.
(26) 4 (27) 2 (28) 2 (29) 3 (30) 1
(31) 3 (32) 1 (33) 4 (34) 1 (35) 3 4. CrO2Cl2 has
(36) 3 (37) 2 (38) 2 (39) 1 (40) 1 (1) tetragonal structure
(41) 3 (42) 2 (43) 3 (44) 2 (45) 3 (2) distorted tetrahedral structure
(46) 2 (47) 1 (48) 3 (49) 4 (50) 1 (3) square pyramidal structure
(51) 3 (52) 4 (53) 1 (54) 2 (55) 2 (4) octahedral structure
(56) 3 (57) 3 (58) 4 (59) 3 (60) 2
(61) 1 (62) 3 (63) 2 (64) 4 5. Consider the statements
   (I)  Bond length in N2+ is 0.02 Å greater than in N2.
 (II)  Bond length in NO+ is 0.09 Å less than in NO.
(III)  O22– has a shorter bond length than O2.
Then, which of the following is correct?
(1) I and III (2)  II and III
 Practice Exercise Level-II
(3) I and II (4)  I, II and III
1. Which of the following statements is correct about
6. Which has maximum dipole moment?
the molecular structure of boron triflouride?
F F (1) Cl (2)  Cl
 I. F – B + – Cl
II. F = B Cl Cl
F F
F+ F
– – Cl
III. F – B IV. F – B
F (3) Cl (4)  Cl
F+

(1) All the structures contribute equally to the

­resonance hybrid.
(2) Structure I contributes maximum to the ­resonance Cl Cl
hybrid. Cl

Chapter_04.indd 32 3/26/2014 2:50:39 PM

 Chemical Bonding and Molecular Structure   4.33

7. The correct order of increasing s-character (in per- (3) FNO is angular with 1.81 D dipole moment while
centage) in the hybrid orbitals of the following FNO2 is planar triangular shape with 0.47  D
­molecules/ions is ­dipole moment.
  (I)  CO32−  (II)  H2S (III)  NH3 (4) FNO is angular with 1.81 D dipole moment while
(IV)  CCl4 (V)  BeCl2 FNO2 is pyramidal with dipole moment 0.47 D.
(1) II < III < IV < I < V 14. In the molecules of the type AXLn (where L repre-
(2) II < IV < III < V < I sents lone pair “n” its number) then exists a bond
(3) III < II < I < V < IV ­between elements A and X. The XAX angle
(4) II < IV < III < I < V
(1) always decreases if n increases
8. Select the pair of compounds in which both have (2) always increases if n increases
different hybridisation but have same molecular (3) will be minimum for n = 3
­geometry.
− (4) will always be less than 180° if n = 0
(1) BF3, BrF3 (2)  ICI 2 , BeCl2
(3) BCl3, PCl3 (4)  PCl3, NCl3 15. Identify the correct statements.
9. PCl5 undergoes   (I)  N3– is linear
(1) s p3 d z2 hybridisation   (II)  ClF3 has a dipole moment.
(2) sp3d x2 − y2 hybridisation   (III)  SF4 has distorted tetrahedral (see-saw) shape.
(3) sp3dxy hybridisation (IV)  XeF4 is tetrahedral in shape.
(4) sp3dxy hybridisation (1) only III and IV are correct
(2) only I, II and III are correct
10. In ICl4–, the shape is square planar. The number of
bond pair-lone pair repulsion at 90° are (3) only I and II are correct
(1) 6 (2)  8 (3)  12 (4)  4 (4) all the above are correct

11. A molecule XY2 contains two s, two p bonds and one 16. Delocalisation of charge may be expected in the spe-
lone pair of electrons in the valence shell of x. The cies of the formula
arrangement of lone pair as well as bond pairs is    (I)  N2H4  (II)  NO3–
(1) Square pyramidal (2) Linear (III)  HNO3 (IV)  NH4+
(3) Triangular planar (4) Unpredictable (1) I, II and III only correct
12. Nodal planes of p-bonds in CH2 = C = C = CH2 are (2) I and III only correct
located in (3) II and IV only correct
(1) all are in molecular plane (4) II and III only correct
(2) two in molecular plane and one in plane perpen-
dicular to molecular plane which contains C-C 17. Arrange the following in the increasing order of their
bonds bond angles.
(3) one in molecular plane and two in plane perpen-    (I)  NH3  (II)  N(CH3)3
dicular to molecular plane which contains C-C- (III)  N(SiH3)3 (IV)  NF3
bonds (1) I > II > III > IV
(4) two in molecular plane and one in a plane per- (2)  II > I > IV > III
pendicular to molecular plane which bisects C-C (3) II > III > I > IV
bonds at right angle (4)  III > II > I > IV
13. Between the molecules FNO and FNO2 one has 18. The electronic configuration of B2 molecule is dif-
­dipole moment of m = 1.81 D and the other has m = ferent from the electron configuration of F2 molecule
0.47 D. On the basis of VSEPR consideration assign due to mixing of
the shapes and dipole moments to the two molecules.
(1) σs and σ2s orbitals
(1) FNO is angular with 0.47 D dipole moment while
(2) σ2s and σ2p orbitals
FNO2 is pyramidal with dipole moment 1.81 D. *
(3) π 2s and σ2p orbitals
(2) FNO is linear with 1.81 D dipole moment while
* *
FNO2 is planar triangular with dipole moment 0.47. (4) π2s and π 2p orbitals

Chapter_04.indd 33 3/26/2014 2:50:41 PM

 4.34  Objective Chemistry - Vol. I

19. Which of the following is not a correct statement? 26. The geometry of ammonia molecule can be best
(1) Every AB5 molecule does not in fact have square ­described as
pyramidal structure. (1) Nitrogen at one vertex of a regular tetrahedron,
(2) Multiple bonds are always shorter than corre- the other three vertices being occupied by the
sponding single bonds. three hydrogens.
(3) The electron-deficient molecules act as Lewis (2) Nitrogen at the centre of the tetrahedron, three of
­acids. the vertices being occupied by three hydrogens.
(4) The canonical structure has no real existence. (3) Nitrogen at the centre of equatorial triangle, three
corners being occupied by three hydrogens.
20. The tetrahedral geometry of methane instead of (4) Nitrogen at the junction of a “T” three open ends
square planar structure is supported by being occupied by three hydrogens.
(1) its dipole moment value
27. In which of the following compounds B-F bond
(2) its monochlorination
length is shortest?
(3) its dichlorination
(1) BF4– (2)  BF3 ← NH3
(4) its trichlorination
(3) BF3 (4)  BF3 ← N(CH3)3
21. Which of the following about SF4, OSF4 and COF2
28. Which molecular geometry is least likely to result
molecules is correct?
from a trigonal bipyramidal electron pair geometry?
(1) Equatorial FSF bond angle in OSF4 will be less (1) Trigonal planar (2)  See-saw
than in SF4molecule. (3) Linear (4)  T-shaped
(2) Hybridisation state of sulphur in SF4 and OSF4
molecules will be different. 29. Give the correct order of initials “T” or “F” for fol-
(3) The bond angle FCO will be greater than 120° in lowing statements. Use “T” if statement is true and
the molecule OCF2. “F” if statement is false
(4) The axial FSF bond angle in SF4 is 180°. (I) The order of repulsion between different pair of
electrons is lp – lp > lp – bp > bp – bp.
22. Which of the following set of species have planar  (II) In general, as the number of lone pair of elec-
structures? trons on central atom increases, value of bond
(1) I 3− .CH 3 , CIO3− , SiF62 − angle from normal bond angle also increases.
(2) I 3− .ICl 4− , Al 2 Cl6 , TeCl 4 (III) The number of lone pairs on O in H2O is 2 while
(3) SCl2, N2O5, SF4, XeO4 on N in NH3 is 1.
(4) I 2 Cl6 , XeF2 , BrF4− , XeF4 (IV) The structure of xenon fluorides and xenon oxy-
fluorides could not be explained on the basis of
23. In the following species, the one having a planar VSEPR theory.
structure is
(1) TTTF (2)  TFTF
(1) BF4– (2)  SnCl4 (3)  TFTT (4)  TFFF
(3) BrF4– (4)  NH4+
30. The compound MX4 is tetrahedral. The number of
24. H2, Li2, B2 each has bond order equal to 1, the order
XMX angles in the compound is
of their stability is
(1) three (2)  four (3) five (4) six
(1) H2 = Li2 = B2 (2)  H2 > Li2 > B2
(3) H2 > B2 > Li2 (4)  B2 > Li2 > H2 31. The HOMO in nitric oxide molecule is
25. Which of the following given facts are correct? (1) π2py = π2px
  (I)  Bond length order: H 2− = H 2+ < H 2. * *
(2)  π2py = π 2px
 (II)  O+2 , NO, N 2− have same bond order of 2.5.
 (III) Bond order can assume any value including (3) σ2pz
zero. *
(4)  σ 2pz
(IV) NO3− , CO32 − have same bonder for X-O bond
(where X is central atom). 32. A simplified application of MO theory to the hypo-
(1) I, II and III (2)  I and IV thetical molecule “OF” would give its bond order as
(3) II and IV (4)  I, II, III and IV (1) 2 (2)  1.5 (3)  1.0 (4)  0.5

Chapter_04.indd 34 3/26/2014 2:50:43 PM

 Chemical Bonding and Molecular Structure   4.35

33. Select the false statement about N2F4 and N2H4 d­ ifference in size between Cl– and Br– ions is due to
  (I) In N2F4, d-orbitals are contracted by electron- the fact that
egative fluorine atoms, but d-orbital contraction (1) the Br– ion contains ten 3d electrons, which fail
is not possible by H atom in N2H4. to shield the nuclear charge effectively.
  (II) The N-N bond energy in N2F4 is more than N-N (2) the Br- ion contains ten 3d electrons, which shield
bond energy in N2H4. the nuclear charge effectively.
  (III) The N-N bond length in N2F4 is more than that (3) the Br- ion contains six 4p electrons which shield
of in N2H4. the nuclear charge effectively.
(IV) The N-N bond length in N2F4 is less than that of (4) the Br- ion contain ten 3d electrons and six 3p
in N2H4. electrons, together they shield the nuclear charge
Choose the correct code. effectively.
(1) I, II and III (2)  I and III
41. Both the lattice energy (∆U0) and hydration ­enthalpy
(3) II and IV (4)  II and II
(∆Hh) of a binary salt are negative quantities.
34. If there is no sp mixing, the bond order and magnetic ­However, if ∆U0 is more negative than ∆Hh then
character in C2 molecule is (1) the salt will not dissolve in water
(1) 1 and paramagnetic (2) 1 and diamagnetic (2) salt will dissolve in water
(3) 2 and paramagnetic (4) 2 and diamagnetic (3) dissolution of salt in water is exothermic
35. The strongest P-O bond is formed in the molecule (4) dissolution of salt in water is endothermic
(1) F3P = O (2)  Cl3P = O 42. The melting point of RbBr is 682 °C while that of
(3) Br3P = O (4)  (CH3)3P = O NaF is 988 °C. The principal reason for this fact is
36. F-As-F bond angle in AsF3Cl2 can be (1) the molar mass of NaF is smaller than that of
(1) 90° and 180° only (2) 120° only RbBr
(3) 90° and 120° only (4) 90° only (2) the bond in RbBr has more covalent character
than the bond in NaF
37. Arrange the ions in the increasing order of their bond (3) the difference in electronegativity between Rb
angles. and Br is smaller than the difference between Na
(1) ClO3– > BrO3– > IO3– and F
(2) IO3– > BrO3– > ClO3– (4) the internuclear distance rc + ra is greater for
(3) ClO3– > IO3– > BrO3– RbBr than for NaF
(4) BrO3– > ClO3– > IO3–
38. In [ICl2] – ion the lone pairs present in iodine atom are Answers
separated at an angle of
(1) 90° (2)  120°   (1) 4   (2) 4   (3) 4   (4) 2   (5) 3
(3)  180° (4)  60°   (6) 2   (7) 1   (8) 2   (9) 1 (10) 2
(11) 3 (12) 2 (13) 3 (14) 3 (15) 2
39. Solubility of alkali metal fluorides increases down the (16) 3 (17) 4 (18) 2 (19) 1 (20) 3
group. Select the correct option for the given ­statement. (21) 3 (22) 4 (23) 3 (24) 3 (25) 4
(1) Hydration energy increases and lattice energy (26) 2 (27) 3 (28) 1 (29) 2 (30) 4
­decreases down the group. (31) 2 (32) 2 (33) 2 (34) 3 (35) 1
(2) Both energies decreases down the group but (36) 1 (37) 1 (38) 2 (39) 3 (40) 1
­decrease in hydration energy is rapid. (41) 1 (42) 4
(3) Both energies decrease down the group but
­decrease in lattice energy is rapid.
(4) Both energies increase down the group but
­increase in hydration energy is rapid.  Statement-Type Questions
–
40. The radius of Cl ion is 38% larger than that of the In the following questions, a statement I is given and a
F– ion but the radius of the Br– ion is only 6.5% c­ orresponding statement II is given below it. Mark the
larger than that of the Cl– ion. The relatively small ­correct answer as

Chapter_04.indd 35 3/26/2014 2:50:44 PM

 4.36  Objective Chemistry - Vol. I

(1) I f both statement I and statement II are true and state- 9. Statement I: The bonds formed by hydrogen are
ment II is the correct explanation of ­statement I. mainly covalent.
(2) If both statement I and statement II are true but state- Statement II: The ionisation potential of hydrogen
ment II is not the correct explanation for statement I. is 13.6 ev, which is very high. The energy required to
(3) If statement I is true but statement II is false. remove the electron from a hydrogen atom (13.6 ev)
(4) If statement II is false but statement II is true. is a very large amount of energy.

1. Statement I: In formaldehyde (HCHO) all four 10. Statement I: HF is the compound most likely to con-
­atoms are in the same plane. tain H+ ions.
Statement II: The carbon atom in formaldehyde is Statement II: Since it has the greatest difference in
sp3 hybridised. electronegativity between H and F.
2. Statement I: Ionic reactions are usually rapid while 11. Statement I: The atoms of a covalent molecule are
covalent compounds usually react slowly. said to share electrons, yet some covalent molecules
are polar.
Statement II: In ionic reactions, the reacting species
have ions only to collide, while covalent compounds Statement II: In a polar covalent molecule the shared
involve reactions which usually involve breaking a electrons spend more time on the average near one of
bond and substitution or addition of another group. the atoms.
Thus collision between the reactant molecules will
12. Statement I: Larger molecules with greater ­number
only cause reaction if they have sufficient energy.
of electrons are generally more polarisable than
3. Statement I: IF7 is perhaps the only example of ­seven smaller molecules.
orbitals and sp3d3 hybridisation.
Statement II: The further away the electrons are
Statement II: Because it has trigonal bipyramidal from nucleus the easier to polarise the electron cloud.
structure.
13. Statement I: Polar molecules have higher melting
4. Statement I: π-bonds are never included in hybridi- and boiling points than non-polar compounds of sim-
sation. ilar nature and molecular size.
Statement II: All the orbitals in the outer shell are Statement II: In addition to Van der Waal’s attractive
hybridised. forces there is also dipole–dipole attraction.
5. Statement I: Generally the polarising power increas-
14. Statement I: Liquids that are hydrogen bonded have
es as ions becomes smaller and more highly charged.
higher boiling points than non-hydrogen bonded liq-
Statement II: The polarisability of a negative ion is uids of similar molecular size and shape.
due to the fact that the electrons are less firmly bound.
Statement II: Because hydrogen bonds are much
6. Statement I: Large negative ions are more polaris- stronger than Van der Waal’s forces.
able than small ones.
15. Statement I: Hydrogen bonds are strongest when all
Statement II: Covalent bonding is favoured by small the atoms lie along the straight line as in HF.
positive ion, large negative ion and large charge on
either ion. Statement II: Each water molecule in ice is hydrogen
bonded to four others in a three-dimensional ­array.
7. Statement I: A white precipitate is formed on
­addition of AgNO3 solution to sodium chloride. No 16. Statement I: Substances of higher molecular weight
such precipitate is obtained on addition of AgNO3 to have higher melting and boiling points.
­methyl chloride. Statement II: The magnitude of Van der Waal’s
Statement II: Silver nitrate is an ionic compound. ­forces increases with increase in molecular size.
8. Statement I: SiF4 is nonpolar even though fluorine is 17. Statement I: Octet theory cannot account for the
much more electronegative than silicon. shape of the molecule.
Statement II: The four bond dipole vectors sum to Statement II: Octet theory can predict relative stabil-
zero. ity and energy of a molecule.

Chapter_04.indd 36 3/26/2014 2:50:44 PM

 Chemical Bonding and Molecular Structure   4.37

18. Statement I: Ionic bond is nondirectional. 29. Statement I: In NH3, the H-N-H bond angle is 107.8°
instead of the expected value of 109°.28°.
Statement II: Each ion is surrounded by a uniformly
Statement II: The lone pair-bond pair repulsion is
distributed electric field.
greater than the bond pair-bond pair repulsion.
19. Statement I: Water is one of the best solvent. 30. Statement I: In N2 molecule, the N atoms are bonded
Statement II: Hydrogen bonding is present in water by one s and two p bonds.
molecule. Statement II: N atoms assume sp2 hybrid state to
constitute N2 molecule.
20. Statement I: Born–Haber cycle is based on Hess’s
law.
Answers
Statement II: Lattice enthalpy can be calculated by
Born–Haber cycle.
  (1) 3   (2) 1   (3) 3   (4) 3   (5) 2
21. Statement I: The lesser the lattice enthalpy the more   (6) 4   (7) 2   (8) 1   (9) 1 (10) 1
stable is the ionic compound. (11) 1 (12) 1 (13) 1 (14) 1 (15) 2
(16) 1 (17) 3 (18) 1 (19) 2 (20) 2
Statement II: The lattice energy is higher for ions of
(21) 4 (22) 2 (23) 4 (24) 4 (25) 1
higher charge and smaller size.
(26) 1 (27) 1 (28) 1 (29) 2 (30) 3
22. Statement I: BF3 molecule has zero dipole moment.

Statement II: F is more electronegative and B-F

bonds are polar in nature.

23. Statement I: LiCl is more ionic than NaCl.  Match the Following Type Questions
Statement II: Smaller the size of cation, greater is 1. Match the type of hybridisation given in List I with
the polarising power. the geometry given in List II.
24. Statement I: Bond energy of F2 is greater than Cl2. List-I List-II
Statement II: F atom is smaller in size than Cl. (A) sp hybridisation   (i) square planar
(B) dsp2 hybridisation  (ii) tetrahedral
25. Statement I : FeCl3 is more covalent than FeCl2. 3
(C) sp d hybridisation (iii) linear
Statement II: Greater the charge on the cation, great- (D) sp3 hybridisation   (iv) trigonal bipyramid
er is the covalent character.
The correct matching is
26. Statement I: The bond angle in PBr3 is greater than
PH3 but the bond angle in NBr3 is less than that of NH3. S.No. A B C D
1. i ii iii iv
Statement II: Size of Br is less than hydrogen.
2. ii iv iii i
27. Statement I: The electronic structure of O3 is 3. iii i iv ii
+ 4. iv ii iii i
O
O O–
O 2. Match the geometry given in List I with the molecule
ion given in List II.
Statement II: O O structure is not allowed
­because octet around “O” cannot be expanded. List-I List-II
28. Statement I: Bond dissociation energy refers to (A) Pyramidal   (i) SF6
­energy changes during the gaseous state. (B) Angular  (ii) ClO3–
(C) Octahedral (iii) PCl5
Statement II: Bonds cannot break in the liquid and
(D) Trigonal bipyramidal   (iv) SO2
solid phase.

Chapter_04.indd 37 3/26/2014 2:50:45 PM

 4.38  Objective Chemistry - Vol. I

The correct matching is The correct matching is

S.No. A B C D S.No. A B C D
1. ii iv iii i 1. i Iii iv ii
2. ii iv i iii
3. iii ii iv i 2. i iv ii iii
4. ii iv i iii 3. iii iv i ii
4. ii iii i iv
3. Match the molecule given List I with the geometry in
List II.
List-I List-II
(A) CH4   (i) Plane triangular
Answers
(B) BeF2  (ii) Linear
(C) BF3 (iii) V-shaped (1) 3 (2) 2 (3) 2 (4) 2 (5) 3
(D) H2O   (iv) Tetrahedral

The correct matching is

S.No. A B C D
hints
1. i ii iv iii
2. iv ii i iii Multiple Choice Questions with Only One
3. ii i iv iii Answer
4. ii iv iii i
1. NOCl can be represented with only one Lewis dia-
4. Match the property given in List I with the molecule gram O::N:Cl. We cannot write other Lewis diagrams
given in List II. for NOCl but for other molecules more than one
Lewis diagram can be written.
List-I List-II
(A) Zero dipole moment, non-polar bonds   (i) BF3
4. Chlorine atom can form only one bond.
(B) Zero dipole moment polar bonds  (ii) O2 6. N≡N-O has octet for atoms but in other atoms some
(C) Molecule with higher dipole moment (iii) CHCl3 atoms are having more than octet or less than octet.
(D) Molecule having lower dipole moment   (iv) CH3Cl 21. Due to small size and more charge Mg2+ has more
­polarising power and also due to more negative
The correct matching is charge and large size S2– has more polarisability.
S.No. A B C D So, MgS will have more covalent character with less
1. i ii iii iv
­solubility.
2. ii i iv iii 22. Fajan’s rules.
3. iv iii ii i
23. Fajan’s rules.
4. i ii iv iii
r
24. With increase in c value, coordination number
5. Match the property given in List I with the compound ­increases. ra
given in List II.
30. Lattice energy involves only due to attraction ­between
List-I List-II ions but formation energy involves different factors
(A) Intermolecular hydrogen bonding   (i) Ne like sublimation, ionisation of neutral atoms, bond
(B) Intramolecular hydrogen bonding  (ii) NaCl breaking, etc.
(C) Van der Waal’s forces (iii) H2O 31. Covalency is the number of electron pairs shared.
(D) Strongest bonding   (iv) OH
32. AlI3 is more covalent.
OH
(NH +4 - zero lp, NH3 1 lp, NH 2− - 2lp with increase in
the number of lp, bond angle decreases.)

Chapter_04.indd 38 3/26/2014 2:50:50 PM

 Chemical Bonding and Molecular Structure   4.39

53. N ≡ C C≡N 167. Bond length is equal to the sum of the covalent radii
of two atoms in a covalent bond.
C = C 169. Chlorine is larger than fluorine, in O2 and N2 there are
double bond and triple bond, respectively.
N≡C C≡N
170. The O-O bond order in O2, O3 and H2O2 is 2, 1.5 and 1.
contains 9 and 9 bonds.
171. CH3Cl will have maximum dipole moment among
88. The TBP structure of PCl5 is asymmetric but PCl +4 chloromethanes.
and PCl6− ions have symmetrical tetrahedral and
­octahedral structures which can pack closely in solid. 175. More the difference in electronegativity of atoms in
P −1 bond more the polarity of the bond.
90. From cos θ = we got more than 75%.
P 180. If Mx3 has zero dipole moment the molecule should
be planar triangular and sp2 hybridisation takes place
110. Both N2 and O22+ have bond order 3.
in M.
130. Though bond order in H 2+ and H 2− is same (0.5), the 183. N-Cl bond is nonpolar since the electronegativities of
electron in anti-bonding MO of H 2− destabilises it. N and Cl are equal (3.0).
131. In both N 2− and O2− electron is added to anti-­bonding 184. Since the dipole moment is a vectorial property the
MO. So, bond order decreases and bonds become dipole moment of polyatomic molecule can be deter-
weaker. mined from the individual bond moments.
141. The strength of hydrogen bond is in the order: water 190. In H − N + ≡ N + − N : positive charges are present on
> alcohol > ether. adjacent atoms. So, they repel.

146. Hydrogen bond length is longer than covalent bond 193. The contributing structure having unlike charges on
length. atoms with more distance will become less stable.

149. Strongest hydrogen bond has the lowest bond length.

150. With increase in the strength of hydrogen bond the Practice Exercise Level-I
enthalpy of vapourisation increases.
1. Some covalent compounds such as HF, HCl, AlCl3,
154. Due to intramolecular hydrogen bonding 2-nitrophenol etc. ionise in water due to more hydration energy.
has low b.pt and hence steam volatile.
2. With increase in number of bonds, bond length
155. Organic compounds containing H and O can form hy- ­decreases. The remaining statements are wrong.
drogen bonds with water molecules and thus soluble.
4. If valence shell gets stability by acquiring 6 electrons
160. The bond energy of polyatomic molecules is an fluorine which has 7 electrons in valence should lose
­average value; so, the bond formation and bond one electron.
breaking energies are not same.
H O
161. With increase in s-character of hybrid orbital, bond
5. H C C O H
length decreases and bond energy increases.
H
360
1 62. C-H bond energy = = 90.
4 6. In a crystal the atoms approach each other until the
attractive forces are in equilibrium with the repulsive
C-C bond energy = 620 – (6 × 90) = 80 kCal.
forces where the potential energy is minimum.
165. 4 g of H2 = 2 moles.
7. The bond formed between two metalic elements is
∴ Dissociation energy = 208/2 = 104 kCal/mol. metallic bond.
166. Si-Si bond energy is less than C-C bond energy due to 8. Silica and diamond have giant polymeric network
increase in bond length in Si-Si bond. structures.

Chapter_04.indd 39 3/26/2014 2:50:52 PM

 4.40  Objective Chemistry - Vol. I

9. Linear molecules have zero dipole moment. 33. Ethanol contains hydrogen bonds but diethyl ether con-
tain comparatively weaker dipole–dipole interactions.
10. Fajan’s rules.
34. %ionic character
13. The bond formed between two similar non-metallic µ obs 1.0
atoms like H2, Cl2, etc. is more covalent. × 100 = = 16.66%
µ cal 1.25 × 4.8
14. Melting SiO2 involves the breaking of covalent in 36. Both LiCl and NaCl ionise completely in water.
polymeric network structure. 37. Fajan’s rules.
15. Since A is not conducting electricity in both solid and 39. In both PCl3 and POCl3, phosphorous atom is in-
liquid state it should be covalent. Polar covalent com- volved in sp3 hybridisation.
pounds ionise in their aqueous solution and conduct
electricity. 40. For similar compounds bond angle decreases down
the group and the bond angle decreases with increase
16. SF4 is see-saw shaped with one lone pair, CF4 is tetra- in the number of lone pairs.
hedral with no lp and XeF4 is square planar with two 41. Six electron pairs will be arranged octahedrally. But
lp on the opposite corners of octahedron. the two lp occupies the opposite corners of octahe-
20. Fajans rule. dron giving square planar structure. So, the number
of L should be 4.
21. Higher the dipole moment more the dipole–dipole
attraction with H2O molecules weaker attraction 44. KI is ionic and is insoluble in benzene.
between ions requires less energy to separate them. 45. % ionic character = % of electric charge present on
Large solvation energy helps the breaking of lattice. atom.
1.2
22. I 3− has 5 electron pairs of which three are lp occupy- % ionic character = = 25%
ing the equatorial positions and the remaining two bp 1× 4.8
occupies the axial positions of TBP structure. 46. Per one mole of Cl2, two moles of KCl are formed but
with calcium only one mole of CaCl2 is formed.
23. AlF3 is ionic while SiF4 is covalent.
47. In the conversion of BF3 to BF4– the hybridisation of
+ −
z ⋅z boron changes from sp2 to sp3.
25. Lattice energy α
rc + ra 48. The energy difference to sublime in the presence and
absence of hydrogen bonds is 30.8 – 14.4 = 16.4 KJ
1× 1 2×2 per mole. To separate 6 neighbours in hydrogen bond
NaCl and for CaO . So, it is 4U.
rc + ra rc + ra the energy required is 2.7 KJ per mole.
49. To minimise the lp–lp repulsions the electron pairs
26. The hydration energy of Al3+ ion exceeds the sum of around the central atom in a molecule will rearrange.
the three ionisation energies (I1 + I2 + I3) of Al atom.
50. In the hydrogen bond formation hydrogen atom hav-
So hydrated AlCl3 . 6H2O is ionic.
ing a partial positive charge only can participate. So,
27. AsO33–, ClO3– and SO3- are pyramidal in shape. the electron density at X increases and at H ­decreases.

28. In a group from top to bottom electronegativities 51. Fajan’s rules.

decrease. The electronegativity differences between 52. MgO have more lattice energy than KCl as per lattice
A and Y will be less. So, AY is least polar. z+ ⋅ z−
energy is proportional to
29. The zero dipole moment of CO2 is due to the cancel- rc + ra
lation of the dipole moments of two C-O bonds. 54. In CO three electron pairs are shared between C and
32. Ionic reactions are very fast, In SnCl2, there are one O. But one pair is donated by oxygen to carbon.
lp and two bp. So, it is angular. With increase in the 55. In XeF2 there are 5 electron pairs, of which three are
number of positive charges on cation polarising pow- lp and two are bp. The 5 electron pairs are arranged in
er increases (Fajan’s rule). So, in their compounds TBP structure in which the three lp occupy equatorial
ionic character decreases. positions.

Chapter_04.indd 40 3/26/2014 2:50:53 PM

 Chemical Bonding and Molecular Structure   4.41

56. Both SO3 and CO3−

2 are planar triangular. 8. In ICl −4 the hybridisation of iodine is sp3d2 white in
BeCl2 hybridisation of Be is sp hybridisation but both
57. In both NO3− and NO2− the N atom is involved in sp2 molecules are linear.
hybridisation.
9. In sp3d hybridisation s, px, py, pz and dz2 orbitals
58. CrO2Cl2 has the structure. ­participate.
O
10. ICl4– ion has the structure.
Cr
Cl Cl
Cl
O
Cl
Cl Cl
59. When PCl5 → + PCl3 + Cl2 the oxidation state of
phosphorous decreases +5 to +3 while in chlorine The bp-lp interactions are 8
oxidation state increases from –1 to 0.
11. Shape of the molecule depends only on s-bonds. So,
60. In the homolytic fission of C-C bond in C2H6 gives the two bp in two s-bonds and the lps are arranged in
­methyl free radical in which carbon is in sp2 hybridi- trigonal planar.
sation. 12. The p-bonds will be perpendicular to the plane of
63. In the formation of BrF5 the sp3d hybrid orbitals of the molecule while the middle p-bond is in the plane
bromine overlap with p-orbitals of fluorine. of molecule. So, two nodal planes are in molecular
plane and one is perpendicular.
13. O–
N +
Practice Exercise Level-II F N
F O
1. In every B-F bond there is some dative bond charac- O
ter in the resonance hybrid. 14. n can have minimum value 3 as in XeF2 where bond
2. XeF5 has 6 EP of which 5 are bp and one is lp. angle is 180°.
So, it is square pyramid. 17. In N(SiH3)3 the structure is planar triangular due to
XeF6 has 7 EP of which 6 are bp and one is lp. back bonding. Bond angle is 120°. The remaining
So, it is distorted octahedron. are pyramidal. More the electronegativity of bonded
atom the lesser the bond angle.
TaF8 have 8 EP of which 8 are bp no lp. So, it is
square antiprismatic. 18. Orbitals having same symmetry mix up.
19. AB5 molecule may have TBP or square pyramid
3. ICl2– have 5 bp with TBP structure 3 lp occupy equa-
structure.
torial positions.
20. If methane has square planar structure it should give
4. CrO2Cl2 has distorted tetrahedral structure due to the
geometrical isomers on dichlorination.
presence of two Cr=O and Cr-Cl bonds.
21. SF4 and SOF4 have same TBP structure but lone pair
When N2 is converted to N 2+ bond order decreases
repulsion is more than double-bonded oxygen and the
from 3 to 2.5 bond length increases.
axial FSF angle is less than FSO.
When NO is converted to NO+ bond order increases 24. B is smaller atom than Li. So, bond length is less and
from 2.5 to 3.0. stability is more.
When O2 is converted to O22– bond order decreases 33. Neither N nor F contains d-orbitals. Further in
from 2 to 1. N2F4 N-N bond is shorter than in N2H4 due to more
7. In BeCl2, Be is sp (50% s-character); CO32− C is sp2 s-­character (Bent’s rule).
(33.3% s-character) and CCl4, NH3 and H2S the cen- 35. Due to strong back bonding in P-F bond electron
tral atoms are in sp3 hybridisation but with decrease ­donating capacity of P → O in p dative bond ­increases
in bond angle s-character of hybrid orbitals ­decreases. (synergic effect).

Chapter_04.indd 41 3/26/2014 2:50:56 PM

 4.42  Objective Chemistry - Vol. I

36. AsF3Cl2 has trigonal bipyramid structure in which 41. If lattice energy is very high than hydration energy
two F atoms are at axial and one F atom is at equato- salt is insoluble because hydration energy is not
rial position (Bent’s rule). ­sufficient to break the lattice.
39. With increase in size of cation both lattice energy and 42. Melting point is directly proportional to lattice
hydration energies decreases but decrease in lattice ­energy, which in turn inversely proportional to re + ra.
energy is more.
40. It is the middle row anomaly where sudden
change appears in electronic configuration in the
penultimate shell.

Chapter_04.indd 42 3/26/2014 2:50:56 PM

 5

Chapter
States of Matter

• All matter exists in three states: solid, liquid and gas. • The dipole moment is due to the shift in the centre of
• A solid is rigid and has definite shape, a liquid can gravity of the negative charge relative to the nuclear
flow and can alter its shape, but it has a definite bound- charge.
ary surface. • Interaction between the dipolar molecules also
• A gas can flow, but differs from both liquid and solid includes additive dipole–dipole induced interactions.
in that it has no surface and the volume of the gas is • The dipole–dipole, dipole-induced dipole and dispersion
the volume of vessel in which it is filled. Change in forces are collectively called as Van der Waal’s forces.
pressure causes change in volume of gas. • The magnitude of Van der Waal’s forces depends on
• By suitable change in conditions like temperature and relative polarisability of the electrons of the atom or
pressure, one state of matter can be changed into another. molecule involved.
• The term vapour is used to describe a material in the • The weak electrostatic attractive force which binds
gaseous state when it can be condensed to the liquid hydrogen of one molecule with the more electronega-
form by increasing the pressure at the same tempera- tive atom (F, O, N) of another molecule is known as
ture. A vapour is therefore a gas below its critical hydrogen bond.
temperature. • Intermolecular hydrogen bond is formed between
• When a substance absorbs energy, it is utilised in in- two different molecules of the same or different
creasing the mechanical energy such as kinetic energy substances.
of motion, rotational energy and vibrational energy. • Liquids in which hydrogen bonds exist between their
• The liquid molecules suffer many more collisions per molecules are called associated liquids. E.g., H2O,
second than the gas molecules. HF, NH3, etc.
• Two miscible liquids diffuse into each other when • Liquids in which hydrogen bonds do not exist
placed together. The diffusion of liquids is a slower between their molecules are called normal liquids.
process than that of gases. E.g., Benzene, CCl4, etc.
• Generally, associated liquids have more boiling points
than normal liquids.
Intermolecular Forces • The bond length of hydrogen bond (1.76 Å) is higher
• At a given instant the asymmetry in the distribution than the O–H covalent bond length (1 Å).
of electrons around the nucleus of an atom cause dis- • The strength of hydrogen bond depends on the magni-
tortion in the distribution in the neighbouring atom or tude of polarity and size of the atoms and number of
molecule itself due to which dipole moment develops. hydrogen bonds.
• Attractive forces arising due to distortion of electron • Though the electronegativities of nitrogen and chlo-
clouds under the influence of nuclei of atoms are rine are same (3.0), chlorine cannot form hydrogen
known as dispersion forces or London forces. bond due to bigger size.

Chapter_05.indd 1 3/26/2014 4:57:34 PM

 5.2  Objective Chemistry - Vol. I

• The hydrogen bond in HF is stronger than in H2O, yet • Melting points and boiling points represent a state of
the boiling point of H2O is greater than HF because balance between the kinetic energy of the molecules
(a) H2O has four hydrogen bonds, two are through lone and the intermolecular or interionic forces.
pairs of oxygen and the remaining two are through
hydrogen atoms.
(b) H2O contains hydrogen bonds in liquid state only  Objective Questions
but water vapour contains free molecules, whereas
HF contains hydrogen bonds in liquid and vapour 1. Which of the following statements is correct about
states. the three states of matter: solid, liquid and gas?
• Boiling point of ethyl alcohol is more than that of (1) Gases and liquids can flow as a common property
dimethyl ether or propane having equal molecular (2) The molecules in all the three states possess ran-
weights because ethyl alcohol molecules are associ- dom translational motion
ated with hydrogen bonds. (3) Gases can be converted into solids without pass-
• The boiling point of acetic acid is more than that ing through the liquid phase
of ethyl alcohol even though both are associated by (4)  Solids and liquids have vapour pressure as a
­hydrogen bonds because acetic acid exists as a dimer. common property
• Intramolecular hydrogen bonding is between the 2. A closed flask contains water in all its three states:
two groups of the same molecule, e.g., ortho­isomers solid, liquid and vapour at 0°C. In this situation the
of nitrophenol, hydroxy benzaldehyde (salicyl­ average kinetic energy of the water molecule will be
aldehyde), hydroxy benzoic acid (salicyclic acid), (1) The greater in the vapour state
nitroaniline, etc. (2) The same in the three states
• Due to intramolecular hydrogen bonding, molecules (3) The greatest in the solid state
of orthoisomers are not associated, so their boiling (4) Greater in the liquid than in the vapour state
points are less and are steam volatile. 3. Vibrational energy is
• In meta- and para-isomers, intramolecular hydrogen (1) Partially potential and partially kinetic
bonding is not possible due to more distance between (2) Only potential
polar groups. (3) Only kinetic
• In meta- and para-isomers the molecules are associ- (4) Only vibrational
ated through intermolecular hydrogen bonding. So,
4. Which of the following statements is correct if the
their melting points and boiling points are high and
intermolecular forces in liquids A, B and C are in the
are not steam volatile.
order A < B < C?
Intermolecular Forces vs Thermal Energy (1) B evaporates more readily than A
(2) A evaporates less readily than B
• Intermolecular forces tend to keep the molecules (3) A and B evaporates at the same rate
together but thermal energy tends to separate them. (4) A evaporates readily than C
• If thermal energy predominates over intermolecu- 5. Kinetic energy of molecule is highest in
lar forces the substance would change from solid → (1) Gases (2)  Liquids
liquid → gas. (3) Solids (4)  Solutions
• If intermolecular forces predominates over thermal
6. Which one of the following statements is not correct
energy the substance would change from gas → liquid
about the three states of matter, i.e., solid, liquid and
→ solid.
gaseous
• The kinetic energy of the molecule will tend to keep
(1) Molecules of a solid possess least energy, where-
them in motion and so move them apart.
as those of a gas possess high energy
• The kinetic energy increases as the temperature (2) The density of solid is highest, whereas that of
increases. gases is lowest
• The molecules are very close together in a solid, a little (3) Gases like liquids possess definite volume
farther apart in a liquid and very far apart in a gas. (4) Molecules of a solid possess vibratory motion

Chapter_05.indd 2 3/26/2014 4:57:34 PM

 States of Matter  5.3

7. Which of the following is true about gaseous state? (3) Dipole-dipole interaction and ion-dipole inter­
(1) Thermal energy = Molecular attraction action
(2) Thermal energy >> Molecular attraction (4) Small size of molecule
(3) Thermal energy << Molecular attraction
(4) Molecular forces >> those in liquids
Answers
8. Among the following, Van der Waal’s forces are
maximum in (1) 1 (2) 2 (3) 1 (4) 4 (5) 1
(1) HBr (2)  LiBr (6) 3 (7) 2 (8) 4 (9) 2 (10) 2
(3) LiCl (4)  AgBr (11) 2 (12) 4

9. The explanation of various intermolecular forces

indicates gASEOUS STATE
(1) the unusual (anomalous) behaviour of H2O, NH3
• The measurable properties of gases are mass (m),
and HF in terms of the relationship between
molecular weight and boiling points is due to volume (V), pressure (P) and temperature (T).
London forces • One mole of a gas contains 6.023 × 1023 Avogadro’s
(2) ion-dipole forces account for the solvation energy number of molecules. The mass of one mole of a gas is
which plays an important role in the dissolving of called molar mass.
ionic solids Mass of the gas (m)
• Number of moles ( n) =
(3) for non-polar molecules in the liquid state an im- Molecular mass of the gas (M )
portant force acting is gravitational attraction • Pressure is the force per unit area, the pressure of gases
(4) that London forces are due to very small perma- is measured using manometer and the atmospheric
nent electric dipoles pressure is measured with barometer.
10. Intermolecular hydrogen bonding increases the • Units of pressure is atmosphere (atm).
enthalpy of vaporisation of a liquid due to the • 1 atm = 76 cm of Hg = 760 mm of Hg = 760 torr =
(1) decrease in the attraction between molecules 1.01325 × 105 Pascals = 101.325 kilopascals.
(2) increase in the attraction between molecules
• In celsius scale boiling point of water is taken as 100°C
(3) decrease in the molar mass of non-associated
and freezing point of water is taken as 0°C.
liquid molecules
(4) decrease in the effective molar mass of hydrogen- • Kelvin proposed the absolute scale of temperature.
bonded molecules Celsius scale can be converted into Kelvin scale by
K = °C + 273.15 @ °C + 273. Absolute temperatures
11. The boiling points of methanol, water and dimethy- are expressed as T.
lether are respectively 65°C, 100°C and 34.5°C.
Which of the following best explains these wide
variations in b.pt? Boyles Law
(1) The molecular mass increase from water (18) to • At constant temperature the volume of a given
methanol (32) to diethyl ether (74) mass of gas is inversely proportional to its pressure.
(2) The extent of H-bonding decreases from water to Mathematically
methanol while it is absent in ether 1
(3)  The density of water 1.00 gm mL–1, metha-     V ∝ (T and n are constants)
p
nol 0.7914 gm mL–1 and that of diethyl ether is
0.1737 gL–1 1
or    P ∝ or PV = K (constant)
(4) The number of H atoms per molecule increases v
from water to methanol to ether or   P1V1 = P2V2
12. Which of the following factors is not responsible for • The graphs plotted between pressure and volumes of
Van der Waal’s force? a given mass of gas at constant temperature are called
(1) Instantaneous dipole-induced dipole interaction isotherms.
(2)  Dipole-induced dipole interaction and ion-­ • Gases obey Boyle’s law at low pressures and high
induced dipole interaction temperatures.

Chapter_05.indd 3 3/26/2014 4:57:35 PM

 5.4  Objective Chemistry - Vol. I

Charles–Gay–Lussac’s Law • Gases which do not obey the gas laws are called real
gases. Real gases show ideal gas behaviour at high
• At constant pressure the volume of a given mass of a
temperatures and low pressures.
gas is directly proportional to its absolute temperature.
• Ideal gas equation is a combination of Boyle’s,
Mathematically, Charles’ law is
Charles’ and Avogadro’s laws.
V ∝ T (at constant P and n)
V
• Ideal gas equation is PV = nRT. This equation is also
or V = KT or = K known as equation of state.
T
• The value of gas constant “R” is the same for all gases.
V1 V2
or = R is called the universal gas constant or molar gas
T1 T2 constant.
• At constant pressure if the temperature of a given mass • 0°C or 273 K and 1 atmosphere pressure or 76 cm or
of a gas is changed by one degree on celsius scale the 760 mm of Hg pressure are called standard tempera-
1
volume changes by times of its volume at 0°C ture and pressure (STP) for gases.
273
• One mole of any gas at STP occupies 22.414 litres.
 v  This is known as gram molar volume (GMV) or
Volume of the gas, V = Vo + o t 
 273  molar volume of gas.
 t  • The weight of 22.414 litres of any gas at STP is equal
or       V = V0 1 +  to its molecular weight.
 273
Value of gas constant (R) in different units
 273 + t 
V = V0 
 273 
Pressure Volume R value
Atmosphere Litre 0.0821 Lit atm mol–1 k–1
• The volume of any gas theoretically becomes zero
Atmosphere cm3 82.1 cm3 atm mol–1 k–1
at –273.16°C. This particular temperature is called
Dyne cm–2 cm3 8.314 × 107 erg mol–1 k–1
absolute zero.
Newton dm3 1.987 cal mol–1 k–1

Gay–Lussac’s Law Gas Density

•
At constant volume, pressure of a fixed amount of gas • From the ideal gas equation, PV = nRT
varies directly with the temperature. Mathematically m m RT
P∝T   PV = RT or M =
W V P
P dRT
= constant ∴ M = where d is the density of the gas
T P
P P • Since the real gases do not exactly follow the ideal gas
or    1 = 2
T1 T2 equation, it is necessary to correct for non-ideal be-
•
haviour. The density is measured at several pressures
Each line in the graph showing the relation pressure vs
usually below atmospheric pressure and the ratio d/p is
temperature is called an isochore.
plotted against P, a straight line is obtained, which can
be extrapolated to zero pressure.
Avogadro’s Law • The value of d/p at zero pressure is known as limit-
• Equal volumes of all gases measured under same ing density from which accurate molar mass can be
conditions of temperature and pressure contain equal determined.
number of molecules.
• At constant temperature and pressure, the ­ number
of molecules of a gas is directly proportional to
 Objective Questions
volume, V ∝ n.
13. A curve drawn at constant temperature is called an
isotherm. This shows relationship between
Ideal Gas Equation 1
(1) P and (2)  PV and V
• The gas which obeys all the gas laws under all condi- V
1
tions of temperature and pressure is called an ideal gas. (3) P and V (4) V and
P

Chapter_05.indd 4 3/26/2014 4:57:37 PM

 States of Matter  5.5

14. Which curve does not represent Boyle’s law? 21. The temperature at which real gases obey the ideal
(1)  (2)  gas laws over a wide range of pressure is called
(1) Critical temperature
P (2) Boyle’s temperature
P
(3) Inversion temperature
(4) Reduced temperature
V log V 22. Equal volumes of two gases are kept in separate con-
(3)  (4)  tainers at the same temperature and pressure. Then
(1) Masses of the two gases are same
P PV (2) Molecular structure of two gases would be similar
(3)  The two gases contain the same number of
molecules
V P (4) The two gases if allowed to diffuse would do so at
the same rate
15. In the gas equation PV = nRT the value of universal
gas constant depends upon 23. To raise the volume of a gas by four times the follow-
(1) The nature of the gas ing method may be adopted. Which of the method is
(2) The pressure of the gas wrong?
(3) The temperature of the gas (1) T is doubled and P is also doubled
(4) The units of measurement (2) Keeping P constant, T is raised by two times
16. The gas constant R has units (3) Temperature is doubled and pressure is halved
(1) erg k–1 mol–1 (4)  Keeping temperature constant pressure is re-
(2) lit atm k–1 mol–1 duced to 1/4 of its initial value
(3) The temperature of the gas 24. Which expression holds good for the general gas
(4) The units of measurement equation
17. The density of a gas equal to (P = pressure, V = vol- (1) P1V1T1 = P2V2T2 (2) P1V1T2 = P2V2T1
ume, T = temperature, R = gas constant, n = number (3) P1V2T1 = P2V1T2 (4) P2V1T1 = P1V2T2
of moles and M = molecular weight) 25. At constant volume the pressure of a monoatomic gas
PM depends upon
(1) nP (2) 
RT (1) Thickness of the walls of the container
(2) The absolute temperature
P M
(3)  (4) 
M (3) The atomic number of the element
RT V (4) The number of valence electrons
18. Which expression is valid for an ideal gas? 26. A flask is filled with CCl4 vapour at a pressure and
(1) PV = RT/n (2)  V1T1 = V2T2 temperature was weighed. The flask was then filled
(3) P1V1 = V1P2 (4)  P1T2d2 = P2T1d1 with oxygen at the same temperature and pressure af-
19. According to the ideal gas laws the molar volume of ter removing CCl4 vapour. The mass of CCl4 vapour
a gas is given by would be about
RT (1) Same as that of oxygen
(1) 22.4 lit (2)  (2) One-fifth as heavy as oxygen
P
(3) Five times as heavy as oxygen
8RT RT (4) Twice as heavy as oxygen
(3)  (4) 
PV PV
27. Pressure remaining the same, the volume of given mass
20. When gases are heated from 20°C to 40°C at constant of an ideal gas increase for every degree centigrade rise
pressure, the volume in temperature by definite fraction of its volume at
(1) increased by the same magnitude (1) zero degree centigrade
(2) becomes double (2) its critical temperature
(3) increase in the ratio of their molecular masses (3) absolute zero
(4) increases but to a different extent (4) its Boyle’s temperature

Chapter_05.indd 5 3/26/2014 4:57:39 PM

 5.6  Objective Chemistry - Vol. I

28. An ideal gas is one which obeys the gas laws under 35. A bubble of air released at the bottom of a pool of
(1) a few selected experimental conditions water becomes larger as it approaches the water sur-
(2) all experimental conditions face. This is due to
(3) low pressure alone (1) decreasing pressure on the bubble as it rises
(4) high temperature alone (2) high temperature of water near the water surface
29. A device used for measurement of gaseous pressure (3) changing surface tension of the water
based on Boyle’s law is known as (4) decreasing stability of the bubble with the height
from the bottom
(1) Macleod gauge (2)  Manometer
(3) Fortim’s Barometer (4)  Screw gauge 36. A certain mass of a gas occupies a volume of 10 litres
at a pressure of one atmosphere at 3000 k. Which of
30. Under what conditions will a pure sample of an ideal
the following changes does not produce any change
gas not only exhibit a pressure of 1 atm but also a
in the volume of a gas ?
concentration of 1 mol litre–1 (R = 0.082 litre atm
mol–1 deg–1) (1)  Pressure doubled and absolute temperature
(1) At STP halved
(2) When V = 22.4 litre (2) Doubling both pressure and absolute temperature
(3) When T = 12 K (3) Pressure halved and absolute temperature doubled
(4) Impossible under any condition (4)  Pressure unchanged and absolute temperature
halved
31. At constant temperature, in the given mass of an
ideal gas 37. When the gas constant R is given as 8.31 the units are
(1) The ratio of pressure and volume always remains (1) Lit atm mol–1 deg–1

constant (2) Cal mole–1 deg–1
(2) Volume always remains constant (3) Joules mole–1 deg–1

(3) Pressure always remains constant (4) Ergs mole deg–1
(4)  The product of pressure and volume always 38. Graphical curves that explain Boyle’s law are called
remains constant
(1) Isobars (2)  Iscohores
32. A gas will approach ideal behaviour at (3) Isotherms (4)  Isomers
(1) Low T and high P 39. Isotherm is the graph drawn for
(2) Low T and low P (1) P – V (2) V–T
(3) High T and low P (3) PV – T (4) PV – V
(4) High T and high P
40. Horizontal line parallel to pressure is obtained in the
33. The four physical quantities that are required to following graph
describe a gas completely are
(1) PV – T (2) PV – P
(1) the amount, the pressure, the volume and its density (3) PV – n (4) PV – V
(2)  the amount, the pressure, the volume and its
­temperature 41. How should the conditions be changed to prevent the
(3) the pressure, the volume, the temperature and the volume of a given gas from expanding when its mass
molecular weight is increased?
(4) The pressure, the volume, the temperature and (1) Temperature is lowered and pressure is increased
the kinetic energy (2) Temperature is increased and pressure is lowered
(3) Temperature and pressure both are lowered
34. The air pressure in a car tyre may increase consider-
(4) Temperature and pressure both are increased
ably on driving the car some distance at high speed.
This is due to 42. If absolute temperature is increased three times and
(1) Friction pressure is reduced to half, then the volume becomes
(2) Frictional heat on tyre leading to expansion of air (1) Eightfold
inside the tyre (2) Sixfold
(3) Leakage of air from the tyre (3) Fourfold
(4) Effect of changing atmospheric pressure (4) Twofold

Chapter_05.indd 6 3/26/2014 4:57:39 PM

 States of Matter  5.7

Numerical (1) 15 mL (2)  10 mL

(3) 32 mL (4)  52 mL
43. If air contains N2 and O2 in volume ratio 4:1 the aver-
age vapour density of air is 53. Figure shows graphs of pressure versus density for
(1)  14.5 (2) 16.5 (3) 14.4 (4) 29.0 an ideal gas at two temperatures T1 and T2. Which is
correct?
44. Pressure remaining constant the volume of a given
sample of a gas at 127°C will be doubled at
T1
(1) 254°C (2)  527°C
T2
(3) 400 K (4)  800°C P
45. V versus T curves at constant pressure P1 and P2 for
an ideal gas are shown in the figure. Which is correct?
P1 d
P2 (1) T1 > T2 (2)  T1 = T2
(3) T1 < T2 (4)  None of these
P
54. 4.4 g of CO2 and 2.24 litres of H2 at STP are mixed in
a container. The total number of molecules present in
T the container will be
(1) 6.022 × 1023 (2) 1.2044 × 1023
(1) P1 > P2 (2)  P1 < P2 (3) 2 (4)  6.0233 × 1024
(3) P1 = P2 (4) all
55. At constant temperature, what would be the percent-
46. If the pressure of a gas contained in a closed vessel age increase in pressure for a 5% decrease in the
is increased by 0.4% when heated by 1°C its initial ­volume of gas?
temperature must be (1) 5% (2)  10%
(1) 250 K (2)  250°C (3) 5.26% (4)  4.26%
(3) 2500 K (4)  25°C
56. At a constant pressure what should be the percent-
47. The density of neon will be highest at age increase in the temperature in Kelvin for a 10%
(1) STP (2)  0°C, 2 atm increase in volume?
(3) 273°C, 1 atm (4)  273°C, 2 atm (1) 10% (2)  20%
48. How many moles of He gas occupy 22.4 litres at (3) 5% (4)  50%
30°C and one atmospheric pressure 57. One litre of a gas collected at NTP will occupy .....
(1) 0.9 (2) 1.11 (3) 0.11 (4) 1.0 litre at 2 atm pressure and 27°C
49. There is 10 litre of a gas at STP. Which of the 300 2 × 300
(1)  litre (2) litre
following changes keeps the volume constant? 2 × 273 273
(1) 273 K and 2 atm (2)  273°C and 2 atm 273 2 × 273
(3)  litre (4) litre
(3) 546°C and 0.5 atm (4)  0°C and 0 atm 2 × 300 300
50. The density of oxygen gas at 25°C is 1.458 mg/litre at 58. 10 g of hydrogen fluoride gas occupy 5.6 litres of
one atmosphere. At what pressure will oxygen have ­volume at NTP. The empirical formula of the gas is
the density twice the value? HF. The molecular formula of the gas will be (at. wt.
(1) 0.5 atm 25°C (2)  2 atm, 25°C of fluorine = 19)
(3) 4 atm, 25°C (4)  None (1) H4F4 (2) HF
51. Molar volume of CO2 is maximum at (3) H2F2 (4) H3F3
(1) STP (2)  0°C, 2 atm 59. In an experiment during the analysis of a carbon com-
(3) 127°C, 1 atm (4)  273°C, 2 atm pound, 145 mL of H2 was collected at 760 mm Hg
52. 26 mL of CO2 is passed over hot coke. The maximum pressure and 27°C. The weight of H2 is nearly
volume of CO formed is (1) 10 mg (2)  12 mg (3) 6 g (4)  8 g

Chapter_05.indd 7 3/26/2014 4:57:41 PM

 5.8  Objective Chemistry - Vol. I

60. The temperature of 20 litres of nitrogen was increased 69. A container has certain gas of mass “m” and at high
from 100 K to 300 K at constant pressure. Change in pressure some of the gas is allowed to escape from
volume will be it after some time, the gas pressure of the container
(1) 80 litres (2)  60 litres becomes half and its absolute temperature is 2/3. The
(3) 40 litres (4)  20 litres amount of gas escaped is
2 1 1 1
61. A pre-weighed vessel was filled with oxygen at NTP (1)  m (2)  m (3)  m (4)  m
and weighed. It was then evacuated and filled with 3 3 4 6
SO2 at the same temperature and pressure and again 70. A cooking gas cylinder can resist a pressure of 15 atm.
weighed. The weight of oxygen is At 27°C the pressure of the gas is 12 atm. Calculate
(1) The same as that of SO2 the minimum temperature in °C above which it burst
(2) Twice that of SO2 (1) 375°C (2)  1002°C
(3) 1/2 that of SO2 (3) 102°C (4)  300°C
(4) 1/2 that of SO2 71. The flask of hydrogen was weighed and then H2 is
62. Two sealed containers of the same capacity and at the evacuated and O2 was filled at the same temperature
same temperature are filled with 44 g of H2 gas in one and pressure. The mass of O2 would be
and 44 g of CO2 in the other. If the P of CO2 is 1 atm (1) same as that of H2 (2)  8 times more
in other the P of H2 in its container will be (3) 16 times more (4)  32 times more
(1) 1 atm (2)  zero 72. A vessel contains some gas at 27°C. At what tem-
(3) 22 atm (4)  4 atm perature half of the gas from the vessel will escape if
P and V remains constant?
63. A gas is found to have the formula [CO]x. Its VD is
70. The value of x must be (1) 327°C (2)  54°C
(3) 540 K (4)  150 K
(1) 3 (2)  5
(3) 6 (4) 2.5 73. At 380 mm pressure and 0°C 11.2 litre container
can hold
64. A gaseous mixture contains oxygen and nitrogen in
the ratio of 1:4 by weight. Therefore, the ratio of their (1) 1/4 mole of an ideal gas
number of molecules is (2) 1/2 mole of ideal
(3) 1 mole of an ideal gas
(1) 1:4 (2)  1:8
(4) 2 moles of ideal gas
(3) 7:32 (4)  3:16
65. It is desired to increase the volume of 800 cc of a gas by 74. At constant pressure a certain gas at 0°C was cooled
20% keeping the pressure constant. To what tempera- until its volume was reduced to half. The temperature
ture the gas be heated, if the initial temperature is 22°C? at this stage
(1) 360°C (2)  87 K (1) –130.5°C (2)  –140.0°C
(3) 454 K (4)  81°C (3) –136.5°C (4)  –120°C
66. What will happen to the pressure of a 5 litres sample 75. An open vessel at 27°C is heated until 3/4 of the air
of a gas at 5 atmospheres if it is heated from 250 K to in it has been expelled. Assuming that the volume of
300 K and the volume is kept constant? the vessel remains constant, the temperature to which
(1) 6 atm (2)  4.16 atm the vessel has been heated
(3) 3 atm (4)  2.0 atm (1) 210°C (2)  1200°C
(3) 220°C (4)  927°C
67. The density of a gas at 27°C and 1 atmosphere is d,
pressure remaining constant, at which of the follow- 76. At 273°C volume of certain mass of a gas is
ing temperatures will density become 0.75d? 0.546 lit. Find the change in volume for every 1°C
(1) 20°C (2)  30°C rise in temperature.
(3) 400 K (4)  300 K (1) 1 mL decrease (2)  6 mL decrease
(3) 3 mL decrease (4)  mL increase
68. A 100 mL sample of a gas at –73°C and 2 atmos-
pheres is heated to 127°C and the pressure is reduced 77. The pressure exerted by a gas in a 10-lit vessel at
to 0.5 atmosphere. What will be the final volume? 27°C is 5 atm. How many balloons of 0.5 litre size
(1) 8000 mL (2)  800 mL can be filled with the outcoming gas?
(3) 400 mL (4)  4000 mL (1) 100 (2) 80 (3) 50 (4) 40

Chapter_05.indd 8 3/26/2014 4:57:41 PM

 States of Matter  5.9

78. A graph in which a straight line passing through the • Rate of diffusion
origin is formed when it is drawn between Volume of the gas diffused, V
(1) P and V at constant T r=
Time of diffusion, t
(2) V and T°C at constant P
(3) V and T at constant P V1 V
r1 = and r2 = 2
(4) P and T at constant V t1 t2
79. Two separate bulbs contain ideal gases A and B. The r1 V1t2
Then, =
density of gas A is twice that of gas B. The molecular r2 V2 t1
weight of A is half that of gas B. The two gases are
• If the diffusion is carried for the same time, then
at the same temperature. The ratio of the pressure of
A to that of gas B is r1 t2 d2 Vd2 M2
= = = =
(1) 2 (2) 0.5 (3) 4 (4) 0.25 r2 t1 d1 Vd1 M1

Answers Applications of Graham’s Law of Diffusion

(13) 3 (14) 3 (15) 4 (15) 4 (16) 4 • Molecular weight of an unknown gas can be calculated
(17) 2 (18) 4 (19) 2 (20) 4 (21) 2 by comparing its rate of diffusion with that of a gas of
(22) 3 (23) 3 (24) 2 (25) 2 (26) 3 known molecular weight.
(27) 1 (28) 2 (29) 2 (30) 4 (31) 4 • In the detection of explosive marsh gas (methane)
(32) 3 (33) 2 (34) 2 (35) 1 (36) 2 using Ansil alarm.
(37) 3 (38) 3 (39) 1 (40) 2 (41) 1 • Graham’s law can be used to calculate extent of diffu-
(42) 2 (43) 3 (44) 2 (45) 2 (46) 1
sion of a gas, to separate the individual gases from a
(47) 2 (48) 1 (49) 2 (50) 2 (51) 3
mixture, poisonous and foul smelling gases are diluted
(52) 4 (53) 1 (54) 2 (55) 3 (56) 1
in atmosphere by diffusion and become harmless.
(57) 1 (58) 3 (59) 2 (60) 3 (61) 3
(62) 3 (63) 2 (64) 3 (65) 2 (66) 1 • Isotopes of the same element can be separated by
(67) 3 (68) 2 (69) 3 (70) 3 (71) 3 gas diffusion method and the process is known as
(72) 1 (73) 1 (74) 3 (75) 4 (76) 4 atmolysis. E.g.: Isotopes of  235U and  238U are converted
(77) 2 (78) 3 (79) 3 into their gaseous fluorides and are separated by gas
diffusion method.
• When a mixture of heavier gas B and a lighter gas A is
placed in contact with a porous barrier, the gas pass-
ing through will be enriched in lighter component by a
Graham’s law diffusion
factor M B / M A called enrichment factor.
• The spontaneous mixing of gases against gravity to • Several barriers are necessary to provide sufficient
form homogeneous mixture is called diffusion. enrichment of heavier component.
• Escape of a gas through a fine hole from a region of high • If required enrichment of a gas A is attained in x opera-
pressure to a region of low pressure is called effusion. tions then
• At constant temperature and pressure the rate of diffu- 2 log [ n′ A / n′ B ]
sion of various gases are inversely proportional to the x=
M 
square root of their density (d), vapour density (vd) log  B 
and molecular weight (M)  MA 
1 1 1 2 log f
r∝ ∝ ∝ =
d Vd M M 
log  B 
• For two different gases  MA 
r1 d2 Vd2 M2 n′A and n′B are the concentrations of two isotopically
∝ ∝ ∝ different components after processing MA and MB­
r2 d1 Vd1 M1
are the molecular weights of gases A and B.

Chapter_05.indd 9 3/26/2014 4:57:43 PM

 5.10  Objective Chemistry - Vol. I

n′A × n′B 86. The rates of diffusion of SO2, CO2, PCl3 and SO3 are
• The enrichment factor = in the following
nA × nB
nA, nB and n′A, n′B are the concentrations of two (1) PCl3 > SO3 > SO2 > CO2
isotopically different components before and after (2) CO2 > SO2 > PCl3 > SO3
processing. (3) SO2 > SO3 > PCl3 > CO2
(4) CO2 > SO2 > SO3 > PCl3
87. Which relation holds good for Graham’s law of
diffusion?
 Objective Questions r M2
(1)  1 = (at same P and T)
r2 M1
80. A bottle of dry NH3 and another bottle of dry HCl
are connected through a long tube are opened simul- r d2
(2)  1 = (at same P and T)
taneously at both ends, the white (NH4Cl) ring first r2 d1
formed will be r M 2 P1
(1) At the centre of the tube (3)  1 = × (at same T)
r2 M1 P2
(2) Near the HCl tube
(3) Near the ammonia bottle (4) All
(4) Throughout the length of the tube 88. According to Graham’s law, at a given temperature
81. Which pair of the gaseous species diffuses through a the rate of diffusion rA/rB of gases A and B is given by
small jet with the same rate of diffusion at same pres- (1) Coal gas (2)  Water gas
sure and temperature? (3) Air (4)  Producer gas
(1) NO, CO (2)  NO, CO2 89. A small amount of a foul smelling gaseous organic
(3) NH3, PH3 (4)  NO, C2H6 sulphur compound is added to the commercial LPG
82. At a given temperature and pressure the rate of diffu- for leak detection. The property of this gas which
sion of a gas is helps in leak detection is
(1) Directly proportional to the density of the gas (1) Sublimation
(2) Directly proportional to the square root of its (2) Molecular vibration
density (3) Molecular association
(3) Inversely proportional to the density of the gas (4) Diffusion
(4) Inversely proportional to the square root of its 90. A sample of Kr(g) escape through an orifice in 90 s
density and the same amount of an unknown gas takes 45 s
under identical conditions. Therefore
83. Four rubber tubes are respectively filled with H2,
O2, N2 and He. The tube which will be reinflated (1) the molar mass of the unknown gas must be less
first is than that of Kr
(2)  the unknown gas must consist of diatomic
(1) H2-filled tube (2)  O2-filled tube
­molecules
(3) N2-filled tube (4)  He-filled tube
(3) the molar mass of the unknown gas must be
84. A balloon filled with N2O is pricked with a sharper ­higher than that of Kr
point and quickly plunged into a tank of CO2 under (4) the unknown gas must also be a noble gas
the same pressure and temperature. The balloon will 91. A gas spreads more rapidly through a room when
(1) be enlarged (1) the gas is of higher molecular weight
(2) shrink (2) the gas is made of monoatomic molecules
(3) remain unchanged in size (3) the room temperature is high compared to when
(4) collapse completely it is low
85. A balloon filled with methane is pricked with a sharp (4) the room temperature is low compared to when
point and quickly plunged into a tank of hydrogen at it is high
the same pressure. After some time the balloon will 92. The rate of diffusion of helium when compared to
have that of methane
(1) enlarged (2) collapsed (1) twice (2)  half
(3) remain unchanged (4) methane inside it (3) one-fourth (4)  4 times

Chapter_05.indd 10 3/26/2014 4:57:44 PM

 States of Matter  5.11

93. Rate of diffusion of gas is effected by 102. One litre of O2 takes 50 min to diffuse out of a vessel.
(1) temperature and molecular weight How long will it take to diffuse through the same con-
(2) pressure and temperature tainer in the same time under the same conditions?
(3) molecular weight and density (1) 100 min (2)  50 min
(4) all of these (3) 25 min (4)  12.5 min
94. Spontaneous mixing of two gases by diffusion is 103. At a given temperature and pressure 20 mL of the gas
(1) reversible (2)  irreversible diffuses through a porous membrane in 5 s. Calculate
(3) exothermic (4)  endothermic the volume of carbon dioxide which diffuses in 10 s
if the vapour density of the gas is
95. Gases cannot settle at the bottom of a container. This
20
fact can be explained by (1) 10 2 (2) 
(1) Charles’ law 2
(2) Amagots’ law 10
(3) 20 2 (4) 
(3) Graham’s law 2
(4) Dalton’s law of partial pressures 104. Some moles of oxygen diffused through a small
opening in 18 s. Same number of moles of an un-
Numerical known gas diffuses through the same opening in 45 s.
Molecular weight of the unknown gas is
96. The rate of diffusion of methane at a given tempera- 18 18
(1) (32)2 × (2) (32)2 ×
ture is twice that of a gas X. The molecular weight­ 45 ( 45)2
of X is ( 45)2 45
(1) 64 (2) 32 (3) 4.0 (4) 8.0 (3) (32) × (4) (32)2 ×
(18)2 18
97. The molecular weights of two gases are 100 and 81, 105. It was observed in an experiment of diffusion of gases
respectively. Their rates of diffusion at the same tem- that 57 mL of hydrogen took the same time to diffuse
perature are in the ratio of through a porous partition as 10 mL of an unknown
(1) 10:9 (2)  9:10 gas under identical conditions. The unknown gas is
(3) 81:100 (4)  100:81 (1) CO2 (2) NO2 (3) SO2 (4) ClO2
98. The rate of diffusion of methane at the same P and T is 106. Two balloons are separately filled with oxygen and
(1) same as that of SO2 (2)  4 times that of SO2 hydrogen under the similar conditions of temperature
(3) twice that of SO2 (4)  twice that of O2 and pressure. If oxygen escapes at the rate of 65 mL
per hour hydrogen escapes at
99. If both gases are at the same temperature, the rate of
(1) 64 mL per hour (2)  54 mL per hour
diffusion of O2 is very close to
(3) 260 mL per hour (4)  240 mL per hour
(1) 8 times that of helium
(2) 0.25 times that of helium 107. There are two cylinders of equal capacity. One is
(3) 2 times that of helium filled with 16 kg of O2 and the other with 1 kg of
(4) twice that of O2 H2 at 5 atm pressure. After one hour due to leakage
into atmosphere if pressure in the cylinder containing
100. The molecular weight of a gas which diffuses through oxygen is 1 atm what will be the pressure of hydrogen
a porous plug of 1/6th of the speed of hydrogen under in the other cylinder?
identical conditions is
(1) 0.25 atm (2)  1 atm
(1) 27 (2)  72 (3) 4 atm (4)  0.5 atm
(3) 36 (4) 48
101. 2 g of hydrogen diffuses from a container in 10 min. Answers
How many grams of oxygen would diffuse through
the same container in the same time under the same   (80) 2 (81) 4 (82) 4 (83) 1 (84) 3
conditions?   (85) 1 (86) 4 (87) 4 (88) 3 (89) 4
(1) 5 g (2)  4 g (3) 6 g (4)  8 g   (90) 1 (92) 1 (93) 4 (94) 2 (95) 3

Chapter_05.indd 11 3/26/2014 4:57:45 PM

 5.12  Objective Chemistry - Vol. I

  (96) 1 (97) 2 (98) 3 (99) 2 (100) 2 109. Oxygen gas is collected by downward displacement
(101) 4 (102) 4 (103) 3 (104) 3 (105) 3 of water in a jar. The level of water inside the jar is
(106) 3 (107) 2 adjusted to the height of water outside the jar. When
the adjustment is made the pressure exerted by the
oxygen is
(1) equal to the atmospheric pressure
Dalton’s law of partial pressures (2) equal to the vapour pressure of oxygen at that
temperature
• Total pressure exerted by a mixture of gases is equal to (3) equal to the atmospheric pressure plus aqueous
the sum of partial pressures tension at that temperature
    Ptotal = P1 + P2 + P3 + ...... + Pn (4) equal to the atmospheric pressure minus aqueous
where P1, P2, P3 .... Pn are the partial pressures of the tension at that temperature
gases in the mixture. 110. In a given mixture of gases which do not react with
• Partial pressure of a gas in a mixture is equal to the one another, the ratio of partial pressure to total pres-
product of its mole fraction and the total pressure of sure of each component is equal to its
the mixture of gases (1) weight per cent (2)  volume per cent
Partial pressure = (3) mole fraction (4)  critical pressure
No. of moles of individual gas 111. Which gas may be collected over water
× Total pressure
Total no. of moles in gaseous mixture (1) NH3 (2) N2 (3) HCl (4) SO2
No. of moles of individual gas 112. A vessel has two equal compartments A and B
Mole fraction =
 
Total no. of moles in gaseous mixture ­containing H2 and O2, respectively, each at 1 atm
pressure. If the wall separating the compartment is
Partial pressure of gas removed, the pressure
% gas in mixture = ×100
Total pressure of gaseous mixture (1) Will remain unchanged in A and B
n +n +n  (2) Will increase in A and decrease in B
Total pressure in terms of moles, Ptotal =  1 2 3  RT (3) Will decrease in A and increase in B
 v  (4) Will increase in both A and B
Applications of Dalton’s Law 113. The partial pressure of dry gas is
• The vapour pressure of water at any particular tem- (1) less than that of wet gas
perature is known as the aqueous tension for that par- (2) greater than that of wet gas
ticular temperature. (3) equal to that of wet gas
• The pressure of gas collected over water is given by (4) none
Pgas = Patmosphere – aqueous tension 114. If a vessel containing hydrogen chloride at a pres-
Pressure of dry gas = Pressure of wet gas – aqueous sure p is connected with another vessel of the same
tension volume containing ammonia at a pressure P so that
Pressure of gas = Total pressure – aqueous tension they mix with each other to form solid ammonium
• Dalton’s law of partial pressures is not applicable to chloride. Then, the gas pressure
a gaseous mixture containing gases which react with (1) is equal to the pressure
each other. p
(2) will be = 1
P
(3) will be doubled, i.e., 2P
(4) drops to zero
 Objective Questions
115. Assuming the solubility of oxygen in water to be
108. Which mixture of gases at room temperature does not ­negligible when 1 litre of dry oxygen is bubbled
follow Dalton’s law of partial pressures? through water and collected at the same temperature
(1) NO2 and O2 and pressure in a bottle over water the volume of the
(2) NH3 and HCl gas collected would be

(3) CO and CO2 (1) less than 1 litre (2)  equal to 1 litre
(4) SO2 and O2 (3) more than 1 litre (4)  only a few cm3

Chapter_05.indd 12 3/26/2014 4:57:46 PM

 States of Matter  5.13

116. Dalton’s law of partial pressures is based on the (3) 2/5 of the total pressure
­assumption that the gas molecules (4) 1/5 of the total pressure
(1) are perfectly spherical
122. Air contains 79% N2 and 21% O2 by volume. If the
(2) do not attract or repel one another
barometric pressure is 750 mm Hg the partial pres-
(3) have the same speed
sure of oxygen is
(4) are small
(1) 157.7 mm of Hg (2)  175.5 mm of Hg
117. When two cylinders containing at the same tempera- (3) 315.0 mm of Hg (4)  None
ture but at different pressures are interconnected, the
pressure of the gas mixture (assuming no reaction 123. If one litre of a gas A at 600 mm and 0.5 litre of gas
­between them) is 13 at 800 mm are taken in a 2 litre bulb, then the
resulting pressure is
(1) less than the sum of their pressures
(2) more than the sum of their pressures (1) 1500 mm (2)  1000 mm
(3) equal to the sum of their pressures (3) 2000 mm (4)  500 mm
(4) zero 124. If the concentration of water vapour in the air is 1%
118. Hydrogen produced by displacement from dilute and the total atmospheric pressure equals to 1 atm
­sulphuric acid by zinc is then the partial pressure of water vapour is
(i) collected over water (1) 0.1 atm (2)  1 mm
(ii) over mercury (3) 7.6 mm Hg (4)  100 atm
If equal volumes of gas at these two conditions are 125. The partial pressure of hydrogen in a flask containing
taken 2 g of hydrogen and 16 g of oxygen is
(1) The amount of hydrogen collected over mercury
(1) 1/8 of the total pressure
was greater
(2) 1/6 of the total pressure
(2) The amount of hydrogen collected over mercury
(3) 1/4 of the total pressure
was the same as the amount of the gas collected
(4) 2/3 of the total pressure
over water
(3) The amount of hydrogen collected over water 126. A cylinder contains a mixture of 0.3 moles of N2,
was greater 0.1 moles of O2 and 0.1 moles of He. If the total
(4) None of these ­pressure equals to one atmosphere the partial ­pressure
119. Equal weights of methane and hydrogen are mixed in of O2 in mm of Hg is
an empty container at 25°C. The fraction of the total (1) 304 (2) 383 (3) 456 (4) 152
pressure exerted by hydrogen is
127. A gaseous mixture contains 56 g of N2, 44 g of CO2
1 8
(1)  (2)  and 16 g of CH4. The total pressure of the mixture is
2 9 720 mm Hg and the partial pressure of CH4 is
16 1 (1) 180 mm (2)  360 mm
(3)  (4) 
17 9 (3) 540 mm (4)  720 mm
120. A closed vessel contains equal number of oxygen and 128. A gaseous mixture of 2 moles of A, 3 moles of B
hydrogen molecules at a total pressure of 740 mm. 5 moles of C and 10 moles of D is taken in a ­vessel.
If oxygen is removed from the system, the pressure If the partial pressure of C is 1.5 atm, the total
(1) becomes half of 740 mm ­pressure is
(2) remains unchanged (1) 3 atm (2)  6 atm
(3) becomes 1/9th of 740 mm (3) 9 atm (4)  15 atm
(4) becomes double of 740 mm
129. One litre of oxygen at a pressure of 1 atm and 2 litres
121. A mixture of helium and argon contains 3 moles of of nitrogen at a pressure of 0.5 atm are introduced in
He for every two moles of Ar. The partial pressure of a vessel of 1 litre capacity, without any change in the
argon is temperature. The total pressure would be
(1) 2/3 of the total pressure (1) 1.5 atm (2)  0.5 atm
(2) 1/3 of the total pressure (3) 2.0 atm (4)  1.0 atm

Chapter_05.indd 13 3/26/2014 4:57:46 PM

 5.14  Objective Chemistry - Vol. I

130. When a litre flask contains 4 g of H2 and 14 g of N2 at • Postulates of kinetic theory of gases:
ordinary temperature the partial pressure is (i) Gases contain large number of tiny and discrete
(1) 6/7 times of the total pressure particles called molecules.
(2) 5/4 times of the total pressure (ii) Molecules in a gas move randomly in all d­ irections
(3) 4/5 times of the total pressure with different velocities but straight until they
(4) None ­collide with each other or with the wall of the v­ essel.
(iii) The actual volume occupied by the molecules is
131. Partial pressures of CO2 in a mixture of CO2 and N2 negligible when compared with the total volume of
is 1.25 atm while the total pressure of the gas mixture gas
is 5 atm. Mole fraction of nitrogen in the mixture is (iv) There exist no attractive or repulsive forces be-
(1) 0.82 (2)  0.75 tween molecules.
(3) 0.80 (4)  0.65 (v) The pressure exerted by the gas is due to the colli-
132. A sample of air contains N2, O2 and H2O. It is satu- sion of molecule on the wall of the vessel.
rated with water vapour and total pressure is 640 torr. (vi) The molecules are spherical and perfectly elastic.
The vapour pressure of water is 40 torr and the molar Hence there is no loss in the kinetic energy due to
ratio of N2:O2 is 3:1. The partial pressure of N2 in the collisions between the molecules or on the wall of
sample is container.
(vii) Molecular collisions are unaffected by gravity.
(1) 480 torr (2)  600 torr
(viii) The total kinetic energy of a gas is directly propor-
(3) 525 torr (4)  450 torr
tional to its absolute temperature
133. A vessel is filled with a mixture of oxygen and ni- KE ∝ T
trogen. At what ratio of the partial pressure will the 1 1
masses of gases be identical? mv2 = KT (∵ KE = mv2)
2 2
(1) PO2 = PN 2 (2)  PO2 = 0.5 PN 2
(3) PO2 = 0.875 PN 2 (4) 
PO2 = 1.14 PN 2 Kinetic Gas Equation
• For the derivation of kinetic gas equation RMS veloc-
134. At room temperature a gas is filled in a rectangular ity is taken.
vessel exerts a pressure of P atmospheres. If the ves-
• The square root of mean of squares of individual ve-
sel is divided into four compartments so that the two
bigger compartments of one side have double the locities of molecules is called Root Mean Square
volume of other two smaller compartments. Then the (RMS) velocity.
pressure in the bigger compartment when compared • The RMS velocity can be resolved into three compart-
to the smaller compartment is ments on the directions x, y and z axes
(1) 2P (2)  P (3) 
P/2 (4)  P/4 u2 = ux2 + uy2 + uz2
• The force transferred to the wall of the vessel by one
Answers 2mu 2
collision of a molecule is .
l
(108) 2 (109) 4 (110) 1 (111) 2 (112) 1 1
• The kinetic gas equation PV = mnu2
(113) 1 (114) 4 (115) 1 (116) 2 (117) 1 3
(118) 1 (119) 2 (120) 1 (121) 3 (122) 1 • From kinetic gas equation, RMS velocity
(123) 4 (124) 3 (125) 4 (126) 4 (127) 1
3RT 3PV 3P
(128) 2 (129) 3 (130) 3 (131) 2 (132) 4 u= or or
(133) 3 (134) 2 M M d
• RMS velocity of an ideal gas is directly proportional
to the square root of the absolute temperature.
• RMS velocity increases with increase in temperature
KINETIC MOLECULAR THEORY OF GASES and decreases with increase in molecular weight.
• Kinetic theory of gases was first proposed by • For two different gases having the same RMS velocity,
D. Bernauli and developed by Classius, Maxwell, T1 T
= 2 .
Bollzmann, Kelvin, etc. M1 M 2

Chapter_05.indd 14 3/26/2014 4:57:48 PM

 States of Matter  5.15

3 (3) Volume of the gas

• From kinetic gas equation, kinetic energy EK = RT (4) Pressure, volume and temperature of the gas
2
R 141. As the velocity of molecules increases the number of
• Boltzmann constant, K = .
N collisions per unit time
• Value of Boltzmann constant K is 1.38 × 10–16 ergs k–1 (1) decreases (2)  increases
molecule–1 or 1.38 × 10–23 Joule k–1. (3) does not change (4)  none
3
• For n moles, the kinetic energy is nEK = nRT 142. According to kinetic theory of gases the average
2
• At absolute zero, kinetic energy of molecules is zero, translational energy (KE) is
i.e., molecular motion ceases for an ideal gas. KT
(1)  per molecule
• The average kinetic energy of one mole of a gas is 2
­directly proportional to its absolute temperature. (2) KT per molecule
(3) RT per molecule
3
(4)  KT per molecule
 Objective Questions 2
143. A liquid is in equilibrium with its vapours at its boil-
135. According to kinetic theory of gases kinetic energy ing point. On average the molecules in the two phases
depends on have equal
(1) Temperature (2)  Pressure (1) Intermolecular forces
(3) Collision (4)  Atomic number (2) Potential energy
136. The number of collisions depends on (3) Total energy
(1) Distance between the molecules (4) Kinetic energy
(2) Pressure 144. A mixture of a light gas and heavy gas is in a closed
(3) Temperature container, the light gas will
(4) All the above (1) have a lower average speed per molecule than the
137. At STP, the order of root mean square speed of mol- heavy gas
ecules H2, N2, O2 and HBr is (2) have a higher average speed per molecule than
(1) H2 > N2 > O2 > HBr the heavy gas
(2) HBr > O2 > N2 > H2 (3) rise to the top of the container
(3) HBr > H2 > O2 > N2 (4) all are wrong
(4) N2 > O2 > H2 > HBr 145. If a gas is expanded at constant temperature
138. Which is not true in case of an ideal gas? (1) Number of molecules of the gas decrease
(1) It cannot be converted into a liquid (2) The kinetic energy of the molecule decreases
(2) There is no interaction between the molecules (3) The kinetic energy of the molecules remains same
(3) All molecules of the gas move with same speed (4) The kinetic energy of the molecule increases
(4) At a given temperature PV is proportional to the 146. At constant volume, for a fixed number of moles of
amount of the gas a gas the pressure of the gas increases with size of
1 39. The molecular speed Urms of gas is temperature due to
(1) Independent of temperature (1) increase in average molecular speed
(2) Proportional to the absolute temperature (2) increase in number of moles
(3) Proportional to the square root of absolute (3) increase in molecular attraction
temperature (4) decrease in the distance between the molecules
(4) Proportional to the square of absolute
147. Certain volume of a gas exerts on its walls some
temperature
pressure at temperature T. If the volume of the gas is
140. The kinetic theory of gases predicts that total kinetic reduced to half, the pressure becomes double at the
energy of gases depends on same temperature T because
(1) Pressure of the gas (1) Weight of the gas increases with pressure
(2) Temperature of the gas (2) Speed of the gas molecule decreases

Chapter_05.indd 15 3/26/2014 4:57:49 PM

 5.16  Objective Chemistry - Vol. I

(3) More number of gas molecules strike the surface 155. Two vessels having equal volumes contain H2 at one
per second atmosphere pressure and He at two atmosphere pres-
(4) Gas molecules attract each other sure respectively. If both samples are at the same tem-
perature the mean velocity of hydrogen molecule is
148. The gas in a gas-filled balloon is used in balloon
flights is heated to (1) equal to helium
(1) increase the kinetic energy of the gas (2) twice that of helium
(2) decrease the density of the gas (3) half that of helium
(3) increase the density of the gas (4)  2 times that of helium
(4) give a comfortable feeling to the balloonist at 156. The root mean square speed of hydrogen molecules
cold altitudes at room temperature is 2400 ms–1. At room tempera-
149. RMS velocity of a gas at STP cannot be calculated by ture the root mean square speed of oxygen molecule
the following expressions would be
(1) 400 ms–1 (2)  300 ms–1
3PV 3RT –1
(1)  (2)  (3) 600 ms (4)  1600 ms–1
M M
157. The molecules of a gas A travel four times faster than
3P 3RT the molecules of gas B at the same temperature. The
(3)  (4) 
d d M 
ratio of their molecular weights  A  will be
150. The root mean square velocity of a gas is doubled  MB 
when the temperature is
(1) 1/16 (2) 4 (3) 1/4 (4) 16
(1) reduced to half
(2) reduced to one-fourth 158. The average kinetic energy of the molecules in 8.0 g
(3) increased four times methane at 27°C in joules is
(4) increased two times (1) 1870.6 J (2)  187.06 J
(3) 18.7 J (4)  180.7 J
Numerical
159. The RMS velocity of an ideal gas at 27°C is 0.3 m/s.
151. At 27°C the ratio of root mean square speeds of ozone Its RMS velocity at 927°C is
to oxygen is (1) 3.0 (2) .24 (3) 0.9 (4) 0.6
3 4 160. The RMS velocity of a gas at 27°C is 4 × 104 cm/s is
(1)  (2) 
5 3 (1) 54°C (2)  108°C
2 (3) 1200 K (4) 273 K
(3)  (4) 0.25
3 161. Four particles have speed 2, 3, 4 and cm/s respectively.
152. At what temperature will be total kinetic energy (KE) Then, RMS speed is
of 0.3 mole of He be the same as the total KE of 27
0.40 mole of Ar at 400 K (1) 3.5 cm/s (2)  cm/s
2
(1) 400 K (2)  373 K
(3) 533 K (4)  300 K 54
(3)  54 cm/s (4)  cm/s
153. The RMS velocity of an ideal gas in a closed container 2
of fixed volume is increased from 5 × 104 cm s–1
to 10 × 104 cm s–1 which statement might correctly
explain that this is accomplished? Answers
(1) By heating the gas, the temperature is doubled
(2) By heating the gas, the pressure is made four times (135) 1 (136) 4 (137) 1 (138) 3 (139) 3
(3) By heating the gas, the volume is tripled (140) 2 (141) 2 (142) 4 (143) 4 (145) 2
(4) By heating the gas, the pressure is made three times (146) 1 (147) 3 (148) 2 (149) 4 (150) 3
154. At room temperature the RMS speed of the molecule (151) 3 (152) 3 (153) 2 (154) 4 (155) 4
of a certain diatomic gas is found to be 1930 m/s. The (156) 1 (157) 1 (158) 1 (159) 4 (160) 3
gas is (161) 4
(1) H2 (2) F2 (3) O2 (4) Cl2

Chapter_05.indd 16 3/26/2014 4:57:51 PM

 States of Matter  5.17

Distribution of molecular
velocities  Objective Questions

• Ratio of the number of molecules with certain velocity 162. The most probable speed in a sample of gas refers to
to the total molecules in a gas is always constant. (1) The maximum speed of the molecules
• This ratio can be determined by statistical methods. (2) The minimum speed of the molecules
(3) The speed of the largest fraction of the molecules
• Maxwell–Boltzmann give the distribution curves of (4) None of the above
molecular velocities.
• 163. For a gas at a given temperature the average velocity
A very small fraction of molecules has either low
(close to zero) or very high velocities. (1) Varies directly with its pressure
(2) Varies inversely with the pressure
• The most probable velocity is the velocity possessed by
(3) Becomes zero at a particular pressure
maximum number of molecules and represented by UP.
(4) Is same in all sample regardless of the pressure
• The average velocity (U ) of the molecules is higher
than the most probable velocity of the molecules. 164. With the increase in temperature of a gas the fraction
of molecules having velocities within a given range
• RMS velocity (U) of the molecules is higher than the around the most probable velocity would
most probable velocity and also average velocity of
(1) increase
the molecules.
(2) decrease
• As the velocities of molecules increases, the fraction (3) remain unchanged
of the molecules possessing low velocities decreases (4) initially increase and then decrease
and the fraction of molecules possessing high veloci-
ties increases. 165. Boltzmann constant is
• The number of molecules having particular en- (1) Ratio of Avogadro’s number and Faraday
ergy can be calculated by using Boltzmann equation (2) Ratio of gas constant and Avogadro’s number
ni = ne − Ei / KT where n is the total number of molecules, (3) Ratio of molar volume and Avogadro’s number
ni is the number of molecules with particular energy (4) Ratio of molar volume and Faraday
Ei, T is the absolute temperature and K is Boltzmann
constant. Numerical
• Equations for calculating different velocities 166. The average molecular speed is highest in
(1) 4.0 mole of N2 at 500 K
3RT 3PV 3P
RMS velocity, U = = = (2) 1.5 mole of Ne at 500 K
M M d (3) 0.2 mole of CO2 at 440 K
U1 + U 2 + U 3 + ... + U n (4) 2.0 mole of He at 140 K
• Average velocity, U =
n 167. The molecular velocities of the two gases at the same
temperature are u1 and u2, their masses are m1 and m2
8 RT 8 PV 8P which of the following expression is correct?
or U = = =
πM πM πd m m
(1)  1 = 2 (2) 
m1u1 = m2u2
u1 u2
• Average velocity, U = 0.9213 × RMS velocity
m u
2 RT 2 PV 2P (3)  1 = 2 (4) 
m1u12 = m2u22
• Most probable velocity, UP = = = u1 m1
M M d
168. The ratio between the RMS velocity of H2 at 50 K and
Most probable velocity, UP = 0.8166 × RMS velocity that of O2 800 K is
(1) 4 (2) 2 (3) 1 (4) 1/4
• Ratio of the three types of velocities =
169. The RMS velocity of ozone at t °C will be equal to the
2 RT 8 RT 3RT most probable velocity of oxygen at
UP : U : U = : :
M πM M 3 2
(1) (273 + k) k (2)  (273 + t) k
8 2 3
= 2: : 3 = 1 : 1.128 : 1.224 3 
         11 (3) (273 + t) K (4)   273  + tk
 2 

Chapter_05.indd 17 3/26/2014 4:57:54 PM

 5.18  Objective Chemistry - Vol. I

170. The temperature at which RMS velocity of SO2

­molecules is half that of the He molecules at 300 K is  Objective Questions
(1) 150 K (2)  600 K
(3) 900 K (4)  1200 K 171. Collision frequency Z of a gas at a particular pressure
(1) decreases with rise in temperature
Answers (2) increases with rise in temperature
(3) decreases initially and thereafter increases
(162) 3 (163) 4 (164) 4 (165) 2 (166) 4 (4) unpredictable
(167) 4 (168) 3 (169) 3 (170) 4 172. If X is the total number of collisions which a gas mol-
ecule registers with others per unit time under par-
ticular conditions, then the collision frequency of the
gas containing N molecules per unit volume is
collision properties
X
(1)  (2)  NX
• Collision free path is the average distance that a mol- N
ecule travels between two successive collisions. It is NX
(3) 2NX (4) 
denoted by λ. 2
• The collision mean free path λ can be calculated by the 173. If the collision frequency of a gas at 1 atm pressure is
relation Z, then its collision frequency at 0.5 atm is
1 RT (1) 1.0 Z (2)  0.25 Z
λ= .
2πσ P
2
(3) 2 Z (4)  0.50 Z

where σ is the collision diameter of a molecule, T is 174. The collision taking place among gas molecules
absolute temperature and P is the pressure of the gas. ­depend upon
(1) mean free path (2)  pressure
• Collision diameter (σ) is the distance between the
(3) temperature (4)  all the above
centres of two such molecules at the point of closest
approach. 175. The closest distance between the centres of two mol-
• Collision frequency is the average rate of collisions ecules of a gas taking part in collision is called
made by molecule denoted by Z. (1) collision diameter (2)  collision number
(3) molecular diameter (4)  both 1 and 3
• Collision frequency is the average number of colli-
sions made by one molecule in a time interval divided 176. With increase in pressure, the mean free path
by the length of interval. (1) increases (2)  becomes zero
1 (3) decreases (4)  remain constant
• is the time of flight, i.e., the average time that
Z
molecules spends in flight between two successive 177. Longest mean free path stands for
collisions (1) Nitrogen (N2) (2)  Oxygen (O2)
Mean free path (λ) (3) Hydrogen (H2) (4)  Chlorine (Cl2)
RMS velocity, U = = λZ
Time of flight (1 / Z ) 178. If the mean free path is l at one atm pressure then its
value at 5 atm pressure is
RT
 λ= 2
2 N A σP (1) 5l (2)  l
5
where σ is the collision cross section of the target area l
(3) (4) unpredictable
presented by one molecule to another and it is the area 5
of the circle of radius r
Answers
∴  σ = pr2
• Mean free path decreases as the pressure increases (171) 2 (172) 4 (173) 2 (174) 4 (175) 4
1 (176) 4 (177) 3 (178) 3
λ∝ .
p

Chapter_05.indd 18 3/26/2014 4:57:55 PM

 States of Matter  5.19

equation of state of real gases the number of attracted molecules. These two numbers
are directly proportional to the density of the gas.
• The ideal gas laws are derived from kinetic theory
1  1
of gases on the basis of the following two important • Attractive forces ∝ 2 ∵ d ∝ 
assumptions: V  V
(i) The actual volume occupied by the molecule is neg- a
Attractive forces = (a is constant)
ligible when compared to the total volume of the gas. V2
(ii) There are no attractive or repulsive forces between a
• The pressure of a real gas is less by 2 than the
the molecules. V
• At low pressures and low temperatures the volume
­pressure of the ideal gas. So, it must be added to the
occupied by the molecules cannot be neglected when pressure of the ideal gas. This is pressure correction.
compared to the total volume of the gas since the total • The ideal gas equation after making the volume
volume of the gas is very low. correction and pressure correction is called Van der
• At low temperatures the Van der Waal’s attractive Waal’s state equation.
forces between the gas molecules cannot be neglected
 a 
because the attractive force will have more influence  P + 2  (v – b) = RT
as the gas molecules have very less kinetic energy.  V 
• For n moles, the Van der Waal’s equation will become
• Taking into account of the volume occupied by the gas
molecules and attractive forces between the gas mol-  an 
ecules Van der Waal’s developed an equation for real
 P + 2  (v – nb) = nRT
 V 
gases by modifying the ideal gas equation known as
• The units of “b” are litre mole–1.
Van des Waal’s equation or equation of state of real
gases • b indicates the incompressibility of the gas molecules.
• The excluded volume is 4 times the actual volume
­occupied by gas molecules.
a
• The units of pressure correction 2 are atm lit2 mol–2.
V
• The constant “a” is a measure of the Van der Waal’s
forces of attraction existing between the molecules of a
gas.
When two spherical molecules of radius “r” are col- • Greater the value of “a” greater is the strength of Van
liding with each other the internuclear distance will der Waal’s forces and more easily will be the liquifica-
be “2r” and if a sphere is built with a radius of 2r, tion of such gases.
4
its volume will be π (2r)3, into which the nuclei of • Easily liquefiable gases like SO2 > NH3 > H2S > CO2
3 possess high value of “a” than the permanent gases
other molecules cannot enter. This volume is known as
excluded volume. like N2, O2, H2 and He.
4
• The excluded volume for 2 molecules = π (2r)3a
3
• The excluded volume for 1 molecule =  Objective Questions
1 4 4 179. Gases often deviate from the ideal gas behaviour be-
× π (2r )3 = 4 × πr 3
2 3 3 cause their molecules
4 (1) possess negligible volume
• The excluded volume for 1 gram mole of gas = 4 ×
pNR3 is represented by “b”. 3 (2) are polyatomic
• While writing the ideal gas equation PV = RT the (3) have forces of attraction between them
­excluded volume “b” must be subtracted from total (4) are not attracted to one another
volume V of the gas. Then, the ideal gas equation 180. The unit of Van der Waal’s constant “a” can be
becomes P(V – b) = RT. This is known as volume (1) litre atm mol–1
correction.
(2)  atm litre2 mol–2
• The attractive forces between the molecules of a gas (3) atm litre mol–2

depend upon the number of attracting molecules and (4)  litre mol–1

Chapter_05.indd 19 3/26/2014 4:57:57 PM

 5.20  Objective Chemistry - Vol. I

181. Gases deviate from ideal behaviour at high pressure. 186. Which of the following gases has the maximum value
Which of the following is correct for nonideality? of “a” in Van der Waal’s equation?
(1) At high pressure, the collision between the gas (1) H2 (2) He (3) O2 (4) NH3
molecules become enormous
187. For a real gas, deviations from ideal gas behaviour are
(2) At high pressure, the gas molecules move only in
maximum at
one direction
(3) At high pressure, the volume of a gas becomes (1) –10°C and 5 atm
insignificant (2) –10°C and 2 atm
(4) At high pressure, the intermolecular interactions (3) 0°C and 1 atm
become insignificant (4) 100°C and 2 atm

182. Which of the following is not true? 188. The strength Van der Waal’s forces increases with
(1) The “b” parameter in Van der Waal’s equation is (1) increase in molecular size
related to the intermolecular forces. (2) increase in number of electrons in the molecule
(2) The actual pressure of gas is always less than the (3) increase in molecular weight
pressure calculated from the ideal gas equation. (4) all are correct
(3) Temperature is a measure of the average kinetic 189. Which does not change during compression of a gas
energy. at constant temperature
(4) The total pressure of the mixture of gases at (1) density of a gas
constant temperature is equal to the sum of their (2) the distance between molecules
­individual partial pressures. (3) average speed of molecules
183. In Van der Waal’s equation of state for a non-ideal gas (4) the number of collisions
the term that accounts for intermolecular forces is
190. The excluded volume of a molecule in motion is
(1) (V – b) (2) RT ........... times the actual volume of a molecule in rest
 a 
(3)  P + 2  (4)  RT–1 (1) 2 (2) 4 (3) 3 (4) 0.5
 V 
184. The Van der Waal’s constant “a” is a correction factor Answers
to the ideal gas law for the intermolecular attractions
within a substance. List 1 contains the substances and (179) 3 (180) 2 (181) 4 (182) 1 (183) 3
List 2 contains the values of “a” (L2 atm mol–2). (184) 3 (185) 2 (186) 4 (187) 1 (188) 4
(189) 3 (190) 2
List-1 List-2
(i) C6H6(g) (a) 0.217
(ii) C6H5CH3(g) (b) 5.464
real gases
(iii) Ne(g) (c) 18.000
  (iv) H2O(g) (d) 24.060 • Real gases are the commonly known gases like N2, O2,
H2, CO2, etc.
Which of the following combinations represents the • Real gases obey gas laws only at low pressures and
correct matching of the substance with the corre- high temperatures.
sponding “a” value. • The deviation from ideal behaviour can be measured
(1) i – a ii – d iii – c iv – b in terms of compressibility factor Z which is the ratio
(2) i – b ii – c iii – a iv – d of product PV and nRT.
(3) i – c ii – d iii – a iv – b
(4) i – d ii – a iii – b iv – c PV PVm
Z= or (Vm is molar volume)
nRT RT
185. Under which of the following conditions of Van der
• The compressibility factor Z is unity for an ideal gas
Waal’s state equation a real gas resemble an ideal
under all conditions.
gas?
• The deviation of real gases from ideality depends upon
(1) “a” and “b” are large
(2) “a” and “b” are small temperature and pressure.
(3) “a” small and “b” is large • The deviation exhibits both positive (when Z > 1) and
(4) “a” is large and “b” is small negative (when Z < 1) deviation from unity.

Chapter_05.indd 20 3/26/2014 4:57:58 PM

 States of Matter  5.21

• Negative deviation (when Z < 1) for gases like CH4, 197. A gas approaches an ideal behaviour when
CO2, etc. is attributed to the predominance of attrac- (1) Temperature is raised keeping the volume con-
tive forces among the molecules of these gases at the stant
temperature of experiment, i.e., if Z < 1 the gas is more (2) Compressed to a smaller volume at constant tem-
compressible. perature
• Positive deviation (when Z > 1) is attributed to the (3) More gas is introduced into the same volume and
dominance of strong repulsive forces among the mol- at the same temperature
ecules, i.e., if Z > 1 the gas is less compressible. (4)  Volume is increased keeping the temperature
constant
• All real gases at sufficiently high pressure, i.e., when
size of the molecules are comparable to the volume 198. The compressibility of a gas is less than unity at STP.
of the gas will have positive deviation (Z > 1) when Hence
repulsive forces are dominant. (1) Vm > 22.4 L (2)  Vm < 22.4 L
• The extent of deviation at any given temperature and (3) Vm = 22.4 L (4)  Vm = 44.8 L
pressure depends upon the nature of gas. 199. At low temperatures all gases show
• The deviation is minimum at low pressures and maxi- (1) Negative deviation
mum at high pressures from Boyle’s law. (2) Positive deviation
• Real gases show minimum deviation at high temperature (3) Positive and negative deviation
and maximum at low temperature from Charles’ law. (4) None
• Every real gas shows positive as well as negative de- 200. Compressibility factor Z has the unit of
viation when its temperature is about near its liquefy- (1) atm L–1 (2) atm–1
ing temperature. –1
(3) litre atm (4)  litre–1
• The temperature at which a gas behaves as an ideal 201. Compressibility factor at very high pressures
gas under a range of pressures is called Boyle’s
(1) becomes negative
temperature.
(2) decreases with increasing pressure
• Boyle’s temperature depends upon the nature of the gas. (3) increases with increasing pressure
• Above Boyle’s temperature, real gases show positive (4) becomes zero
deviation. 202. Positive deviation from ideal behaviour takes place
• Below Boyle’s temperature real gases show negative because of
deviation in the beginning, i.e., at low pressure but at (1)  Molecular interaction between atoms and
high pressure they show positive deviation. PV/nRT > 1
• The lines present in the graph plotted showing the re- (2)  Molecular interaction between atoms and
lation between pressure and volume at constant tem- PV/nRT < 1
perature is known as isotherms. (3) Finite size of atoms and PV/nRT > 1
(4) Finite size of atoms and PV/nRT < 1
• The lines present in the graph plotted showing the
relation between temperature and volume at constant
pressure is known as isobar. Answers
• Boyle’s temperature is always greater than critical
temperature. (196) 3 (197) 4 (198) 2 (199) 3 (200) 2
(201) 3 (202) 1

 Objective Questions
heat capacities of gases
196. The compressibility factor of a gas is defined as Z =
PV/RT. The compresibility factor of an ideal gas is • The heat capacity of a substance is the quantity of heat
(1) 0 (2)  infinity required to rise the temperature of substance by one
(3) 1 (4)  –1 degree. The units of heat capacity are JK–1.

Chapter_05.indd 21 3/26/2014 4:57:58 PM

 5.22  Objective Chemistry - Vol. I

• The quantity of heat required to rise the temperature

of 1 g of substance by one degree is known as specific  Objective Questions
heat of that substance.
203. When an ideal gas undergoes unrestrained expansion
• The heat capacity of one mole of substance is called no cooling occurs because the molecules
molar heat capacity or molar heat.
(1) are above the inversion temperature
• Molar heat = specific heat × molecular weight. (2) exert attractive forces on each other
• The amount of heat required to rise the temperature of (3) do work equal to the loss in kinetic energy
one mole of gas by one degree at constant volume for (4) collide without loss of energy
a gas is called molar heat at constant volume (Cv). 204. When helium is allowed to expand into vacuum heat-
• Molar heat at constant volume increases the kinetic ing effect is observed. This is because
energy of the gas EK and is equal to 3/2R. (1) helium is a noble gas
(2) the inversion temperature of helium is very low
Thus, Cv = 3 / 2 R
(3) helium is an ideal gas
 
• The amount of heat required to rise the temperature of (4) the boiling point of helium is the lowest among
one mole of gas by one degree at constant pressure is the elements
called molar heat at constant pressure (CP).
205. Consider the following statement
• The ratio of molar heat capacities (γ) for monoatomic  (I) Joule–Thomson experiment is isoenthalpic as
gases is 1.66. well as adiabatic
• Since in the molecules that contain more than one  (II) A negative value of µJT (Joule–Thomson coef-
atom have rotational and vibrational energy in addi- ficient) corresponds to warming of a gas on ex-
tion to kinetic energy of motion, part of the energy pansion
supplied is utilised to increase these other forms of (III) The temperature at which neither cooling nor
energy, so that heat capacities of polyatomic gases heating effect is observed is known as inverson
will be greater than that of monoatomic gases by an temperature
amount depending on the complexity of the molecule Which of the above statements are correct?
but the difference between CP and CV remain constant (1) I and II
because work done in expansion is not affected. (2) I and II
• For diatomic gases, the ratio CP/CV = 1.40 and for tria- (3) II and III
tomic gas it is 1.33. (4) I, II and III
• The more complex the molecule of a gas, the smaller
does the ratio become. In no case γ is less than one. Answers
• The value of γ provides a means of determining the
atomicity of gas which may help to determine its mo- (203) 3 (204) 2 (205) 3
lecular formula.

Joule– Thomson Effect

liquefaction of gases
• When a gas is allowed to expand from high pressure
to low pressure, cooling takes place. This is known as • Any gas can be liquefied if cooled to a sufficiently low
Joule–Thomson Effect. temperature, that is, to a point where the kinetic energy
• The cooling is due to consumption of kinetic energy to of the molecules is no longer great enough to over-
do work against the forces of intermolecular attraction come the intermolecular forces.
forces. • Many gases can be converted into liquids simply by
• If the temperature of a gas is above a particular tem- increasing the pressure. e.g., NH3, CO2, SO2 etc.
perature, in Joule–Thomson effect heating of gases • Gases can be liquefied by increasing the pressure and
takes place and this particular temperature is known as decreasing the temperatures.
inversion temperature. • Critical temperature Tc is the temperature above
• An ideal gas is neither cooled nor heated during which the gas cannot be liquefied, no matter how high
Joule–Thomson effect. the pressure is applied.

Chapter_05.indd 22 3/26/2014 4:57:58 PM

 States of Matter  5.23

• The minimum pressure required to liquefy a gas at the

critical temperature is known as critical pressure, Pc.  Objective Questions
• At critical temperature and critical pressure (critical 206. Critical temperature of gas is the temperature
state) the volume occupied by 1 mole of gas is called (1) below which it cannot be liquefied
critical volume Vc. (2) at which it solidifies
• At critical temperature and critical pressure there is (3) above which it cannot be liquefied
no difference between liquid and gas and at this point (4) above which it can no longer remain in the gase-
the liquid instead of evaporating reaches the same ous state
density as that of the gas above it. This state is called 207. The values of Van der Waal’s constant “a” for the gas-
critical state and the phenomenon is called critical eous O2, N2, NH3 and CH4 are 1.360, 1.390, 4.170
phenomenon. and 2.253 L2 atm mol–2, respectively. The gas that can
• In critical state there is continuity between gaseous most easily be liquefied is
state and liquid state and the term fluid is used for (1) O2 (2) N2 (3) NH3 (4) CH4
either a liquid or a gas. 208. An ideal gas cannot be liquefied because
• In the critical state the density of the gaseous state is (1) Its critical temperature is always above 0°C
equal to that of the liquid state. (2) Its molecules are relatively smaller in size
• Gases below that critical temperature are called (3) It solidifies before becoming liquid
vapours and fluids above critical temperature are (4)  Forces operative between the molecules are
known as supercritical fluids. negligible
• From Van der Waal’s equation, the values of critical 209. A gas can be liquefied by pressure alone when its
constants are as follows. temperature is
(1) higher than its critical temperature
an2 8a
   Vc = 3nb;  Pc = ; Tc = (2) lower than its critical temperature
3Vc2 27 Rb (3) higher than its Boyle’s temperature
(4) lower than its Boyle’s temperature
law of corresponding 210. The liquefaction behaviour of temporary gases like
states CO2 approaches that of the permanent gases like N2,
O2, etc. as we go
• From Pc, Vc and Tc values, the values of Van der Waal’s (1) below critical temperature
constants “a” and “b” and the values of gas constant R (2) above critical temperature
V 8 PV (3) above absolute zero
b = c ; a = 3PcVc2 ; R = c c

3 3 Tc (4) below absolute zero

• The ratio of P/Pc, V/Vc and T/Tc are called reduced 211. A gas cannot be liquefied if
pressure, reduced volume and reduced temperature (1)  forces of attraction are low under ordinary
and represented by π, φ and θ, respectively. ­conditions
•
(2)  forces of attraction are high under ordinary
Two or more substances which have the same reduced
­conditions
temperature and the same reduced pressure have the
(3)  forces of attraction are zero under ordinary
same reduced volume and are called in correspond-
­conditions
ing states and this is known as law of corresponding
(4)  forces of attraction either high or low under
states.
­ordinary conditions
• All gases in the corresponding states deviate almost
212. Which forces of attraction are responsible for
equally from ideal behaviour.
­liquefaction of H2?
• The values of Boyle’s temperature TB can be calculated (1) Coulombic forces
by the relation (2) Dipole forces and Van der Waal’s’ forces
a (3) Hydrogen bonding
TB =
Rb (4) None

Chapter_05.indd 23 3/26/2014 4:57:59 PM

 5.24  Objective Chemistry - Vol. I

213. It is easier to liquefy oxygen than hydrogen because 220. An ideal gas obeying kinetic theory of gases can be
(1) Oxygen has higher critical temperature and lower liquefied if
inversion temperature than hydrogen (1)  Its temperature is more than critical tempe-
(2) Oxygen has lower critical temperature and higher ­rature, Tc.
inversion temperature than hydrogen (2) Its pressure is more than critical pressure, Pc.
(3)  Oxygen has higher critical temperature and (3) Its pressure is more than Pc at a temperature less
­higher inversion temperature than hydrogen than Tc
(4) The critical temperature and inversion tempera- (4) It cannot be liquefied at any value of P and T
ture of oxygen is very low

214. A larger value of Van der Waal’s constant b means Answers

(1) a larger force of attraction between gas molecules
(206) 3 (207) 3 (208) 4 (209) 2 (210) 2
(2) a larger molecular volume
(211) 3 (212) 2 (213) 3 (214) 2 (215) 3
(3) a lesser molecular volume
(216) 2 (217) 4 (218) 3 (219) 1 (220) 4
(4) there exists no molecular volume

215. A gas which has high critical temperature

(1) has a high critical pressure vapour pressure
(2) has a low critical pressure
• The pressure exerted by the vapour when it is in equi-
(3) has a high or low critical pressure depending on
the nature of gas librium with the liquid from which it is formed is
called saturated vapour pressure or simply vapour
(4) has a high critical volume
pressure.
216. The temperature at which the physical properties of • As the temperature increases the vapour pressure of a
liquid and vapour become identical is called liquid increases.
(1) absolute temperature • The temperature at which vapour pressure of a liquid
(2) critical temperature is equal to the atmospheric pressure (generally 1 atm)
(3) reduced temperature is known as the boiling point.
(4) transition temperature • As the external pressure is increased the boiling point
of the liquid will be increased, whereas a decrease in the
217. If the critical density of a gas is 0.2 g cm–3 and its external pressure leads to the lowering of boiling point.
molecular weight is 40 then its critical volume is
• At high altitudes the atmospheric pressure is less than
(1) 8 (2)  80 1 atm and hence liquids boil at a lower temperature at
(3) 20 (4) 200 high altitudes. Hence, it will become difficult to soften
218. Which of the following statement is false? (cook) over hills.
• In pressure cookers used in houses or the autoclaves
(1) A gas above its inversion temperature cannot be
liquefied by compression used in hospitals to sterilise the surgical instruments
the boiling point of water is increased by increasing
(2) A gas above its critical temperature cannot be
the external pressure.
­liquefied by Joule–Thomson effect
(3) A gas below its critical temperature but above • When a liquid is heated, if it boils with sudden violent
inversion temperature may be liquefied by evolution of bubbles, it is called bumping. In such a
­compression case the boiling point of liquid is more than the true
(4) None of these boiling point and the liquid is said to be superheated.
• Bumping is more when the liquid is dust free and the
219. The inversion temperature of a gas is surface of the vessel in which the boiling of liquid is
(1) higher than the critical temperature smooth.
(2) lower than the critical temperature • Bumping is due to the surface tension of the liquid
(3) depends on the nature of the gas which causes contraction of the surface of bubble, so
(4) none of these that some addition pressure is required to balance this.

Chapter_05.indd 24 3/26/2014 4:58:00 PM

 States of Matter  5.25

• The excess pressure becomes larger as the size of the • Copper (II) sulphate forms three hydrates
bubble is reduced much above the external pressure CuSO4 . 5H2O, CuSO4 . 3H2O and CuSO4 . H2O.
on the liquids and therefore a temperature above the • As the saturated solution of CuSO4 has vapour p­ ressure
normal boiling point is required. of 23 mm which is higher than the water ­ vapour
• Once a bubble is formed, its size rapidly increases ­pressure (15 mm) in air. So, it is not deliquescent.
which causes sudden evolution of large quantities of • When pentahydrate CuSO4 . 5H2O is kept in a
vapour resulting in bumping. ­dessicator containing CaCl2 . 6H2O + saturated solu-
• Bumping can be prevented by adding small pieces tion ­(vapour pressure 6.8 mm), then CuSO4 . 3H2O is
of unglazed tiles and by providing rough surface on formed because it is stable between 5 and 7.8 mm.
which bubbles of vapour can be formed easily. • If anhydrous CuSO4 is kept in a dessicator containing
• When a liquid is heated in a closed vessel boiling does any hydrate of calcium chloride, water vapour passes
not occur and at critical temperature the critical state, form calcium chloride hydrate to copper (II) sulphate.
(i.e., the density of liquid and vapours become equal) So, anhydrous CuSO4 cannot be prepared by keeping
will be formed and the meniscus of liquid disappears. pentahydrate in calcium chloride dessicator.
The liquid and vapours cannot be distinguishable. • To get anhydrous CuSO4 the pentahydrate must be
­heated to a temperature at which its vapour pressure is
Vapour Pressure of Salt Hydrates less than the vapour pressure of air, i.e., at least to 105°C.
• The property of taking water from air by a salt and • Water vapour adsorbed on the surface of many solids
dissolving it is known as deliquescence, e.g., calcium when exposed to moist atmosphere is called hygro-
chloride. scopic water in contrast to water chemically united
with ions of a compound such as Cu2+ and SO42– ions.
• The giving out of water vapour to the air from a
compound is known as efflorescence, e.g., sodium
­
carbonate decahydrate.
Actual pressure of water vapour
• Relative humidity =  Objective Questions
Saturation pressure of water vapour
• 221. Which of the following statements is wrong?
The average value for the actual pressure of water va-
pour in air is taken as 15 mm, whereas at 25°C the (1) Evaporation is a spontaneous process
saturation vapour pressure is 23.5 mm. (2) Evaporation is a surface phenomenon
(3)  Vapour pressure decreases with increases of
• The vapour pressure of calcium chloride CaCl2 . 6H2O ­temperature
is 6.8 mm and when this is exposed to air it absorbs (4) Vapour pressure of a solution is less than the
water from air until a solution of vapour pressure of ­vapour pressure of a pure liquid
15 mm is reached.
• A deliquescent substance is capable of lowering the 222. Pressure cooker reduces cooking time because
saturation vapour pressure of water vapour 23.5 mm to (1) The heat is more easily distributed
15 mm. (2) The higher pressure tenderses the food
(3) The boiling point of water inside is elevated
• The amount of water vapour absorbed by calcium (4) A large flame is used
­chloride when exposed to air depends on (i) the p­ ressure
of the saturated solution of the substance, (ii) its solu- 223. The liquid is in equilibrium with its vapours at its
bility in water and (iii) the humidity of the atmosphere. boiling point. On the average the molecules in the
• two phases have equal
The vapour pressure of saturated solution of sodium
carbonate is about 22 mm at 25°C which is much (1) Potential energy
higher than the average water vapour pressure of (2) Total energy
atmosphere. (3) Kinetic energy
(4) Intermolecular forces
• When the solution of sodium carbonate is ­exposed
to air, water evaporates and crystallisation of 224. The boiling point of water in a pressure cooker is
Na2CO3 . 10H2O takes place. The vapour pressure (1) below 100°C
of Na2CO3 . 10H2O is about 18 mm which is higher (2) Above 100°C
than the average water vapour pressure (15 mm) the (3) 100°C
­decahydrate efforesces to form monohydrate. (4) depends upon the size of pressure cooker

Chapter_05.indd 25 3/26/2014 4:58:00 PM

 5.26  Objective Chemistry - Vol. I

225. The vapour pressure of water at 0°C is • The force acting along the interface of a liquid and gas
(1) 76 cm (2)  760 cm or vapour is known as surface tension while the force
(3) 0.1 atm (4)  0 atm acting along the interface of two liquids or a liquid and
a solid is known as interfacial tension.
226. Evaporation is accompanied by
• The value of the interfacial tension for a given liquid is
(1) absorption of heat
always less than the value of surface tension of a liquid
(2) evolution of heat
with higher value due to the unbalanced forces acting
(3) Neither absorption nor evolution of heat
along the surface of each liquid are partly balanced
(4) either absorption or evolution of heat
by mutual attraction between the molecules of the two
227. At higher altitudes the boiling point of water lowers liquids.
because • The interfacial tension plays a vital role in the proper-
(1) atmospheric pressure is low ties of the emulsions and detergents.
(2) temperature is low • The substances that added to water to decrease the
(3) atmospheric pressure is high
­surface tension are called surface active substances,
(4) none of these
e.g., methyl alcohol, acetone, acetic acid, etc.
• Cleaning action of soap and detergent is due to
Answers lowering of interfacial tension between water and
­
greasy substances.
(221) 3 (222) 2 (223) 3 (224) 2 (225) 1 • Liquids wet the things because they spread across their
(226) 1 (227) 1
surfaces as thin film.

Viscosity
surface tension
• The resistance that one part of a liquid offers to the
• Surface tension is the force acting at right angles to the flow of another part of a liquid is known as viscosity.
surface along one cm length in the surface. • The resistance to flow occurs due to attraction between
• A molecule in the surface of a liquid is attracted the molecules.
­inward by other molecules due to which the surface of • The measurement of viscosity of a liquid gives
liquid tends to contract to the simplest area. an ­estimate of the strength of the intermolecular
• In CGS system the unit of surface tension is newton attractions.
m–1 (1 newton = 105 dyne) • Coefficient of viscosity of a liquid is defined as the
• The magnitude of surface tension is a measure of the tangential force unit area required to maintain a unit
strength of intermolecular forces. difference of velocity between two parallel layers of
• The energy required to increase the surface area of the the liquid held apart at a unit distance.
liquid by one unit is called surface energy. • In SI system, the unit of viscosity is newton m–2s or
• Mathematically surface tension = work to increase the Pascal. 1 Newton m–2s = 1 Pascal s = 10 dyne cm–2s =
surface area by unit area. 10 poise.
• Surface tension, • Liquids with small, spherical molecules are less viscous
Work done than the liquids with large irregularly shaped molecules.
γ=
Change in area • As the temperature is increased, the viscosity of liquid
Newton × metre decreases. For every rise in one degree temperature the
= = Newton metre2 viscosity decreases by about 2%.
metre2
• Surface energy is equal to surface tension. • As the pressure increases, the viscosity of liquid
increases.
• With increase in temperature, kinetic energy of the
molecules increases resulting in the decrease in • The viscosity of gases increases with increase in
­intermolecular forces. Hence, surface tension decreases. temperature.

Chapter_05.indd 26 3/26/2014 4:58:00 PM

 States of Matter  5.27

237. With increase in temperature the surface tension and

 Objective Questions viscosity coefficient of a liquid
(1) increases for both
229. Viscosity coefficient (η) of the liquids CH3(CH2)3
(2) decreases for both
CH3; CH3(CH2)4 CH3 and CH3(CH2)5CH3 at 30°C
(3)  surface tension decreases while viscosity
is 2.11, 2.89 and 3.68 millipoise, respectively.
­coefficient increases
The o­ rder of η of the liquids
(4)  surface tension increases while viscosity

(1) a > b > c (2) a > b = c ­coefficient decreases
(3) a < b < c (4) all are the same
238. Which of the following expression regarding the unit
230. The spherical shape of liquid drops is due to of coefficient of viscosity is not true?

(1) viscosity (2)  vapour pressure (1) dyne cm–2 s
(3) surface tension (4)  molecular size (2) dyne cm–2 s–1
231. When a student was given a viscometer, the liquid (3) Nm–2 s
was sucked with difficulty, the liquid may be (4) 1 poise = 10–1 Nm–2 s
(1) benzene (2)  toluene 239. With increasing molecular weight of a liquid the
(3) water (4)  glycerine ­viscosity
(1) decreases (2)  increases
232. Choose the correct statement
(3) no effect (4)  all are wrong
(1) Surface tension of a liquid increases with tem-
perature. 240. When the temperature is raised, the viscosity of the
(2) Addition of chemicals reduce the surface tension liquid decreases. This is because of
of a liquid. (1) decreased volume of solution
(3) Stalagmometer is used for measuring viscosity of (2)  increase in temperature increases the average
the liquid. ­kinetic energy of molecules which overcome the
(4) Viscosity of the liquid does not depend on inter- attractive force between them
molecular forces. (3) decreased covalent and hydrogen bond forces
(4) increased attraction between the molecules
233. When a solute accumulates on the surface of a solu-
tion the surface tension 241. The presence of ionic salts in liquid
(1) remains unaffected (1) decrease the viscosity of the liquid
(2) increases (2) increase the viscosity of the liquid
(3) decreases (3) does not affect the viscosity of the liquid
(4) keeps on fluctuating (4) none of the above is correct
242. The presence of an air bubble in blood stream is
234. Which of these is not correct?
­dangerous to life because
(1) Viscosity of a liquid usually decreases with
(1) air combines with blood forming a complex
increased temperature.
(2)  the flow of blood increases manifold due to
(2) Viscosity of a gas usually increases with
­concentration of surface active substances at the
increased temperature.
blood–air interface
(3) Viscosity of a gas usually decreases with
(3)  the flow of blood is obstructed due to the
increased temperature.
­concentration of surface active substances at the
(4) Surface tension of a liquid decreases with
­blood–air interface
temperature.
(4) none of these
235. The surface tension of water at 20°C is 72.75 dyne
cm–1. Its value in SI system is
(1) 7.275 Nm–1 (2)  0.7275 Nm–1 Answers
–1
(3) 0.07275 Nm (4)  72.75 Nm–1
(229) 1 (230) 3 (231) 4 (232) 2 (233) 1
236. In SI system units of coefficient of viscosity η are (234) 3 (235) 3 (236) 2 (237) 2 (238) 2
(1) kg s–2 m–2 (2)  kg m–1s–1 (239) 2 (240) 2 (241) 2 (242) 3
–1 –1
(3) kg cm s (4)  g m–1 s–1

Chapter_05.indd 27 3/26/2014 4:58:00 PM

 5.28  Objective Chemistry - Vol. I

9. A vessel is at a total pressure of 800 mm. N ­ umber

 Practice Exercise of N2 molecules is thrice to the number of CO2
­molecules. The partial pressure of N2 in the mixture is
1. Pressure remaining the same the volume of an ideal
gas increases, for every degree centigrade rise in tem- (1) 100 mm (2)  200 mm
perature by a definite fraction of its volume at (3) 300 mm (4)  600 mm
(1) zero degree centigrade 10. Which of the following statement is correct?
(2) its critical temperature (1) 3PV = mnV2 is the expression for the real gases
(3) absolute zero (2) At normal temperature and pressure most gases
(4) its Boyle’s temperature behave nearly as ideal gases
2. A bottle of cold drink has 200 mL liquid in which (3) The molecules of real gases have both volume
CO2 is 1 molar. If CO2 behaves as an ideal gas, the and mutual attraction
volume of CO2 at STP in solution of cold drink is (4) Pressure depends on number of molecules and
volume
(1) 0.224 litres (2)  4.48 litres
(3) 22.4 litres (4)  2.24 litres 11. The root mean square velocity of hydrogen molecule
of at any temperature is
3. A gas of volume 100 mL is kept in a vessel at a
­pressure 104 Pa maintained at a temperature 24°C. (1) 8 times that of oxygen molecules
If now the pressure is increased to 105 Pa keeping the (2) 4 times that of oxygen molecules
temperature constant the volume of the gas becomes (3) average velocity of molecules
(4) The number of collisions in one sq.cm. per second
(1) 10 mL (2)  100 mL
(3) 1 mL (4)  1000 mL 12. Which of the following statements is false?
4. One litre of a gas is 2 gm at 300 K and 1 atm pressure. If (1) The product of pressure and volume of a fixed
the pressure is made 0.75 atm at which of the following amount of gas is independent of temperature.
temperature will one litre of the same gas weigh 1 gm? (2)  Molecules of different gases have the same
(1) 450 K (2)  600 K ­kinetic energy at a given temperature.
(3) 800 K (4)  900 K (3) The gas equation is not valid at high pressures
and low temperature.
5. In two containers A and B, same gas is filled. If the (4)  The gas constant per molecule is known as
pressure, volume and absolute temperature of gas ­Boltzmann constant.
in A are three times as compared to that in B and if
the mass of gas in A is m gm the mass of gas in B is 13. The kinetic energy of N molecules of O2 is X Joules
at –123°C. Another sample of O2 at 27°C has kinetic
(1) m gm (2)  m/3 gm
energy of 2X Joules. The latter sample contains
(3) m/2 gm (4)  2m gm
(1) N molecules of O2
6. One mole of N2O4(g) at 300 K is kept in a closed (2) 2N molecules of O2
container under one atmosphere pressure. It is heated (3) N/2 molecules of O2
to 600 K when 20% by mass of N2O4(g) decomposes (4) None of these
to NO2(g). The resultant pressure is
(1) 1.2 atm (2)  2.4 atm 14. At constant temperature the ratio of kinetic energy of
(3) 2.0 atm (4)  1.0 atm two gases is nothing but the ratio of their
(1) molecular weights
7. A vessel contains equal volumes of SO2 and CH4 (2) number of atoms
through a small hole the gases effused into vacuum. (3) density values
After 200 s the total volume is reduced to half. What (4) number of moles
is the ratio of SO2 and methane remaining in the
vessel? 15. Which of the following statements is correct?
(1)  1:2 (2) 2:1 (3) 1:1 (4) 1:4 (1) The volume of a gas always increases when the
temperature is increased.
8. The partial pressure of oxygen in air is 152 mm. What (2) Equal volumes of gases under the same condi-
is the percentage by volume of oxygen in air? tions of temperature and pressure contain the
(1)  43.4 (2) 21.7 (3) 11 (4) 20 same number of molecules.

Chapter_05.indd 28 3/26/2014 4:58:01 PM

 States of Matter  5.29

(3) The kinetic energy of a molecule is zero at 0°C. (3) kinetic energy of molecules increases
(4) A gas in a closed container exerts higher pressure (4) kinetic energy of molecules remains same
at the bottom than at the top due to gravity.
23. The RMS velocity of hydrogen is 7 times the RMS
16. One mole of an ideal gas of relative molecular mass velocity of nitrogen. If T is the temperature of the gas
M and density d gm L–1 occupies a volume of V litres (1) T(H2) = T(N2)
at a temperature T K. The gas constant is R in appro- (2) T(H2) > T(N2)
priate units and n is the number of moles. Which of (3) T(H2) < T(N2)
the following relationship is correct? (4) T(H2) = 7 T(N2)
M d
(1) PV = RT (2)  PV = RT
d nM 24. An electric discharge is passed through a mixture
M containing 50 cc of O2 and 50 cc of H2. The volume
(3) PVd = RT (4)  P = RT of gases formed (i) at room temeprature and (ii) at
d
17. 20 cc of a gaseous element X reacts with excess of an 110°C will be
element Y to form 40 cc of a gaseous compound of (1) 25 cc and 50 cc (2)  50 cc and 95 cc
X and Y, all volumes being measured under the same (3) 25 cc and 95 cc (4)  75 cc and 75 cc
conditions of temperature and pressure. From this in- 25. A mixture of 50.0 mL of NH3 and 60 mL of O2 gas
formation it can be deduced that reacts as
(1) the molecule of X contains at least two atoms of X
(2) equal volumes of gases contain equal number of  4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
molecules If all the gases are at the same temperature and
(3) X is less denser than the compound of X and Y ­pressure and the reaction continues until one of the
(4) molecules of X cannot consist of more than two gases is completely consumed, what volume of water
atoms vapour is produced?
18. A sample of pure gas has density of 1.83 g L–1 at (1) 48 mL (2)  60.0 mL
27°C and 760 mm Hg. Which of the following could (3) 72 mL (4)  75.0 mL
be sample be
26. At 27°C a closed vessel contains a mixture of equal
(1) CH4 (2) C2H6 weights of helium (mol. wt. = 4), methane (mol. wt. =
(3) CO2 (4) Xe 16) and sulphur dioxide (mol. wt = 64). The pressure
20. A closed bulb contain inert He gas and solid NH4Cl. exerted by the mixture is 210 mm. If the partial pres-
All the NH4Cl decomposes according to the equation sures of helium, methane and sulphur dioxide are P1,
at 327°C P2 and P3, respectively, which one of the following is
NH4Cl(s) → NH3(g) + HCl(g). At this tempera- correct?
ture, the final total pressure in the bulb is 908 mm (1) P3 > P2 > P1
Hg. What is the partial pressure of HCl in the bulb (2)  P1 > P2 > P3
at 327°C when the reaction is complete and partial (3) P1 > P3 > P2
pressure of He is 228 mm Hg? (4)  P2 > P3 > P1
(1) 340 (2)  680 27. If most probable velocity is represented by α and
(3) 568 (4) 780 fraction possessing it by “f  ” then with the increase in
21. According to the kinetic molecular theory, molecules temperature which one of the following is correct?
increase in kinetic energy when they (1) α increases,  f  decreases
(1)  are mixed with other molecules at lower (2) α decreases,  f  increases
­temperature (3) Both α and  f  decreases
(2) collide with each other in a container at low (4) Both α and  f  increases
temperature
28. According to kinetic theory of gases for a diatomic
(3) are condensed into liquid
molecule
(4) are vaporised from a liquid to gaseous state
(1) The pressure exerted by the gas is proportional to
22. At a constant pressure if a gas expands the mean velocity of the molecules
(1) temperature decreases (2) The pressure exerted by the gas is proportional to
(2) kinetic energy of molecules decreases the root mean square velocity of the molecules

Chapter_05.indd 29 3/26/2014 4:58:02 PM

 5.30  Objective Chemistry - Vol. I

(3) The root mean square velocity is inversely of 100 mL and contained the gas while bulb B was
­proportional to the temperature empty and has a volume of 150 mL on opening the
(4) The mean translational kinetic energy of the mol- stop cock, the pressure of the gas in bulb A will fall
ecules is proportional to the absolute temperature down to
29. Which one of the following statements is wrong for (1) 80% (2) 60% (3) 40% (4) 20%
gases?
35. The density of H2 is 0.09 while that of O2 is 1.44;
(1) Gases do not have a definite shape and volume therefore, the rate of diffusion of H2 and the rate of
(2) Volume of the gas is equal to the volume of the diffusion of O2 are related as
container confining the gas
(3)  Confined gas exerts uniform pressure on the (1.44)1/ 2
(1) rH 2 = rO2 ×
walls of its container in all directions (0.09)1/ 2
(4) Mass of the gas cannot be determined by weigh-
(0.09)1/ 2
ing a container in which it is enclosed (2) rH 2 = rO2 ×
(1.44)1/ 2
30. Which of the following statement is not true?
(3) rH 2 = rO2 × (1.44)1/ 2 − (0.09)1/ 2
(1) The pressure of a gas is due to collision of the gas
molecules with the walls of the container rH
(2) The molecular velocity of any gas is proportional (4)  2 = 1
rO2
to the square root of the absolute temperature
(3) The rate of diffusion of a gas is directly p­ roportional 36. A certain gas diffuses from two different vessels
to the density of the gas at constant pressure A and B. The vessel A has a circular orifice while
(4)  Kinetic energy of an ideal gas is directly ­vessel B has a square orifice of length equal to the
­proportional to the absolute temperature radius of the orifice of the vessel A. The ratio of rates
of ­diffusion of the gas from vessel A to vessel B
31. A weather balloon filled with hydrogen at 1 atm and
­assuming same temperature and pressure is
27°C has volume equal to 1200 litres. On ascending
it reaches a place where the temperature is –23°C and (1) π (2) 1/π
pressure is 0.5 atm. The volume of the balloon is (3) 1:1 (4)  2:1
(1) 24000 litres 37. What percent of a sample of nitrogen must be allowed
(2)  20000 litres to escape if its temperature, pressure and volume are
(3) 10000 litres to be changed from 273°C, 3.00 atm and 1.65 L to
(4)  12000 litres O°C, 0.75 atm and 0.55 L?
32. An electronic vacuum tube was sealed off during an (1) 16.67% (2) 83.33%
experiment at a pressure of 8.2 × 10–10 atm at 27°C. (3) 75% (4) 25%
The volume of the tube was 30 dm3. The number of
38. Which of the following graph represents Boyle’s law?
gas molecules remaining in the tube are
(1) 6.02 × 1014
(2) 8.2 × 6.02 × 1023
(3) 24.6 × 106 (i) P (ii) PV
(4) 8.2 × 30 × 6.02 × 1023
33. Two flasks X and Y have capacity 1 L and 2 L, V P
respectively and each of them contains 1 mole of a
gas. The temperatures of two flasks are so adjusted
that average speed of molecules in X is twice as those (iii) PV (iv) PV
in Y. The pressure in flask Y would be
(1) same as that in X
(2) half of that in X
(3) twice of that in X V P
(4) 8 times of that in X
The correct combination is
34. Two glass bulbs A and B are connected by very (1) (ii), (iii) (2)  (i), (iv)
small tube having stop cock. Bulb A has a volume (3) (i), (iii) (4)  All are correct

Chapter_05.indd 30 3/26/2014 4:58:03 PM

 States of Matter  5.31

39. What conclusion would you draw from the following 44. Which of the following is correct for critical
graphs? temperature?
V (1) It is the lowest temperature at which liquid and
P
vapour can coexist
(2)  Beyond the critical temperature there is no
­distinction between the two phases and a gas
­cannot be liquefied by compression
(3) At critical temperature, (Tc), the surface tension
–273.15°C t°C –273.15°C t°C of the system is not zero
(4) At critical temperature, the gas and the liquid
(i) As the temperature is reduced, the volume as phases have different critical densities
well as the pressure increases
(ii) As the temperature is reduced the volume be- 45. The Van der Waal’s constants a and b
comes zero and pressure reaches infinity (1) are the same for all gases
(iii) As the temperature is reduced, the volume as (2) are the same for all gases composed of molecules
well as pressure decreases of same atomicity
 (iv) A point is reached where, theoretically, the (3) are different for different gases
volume as well as the pressure become zero (4) are independent of temperature and pressure
The correct combination is
46. When CO2 is put under pressure at 20°C it liquefies
(1) (iii), (iv) (2)  (i), (ii), (iii) but when O2 at 20°C is put under similar conditions it
(3) (i), (iv) (4)  All are correct does not liquefy. This is because
40. Indicate the correct statement for equal volumes of (1) the molecular weight of CO2 is higher than that
N2(g) and CO2(g) at 298 K and 1 atm of O2
(i) the average transitional KE per molecule is same (2) the critical temperature of O2 is much below the
for N2 and CO2 room temperature, whereas for CO2 it is above
(ii) the RMS speed remains constant for both N2 and the room temperature
CO2 (3) liquid CO2 is stable but liquid O2 is unstable
(iii) the density of N2 is less than that of CO2 (4) the critical pressure for CO2 is less than that for O2
 (iv)  the total translational KE of both N2 and CO2 is
47. A real gas obeying Van der Waal’s equation will
the same
­resemble ideal gas if
The correct statements are
(1) (ii), (iv) (2)  (i), (iii) (1) constants a and b are small
(3) (i), (ii), (iv) (4)  (i), (ii), (iii) (2) a is large and b is small
(3) a is small and b is large
41. A larger value of the Van der Waal’s constant b means
(4) a and b both are large
(1) a larger force of attraction between gas molecules
(2) a larger molecular volume 48. One litre flask contains air, water vapour and a small
(3) a lesser molecular volume amount of liquid water at a pressure 200 mm Hg.
(4) there exists no molecular volume It is connected to another one litre evacuated flask.
­Aqueous tension at this temperature is 93 mm Hg.
42. At a given temperature and volume, the pressure of a
The final pressure of the gas is
gas obeying Van der Waal’s equation is
(1) 100 mm (2) 146.5 mm
(1) equal to that of an ideal gas
(2) less than that of an ideal gas (3) 172 mm (4) 200 mm
(3) more than that of an ideal gas 49.
(4) none of the above
LS RS
43. The normal boiling point of the liquid is approximately
(1) 1.55 times its critical temperature As shown in the figure a vessel is partitioned by a
(2) two-third of its critical temperature fixed diathermic separation. Different ideal gases are
(3) half of its critical temperature filled in the two parts. The rms speed of molecules in
(4) one-third of its critical temperature the left part equals the average speed in the right part.

Chapter_05.indd 31 3/26/2014 4:58:03 PM

 5.32  Objective Chemistry - Vol. I

If right side contains Cl2 gas then molecular mass of  (III) Ideal gas does not exist but is a useful concept.
gas present in the left side should be (IV)  For 1 mole of a Van der Waal’s gas
(1) 42.6 (2) 33.6 (3) 
52.6 (4) 83.6
 a
50. Assuming that dry air contains 79% N2 and 21% O2  P + 2  (v – b) = RT
 v 
by volume. Calculate the density of moist air at 25°C
at one atmosphere when the relative humidity is 60%. (1) I, II, III, IV (2)  II, III, IV
The vapour pressure of water at 25°C is 23.76 mm Hg. (3) I, III, IV (4)  I, IV
(1) 1.16 (2) 2.16 (3) 
3.12 (4) 4.16
56. Choose the wrong statement from the following:
51. The behaviour of a real gas is usually depicted by plot- an2
ting compressibility factor Z versus P at a constant (1) The corrected pressure P + 2 in Van der Waal’s
V
temperature. At high temperature and high pressure, Z equation (symbols have their usual m ­ eanings) is
is usually more than one, this fact can be explained by the pressure which the gas would exert if it were
Van der Waal’s equation if ideal.
(1) the constant a is negligible and not b (2)  Above their respective Boyle’s temperature,
(2) the constant b is negligible and not a N2 shows throughout positive deviation (Z > 1)
(3) both the constants a and b are negligible while O2 shows negative deviation (Z   <  1)
(4) both the constants a and b are not negligible followed by positive deviation
(3) A gas shows negative deviation when long range
52. A vessel has nitrogen gas and water vapour at a to- attractive intermolecular forces are dominating.
tal pressure of 1 atm. The partial pressure of water (4) The intercept of PV vs P isotherm of an ideal gas
vapour is 0.3 atm. When the contents of this vessel at 27°C is equal to 24.6 L atm mol–1.
are transferred to another vessel having one-third ca-
57. Boyle’s temperatures of various gases are given below:
pacity of the original vessel completely at the same
temperature, the total pressure of the system in the Gas A1 A2 A3 A4
new vessel would be TB (K) 117 23 498 406
(1) 2.4 atm (2)  1 atm
Which can be liquefied easily
(3) 3.33 atm (4)  0.3 atm
(1) A1 (2) 
A2 (3)  A3 (4)  A4
53. “a” and “b” are Van der Waal’s constants for gases
Chlorine is more easily liquefied than ethane because 58. A certain unusual compound reacts with nitrogen
(1) a for Cl2 < a for C2H6 but b for Cl2 > b for C2H6 but not with oxygen in air to form a solid. Given
(2) a for Cl2 > a for C2H6 but b for Cl2 > b for C2H6 that the volume of air in contact with this compound
(3)  Cl2 < a for C2H6 but b for Cl2 > b for C2H6 decreases by a factor of 2 at 1 atm pressure and con-
(4) a and b for Cl2 < a and b for C2H6 stant temperature, calculate the partial pressure of N2
and O2, respectively after the reaction. Assume that
54. Which of the following statements are correct? original sample of air consists of 80% N2 and the rest
(I) Larger is the value of “a” for a gas, the larger is O2
would be its excluded volume. (1) 0.6 and 0.4 (2)  0.4 and 0.6
(II) Larger is the excluded volume of a gas, the (3) 0.5 and 0.5 (4)  0.7 and 0.3
more will be its critical volume.
 (III) The slope for an isochore (P vs T ) obtained for 59. A mixture of hydrogen and helium is prepared such
nR that the number of collisions on the wall per unit time
a gas showing is
V by molecules of each gas is the same. Which gas has
(IV) The excluded volume for He is more than H2. higher concentration?
(1) II, III (2)  I, II, IV (1) helium
(3) II, III, IV (4)  II, IV (2) hydrogen
(3) both have same concentration
55. Which of the following statements are correct?
(4) cannot be determined
(I) Rise in compressibility factor Z with increase in
pressure is due to “a” 60. For two gases A and B with molecular weights MA
(II) Rise in compressibility factor Z with increase in and MB it is observed that at a certain temperature
pressure is due to “b” T the mean velocity of A is equal to the root mean

Chapter_05.indd 32 3/26/2014 4:58:04 PM

 States of Matter  5.33

square velocity B. Thus the mean velocity of A can be Type of gas a/dm6 bar mol–2 b/dm3 mol–1
made equal to the mean velocity of B if
3π Gas A 6.5 0.056
(1) A is lowered to a temperature T2 = T
8 Gas B 18.0 0.011
8T (a) Critical volume of A < Critical volume of B
(2) A is lowered to a temperature T2 = (b) Critical pressure of A < Critical pressure of B
3π
(c) Critical temperature A > Critical temperature of B
3πT
(3) B is lowered to a temperature T2 = then, which of the above statements is/are correct?
8
(1) b alone (2)  a and b only
8
(4) B is lowered to a temperature T2 = (3) a, b and C (4)  b and c only
3π
61. The given graph represents the variaton of Z (com- 65. For the reaction 2NH3(g) → N2(g) + 3H2(g) what is
PV the %NH3 converted if the mixture diffuse twice as
pressibility factor = ) versus P, for three real
nRT fast as that of SO2 under similar conditions?
gases A, B and C. Identify the correct statement. (1) 3.125 (2)  6.25
Z C (3) 12.5 (4)  none
66. Figure shows two vessels A and B with rigid walls
A containing ideal gases. The pressure, temperature and
I the volume are PA, TA and V in the vessel A and PB,
ideal gas TB and V in vessel B. The vessels are now connected
through a small tube. P/T value is equal to
B P

A B
P(atm)
(1) For the gas A, a = 0 and its dependence on P is
P 1 P P  P 1  PA PB 
linear at all pressures. (1)  =  A + B  (2) =  + 
(2) For the gas B, b = 0 and its dependence on P is T 2  TA TB  T 2  TB TA 
linear at all pressures.
P P P  P  PA PB 
(3) For the gas C, which is a typical real gas for which (3)  =  A + B  (4) = + 
neither a nor b = 0. By knowing the minima and T  TB TA  T  TA TB 
the point of intersection with Z = 1, a and b can 67. One mole of an ideal gas undergoes a process P =
be calculated. Po
where Po and Vo are constants. Find the
(4) At high pressure, the slope is positive for all real
(1 + V / Vo )
2

gases.
temperature of the gas when V = Vo
62. If density of vapours of a substance of molar mass 18
PV PoVo 2
g/mole at 1 atm pressure and 500 K is 0.36 kg m–3, (1)  o o (2) 
then the value of (Z) compressibility factor for the 2R 2R
vapour is: (Take R = 0.0821 L atm mole–1 k–1) P 2V PoVo
(3)  o o (4) 
(1) 41/50 (2) 50/41 (3) 1.1 (4) 0.9 2R R
68. The compressibility factor of He as a real gas is
63. A one litre vessel at pressure P1 and a two litre v­ essel
a
at pressure P2 contain one mole each of oxygen gas. (1) 1 (2)  1−
If the temperatures are so adjusted such that the RTV
­velocities of O2 molecules in 1 lit vessel are 4 times Pb
(3) 1 + (4)  RTV / (1− a)
that of 2 lit vessel, then at what ratio P1 and P2 will be RT
69. A balloon blown up with one mole of gas has volume
(1)  4:1 (2) 8:1 (3) 16:1 (4) 32:1
of 700 mL at 27°C. The balloon is filled to 7/8th of
64. Consider the following statements. maximum capacity. The pressure inside the balloon is
If the Van der Waal’s parameters of two gases are (1) 3.518 atm (2)  35.18 atm
­given as (3) 4.518 atm (4)  45.18 atm

Chapter_05.indd 33 3/26/2014 4:58:07 PM

 5.34  Objective Chemistry - Vol. I

70. A volume V of a gas at a temperature T and pres- 75. A mixture of C3H8 and CH4 exerts a pressure of 320
sure “P” is enclosed in a sphere. It is connected to an- mm Hg at temperature TK in a 5-litre flask. On com-
other sphere of volume V/2 by a tube and stop cock. plete combustion gaseous mixture contains CO2 only
The second sphere is initially evacuated and the stop and exerts a pressure of 448 mm Hg under i­dentical
cock is closed. If the stop cock is opened the tempera- conditions. Hence, mole fraction of C3H8 in the
ture of the gas in the second sphere becomes T2. The ­mixture is
first sphere is maintained at “T1”. What is the final (1) 0.2 (2) 0.8 (3) 0.25 (4) 0.75
­pressure within the apparatus?
2 PT2 2 PT2 76. At 27°C and 1 atm pressure 5 lit of a gas has n1 mol-
(1)  (2)  ecules. At 300 K and 760 mm Hg pressure 10 lit of
2T2 + T1 T2 + 2T1
another gas has n2 molecules. The molecular weight
PT2 2 PT2 of first gas is twice that of a second gas then
(3)  (4) 
2T2 + T1 T1 + T2 (1) n1 = n2
71. For a closed (non-rigid) container containing 10 (2)  n2 = 2n1
moles of an ideal gas, fitted with movable friction- (3) n1 = 2n2
less, weightless piston operating such that pressure of (4)  n1 = 4n2
gas remains constant at 0.821 atm, then which of the
following curves represent correct variation of log10V 77. On a certain day the vapour pressure is 14 mm of Hg
versus log10 T where V is in litre and T in Kelvin? for water vapour in air at 20°C. The saturated ­vapour
pressure is 17.5 mm. How many moles of water
(1) (2) ­vapour per litre of air would be required to saturate
air at this temperature?
log10V log10V
(1) 9.41 × 10–4

(2) 9.14 × 10–4
45° 30°
log10T (3) 1.914 × 10–4
log10T
(4) 4.19 × 10–4
(3) (4) 78. A collapsed polythene bag of 3 litre capacity is par-
tially filled by 1 litre of helium gas at 0.3 atm pres-
log10V 45° log10V sure at 300 K. Subsequently, enough Ne gas is filled
to make total pressure of 0.4 atm at 300 K. The mole
60° fraction of Ne gas in bag is
log10T log10T 1 1
(1)  (2) 
4 2
72. Compressibility factor for N2 at 27°C and 100 atm 3
1
pressure is 1.66. Calculate the number of mole of N2 (3)  (4) 
gas required to fill a gas cylinder of 821 mL under 3 4
these conditions.
79. Compressibility factor of CO2 is, if one mole gas
(1) 3.5 (2) 3 (3) 
2.5 (4) 2 ­occupies 0.41 lit at 300 k and 30 atm.
73. Two moles of a gas in a 4-litre flask exerts a pressure (1) 0.4 (2) 0.45 (3) 0.50 (4) 0.5
of 11 atm at a temperature of 27°C. The value of “b”
is 0.05 lit mol–1. The vlaue of “a” in Van der Waal’s 80. The density of a mixture of O2 and N2 at 1 atm and
equation is 27°C is 1.22 kg/m3. The partial pressure of O2 is
(1) 1.63 atm lit2 mol–2 (2)  4.89 atm lit2 mol–2 (1) 0.2 (2)  0.3
2
(3) 3.26 atm lit mol –2
(4)  6.46 atm lit2 mol–2 (3) 0.4 (4)  0.5
74. A 4:1 mixture of helium and methane is contained 81. A spherical balloon of volume 3 litres is filled with H2
in a vessel at 10 bar pressure. Due to a hole in the at 1 atm, 300 K. A cylinder contains H2 gas at 10 atm
vessel, the gas mixture leaks out. The composition of 400 K. The volume of cylinder is 4 litres. The no. of
mixture effusing out initially is balloons required to fill the gas is
(1) 8:1 (2) 8:3 (3) 
4:1 (4) 1:1 (1) 1 (2) 2 (3) 9 (4) 10

Chapter_05.indd 34 3/26/2014 4:58:09 PM

 States of Matter  5.35

82. Consider the apparatus shown a 2a

(1)  , b (2)  , b
RT RT
HCl gas a a
Flask (3) 1, b − (4)  1,
RT 2Tb

86. What is the pressure exerted by 1023 gas particles

each of mass 10–22 g in a container of volume 1 dm3?
Rubber bulb
Long tube The root mean square speed is 105 cm s–1.
(containing H2O)
1 1
(1)  × 10 7 Pa (2)  × 106 Pa
3 3
Beaker
1 1
(3)  × 109 Pa (4)  × 108 Pa
3 3
Blue litmus 87. A 5-litre bulb contains n moles of N2 at 0.5 atm and
solution at TK on adding 2.5 × 10–2 moles of O2. Cooling to
10°C is necessary to maintain the same pressure.
­Calculate n and T.
When “rubber bulb” of the medicine dropper will be
squeezed? (1) 0.0268 mole, 286.63 K
(2) 0.0826 mole, 368.65 K
(1) The litmus solution in the beaker will turn red
(3) 0.0286 mole, 268.69 K
with a slight increase in volume
(4) 0.628 mole, 399.65 K
(2) The litmus solution in the beaker will turn red
with slight decrease in volume 88. In the graph between the volume of gas and t°C the
(3) The litmus solution will rush up through the long slope/intercept value is equal to
tube to create a blue fountain in the flask 1
(4) The litmus solution will rush up through the long (1) K (2) 
K
tube to create a red fountain in the flask
1
(3) 273 (4) 
83. The critical volume of a gas is 0.072 lit mol–1. The 273
radius of the molecule will be in cm 89. Compressibility factor for H2 above 108 K (TB for
1/ 3 1/ 3
9   4π −23  H2 = 108 K)
(1)  × 10 −23  (2) 
 3 × 10 
 4π   a 
(1) 1 (2)  1− 
 4π 
1/ 3
 3 
1/ 3  RTV 
(3)  × 10 −23  (4) 
 × 10 −23 
9   4π   Pb  RTV
(3) 1+
  (4)
 Rt  (1− a)
84. NH3 gas at 1 atm and HCl gas at P atm are allowed
to effuse through opposite ends of a glass tube of 1
metre length of uniform cross section. They will meet
60 cm distance from the HCl. The value of P is Answers
(1) 1.414 atm  (1) 1  (2) 2  (3) 1  (4) 1  (5) 2
(2)  2.12 atm  (6) 2  (7) 2  (8) 4  (9) 4 (10) 3
(3) 2.85 atm (11) 3 (12) 2 (13) 1 (14) 4 (15) 2
(4)  3.23 atm (16) 4 (17) 1 (18) 3 (19) 4 (20) 1
(21) 4 (22) 3 (23) 3 (24) 3 (25) 3
85. A general form of equation of state for gases is PV =
(26) 2 (27) 1 (28) 4 (29) 4 (30) 3
 B C  (31) 2 (32) 1 (33) 4 (34) 3 (35) 1
RT  A + + 2 + ... where V is the molar volume
 V V  (36) 1 (37) 2 (38) 1 (39) 1 (40) 3
of the gas and A, B, C, ... are constants for the gas. (41) 2 (42) 2 (43) 2 (44) 2 (45) 3
The values of A and B, if the gas obeys Van der Waal’s (46) 2 (47) 1 (48) 2 (49) 4 (50) 1
equation, are respectively (51) 1 (52) 1 (53) 2 (54) 3 (55) 2

Chapter_05.indd 35 3/26/2014 4:58:12 PM

 5.36  Objective Chemistry - Vol. I

(56) 2 (57) 3 (58) 1 (59) 1 (60) 2 7. Statement I: If Z > 1 repulsive forces determinate the
(61) 2 (62) 2 (63) 4 (64) 1 (65) 2 behaviour of a particular gas.
(66) 1 (67) 1 (68) 3 (69) 2 (70) 1 Statement II: With increase of pressure, Z decreases
(71) 1 (72) 4 (73) 4 (74) 1 (75) 1 continuously.
(76) 2 (77) 4 (78) 4 (79) 3 (80) 4
(81) 3 (82) 4 (83) 4 (84) 2 (85) 3 8. Statement I: The value of Boyle’s temperature
a
(86) 1 (87) 2 (88) 4 (89) 2 TB = for Van der Waal’s gases.
Rb
Statement II: At Boyle’s temperature, TB, real gases
behave ideally over a large range of pressure.
 Statement-Type Questions
9. Statement I: In low speed region, fraction of mol-
In the following questions, a statement I is given and a ecules having a particular speed range increases with
corresponding statement II follows it. Mark the correct increase in temperature.
answer as Statement II: Increase in temperature of a gas sys-
(1) If both statement I and statement II are true and tem decreases the fraction of molecules possessing
­statement II is the correct explanation of statement I the most probable speed.

(2) I f both statement I and statement II are true but state- 10. Statement I: SO2 gas is easily liquefied while H2 is not.
ment II is not the correct explanation of s­ tatement II Statement II: SO2 has low critical temperature while
H2 has high critical temperature.
(3) If statement I is true but statement II is false
11. Statement I: If ‘a’ is Van der Waal’s constant a I 2 > a cl2
(4) If statement I is false but statement II is true Statement II: Dipole-dipole attractions among the
above gaseous molecules is proportional to m ­ olecular
1. Statement I: NH3 is more adsorbed in activated char-
weight
coal than H2.
Statement II: Critical temperature for NH3 is more 12. Statement I: Gas with lower molecular weight will
than that of H2. effuse or diffuse faster at constant temperature and
pressure.
2. Statement I: Van der Waal’s constant “a” is larger
Statement II: Kinetic energy of any gas depends
for N2 than NH3.
upon its mass.
Statement II: There is hydrogen bonding in NH3.
13. Statement I: Greater the value of Van der Waal’s
3. Statement I: The measurement of the pressure of dry ­constant “a” greater is the liquefaction of gas.
gas collected over water is based upon Boyle’s law.
Statement II: “a” indirectly measures the magnitude
Statement II: Volume of a given mass of gas is in-
of attractive forces between the molecules.
versely proportional to its absolute temperature at
given pressure. 14. Statement I: Critical temperature is the tempera-
ture at which the real gas exhibit ideal behaviour for
4. Statement I: 1/4th of the gas is expelled if air present
­considerable range of pressure.
in an open vessel is heated from 27°C to 127°C.
Statement II: At critical point the densities of a
Statement II: Rate of diffusion of a gas is directly
­substance in gaseous and liquid states are the same.
proportional to the square root of its molecular mass
at constant temperature and pressure. 15. Statement I: Aqueous tension is the force experi-
enced by water molecules on its surface.
5. Statement I: Compressibility factor (Z) for non-ideal
gases is always greater than 2. Statement II: Aqueous tension is the force experi-
Statement II: Non-ideal gases always exert less enced by water molecules on its surface.
pressure than expected. 16. Statement I: Vapour pressure of CO2 is higher than
6. Statement I: At constant temperature, if pressure on that of O3.
the gas is doubled, density is also doubled. Statement II: VD of O3 is more than that of VD
Statement II: At constant temperature molecular of CO2.
masses of a gas is directly proportional to the density 17. Statement I: Vapour pressure of liquid depends on
and inversely proportional to pressure. only temperature.

Chapter_05.indd 36 3/26/2014 4:58:13 PM

 States of Matter  5.37

Statement II: Rate of diffusion of a gas at constant (T ) 2. List-I List-II

and (P) is inversely proportional to square root of VD.
(A) Density of ideal gas  (i) Effusion
18. Statement I: The pressure of fixed amount of an
­ideal gas is proportional to its temperature at constant (B) Escape of gas from a 8RT
volume.  (ii)
punctured tube πM
Statement II: Frequency of collisions and their impact, PM
both increase in proportion to the square root of (T). (C) Average speed (iii)
RT
19. Statement I: Separation of 235U from relatively more
3RT
abundant 238U is caused by converting all uranium (D) RMS velocity  (iv)
to UF6. M

Statement II: UF6 exists as gaseous compound u­ nder The correct matching is
ordinary conditions.
S. No. A B C D
20. Statement I: Process of diffusion is always followed
1. iii i ii iv
by effusion.
2. iv ii iii i
Statement II: Both diffusion and effusion deal with 3. iii ii i iv
spreading of gases. 4. ii iii i iv

Answers 3. List-I List-II

 (1) 1  (2) 4  (3) 4  (4) 3  (5) 4 (A) Pascal  (i) Rate of diffusion of gas
 (6) 3  (7) 3  (8) 2  (9) 4 (10) 4 (B) dyne cm  (ii) Newton m–2
(11) 3 (12) 2 (13) 1 (14) 4 (15) 3 (C) 4.18 Joule (iii) erg
(16) 1 (17) 2 (18) 1 (19) 1 (20) 4
(D) Fountain experiment  (iv) Joule

The correct matching is

S. No. A B C D
 Match the Following Type Questions
1. i ii iii iv
Match the following volume strength given in List I with 2. i ii iv iii
the value given in List II. 3. ii iii v i
4. ii iii i iv
1. List-I List-II
(A) (2RT/M)1/2  (i) Torr
(B) Work done degree–1 mol–1  (ii) Gram molar volume
(C) 22.4 lit at STP (iii) Universal gas constant
Answers
(D) Unit of low pressure  (iv) Most probable velocity
(1) 1 (2) 1 (3) 3
 (v) atm

The correct matching is

S. No. A B C D HINTS
1. iv iii ii i 28 × 4 + 32 × 1
43. Molecular weight of a sample of air =
2. ii iii i iv 5
= 28.8
3. iv iii ii i 28.8
4. ii i iii ii ∴ Vapour density = = 14.4
2

Chapter_05.indd 37 3/26/2014 4:58:14 PM

 5.38  Objective Chemistry - Vol. I

44. T = 127 + 273 = 400 K 55. P1 = 1 atm; P2 = ?

When T is doubled in absolute scale, volume will be V1 = 1 lit; V2 = 0.95
doubled as 30800 K or 527°C. (∴ decrease in volume is 5%)
1 Applying P1V1 = P2V2
45. According to Boyle’s law, P ∝
v 1× 1
P2 = = 1.0526 atm
∴ P1 < P2 at constant T 0.95
For every 1 atm, the increase in pressure is 0.0526 atm.
46. P1 = 1 atm; P2 = 1.004 (∴ The increase in pressure is
So, percentage increase in pressure is 5.26.
0.4% per 1°C)
T1 = x°C; T2 = (x + 1)°C 56. V1 = 1; V2 = 1.1 (∴ increase in volume is 10%)
P P 1 1.004 T1 = 1; T2 = ?
1 = 2 or =
T1 T2 x x +1 V V
Applying 1 = 2 ; T2 = 1.1
T1 T2
x + 1 = 1.004x or 0.004x = 1
At constant pressure if the increase in temperature is
1
x = = 250 K 0.1 for increase in volume from 1.0 lit to 1.1 lit, the
0.004 percentage increase in temperature is 10.
m PV PV
47. d= 1 1
57. = 2 2
v T1 T2
At lowest temperature and highest pressure, the 1× 1× 300 300
­volume of a gas will be lowest. Hence, at 0°C and ∴ V2 = or
273 × 2 273 × 2
2 atm neon will have highest density.
58. If the weight of 5.6 lit of HF at NTP is 10 g the MW
48. At STP, i.e., 0°C and 1 mole of He occupies
of HF will be
22.4 litres. Since the temperature is more than 0°C
22.4 × 10
(30°C), 22.4 litre of He contain less than 1 mole. So, = 40
0.9 mole. 5.6
Empirical formula wt. of HF = 20
49. When temperature is doubled, volume will be 40
­doubled. When pressure is doubled, volume will be ∴ =2
20
halved. So, doubling the temperature and pressure
Hence, molecular formula of HF is H2F2.
keeps the volume of the gas constant.
∴ 273°C and 2 atm 59. At STP, 22400 mL of H2 weighs 2 g
m After converting 145 mL at 760 mm of Hg and 27°C
50. d = to STP is 132 mL
v 132 × 2
∴ When volume of the gas is halved density will be ∴ The weight of 132 mL of H2 =
= 0.012 g or 12 mg 22400
­doubled since at 2 atm and 25°C the volume of the
gas will be halved, the density will doubled. V1 V2 20 V 20
60. = ⇒ = 2 or × 300 = 60 litre
51. Volume of gas will be maximum at high ­temperature T1 T2 100 300 100
and low pressure. So, molar volume of CO2 is Change in volume is 60 – 20 = 40 litres
­maximum at 127°C and 1 atm.
61. Equal volumes of all gases under the same conditions
52. According to the reaction, CO2 + C → 2CO of temperature and pressure contain equal number of
1 mL of CO2 converts into 2 mL of CO (Q v ∝ n) molecules since the volume of containers is the same.
∴ The maximum volume of CO formed is 52 mL. Number of molecules of O2 is equal to the number of
molecules of SO2. But the molecular weight of SO2
53. For same d when compared the pressure at T1 is more (64) is twice that of O2 (32). So, the weight of oxygen
than at T which indicates volume is more. So, T1 > T2. is 1/2 that of SO2.
54. 4.4. g of CO2 contain 6.023 × 1022 molecules 62. When volume and temperature are constant P ∝ T.
2.24 lit of H2 contain 6.023 × 1022 molecules Since the number of moles of H2 is 22 and number of
∴ Totally, there are 1.2046 × 1023 molecules. moles of CO2 is 1 the P of H2 will be 22 atm.

Chapter_05.indd 38 3/26/2014 4:58:17 PM

 States of Matter  5.39

63. MW = VD × 2 The MW of  O2 is 16 times greater than that of hydrogen.

∴ MW = 70 × 2 = 140 Hence, the mass of O2 would be 16 times more.
MW 140 72. At constant pressure if temperature is doubled, the
X = = =5
Empirical formula wt 28 volume of a gas will be doubled and half of
the ­volume will be escaped from an open vessel since
64. The ratio of moles of O2 and N2 is 1:4 and by weight the volume of the container is same. Therefore, the
1 4 vessel must be heated to 600 K or 327°C.
is : = 7: 32.
32 28 PV PV
73. Applying 1 1 = 2 2 , the volume at STP will be
65. The increase in volume is 20%. So, 800 cc becomes T1 T2
960 cc. 5.6 litres. So, the container can hold 1/4 mole of an
V V ideal gas.
Applying 1 = 2 , T2 = 360 K or 87°C.
T1 T2
74. At constant pressure if temperature is halved the
5 volume will be halved. So, the gas should be cooled
66. P2 = × 300 = 6 atm from 0°C or 273 K to 136.5 K.
250
75. Let the number of moles at T1 is 1.
d1 T2 1
67. Applying = ; T2 = × 300 = 400 K When heated 3/4 moles are expelled, so the remain-
d2 T1 0.75
ing moles are ¼.
PV PV Applying n1T1 = n2T2
68. Applying 1 1
= 2 2 T2 = 1200 K or 927°C
T1 T2
76. At constant pressure if the temperature of a given mass
100 × 2 400 of gas is changed by one degree in celsius scale the
V2 = × = 800 mL
200 0.5 volume changes by 1/273 times of its volume at 0°C.
69. P1V1 = n1RT1 where P1 = P, V1 = V, n = m/M, T1 = T  273 + t   273 + 273 
Applying V = Vo   = 273  = 546
Then, PV =
m
RT   (1)  273   273 
M The increase in volume for the rise in temperature
Let X gm of the gas remain in a flask when final pres- of 273 is 273 K. Therefore, for every 1°C rise in
sure ­temperature 1 mL increases.
P 2
P2 = , T2 = T (Q V remains constant) 77. Applying P1V1 = P2V2 to convert the volume to 1 atm
2 3
5 × 10
P x 2T V2 = = 50 litres
V = R    (2) 1
2 M 3
Since 10 litres of gas remain in container and 40 litres
Dividing (1) by (2) and solving for X of gas come out, the number of balloons of 0.5 litre
3m 4.0
X = size can be filled is = 80.
4 0.5
3m 1 78. The volume of a gas is directly proportional to its
So, the gas escaped is m − = m. ­absolute temperature at a constant pressure. So, a
4 4
graph drawn between V and T at constant P gives a
P1 P2 straight line passing through the origin.
70. Applying =
T1 T2
dA RT d RT
79. PA = and PB = B
300 MA MB
T2 = 15 × = 375 K or 102°C
12
r1 M2 2 Mx
The cylinder will burst above 102°C. 96. Apply = or =
r2 M1 1 16
71. Since V is constant, number of moles of H2 is equal to
Mx
number of moles of O2. 4 = or Mx = 4 × 16 = 64
16

Chapter_05.indd 39 3/26/2014 4:58:22 PM

 5.40  Objective Chemistry - Vol. I

r1 M2 81 107. The rate of diffusion of hydrogen is 4 times to that

97. = = oxygen so the pressure inside the hydrogen cylinder
r2 M1 100 may decrease to 0.25 atm. As the pressure inside the
r1 9 cylinder cannot be less than atmospheric pressure as
= or r1:r2 = 9:10
r2 10 the gases leaked into atmosphere the hydrogen leaked
until the pressure in side is 1 atm only.
rCH 4
64
98. = =2 119. The fraction of the total pressure exerted by a gas is
rSO2 16 equal to its mole fraction.
So, the rate of diffusion of methane is twice that of Let the weight of methane and hydrogen is 16 g each.
SO2. ∴  The number of moles of methane is 1 and number
rO 2
4 1 1 of moles of hydrogen is 8.
99. = = = 8
rHe 32 8 2 2 ∴ Mole fraction of H2 =
9
∴ The rate of diffusion of O2 is nearly 0.25 times 120. P ∝ n. Since oxygen and hydrogen molecules in the
that of He. ­container are equal and oxygen, i.e., half the molecules
rH 2 Mx 6 Mx are removed and thus pressure becomes half of 740 mm.
100. = ; =
rx M H2 1 2 121. Partial pressure of argon = Total pressure × mole
∴ M2 = 72 ­fraction of argon
2
∴ The partial pressure of argon = of the total
W1 M1 2 2 ­pressure. 5
101. = ; =
W2 M 2 W2 32 21
122. V ∝ n ∴ mole fraction of O2 =
2 1 100
= or W2 = 8 Partial pressure = Total pressure × mole fraction
W2 4
21
PO 2 = 750 × = 157.7 mm of Hg
t1 M1 50 32 100
102. = or =
t2 M2 t2 2
1 1 + P2V2
PV
123. = Pressure of mixture of gases
50 Total volume
= 4 or t2 = 12.5 min
t2 (600 × 1) + (800 × 0.5)
∴ = 500 mm
2000
r1 Vd1 V V
103. = r1 = 1 , r2 = 2 and Vd1 = 11 124. Partial pressure of water vapour = Mole fraction ×
r2 Vd2 t1 t2 Total pressure
1
20 10 22 20 × 10 = × 760 = 7.6 mm
× = or v2 = or 20 2 100
5 V2 11 5× 2
125. Partial pressure of H2 = Mole fraction of X2 × Total
T M2 45 M2 pressure
1 04. 2 = or =
T1 M1 18 32 1 2
= or of the total pressure
1.5 3
( 45)2 0.1
∴ M 2 = × 32 126. Partial pressure of O2 = × 760 = 152
(18)2 0.5
127. Partial pressure of CH4 = Mole fraction (0 Total
V1 M1 57 M2 ­pressure)
105. = or =
V2 M2 10 2 1
= × 720 = 180
M2 = 64 approximately. So, the gas is SO2. 4
128. p α n
V1 M2 65 2
106. = or = Number of moles of C is 5 and its pressure is 1.5 atm
V2 M1 V2 32 1.5
∴ For each mole, the pressure will be = 0.3 atm
V2 = 260 5

Chapter_05.indd 40 3/26/2014 4:58:28 PM

 States of Matter  5.41

Hence partial pressure of A = 0.6 atm; B = 0.9 atm; 3RT

C = 1.5 atm and D = 3.0 atm. So, total pressure = 6 atm. 153. RMS velocity, C =
M
129. Total pressure
PV + P2V2 (1 × 1) + (0.5 × 2) Therefore, RMS velocity C ∝ T or P for a
    = 1 1 = = 2 atm ­particular gas when V is constant. So, when RMS
Total volume 1
­velocity is doubled the pressure will be increased by
130. 4 g of H2 = 2 moles, 14 g of N2 = 0.5 mole four times. (Ans. 2)
Total no. of moles = 2.5
2 4 3RT
Partial pressure of H2 = or times of total pres- 154. C =
2 . 5 5 M
sure
3 × 8.314 × 10 7 × 300
131. Partial pressure of N2 = 5 – 1.25 = 3.75 193000 =
M
3.75
Mole fraction of N2 = = 0.75 atm (Room temperature is taken as 27°C)
5 3 × 8.314 × 10 7 × 300
132. Pressure of N2 and O2 = 193000 × 193000 =
M
Total pressure – Vapour pressure of water M = 2. Therefore, the gas is H2.
= 640 – 40 = 600 torr
3
Partial pressure of N2 = 600 × = 45 torr T
4 155. Mean velocity ∝
M
133. Let the masses of N2 and O2 are 28 g each CH2
4
No. of moles of N2 = 1 ∴ =
  Q T is equal.
C He 2
28 7 So, the mean velocity of H2 is 2 times that of He.
No. of moles of O2 = =
32 8 CH2 M O2 2400 32
7 156. = ∴ =
No. of moles of O2: N2 = : 1 C He M H2 CO2 2
8
= 0.825:1 2400
CO2 = = 600 ms–1
PO2 0.825 4
∴ =
PN 2 1 CA MB MB
4
157. = ⇒ =
PO2 = 0.825 PN 2 CB MA 1 MA
134. When the same container is divided into compart- MB MB 1
16 = ∴ =
ments the pressure in all compartments will be equal MA M A 16
though their sizes are different because v α n.
3
158. KE =
nRT
3RT 2
151. RMS velocity, C = 3 8
M = × × 8.314 × 300 = 1870.6 J
CO3 2 16
C M2 32 2
1 = ∴ = =
C2 M1 CO2 48 3 C2 T
159. = 2
C1 T1
3 C 1200
152. KE = nRT 2 =
2 0.3 300
Since KE for both He and Ar are equal
∴ C2 = 2 × 0.3 = 0.6
3 3
n1RT1 = n2RT2
2 2 160. C ∝ T
3 8 × 104 cm/s is double to that of
or × 0.3 × T1 = × 0.4 × 400
2 4 × 04 cm/s
0.4 × 400 ∴ The temperature must increase by four times, i.e.,
T1 = = 533 K 1200 K.
0.3

Chapter_05.indd 41 3/26/2014 4:58:36 PM

 5.42  Objective Chemistry - Vol. I

Hints to Objective Question of

C12 + C22 + C32 + ... + cm2
161. RMS velocity = Practice Exercise
n
2. Moles of CO2 = 1 × 0.2 = 0.2
22 + 32 + 4 2 + 52 54 54
= = = cm/s 1 mole occupies 22.4 lit
4 4 2 0.2 mole occupies 4.48 lit
166. Ratios of the average velocities are proportional to 3. P1V1 = P2V2
T 104 × 100 = 105x
M x = 10 mL

500 500 440 140 W

: : : 4. PV =RT
28 20 44 4 M
P W T
500 500 440 140 1 = 1 × 1
Or : : : P2 W2 T2
28 20 44 4
1 2 × 300
= 17.89:25:10:35 =
∴ He at 140 K will have the highest speed. 0.75 1× T
T = 450 K
167. At the same temperature, the kinetic energies of
m
­different gases are equal. 5. According to PV = R T, then P, V and T are thrice
M
1 1 the mass in container A is three times that of B. So,
m1u12 = m2u22 ∴ m1u12 = m2u22 maps of B is m/3.
2 2

N 2 O4 
 2 NO2
6.
3R50 3R 800 1− x 2x
168. C H 2 = ; CO2 =
2 32 Total moles = 1 + x = 1.2
CH2 50 32 P nT
1 = 1 1
= × =1 P2 n2T2
CO2 2 800
1 1  300 
=  
169. t°C = (273 + t) K P 1.2  600 
P = 2.4 atm
3RT 2RT
C = and CP = r1 M2
M M 7. =
Since C = CP r2 M1

3TO3 2TO2 rSO2 16 1

= = =
M O2 M O2 rCH 4 64 2

∴TO2 = (273 + t) K 8. PO2 = χO2 P

152 = χO2 × 760
170. The rms velocity of He will be decreased to half when
χO2 = 0.2
its absolute temperature is decreased by 4 times.
% = 0.2 × 100 = 20
∴ To have half the rms velocity, the temperature of
3
He is 75 K. 12. PN 2 = × 800 = 600 mm
4
T1 T 13. KE ∝ T
Applying = 2
M1 M 2 –123°C = –123°C + 273 = 150 K
27°C = 27°C + 273 = 300 K
75 T Since T is doubled KE is doubled but the no. of
= 2 or T2 = 1200 K
4 64 ­molecules are the same.

Chapter_05.indd 42 3/26/2014 4:58:40 PM

 States of Matter  5.43

14. At constant T, KE ∝ n. 34. P1V1 = P2V2

dRT 1.83 × 0.082 × 300 P × 100 = P2 × 250
18. M== ≈ 45 P2 = 0.4 P
P 1
∴ The pressure of gas in bulb A will fall by 40%.
∴ The gas is CO2
48. Pgas = 200 – 93 = 107
20. PNH3 + PHCl = 908 – 228 = 680 mm
Volume doubled
nNH3 = nHCl 107
Pgas = = 53.5
PNH3 = 340 mm 2
Pmix = 53.5 + 93 = 146.5
3RTH 2 3RTN 2
23. × T =
2 28 3RT 8 RT
49. =
∴ T(H2) < T(N2). M π × 71
24. 50 cc of H2 react with 25 cc of O2 forming liquid water 3 8×7 1
= ×
at room temperature. The remaining gas is 25 cc of O2. M 22 71
Assuming 50 cc of H2O gas at room temperature and M = 83.6
25 cc O2 changes to approximately 95 cc gas at 110°C.
PH 2O = 23.76 × 0.06 = 14.25 mm
25. 4NH3 + 5O2 → 4NO + 6H2O
PO2 + PN 2 = 760 – 14.25 = 745.7 mm
50 60 initial
excess limiting final PN 2 = 745.7 × 0.79 = 589.1 mm
60 × 6
Vol. of H2O = = 72 ml. PO2 = 745.7 × 0.21 = 156.6 mm
5
26. Since volume is constant partial pressure of a gas is (14.25 × 18) + (589 × 28) + (156.6 × 32)
proportional to number of moles. As the masses of MWmix =
760
three gases are equal, number of moles is inversely
proportional to molecular weights. = 28.63
PM 1 × 28.63
27. With increase in temperature most probable velocity a = =
RT 0.0821 × 298
increases but the fraction decreases.
a = 1.17 gm/lit
PV PV
31. 1 1
= 2 2
T1 T2 52. Pg = 0.7

1 × 12000 0.5 × V2 PH 2O = 0.3

=
300 250 Volume is one-third.
∴ V2 = 20,000 lit. Pg = 2.1
PH2O = 0.3
32. PV = nRT
Pmix = 2.4
8.2 × 10 −10 × 30
n = = 10 −9 57. More the TB easily liquefies
300 × 0.0821
No. of molecules = 6.02 × 1023 × 10–9 58. Initial composition of air is 0.8: 0.2 at 1 atm.
  = 6.02 × 1014 The volume decrease by half means final mole is 0.5

C1 PV Then nO2 , nN 2 = 0.3

33. = 1 1

C2 P2V2 P = 0.4 , PN 2 = 0.6

O2
2a P1 × 1
= 59. H2 have more velocity than He if they are in 1:1 mole
a P2 × 2 ratio H2 exerts more collisions on the wall so concen-
Px = 8Py tration of He is more

Chapter_05.indd 43 3/26/2014 4:58:45 PM

 5.44  Objective Chemistry - Vol. I

8 RT 3RT 67. PoVo2

60. = V = RT
πM A MB Vo2 + V 2
8 M B 8M B PoVo
= 3M A ∴ M A = T =
π 3π 2R
Case II PV = RT + Pb
68.
8 RT2 8 RT PV Pb
= Z = = 1+
π8 M B / 3π πM B RT RT

8 69. PV = RT
∴ T2 = T PV
3π 70. Moles of gas in Ist sphere =
RT1
dideal After stop clock is opened
62. 2 =
dreal PV
Moles in Ist sphere = 1
18 1 RT1
×
0.0821× 500 0.36 PV
Moles in IInd sphere = 1
RT1
2
3RT1
63. 4 mn T1 16 PV PV PV
= ∴ = RT = RT + 2 RT
1 1
1 3RT2 T2 1 1 1 2
mn
2 PT2
P RT1 / 1 32 P1 = 2T + T
1 = = 2 1
P2 RT2 / 2 1
nRT
71. V =
64. Vc = 3b P
a nR
Pc = log V = log + log T
27b 2 P
8a nR
Tc = = 1
27 Rb P

rmix 64 PVreal
65. = 72. Z =−
rso2 M mix nRT

MWmix = 16  n2 a 
73.  P ×  ( v − nb) = n RT
2 NH 3  → N 2 + 3H 2  V2 
1− α α / 2 3α / 2 n1′ 4 16
(1 − α)17 × (α / 2)28 + (3α / 2)2 74. =
n2′ 1 4
1− α
17 75. C3 H8 + 5O2 
→ 3CO2 + 4 H 2 O (l )
1+ α = = 1.0625
16
CH 4 + 2O2 
→ CO2 + 2H 2 O (l )
PA V PV
66. nA = ; nB = B a + b = 320 ; 3a + b = 448
RTA RTB
a = 64 ; b = 256
after connecting
X = 0.2
 PAV PBV  C3 H8
P (2V ) =  +  RT
 RTA RTB  76. V αn

Chapter_05.indd 44 3/26/2014 4:58:51 PM

 States of Matter  5.45

77. PV = nRT 60 1 17
84. =
3.5 40 P 36.5
× 1 = n (0.0821)293
760
3PV
78. After filling PN 2 = 0.2 atm 86. C=
mn
PO2 = 1 − 0.3 = 0.7 atm
3P 10 −3
10 =
3
PVreal 10 −25 × 10 23
80. Z=
nRT
81. Volume of gas at 300 K, 10 K 87. P (5) = nRT
1V
=
(10) 4 P (5) = ( n + 0.025) R (283)

300 400 Vt
88. Vo = Vo + o
V = 30 lit 273
Slope 273 1
Out coming gas = 30 – 3 = 27 Intercept = V = 273
No. of balloons = 9 o

83. Vc = 3b

b = 0.024 lit
4
b = 4 π r N o
3

Chapter_05.indd 45 3/26/2014 4:58:55 PM

 This page is intentionally left blank.

Chapter_05.indd 46 3/26/2014 4:58:55 PM

 6a

Chapter
Thermodynamics

• The energy changes associated with physical and • If the walls of a system allow the transmission of heat
chemical process may be used to do mechanical work through them into or out of the system are called dia-
or to provide electrical energy or radiant energy or thermal walls and those walls of a system which do not
chemical energy or nuclear energy. permit any heat through them into or out of the system
• The different forms of energy may be transformed are called adiabatic walls.
from one into the other and the branch of science which • A system which can exchange energy and matter with
deals with these energy transformations is r­ eferred to the surroundings is known as an open system, e.g., ice
as thermodynamics. in an open beaker.
• Thermodynamics means flow of heat and it deals • A system which can exchange energy but not matter
with quantitative relationships between heat and other with the surroundings is known as a closed system,
forms of energy in physicochemical transformations. e.g., ice in a closed beaker.
• Thermodynamics mainly deals with basic laws gov- • A system which cannot exchange energy or matter
erning heat, followed latter by statistical mechanics with the surroundings is known as an isolated system,
which explains the laws of thermodynamics. e.g., ice in a thermoflask.
• Thermodynamics is based on four experimental laws
namely zero, the first, the second and third laws. Thermodynamic Variables
• Laws of thermodynamics are based on experimental
facts but not theoretical facts. • Quantities such as pressure, temperature and volume
which define a system are called thermodynamic
• Thermodynamic laws provide the criteria for predict- variables and these are of two categories, namely
ing the feasibility of a reaction and energy transforma- ­intensive and extensive.
tions that occur in the processes.
• The properties of the system which depend on the
• Laws of thermodynamics do not give any information amount of the substance are called extensive prop-
regarding the rates of reactions or processes. erties, e.g., mass, volume, energy, internal energy,
free energy, molar entropy, molar enthalpy and heat
Types of Systems
capacity.
• In thermodynamics, the entire universe is considered • The properties of a substance which depend on the
as two parts, system and surroundings. nature of the substance and are independent of the
• A system is defined as any specified position of m
­ atter amount of the substance are called intensive prop-
in the universe which is chosen for thermodynamic erties, e.g., pressure, temperature, density, viscosity,
studies. specific heat, surface tension, refractive index, boiling
• The part of the universe other than the system which point, freezing point.
can exchange energy and matter with system is called • The operation which brings about the changes from
surroundings. one state to another state is thermodynamic process.

Chapter_6a.indd 1 3/26/2014 3:12:25 PM

 6A.2  Objective Chemistry - Vol. I

Thermodynamic Equilibrium • The thermodynamic properties whose values depend

only upon the initial and final states of the system and
• A system is said to be in a mechanical equilibrium are independent of matter of the manner as how the
when there is no unbalanced force existing between change occur are called state functions.
different parts of the system or between the system and e.g., Internal energy (U), enthalpy (H), entropy (S)
the surroundings. Gibbs energy (G), pressure (P), temperature (T),
• A system is said to be in a thermal equilibrium if the volume (V), etc.
temperature is the same throughout the whole system • The parameters which depend on the path into which a
including the surroundings. system is brought are called path functions.
• A system is said to be in a chemical equilibrium if e.g., heat (q) and work (w).
the composition of the system remains constant and • Thermodynamic laws are not applicable to microscop-
definite. ic systems as the mass energy transformations are not
• Mechanical equilibrium implies the uniformity of being considered except as a carrier of energy.
pressure, thermal equilibrium to the uniformity of
temperature and chemical equilibrium to the uniform-
ity of chemical composition. Types of Processes
• A system may be in mechanical and thermal equilib- • The process in which the system does not exchange
rium without being in chemical equilibrium. heat (q) with the surroundings is known as adiabatic
• A system is said to be in a thermodynamic equilibri- ­process. In adiabatic processes, in the case of an
um if it satisfies all the three equilibria, viz. mechani- exothermic process, the heat evolved remains in the
cal, thermal and chemical. system and therefore the temperature of the system
rises while in endothermic processes the heat absorbed
is supplied by the system and hence the temperature of
State Variables
the system decreases.
• The variable properties such as temperature, pres- • A process in which the temperature “T” of the system
sure, volume and composition required for completely remains constant during each step of the process is
defining a system thermodynamically are known as known as an isothermal process. For the isothermal
thermodynamic properties or parameters or state process, dT = 0.
variables.
• A process in which the pressure (P) of the system
• A state variable is one that has definite value when remains constant, during each step of the process,
the state of a system is specified. is known as an isochoric process. For the isochoric
• In the gas equation PV = RT, if two variables are process, dV = 0.
known, the third can be easily calculated as R is a • A process is said to be a cyclic process if a system
gas constant. The two variables usually specified are after completing a series of changes returns to its
temperature and pressure and are called independent original state.
variables. The third variable, i.e., volume depends on
temperature and pressure and is said to be a depend- • Sequence of steps starting from the initial to the final
ent variable. state of the system is called a path and the path of a
cyclic process is called a cycle.
• A process which is carried out infinitesimally slowly
Homogeneous and Heterogeneous Systems so that the driving force is infinitesimally greater than
• A system is said to be homogenous if it is uniform the opposing force is known as a reversible process.
throughout A homogeneous system consists of only • A process which takes place suddenly and sponta-
one phase. neously without occurring infinitesimally slowly is
• A system is said to be heterogeneous if it is not known as an irreversible process.
­uniform throughout. A heterogeneous system consists • In thermodynamics work may be defined as the quan-
of two or more phases which are separated from each tity that flows across the boundary of a system during
other by definite boundaries. However, each phase a change in its state and is completely convertible into
­itself is uniform throughout. the lifting of a weight in the surroundings.

Chapter_6a.indd 2 3/26/2014 3:12:25 PM

 Thermodynamics  6A.3

Zeroth Law (3) in the form of light only

(4) in any form depending upon the nature of the
• Zeroth law states that equality of temperature is a con- system
dition for thermal equilibrium between two systems or
between two parts of a single system. 8. For the process to occur under adiabatic conditions
• If two systems are separately in thermal equilibrium (1) DT = 0 (2)  dq = 0
with a third, then they must also be in thermal equilib- (3) DP = 0 (4)  dw = 0
rium with each other. 9. A cup of tea placed in the room eventually acquires a
room temperature by losing heat. The process may be
considered close to
  Objective Questions (1) cyclic process
(2) reversible process
1. Any series of operation so carried out that at the end,
(3) isothermal process
the system is back to its initial state is called
(4) zeroth law
(1) a cycle
(2) an adiabatic process 10. A gaseous system changes from state A (P1, V1, T1)
(3) a reversible process to B (P2, V2, T2) to C (P3, V3, T3) and finally from
(4) A Boyle’s cycle C to A. The whole process may be called
2. Which of the following does not come under the (1) Reversible process
­preview of thermodynamics? (2) Cyclic process
(1) Predicting the feasibility of chemical change (3) Isobaric process
(2) Predicting the extent of the chemical change (4) Spontaneous process
(3) Rate at which a chemical change occurs at a 11. A well stoppered thermosflask contain some ice
­particular set of conditions cubes. This is an example of
(4) Effect of temperature on the extent of reaction
(1) Closed system
3. Which among the following state functions is an (2) Open system
extensive property of the system? (3) Isolated system
(1) Temperature (2) Volume (4) Non-thermodynamic system
(3) Refractive index (4)  Viscosity
12. A thermodynamic state function is
4. A chemical process is carried out in a thermostat (1) one which obeys all the laws of thermodynamics
maintained at 25°C. The process may be termed as (2)  a quantity which is used to measure thermal
(1) isobaric process changes
(2) isoentropic process (3) a quantity whose value is independent of the path
(3) adiabatic process (4) a quantity which is used to express pressure–­
(4) isothermal process volume work
5. Which of the following process cannot be realized in 13. Which of the following is an intensive property?
reality? (1) volume
(1) cyclic process (2) mass
(2) irreversible process (3) density
(3) reversible process (4) energy
(4) isothermal process
14. Energy can be transferred from a system to its sur-
6. Which of the following is not a state function? roundings as work if
(1) internal energy (2)  free energy (1) there is thermal equilibrium between system and
(3) work (4) enthalpy surroundings
7. Energy changes accompanying the chemical reac- (2) there is mechanical equilibrium between system
tions can take place and surroundings
(1) in the form of heat only (3) if pressure of system > atmospheric pressure
(2) in the form of heat as well as light only (4) if pressure of system < atmospheric pressure

Chapter_6a.indd 3 3/26/2014 3:12:25 PM

 6A.4  Objective Chemistry - Vol. I

Answers be determined by measuring the heat liberated or

absorbed when the reaction is carried at a constant
  (1) 1  (2) 3  (3) 2  (4) 4  (5) 3 temperature and volume.
 (6) 3  (7) 4  (8) 2  (9) 4 (10) 2 • For a chemical reaction, A  → B, DU can be writ-
(11) 3 (12) 3 (13) 3 (14) 3 ten as DU = UP – UR. If DU is negative the reaction is
exothermic while the positive DU indicates the endo-
thermic reaction.

internal energy First Law of T

  hermodynamics
• Every system is associated with definite amount of • First law of thermodynamics explains the heat changes
energy known as internal energy or intrinsic energy accompanying chemical reactions.
denoted by U. • The law states that energy can neither be created nor
• Internal energy of different substances is different and destroyed but energy can be converted from one form
depends on the state conditions. to the other.
• The internal energy is the sum of all energies, i.e., • First law of thermodynamics rules out “the possibility
kinetic and potential energies of the particles making of construction of a perpetual motion machine of first
up the substance. kind”.
• The kinetic energy includes the translational, vibra- • A perpetual motion machine is one which while
tional and rotational energies of the molecules. operating in cycles can produce work without any
expenditure of energy on it.
• The potential energy comprises attraction between
atoms in a molecule (chemical bonds) attraction
• According to the first law of thermodynamics the total
between molecules, the arrangement of electrons
­ energy of the system and the surroundings is constant
outside the nucleus and the arrangement of protons or conserved.
and neutrons inside the nucleus. • Mathematically first law of thermodynamics can be
represented as q = DU + W where q is the amount of
• Internal energy depends only on the initial and final
heat absorbed by the system from the surroundings,
states of the system but not on the path through which
DU is the increase in the internal energy of the system
the change was brought.
and W is the work done by the system. For infinitesi-
• Change in internal energy is a state function but mally small changes, q = dU + w.
not path function. Heat (Q) and work (W) are path • The work done in isothermal and reversible expansion
functions.
of an ideal gas is given by the equation
• Internal energy of a system depends on the state of the Vf
substance governed by temperature, pressure, volume     Wrev = – 2.303 nRT log
and concentration which are known as state variables. Vi
Pf
• The magnitude of internal energy (U) of a substance = 2.303 nRT log
         
cannot be determined experimentally but the change Pi
in internal energy (DU) due to change in volume, pres- Vi and Pi are the initial volume and pressure while Vf
sure, temperature and chemical composition can be and Pf are the final volume and pressure of the gas.
determined experimentally.
• Work done in an isothermal irreversible expansion of
• The energy change can be measured in the form of an ideal gas is given by
heat exchanged with surroundings and the work done
with the change in volume against pressure.  P 
    W = nRT 1 − 2 
• If the volume and temperature are kept constant the  P1 
change in internal energy (DU) is equal to the heat • The work done in an irreversible process is less than
exchanged with the surroundings DUv = Q (because the work done in the reversible process.
W = 0). • Heat absorbed in an irreversible expansion of an ideal
• In a chemical reaction the change in internal energies gas is less than heat absorbed during the reversible
(DU) when reactants convert into products can process.

Chapter_6a.indd 4 3/26/2014 3:12:27 PM

 Thermodynamics  6A.5

• The magnitude of work involved in an irreversible

compression will be more than that in a reversible   Objective Questions
process.
15. A change from state A to state B
• In adiabatic expansion of an ideal gas since heat is
not allowed into the system, the work done is due to (1) q depends only on the initial and final states
the decrease in internal energy (DU = W) thus causing (2) w depends only on the initial and final states
a decrease in temperature. (3) DU depends only on the initial and final states
Thus, (4) DU depends upon the path adopted by A to
change into B
P1V1γ = P2V2γ or PV γ = constant
r 1− r
16. A monoatomic helium molecule possesses
T  P  (1) Only potential energy
∴  1  = 2 
 T2   P1  (2) Potential as well as vibrational energy
(3) Vibrational as well as translational energy
• Work done in the irreversible expansion of an ideal gas (4) Translational as well as potential energy
in adiabatic process is given by
17. Under which of the following conditions work is a
T P  state function
W = nRT  2 − 2 
 T1 P1  (1) adiabatic process (2)  isothermal process
• Internal energy change for an adiabatic process is (3) constant pressure (4)  none of these
18. Vibrational energy is
 nRT1 nRT2 
∆U = P2  −  (1) Partially potential and partially kinetic
 P1 P2  (2) Only potential
(3) Only kinetic
  P  (4) None of the above
∴ T2 = Cv + R  2   . T1
  P1   19. A gas expands isothermally and reversibly. The work
• Enthalpy change in an adiabatic irreversible expansion done by the gas is
of an ideal gas is given by (1) zero (2) maximum
(3) minimum (4)  cannot be predicted
∆H = nCp (T2 – T1)
• In an isothermal process, temperature of the system 20. Which among the following gives the expression for
remains constant, whereas in an adiabatic process the reversible isothermal expansion of an ideal gas?
­temperature has to be changed. V2
(1) –PDV (2) –nRT ln
• The pressure–volume relation for a reversible isother- V1
mal process is given by Boyles law, PV = constant (at (3) Both 1 and 2 (4)  Neither 1 nor 2
constant T).
21. Internal energy does not include
• The pressure–volume relation for reversible adiabatic
(1) vibrational energy
process is given by PV γ = constant.
(2) rotational energy
• The increase in volume for a given decrease of pres- (3) energy arising due to gravitational pull
sure will be less in an adiabatic expansion than that in (4) nuclear energy
an isothermal expansion.
22. A thermally isolated gaseous system can exchange
• The smaller change in volume in an adiabatic pro- energy with the surroundings. The mode of transfer-
cess than in an isothermal process is due to decrease ence of energy can be
in temperature with the decrease in internal energy,
(1) heat (2) work
whereas in an isothermal expansion heat is absorbed
(3) heat or radiation (4)  only radiation
from the surroundings to make up for work done
by the expansion of the gas and hence temperature 23. Which is correct about isothermal expansion of an
­remains constant. ideal gas?
• The work done by an ideal gas is greater in an isother- (1) Wrev = Wirr (2)  Wrev + Wirr = 0
mal expansion than that in an adiabatic expansion. (3) Wrev > Wirr (4)  qrev = qirr

Chapter_6a.indd 5 3/26/2014 3:12:28 PM

 6A.6  Objective Chemistry - Vol. I

24. Which of the following expression is true for an ideal • The amount of heat exchanged is at constant volume
gas? and temperature.
 ∂V   ∂P  • If a gas absorbs heat at constant volume all the heat
(1)    = 0
 = 0 (2)  content is used to raise the internal energy of gas (DU).
 ∂T  P ∂T V
• If a gas absorbs heat at constant pressure some heat
 ∂E   ∂E  content is used to raise the internal energy of the gas
(3)    = 0
 = 0 (4) 
 ∂V T ∂T V and the remaining heat content is used to do work by
the expansion of the gas (DU + W).
25. The efficiency of a heat engine is maximum when
• Since work done W is equal to PDV, then DU + W can
(1) temperature of a source is greater than that of a sink
be written as DU + PDV.
(2) temperature of a sink is greater than that of a source
(3) temperature difference of a source and a sink is • The energy change at constant pressure and tempera-
minimum ture is called the enthalpy change denoted by ∆H.
(4) temperature difference of a source and a sink is • The total heat content of a substance or a system at
maximum constant pressure and temperature is called enthalpy.
26. Which of the following is correct about adiabatic • Enthalpy (H) is the amount of heat exchanged by a
­expansion of an ideal gas? system with surroundings at constant pressure and
(1) PV = constant (2)  PV γ = constant constant temperature.
(3) PT  = constant
r
(4)  TV γ = constant • Enthalpy of a system is equal to the sum of internal en-
ergy (U) and the product of pressure (P) and volume (V )
27. The law of conservation of energy states that
of the system, i.e., PV.
(1) the internal energy of a system is constant
(2) the heat content of the system is constant
• The energy change taking place at constant pressure and
(3) energy is neither created nor destroyed constant temperature is called enthalpy change (∆H ).
(4) there is an equivalence between energy and mass • Enthalpy is a state function but not path function and
it is an extensive property.
28. According to the latest sign convention the correct
expression representing the first law of thermody- • Enthalpy (H) of a substance cannot be determined
namics is ­experimentally but the change in enthalpy (∆H) can be
calculated or determined.
(1) DU = q + w (2)  DU = ∆H + Pv
(3) DU = q – w (4)  All are correct • For a chemical reaction taking place at constant pres-
sure and temperature the enthalpy change (∆H) is the
Answers difference in the heat contents of the products (HP) and
reactants (HR); ∆H = HP – HR.
(15) 3 (16) 4 (17) 1 (18) 1 (19) 2 • For a cyclic chemical change ∆H = 0 since the initial
(20) 2 (21) 3 (22) 2 (23) 3 (24) 3 and final states are the same.
(25) 4 (26) 2 (27) 3 (28) 1 • At constant volume since DV = 0, ∆H = DU.
• ∆H is the change in heat content at constant pressure
and constant temperature while DU is the change in
heat capacity or enthalpy, H heat content at constant volume and constant pressure.
• If a reaction is carried between solids and liquids, • The energy change taking place at constant volume
pressure has no effect. Hence, these reactions are con- and constant temperature is called internal energy
sidered as carried at constant volume. change (DU).
• If the substance in a reaction is a gas, the reaction may • For gaseous reactions ∆H and DU are related as ∆H =
be carried out at two different conditions: (i) at con- DU + DnRT where Dn = (Total number of molecules
stant volume and (ii) at constant pressure. of gaseous products) – (Total number of molecules of
• Since atmospheric pressure is practically constant, gaseous reactants), R = gas constant and T = absolute
chemical changes in open containers can be consid- temperature.
ered as taking place at constant pressure but not at • Heat capacity of a substance is the amount of heat
constant volume. required to rise its temperature through one degree.

Chapter_6a.indd 6 3/26/2014 3:12:29 PM

 Thermodynamics  6A.7

• Specific heat is the amount of heat required to rise the 31. Which of the following statements is not true?
temperature of 1 g of the substance through 1°C. (1) The heat content of a system is called intrinsic
• At constant volume the total heat capacity is utilized energy.
for the change of internal energy (DU) of the system (2) When solids melt, there is increase in enthalpy.
with temperature. (3) The enthalpy change in a chemical reaction is
 ∂E  ­determined from the initial and final states of the
CV =   reacting system.
 ∂T V
• At constant pressure a part of the heat capacity is (4) The absolute values of E and H can be estab-
utilized for changing the internal energy and the lished.
remaining part is utilized for the work: 32. At constant T and P which one of the statement is
CP = DU + PDV correct for the reactions given below?
PDV = W, i.e., work done. (1) ∆H = ∆U
• The relation between CP and CV is (2) ∆H < ∆U
CP – Cv = R (3) ∆H > ∆U
C (4) ∆H is independent of physical state of the reactants
or P = γ
CV
33. If ∆ Hf (X), ∆ Hf (Y), ∆ Hf (R) and ∆ Hf (S) denote the
• The enthalpy change measured at standard pressure enthalpies for the formation of X, Y, R and S respec-
is called standard enthalpy change and represented tively, the enthalpy of reaction X + Y  → R + S is
by ∆Ho also known as molar standard enthalpy change given by:
∆Hmo. (1) ∆ Hf (X) + ∆ Hf (Y)
• For special type of enthalpy changes, to emphasize (2) ∆ Hf (R) + ∆ Hf (S)
subscripts are used, e.g., for enthalpy change of com- (3) ∆ Hf (X) + ∆Hf (Y) – ∆ Hf (R) – ∆ Hf (S)
bustion of a compound enthalpy is denoted as ∆HC°. (4) ∆ Hf (R) + ∆ Hf (S) – ∆ Hf (X) – ∆ Hf (Y)
• Standard enthalpy change ∆Ho refers to 101.325 Pa
34. For which of the following reactions the change in
(1 atm) and normally refers to 298 K. enthalpies is equal to the change in internal energy?
(1) H2 + I2  → 2HI
(2) PCl5  → PCl3 + Cl2
  Objective Questions
(3) 2H2O2  → 2H2O + O2
29. Which of the following statement is false? (4) C + O2  → CO2
(1) Internal energy of an ideal gas depends only on 35. For a reaction, 2NH3(g)  → N2(g) + 3H2(g) which
the temperature. of the following statements is correct?
(2) The relation between DU and ∆H is ∆H = DU + (1) ∆H > ∆U (2)  ∆H < ∆U
PDV. (3) ∆H = ∆U (4)  ∆H = 0
(3) Heat of a reaction at constant pressure is equal to
HR – HP. 36. Change in enthalpy is defined as
(4) Heats of reaction at constant pressure (∆H) and at (1) The change in heat content
constant volume (DU) are related as ∆H – DU = (2) The total energy change at constant pressure and
DnRT. temperature
(3) The heat change at constant volume if ∆n = 0
30. Among the following, the wrong statement is (4) All are correct
(1) Heat of reaction at constant pressure is represent-
ed by ∆H. 37. The false statement among the following is
(2) The relation ∆H = DU + PDV is valid for a closed (1)  Vapourisation of liquid is accompanied by
system when temperature and pressure are con- ­increase in enthalpy
stant. (2) The difference between ∆H and ∆U is equal to
(3)  The heat absorbed in a reaction at constant 3/2 R.
temperature and volume is equal to ∆H of the (3) It is the general principle that the less energy a
reaction. system contains, it is more stable.
(4) The enthalpy change for chemical reactions de- (4) The sum of the internal energy and work form of
pends upon the states of two substances involved. energy is called enthalpy.

Chapter_6a.indd 7 3/26/2014 3:12:31 PM

 6A.8  Objective Chemistry - Vol. I

38. A gaseous reaction was carried out first keeping the at 25°C. The heat of reaction at constant volume
volume constant and next keeping the pressure con- would be
stant. In the second experiment, there was an increase in (1) 19096 cal (2)  18798 cal
volume. The heats of reactions were different because (3) 18202 cal (4)  17904 cal
(1) In the first case, the energy was spent to keep the
volume constant. 45. C6H12 (l) + 9O2 (g) 
→ 6H2O (l) + 6CO2 (g); ∆H at
(2)  In the second case, the energy was spent to 298 K = –936.9 k.ca.
expand the gases. (1) –936.9 = ∆U – (2 × 10–3 × 298 × 3) k.cal
(3) Specific heats of compressed gases are more. (2) –936.9 = ∆U + (2 × 10–3 × 298 × 3) k.cal
(4) Specific heats of rarefied gases are more. (3) –936.9 = ∆U – (2 × 10–3 × 298 × 2) k.cal
(4) –936.9 = ∆U + (2 × 10–3 × 298 × 2) k.cal
39. If ∆H is the change in enthalpy and ∆U is the change
in internal energy, then 46. A mixture of 2 moles of CO and 1 mole of O2 in a
(1) ∆H is always less than ∆U closed vessel is ignited to convert to CO into CO2 then
(2) ∆H is always greater than ∆U (1) ∆H = ∆U
(3) ∆H < ∆U only if the number of moles of gaseous (2)  ∆H > ∆U
products is greater than the number of moles of (3) ∆H < ∆U
gaseous reactants (4) The relationship depends upon the capacity of
(4) ∆H < ∆U only if the number of moles of gase- the vessel
ous products is less than the number of moles of
gaseous reactants 47. A system has internal energy U ⋅ 500 joules of heat is
taken out of it and 650 joules of work is done on it.
40. When 1 g of carbon is converted to 1 g molecule of
The final energy of the system is
CO2 the heat liberated is same
(1) U + 1150 (2)  U – 150
(1) Irrespective of whether the volume is kept con-
(3) U – 1150 (4)  U + 150
stant or pressure is kept constant
(2) Irrespective of the temperature at which the reac- 48. For the decomposition of Ag2O(s)  → 2Ag(s) +
tion is carried out 1/2 O2 (g), the heat absorbed is 30.66 J. If the process
(3) Whether the carbon is in the form of diamond or is carried out at constant volume, the value of ∆H of
graphite the process is
(4) None
(1) –30.66 J (2)  +30.66 J
41. ∆n value in ∆H = ∆U + ∆nRT may have (3) +32.66 J (4)  None
(1) integer nature
49. In which of the following reaction ∆H is less than DU
(2) fractional value
(3) positive or negative value (1) H2 (g) + I2 (g)  → 2HI (g)
(4) all (2) PCl5 (g)  → PCl3 (g) + Cl2 (g)
(3) N2 (g) + 3H2 (g)  → 2NH3 (g)
Numerical (4) N2O2 (g)  → 2NO (g)
42. The difference between heat of reaction at constant 50. One mole of naphthalene C10H8 was burnt in oxygen
pressure and constant volume for the reaction at 25°C at constant volume. The heat evolved was 1228.2 k.cal.
in kJ is The heat of reaction at constant pressure is (R = 2 ×
(1) –7.43 (2) +3.72 10–3 k.cal)
(3) –3.72 (4) +7.43 (1) 1122.38 k.cal (2)  –1229 k.cal
43. ∆H for the reaction CaCO3(s)  → CaO(s) + CO2 (3) 1228.2 k.cal (4)  None of these
(g) is 176 kJ mol–1 at 1240 K. The ∆U for the change
51. A system is changed from A  → B in another
is equal to
path. The change in internal energy is E1. The same
(1) 160 kJ (2)  165.6 kJ system is changed from B  → A in another path.
(3) 186.3 kJ (4)  180.0 kJ The change in internal energy is now E2. Then
44. The heat of formation of methane C(s) + 2H2(g) (1) A + B (2)  Zero
 → CH4(g) at constant pressure is 18500 cal (3) Unity (4)  A – B

Chapter_6a.indd 8 3/26/2014 3:12:32 PM

 Thermodynamics  6A.9

Answers • The increase in entropy which occurs when gases

mix without interaction is given by the following
(29) 3 (30) 3 (31) 1 (32) 2 (33) 4 ­mathematical equation
(34) 1 (35) 1 (36) 1 (37) 2 (38) 2 2V × 2V1
DS = R log e 1
(39) 3 (40) 1 (41) 1 (42) 1 (43) 2 V1 × V1
(44) 1 (45) 1 (46) 3 (47) 4 (48) 4 in which R is gas constant when 1 mole of each gas is
(49) 3 (50) 2 (51) 2 involved and 1 mole of each of the two gases ­occupying
a volume V1 initially but after mixing a volume of 2V1.
• Increase in entropy is associated with maximum
­number of ways in which the energy of the system can
second law of thermodynamics
be distributed.
• First law of thermodynamics failed in predicting • According to quantum theory, energy is held in a
(i) Whether a process is spontaneous or not in the series of definite energy levels. This is because for a
specified direction given energy range there are more translational e­ nergy
(ii) If a transformation occurs, what fraction of one levels than rotational energy levels, and there are
form of energy is converted into another form of more rotational energy levels than vibrational energy
energy in this transformation. levels. Thus there are several ways of distributing a
• The process which takes place on its own accord with- given ­energy. The various translational energy levels
out the aid of an external agency is called spontane- are more than among either rotational or vibrational
ous process. energy levels.
• All naturally occurring processes are spontaneous and • When ammonium nitrate is dissolved in water
thermodynamically irreversible.    (i) The solid breaks up and hydrated ions are dispersed
• All spontaneous processes proceed till equilibrium is in solution. So, energy of vibration is r­eplaced
achieved. by energy of translation and thus ­increase in the
number of energy levels resulting in i­ncrease of
• Examples of spontaneous processes are given
entropy.
hereunder:
 (ii) The process of dissolution of ammonium nitrate
   (i) Water flows from higher level to lower level but
is endothermic due to which air in the surround-
cannot be reversed with regard to the direction of
ings is cooled down resulting in the decrease of
flow without some external aid.
translation, rotational and vibrational energy
 (ii) Heat can flow from a hotter body to a colder body ­levels. Thus, entropy decreases.
and it cannot be reversed. (iii) Due to hydration of ions the translational and
(iii) If two solutions of different concentrations are ­rotational motion of water molecules is restricted.
mixed, it becomes homogeneous due to diffusion So, entropy decreases.
of solute from a more concentrated solution to a
less concentrated solution. The conversion of vibrational energy of NH4NO3 into
  (iv) Electricity flow from a higher potential to a lower translational energy of the hydrated ions results in
potential and its direction can be reversed by apply- large increase in entropy causing an overall increase
ing an external potential in the opposite direction. in entropy.
• A non-spontaneous process is that which has no ten- • Changes take place in an isolated system in a direction
dency to occur or which is forbidden and made to occur such that when equilibrium is achieved the number of
only if energy from outside is continuously supplied. ways in which the total energy of the system can be
• The reverse directions of all spontaneous processes are distributed is maximum, i.e., the entropy of the system
non-spontaneous processes. is maximum.
• Entropy is a measure of the number of ways that
Entropy and Spontaneity ­energy can be shared out among molecules.
• Each arrangement for the distribution of energy
• Entropy means transformation and is denoted by S. ­between different molecules is complexion. With in-
Entropy is a measure of disorder or randomness in a crease in temperature, the number of complex ions
system. increases. More the number of complexions, the more
• Units of entropy change is J/K or JK–1. is the increase in entropy.

Chapter_6a.indd 9 3/26/2014 3:12:33 PM

 6A.10  Objective Chemistry - Vol. I

• Quantitatively the entropy change DS is given by the Entropy Change During Phase
mathematical expression DS = qrev/T where qrev is the Transformations
heat absorbed when the process is carried reversibly
and isothermally, i.e., at constant T. • The entropy change when one mole of a solid sub-
• Entropy is a state function and is independent of the stance changes into liquid form at its melting point is
path. It is an extensive property. known as entropy of fusion.
• Second law of thermodynamics states that the • For the conversion of a solid to liquid the heat required
­entropy of the universe always increases in the course is latent heat equal to standard enthalpy of fusion
of every spontaneous (natural) change (or) the energy Dfus Ho at constant temperature and pressure.
of the ­universe is conserved, whereas the entropy of For water Dfus = 6.0 kJ mol–1
the ­universe always increases in any natural process qrev ∆ fus H o 6.0 × 1000 J mol −1
(or) heat cannot flow from a colder body to a hotter Dfus So = = =
T 273 K 273
body on its own (or)
    = 219.9 J mol–1 k–1
Heat cannot be converted into work completely
without causing some permanent changes in the
­ • The entropy change when one mole of a liquid changes
­system involved or in surroundings (or) into vapour at its boiling point is the entropy of
vaporisation.
All spontaneous processes are thermodynamically
­irreversible and entropy of the system increases in all ∆ vap H o
• Dvap So = (T is boiling point)
spontaneous processes (or) T
It is impossible to construct a machine working in 40.79 kJ
Dvap So =
­cycles which transforms heat from a lower tempera- 373
ture region to a higher temperature region without the (\ Dvap Ho for water = 40.79 kJ mol–1)
intervention of any external agency.
   = 109.356 J k–1 mol–1
• A perpetual motion machine is that which can trans-
fer heat from a lower temperature to a higher tempera- • The standard entropy change DrSo for a reaction can
ture on its own. be determined by subtracting the standard entropies of
reactants from the standard entropies of products
• For a spontaneous process in an isolated system, the
change in entropy (DS) is positive.   DrSom = SVP Som (products) – SVrSom (reactants)
• If the system is not isolated the total entropy change, (VP and Vr are stoichiometric coefficients and Som is
i.e., DStotal the sum of the entropy change of the sys- standard molar entropy.)
tem (DSsystem) and the entropy change in surroundings • The entropy per unit amount of substance in its
(DSsurroundings) must be positive. ­standard state at the specified temperature is ­standard
  DStotal = DSsystem + DSsurroundings > 0 ­molar entropy denoted by Som. The standard ­entropy
• When an isolated system is in equilibrium, the entropy of a substance or ion is also called as absolute entropy.
is maximum.
• The mathematical condition for entropy (S) to be max-
imum is that the change in entropy (DS) is zero.   Objective Questions
• In some exothermic reactions the entropy of the s­ ystem
52. Which of the following statements is false?
may decrease but the heat liberated may increase the
entropy in surroundings leading to the total entropy (1) The units of entropy are J k–1 mol–1
change to become positive and in such a situation the (2)  The evaporation water is accompanied with
reaction will be spontaneous. ­increase in entropy
(3) A boiled egg shows an increase in entropy
• When magnesium burns in oxygen, conversion of
(4) Entropy of the universe tends to maximum
­oxygen into oxide results in decrease of entropy but the
heat liberated will increase the entropy of surroundings. 53. Among the following, the wrong statement is
• In endothermic reactions entropy of surroundings (1) Entropy decreases during the crystallization of a
­decrease due to the flow of heat from surroundings solute from solution.
into system, but the entropy of the system increases so (2)  At a certain temperature T, the endothermic
that overall entropy increase is positive, the reaction is reaction A → B proceeds almost to completion
spontaneous. if DS > 0.

Chapter_6a.indd 10 3/26/2014 3:12:33 PM

 Thermodynamics  6A.11

(3) In a spontaneous irreversible process the total 62. DS is positive for the change
entropy of the system and surroundings (1) mixing of two gases
increases. (2) boiling of liquid
(4) When the value of entropy is greater, then the (3) dissolution of substance
ability to work is minimum. (4) all
54. DSo will be highest for the reaction 63. Which is not a spontaneous process?
(1) Ca(s) + 1/2 O2(g)  → CaO(s) (1) Expansion of a gas into vacuum
(2) CaCO3(s)  → CaO(s) + CO2(g) (2) Water flowing down a hill
(3) C(s) + O2(g)  → CO2(g) (3) Heat flowing from a colder body to a hotter body
(4) N2(g) + O2(g)  → 2NO(g) (4) Evaporation of water from clothes during drying
55. For the process CO2(s) 
→ CO2(g) 64. Regarding entropy which of the following is not correct?
(1) Both ∆H and DS are +ve (1) Change in entropy for fusion at constant pressure
(2) ∆H is negative and DS is +ve ∆H f
is given by ∆S f = .
(3) ∆H is +ve and DS is –ve ∆T
(4) Both ∆H and DS are –ve (2) Change in entropy for vaporisation at constant
∆EV
56. The second law of thermodynamics introduced the pressure is given by ∆SV =
T
concept of (3) In a reversible process the value DSsystem + DSsurr
(1) Third law of thermodynamics is zero.
(2) Work (4) In an irreversible process the value of DSsystem +
(3) Entropy DSsurr > 0.
(4) Internal energy
65. Enthalpy of vapourisation for water is 186.5 kJ mol–1.
57. Which of the following have the same units? The entropy change during vapourisation is ..... kJ mol–1
   (i)  work    (ii)  heat (1) 0.5 (2) 1.0 (3) 1.5 (4) 2.0
(iii) energy (iv) entropy
66. The entropy change for vapourisation of liquid water
(1) (i), (ii) and (iii) (2)  (i), (ii) and (iv) to steam at 100°C is ......... JK–1 mol–1. Given that heat
(3) (ii), (iii) and (iv) (4)  (iii) and (iv) of vapourisation is 40.8 kJ mol–1.
58. Which is not a state function? (1) 109.38 (2) 100.38
(1) internal energy (2)  entropy (3) 10.38 (4) 120.38
(3) work (4) enthalpy 67. One mole of an ideal gas is 25°C is subjected to
59. Change in entropy is negative for ­expand reversibly 10 times of its initial volume. The
(1) Bromine (l)  → Bromine (g) change in entropy of expansion is
(2) C(s) + H2O(g)  → CO2(g) + H2(g) (1) 19.15 Jk–1 mol–1 (2)  16.15 Jk–1 mol–1
–1 –1
(3) N2(g, 10 atm)  → N2 (g, 1 atm) (3) 22.15 Jk mol (4)  11.25 Jk–1 mol–1
(4) Fe (1 mol, 400 K)  → Fe (1 mol, 300 K) 68. The entropy change for the reaction given below
60. For the reaction having ∆H and DS both positive, the  2H2(g) + O2(g)  → 2H2O(l)
rate of reaction is ...... at 300 K. Standard entropies of H2(g), O2(g)
(1) increases with the increase in temperature and H2O(l) are 126.6, 201.20 and 68.0 Jk–1 mol–1,
­respectively
(2) decreases with the increase in temperature
(1) 318.4 Jk–1 mol–1 (2)  318.4 Jk–1 mol–1
(3) has no effect on temperature –1 –1
(3) 31.84 Jk mol (4)  –31.84 JK–1 mol–1
(4) decreases with the increase in pressure
69. The temperature at which the reaction
61. The total amount of energy in the universe is fixed, but
Ag2O(s)  → 2Ag(s) + O2(g)
(1) matter is increasing is at equilibrium is .......... Given DH = 30 kJ mol–1
(2) gravitation is decreasing and DS = 0.066 kJ k–1 mol–1.
(3) disorder is increasing (1) 462.12 K (2)  362.12 K
(4) lightening is increasing (3) 262.12 K (4)  562.12 K

Chapter_6a.indd 11 3/26/2014 3:12:36 PM

 6A.12  Objective Chemistry - Vol. I

70. If So for H2, Cl2 and HCl are 0.13, 0.22 and 0.19 kJ • The reactions which take place at high temperature are
K–1 mol–1, respectively. The total change in standard mainly due to increase in entropy and are generally
for the reaction termed as entropy-driven reactions.
H2 (g) + Cl2 (g)  → 2HCl (g) • If ∆G is negative, the process is spontaneous.
(1) 30 JK–1 mol–1 (2)  40 JK–1 If ∆G is zero, then the process is in an equilibrium

(3) 24 cal mol–1 (4)  28.0 cal mol–1 K–1 state and there is no net reaction in either direction.
71. Entropy of vaporisation of water at 100°C, if molar If ∆G is positive the process does not occur in the
heat of vaporisation is 9710 cal mol–1 will be forward direction; however, it may take place in the
(1) 20 cal mol–1 k–1 (2)  26 cal mol–1 k–1 reverse direction.
–1 –1
(3) 24 cal mol k (4)  28 cal mol–1 k–1 • ∆G will be negative under the following conditions:
(i) Both the energy and the entropy factors are favour-
Answers able and may have any magnitude i.e., ∆H is nega-
tive and TDS is positive.
(52) 3 (53) 4 (54) 2 (55) 1 (56) 3 (ii) When energy factor favours the change (∆H = –ve)
(57) 1 (58) 3 (59) 4 (60) 1 (61) 3 but entropy factor opposes the change (TDS = –ve)
(62) 4 (63) 3 (64) 2 (65) 2 (66) 1 then the magnitude of ∆H should be more than TDS.
(67) 1 (68) 1 (69) 1 (70) 1 (71) 2 (iii) When energy factor is not favouring (∆H = +ve)
but entropy factor favours the change (TDS = +ve)
then the magnitude of TDS should be more than
that of energy factor.
gibbs energy and spontaniety Spontaneous and non-spontaneous reactions
• Gibbs energy is the amount of energy available from DH DS –TDS DG
a system which can be put to useful work at constant
–ve +ve –ve –ve at all T Spontaneous at all T
temperature and pressure.
–ve –ve +ve –ve at low T Spontaneous at low T
• Gibbs energy is an extensive property. +ve at high T Non-spontaneous at
• Gibbs energy or Gibbs function has been defined as high T
G = H – TS. +ve +ve –ve –ve at high T Spontaneous at high
• The change in Gibbs energy for the system ∆Gsystem at T, entropy driven
constant temperature is ∆Gsystem = ∆Hsystem – T∆Ssystem +ve at low T Non-spontaneous at
low T
• Only a part of the energy released in a reaction can
+ve –ve +ve +ve at all T Non-spontaneous at
be used to do work, the rest is involved in the entropy
all T
change.
• The Gibbs energy change (∆G) is the amount of ­energy
available to do work. Gibb’s Energy Change and Equilibrium
Constant
• Spontaneous reactions can do work. Spontaneous
­reactions have negative Gibbs energy change. • Gibb’s energy change of reaction ∆G is related to the
• Non-spontaneous reactions cannot do work. composition of the reaction mixture and to a standard re-
action Gibbs energy change ∆Go is given by the equation
• Non-spontaneous reactions have positive Gibbs e­ nergy
∆G = ∆Go + RT in Q where Q is the reaction quotient and
change.
R is the gas constant with the value of 8.314 JK–1 mol–1.
• Gibbs–Helmholtz equation is At equilibrium, Q = equilibrium constant
∆G ∆H
− =− + ∆S • At equilibrium, ∆G = 0
T T ∴ O = ∆Go + 2.303 RT log kp or ∆Go
Each term in the above equation represents entropy   = –2.303 RT log kp
change. The equation implies
• Gibbs energy change for isothermal expansion of an
Entropy change in the universe = Entropy change in ideal gas is given by
the surroundings + Entropy change in the system
P V
• Gibbs energy of an element in its standard state is zero. (∆G)T = 2.303 nRT log 2 = 2.303 nRT log 1
P1 V2

Chapter_6a.indd 12 3/26/2014 3:12:37 PM

 Thermodynamics  6A.13

where V1 = initial volume, V2 = final volume, P1 = Coupled Reactions

­initial pressure and P2 = final pressure
• ∆Go = ∆Ho – T∆So = –RT lnk
• The reactions in which ∆G is positive cannot take
place spontaneously but they can be made spontane-
Since ∆Go depends on the value of ∆Ho for highly
ous by coupling with some other reactions have very
­exothermic reactions the value of ∆Ho may be large and
large n­ egative Gibbs energy values so that the resultant
positive and hence the value of K will be much smaller
Gibbs energy of the two combined reactions becomes
than 1 and the reaction is unlikely to form much ­product.
negative.
• In case of exothermic reactions ∆Ho is large and nega-
tive and ∆Go is also likely to be large and negative.
• Most of the metallurgical processes and biological
Hence, the value of K will be much larger than 1 and reactions involve coupled reactions. For example,
reaction can go to near completion. the hydrolysis of adenosine triphosphate (ATP) in the
presence of an enzyme to give adenosine diphosphate
Gibb’s Energy and Work (ADP) and a phosphate is coupled with various other
necessary reactions in biological systems which are
• Gibbs energy change for a process taking place otherwise not spontaneous.
­reversibly at constant T and P is equal to the maximum
­possible useful work. Gibbs Energy and Non-Mechanical Work
∆G = Wmax
• In the case of galvanic cells Gibbs energy change ∆G • The work due to expansion at constant temperature is
is related to electrical work done by the cell known as pressure–volume work and is given by PDV.
∆G = –nFE • The work that can be obtained from the system by
where E is the emf of the cell, n is the number of non-expansion work such as electrical work is non-
­electrons involved and F is Faraday. mechanical work.
• If the reactants and products are in their standard state,
then
∆Go = nFEo   Objective Questions
Eo is the standard cell potential.
72. The ∆G in the process of melting of ice at –15°C is
Third Law of T
  hermodynamics (1) ∆G < 0 (2)  ∆G > 0
(3) ∆G = 0 (4)  All
• The third law of thermodynamics states that the
­entropy of a pure and perfectly crystalline substance at 73. In which case, a spontaneous reaction is impossible at
absolute zero is zero. any temperature?
• The entropy of a solution and supper cooled liquid is (1) ∆H > 0, DS > 0
not zero at 0 K. For example, glycerol and glass e­ xhibit (2)  ∆H > 0, DS > 0
positive entropy at 0 K. (3) ∆H < 0, DS < 0
• Third law of thermodynamics is also referred as Nernst (4)  In all the cases
heat theorem. 74. Which of the following statements is false?
• Unlike first and second laws, the third law does not (1) A spontaneous reaction is possible at any tem-
lead to any new concept of thermodynamics but im- perature if ∆H < 0, DS < 0.
poses a limitation on the volume of entropy: (2)  For a spontaneous chemical change, Gibbs
1
C ­energy change is negative.
S1 = ∫ P .dT (3) Gibbs energy change for a reversible reaction at
0
T
equilibrium is zero.
• One of the most important applications of third law
(4) The relation ∆G = ∆H – T∆S was given by Gibbs–
is the calculation of entropy changes in chemical
Helmhotz.
reactions
For the general reaction 75. In a reaction, ∆H and DS both are more than zero. In
aA + bB + .........  → lL + mM + ........... which of the following cases, the reaction would not
be spontaneous?
∆S is given by DS = [l.SLo + m.SMo + ....] – [a ⋅ SAo +
o o
∆H
b ⋅ SBo + ......] (1) ∆H > T∆S (2)  ∆S =
T
∆So implies molar entropies. (3) ∆H = T∆S (4) All

Chapter_6a.indd 13 3/26/2014 3:12:37 PM

 6A.14  Objective Chemistry - Vol. I

76. The process of evaporation of a liquid is accompa- (1) spontaneous (2) reversible

nied by (3) irreversible (4) nonspontaneous
(1) increase in enthalpy 84. On dissolving NaCl in water there occurs
(2) decrease in Gibbs energy (1) increase in Gibbs energy
(3) increase in entropy (2) increase in entropy
(4) all (3) increase in enthalpy
77. Which reaction characteristics has the greater chance (4) increase in internal energy
of occurring spontaneously 85. The second law of thermodynamics introduced the
(1) one in which entropy change is positive concept of
(2) one in which entropy change is negative (1) third law of thermodynamics
(3) one in which Gibbs energy change is negative (2) work
(4) one in which equilibrium has been established (3) entropy
78. The spontaneous nature of a reaction is impossible if (4) internal energy
(1) ∆H is +ve; DS is also +ve 86. The Vant Hoff reaction isotherm is
(2) ∆H is –ve; DS is also –ve (1) ∆G = RT loge kp (2) –∆G = RT loge kp
(3) ∆H is –ve; DS is +ve (3) ∆G = RT 2 ln kp (4) none
(4) ∆H is +ve; DS is –ve
79. Which of the following statements is not true?
Answers
(1) All naturally occurring processes proceed spon-
taneously in the direction which leads to decrease (72) 2 (73) 2 (74) 1 (75) 4 (76) 4
in Gibbs energy. (77) 3 (78) 4 (79) 2 (80) 1 (81) 3
(2) For an endothermic reaction to be spontaneous, (82) 2 (83) 1 (84) 2 (85) 3 (86) 2
∆G > 0.
(3) For the reversible vaporisation of water at 100°C
and 1 atmospheric pressure, ∆G is equal to zero.
(4) If ∆Go > 0 for a reaction, then kp < 1.
Practice Exercise
80. Equilibrium constant of a reaction is related to
(1) Standard Gibbs energy change ∆Go 1. When no heat energy is allowed to enter or leave a
(2) Gibbs energy change ∆G system, then it is called
(3) Heat enthalpy (1) isothermal process
(4) None (2) reversible process
81. Which correctly represents the physical significance (3) adiabatic process
of Gibbs energy change? (4) irreversible process
(1) –∆G = Wcompression 2. Warming ammonium chloride with sodium hydrox-
(2) ∆G = Wcompression ide in a test tube is an example of
(3) ∆G = –Wexpansion = Wnonexpansion (1) closed system (2)  isolated system
(4) ∆G = Wexpansion (3) open system (4)  none of these
82. Identify the correct statement regarding entropy
3. An adiabatic process is one in which
(1) At absolute zero of temperature, the entropy of
(1) the system is not closed to energy transfer
perfectly crystalline substance is taken to be zero.
(2) the system is not closed to heat transfer
(2) At absolute zero of temperature, the entropy of a
(3) there is no enthalpy change
perfectly crystalline substance is taken to be zero.
(4) there is no change in mass of the system
(3) At 0 °C, the entropy of a perfectly crystalline
substance is taken to be zero. 4. When an ideal gas is compressed adiabatically and
(4) At absolute zero of temperature, the entropy of reversibly the final temperature is
all crystalline substances is taken to be zero. (1) Higher than the initial temperature
83. The enthalpy and entropy change for a chemical reac- (2) Lower than the initial temperature
tion are –2.5 × 103 cal and 7.4 cal deg–1, respectively. (3) The same as the initial temperature
Predict that nature of reaction at 298 K is (4) Dependent on the rate of compression

Chapter_6a.indd 14 3/26/2014 3:12:37 PM

 Thermodynamics  6A.15

5. The final temperature in an adiabatic expansion is 14. In enthalpy, ∆H is written instead of DU in case of
(1) greater than the initial temperature (1)  Atmospheric pressure increase to create any
(2) same as the initial temperature ­temperature
(3) half of the initial temperature (2)  Chemical reaction is carried out at normal
(4) less than the initial temperature ­atmospheric pressure
(3) Reaction takes place below normal atmospheric
6. In an adiabatic process
pressure
(1) the system exchanges heat with surroundings (4) None of the above
(2) pressure is maintained constant
(3) there is perfect heat insulation 15. If a system expands from a volume V1 to V2 at a con-
(4) the gas is isothermally expanded stant pressure, the work done by the system will be
(1) W = +P∆V (2)  W = –P (V2 – V1)
7. The temperature of the system decreases in an
(3) W = –P(V2 – V1) (4)  None of the above
(1) adiabatic expansion
(2) isothermal compression 16. Standard entropy of X2, Y2 and XY3 are 60, 40 and 50
(3) isothermal expansion JK–1, respectively for the reaction
(4) adiabatic compression 1 3
X2 + Y2  → XY3, ∆H = –30 kJ to be at
8. An isolated system is that system in which 2 2
­equilibrium, the temperature will be
(1) there is no exchange of energy with the surround- (1) 500 K (2)  750 K
ings (3) 1000 K (4)  1250 K
(2) there is exchange of mass and energy with the
surroundings 17. Assuming that water vapour is an ideal gas, the internal
(3) there is no exchange of mass and energy with the energy change (DU) when 1 mol of water is vapourised
surroundings at 1 bar pressure and 100°C (given molar enthalpy of
(4) there is exchange of mass with the surroundings vapourisation of water at 1 bar and 373 K = 41 kJ mol–1
and R = 8.3 J mol–1 K–1) will be
9. A gas on subjecting to an adiabatic expansion gets
cooled due to (1) 41.00 kJ mol–1 (2)  4.100 kJ mol–1
–1
(3) 3.79 or kJ mol (4)  37.904 kJ mol–1
(1) fall in temperature
(2) loss of kinetic energy 18. An ideal gas expands in volume from 1 × 10–3 m3 to
(3) decrease in velocity 1 × 10–2 m3 at 300 K against a constant pressure of
(4) energy used in doing work 1 × 105 Nm–2. The work done is
10. The process in which pressure remains constant (1) –900 J (2)  –900 kJ
throughout a change is (3) 270 kJ (4)  900 kJ
(1) adiabatic (2)  isochoric 19. A reaction is non-spontaneous at the freezing point of
(3) isobaric (4) isothermal water but is spontaneous at the boiling point of water
then
11. The temperature of the system increases during
(1) isothermal expansion ∆H ∆S
(2) adiabatic compression (1) +ve +ve
(2)  –ve –ve
(3) adiabatic expansion
(3) +ve +ve
(4) isothermal compression
(4)  +ve –ve
12. Temperature and heat are
(1) extensive properties 20. Maximum work can a gas do, if it is allowed to
(2) intensive properties ­expand isothermally against
(3) intensive and extensive properties, respectively (1) vacuum
(4) extensive and intensive properties, respectively (2) high pressure of surroundings
(3) low pressure of surroundings
13. Work done in reversible adiabatic process is given by (4) atmospheric pressure
V nR
(1) 2.303 RT log 2 (2)  (T2 – T1) 21. If w1, w2, w3 and w4 are the magnitudes of work
V1 ( r −1)
done in isothermal, adiabatic, isobaric and isochoric
V1
(3) 2.303 RT log (4) None ­reversible expansion, respectively, of an ideal gas, the
V2 correct order (for expansion) will be

Chapter_6a.indd 15 3/26/2014 3:12:38 PM

 6A.16  Objective Chemistry - Vol. I

(1) w1 > w2 > w3 > w4 (1) 32 × 0.22 × 27.3 × 4.2

(2)  w3 > w2 > w1 > w4 (2) 16 × 0.22 × 27.3 × 4.2
(3) w3 > w2 > w4 > w1 32 × 0.22 × 2.73
(4)  w3 > w1 > w2 > w4 (3)
4.2
22. The volume of a system becomes twice its original 16 × 0.22 × 27.3
(4)
volume on the absorption of 300 cal of heat. The work 4.2
done on the surroundings was found to be 200 cal.
30. If all the following gases are in monoatomic form,
What is the DU for the system?
which has greater entropy?
(1) 500 cal (2)  300 cal
(1) H (2) N (3) O (4) Cl
(3) 100 cal (4)  –500 cal
31. Ammonium chloride when dissolved in water leads
23. The internal energy change when a system goes from
to cooling sensation. The dissolution of NH4Cl at
state A to B is 40 kJ/mol. If the system goes from
constant temperature is accompanied by
A to B by a reversible path and returns to state A by
an irreversible path what would be the net change in (1) increase in entropy
internal energy? (2) decrease in entropy
(3) no change in entropy
(1) 40 kJ (2)  > 40 kJ
(4) no change in enthalpy
(3) < 40 kJ (4)  zero
32. When one mole of an ideal gas is compressed to half
24. The internal energy of an ideal gas increases during
of its initial volume and heated twice its temperature
an isothermal process when the gas is
the change in entropy is
(1) expanded by adding more molecules to it
(1) Cv ln 2 (2)  Cp ln 2
(2) expanded by adding more heat to it
(3) R ln 2 (4)  (Cv – R) ln 2
(3) expanded against zero pressure
(4) compressed by doing work on it 33. The efficiency of the reversible heat engine is nr and
that of irreversible heat engine is ni. Which of the fol-
25. One mole of an ideal gas at 300 K is expanded iso-
lowing relations is correct?
thermally from an initial volume of 1 L to 10 L. The
DU for this process is (1) nr = ni
(2)  nr > ni
(1) 163.7 cal (2)  Zero
(3) nr < ni
(3) 1381.1 cal (4)  9 L atm
(4) ni may be less than, greater than to nr, depending
26. If one mole of a monoatomic gas (γ = 5/3) is mixed on the gas
with one mole of diatomic gas (γ = 7/5) the value of
34. One mole of ice is converted into water at 273 K.
g for the mixture is
The entropies of H2O(s) and H2O(l) are 38.20 and
(1) 1 (2) 1.5 (3) 2 (4) 3.07 60.01 J/k mol, respectively. The enthalpy change for
27. How many times a diatomic gas should be expanded the conversion is
adiabatically so as to reduce the rms velocity to half? (1) 59.54 J/mol (2)  5954 J/mol
(1) 8 (2) 16 (3) 32 (4) 64 (3) 95.4 J/mol (4)  320.6 J/mol
35. The solubility of NaCl in water at 298 K is about 6 moles
28. Work done by a sample of an ideal gas in a process
per litre. Suppose you add 1 mole of NaCl to a litre of
A is double the work done in another process B. The
water. For the reaction, NaCl + H2O → salt solution
temperature rises through the same amount in the two
processes. If CA and CB be the molar heat capacities (1) ∆G > 0, ∆S > 0 (2)  ∆G < 0, ∆S > 0
for the two processes (3) ∆G > 0, ∆S < 0 (4)  ∆G < 0, ∆S < 0
(1) CA = CB (2)  CA > CB 36. The factor of ∆G value is important in metallurgy.
(3) CA < CB (4)  Both undefined The ∆G values for the following reactions at 800°C
are given as
29. One mole of oxygen is heated from 0°C at constant
pressure till its volume increased by 10%. The spe-   (i) S2(s) + 2O2(g)  → 2SO2(g); ∆G = –544 kJ
cific heat of oxygen under these conditions, is 0.22  (ii)  Zn(s) + S2(g)  → 2ZnS(s); ∆G = –293 kJ
cal/g k. The amount of heat required (in J) is (iii)  2Zn(s) + O2(g)  → 2ZnO(s); ∆G = –480 kJ

Chapter_6a.indd 16 3/26/2014 3:12:44 PM

 Thermodynamics  6A.17

 The ∆G for the reaction 43. Assuming ∆Ho and ∆So do not change with tempera-
 2ZnS(s) + 3O2(g)  → 2ZnO(s) + 2SO2(g) ture, calculate the boiling point of liquid A using the
will be thermodynamic data given below.
(1) –357 kJ (2)  –731 kJ Thermodynamic data Alig Agas
(3) –773 kJ (4)  –229 kJ H (kJ/mol) –130 –100
37. The enthalpy of formation steadily changes from S (J/k/mol) 100 200
–17.89 k.cal/mol to –49.82 k.cal/mol as we go from (1) 300 K (2)  130 K
CH4, C2H6 to C8H18. The value of ∆G, however, (3) 150 K (4)  50 K
shows opposite trend from –12.12 k.cal/mol for CH4 44. Haber’s process for the production of ammonia
to 4.14 k.cal/mol for C8H18. Why? 
involves the equilibrium N2(g) + 3H2(g)  
(1) As the number of carbon atoms increases the 2NH3(g). Assuming that ∆H and ∆S for the reaction
o o

number of possible isomers increases. The does not change with temperature, which of the state-
­reverse is the expected trend of ∆G values ments is true (∆Ho = –95 kJ and ∆So = –190 J/K)
(2) The increase in the number of C–C bonds in rela- (1) Ammonia dissociates spontaneously below 500 K
tion to the number of C–H bonds modifies the (2) Ammonia dissociates spontaneously above 500 K
trend of ∆G values in relation to ∆H values. (3) Ammonia dissociates at all temperatures
(3) In the formation of Cn H2n + 2 from n carbon atoms (4) Ammonia does not dissociate at any temperature
and (n + 1) hydrogen molecules there is large
­decrease in entropy. 45. Which of the following pair represents the intensive
(4) No simple reason possible properties?
(1) Specific heat and temperature
38. What is the free energy change, ∆G, when 1.0 mole
(2) Entropy and density
of water at 100°C and 1 atm pressure is converted
(3) Enthalpy and mole fraction
into steam at 100°C and 1 atm pressure
(4) Heat and temperature
(1) 540 cal (2)  –9800 cal
(3) 800 cal (4)  0 cal
Answers
39. Pick out the correct statement from among the following
(1) In the process of boiling of a liquid, work is done  (1) 3  (2) 3  (3) 3  (4) 3  (5) 4
on the system.  (6) 3  (7) 1  (8) 3  (9) 4 (10) 3
(2) When a liquid boils at its normal boiling point, (11) 2 (12) 3 (13) 2 (14) 2 (15) 2
Q = ∆H. (16) 2 (17) 4 (18) 1 (19) 1 (20) 2
(3) Joule–Thomson effect is an isochoric process. (21) 3 (22) 3 (23) 4 (24) 1 (25) 2
(4) Molar heat of fusion is an extensive property. (26) 2 (27) 3 (28) 2 (29) 1 (30) 1
(31) 4 (32) 4 (33) 2 (34) 2 (35) 2
40. During an adiabatic process the pressure of a gas is (36) 2 (37) 3 (38) 4 (39) 2 (40) 1
found to be proportional to the cube of its (41) 3 (42) 3 (43) 1 (44) 2 (45) 1
3 7
(1) (2) 
2 2
5 9
(3) (4)    Numerical Problems
3 765
41. One mole of an ideal gas (Cv,m = 5/2 R) at 300 K, 1. The latent heat of vaporisation of water at 25°C is
5 atm is expanded adiabatically to a final pressure of 10.5 k cal mol–1 and the standard heat of formation
2 atm against a constant pressure of 2 atm. The final of liquid water is –68.3 k cal. The enthalpy change of
temperature is the reaction:
(1) 270 K (2)  273 K H2(g) + O2(g)  → H2O(g) is, therefore
(3) 248.5 K (4)  200 K (1) –57.8 k cal (2)  –78.8 k cal
42. The entropy change involved in the isothermal (3) 78.8 k cal (4)  –47.3 k cal
­reversible expansion of 2 moles of an ideal gas from  
2. For, SR  SM, ∆G = 76.5 joule, ∆H = 2765 joule
a volume of 10 dm3 to a volume of 100 dm3 at 27°C is at 300 K, equilibrium temperature will be
(1) 32.3 J mol–1k–1 (2)  42.3 J mol–1k–1 (1) 298 K (2)  414.5 K
–1 –1
(3) 38.3 J mol k (4)  35.8 J mol–1k–1 (3) 596 K (4)  207.25 K

Chapter_6a.indd 17 3/26/2014 3:12:45 PM

 6A.18  Objective Chemistry - Vol. I

3. The work done in an open vessel when 112 g of Fe (1) Zinc can be oxidized by CO
reacts with dil. HCl to form FeCl2 at 27°C will be (2) Zinc oxide can be reduced by carbon
(1) 1200 cal (2)  600 cal (3) Both are correct
(3) 300 cal (4)  200 cal (4) None is correct
1
4. One mole of an ideal gas is allowed to expand revers- 11. For the reaction CO(g) + O2(g)  → CO2(g), ∆H
ibly and adiabatically from a temperature of 27°C. 2
If the work done during the process is 3 kJ, the final and DS are –283 kJ and –87 JK–1, respectively. It was
temperature will be equal to (Cv = 20 JK–1) intended to carry out this reaction at 1000, 1500, 3000
and 3500 K. At which of these temperatures would
(1) 150 K (2)  100 K
this reaction be thermodynamically spontaneous?
(3) 26.85 K (4)  295 K
(1) 1500 and 3500 K
5. One mole of ice is converted into water at 273 K. The (2) 3000 and 3500 K
entropies of H2O (s) and H2O (l) are 38.20 and 60.01 (3) 1000, 1500 and 3000 K
J mol–1 K–1, respectively. The enthalpy change for the (4) 1500, 3000 and 3500 K
conversion is:
12. What should be the ∆Hfo of OH– ion, if the standard
(1) 59.54 J mol–1 (2)  5954 J mol–1
–1 enthalpy of formation of liquid water is –68.31 k cal
(3) 595.4 J mol (4)  320.6 J mol–1
and ∆Hfo (H+) = 0? Given the standard enthalpy of neu-
6. 3N2O(g) + 2NH3(g)  → 4N2(g) + 3H2O(g); ∆H = tralization of strong base is –13.7 k cal equivalent–1.
–879.6 kJ (1) –16.54 k cal (2)  –54.61 k cal
What is ∆Hfo for N2O in kJ/mol–1? (3) 65.41 k cal (4)  61.54 k cal
Heat of formation
13. The change in entropy of the system when 2 moles of
NH3 –45.9 kJ/mol–1
an ideal diatomic gas is heated from 400 K to 800 K
H2O –241.8 kJ/mol–1
under constant pressure is
(1) 246 (2) 82
(3) –82 (4) –246 (1) 3R ln 2 (2)  7R ln 2 (3)  5R ln 2 (4)  R ln 2

7. What is the entropy change (in JK–1 mol–1) when one 14. A gas expands adiabatically such that its temperature,
mole of ice is converted into water is 6 KJ/mol at 1
T∝ . The value of g of the gas will be:
0°C? V
(1) 20.13 (2) 2.013 (1) 1.30 (2) 1.50 (3) 1.70 (4) 2
(3) 2.198 (4) 21.98 15. The vapour pressure of water at 310 K is 25 torr. If
8. A heat engine absorbs heat q1 from a source at tem- the standard state pressure is defined 1 bar (750 torr),
perature T1 and heat q2 from a source at temperature then the ∆Go for the process
T2. Work done is found to be J (q1 + q2). This is in   H2O (l)  → H2O (g) at 310 K
accordance with Assuming ∆H and DS remains constant with pressure
(1) First law of thermodynamics for liquid (Given log 3 = 0.47).
(2) Second law of thermodynamics (1) –8.76 kJ (2)  +8.76 kJ
(3) Joules equivalent law (3) –4.38 kJ (4)  +4.38 kJ
(4) None of the above
16. The value of log10 K for a reaction A 
 B is
9. 100 Joules of heat flow from a body of 50 kg at 27°C
(Given ∆Hr 298 K = –54.07 kJ mol , DSro 298 K =
o –1
into a large Cu block 100 kg at –23°C. What is the
10 JK–1 and R = 8.314 JK–1 mol–1, 2.303 × 8.314 ×
total change in entropy?
298 = 5705)
(1) 0.67 J/K (1) 5 (2) 10 (3) 95 (4) 100
(2)  15.7 J/K
(3) 0.067 J/K 17. One mole of an ideal monoatomic gas expands iso-
(4)  6.7 J/K thermally against constant external pressure of 1 atm
from initial volume of 1 L to a state where its final
10. Consider the following reactions at 1100°C pressure becomes equal to external pressure. If initial
(i) 2C + O2  → 2CO, ∆Go = –460 kJ/mol temperature of gas is 300 K then total entropy change
(ii) 2Zn + O2  → 2 ZnO, ∆Go = –360 kJ/mol of the system in the above process is [R = 0.082 L atm
Based on these, select the correct alternate mol–1K–1 = 8.3 J mol–1 K–1]

Chapter_6a.indd 18 3/26/2014 3:12:46 PM

 Thermodynamics  6A.19

(1) 0 (2)  Rln (24.6) S2: Change in internal energy of a system is equal to
(3) Rln (2490) (4)  R ln (24.6) zero in a cyclic process.
18. When an ideal gas undergoes unrestrained expansion, S3: Heat given at constant pressure is equal to change
no cooling occurs because the molecules in enthalpy of a closed system when only PV work is
considered.
(1) are above the inversion temperature
(2) exert no attractive force on each other S4: In a closed system, capable of doing only PV
(3) do work equal to the loss in kinetic energy work, the constant temperature and pressure
(4) collide without loss of energy (1) T T T T (2)  F T T F
(3) F T F T (4)  T T F T
19. Consider the modes of transformations of a gas from
state A to state B as shown in the following P–V dia- 23. The standard heat of combustion of Al is –837.8 kJ
gram. Which one of the following is true? mol–1 25 °C. If Al reacts with O2 at 25 °C, which of
the following release 250 kJ of heat?
A
(1) The reaction of 0.624 mol of Al
(2) The formation of 0.624 mol of Al2O3
P (3) The reaction of 0.312 mol of Al
(4) The formation of 0.150 mol of Al2O3
C B 24. 2 mole of an ideal gas at 27°C temperature is expand-
ed reversibly from 2 lit to 20 lit. Find entropy change
V (R = 2 cal/mol/K).
(1) 92.1 (2) 0 (3) 4 (4) 9.2
(1) ∆H = q along A → C
(2) DS is same along both A → B and A → C → B 25. If for the cell reaction Zn + Cu2+    Cu + Zn2+
(3) w is same along both A → B and A → C → B entropy change DSo is 96.53 mol–1 K–1 then tempera-
(4) w > 0 along both A → B and A → C ture coefficient of the e.m.f. of a cell is:
20. Predict in which of the following, entropy increases/ (1) 5 × 10–4 VK–1 (2) 1 × 10–3 VK–1
decreases (3) 2 × 10 VK –3 –1
(4) 9.65 × 10–4 VK–1
  (i)  A liquid crystallizes into a solid 26. ∆Cp for a reaction is given by 2.0 + 0.2 T cal/°C. Its
(ii) Temperature of a crystalline solid is raised from enthalpy of reaction at 100 K in k cal will be
0 to 115 K (1) –13.21 (2) –16.02
(iii) 2NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(g) (3) –15.3 (4) 7.08
  (iv)  H2(g)  → 2H(g) 27. Which of the following is true for an ideal gas?
(1) Increase in all
 ∂H   ∂H   ∂H   ∂E 
(2) Decrease in (i) and (ii) (1)   −  = R (2)   > 
(3) Decreases in (i) only  ∂T  p  ∂T  v  ∂T  p  ∂T  v
(4) Increases in (i) and (iv)
 ∂E 
(3)   =0 (4)  All of these

21. Fe2O3(s) + 3CO (1 g atom)  2Fe(s) + 3CO2 (1 g  ∂V T
atom), ∆G25°C = –10 kJ
28. CO (g) + NO2 (g)  → CO2 (g) + NO (g)
The ∆G for the reaction
The standard enthalpies of formation of gaseous
2Fe(s) + 3CO2 (2 g atom)  
 Fe2O3(s) + 3CO (20 g CO, NO, CO2 and NO2 are –110.5, 90.2, –393.5 and
atom) 33.2 kJ mol–1, respectively. Energy of activation for
at the temperature of 25°C is equal to the forward reaction is 465.2 kJ. Calculate energy of
(1) +17.11 kJ (2)  +7.11 kJ activation for the backward reaction.
(3) +27.11 kJ (4)  +5.70 kJ (1) 239.2 kJ (2)  691.2 kJ
22. Pick out the correct option, where T stands for true (3) 226 kJ (4)  303 kJ
and F stands for false. 29. What is DrG (kJ/mole) for synthesis of ammonia at
S1: Thermodynamic ­equilibrium in an isolated system 298 K at the following sets of partial pressure?
is reached when the s­ ystem’s ­entropy is maximized. N2 (g) + 3H2 (g)  → 2NH3 (g) ;

Chapter_6a.indd 19 3/26/2014 3:12:48 PM

 6A.20  Objective Chemistry - Vol. I

D  rGo = –33 kJ/mole 36. P–V plot for two gases during adiabatic processes are
[Take R = 8.3 J/K mole, log 2 = 0.3 and log 3 = 0.48.] given in the figure. Plots A and B should correspond
Gas N2 H2 NH3 respectively to:
Pressure (atm) 1 3 0.02
(1) +6.5 (2) –6.5 (3) +60.5 (4) –60.5
30. A sample of an ideal gas with initial pressure “P” and
volume “V” is taken through an isothermal process A
P B
during which entropy change is found to be DS. The
work done by the gas is
PV ∆S V
(1) (2) nRDS
nR (1) He and O2 (2)  O2 and He
P ∆S (3) He and Ar (4)  O2 and F2
(3)  PV (4) 
nRV 37. PbO2  → PbO, ∆G298 < 0
31. If ∆G298 for the reaction: SnO2  → SnO, ∆G298 > 0
2H2(g)(1 atm) + O2(g)(1 atm) → 2H2O(g)(1 atm) is –240 kJ, Most probable oxidation state of Pb and Sn will be
what is ∆G298 for the reaction H2O (1) Pb4+, Sn4+ (2) Pb4+, Sn2+
(1) 245.7 kJ (2)  239.3 kJ 2+
(3) Pb , Sn 2+
(4) Pb2+, Sn4+
(3) 125.70 kJ (4)  –245.7 kJ 38. One mole of a monoatomic gas behaving as per
32. Molar heat capacity of CD2O at constant pressure is PV @ nRT at 27°C is subjected to reversible ­isoentropic
10 cal/K/mol at 1000 K. The entropy change when compression until final temperature is reached at
3.2 g of CD2O vapour are heated from 1000 K to 327°C. If the initial pressure was 1.0 atm then the
2000 K at constant pressure is value of ln P(final) (ln 2 = 0.7) is
(1) 0.15 cal/K (2)  0.32 cal/K (1) 1.75 atm (2)  0.176 atm
(3) 0.46 cal/K (4)  0.69 cal/K (3) 0.0395 atm (4)  2.0 atm
 3   39. 5The  decomposition of limestone
33. 0.5 mole each of two ideal gas A  Cv = R and andB  Cv = R
 2    3(S) 
2 CaCO → CaO(s) + CO2(g)
 3   5 
A  Cv = R and B  Cv = R are taken in a container and expanded is nonspontaneous at 298 K. The ∆Ho and DSo values
 2   2  for the reaction are 176.0 kJ and 160 JK–1, respective-
reversibly and adiabatically from V = 1 litre to V = 4
ly. At what temperature the decomposition becomes
litre starting from initial temperature T = 300 K. ∆H
spontaneous?
for the process (in cal/mol) is
(1) at 1000 K
(1) –500 cal (2)  –900 cal
(2)  above 827°C
(3) –450 cal (4)  –600 cal
(3) at 500°C
34. The efficiency of a fuel cell is given by (4)  between 500°C and 600°C
∆G ∆G
(1) (2)  40. ∆H and DS for a reaction are +30.558 kJ mol–1 and
∆S ∆H 0.066 kJ mol–1 at 1 atm pressure. The temperature at
∆S ∆H which free energy is equal to zero and the nature of
(3) (4) 
∆G ∆G the reaction below this temperature are
(1) 483 K, spontaneous
35. Which of the following reaction is spontaneous?
(2) 443 K, non-spontaneous
(1)  Endothermic reaction with positive entropy (3) 443 K, spontaneous
change and high temperature (4) 463 K, non-spontaneous
(2)  Endothermic reaction with negative entropy
change and low temperature 41. Only gases remain after 12 g of carbon is treated
(3)  Exothermic reaction with positive entropy with 49.26 litres of air at 300 K and 2 atm pressure
change and high temperature (­assume 20% by volume O2, 79% N2 and 1% CO2)
(4)  Exothermic reaction with negative entropy   ∆Hf for CO and CO2 are –26 k cal, –94 k cal.
change and high temperature The amount of heat evolved under constant pressure is

Chapter_6a.indd 20 3/26/2014 3:12:50 PM

 Thermodynamics  6A.21

(1) –96.8 k cal (2)  –66.8 k cal (41) 2 (42) 3 (43) 1 (44) 3 (45) 2
(3) –23.4 k cal (4)  –33.4 k cal (46) 1
42. For the reaction at 300 K, A (g) + B (g)  → C (g),
∆E = –3 k cal; DS = –10.0 cal/k. The value of ∆G is
(1) 6000 cal (2)  –6600 cal
(3) –600 cal (4)  None   Statement-Type Questions
43. The molar volume of ice and water were 0.0196 and
In case of the following questions a statement I is given fol-
0.0180 litres, respectively. When ice (1 mole) melts at
lowed by a corresponding statement II just below it. Mark
0°C and 1 atm, 1.44 k cal of heat in absorbed value of
the correct answer.
∆E is ....... cal
(1) If both statement I and statement II are true and state-
(1) 1440.039 (2)  1448.86 ment II is a correct explanation of statement I.
(3) 844.23 (4) 14.0196 (2) If both statement I and statement II are true but state-
44. The molar heat capacities at constant pressure (assumed ment II is not a correct explanation of statement I.
constant with respect to temperature) of A, B and C are (3) If statement I is true and statement II is false.
in ratio of 1.5:3.0:2.5, respectively. If enthalpy change (4) If statement I is false and statement II is true.
for the exothermic reaction A + 2B  → 3C at 300 K 1. Statement I: A process is called adiabatic if the sys-
and 310 K is DH1 and DH2 respectively then tem does not exchange heat with the surroundings
(1) ∆H1 > ∆H2 Statement II: It does not involve increase or decrease
(2) ∆H1 < ∆H2 in temperature of the system.
(3) ∆H1 = ∆H2
(4) If T2 > T1 then ∆H2 > ∆H1 and if T2 < T1 then 2. Statement I: Heat absorbed in a reaction at constant
∆H2 < ∆H1 temperature and constant volume is –∆G.
Statement II: ∆G should be negative for the reaction
45. The value of log10K for a reaction
to be spontaneous.
A
 B is
(Given DrH 298K = –54.07 kJ mol–1, DrSo298K = 10 JK–1
o 3. Statement I: For isomeric liquids with same kind of
mol–1 and R = 8.314 JK–1 mol–1; 2.303 × 8.314 × 298 association, higher the b.pt, higher is the molar eleva-
= 5705) tion constant Kb.
(1) 5 (2) 10 (3) 95 (4) 100 MT0
Statement II: kb ∝ and Sv is almost same for
∆Sv
46. An ideal gas is allowed to expand both reversibly and liquids (T0 = normal b.pt., M = M.wt. of liquid and
irreversibly in an isolated system. If T1 is initial tem- DSv = entropy of vaporisation).
perature and Tf is the final temperature, which of the
following statement is correct? 4. Statement I: For an isothermal reversible process,
Q = +w
(1) (Tf)irr > (Tf)rev
(2) Tf > T1 for reversible process but Tf = T1 for Statement II: Enthalpy change ∆H is zero for an
­irreversible process ­isothermal process.
(3) (Tf)rev = (Tf)irr 5. Statement I: There is a natural asymmetry between
(4) (Tf) = T1 for reversible and irreversible process converting work to heat and converting heat to
work.
Answers Statement II: No process is possible in which the
sole result is the absorption of heat from a reservoir
 (1) 1  (2) 2  (3) 1  (4) 1  (5) 2 and its complete conversion into work.
 (6) 2  (7) 4  (8) 3  (9) 3 (10) 2 6. Statement I: For the spontaneity of a process, Gibb’s
(11) 3 (12) 2 (13) 2 (14) 2 (15) 2 energy changes.
(16) 2 (17) 2 (18) 2 (19) 2 (20) 3
(21) 3 (22) 3 (23) 4 (24) 4 (25) 1 Statement II: DS is invariably positive for any spon-
(26) 1 (27) 4 (28) 2 (29) 3 (30) 1 taneous process.
(31) 3 (32) 4 (33) 2 (34) 2 (35) 3 7. Statement I: Reduction of ZnO with CO is done at
(36) 2 (37) 4 (38) 1 (39) 2 (40) 4 1200°C.

Chapter_6a.indd 21 3/26/2014 3:12:51 PM

 6A.22  Objective Chemistry - Vol. I

Statement II: ∆G is negative at this temperature, 42. ∆n = 1

thus the process is spontaneous.  8.314 
∆U = 176 – 1× × 1240  = 165.6 kJ
8. Statement I: The amount of work done in the iso-  1000 
thermal reversible expansion is greater than work
done in the adiabatic process. 43. ∆H = DU + DnRT
18500 = DU + (–1 × 2 × 298)
Statement II: In the adiabatic reversible expansion
of a gas, temperature and volume both decreases due ∆U = 18500 + 596 = 19096 cal.
to decrease in internal energy of the system. 44. ∆n = 6 – 9 = –3
9. Statement I: The temperature of a gas does not ∴ –936.9 = DU – (2 × 10–3 × 298 × 3) k cal.
change when it undergoes an adiabatic expansion.
45. ∆n = 2 – 3 = –1
Statement II: During adiabatic process, heat energy is
∆H = DU – (–1 × RT) ∴ ∆H < DV
not changed between the system and the surroundings.
10. Statement I: A cup of tea placed in a room is an ex- 46. 500 Joules of heat taken out means the internal
ample of an open system. energy is decreased. 650 Joules of work is done on the
system means its internal energy is increased by 650 J.
Statement II: Transfer of heat and water vapour can
Therefore, the increase in internal energy is 150 J.
take place with the surroundings in the above s­ ystem.
11. Statement I: In irreversible processes changes are 47. ∆n = 0.5
carried out through quasi-equilibrium state. ∆H = 30.66 × (0.5 × 8.3 (0 T)
Statement II: In reversible process changes are Since T is not given Dh cannot be calculated.
­carried out so slowly that the system and surround- 48. ∆H < DU when Dn is negative
ings are always in near equilibrium.
Since for the reaction N2 + 3H2 
→ 2NH3; Dn = –2
12. Statement I: There is no exchange in internal energy ∴ ∆H < DU.
in a cyclic process.
Statement II: Cyclic process is the one in which 49. C10H18(g) + 12O2(g) 
→ 10CO2(g) + 4H2O(l)
the system returns to initial state after a number of ∆n = 10 – 12 = –2
­reactions and internal energy is a state function. ∆H = –1228.2 + (–2 × 2 × 10–3 × 300)
Temperature is taken as room temperature, i.e., 27°C.
13. Statement I: Entropy change in reversible adiabatic
expansion of an ideal gas is zero. ∆H = –1228.2 – 1.2 = –1229.4
Statement II: The increase in entropy due to volume 50. According to first law of thermodynamics, internal
increase just compensate the decrease in entropy due energy is a state function but not path function.
to fall in temperature. ∴ E1 + E2 must be zero.
∆H f 186.5
Answers 64. ∆S = = = 0.5 kJ K–1 mol–1
Tf 273
 (1) 3  (2) 4  (3) 1  (4) 1  (5) 2 ∆H f 40.8
 (6) 3  (7) 1  (8) 3  (9) 4 (10) 1 65. ∆Sv = = = 0.10938 JK–1 mol–1
(11) 4 (12) 1 (13) 1 Tf 373
66. For reversible isothermal expansion
v2 10
S = nR ln = 1 × 8.314 = ln
hints v1 1

41. ∆H = DU + DnRT = 19.143 = 19.15 J mol–1 K–1

∆H – DU = DnRT 67. Enthalpy change DS
∆n = 12 – 15 = –3 = Total entropy of products – Total entropy of reactants
8.314 = 2 × 68.0 – 201.20 – 2(126.6)
∴ DnRT = 3 × × 298 = –7.43 K.
1000 = –318.4 JK–1 mol–1

Chapter_6a.indd 22 3/26/2014 3:12:52 PM

 Thermodynamics  6A.23

68. At equilibrium ∆G = 0 25. ∆U = nCv∆T

⇒ ∆G = ∆H – T∆S = O ⇒ ∆H = T∆S ∆T = 0
∆H 30.5 ∆U = 0
⇒ =T= = 462.12 K
∆S 0.066
3 5
69. ∆G = ∆H – T∆S R+ R
26. Average Cv = 2 2 = 2R
= –2.5 × 103 – 298 × 7.4 = –4705.2 2
⇒ ∆G = –ve. So, the reaction is spontaneous.
5 7
R+ R
∆H f 9710 Average C p = 2 2 = 3R
70. ∆S = = = 26.032 cal mol–1 K–1 2
T 373
71. Melting of ice at –15°C is not spontaneous. So, Cp 3
γ= = = 1.5
∆G > O. Cv 2
72. If ∆H is > 0 and DS < 0 then, ∆G will be positive at
C1 T
any temperature. 27. = 1
C2 T2
73. If ∆H is –ve and also DS is –ve, the reaction is spon-
taneous only at low temperatures. 2C T T1 4
1 = 1 ∴ =
C1 T2 T2 1
74. For a reaction to be non-spontaneous, ∆G should be > 0
T1
∆H T1 = 4T2:T2 =
⇒ ∆H – T∆S > O or ∆H > T∆S ⇒ > DS 4
T
T1V1r–1 = T2V2r–1
75. Due to evaporation, heat content of the system
­increases and entropy also increases. T

T1V10.4 = 1 V20.4
4
82. ∆G = ∆H – T∆S
V2
= –2.5 × 103 – 2.98 × 7.4 = –4705.2 = 32
V1
Since ∆G is negative, the reaction is spontaneous.
28. Work done by the gas by using internal energy
∆U = P∆v
Practice Exercise V1 T1
29. =
1 3 T1 T2
16. x2 + y2 
→ xy3
2 2 110 T2
3  =
∆S = 50 – (60) –  × 40  = –40 JK–1 100 273
2 
T2 = 300.3
∆H −30000 q = ms∆T

T= = = 750 K
∆S 40 = 32 × 0.22 × 4.2 × (300.3 – 273)
17. ∆H = DU + DnRT
41 = DU + 
34. H2O (s) 
 H2O (l)
∴ DU = 37.9 kJ/mol ∆S = SH2 O(l) − SH2 O(g)
18. Work = –P∆V = 60.01 – 38.2
= –1 × 105 (1 × 10–2 – 10–3) = 21.81 J/K/mol
= –900 J ∆H
∆S =
22. q = DU – W T
300 = DU – (–200) ∆H = T∆S
∆U = 100 cal = 273 (0 21.81)
23. Internal energy is a state function. = 5954 J/mol

Chapter_6a.indd 23 3/26/2014 3:12:56 PM

 6A.24  Objective Chemistry - Vol. I

36. 2ZnS + 3O2  → 2ZnO + 2SO2 5. At 273 K, it is in equilibrium. So, ∆G = 0.

∆G = + 293 – 480 – 544 ∆H
T =
∆G = –731 kJ ∆S
38. When water is at 100°C, 1 atm is converted into steam ∴ ∆H = T∆S = 273 (60.1 – 38.2) = 5978 kJ.
and it is in equilibrium state 6. Heat of formation is enthalpy of the compound
∴ ∆G = 0 3N2O + 2NH3  → 4N2 + 3H2O
41. nCvdT = –PdV ∆H = 3H H2O + 4 H N2 − 3H N2 O − 2H NH3
5  1 RT 1R 300 
1× R (T – 300) = –2  −  –879.6 = 3 (–241.8) – 3x – 2 (–45.9)
2  2 5 
∴ H N2 O = 82 kJ/mol
T = 248.5 K
v ∆H 6000
42. ∆S = nR ln 2 7. ∆S = = = 21.98 J/K/mol
v1 T 273
= 2.303 × 2 × 8.314 log 10
9. ∆Stotal = DSsystem + DSsurroundings
= 38.3 J/K/mol
−100 100

43. A (liquid)  
 A (gas) = + = 0.067 J/K
300 250
∆H = –100 – (–130) = 30 kJ
∆S = 200 – 100 = 100 J/K/mol 10. 2ZnO + 2C → 2Zn + 2CO2, ∆G = –100 kJ
∆H 1
T = = 300 K 12. H2 + O2  → H2O, ∆H = –68.3 k cal
∆S 2
H+ + OH–  → H2O, ∆H = –13.7 k cal
1
Numerical Problems H2  → H+ + e–, ∆H = 0 k cal
2
1 1 1
1. H2 + O2  → H2O (l), ∆H = –68.3 k cal H2 + O2 + e–  → OH–, ∆H = ?
2 2 2
H2O (l)  → H2O (g), ∆H = 10.5 k cal –68.3 – (–13.7) = –54.6
1 T2
So, H2 + O2  → H2O (g) 13. ∆S = nCp ln
2 T1
∆H = –68.3 + 10.5 = –57.8 k cal 7  800
= 2  R  ln
2. ∆G = ∆H – T∆S 2  400
76.5 = 276.5 – 300 (∆S) 14. TV 0.5 = constant
2 15. ∆Go = –2.303 RT log kp
∆S =
3 25
At equilibrium, ∆G = 0 = –2.303 × 8.314 × 310 log = 8.76 kJ
750
∆H 276.5 16. ∆Go = ∆Ho – T∆So
Equilibrium temperature = = = 414.5 K
∆S 2/3 = – 54.07 – 298 (10–2) = –57.05 kJ
3. Fe + 2HCl  → FeCl2 + H2 ∆Go = –2.303 RT log kp
112 ∴ log kp = 10
Moles of Fe = =2
56 nRT
Moles of H2 = 2 17. Final pressure, P =
V
Work = nR∆T = 2 × 2 × 300 = 1200 cal = 1 × 0.0821 × 300 = 24.6 atm
nR(T1 − T2 ) P
4. Work = ∆S = nR ln 2
γ −1 P1
8.314 (300 − T ) 21. ∆G = ∆Go + RT ln Q
3000 = 3
1.414 − 1  20 
= 10000 + 8.314 × 298 ln   = 27.11 kJ
T = 150 K  2 

Chapter_6a.indd 24 3/26/2014 3:13:03 PM

 Thermodynamics  6A.25

23. 2Al + O2  → Al2O3 38. Isoentropic compression means adiabatic reversible

∆H = –837.8 × 2 = –1674.4 kJ compression
V T1γ P11–γ = T2P21–γ
24. ∆S = nR ln 2 = 9.2 cal (300)1.66 (1)–0.66 = (600)1.66 (P)–0.66
V1
P0.66 = 21.66
∂E 0.66 ln P = 1.66 ln 2 ln P = 1.75 atm
25. ∆S = nF ln
∂T
39. At equilibrium, ∆G = O
∂E 96.53 ∆H
∴ = = 5 × 10–4 V/k Equilibrium temperature, T = = 1000
∂T 2 × 96500 ∆S
So, the reaction is spontaneous above 1000 K.
26. ∆H = nCp DT
100 2 × 49.26
41. Moles of air = =4
∆H = ∫
10
(2 + 0.2T ) ∆T 0.0821× 300
Moles of O2 in air = 0.8
∴ H = –13.27 k cal
1
C + O2  → CO, ∆H = –26 k cal
28. Heat of reaction, ∆H = H CO2 + H NO − H CO − H NO2 2
= –226 kJ 1 0.8 – initial moles
Activation energy of forward reaction = 465.2 kJ – 0.3 1 Final moles
Activation energy of backward reaction = 465.2 + 1
226 = 691.2 kJ CO + O2 
→ CO2, ∆H = –68 k cal
2
2
PNH 1 0.3 – initial mole
29. Reaction quotient = 3
3
PN2 .P H2 0.4 – 0.3 final mole
∴ Q = 1.48 × 10–5 Heat evolved = 26 + 68(0.6) = 66.8 k cal
∆G = ∆Go + 2.303 RT log a = 60.5 kJ
42. A(g) + B(g) → C(g)
Work ∆n = 1 – 2 = –1
30. ∆S =
T ∆H = DU + DnRT
PV ∆S = –3000 + (–1) (2) (300) = –3.6 k cal
Work =
nR ∆G = ∆H – T∆S
1 = –3.6 × 103 – 300 (–10)
31. H2O 
→ H2 + O2, ∆Go = 120 kJ
2 ∆G = –60 cal
1
4 × (0.25) 2 43. ∆q = DU + P∆V
Reaction quotient = = 10
0.2 2
1440 = DU + 1 (0.018 – 0.0196)
∆G = ∆Go – 2.303 RT log Q = 125.7 kJ 0.0821
T2 ∴ DU = 1440.039
32. ∆S = nCp ln = 0.693 k cal/K
T1 ∆H 2 − ∆H1
44. = ∆Cp
33. TV  = constant
γ–1
T2 − T1
300 × 10.53 = T × 40.53
T = 150 K 45. ∆Go = ∆Ho – T∆So
∆H = nCpDT = –900 cal/mol ∆Go = –2.303 RT log kp

Chapter_6a.indd 25 3/26/2014 3:13:07 PM

 This page is intentionally left blank.

Chapter_6a.indd 26 3/26/2014 3:13:07 PM

 6b

Chapter
Thermochemistry

Exothermic and Endothermic Z is heat capacity of calorimeter system, DT is rise in

Reactions temperature, M is molecular mass of substance and
W is mass of substance taken.
• The chemical reactions accompanied by the liberation • Measurements in an open calorimeter determine the
of heat are called exothermic reactions. In exother-
amount of heat liberated or absorbed when known
mic reactions, the enthalpy change ∆H is negative.
amounts of substance react at constant pressure.
• The chemical reactions accompanied by the absorp- • Since the heat liberated in bomb calorimeter is at con-
tion of heat are called endothermic reactions. In
stant volume qv, it can be converted into heat at con-
endothermic reactions, the enthalpy change ∆H is
stant pressure by using the equation.
positive.
qp = qv + DnRT
• The energy change that occurs in a chemical reaction
• n is the change in the number of gaseous molecules in
is usually known as chemical energy.
the combustion reaction.
• The energy change in a chemical reaction is mainly
• Heat liberated during neutralization, dilution, phase
due to the change in potential energy that results due
to the breaking of bonds in reactants and formation of transition, etc. are measured in second type of calorim-
new bonds in products. eter where the rise in temperature of water is measured
in calorimeter or Dewar flask.
• The heat change that takes place at constant volume
is the change in internal energy (∆U) while the heat  m (t − t ) 
   W =  2 2 3 − m1 
change that takes place at constant pressure is the  t3 − t1 
­enthalpy change (∆H).
W is water equivalent of calorimeter, m1 mass of water
at lower temperature t1, m2 is the mass of water at high
Measuring Heats of Reaction temperature t2 and t3 is resultant temperature by mix-
ing the two water samples of m1 and m2 at t1 and t2.
• The technique of measuring heats of reactions is
Heat liberated = (W + volume of reaction mixture)
called calorimetry and the instrument used is called
× rise in temperature
calorimeter.
• For combustion reactions bomb calorimeter is used.
Bomb is made with non-oxidizable material. In bomb Thermochemical Equation
calorimeter, combustion reactions are carried at constant • Thermochemical equation is the equation in which the
volume.
heat change accompanying the chemical reaction is
• The heat liberated during the combustion reactions in also specified numerically.
bomb calorimeter is calculated using the formula • Unless otherwise mentioned, ∆H values are given for
M standard state of substance, i.e., when reactions occur at
   DU = –Z × DT ×
W 298 K (25°C) and standard atmospheric pressure (1 atm).

Chapter_6b.indd 1 3/26/2014 3:08:38 PM

 6B.2  Objective Chemistry - Vol. I

• The most stable physical state of a substance at 298 K 6. Bomb calorimeter is used to determine the heat of
and 1 atmospheric pressure is called its standard state. reaction at
• For indicating physical state of each substance in a (1) constant pressure (2)  constant volume
chemical equation designation such as “g” for gas “l” (3) 298 K (4)  373 K
for liquid, “s” for solid and “aq” for aqueous solution 7. “A” gram of ethanol was subjected to combustion in a
are given along with chemical formula of reactants bomb calorimeter producing “B” Joules of heat; Then
and products. For example
(1) DUcombustion = –A Joules
Cgraphite(s) + O2(g)  → CO2 (g); ∆H = –393.5 kJ (2) DUcombustion = –B Joules
HCl(aq) + NaOH(aq) 
→ NaCl(aq) + H2O(l); 46B
(3) DUcombustion = – Joules mol-1
∆H = –57.3 kJ A
46B
(4) DUcombustion = – Joules mol-1
A
 Objective Questions
8. The bomb calorimeter is used to find the
1. Which of the following statement is false? (1) heat of combustion
(1) Thermochemistry is the study of relationship (2) heat of neutralization
­between the heat energy and chemical energy. (3) heat of solution
(2) An exothermic reaction is one which is accompa- (4) heat of dilution
nied by evolution of heat.
(3) An endothermic reaction is one in which heat is Answers
absorbed.
(4) The unit that represents largest amount of energy   (1) 4   (2) 4   (3) 4   (4) 3
is electron volt.   (5) 1   (6) 2   (7) 3   (8) 1
2. The wrong statement among the following is
(1) An exothermic reaction is that in which the react-
ing substances have more energy than the products. Enthalpies of Different Processes
(2) Electrolysis of water is accompanied with ab- • The enthalpy content of an element in its standard
sorption of energy. state is zero.
(3) Evaporation of water is an endothermic change.
(4) The law of conservation of energy states that the • The standard heat of formation is the enthalpy
internal energy of a system is constant. change when one mole of the substance is made from
its elements in their states.
3. Which is not characteristic of a thermochemical
• Compounds formed from their elements with the
equation?
evolution of heat are called exothermic compounds,
(1) It indicates physical state of reactants and products. whereas the compounds formed from their elements
(2) It indicates whether the reaction is exothermic or with absorption of heat are called endothermic
endothermic. compounds.
(3) It indicates allotrope of the reactants if present.
(4) It indicates whether a reaction would occur or not. • The enthalpy of a reaction is the enthalpy change
(amount of heat evolved or absorbed) in a reaction
4. The correct thermochemical equation is when the number of moles of reactants react com-
(1) C + O2  → CO2; ∆H = –94 kcal pletely to give the products as given by the balanced
(2) C + O2  → CO2; ∆H = +94 kcal chemical equation.
(3) C(s) + O(g) → CO2(g); ∆H = –94 kcal • The enthalpy of formation of compound is the stand-
(4) C(s) + O(g) → CO2(g); ∆H = +94 kcal ard enthalpy of the compound since the standard
5. For the reactions enthalpies of the elements from which it is formed is
H2(g) + Cl2(g)  → 2HCl(g) + X1 kJ zero.
2HCl(g)  → H2(g) + Cl2(g) – X2 kJ • Exothermic substances are stable while endothermic
(1) X1 and X2 are numerically equal. substances are unstable.
(2) X1 and X2 are numerically different. • In endothermic reactions the sum of the internal
(3) X1 – X2 > O energies of the products is greater than the sum of
(4) X1 – X2 < 0 the ­internal energies of the reactants while in the

Chapter_6b.indd 2 3/26/2014 3:08:40 PM

 Thermochemistry  6B.3

exothermic reactions the sum of the internal energies • The enthalpy of neutralization involving a weak acid
of products is greater than the sum of the internal ener- or weak base is less than 57.1 kJ since some energy is
gies of reactants. used to dissociate the weak electrolytes.
• The change in enthalpy of reaction at constant • If dilute acids and bases are used, the rise in ­temperature
­pressure per degree change of temperature is equal is less because the volume is more, the heat will be
to the difference in the heat capacities of the products distributed.
and the ­reactants at constant pressure and is given by • The amount of heat required to break one mole of a
Kirchoff’s equation. simple molecule in the gaseous state into its constitu-
∆H 2 − ∆H1 ent atoms is called enthalpy of atomization.
  ∆Cp =
T2 − T1 • The enthalpy change in the formation of an ion at unit
activity (or concentration) from its element in aqueous
where ∆Cp is difference in the heat capacities of pro­ solution is called enthalpy of ionization.
ducts and reactants at constant pressure. • Since absolute enthalpies of ionization cannot be de-
• The change in heat of reaction at constant volume termined, they are calculated by taking the enthalpy of
per degree change of temperature is given by the dif- H (+aq ) at 298 K as zero.
ference in the heat capacities of the products and the
­reactants at constant volume. • Enthalpy of solution is the quantity of heat liberated
or absorbed when one mole of solute is dissolved com-
• The standard heat of combustion is the enthalpy
pletely in large excess of the solvent, so that further
change when one mole of the substance is completely
dilution will not produce any heat change. Enthalpy of
burned in oxygen.
solution depends on the concentration of a solute.
• Calorific value of fuels and foods can be determined
• The enthalpy change per mole of solute when it is dis-
by heat of combustion. Calorific value is the amount
solved in a pure solvent in the required volume to give
of heat produced in calories (or joules) when 1 g of a
a solution of specified concentration is called integral
substance (food or fuel) is completely burnt.
heat of solution.
• The enthalpy change when 1 mole of a solid substance
• Enthalpy of dilution is the enthalpy change when a
is converted into its liquid state at its melting point is
solution containing 1 mole of solute is diluted from a
called enthalpy of fusion or molar enthalpy of fusion.
known concentration to another concentration.
• The enthalpy change when 1 mole of a liquid is con-
• Enthalpy of hydration is the enthalpy change when
verted into gaseous state at its boiling point is called
1 mole of an anhydrous substance combines with
enthalpy of vapourisation or molar enthalpy of
requisite number of molecules of water to form the
vapourisation.
hydrate.
• The enthalpy change when 1 mole of a solid is directly
• The heat of hydration is the difference in the heats of
converted into its gaseous state at a temperature below
solutions of the anhydrous salt and the hydrated salt.
its melting point is called enthalpy of sublimation or
molar enthalpy of sublimation. • Heat of transition is the change in enthalpy when 1
mole (or 1 g atom, in case the molecular formula is not
• Heat of neutralization of an acid (or base) at a given
decided) of the substance transits from one allotropic
temperature is the heat change when one gram equiva-
form to another.
lent of an acid (or base) in dilute aqueous solution
is neutralized by 1 g equivalent of a dilute aqueous • The enthalpy of hydrogenation is the heat change
­solution of a base (or acid). when 1 mole of an unsaturated compound reacts with
hydrogen and is completely changed into the corre-
• The enthalpy of neutralization of all strong acids and
sponding saturated compound.
strong bases is always equal to 57.1 kJ mol–1 irrespec-
tive of the nature of acid or base.
• The enthalpy of neutralization is merely the heat of  Objective Questions
­formation of water from H+ of an acid and OH– of a
base. 9. The enthalpy change for the formation of H2O (l) from
its elements in their standard state is –572 kJ; therefore,
H (+aq ) + OH (−aq ) 
→ H2O; ∆H = –57.1 kJ
(1) the reaction is endothermic
• The enthalpy of neutralization of a strong acid and strong (2) the sum of the enthalpy of hydrogen and that of
base is always constant because they ionize completely. oxygen must be greater than that of water

Chapter_6b.indd 3 3/26/2014 3:08:41 PM

 6B.4  Objective Chemistry - Vol. I

(3) the sum of the enthalpy of hydrogen and that of its ­elements at 298 K and 1 atm pressure. Since the
oxygen must be less than that of water enthalpies of elements in their most stable state are
(4) the enthalpy of water must be zero taken to be zero, the heat of formation of compound is
10. The false statement among the following is (1) always negative
(2) always positive
(1) An exothermic reaction is spontaneous if tem-
(3) standard heat enthalpy of that compound
perature is too low.
(4) zero
(2) If a reaction is exothermic, the reverse reaction is
endothermic. 17. From the reaction Pwhite 
→ Pred; ∆H = –18.4 kJ
(3) The heat lost or gained in a chemical reaction is follows that
called free energy of the reaction. (1) Red P is readily formed from white P.
(4) Exothermic compounds are stable. (2) White P is readily formed from red P.
11. Which of the following statements is wrong? (3) White P cannot be converted to red P.
(4) White P can be converted into red P and red P is
(1) An endothermic reaction must absorb energy
more stable.
­before it can take place.
(2) During the exothermic reaction heat is evolved. 18. The false statement among the following is
(3) If heat of formation of a compound is negative, (1) The heat liberated during the neutralization of a
the compound is more stable than its elements. strong acid and a strong base in an aqueous solu-
(4) After an endothermic reaction, there is no change tion is constant.
in the temperature of the reaction mixture. (2) The heat of combustion is always an exothermic
12. The false statement among the following is change.
(3) The enthalpies of formation of organic sub­
(1) ∆H for the thermal decomposition process is
stances can be conveniently determined from
­always positive.
heat of combustion data.
(2) Bond-breaking energy of a molecule is always
(4) Heat of formation of a compound is equal in
positive.
magnitude to heat of combustion.
(3) Conversion of oxygen into ozone is endothermic
reaction and hence it is more stable than oxygen. 19. Heat of solution is defined as
(4) The heat change in a chemical reaction is repre- (1) Heat required in dissolving 1 mole in excess of
sented by enthalpy change. water.
13. The positive change in enthalpy occurs in (2) Heat evolved when 1 mole is dissolved in excess
1 of water.
(1) H2(g) + O2(g)  → H2(g) (3) Change in heat content of the system when
2
1  mole of the solute is dissolved in excess of
(2) N2(g) + 3H2(g)  → 2NH3(g)
­water so that further dilution of solution does not
(3) MgCO3(s)  → MgO(s) + CO2(g) bring any heat change.
1 (4) None of the above.
(4) H2(g) + O2(g)  → H2O(l)
2
20. The wrong statement among the following is
14. In a chemical reaction if all the reactants and products
(1) The heat change for the reaction H2O(l) →
are in a liquid state then
H2O(g) is known as heat of vapourisation.
(1) ∆H > DU (2)  ∆H < DU (2) The heat change in the reaction C(s) + 2S(s) →
(3) ∆H = DU (4)  None CS2 (l) is called heat of formation of CS2.
15. In a flask colourless N2O4 is in equilibrium with (3) The standard heat enthalpy of diamond is zero.
brown-coloured NO2. At equilibrium when the flask (4) The enthalpy change C(s) → C(g) is known as
is heated at 100° the brown colour deepens and on ­enthalpy of sublimation.
cooling it becomes less coloured. Now, the change in 21. When ammonium chloride is dissolved in water the
enthalpy ∆H for the system is solution becomes cold because
(1) Negative (2)  Positive (1) Heat of solution of ammonium chloride is positive.
(3) Zero (4)  none (2) Heat of solution of ammonium chloride is negative.
16. The heat of formation is the change in enthalpy (3) Heat of dilution of ammonium chloride is positive.
­accompanying the formation of a substance from (4) Heat of formation of ammonium chloride is ­positive.

Chapter_6b.indd 4 3/26/2014 3:08:42 PM

 Thermochemistry  6B.5

22. The enthalpy of formation of HI is 30.4 kJ. Which numerical PROBLEMS

statement is false according to this observation?
29. Equal volumes of C2H2 and H2 are combusted under
(1) HI is an endothermic compound. identical conditions. The ratio of their heat of com-
(2) For the reaction H2(g) + I2 (g) → 2HI(g), ∆H = 60.8 kJ 1
(3) HI is a stable compound. bustion is H2(g) + O2(g)  → H2(g); ∆H = –241.8 kJ
2
(4) HI is an unstable compound. 1
C2H2(g) + 2 O2(g)  → 2CO2(g) + H2O(g); ∆H =
23. ∆H for the transition of carbon in the diamond form 2
to carbon in the graphite form is –453.5 cal. This sug- –1300 kJ
gests that (1) 5.37/1 (2)  1/5.37 (3)  1/1 (4)  4/5
(1) Graphite is chemically different from diamond. 30. The temperature of 5 mL of a strong acid increases by
(2) Graphite is as stable as diamond. 5°C when 5 mL of a strong base is added to it. If 10 mL
(3) Graphite is more stable than diamond. of each are mixed, temperature should increase by
(4) Diamond is more stable than graphite. (1) 5°C (2)  10°C
24. If CH3COOH + OH–  → CH3COO– + H2O + q1 (3)  15°C (4)  cannot be known
and H + OH → H2O + q2, then enthalpy change for
+ –
31. If H2(g) → 2H(g); ∆H = 104 kcal then heat of atomiza-
the reaction tion of hydrogen is
CH3COOH  → CH3COO– + H+ is equal to (1) 52 kcal (2)  104 kcal
(1) q1 + q2 (3) 208 kcal (4)  None of these
(2) q1 – q2
32. Heat of combustion of CH4, C2H4 and C2H6 are –890,
(3) q2 – q1
–1411 and –1560 kJ/mol, respectively. Which has the
(4) –q1 – q2
lowest calorific fuel value in kJ/g?
25. The magnitude of heat of solution .... on addition of (1) CH4 (2)  C2H4 (3)  C2H6 (4)  All
solvent to solution. 33. The standard heats of formation of NO2(g) and
(1) decreases N2O4(g) are 8.0 and 2.0 kcal mol–1, respectively. The
(2)  increases heat of dimerization of NO2 in kcal is
(3) remains constant (1) 10.0 (2)  –6.0 (3)  –12.0 (4)  –14.0
(4)  increases or decreases
1
26. Heat of neutralization of any strong acid by any 34. H2(g) + O2(g) → H2O(l); ∆H298K = –68.32 kcal.
2
strong base is the same because Heat of vapourisation of water at 1 atm and 25°C is
(1) Basically it is the same reaction taking place in 10.52 kcal. The standard heat of formation (in kcal)
all such cases. of 1 mole of water vapour at 25°C is
(2) Basically it is the reaction of H+ + OH– → H2O (1) –78.84 (2)  78.84 (3)  +57.8 (4)  –57.8
(3) Strong acids and strong bases ionize completely
15
in water. 35. According to the equation C6H6(l) + O2(g) →
(4) All the above. 2 
6CO2(g) + 3H2O(l), ∆H = –3264.4 kJ/mol, the energy
27. Which of the following about the endothermic com- evolved when 7.8 g of benzene is burnt in air will be
pound C2H2 is false (1) 163.32 kJ/mol (2)  326.4 kJ/mol
(1) It is formed with the absorption of energy. (3) 32.64 kJ/mol (4)  3.264 kJ/mol
(2) It is an efficient fuel. 36. Given that standard heat enthalpy of CH4, C2H4 and
(3) If gives off more heat in its combustion than C3H8 are –17.9, 12.5 and –24.8 kcal/mol, respective-
would if it were an exothermic compound. ly. The ∆H for the reaction CH4 + C2H4 → C3H8 is
(4) It is more stable than the exothermic compound
(1) –55.2 kcal (2)  –30.2 kcal
CH4.
(3) 55.2 kcal (4)  –19.4
28. Heat of neutralization is least in 37. In which case of mixing of a strong acid and a strong
(1) NaOH + CH3COOH   (2)  NaOH + HCl base each of 1 N concentration, temperature increase
(3) NH4OH + CH3COOH   (4)  NH4OH + HCl is highest in

Chapter_6b.indd 5 3/26/2014 3:08:44 PM

 6B.6  Objective Chemistry - Vol. I

(1) 20 mL acid – 30 mL alkali (1) –121 kJ/mole (2)  +121 kJ/mole
(2) 10 mL acid – 40 mL alkali (3) –242 kJ/mole (4)  +242 kJ/mol
(3) 25 mL acid – 25 mL alkali
45. The heat of neutralization of a strong base and
(4) 35 mL acid – 15 mL alkali
a strong acid is 57.0 kJ. The heat released when
38. 2.1 g of Fe combines with S evolving 3.77  kJ. The 0.5 mole of HNO3 solution is added to 0.20 moles of
heat of formation of FeS in kJ/mol is NaOH ­solution is
(1) –3.77 (2)  –1.78 (1) 11.40 kJ (2)  57.0 kJ
(3)  –100.5 (4)  None (3) 28.5 kJ (4)  34.9 kJ

39. The heat evolved during the combustion of 112 litre of Answers

water gas (mixture of equal volumes of H2 and (CO) is
1   (9) 2 (10) 3 (11) 4 (12) 3 (13) 3
 (i)  H2(g) + O2(g) → H2O(g); ∆H = –241.8 kJ
2 (14) 3 (15) 2 (16) 3 (17) 4 (18) 4
1 (19) 3 (20) 3 (21) 1 (22) 3 (23) 3
(ii)  CO(g) + O2(g) → CO2(g); ∆H = –283 kJ (24) 3 (25) 3 (26) 4 (27) 4 (28) 3
2
(29) 2 (30) 1 (31) 1 (32) 2 (33) 4
(1) 241.8 kJ (2)  283.3 kJ (34) 4 (35) 2 (36) 4 (37) 3 (38) 3
(3) 1312 kJ (4)  1586 kJ (39) 3 (40) 1 (41) 2 (42) 1 (43) 4
40. A person requires 2870 kcal of energy to lead a nor- (44) 1 (45) 1
mal daily life. If heat of combustion of cane sugar is
–1349 kcal, then his daily consumption of sugar is
(1) 728 g (2)  0.728 g laws of thermochemistry
(3)  342 g (4) 0.342 g • Lavoisier and Laplace law states that the amount
of heat required to decompose a compound into its
41. Equal volumes of 1 M HCl and 1 M H2SO4 are ­elements is equal to heat of formation of that com-
­neutralized by dilute NaOH solution and X and Y pound from its elements.
kcal of heat are liberated, respectively. Which of the
• Hess’s law states that the heat of reaction is same
following is true?
whether the reaction takes place in one step or in
(1) X = Y (2)  X = 0.5 Y ­several steps (or)
(3) X = 0.4 Y (4)  None
the enthalpy change involved in a reaction is the same
42. To a solution of 500 mL of KOH is added 50 mL of 2 M whether the reaction takes place in one single step or
HCl and the mixture is well shaken. The rise in tem- in several steps (or)
perature T1 is noted. The experiment is then repeated the amount of heat evolved or absorbed in a chemical
using 250 mL of each solution and rise in temperature reaction or process is the same whether the reaction
T2 is again noted. Assume all heat is taken up by the takes place in a single step or several steps.
solution. Now, which of the following is correct? • Mathematically, Hess’s law can be represented for a
(1) T1 = T2. reaction A gives D in a single step or in three steps.
(2) T1 is twice as larger as T2. Single step A  → D+Q
(3) T2 is twice as larger as T1. Three steps A  → B + q1
(4) T1 is 4 times as larger as T2. B → C + q2
C → D + q3
43. Under the same conditions, how many mL of 1 M
Q = q1 + q 2 + q 3
KOH and 0.5 M H2SO4 solutions respectively when
• According to Hess’s law the heat of a reaction depends
mixed for a total volume of 100 mL produce the
­highest rise in temperature? only on the initial reactants and final products but
not on the intermediate products formed. The heat of
(1) 67:33 (2)  33:67 (3) 40:60 (4)  50:50
­reaction is also independent of the path or manner by
44. The enthalpy of combustions at 25°C of H2, cyclo­ which a reaction is carried out.
hexene (C6H10) and cyclohexane (C6H12) are –241, • Using Hess’s law the heat of formation of intermediate
–3800 and –3920 kJ/mol, respectively. The heat of compounds which cannot be determined experimen-
hydrogenation of cyclohexane is tally can be calculated.

Chapter_6b.indd 6 3/26/2014 3:08:45 PM

 Thermochemistry  6B.7

• The heats of formation of compounds like CO, 49. Hess’s law is used in the determination of
­benzene, etc. which cannot be determined directly can (1) Heat of formation (2)  Heat of reaction
be calculated by using Hess’s law. (3) Heat of transition (4)  All of these
• Heat changes of slow reactions can be calculated using
50. A hypothetical reaction A  → B proceeds via
Hess’s law.
­following sequence of steps.
• The heat of transition of α–sulphur to β–sulphur
   (i)  A  → C; ∆H = q1
which is slow can be calculated from their heats of
   (ii)  C  → D; ∆H = q2
combustion. 1
• Heats of formation or enthalpy of formation of certain (iii)  D  → B; ∆H = q3
2
compounds such as C2H4 which require drastic condi- The heat of reaction is
tions can be calculated by using Hess’s law. (1) q1 – q2 + 2q3 (2)  q1 + q2 – 2q3
• Determination of lattice energy of ionic compounds (3) q1 + q2 + 2q3 (4)  q1 + 2q2 + 2q3
using Born–Haber cycle is based on Hess’s law.
51. Hess’s law of heat summation is
• Using Hess’s law, bond energies in some compounds
(1) Law of conservation of energy
can be calculated.
(2) Really another way of stating that energy can
• Bond enthalpy or bond dissociation enthalpy is the ­neither be created nor destroyed
amount of energy required to break the covalent bonds in (3) Helpful in calculating heat of reaction which are
1 mole of diatomic molecules such as H2, Cl2, HCl etc. impossible in practice
• In the case of polyatomic molecules, bond dissociation (4) All the above
enthalpy is the average bond energies.
52. Heat of transition is the heat evolved or absorbed
• Lattice energy is the amount of energy liberated when when a substance is converted from
1 mole of gaseous cations and 1 mole of gaseous ani-
(1) solid to liquid
ons are brought together from infinite distance apart to
(2) solid to vapour
their equilibrium position in the crystal lattice at 0 K,
(3) liquid to vapour
i.e., the change in internal energy, ∆U.
(4) one allotropic form to another allotropic form
   (or)
the amount of energy required to break 1 mole of an
ionic crystal and to separate the constituent ions from numerical PROBLEMS
their position in the crystal to infinite distance but
53. C(diamond) + O2(g) → CO2(g); ∆H = –395 kJ
with a positive sign to ∆U.
C(graphite) + O2(g) → CO2(g); ∆H = –393.5 kJ
The ∆H when diamond is formed from graphite
 Objective Questions
(1) –1.5 kJ (2)  +1.5 kJ
46. The heat change in a reaction does not depend upon the (3)  +3.0 kJ (4)  –3.0 kJ
(1) Conditions of P or V under which a reaction is 1
carried out. 54. H2 + O2  → H2O; ∆H = –68.39 kcal
2
(2) Initial and final enthalpies of the reactants and 1
K + aq  → KOH(aq) + H2(g); ∆H = –48 kcal
products. 2
(3) State of reactants and products. KOH + aq  → KOH(aq); ∆H = –14 kcal
(4) Number of intermediate stages involved. The heat of formation (in kcal) of KOH is
47. For the reactions, where experimental determination of (1) –68.39 48 – 14 (2)  –68.39 – 48 + 14
enthalpy is not possible the enthalpy can be calculated by (3) 68.39 – 48 + 14 (4)  68.39 + 48 + 14
(1) Kirchoff’s law (2)  Hess’s law
55. If S + O2 
→ SO2; ∆H = –298.2 kJ
(3) Henry’s law (4)  Clapeyron equation
1
48. Hess’s law of heat summation is an application of SO2 + O2  → SO3; ∆H = –98.7 kJ
2
(1) Entropy
SO3 + H2O  → H2SO4; ∆H = –130.2 kJ
(2) Kirchoff’s law
(3) First law of thermodynamics 1
H2 + O2  → H2O; ∆H = –227.3 kJ
(4) Second law of thermodynamics 2

Chapter_6b.indd 7 3/26/2014 3:08:47 PM

 6B.8  Objective Chemistry - Vol. I

The enthalpy of formation of H2SO4 at 298 K will be (1) less than in the second case by 1.89 kJ
(1) –813.9 kJ (2)  +320.5 kJ (2) less than in the second case by 11.34 kJ
(3)  –650.3 kJ (4)  –433.7 kJ (3) less than in the second case by 14.34 kJ
(4) more than in the second case by 0.945 kJ
56. From the following data, the heat of formation of
Ca(OH)2 (s) at 18°C is ..... kcal. 
63. Given NH3(g) + 3Cl2(g) 
 NCl3(g) + 3HCl(g); –H1
∆H18°c = –15.26 kcal 
N2(g) + 3H2(g)  
 2NH3(g); H2
1
H2O(l) + H2(g) + O2(g); ∆H18°C = 68.37 kcal 
H2(g) + Cl2(g)  2HCl; H3
1 2
Ca(s) + O2(g)  → CaO(s); ∆H18°C = –151.8 kcal The heat of formation of NCl3(g) in the terms of ∆H1
2 ∆H2 and ∆H3 is
(1) –98.69 (2)  –235.43 ∆H 2 3
(1) ∆Hf  = –∆H1 + − ∆H3
(3)  194.91 (4)  98.69 2 2
57. C(graphite) + O2(g) → CO2(g); ∆H = –94.05 kcal ∆H 2 3
(2) ∆Hf  = ∆H1 + − ∆H3
 mol–1 2 2

C(diamond) + O2(g)  → CO2(g); ∆H = –94.50 kcal ∆H 2 3
 mol–1 (3) ∆Hf  = ∆H1 + − ∆H3

2 2
Therefore, (4) None
θ
(1) C(diamond) → C(graphite); ∆ H 298K = –450 cal mol–1
θ
(2) C(graphite) → C(diamond); ∆ H 298K = –450 cal mol–1 64. On the basis of the thermochemical equations
H2O(g) + C(s)  → CO(g) ∆H = 131 kJ
(3) Diamond is harder than graphite.
(4) Graphite is stable isotope. 1
CO(g) + O2(g)  → CO2(g) ∆H = –282 kJ
2
58. If H2(g) + Cl2(g) 
→ 2HCl; DH° = –44 k.cal
1
2Na(s) + 2HCl(g)  → 2NaCl(s) + H2(g); H2(g) + O2(g) 
→ H2O(g) ∆H = –242 kJ
2
∆H = –152 kcal
C(s) + O2(g) 
→ CO2(g) ∆H = X kJ
Then, Na(s) + 0.5 Cl2(g) 
→ NaCl(s); ∆H° = ?
(1) 108 kcal (2)  196 kcal The value of X will be
(3) –98 kcal (4)  54 kcal (1) –393 kJ (2)  –655 kJ
(3)  393 kJ (4) 655 kJ
1
59. If C(s) +O2(g) → CO2(g); ∆H = S
2 5
65. Given that CH3CHO + O2 → 2CO2 + 2H2O; ∆H =
C(s) + O2(g) → CO2(g); ∆H = R 2
Then, the heat of formation of CO –1168 kJ/mole; CH3COOH + 2O2  → 2CO2
(1) R + S (2)  R – S + 2H2O; ∆H = –876 kJ/mole. ∆H for the reaction
(3)  S – R (4)  R × S 1
CH3CHO + O2  → CH3COOH is
2
60. Given the bond energies of N ≡ N, H – H and N – H
bonds as 945, 436 and 391 kJ mol–1, respectively, the (1) –292 kJ/mole (2)  378 kJ/mole
enthalpy of the reaction N2(g) + 3H2(g) → 2NH3(g) is (3) 195 kJ/mole (4)  –2044 kJ/mole
(1) –93 kJ (2)  102 kJ 66. From the following data, the heat of formation of PCl5
(3) 90 kJ (4)  105 kJ 2P(s) + 3Cl2(g) → 2PCl3(g); ∆H = 151.8 kcal
61. Bond energies of (H – H), (O = O) and (O – H) are PCl3 + Cl2(g) → PCl5(g); ∆H = –32.8 kcal
105, 120 and 220 kcal/mol, respectively, then ∆ in the (1) –217.4 kcal (2)  +217.4 kcal
reaction is equal to (3) –108.7 kcal (4)  +108.7 kcal
2H2(g) + O2(g)  → 2H2O(l)
(1) –115 (2)  –130 (3)  –118 (4)  –550
Answers
62. For the change Cdiamond  → Cgraphite, ∆H = –1.89 kJ.
If 6 g of diamond and 6 g of graphite are separately (46) 4 (47) 3 (48) 3 (49) 4 (50) 3
burnt to yield CO2 the heat liberated in the first case is (51) 4 (52) 4 (53) 2 (54) 2 (55) 1

Chapter_6b.indd 8 3/26/2014 3:08:50 PM

 Thermochemistry  6B.9

(56) 2 (57) 4 (58) 3 (59) 2 (60) 1

From the data the enthalpy change ∆H for the reaction
•
(61) 4 (62) 4 (63) 1 (64) 1 (65) 1 2CH3 – CH 2  → CH3 – CH3 + CH2 = CH2 is
(66) 3
(1) +250 kJ (2)  +588 kJ
(3)  –252 kJ (4) –588 kJ
7. The lattice energy of solid NaCl is 180 kcal/mol.
The dissolution of the solid in water, in the form of
 Practice Exercise Level-I ions is endothermic to the extent of 1 kcal/mol. If the
­solvation energies of Na+ and Cl– ions are in the ratio
1. Standard heat of combustion of solid boron is equal to 6:5, what is the enthalpy of hydration of sodium ion?
1 (1) –85.6 kcal/mol (2)  –97.6 kcal/mol
(1)  ∆H θf (B2O3) (2)  ∆H θf (B2O3)
2 (3) 82.6 kcal/mol (4)  100 kcal/mol
1
(3) – ∆H θf (B2O3) (4)  – ∆H θf (B2O3) 8. Heat of neutralisation of oxalic acid is –25.4 kcal/mol
2
using strong base, NaOH. Hence enthalpy change in
2. Which of the following salts shall cause more cooling the process H2C2O4  → 2H+ + C2O42– is
when one mole of the salt is dissolved in the same (1) 2.0 kcal (2)  –11.8 kcal
amount of water? (3) 1.0 kcal (4) –1.0 kcal
(Integral heat of solution at 298 K is given for each
solute). 9. The standard heat of combustion of propane is
–2220.1 kJ/mol. The standard heat of vapouri­sation
(1) KNO3; ∆H = 35.4 kJ/mol
of liquid water is 44 kJ/mol. What is the ∆Hq of
(2) NaCl; ∆H = 5.35 kJ/mol C3H8(g) + 5O2 → 3CO2(g) + 4H2O(g)?
(3) KOH; ∆H = –55.6 kJ/mol
(1) – 2220.1 kJ (2)  –2044 kJ
(4) HBr; ∆H = –83.3 kJ/mol (3) –2396 kJ (4)  –2176.1 kJ
3. The heat evolved in the combustion of glucose 10. A geyser operating on liquefied petroleum gas (LPG)
C6H12O6 is –680 kcal/mol. The weight of CO2 heats water flowing at the rate of 3.0 litres per minute,
produced
­ when 170 kcal of heat is evolved in the from 27°C to 77°C. If the heat of combustion of LPG
combustion of glucose is is 40,000 J/g, how much fuel in gram is consumed per
(1) 264 g (2)  66 g (3)  11 g (4)  44 g minute?
4. One gram sample of NH4NO3 is burnt in a bomb (1) 15.25 (2)  15.5 (3)  15.75 (4)  16.0
calorimeter. The temperature of the calorimeter in- 11. The heat capacity of bomb calorimeter is 500 J/°C.
creases by 6.12 K. The heat capacity of the calorim- A 2°C rise in temperature has been observed on the
eter system is 1.23 kJ/deg. What is the molar heat of combustion of 0.1 g methane. What is the value of
combustion for NH4NO3? DU per mole of methane?
(1) 7.53 kJ/mol (2)  813 kJ/mol (1) 1 kJ (2)  160 kJ
(3) –602.2 kJ/mol (4)  602.2 kJ/mol (3) –160 kJ (4)  –1 kJ
5. C12H22O11(s) + 12O2(g)  → 12CO2(g) + 11H2O(l) 12. Heat evolved in the reaction H2 + Cl2 → 2HCl
∆H = –5.65 × 10 kJ. Complete combustion of 1 kg
3
is 182  kJ. Bond energies of H – H = 430 kJ/mole,
sucrose is done. Heat evolved will be Cl – Cl = 242 kJ/mole
(1) 1.65 × 104 kJ (2)  5.25 × 103 kJ Then, H – Cl bond energy is
(3) 7.38 × 10 kJ
5
(4)  3.51 × 105 kJ (1) 763 kJ/mole (2)  245 kJ/mole
6. The data below refers to gas phase reaction at con- (3) 336 kJ/mole (4)  427 kcal/mole
stant pressure at 25°C 13. The heat of hydrogenation of benzene is –51.0 kcal/
• •
CH3 – CH3  → CH3 – CH 2 + H mole. If heat of hydrogenation of cyclohexadiene and
cyclohexane is –58 kcal/mole and –29 kcal/mole,
∆H1 = +420 kJ mol–1
• • ­respectively, what is the resonance energy of benzene?
CH3 – CH 2  → CH2 = CH2 + H (1) 29 kcal/mole (2)  36 kcal/mole
∆H2 = +168 kJ mol–1 (3) 58 kcal/mole (4)  7 kcal/mole

Chapter_6b.indd 9 3/26/2014 3:08:52 PM

 6B.10  Objective Chemistry - Vol. I

14. ∆Hfq for NF3 is –113 kJ/mol. Bond energy for N – F 20. The standard enthalpy of atomization of PCl3 (g)
bond is 27.5 kJ/mol. Calculate the bond energies of is 195 kcal/mol. What will be standard enthalpy
N2 and F2 if their magnitudes are in the ratio 6:1. of ­atomization of PCl5(g), if the bond dissociation
(1) 822.6, 137.1 kJ/mol ­energies of axial P – Cl bonds in PCl5(g) are 10%
(2) 979.8, 163.3 kJ/mol lesser and the bond dissociation energies of equatorial
(3) 943.32, 157.22 kJ/mol P – Cl bonds in PCl5(g) are 10% higher than the bond
(4) 762.6, 127.1 kJ/mol dissociation energies of P – Cl bonds in PCl3(g)?
(1) 195 kcal/mol (2)  325 kcal/mol
15. AB, A2 and B2 are diatomic molecules. If the bond
(3) 331.5 kcal/mol (4)  318.5 kcal/mol
enthalpies of A2, AB and B2 are in the ratio 2:2:1
and enthalpy of formation of AB from A2 and B2 is
–100 kJ mole–1, what is the bond energy of A2? Answers
(1) 200 kJ mol–1 (2)  100 kJ/mol–1
(3) 300 kJ mol –1
(4)  400 kJ mol–1   (1) 1   (2) 1   (3)  2   (4) 3   (5) 1
  (6) 3   (7) 2   (8) 1   (9) 2 (10) 3
16. Among the following, for which reaction, heat of (11) 3 (12) 2 (13) 2 (14) 3 (15) 1
­reaction represents bond energy of HCl? (16) 1 (17) 2 (18) 1 (19) 2 (20) 4
(1) HCl(g)  → H(g) + Cl(g)
(2) 2HCl(g)  → H2(g) + Cl2(g)
1 1
(3) HCl(g)  → H2(g) + Cl2(g)
2 2
(4) HCl(g)  → H (g) + Cl (g)
+ –  Practice Exercise Level-II
1. The bond energies of C ≡ C, C – H, H – H and C = C
17. H H
are 198, 98, 103 and 145 kcal, respectively. The
+H–H→ H
H ­enthalpy change for the reaction HC ≡ CH + H2 →
H H CH2 = CH2 is
The bond energies at 25 °C are (1) 48 kcal (2)  96 kcal
   (i)  C – C; 346 kJ mol–1 (3) –40 kcal (4)  –152 kcal
 (ii)  C – H; 413 kJ mol–1 2. 1.2 g of carbon is burnt completely in oxygen (­limited
(iii)  H – H; 437 kJ mol–1 supply) to produce CO and CO2. This mixture of gas-
  (iv)  C = C; 611 kJ mol–1 es if treated with solid I2O5 (to know the amount of

From this data calculate the value of ∆H at 25°C for CO produced); the liberated iodine required 120 mL
the above reaction is of 0.1 M hypo solution for complete titration. The %
(1) –289 kJ mol–1 (2)  –124 kJ mol–1 of carbon converted into CO is
–1
(3) 124 kJ mol (4)  289 kJ mol–1 (1) 60 % (2)  100 % (3)  50% (4)  30 %
18. Use the following data to calculate the enthalpy of 3. The standard enthalpy of formation (DfHq) at 298 k
hydration for caesium iodide and caesium hydroxide for methane CH4(g) is –74.8 kJ mol–1. The additional
respectively. information required to determine the average energy
Compound Latice energy ∆H solution for C – H bond formation would be
CsI +604 kJ/mol 33 kJ/mol (1) Latent heat of vapourisation of methane.
CsOH +724 kJ/mol –72 kJ/mol (2) The dissociation energy of hydrogen molecule.
–1
(1) –571 kJ mol and –796 kJ mol –1 (3) The dissociation energy of H2 and enthalpy of
(2) 637 kJ mol–1 and 652 kJ mol–1 sublimation of carbon.
(3) –6371 kJ mol–1 and –652 kJ mol–1 (4) The first four ionization energies of carbon and
(4) 571 kJ mol–1 and –79 kJ mol–1 electron gain enthalpy of hydrogen.

4. The enthalpy of combustion of methane gas in terms

19. Molar heat capacity of water in equilibrium with ice
of the given data is
at constant pressure is
Bond energy (kJ/mol)
(1) zero (2) infinity
(3) 40.45 kJ/K – mol (4) 75.48 J/k–mol eC − H eO − H eC = H eO = O
X1 X2 X3 X4

Chapter_6b.indd 10 3/26/2014 3:08:54 PM

 Thermochemistry  6B.11

Resonance energy of CO2 = + Y kJ/mol conditions. What is ∆H in kcal/mol) for the following
∆Hvap (H2O. l) = Z kJ/mol reaction under same conditions?
(1) 4X1 + 2X4 – 2X3 – 4X2 + Y + Z
(2) 4X1 + 2X4 – 2X3 – 4X2 + Y – 2Z
(3) 4X1 + 2X4 – 2X3 – 4X2 – Y + 2Z
(4) 4X1 + 2X4 – 2X3 – 4X2 –Y – 2Z    
5. Select the option in which heat evolved is maximum. (1) 2 (2)  – 4 (3)  4 (4)  –2
Df Hq (CO2, g) = –75 kcal/mol 1
10. C + O2  → CO, ∆H = –110 kJ
Df Hq (CO2, g) = –25 kcal/mol 2
The product will be CO if excess amount of carbon C + H2O(g)  → CO + H2(g), ∆H = 132 kJ
and CO2 if excess of O2 is present Calculate the mole composition of the mixture of
(1) 10 moles of carbon and 4.5 moles of O2 steam and oxygen on being passed over coke at
(2) 24 g of carbon and 64 g of O2 1000°C keeping temperature constant.
(3) 4 moles of carbon and 3.5 moles of O2 (1) 1:0.4 (2)  0.4:1 (3)  1:0.6 (4)  0.6:1
(4) 30 g of carbon and 80 g of O2 11. The heat of solution of anhydrous CuSO4 is –15.9
3 kcal and that of CuSO4 · 5H2O is 2.8 kcal. The heat of
6. S(s) + O2(g)  → SO3(g) + 2x kcal hydration of CuSO4 is
2
1 (1) –18.7 kcal (2)  18.7 kcal
SO2(g) + O2(g)  → SO3(g) + y kcal
2 (3) –13.1 kcal (4)  13.1 kcal
Find the heat of formation of SO2(g). 12. HA + NaOH  → NaA + H2O; ∆H = –12 kcal
(1) (y – 2x) (2)  (2x + y) HB + NaOH  → NaB + H2O; ∆H = –11 kcal
(3) (x + y) (4)  2x/y
Equimolar solution of which acid has higher pH?
7. Read the following statements I and II carefully and (1) HA (2)  HB
select the correct option. (3) Both have same pH (4)  Data insufficient
 I. The solution of CaCl2 · 6H2O in a large volume 13. In the reaction CS2(l) + 3O2(g)  → CO2(g) +
of water is endothermic to the extent of 3.5 kcal/ 2SO2(g), ∆H = –265 kcal.
mol if ∆H = –23.2 kcal for the reaction CaCl2(s) +
The enthalpies of formation of CO2 and SO2 are both
6H2O(l)  → CaCl2 · 6H2O(s).
negative and are in the ratio of 4:3. The enthalpy
II. For the reaction 2Cl(g)  → Cl2(g); the signs of of formation of CS2 is +26 kcal/mol. Calculate the
∆H and DS are negative. ­enthalpy of formation of SO2.
(1) Statement I and II both are wrong (1) –90 kcal/mol (2)  –52 kcal/mol
(2) Both are correct (3) –78 kcal/mol (4)  –71.8 kcal/mol
(3) Only I is correct
14. If the bond dissociation energies of XY, X2 and Y2
(4) Only II is correct (all diatomic molecules) are in the ratio of 1:1:0.5
8. At 300 K the standard enthalpies of formation of and ∆Hf for the formation of XY is –200 kJ mol–1,
C6H5COOH(s), CO2(g) and H2O(l) are –408, –393 the bond dissociation energy of X2 will be
and –286 kJ mol–1, respectively. The heat of combus- (1) 100 kJ mol–1 (2)  200 kJ mol–1
tion of benzoic acid at constant pressure and constant
(3) 300 kJ mol–1 (4)  800 kJ mol–1
volume are respectively (R = 8.31 J mol–1)
15. Both the lattice energy (DUo) and hydration enthal-
(1) –3201 kJ mol–1 and –3199 .7335 kJ mol–1 py (∆Hh) of a binary salt are negative quantities.
(2) +3201 kJ mol–1 and +3199 .7335 kJ mol–1 ­However, if DUo is more negative than ∆Hh then
(3) –2103 kJ mol–1 and –3799.3175 kJ mol–1 (1) the salt will not dissolve in water
(4) +2103 kJ mol–1 and +3799.3175 kJ mol–1 (2) salt will dissolve in water
9. The heat of hydrogenation for 3-methyl butene and (3) dissolution of salt in water is exothermic
2-pentene are –30 kcal/mol and –28 kcal/mol, respec- (4) dissolution of salt in water is endothermic
tively. The heats of combustion of 2-methylbutane 16. Heat of combustion of two isomers A and B are
and pentane are –784 kcal/mol and –782 kcal/mol, –17  kJ mol–1 and –12 kJ mol–1, respectively. From
respectively. All the values are given under standard this information it may be concluded that

Chapter_6b.indd 11 3/26/2014 3:08:56 PM

 6B.12  Objective Chemistry - Vol. I

(1) isomer A is 5 kJ mol–1 and is more stable 24. Bond energy of C–C and C–H are 340 and 410 kJ/
(2) isomer B is 5 kJ mol–1 and is less stable mol, respectively. The heat of formation of H atom is
(3) isomer B is 5 kJ mol–1 and has more potential ­energy 215 kJ/mol.
(4) isomer A is 5 kJ mol–1 and is less stable 2C4H10  → C8H18 + H2. Heat of reaction is
17. When 10 g anhydrous CaCl2 was dissolved in water, (1) 50 kJ (2)  100 kJ
6.82 kJ of energy was evolved. When 10 g of a crystal (3) 265 kJ (4)  132.5 kJ
hydrate CaCl2 · 6H2O was dissolved in water, 0.87 kJ 1
25. For a reaction M2O(s)  → 2M(s) + O2(g),
was absorbed. Calculate the enthalpy of formation of 2
the crystal hydrate from the anhydrous salt and water. ∆H = 30 kJ/mol and DS = 0.06 kJ/k/mol at 1 atm.
(1) –0.87 kJ (2)  +0.87 kJ The temperature at which the reaction is spontaneous
(3)  –94.8kJ (4) –56.7 kJ (1) < 500 K (2)  > 500 k
(3) = 500 k (4)  any temperature
18. A solution of 6 g of haemoglobin (M. W. = 60,000)
in 100 cc of a solution shows a temperature rise of 26. The enthalpy change involved in the oxidation of
0.03°C for complete oxygenation. Each mole of hae- glucose is –2880 kJ/mol. Twenty five per cent of this
moglobin binds 4 moles of oxygen. If heat capacity energy is available for muscular work. If 100 kJ of
of solution is 4 cal/k/mL, calculate ∆H mole per gram muscular work is need to work 1 km. What is the
mole of oxygen bounded. maximum distance that a person will be able to work
(1) –30 kcal (2)  30 kcal eating 120 g of glucose?
(3)  7.5 kcal (4)  –7.5 kcal (1) 7.9 km (2)  9.7 km
(3) 4.8 km (4)  8.l4 km
19. The combustion of 5.0 g of coke raised the temperature
of 1.0 kg of water from 10°C to 47°C. The calorific 27. When 1 g equivalent of a strong acid is neutralized with
value of coke is a strong base heat released is 13.5 kcal, when 1 g equiv-
(1) 5.4 kcal/g (2)  6.4 kcal/g alent H2A is completely neutralized against strong base
(3) 7.4 kcal/g (4)  8.4 kcal/g 13 kcal is released, when 1 g equivalent B(OH)2 is com-
pletely neutralized against strong acid 10 kcal heat is
20. C2H6(g) + O2(g)  → 2CO2(g) + 3H2O(g) released. Calculate enthalpy change when 1 g mole
DSvap H2O (l) = X1 cal/K (b.Pt = T1) H2A is completely neutralized by B(OH)2 .
∆Hf H2O (l) = X2 cal, ∆Hf CO2 = X3, (1) –27 kcal (2)  –10 kcal
∆Hf C2H6 = X4. Hence, heat of reaction is (3) –20 kcal 4) 19 kcal
(1) 2X3 + 3X2 – X4
(2) 2X3 + 3X2 – X4 + 3X1T1 Answers
(3) 2X3 + 3X2– X4 – 3X1T1
(4) X1T1 + X2 + X3 – X4   (1) 3   (2) 4   (3) 3   (4) 4   (5) 3
  (6) 1   (7) 2   (8) 1   (9) 2 (10) 3
21. Standard heat of formation of HgO (s) at 298 k and (11) 1 (12) 2 (13) 4 (14) 4 (15) 4
constant pressure is –90 kJ/mol. Excess HgO(s) (16) 4 (17) 3 (18) 1 (19) 3 (20) 2
­absorb 45 kJ of heat at constant pressure. The amount (21) 3 (22) 4 (23) 2 (24) 1 (25) 2
of Hg obtained is (A. Wt. of Hg = 200). (26) 3 (27) 4
(1) 200 g (2)  150 g (3) 100 g (4)  50 g
22. The specific heat of a gas at constant volume and con-
stant pressure are 0.075 cal/g and 0.125 cal/g, respec-
tively. The molecular weight of gas is  Statement-Type Questions
(1) 20 (2)  25 (3) 30 (4)  40 In case of the following questions, a statement I is given
followed by a corresponding statement II just below it.
23. The heat evolved on combustion of 1 g starch Mark the correct answer.
(C6H10O5) into CO2 and H2O (l) is 15 kJ/g, ∆Hf for
H2O (l) = –280 kJ/mol, ∆Hf of CO2 = –300 kJ/mol. 1. I f both statement I and statement II are true and
The enthalpy of formation of 1 g starch is ­statement II is the correct explanation of statement I.
(1) 4.75 kJ (2)  –4.75 kJ 2. I f both statement I and statement II are true and
(3) 2.25 kJ (4)  –2.25 kJ ­statement II is not the correct explanation of statement I.

Chapter_6b.indd 12 3/26/2014 3:08:57 PM

 Thermochemistry  6B.13

3. Statement I is true and statement II is false. 11. Statement I: Enthalpy of graphite is lower than that
of diamond.
4. Statement I is false and statement II is true.
Statement II: Entropy of graphite is greater than that
1. Statement I: Heat of combustion is always negative. of diamond.
Statement II: Heat of combustion is used to calcu- 12. Statement I: In the following reaction
late calorific value of fuels.
C(s) + O2(g) → CO2(g), ∆H = DU – RT
2. Statement I: Ammonium chloride dissolved in water Statement II: ∆H is related to DU by equation.
results in cooling of solution. ∆H = DU + Dng RT
Statement II: Reaction is endothermic.
13. Statement I: As temperature increases, heat of
3. Statement I: When a solid melts decrease in ­enthalpy reaction also increases for exothermic as well as for
is observed. endothermic reactions.
Statement II: Melting of a solid is endothermic. Statement II: ∆H varies with temperature as given
by ∆H2 (at T2) = ∆H1 (at T1) + ∆CP (T2 – T1).
4. Statement I: The enthalpy of formation of O2
­molecule at STP is zero.
Answers
Statement II: The enthalpy of all elements at STP
is zero.   (1) 1   (2) 1   (3) 1   (4) 3   (5) 3
  (6) 1   (7) 4   (8) 1   (9) 2 (10) 1
5. Statement I: The value of enthalpy of neutralization
(11) 2 (12) 4 (13) 4
of weak acid and strong base is numerically less than
57.1 kJ.
Statement II: All the OH– ions furnished by 1 g equiv-
alent of strong base are not completely ­neutralized. hints
6. Statement I: Heat sublimation is the sum of heat of 29. One mole of each C2H2 and H2 occupy equal volumes
fusion and heat of vapourisation. under identical conditions. So, the ratio of their heat
of combustion is in their molar heat of combustion
Statement II: Heat of reaction or enthalpy change is
ratio.
same whether a reaction takes place in one step (or)
in a number of steps. 241.8 1
∴ =
1300 5.37
7. Statement I: Enthalpy of combustion is always –ve 30. The heat liberated during the neutralization of 10 mL
but enthalpy of oxidation may be –ve or +ve. of strong acid with 10 mL of strong base is double
Statement II: Oxidation reaction involving combina- to that of heat liberated during the neutralization of
tion with O2 is always a combustion reaction. 5 mL each. But the quantity of solution is also
­doubled. So, the rise in temperature is same in both
8. Statement I: Enthalpy of graphite is zero but not for
cases, i.e., 5°C.
diamond.
Statement II: Enthalpy of formation of most stable 31. Heat of atomization of hydrogen means bond
allotrope is taken as zero. energy of H2.

9. Statement I: A reaction which is spontaneous and 32. Calorific value = –heat of combustion per 1 g of fuel.
accompanied by decrease in randomness must be For C2H4 it is –1411/28 the lowest value.
exothermic. 
33. 2NO2(g)  
 N2O4(g)
Statement II: All exothermic reactions are accompa- 2 × 8 2
nied by decrease in randomness. Heat of dimerization
∆H = Hp – HR
10. Statement I: Enthalpy of formation of H2O(l) is
= 2 – 16 = –14 kcal
greater than that of H2O(g).
Statement II: Enthalpy change is negative for the 
34. H2O(l) 
 H2O(g); ∆H = 10.52 kcal
condensation reaction H2O(g) → H2O(l). –68.32 HP

Chapter_6b.indd 13 3/26/2014 3:08:58 PM

 6B.14  Objective Chemistry - Vol. I

∆H = HP – HR 1
44.     (i)  H2 +
O2 → H2O, ∆H = –241 kJ
HP = ∆H + HR = 10.52 – 68.32 = –57.80 kcal 2
1
3264 × 7.8  (ii) C6H10 + 8 O2  → 6CO2 + 5H2O, ∆H =
35. ∆H per 7.8 g = = 326.4 kJ 2
78 –3800 kJ
36. CH4 + C2H4 
→ C3H8 (iii) C6H12 + 9O2 
→ 6CO2 + 6H2O, ∆H = –3920 kJ
By reversing the equation (iii) and summing all the
–17.9 12.5 –24.8
equations wet get ∆H = –121 kJ.
∆H = Hp – HR = –24.8 + 5.4 = –19.4
45. The heat of neutralization is the heat liberated when
37. The heat liberated by the neutralization of 25 mL of
1 g equivalent of an acid is neutralized by 1 g equiva-
acid with 25 mL of alkali will be more and thus the
lent of base. Since the base is only 0.2 g equivalent
rise in temperature will be more. 57.0
the heat liberated will be = 11.40 kJ.
38. If 2.1 g of Fe combines with sulphur evolving heat of 5
3.77 kJ, the heat of formation of FeS is 53.   (i)  Cdiamond + O2(g) → CO2(g), ∆H = –395 kJ
3.77 × 56 (ii)  Cgraphite + O2(g)  → CO2(g), ∆H = –393 kJ
= 100.5 kJ
2.1 By reversing the reaction (i) and adding we get
∆H = 1.5 kJ
39. 112 litres of water gas contain 56 litres of H2 and
56 litres of CO. 54. To get heat of formation of KOH sum up of all the
∆H for combustion of 56 litres of H2 is three equations, after reversing the third equation:
56 × 241.8 –68.39 – 48 + 14 kcal
H2 = = 604.5
22.4 55. To get the enthalpy of formation of H2SO4 sum up all
∆H for combustion of 56 litres of CO is the four equations.
56 × 283
CO = = 707.5 56. CaO(s) + H2O(l)  → Ca(OH)2(s), ∆H = –15.26
22.4
kcal –151.8 –68.37
Total ∆H = –1312 kJ
∆H = HP – HR
40. M. Wt. of cane sugar is 342. HP = –15.26 – 220.17 = –235.43
When 342 g of cane sugar burns the heat liberated is
1349 kcal. To get 2870 kcal of energy the amount of 57. The reaction indicates the conversion of diamond to
cane sugar required is graphite is exothermic and thus graphite is a stable
allotrope.
2870 × 342
= 728 g
1349 58. By adding two equations and then dividing by 2 we get
+
41. 1 M HCl contain 1 g equivalent of H ion. Na(s) + 0.5 Cl2(g)  → NaCl(s), ∆H = –98 kcal
1 M H2SO4 contain 2 g equivalent of H+ ion. 59. Subtract equation 2 from equation 1 after reversing
∴ The heat liberated in the neutralization of 1 M equation 2:
H2SO4 is more and X = 0.57. 1
C + O2  → CO, ∆H = R – S
42. In the neutralization of 50 mL of 2 M HCl with 2
500 mL of 2 M KOH the heat liberated is double to the 60. N2(g) + 3H2(g) 
→ 2NH3(g)
heat ­liberated in the neutralization of 250 mL of 2 M –945 –3 × 436 –6 × 391
HCl with 250 mL of 2 M KOH. Since the volume is ∆H = –2346 + 2253 = –93 kJ
also double the rise in temperature is same and T1 = T2.
61. 2H2(g) + O2(g) 
→ 2H2O(l)
43. 2KOH + H2SO4  → H2SO4 + 2H2O (–2 × 105) –120 –4 × 220
1 M KOH contain 1 g equivalent of KOH per litre. ∆H = –880 – (–330) = –550
0.5 M H2SO4 also contain 1g equivalent of H2SO4 ­
per litre. 62. Cdiamond 
→ Cgraphite, ∆H = –1.89
So, 50:50 mL of H2SO4 and KOH produce the highest  (i)  Cdiamond + O2 
→ CO2; ∆H = –q1
rise in temperature. (ii)  Cgraphite + O2 
→ CO2; ∆H = –q2

Chapter_6b.indd 14 3/26/2014 3:09:01 PM

 Thermochemistry  6B.15

Add the reactions after reversing the reaction (ii) Enthalpy of hydration of Na+ ion
∆H = –q1 + q2 = 1.89 for 12 g Cdiamond → Cgraphite 6
= –179 × = –97.6 kcal
−1.89 11
For 6 g of Cdiamond → Cgraphite = = –0.945
2 8. H2C2O4 → 2H + C2O42_
1 3 ∆H = (13.7) × 2 – 25.4
63. To get N2 + Cl2  → NCl3; ∆Hf
2 2
1 3 9. C3H8 + 5O2 → 3CO2 + 4H2O
Multiply equation (ii) by and (iii) by and
­subtract from (i) 2 2 ∆H = –2220.1 + (4 × 44)
∆H 2 3 = –2044.1 kJ
∆H = ∆H1 + − ∆H3
2 2 10. The amount of heat evolved
64. Add equations (i) to (iii). Now, we get = 3000 × 4.18 × (77 – 27) = 627 kJ
C(s) + O2(g) → CO2 627
∆H = 131 – 282 – 242 = –393 kJ
The amount of fuel is = = 15.75 g.
40
65. Reverse the second reaction and then add to get 11. q = mST = 500 × 2 = –1000 J
1 −1000 × 16
CH3CHO + O2 → CH3COOH, ∆H = –292 kJ \ DU = = –160 kJ
2 0.1
66. Add the two equations after dividing the first reaction 12. ∆H = eH – H + eCl – Cl – 2eH – Cl
with 1/2:
182 = 430 + 242 – 2x
3
P + Cl2 → PCl3 ∆H = − 75.9 x = 245 kJ/mol
2
PCl3 + Cl2 → PCl5 ∆H = − 32.8 13. From the heats of hydrogenation of cyclohexadiene
1 and cyclohexene the heat of hydrogenation of one
P + 2 Cl2 → PCl5 ∆H = − 108.7 double bond is –29 kcal/mol. Thus, the heat of hydro-
2
genation of benzene must be –29 × 3 = 87 kcal. So,
Practice Exercise Level-I based on the difference in calculated and experimen-
tal heat of hydrogenations the resonance energy of
1. It is the heat of combustion of 1 g atom of boron. ­benzene is 36 kcal/mole.
1 3
2. Since more heat is absorbed in the dissolution of KNO3. N2 +
14. F2 → NF3
2 2
3. C6H12O6 + 6O2 → 6CO2 + 6H2O 1 3
∆H = eN ≡ N + eF–F – 3eN–F
When 680 kcal released when 6 moles of CO2 is 2 2
­obtained. 1 3
Then, 170 kcal released from mole of CO2 formed is –113 = (6x) + x – 3(273.5)
2 2
170 × 6
= 1.5 x = 157.22 kJ/mol
680
So, wt. of CO2 = 1.5 × 44 = 66 g. 6x = 943.32

4. Amount of heat released = 1.23 × 6.12 = 7.52 kJ 1 1

A2 +
15. B2 → AB,  ∆H = –100 kJ
7.52 × 80 2 2
Heat of combustion = – = –602.2 kJ 2x x 2x
1
∆H = HP – HR
1000
5. × (–5.65 × 10–3) = 1.65 × 104 kJ –100 = (2x) – (2x + x)
342
∴ x = –100
6. Reverse the first reaction and then add to second ­reaction
So, A–A bond energy = –200 kJ/mol–1
–420 + 168 = –252 kJ
17. ∆H = eC = C + eH – H – eC – C – 2eC – H
7. ∆H = lattice energy + hydration energy
= 180 + x = 611 + 437 – 346 – 2 (413)
Hydration energy = –179 = –124 kJ/mol

Chapter_6b.indd 15 3/26/2014 3:09:04 PM

 6B.16  Objective Chemistry - Vol. I

18. Enthalpy of hydration = Lattice energy – ∆H of the

solution
For CsI: –604 + 33 = –571 kJ mol–1 9. a  + H2 →   ∆H = –36 kcal
For CsOH: –724 + (–72) = –796 kJ mol
–1

195 + H2 →   ∆H = –28 kcal

20. Bond enthalpy of P–Cl in PCl3 = = 65 kcal/mol
3
Bond energy of P–Cl in PCl5 = 58.5 kcal/mol
+ 8O2 → 5CO2 + 6H2O  ∆H = –784 kcal
Bond energy of equatorial P–Cl in PCl5 = 71.5 kcal/
mol
Enthalpy of atomization of PCl5 + 8O2 → 5 CO2 + 6H2O  ∆H = 782 kcal
= (3 × 58.5) + (2 × 71.5) According to Hess’s law
= 318.5 kcal/mol

Practice Exercise Level-II     ∆H = –4 kcal.

10. Evolved heat = Absorbed heat

1. HC ≡ CH + H2 → C2H2
∆H = eC ≡ C + eH – H – e C = C – 2eC – H 132x = (110y)2
= 198 + 103 + (–145) – 2 (98) = –40 kcal x 220
=
y 132
2. I2 = 2Na2S2O3 → 2NaI + Na2S4O6
x:y = 1:0.6
120 × 0.1 1
Moles of I2 = × = 0.006
1000 2 11. CuSO4 + H2O → CuSO4 (aq), ∆H = –15.9 kcal
I2O5 + 5 CO → I2 + 5CO2 CuSO4 · 5H2O + aq → CuSO4 (aq), ∆H = 2.8 kcal
∴ Moles of CO in the mixture = 0.006 × 5 = 0.03 CuSO4 + 5H2O → CuSO4 · 5H2O, ∆H = –18.7 kcal
Moles of carbon = 0.1 12. The acid which has less heat of neutralization is the
Moles of CO and CO2 = 0.1 weak acid. So, its pH will be more.
∴ Moles of carbon converted into CO is = 30%
13. CS2 + 3O2 → CO2 + 2SO2, ∆H = –265 kcal
4. CH4 + 2O2 → CO2 + 2H2O ∆H = H CO2 + 2HSO2 − H CS2
∆H = 4eC – H + 2eO = O – 2eC = O – 4eO – H – Resonance
∴ HSO2 = –71.7 kcal
energy of CO2: –2 ∆Hvap H2O
5. Since 48 g (4 moles) of carbon and 112 g of O2 are 1 1
14. X2 + Y2 → XY
participating in reaction more heat will be liberated. 2 2
1 1 a
6. S + O2 → SO2 = –2x + y. –200 = (a) +   – a
2 2 2
7. Heat of solution of anhydrous CaCl2 is equal to the a = 800 kJ/mol
sum of heat of formation of CaCl2 · 6H2O from anhy-
drous CaCl2 and heat of solution of CaCl2 · 6H2O. 16. The isomer having lesser heat of combustion will be
In the 2Cl (g) → Cl2 (g) bond energy is liberated and more stable.
entropy decreases. 17. CaCl2 + H2O → CaCl2 (aq)
15 6.82 × 111
8. C6H5COOH + O2 → 7CO2 + 3H2O (l) ∆H1 = – = –75.7 kJ
2 10
∴ ∆H = 7 (–393) + 3 (–286) – (–408) = –3201 kJ
CaCl2 . 6H2O + H2O → CaCl2 (aq)
∆H = ∆U + DnRT
0.81 × 219
∴ DU = –3199.75 kJ ∆H2 = + = 19 kJ
10

Chapter_6b.indd 16 3/26/2014 3:09:08 PM

 Thermochemistry  6B.17

CaCl2 + 6H2O → CaCl2 · 6H2O 23. (C6H10O5)n + O2 → 6nCO2 + 5nH2O

∆H = ∆H1 – ∆H2 ∴ ∆H = 15 × 162n = –2430n kJ
= –94.7 kJ ∆H = 6nH CO2 + 5nH H2 O − H (C6 H10 O5 ) n
∴ H = H (C6 H10 O5 )n H = –770n kJ
18. The amount of heat evolved
= 100 × 4 × 0.03 = 12 cal Enthalpy of formation of 1 g starch
The amount of heat evolved for complete oxygena- −770 n
= –4.75 kJ
tion of 1 mole of haemoglobin 162 n
60000 24. ∆H = 2eC–H – eC – C – eH– H
= 12 × = 120 kcal
6 ∆H = (2 × 410) – 340 – (2 × 215)
120
∆H for gram mole of oxygen is = 30 kcal ∆H = 50 kJ
4
25. At equilibrium, ∆G = 0
19. The amount of heat evolved = 1000 × 37 = 37 kcal 30
37 Teq = = 500 K
Calorific value = = 7.4 kcal/g 0.06
5 Above 500 K the reaction is spontaneous.
7 128 2
20. C2H6 (g) +
O2 (g) → 2CO2 (g) + 3H2O (l) 26. Mole of glucose = =
2 180 3
∆H = 2x3 + 3x2 – x4 The value of heat = 1920 kJ
∆H
H2O (l) → H2O (g), DS = Energy available for muscular work = 480 kJ
T
∆Hvap = T1X1 So, distance covered is = 4.8 km
∴∆H = 2x3 + 3x2 – x4 + 3x1T1 27. Heat of ionization of H2A is
1 (13.5 × 2) – 26 = 1 kcal
21. HgO → Hg + O2, ∆H = 90 kJ/mol Heat of ionization of B(OH)2 is
2
When 45 kJ heat is absorbed half-mole of Hg is (13.5 × 2) – 20 = 7 kcal
formed. So, heat of neutralization of
1.987 H2A + B(OH)2 → H2O + BA
22. (Cp – Cv) M = R M= = 40
0.05 – (13.5 × 2) + (1 + 7) = –19 kcal

Chapter_6b.indd 17 3/26/2014 3:09:10 PM

 This page is intentionally left blank.

Chapter_6b.indd 18 3/26/2014 3:09:10 PM

 7a

Chapter
Chemical Equilibrium

• The transformation of one substance into another sub- For example, when lime stone is heated in a lime kiln,
stance is known as a reaction. The chemicals that are it decomposes completely since CO2 goes into air but
used to start the reaction are called reactants and the when heated in a closed vessel the decomposition
chemicals that are formed in the reaction are called ­becomes reversible.
products. CaCO3(s) lime  kiln
→ CaO(s) + CO2(g)↑
• The amount of substance reacting per unit time is CaCO3(s) 
closed vessel

  CaO(s) + CO2(g)
called rate of reaction. • Reversible reactions must be carried out in a closed
• The concentration of reactants or products are ex- vessel.
pressed in moles/litres and is commonly known as • In the beginning in a reversible reaction the rate of for-
activity or effective concentrations or effective mass ward reaction is more since the concentrations of re-
usually expressed in square brackets [x]. actants are more. As time proceeds the rate of forward
• Reactions which proceed in one direction till one or reaction decreases as the concentrations of reactants
both the reactants are completely used up are referred decreases.
to as irreversible or unidirectional reactions. • In the beginning of a reversible reaction the rate of
• The reactions in which the products can be reconverted backward reaction is absolutely zero because the con-
into reactants or if the reaction mixture contains both centrations of products are zero.
the reactants and products and if the reaction can take • As time proceeds the rate of backward reaction
place in both directions under a given experimental ­increases since the concentrations of products also
condition is called a reversible reaction. increases.
• In a reversible reaction, the reaction proceeding for- • In a reversible reaction the stage at which the rate of
ward in which reactants convert into products is called forward reaction is equal to the rate of backward reac-
a forward reaction and the reaction proceeding back- tion is called equilibrium state or stage.
ward direction in which the products convert into reac-
• Reversible reactions do not go to completion in either
tants is called a backward reaction.
direction.
• Reversible reactions are represented by writing a pair
of half-headed arrow pointing in opposite directions in
between the reactants and products. Equilibrium in physical
 processes
Reactants  
 Products
• Some reversible reactions behave as irreversible or • If equilibrium exists between two different physical
unidirectional reactions and go to completion under states or between two different allotropic forms of the
some specific conditions. same substance, it is called physical equilibrium.
• The removal of one of the products of a reversible re- e.g., equilibria.
action leads to the completion of the forward reaction. Solid  liquid melting or fusion

Chapter_7a.indd 1 3/26/2014 3:14:04 PM

 7A.2  Objective Chemistry - Vol. I


Solid  
 vapour sublimation • In a saturated solution, the solution is in equilibrium
Liquid 
  vapour vapourisation with an excess of solid present in it at a given tempera-
ture. In such cases, the rates of dissolution and crystal-

α-sulphur 
 β-sulphur Allotropic
lization are in dynamic equilibrium.
modification
• In a saturated solution of a gas in a liquid at constant
• If a solid–liquid system at melting point is taken in pressure, the rate of dissolution of the gas in the liquid
a well-insulated container, it constitutes a system in and escape of gaseous molecules from the solution are
which the solid is in dynamic equilibrium with the in dynamic equilibrium.
­liquid. It is known as solid–liquid equilibrium.
• Henry’s law states that the mass of a gas in a given
• If a liquid or solid is taken in a closed container, mass of a solvent at a given temperature is directly pro-
the liquid or solid vapourises called vapourisation portional to the pressure of the gas above the solvent.
or ­evapouration while the vapour condenses into 
­liquid or ­solid called condensation. When the rate of
• For solid   liquid equilibrium there is only one
temperature (melting point) at 1 atm at which the two
­vapourisation (sublimation for solid) is equal to rate
phases can coexist. If there is no exchange of heat with
of ­condensation a dynamic equilibrium exists ­between
the surroundings the mass of the two phases remain
the two physical states constituting the physical
constant.
equilibria.
• For liquid  
 vapour equilibrium the vapour pres-
• The pressure necessary to achieve equilibrium in
sure is constant at a given temperature.
physical equilibria does not depend on the amount of
solid or liquid that is present in a container. • For dissolution of solids in liquids, the solubility is
constant at a given temperature.
• Equilibrium in molecular systems is dynamic and is
a consequence of equality of the rates of opposing • For dissolution of gases in liquids, the concentration
reactions. of a gas in liquid is proportional to pressure of the gas
over the liquid.
• A system moves spontaneously toward a state of
equilibrium. If a system initially at equilibrium is per-
turbed by some change in its surroundings, it reacts in General characteristics of
a manner that restores it to equilibrium.
Equilibrium involving physical
• The nature and properties of an equilibrium state are process
the same regardless of how it is reached.
• The condition of a system at equilibrium represents • Equilibrium is possible only in a closed system at a
a compromise between two opposing tendencies; given temperature.
the drive for molecules to assume the state of lowest • Both the opposing processes occur at the same rate
­energy and the urge toward molecular chaos or maxi- and there is a dynamic but stable condition.
mum entropy. • All measurable properties of the system remain
• Every solid is in equilibrium with its vapour when constant.
kept in a closed container. At a fixed temperature each • When equilibrium is attained for a physical process it
solid has its characteristic fixed vapour pressure but is characterized by constant value of one of its param-
increases with increasing temperature. eters at a given temperature.
• With increase in temperature the vapour pressure of • The magnitude of such quantities at any stage indi-
a solid increases more rapidly than does the vapour cates the extent to which the reaction has proceeded
pressure of the liquid since the solid has the greater before reaching the equilibrium.
heat of vapourisation. • Super cooling is a process of cooling a liquid below
• The temperature at which all the three physical states, its freezing point without solidification. Super-cooled
viz. solid, liquid and vapour of the same substance liquids are said to be in a metastable state since a
exist in equilibrium is called a triple point. The triple slight disturbance, such as stirring or the addition of a
point is usually very close to the freezing point. solid piece some of the liquid solidify instantly. Super-
• If each of two phases is in simultaneous equilibrium cooled liquids in equilibrium with their vapours are
with a third, then the two phases are in equilibrium called metastable equilibrium.
with each other. Super-cooled water   Vapour

Chapter_7a.indd 2 3/26/2014 3:14:05 PM

 Chemical Equilibrium  7A.3

Characters of chemical • The equilibrium in which the reactants and products

Equilibrium are in different phases is known as heterogeneous
chemical equilibrium.
• Though the reversible reaction appears to be stopped e.g., CaCO3(s) 
 CaO(s) + CO2(g).
at the equilibrium, it takes place in both directions
with same velocity. Hence, it is known as dynamic
equilibrium.  Objective Questions
• The concentration of reactants and products remain 1. Which of the following statements is false about
constant. Pressure, density and colour remain un- when a chemical reaction is in equilibrium?
changed with time in equilibrium state.
(1) The rate of forward and backward reactions is equal
• Equilibrium is not affected by the presence of a cata- (2) Concentrations of all substances are constant
lyst but attains equilibrium state quickly. (3) For a reaction in a gaseous state to reach equilibrium
• Equilibrium can be approached from both sides. the reaction should be carried out in closed vessel
• Equilibrium readjusts with the changing conditions (4) The ratio of the product of the mass of products
and spontaneously goes back to the original state when and that of reactants varies continuously.
the disturbing factors are removed. 2. In lime kiln, the reversible reaction CaCO3(s)  

• By observing pressure concentration, density or col- CaO(s) + CO2(g) proceeds to completion because
our the attainment of equilibrium may be identified. (1) of high temperature (2)  CO2 escapes out
• The equilibrium equation does not tell us how long it (3) CaO is removed (4)  of low pressure
takes for a reaction to attain equilibrium. 3. A chemical reaction is in equilibrium. Addition of a
• In the equilibrium state addition of products shifts the catalyst would not result in
equilibrium in the backward direction while the addi- (1) the rates of forward and backward reactions are
tion of reactants shifts the equilibrium in the forward equally altered
direction but the equilibrium constant remains constant. (2) a new reaction pathway to reaction
(3) attainment of equilibrium quickly
(4) increase in the amount of heat evolved in the
Types of Chemical Equilibria
­reaction
• The equilibrium in which reactants and products are 4. All reactions involving chemical decomposition are
in the same phase is known as homogeneous chemical
(1) Reversible
equilibrium.
(2) Reversible and endothermic
• Homogeneous chemical equilibria are two types: (3) Exothermic
(a)  Gas phase (4) May be reversible or irreversible and endother-
e.g., H2(g) + I2(g)   2HI(g) mic or exothermic
The reactants and products are in the same gaseous
5. A cylinder fitted with a movable piston contains liq-
phase forming a homogeneous mixture.
uid water in equilibrium with water vapour at 25°C.
(b)  Liquid phase
Which operation results in a decrease in the equilib-
e.g., CH3COOH(aq) + C2H5OH(aq) →
rium vapour pressure?
 CH3COOC2H5(aq) + H2O(l)
(1) Moving the piston downward a short distance
• The reactants and products are in the same liquid
(2) Removing a small amount of vapour
phase forming a homogeneous mixture. (3) Removing a small amount of the liquid
• Homogeneous chemical equilibria in gas phase are of (4) Dissolving the salt in water
two types:
6. Which statement is false in case of equilibrium state?
(a) Which have total number of moles of reactants are
(1) There is no apparent change in the properties
equal to the total number of moles of products.
with time.
e.g., H2(g) + I2(g)  

 2HI(g) (2) It is dynamic in nature since both forward and back-
(b) Which have the total number of moles of reactants ward reactions occur at all times with same speed.
not equal to the total number of moles of products. (3) It can be attained from either side of the reaction.
e.g., N2(g) + 3H2(g)  
 2NH3(g) (4) It does not change with temperature.

Chapter_7a.indd 3 3/26/2014 3:14:12 PM

 7A.4  Objective Chemistry - Vol. I

7. Just before a reversible reaction attains equilibrium it 13. Which of the following is not homogeneous
is found that ­equilibrium?
(1) The velocity of the forward reaction is increasing (1) PCl5(g)  

 PCl3(g) + Cl2(g)
and that of a backward reaction is decreasing. (2) C(s) + O2(g) 
 CO2(g)
(2) The velocity of the forward reaction is decreas- (3) H2(g) + I2(g) 
  2HI(g)
ing and that of a backward reaction is increasing. (4) 2H2(g) + O2(g) 
 2H2O(g)
(3) The velocity of both forward and backward reac-
14. Considering the influence of a catalyst on a chemical
tions is decreasing.
equilibrium, which one of the following is wrong?
(4) The velocities of both forward and backward
The catalyst
­reactions are decreasing.
(1) increases the speed of both forward and reverse
8. For the reaction N2 + 3H2   2NH3 in a vessel, reactions to the same extent
after the addition of equal number of moles of N2 and (2) does not change the relative amount of substanc-
H2, equilibrium state is formed. Which of the follow- es present at equilibrium
ing is correct? (3) changes the time required for reacting the equi-
(1) [H2] = [N2] (2)  [H2] [N2] librium
(3) [H2] > [N2] (4)  [H2] [NH3] (4) changes the equilibrium constant
9. The false statement among the following is 15. On which of the following the relative amounts of re-
(1) A reversible reaction never goes to completion. actants and products at equilibrium do not depend?
(2) A reversible reaction attains equilibrium when (1) The nature of the substances involved.
Gibbs energy change accompanying the reaction (2) The state of the system.
is zero. (3) The temperature.
(3) The reaction between barium chloride and sodi- (4) The direction from which the equilibrium is
um sulphate goes to completion because barium ­approached.
sulphate formed is insoluble. 16. Which of the following is not associated with equilib-
(4) The rate of forward reaction in a reversible reac- rium condition?
tion increases as the reaction proceeds.
(1) The vapour pressure of a liquid.
10. An example of reversible reaction is (2) The solubility of a solute.
(1) AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq) (3) The distribution of coefficient of a solute ­between
(2) 2Na + 2H2O → 2NaOH + H2 two immiscible solvents.
(3) NaOH + CH3COOH → CH3COONa + H2O (4) The formation of an alloy by two metals.
(4) Pb(NO3)2 + 2NaI → PbI2 + 2NaNO3 17. When an inert gas, such as helium, is added to a
­system at equilibrium
11. The reaction that proceeds in the forward direction is
(1) No effect on the equilibrium would occur.
(1) SnCl4 + Hg2Cl2 → SnCl2 + 2HgCl2
(2) The product would be favoured.
(2) NH4Cl + NaOH → H2O + NH3 + NaCl (3) It would effect equilibrium only if it produces
(3) Mn2+ + 2H2O + Cl2 → MnO2 + 2H+ + 2Cl– changes in concentration (or partial pressures) of
(4) S4 O62− + 2I– → + I2 the reactants or products.
12. Which of the following is not true for a chemical (4) It would effect equilibrium only if it reacts with
equilibrium? one of the substances involved in the equilibrium.
(1) When the experimental conditions are not 18. Which of the following statement is false?
changed, no change in the concentration of any (1) The number of gram molecules of a substance
of the substance occurs. present in unit volume is known as active mass.
(2) No reaction, neither forward nor reverse occurs (2) Active mass of 56 g of N2 contained in a 2-litre
at equilibrium. flask is 0.1 mole lit–1.
(3) The ratio of the rate constants of forward and (3) The attainment of equilibrium state in a gaseous
­reverse reactions is constant. reaction is known by constancy of pressure.
(4) The relative amounts of reactants and products (4) There is no effect of pressure on the equilibrium
at equilibrium vary greatly for different chemical in which all the reactants and products are in
reactions. ­liquid state.

Chapter_7a.indd 4 3/26/2014 3:14:13 PM

 Chemical Equilibrium  7A.5

19. For the reaction • At the equilibrium the rate of forward reaction is equal
CO(g) + H2O(g)  
 CO2(g) + H2(g) to the rate of backward reaction.
at a given temperature, the equilibrium amount of Kf [A]a [B]b = Kb [C]c [D]d
CO2(g) can be increased by Kf [C]c [D]d
(1) adding a suitable catalyst

K = [A]a [B]b = K C
b
(2) adding an inert gas KC is known as equilibrium constant.
(3) decreasing the volume of container • The equilibrium constant is the ratio of the velocity
(4) increasing the amount of CO
constants of forward and backward reactions.
20. Thiocyanate and iron (III) ions react according to the Kf
equation Kc =
Kb
SCN–(aq) + Fe3+(aq)   [Fe(SCN)]2+(aq) Equilibrium constant, Kc =
Colourless Yellow Deep red
Product of the concentrations of the products
Now, which of the following will occur on the addi-
Product of thee concentrations of the reactants
tion of the thiocyanate ions to this equilibrium mix-
ture? • If the reactants as well as products are gases then
(1) The solution will become deep red in colour. partial pressures may be substituted in place of molar
(2) The solution will become colourless. concentrations or active masses. Then, the equilibrium
(3) The solution will become yellow. constant is known as KP.
(4) The concentration of [Fe(SCN)]2+ (aq) ions will PCc × PDd
KP =
decrease. PAa × PBb
• The KC and KP are related as KP = KC [RT]Dn
Answers
Dn = Number of gaseous moles of products – Number
of gaseous moles of reactants
  (1) 4   (2) 2   (3) 4   (4) 4   (5) 4
R is gas constant and T is absolute temperature.
  (6) 4   (7) 2   (8) 2   (9) 4 (10) 3
(11) 2 (12) 2 (13) 2 (14) 4 (15) 4 • If Dn = 0 then KP = KC
(16) 4 (17) 3 (18) 2 (19) 4 (20) 1 Dn > 0 then KP > KC(Dn is positive)
Dn < 0 then KP = KC(Dn is negative)

law of mass action and its characteristics of equilibrium

applications constant

• Law of mass action was proposed by C. M. Guldberg • Equilibrium constant has a constant value at a given
and P. Wage in 1983. temperature.
• Law of mass action states that “the rate of chemical • The value of equilibrium constant changes with
reaction under a given set of conditions is directly change in temperature.
proportional to the product of the active masses of the • At a given temperature and pressure its value remains
reactants”. constant irrespective of the concentrations or pres-
• Since the active masses are directly proportional to sures of the reactants and products.
their molar concentrations, law of mass action can be • If the concentrations or pressures changes, the equi-
defined as “the rate of a reaction is proportional to the librium shifts but the equilibrium constant does not
product of the molar concentrations of the reactants. change.
• Law of mass action is applicable to all reactions occur- • The value of the equilibrium constant does not change
ring in gas phase or in the liquid (or solution) phase. with the presence of a catalyst.
• For a general reaction aA + bB   cC + dD • At a given temperature the equilibrium constant
The rate of forward reaction ∝ [A]a [B]b ­denotes to which extent the reaction proceeds and in
or the rate of forward reaction = Kf [A]a [B]b which direction.
The rate of backward reaction ∝ [C]c [D]d • If KC > 1; forward reaction take place more than back-

or the rate of backward reaction = Kb [C]c [D]d ward reaction.

Chapter_7a.indd 5 3/26/2014 3:14:15 PM

 7A.6  Objective Chemistry - Vol. I

• If KC < 1; backward reaction take place more than (ii)  H2 + I2 

K c1

  2HI
­forward reaction.
1 1
• If KC = 1; both forward and backward reactions 
HI   H2 + I2
2 2
­proceed equally.
• If the value of equilibrium constant is more than 1, 1 1
K c2 = or K 2 c 2 =
then concentrations of products are more than the con- K c1 K c1
centrations of reactants at equilibrium. K C1

(iii)  N2 + 3H2   2NH3
• If the value of equilibrium constant is less than 1, then
concentrations of products are less than the concentra- 1 3 
N 2 + H2 
 NH 3
tions of reactants at equilibrium. 2 2
K c 2 = K c1 or K c1 = K 2c 2
Units of KP and KC
K p2 = K p1 or K p1 = K 2p2
• The units of KC depend upon the units of molar con-
centrations represented in equilibrium constant equa-   (iv)  N2 + 3H2 K c1
  2NH3
tion and on the difference in the number of moles of 1 3
products and reactants. 
NH 3  
 N 2 + H2
2 2
Units of KC = (Units of concentration)Dn
1 1
• The units of Kp depend upon the units of pressure K c2 = or K 2c 2 =
expressed in equilibrium constant equation and differ- K c1 K c1
ence in the moles of product and reactants. 1 1
Unit of Kp = (units of pressure)Dn K p2 = or K 2p 2 =
K p1 K p1
Change in the Values of KC and KP with the K c1
  (v)  2SO2 + O2  
  2SO3
Change in the form of Chemical Equation
K c2
 1
SO3    SO2 + O2
• The reciprocal of the equilibrium constant value of a 2
chemical reaction in one direction will be the equilib- 1 1
Kc2 = or K 2 c 2 =
rium constant of the same reaction in the reverse direc- K c1 K c1
tion. e.g.,

K c1 1 1
(i)  H2 + I2    2HI K p2 = or K 2 p 2 =

Kc 2
 K p1 K p1
2HI   H2 + I2
1 1
Kc2 = or K c1 =
K c1 K c2 calculation of Active Masses at
 K c1 Equilibrium state
(ii)  N2 + 3H2 
 2NH3
 Kc 2 • Calculation of active masses at equilibrium can be
2NH3    N2 + 3H2 ­explained by taking two types of examples.
1 1 (i)  Synthesis of NO from N2 and O2 may be given as
K c2 =   or  K c1 =
K c1 K c2 a b o

N 2 + O2  
 2 NO
 (or)
1 1 a− x b− x 2x
K p2 =   or  K p1 =  
K p1 K p2 1 1 initial concentration

N 2 + O2 
 2 NO
• If the form of the chemical equation changes, then Kc 1− x 1− x 2x equilibrium concentration
amd Kp values are related as follows e.g.
K c1
where a or 1 and b or 1 are the g moles per litre of

(i)  H2 + I2   2HI the reactants N2 and O2, respectively at the start of the
1 1  Kc 2 reaction. Let x be the degree of formation of NO at

H2 + I2   HI equilibrium, the equilibrium molar concentrations will
2 2
be a – x or 1 – x and b – x or 1 – x g moles/litre for N2
K c 2 = K c1 or K c1 = ( K c 2 )2 and O2, respectively.

Chapter_7a.indd 6 3/26/2014 3:14:21 PM

 Chemical Equilibrium  7A.7

(ii) Dissociation of NH3 a b 0

O O 
H2 + I2 
 2HI   (or)
a initial concentration a− x b− x2x

 1 3

 2 N 2 + H2
V
NH 3    (or) V V

a− x 2 equilibrium concentration 1 1 0 initial concentration

x
2
3x
2

H2 + I2 
 2HI
1− x 1− x2x
V V V equilibrium concentration
1
 1 0 3 0 initial concentration
NH 3  
 N 2 + H2 [HI] (2 x / V )
2
(2 x / V ) 2 2

1− x 2 x 2 3x Kc = = a − x b − x (or) 1− x 1− x
2 2 equilibrium concentration [H 2 ][I 2 ] ( V ) ( V ) ( V )( V )
When a or 1 g mole/litre NH3 is taken initially let x be 4 x2 4 x2
the degree of dissociation of NH3 at the equilibrium Kc = (or)
( a − x )(b − x ) (1 − x )2
the concentrations of NH3, N2 and H2 at equilibrium
x 3x The above equation do not involve the term V indicat-
becomes a – x or 1–x, and g moles/litre, ing that the state of equilibrium is not effected by the
2 2
­respectively. change in volume of the reaction mixture.
• Dissociation of HI
a O initial concentration
calculation of partial pressures
a
2aHI 

 H2 + I2   (or)
at equilibrium state −x
V
x
2V
x
2V equilibrium concentration

initial concentration
• The partial pressures of different gases at the equi- 1

a O
21HI 
 H2 + I2
librium state can be obtained by multiplying the total −x
V
x
2V
x
2V equilibrium concentration
pressure at the equilibrium with the mole fractions of
each gas at equilibrium. [H 2 ][I 2 ] ( x / 2V )( x / 2V ) ( x / 2V )2 ( x / 2V )2
Kc = = 2
= 2
a 0 0 [HI]2 a−x 1− x 

PCl5 (g)  
 PCl3 (g) + Cl 2 (g)   (or)
    
a −x x x  V   V 
1 0 0 initial concentration x2 x2

PCl3 (g)  
 PCl3 (g) + Cl 2 (g)
 Kc = (or)
1− x x x equilibrium concentration
4( a − x ) 2
4(1 − x )2
If the reaction is started with a or 1 g mole/litre of PCl5 • When the number of moles of products and reactants
and if the degree of dissociation of PCl5 is x at the are not equal:
equilibrium, then x g moles/litre of PCl3 and Cl2 each Synthesis of ammonia
will be formed at the equilibrium. Let the total pres- a b 0 initial concentration
sure at equilibrium state is P, then the partial pressures 
N 2 + 3 H2 
 2 NH 3   (or)
a− x b −3 x 2x
can be calculated as v v v equilibrium concentration
Partial pressure of the gas = 1 1 0 initial concentration


N 2 + 3 H2 
 2 NH 3
No. of moles of a substance Total pressure
× 1− x 1− 3 x 2x
Total No. of moles at equilibrium at equilibrium V V V equilibrium concentration

Total No. of moles = (a – x) + x + x = a + x (or) (1 – x) [ NH 3 ]2 (2 x / V )2

Kc = =   (or)
+x+x=1+x [ N 2 ][H 2 ]3
 a − x   b − 3x 
a−x 1− x   
Partial pressure of PCl5 = P (or) P  V  V 
a+ x 1+ x
x x ( 2Vx )2
Partial pressure of PCl3 = P (or) P 3
a+ x 1+ x  1 − x   1 − 3x 
x x   
Partial pressure of Cl3 = P (or) P  V  V 
a+ x 1+ x
4 x 2V 2 4 x 2V 2
Kc = (or)
( a − x ) (b − 3x ) 3
(1 − x ) (1 − 3 x )3
application of law of mass action
to chemical equilibria In the above equation the volume term “V” is in the
n­ umerator and indicates that increase in volume
• When the number of moles of both reactants and ­favours the dissociation of ammonia and decrease in
­products are equal, then volume favours the formation of ammonia.

Chapter_7a.indd 7 3/26/2014 3:14:27 PM

 7A.8  Objective Chemistry - Vol. I

• Oxidation of sulphur dioxide • Esterification Reaction

a b 0 initial concentration a b +

 
CH 3 COOH + C2 H 5 OH 
H
2SO2 + O2 
 2SO3   (or)
a− x

b− x
a−2 x b− x 2x
v v v V V
equilibrium concentration

initial concentration 0 0 initial concentration

1

b 0
CH 3 COC2 H 5 + H 2 (or)
2SO2 + O2 
 2SO3 x x
1− 2 x 1− x 2x
V V equilibrium concentration
v v v equilibrium concentration  
2 2 1 2 o 0
[SO3 ] (2 x / V ) 
CH 3 COOH + C2 H 5 OH 
 CH 3 COC2 H 5 + H 2 O
Kc = =   (or) 1− x 1− x
[SO2 ] [O2 ]  a − 2 x 2  b − x 
2
V V
x
V
x
v
   
 V   V  [CH 3 COOC2 H 5 ][H 2 O]
(2 x / V )2 Kc = =
[CH 3 COOH ][C 2 H 5 OH]
2
 1 − 2x   1 − x  (x /V ) (x /V ) ( Vx ) ( Vx )
    (or)
 V   V 
( aV− x )( bV− x ) ( 1V− x )( 1V− x )
2 2
4x V 4x V x2 x2
Kc = (or) Kc = (or)
( a − 2 x ) (b − x )
2
(1 − 2 x ) (1 − x ) ( a − x )(b − x ) (1 − x )2
In the above equation the volume term “V” is in the • In the above equation there is no volume “V” showing
n­ umerator indicating that increase in the volume that the equilibrium is not effected by dilution.
favours the dissociation of SO3 and decrease in the • Acid catalyzed hydrolysis of ester
­volume favours the formation of SO3. a b +
H
• Dissociation of PCl5 
CH 3 COOH + C2 H 5 OH  

a− x b− x
a 0 0 initial concentration V V

PCl5 
 PCl3 + Cl 2   (or) initial concentration
0 0
a− x x x CH 3COOC2 H 5 + H 2 O   (or)
V V V equilibrium concentration x
x equilibrium concentration
v v
1 0 0 initial concentration

PCl5 
 PCl3 + Cl 2 1 1
1− x x x 
CH 3 COOH + C2 H 5OH 

V V V equilibrium concentration 1− x 1− x
V V
[PCl3 ][Cl 2 ] ( x / V ) ( x / V ) ( x / V ) ( x / V )
Kc = = = 0 0 intial concentration
[PCl5 ] a−x 1− x  CH 3 C OOC2 H 5 + H 2 O
    x
 V   V  x
V V
equilibrium concentration

x2 x2
Kc = (or)
Kc =
[CH3COOC2 H5 ] [ H 2 O] = ( x / V ) ( x / V )
( a − x )V (1 − x )V
[CH3COOH ] [C2 H5 OH ]  a − x   b − x 
x2 p x2 p   
Kp = or  V  V 
( a + x )( a − x ) (1 + x )(1 − x ) or
 x  x
• In the equation for Kc, the volume V is in the denomi-    
V V
nator. Increase in volume favours the dissociation of
PCl5 and decrease in the volume favours the formation  x
1 − 1− x
   
of PCl5. V  V 
• In the equation for Kp the pressure term “P” is in the x2 x2
numerator. Increase in pressure favours the formation Kc = or
( a − x ) (b − x ) (1 − x )2
of PCl5 and decrease in pressure favours the dissocia-
tion of PCl5. In the above equation there is no volume term showing
Homogeneous chemical equilibria in liquid phase that the equilibrium is not effected by dilution.

Chapter_7a.indd 8 3/26/2014 3:14:33 PM

 Chemical Equilibrium  7A.9

heterogeneous chemical • K for endothermic reaction increases while K for

equilibria ­exothermic reaction decreases with rise in temperature.
• The relation between the equilibrium constant, the
• Decomposition of calcium carbonate standard enthalpy change for the reaction, ∆H and the
CaCO3(s) 
 CaO(s) + CO2(g) temperature T can be shown as
[CaO] [CO2 ]
Kc = K2 ∆H  T2 − T1 
[CaCO3 ] log =  
K1 2.303  T1 T2 
Since the activities of solids are unity
where K1 is the equilibrium constant measured at tem-
Ka = [CO2] perature T1 and K2 that measured at T2 and R is the gas
KP = PCO2 ∵ [CO2 ]α PCO constant.
2

• Dissociation of ammonium hydrogen sulphide • By using the above equation, if we know the value of
NH4HS(s)   
 NH3(g) + H2S(g) ∆H ° and the equilibrium constant at one temperature,
[ NH 3 ] [H 2S] we can calculate the equilibrium constant at different
KC = temperatures. Also if the equilibrium constant at two
[ NH 4 HS]
different temperatures has to be calculated, we can
Since the activities of solid NH4HS is unity. work out for the value of the enthalpy change.
Ka = [NH3] [H2S] and K P = PNH3 × PH2S
∵[ NH 3 ] ∝ PNH3 and [H 2S] α PH S Effect of Adding an Inert Gas
2

• If an inert gas is added to the reaction mixture at constant

applications of equilibrium volume, the concentration of PCl5, PCl3 or Cl2 will not al-
constant ter. Thus the degree of dissociation of PCl5 is not changed
by the addition of an inert gas at constant volume.
• Depending on the value of equilibrium constant the ex- • The addition of an inert gas to the reaction mixture
tent to which a reaction can proceed can be predicted. at constant pressure, volume increases causing the de-
• Larger the value of KC, the greater will be the equi- crease in concentrations of different gases, thus caus-
librium concentrations of products relative to those of ing the decrease in the partial pressure. So equilibrium
reactants, i.e., the reaction proceeds to a greater extent. shifts in the direction where the number of gaseous
• Very small Kc values such as 4.8 × 10–31 for the reac- moles is more.
tion N2(g) + O2(g)   2NO(g) indicates that the
reactants N2 and O2 will be predominant in the reac- degree of dissociation from
tion mixture at equilibrium. density Measurements
• The ratio of product of concentrations (or partial pres-
sures) of products to that of reactants at any stage of • The degree of dissociation x may be calculated by
the reaction is called the reaction quotient, Qc. If par- ­using the equation
tial pressures are taken in the place of molar concen- D−d
x=
trations Qc is taken as QP. d ( n − 1)
At equilibrium, Qc = Kc where D is the density before dissociation while d is
If Qc > Kc the reaction will proceed in the backward the density after dissociation, n is the number of gase-
direction. ous molecules formed from one molecule of reactant
If Qc < Kc the reaction will proceed in the forward and x is the degree of dissociation.
­direction.
relation between KC, QC and Gibb’s
temperature dependence of Energy, G
equilibrium constant
• At equilibrium, Gibb’s energy change for any reaction
• With increase in temperature the rates of forward and
is zero.
backward reactions change differently because they
have different activation energies, consequently the • Gibb’s energy change for a reaction is given by the
ratio of Kf /Kb, i.e., equilibrium constant will change expression
with rise in temperature. ∆G = ∆G° + 2.303 RT log KC

Chapter_7a.indd 9 3/26/2014 3:14:35 PM

 7A.10  Objective Chemistry - Vol. I

• If ∆G is negative, the reaction is spontaneous and pro- (1) KP does not change with pressure.
ceeds in forward direction. (2) α does not change with pressure.
• If ∆G is positive, the reaction is nonspontaneous. (3) Concentration of NH3 does not change with pres-
Instead, its reverse reaction is favourable as the ∆G sure.
become negative for reverse reaction. (4) Concentration of hydrogen reacting is less than
that of N2.
• If ∆G is zero, the reaction has attained equilibrium.
At this point there is no longer any free energy left to 27. For which reaction does the equilibrium constant de-
drive the reaction. pend on the units of concentration?
 1 1
(1) NO(g)   N2(g) + O2(g)
2 2
 Objective Questions (2) Zn(s) + Cu2+(aq)  
 Cu(s) + Zn2+(aq)
 (3) C2H5OH(l) + CH3COOH(l)  

21. For N2 + 3H2 
 2NH3; ∆H = –ve, then
(1) KP = KC (2)  KP = KC RT  CH3COOC2H5(l) + H2O(l)
(4) COCl2(g)    CO(g) + Cl2(g)
(3) KP = KC [RT]–2 (4)  KP = KC [RT]–1
22. The equilibrium constant of a reversible chemical 28. When NaNO3 is heated in a closed vessel, oxygen is
­reaction at a given temperature liberated and NaNO2 is left behind. At equilibrium
(1) depends on the initial concentration of the (1) Addition of NaNO2 favours reverse reaction
­reactants (2) Addition of NaNO2 favours forward reaction
(2) depends on the concentration of one of the (3) Increasing temperature favours forward reaction
­products at equilibrium (4) Decreasing pressure favours reverse reaction
(3) does not depend on the initial concentration of 29. For the reaction CuSO4  ⋅  5H2O(s)  
 CuSO4  ⋅ 
reactants 3H2O(s) + 2H2O(g), which one is the correct repre-
(4) is not characteristic of the reaction sentation?
23. At a constant temperature the concentration of a (1) KP = PH2 2 O (2)  KC = [H 2 O]2
reactant is increased at equilibrium, the equilibrium (3) KP = KC [ RT ]
2
(4)  All
constant 30. The equilibrium constant for the reactions are
(1) increases  
−
H3PO4   H+ + H2PO 4 ; K1
(2) decreases −
H 2 PO 4  
2−
 H+ + HPO 4 ; K2
(3) remains unaffected
(4) first increases and then decreases HPO 4 
2−

3−
 H+ + PO 4 ; K3.
The equilibrium constant for
24. The equilibrium constant for equilibria
H3PO4   
3−
 3H+ + PO 4 is
SO2(g) + O2(g)   
 SO3(g) and (1) K1/K2 ⋅ K3 (2)  K1 × K2 × K3
  
2SO3(g)  2SO2(g) + O2(g) are K1 and K2, (3) K2 /K1 ⋅ K3 (4)  K1 + K2 + K3
­respectively. Then
31. The equilibrium 2SO2(g) + O2(g)  
 2SO3(g)
(1) K2 = K1 (2)  K2 = K12
shift forward if
1 1 (1) a catalyst is used
(3) K2 = (4)  K2 =
K1 K 21 (2) an adsorbent is used to remove SO3 as soon as it
25. A higher value of equilibrium constant K shows that is formed
(3) small amounts of reactants are used
(1) The reaction has gone to near completion ­towards
(4) none
right.
(2) The reaction has not yet started. 
32. Which one is correct representation for 2SO3 

(3) The reaction has gone to near completion ­towards 2SO2 + O2?
left. 2
PSO × PO2
(4) None of these. (1) KP = 2
2
PSO 3
26. Pure ammonia is placed in a vessel at a temperature
where its degree of dissociation (α) is appreciable. [SO2 ]2 [O2 ]
(2) KC =
At equilibrium [SO3 ]2

Chapter_7a.indd 10 3/26/2014 3:14:40 PM

 Chemical Equilibrium  7A.11

(mole of SO2 )2 (mole of O2 ) 39. The correct relation between KP and KC for the reac-
(3) KP = tion aX + bY   bZ + aW is
(mole of SO3 )2 KC
(1) KP = KC [RT] a + b
(2)  KP =
P ( a + b) 2
×
Total mole at equilibrium (2) KP = KC [RT] (4)  KP = KC
(4) All 1
40. KP /KC for the reaction CO(g) + 
O2(g) 

33. In KP = KC [ RT ] , Dn may have
∆n

CO2(g) is 2
(1) +ve values
(1) RT (2)  1/ RT
(2) –ve values
(3) RT (4)  1
(3) integer or fractional values
(4) either of these 41. If the equilibrium constants of the following equilib-
rium
34. In which of the following cases, does the reaction go 
farthest to completion
SO3  
 SO2 + O2 and
SO2 + O2   
 SO3 are given by K1 and K2,
(1) K = 103 (2)  K = 10–2
­respectively, which relation is correct?
(3) K = 10 (4)  K = 1
(1) K1 = (1/K2)2 (2)  K2 = [1/K1]2
35. If K1 and K2 are the respective equilibrium constants
(3) K1 = 1/K2 (4)  K1 = (K2)2
for the two reactions 

42. For the equilibrium PCl5  
 PCl3 + Cl2; Kc =
XeF6(g) + H2O(g)  
 XeOF4(g) + 2HF(g) a /(1 – α) V, temperature remaining constant
2

XeO6(g) + XeF6(g)  

 XeOF4(g) + XeO4F2(g) (1) KC will increase with increase in volume.
The equilibrium constant for the reaction (2) KC will increase with decrease in volume.
XeO4(g) + 2HF(g)   XeO3F2(g) + H2O(g) is (3) KC will not change with the change in volume.
(1) K1K2 (2)  K1/ K 22 (4) KC may increase or decrease with the change in
(3) K2/K1 (4)  K1/K2 volume depending upon its numerical value.
36. The volume of the reaction vessel containing an 43. When CaCO3 is heated at a constant temperature in
­equilibrium mixture in the reaction a closed container, the pressure due to CO2 produced
SO2Cl2(g)  
 SO2(g) + Cl2(g) will
is increased when equlibrium is reestablished. (1) change with the amount of CaCO3 taken
(1) The amount of SO2(g) will decrease. (2) change with the size of the container
(2) The amount of SO2Cl2(g) will increase. (3) remain constant so long as the temperature is
(3) The amount of Cl2(g) will increase. constant
(4) The amount of Cl2(g) will remain unchanged. (4) remain constant even if the temperature is
changed
37. For which system at equilibrium, at constant tempera-
ture will the doubling of the volume cause a shift to 
44. For the chemical reaction 3X(g) + Y(g)  
 X3Y(g);
the right? the amount of X3Y at equilibrium is affected by
 (1) Temperature and pressure
(1)  H2(g) + Cl2(g)  2HCl(g) (2) Temperature only
(2) 2CO(g) + O2(g) 
 2CO2(g) (3) Pressure only

(3)  N2(g) + 3H2(g)   2NH3(g) (4) Temperature, pressure and catalyst

(4)  PCl5(g)   PCl3(g) + Cl2(g)
45. At 1000°C, the equilibrium constant for the reaction
38. Consider the reaction CaCO3(s)   CaO(s) + of the system
CO2(g) in a closed container at equilibrium. At a fixed 2H2(g) + O2(g)  
 2H2O(g) is very large. This
temperature what will be the effect of adding more implies that
CaCO3 on the equilibrium concentration of CO2? (1) H2O(g) is unstable at 1000°C
(1) it increases (2) H2(g) is unstable at 1000°C
(2) it decreases (3) H2 and O2 have very little tendency to combine at
(3) it remains same 1000°C
(4) cannot be predicted unless the values of KP is (4) H2O(g) has very little tendency to decompose
known into H2(g) and O2(g) at 1000°C

Chapter_7a.indd 11 3/26/2014 3:14:45 PM

 7A.12  Objective Chemistry - Vol. I

46. The equilibrium constant for the formation of H2O(g) (3) same as initial concentration
from the elements is extremely large and that for the (4) one-fourth of the initial concentration
formation of NO(g) from its elements is very small. 
This implies that
52. In the system CaF2(s)   Ca2+ + 2F–, if the con-
2+
centration of Ca ions is increased by 4 times the
(1) H2O has a tendency to decompose into its elements. equilibrium concentration of F– ions will change to
(2) NO has low tendency to decompose into its
(1) 1/2 of the initial value
elements.
(2) 1/4 of the initial value
(3) NO has appreciable tendency to decompose into
(3) 2 times of the initial value
its elements.
(4) 4 times of the initial value
(4) NO cannot be produced from direct reaction
between nitrogen and oxygen. 53. In the case of PCl5(g)   PCl3(g) + Cl2(g) the
­degree of dissociation “x” is related to the equilib-
47. The chemical equation for the equilibrium denoted
rium pressure P as
by the following equilibrium constant expression
1 1
[H 2 O] [NH 3 ]2 (1) x α (2)  x α
KC = is P P
[N 2 O] [H 2 ]4
(3) x α P (4)  x α P 2
(1) H2O + NH3   
 N2O + H2
(2) H
 O + 2NH 
3   N2O + 2H2
2
Numerical PROBLEMS
  
(3) N2O + 4H2  H2O + 2NH3
(4) N2O + H2    H2O + NH3 54. 2 moles of PCl5 were heated in a closed vessel of a
2 litre capacity. At equilibrium 40% of PCl5 dissoci-

48. For the reaction X + Y 
 Z ated into PCl3 and Cl2. The value of the equilibrium
KC = 6 × 10 ; then at equilibrium
–7
constant is
(1) Z would be favoured (1) 0.267 (2)  0.53
(2) X would be favoured (3) 2.63 (4)  5.3
(3) Both X and Y would be favoured
55. Kc for A + B    C + D is 10 at 25°C. If a con-
(4) X, Y and Z would be favoured
tainer contains 1, 2, 3, 4 moles per litre of A, B, C and

49. At 25°C, KC for the equilibrium 2O3(g) 
 3O2(g) D, respectively at 25°C the reaction shall
is 5.5 × 1057. This explains (1) Proceed from left to right
(1) the oxidizing power of ozone (2) Proceed from right to left
(2) the absence of detectable amounts of ozone in the (3) Be at equilibrium
lower atmosphere (4) None
(3) the formation of ozone layer in the upper
56. HI was heated in a sealed tube at 440°C till the equi-
­atmosphere
librium was reached. HI was found to be 22% decom-
(4) the polluting nature of ozone
posed. The equilibrium constant for dissociation is
50. For the reaction Ag2CO3(s)  
 Ag2O(s) + CO2(g), (1) 0.282 (2)  0.0796
the value of the equilibrium constant KP is 3.16 × 10–3 (3) 0.0199 (4)  1.99
atm at 298 K and is 1.48 atm at 500K; then which one
of the following statements is correct? 57. The equilibrium constant for the reaction A + B

 
 C + D is 10. If rate constant of forward reac-
(1) The yield of CO2 is independent of temperature.
tion is 203, the rate constant of backward reaction is
(2) The yield of CO2 will increase at high pressure.
(3) The value of ∆H for the forward reaction is (1) 20.3 (2)  10.3 (3)  2.03 (4)  203
­negligible. 58. The equilibrium constant for
(4) The forward reaction is endothermic. 
H2(g) + CO2(g)   H2O(g) + CO(g) is 1.80 at
51. If the equilibrium concentration of A is doubled in the 1000°C. If 1.0 mole of H2 and 1.0 mole of CO2 are
following equilibrium AB2(s)   A(g) + B2(g) the placed in 1-L flask, the final equilibrium concentra-
equilibrium concentration of B2 would be tion of CO at 1000°C will be
(1) half the initial concentration (1) 0.573 M (2)  0.385 M
(2) doubled (3) 5.73 M (4)  0.295 M

Chapter_7a.indd 12 3/26/2014 3:14:48 PM

 Chemical Equilibrium  7A.13

59. The equilibrium constant for the reaction 3C2H2 (1) 0.36 litre mol–1 (2)  0.46 litre mol–1

  C6H6 is 4.0 at T K. If the equilibrium concen-
(3) 0.5 mol–1 litre (4)  0.2 mol–1 litre
tration of C2H2 is 0.5 mole/litre, the concentration of
67. 1.1 mole of A is mixed with 2.2 mole of B and the
C6H6 is
mixture is then kept in 1-L flask till the equilibrium
(1) 0.5 M (2)  1.5 M 
is attained A + 2B   2C + D. At the equilibrium
(3) 5× 10–2 M (4)  0.25 M 0.2 mole of C are formed. The equilibrium constant
60. For the reaction C(s) + CO2(g)   2CO(g) the of the reaction is
partial pressure of CO2 and CO are 4 and 8 atm, (1) 0.001 (2)  0.222
­respectively, then KP for the reaction is (3) 0.003 (4)  0.004
(1) 16 atm (2)  2 atm 68. For the reaction 2NO2(g) 
 2NO(g) + O2(g),
(3) 5 atm (4)  4 atm 1
KC = 1.8 × 10 at 185°C and KC for NO(g) + O2(g)
–6
61. The equilibrium constant for the reaction 2X(g) + 
   NO(g) is
2
Y(g) 
 2Z(g) is 2.25 litre mol–1. What would be (1) 0.9 × 106 (2)  7.5 × 102
the concentration of Y at equilibrium with 2.0 moles
(3) 1.95 × 10
–3
(4)  1.95 × 103
of X and 3.0 moles of Z in 1-L vessel?
(1) 1.0 M (2)  2.25 M 69. At a given temperature, the KC for the reaction
(3) 2.0 M (4)  4.0 M 
PCl5(g) 
 PCl3(g) + Cl2(g) is 2.4 × 10–3. At the
same temperature, the KC for the reaction PCl3(g) +
62. At constant temperature in a 1-L vessel when 
Cl2(g) 
 PCl5(g) is
the ­reaction 2SO3(g)  
 2SO2(g) + O2(g) is (1) 2.4 × 10–3 (2)  –2.4 × 10–3
at ­equilibrium, the SO2 concentration is 0.6 M, (3) 4.2 × 10
2
(4)  4.8 × 10–2
initial concen­tration of SO3 is 1 M. The equilibrium
constant is 70. The reaction A + 2B  
 2C + D was studied using
(1) 2.7 (2)  1.36 an initial concentration of B which was 1.5 times that
(3) 0.34 (4)  0.675 of A. But equilibrium concentrations of A and C were
found to be equal. Then, the KC for the equilibrium is
63. In equilibrium 2SO2(g) + O2(g)   
 2SO3(g), the (1) 4 (2)  8 (3)  6 (4)  0.332
partial pressure of SO2, O2 and SO3 are 0.662, 0.101
and 0.331 atm, respectively. What would be the par- 71. If 340 g of a mixture of N2 and H2 in the correct ratio
tial pressure of oxygen so that the equilibrium con- gave 20% yield of NH3, the mass produced would be
centration of SO2 and SO3 are equal? (1) 16 g (2)  17 g (3) 20 g (4)  68 g
(1) 0.4 atm (2)  1.0 atm 72. If the pressure of the N2 and H2 mixture in a closed
(3) 0.8 atm (4)  0.25 atm apparatus is 100 atm and 20% of the mixture then
64. When CO2 dissolves in water, the following equilib- reacts, the pressure at the same temperature would be
rium is established (1) 100 (2)  90 (3)  85 (4) 80
CO2 + 2H2O  
 H3O+ + HCO3− for which the 
73. The equilibrium constant for the reaction Br2 

equilibrium constant is 3.8 × 107 and pH = 6.0. The 2Br at 500 K and 700 K are 1 × 10–0 and 1 × 10–5,
ratio of [HCO4–]/CO2 is respectively. The reaction is
(1) 3.8 × 10–18 (2)  3.8 (1) endothermic (2)  exothermic
(3) 0.38 (4)  13.8 (3) fast (4)  slow

65. For the reaction PCl3(g) + Cl2(g)   PCl5(g), the 74. The value of KC at 3000°C is 100 for the equilibrium
value of KC at 250°C is 26. The value of KP at this 2NO(g)   
 N2(g) + O2(g). If the [NO] at equilib-
temperature will be rium is 0.1 mol/litre, the equilibrium concentration of
(1) 0.605 (2)  0.57 N2 is
(3) 0.83 (4)  0.46 (1) 1 (2)  10 (3) 0.01 (4)  0.001
66. One mole of nitrogen was mixed with 3 moles of 75. The equilibrium constant for the reaction N2(g) + I2(g)
­hydrogen in a closed 3 litre vessel. 20% of nitrogen is 
 
 2HI(g) is 60 at 450°C. The number of moles
converted into NH3. Then, KC for the 1/2 N2 + 3/2H2 of hydrogen iodide in equilibrium with 2 moles of

  NH3 is hydrogen and 0.3 mole of iodine at 450°C is

Chapter_7a.indd 13 3/26/2014 3:14:52 PM

 7A.14  Objective Chemistry - Vol. I

(1) 6 (2)  36 • Le Chatelier’s principle states that if system at equilib-

(3) 0.6 (4)  None of the above rium is subjected to a stress, the system shifts or tends
to shift the equilibrium in such a way as to reduce or
76. At certain temperature, the equilibrium constant for a
 nullify the stress
reaction A + B  
 2C was found to be 81. Start- (or)
ing with one mole of each of A and B what would be
the mole fraction of C at equilibrium? • If a system in equilibrium is subjected to a change
in temperature, or pressure or concentration then the
(1) 9/11 (2)  1/11 (3) 2/11 (4)  7/9
equilibrium shifts in such a way that the effect of the
77. The equilibrium constant of the reaction Cu(s) + changed condition is nullified or reduced.
2Ag+(aq)   Cu2+(aq) + 2Ag(s) is 2 × 1015 litre • With the help of Le Chatelier’s principle most favour-
mol . The concentration Cu2+ ions in the solution is
–1
able conditions for a particular reaction in a particular
1.8 × 10–2 mole/litre, then the concentration of Ag+ direction can be predicted. Le Chatelier’s principle is
ion is applicable for both physical and chemical equilibria,
(1) 9.8 × 10–18 (2)  3 × 10–9 • Effect of temperature: In a reversible reaction
(3) 3 × 10 –18
(4)  9 × 10–9
  (i) if forward reaction is exothermic, the backward
78. AB2 dissociates as AB2(g)    AB(g) + B(g). reaction will be endothermic.
When the initial pressure of AB2 is 600 mm Hg, the (ii) if forward reaction is endothermic, the backward
total equilibrium pressure is 800 mm kg. Calculate reaction will be exothermic.
KP for the reaction assuming that the volume of the (iii) increase in temperature always favours the
system remains unchanged. ­endothermic reaction.
(1) 50 (2)  100 (3) 166.8 (4)  400  (iv) decrease in temperature always favours the
 ­exothermic reaction.
79. The KP for the reaction NH4 HS(g)  
 NH3(g) +
H2S(g) at 20 atm pressure is • Effect of pressure: In a reversible reaction if the pres-
(1) 1.50 atm2 (2)  100 atm2 sure is increased equilibrium shifts in such a direction
in which there is decrease in pressure.
a2
(3)  × 20 (4)  None • When pressure is increased the equilibrium shifts
1 − a2
in the direction in which the number of molecules
Answers ­favours for which the volume decrease.
• If pressure is decreased equilibrium shifts in the direc-
(21) 3 (22) 3 (23) 3 (24) 4 (25) 1
tion in which there is increase in pressure or increase
(26) 1 (27) 4 (28) 3 (29) 4 (30) 2
in number of molecules or increase in volume.
(31) 4 (32) 4 (33) 1 (34) 4 (35) 3
(36) 4 (37) 3 (38) 4 (39) 4 (40) 3 • Pressure has no effect on chemical equilibrium in
(41) 3 (42) 3 (43) 3 (44) 1 (45) 4 which the number of molecules of both reactants and
(46) 3 (47) 3 (48) 3 (49) 2 (50) 4 products are equal.
(51) 1 (52) 1 (53) 2 (54) 1 (55) 1 • Effect of concentration: If the concentration of one
(56) 3 (57) 1 (58) 1 (59) 1 (60) 1 or more substances in the equilibrium increases, the
(61) 1 (62) 4 (63) 1 (64) 3 (65) 1 equilibrium shifts in the direction so that the increased
(66) 1 (67) 1 (68) 2 (69) 3 (70) 4 concentration should decrease.
(71) 4 (72) 2 (73) 1 (74) 1 (75) 1 • If the concentration of reactants is increased, the for-
(76) 1 (77) 2 (78) 2 (79) 2 ward reaction takes place more.
• If the concentration of products is increased, the back-
ward reaction takes place more.
Le chatelier’s principle and its
• Effect of catalyst: A catalyst increases the velocities
Applications
of both forward and backward reactions to the same
• The effect of concentration, pressure and temperature extent.
on a reversible chemical reaction was studied by Henry • Catalyst has no effect on the equilibrium constant.
Lewis Le Chatlier and F. Brawn and gave a principle
called Le Chatelier–Brawn principle or simply Le • Catalyst has no effect on the yield of products.
Chatelier’s principle. • Catalyst makes the equilibrium to attain quickly.

Chapter_7a.indd 14 3/26/2014 3:14:53 PM

 Chemical Equilibrium  7A.15

(1) Temperature is increased and pressure is kept

 Objective Questions constant.
(2) Temperature is reduced and pressure is increased.
80. Favourable conditions for the manufacture of ammo-
(3) Both temperature and pressure are increased.
nia by the reaction
(4) Both temperature and pressure are reduced.
N2(g) + 3H2(g)  
 2NH3(g), ∆H = –21.9 kcal are
(1) Low temperature, low pressure and catalyst. 86. For which reaction high pressure and high tempera-
(2) Low temperature, high pressure and catalyst. ture is helpful in obtaining a high equilibrium yield?
(3) High temperature, low pressure and catalyst. (1) 2NF3(g)    N2(g) + 3F2(g) – 54.40 kcal
(4) High temperature, high pressure and catalyst. (2) N2(g) + 3H2(g)   2NH3(g) + 22.08 kcal
(3) Cl2(g) + 2O2(g)   
 2ClO3(g) – 49.4 kcal
81. For the reaction 2X(g) + Y(g) 
 2Z(g); ∆H = (4) 2Cl2O7(g)  
 2Cl2(g) + 7O2(g) + 126.8 kcal
–80  kcal. The highest yield of Z at equilibrium
87. Which oxide of nitrogen is the most stable?
­occurs at
(1) 2NO2(g)   
 N2(g) + 2O(g) k = 6.7 × 106 mol
(1) 1000 atm and 500°C –1
litre
(2) 500 atm and 500°C
(2) 2NO(g)    N2(g) + O2(g) k = 2.2 × 1030 mol
(3) 1000 atm and 100°C –1
litre
(4) 500 atm and 100°C
(3) 2N2O5(g)  
 N2(g) + 5O2(g) k = 1.2 ×1034
–1
82. The Haber’s process for the manufacture of ammonia mol litre
is usually carried out at about 500°C. If a temperature (4) 2N2O(g)   2N2(g) + O2(g) k = 3.5 × 1023
–1
of about 250°C was used instead of 500°C. mol litre
(1) No ammonia will be formed. 88. A reaction in which an increase in pressure will in-
(2) The percentage of ammonia in the equilibrium crease the yield of products
mixture would be too low. (1) H2(g) + I2(g)   2HI(g)
(3) A catalyst would be of no use at all at this tem- (2) H2O(g) + CO(g)  
 CO2(g) + H2(g)
perature.  
(3) H2O(g) + C(g)  CO(g) + H2(g)
(4) The rate of formation of ammonia would be too (4) CO(g) + 3H2(g)   CH4(g) + H2O(g)
slow.
89. The following equilibrium exists in aqueous solution
83. Does Le Chatelier’s principle predict a change of CH3COOH  
 CH3COO– + H+
equilibrium concentration for the following reaction If dilute hcl is added without a change in tempera-
if the gas mixture is compressed. ture then
N2O4(g)  
 2NO2(g) (1) concentration of CH3COO– will decrease
(1) Yes, backward reaction is favoured. (2) concentration of CH3COO– will increase
(2) Yes, forward reaction is favoured. (3) the equilibrium constant will increase
(3) No change. (4) the equilibrium constant will decrease
(4) No information.
90. In a vessel containing SO3, SO2 and O2 at equilibrium
84. An aqueous solution of hydrogen sulphide shows the some helium gas is introduced so that the total pres-
equilibrium sure increases while temperature and volume remains
H2S  
 H+ + HS– constant. According to Le Chatelier’s principle, the
If dilute hydrochloric acid is added to an aqueous so- dissociation of SO3
lution of hydrogen sulphide without any change in (1) increases
temperature, then (2) decreases
(1) the equilibrium constant will change (3) remains unaltered
(2) the concentration of HS– will increase (4) changes unpredictably
(3) the concentration of nondissociated hydrogen 91. Le Chatelier’s principle is not applicable
sulphide will decrease 
(4) the concentration of HS– will decrease
(1) Fe(s) + S(s)  
 FeS(s)
(2) H2(g) + I2(g)  
 2HI(g)
85. Oxidation of SO2 to SO3 by O2 is an exothermic (3) N2(g) + 3H2(g)   2NH3(g)
­reaction. The yield of SO3 will be maximum when  
(4) N2(g) + O2(g)  2NO(g)

Chapter_7a.indd 15 3/26/2014 3:14:56 PM

 7A.16  Objective Chemistry - Vol. I

92. Which information can be obtained from Le ­Chatelier’s 2. For the equilibrium 2H X(g)    H2(g) + X2(g) the
principle ? equilibrium constant is 1 × 10–5. What is the concen-
(1) Shift in equilibrium position on changing P, T and tration of HX if the equilibrium concentrations of H2
concentration and X2 are 1.2 × 10–3 and 1.2 × 10–4 M, ­respectively ?
(2) Dissociation constant of weak acid (1) 12 × 10–4 M (2)  12 × 10–3 M
(3) Energy change in reaction (3) 12 × 10 M
–2
(4)  12 × 10–1 M
(4) Equilibrium constant of a chemical reaction
3. A reversible reaction is in equilibrium. If a factor is
93. Le Chatelier’s principle suggests changed which effect it, then
(1) If a system in equilibrium is subjected to a (1) the speed of forward and backward reactions
change of concentration, pressure or temperature ­increases
the equilibrium shifts in the direction that tends (2) the speed of the forward and backward reactions
to annual the effect of change. decreases
(2) It is applicable to all types of dynamic equilibria. (3) only the speed of that reaction increases which
(3) Given to study the effect of state variables on the nullifies the factor causing increase of speed
equilibrium. (4) No difference
(4) All.
4. What would happen to a reversible reaction at equilib-
94. A chemist who is concerned with large-scale manu- rium when pressure is lowered (given that Dn is –ve)?
facture of useful compounds is primarily interested in (1) More of the products are formed
(1) minimizing the energy consumption (2) Less of the products are formed
(2) maximizing the backward reaction (3) More of the reactants are formed
(3) minimizing the reverse reaction (4) It remains at equilibrium
(4) decreasing the acidity of the product
5. When a graph is drawn showing the relation rate of
95. In a chemical reaction reactants   
 products is reaction and concentration of reactants, the curve
shifted towards the products both by increase of pres- ­appears parallel to the concentration axis after some
sure and rise in temperature then the forward reaction is time indicating that
(1) endothermic with Dn positive (1) Change in concentration of reactant is negligible
(2) exothermic with Dn positive (2) The reaction is stopped
(3) exothermic with Dn negative
(3) Equilibrium is established
(4) endothermic with Dn negative
(4) The reaction is complex
Answers 6. If a reversible reaction attains equilibrium quickly, it
predicts that
(80) 2 (81) 3 (82) 4 (83) 1 (84) 4 (1) KC > 1 (2)  KC < 1
(85) 2 (86) 1 (87) 1 (88) 4 (89) 1 (3) KC = 1 (4)  None of these
(90) 3 (91) 1 (92) 1 (93) 4 (94) 3
(95) 4 7. Which of the following is correct?
(1) KP will always have some unit.
(2) KC will always have some unit.
(3) KP and KC will never have units.
(4) KP and KC will have some unit if Dn ≠ 0.
 Practice Exercise Level-I 8. A 1-litre vessel contains 2 moles of each of the four
gases A, B, C and D at equilibrium. If one mole of
1. In the reaction CH3COOH   +   C2H5OH  
 each A and B are removed, KC for A + B   C+
CH3COOC2H5 + H2O, the reaction mixture is always
D will be
expected to contain
(1) 4 (2)  1 (3)  1/4 (4)  2
(1) All the four substances
(2) Only products 9. The samples of HI each of 5 g were taken separately
(3) Only reactions in two vessels of volume 5 litres and 10 litres, respec-
(4) CH3COOH and CH3COO C2H5 only tively at 27°C. The extent of dissociation of HI will be

Chapter_7a.indd 16 3/26/2014 3:14:57 PM

 Chemical Equilibrium  7A.17

(1) more in 5-litre vessel 1 3

(2) more in 10-litre vessel 
(1) 2C 
 A + 3B 
(2)  C 
 A+ B
2 2
(3) equal in both vessels
1 3  
(4) nil in both (3)  A + B  C (4)  A + 3B 
 2C
2 2
10. In separate vessels of volume 5 litres and 10 litres, 6 g
17. When pressure is applied to the equilibrium system
of H2 and 28 g of N2 are mixed in each vessel at 27°C.

Ice  
 water, which of the following phenom-
The ammonia formed is
enon will happen?
(1) more in 5-litre vessel
(1) More ice will be formed
(2) more in 10-litre vessel
(2) Water will evaporate
(3) equal in both vessels
(3) More water will be formed
(4) cannot be predicted
(4) High temperature, high pressure and catalyst
11. At 600°C, KP for the following reaction is 1 atm X(g)
 18. The standard Gibbs energy change ∆G is related to
 
 Y(g) + Z(g)
equilibrium constant KP and is given as
At equilibrium, 50% X(g) is dissociated. The total θ

pressure of equilibrium system is “P” atm. What is (1) K P = −RT ln ∆G θ (2)  K P = (e /RT ) − ∆G
the partial pressure (in atm) of X(g) at equilibrium? (3) K P = −∆G θ /RT (4)  K P = e − ∆G
θ
/RT

(1) 1 (2)  4 (3)  2 (4)  0.5

19. Regarding an equilibrium which of the following
12. At 550 K the KC for the following reaction is 104 mol–1 statements is true

lit X(g)   Y(g) + Z(g). At equilibrium, it was ob- (1) The pressure changes do not affect the equilibrium.
served that
(2) More of ice melts if pressure on the system is
1 1
[ X ] = [ Y ] = [ Z ] increased.
2 2 (3) More of liquid H2O freezes if pressure on the
What is the value of [Z] (in mol lit–1) at equilibrium? system is increased.
(1) 2 × 10–4 (2)  10–4 (4) The pressure changes may increase or decrease

(3)  2 × 10
4
(4)  104 the degree of advancement of the reaction de-
13. In the reaction PCl5(g)  
 PCl3(g) + Cl2(g) the pending upon the temperature of the system.
equilibrium concentration of PCl5 and PCl3 are 0.4 20. For an equilibrium, which of the following statements
and 0.2 mole/litre, respectively. If the value of KC is is false?
0.5, what is the concentration of Cl2 in moles/litre? (1) If the reaction quotient of the reaction is ­greater
(1) 2.0 (2)  1.5 (3)  1.0 (4)  0.5 than Keq the reaction moves in the backward
14. The reaction for which KC = 2.3 × 10–3 moles/litre is ­direction.
 (2) If the reaction quotient of the reaction is ­lesser
(1) 2SO2 + O2  
 2SO3
  than Keq the reaction moves in the forward
(2) N2 + 3H2  2NH3
 ­direction.
(3) N2 + O2  2NO
  (3) If the reaction quotient of the reaction is equal to
(4) PCl5  PCl3 + Cl2
Keq the reaction is at equilibrium.
15. PCl5(g)   PCl3(g) + Cl2(g) equilibrium is (4) There is no correlation between the reaction quo-
­established in a closed container at 25°C. If the tient and Keq in predicting the direction in which
­volume of the container is reduced to half of the orig- the reaction proceeds.
inal keeping the temperature constant, the changes in
21. The concentration of pure solid or liquid phase is not
the equilibrium constant and degree of dissociation
included in the expression of equilibrium constant
(α) of PCl5 include
because
(1) K remains constant but α changes
(1) Solid and liquid concentrations are independent
(2) K changes but α remains constant
of these quantities.
(3) Both the K and α changes
(2) Solids and liquids react slowly.
(4) Neither K nor α changes
(3) Solids and liquids at equilibrium do not interact
16. Molar concentrations of A, B and C at equilibrium with gaseous phase.
for the reaction A + 3B   
 2C are 1, 2 and 4 mole (4) The molecules of solids and liquids cannot
lit–1, respectively. The value of KC is 2 for ­migrate to the gas phase.

Chapter_7a.indd 17 3/26/2014 3:15:01 PM

 7A.18  Objective Chemistry - Vol. I

22. In a system A(s)   2B(g) + 3C(g) if the concen- (3) If  Y mole of I2 is used up in the reaction the
tration of C at equilibrium is increased by a factor quantity of HI present at equilibrium is 2Y mole.
of 2, it will cause the equilibrium concentration B to (4) If  Y mole of I2 is used up in the reaction the
change to quantity of H2 present at equilibrium is 0.2 –
(1) two times the original value (Y/2) mole.
(2) one-half of its original value 29. A mixture of NO2 at initial pressure of 1.0 atm and
(3) 2 2 times of the original value NO at initial partial pressure of 0.5 atm is brought to
(4) 1/2 2 times of the original value the equilibrium. The reaction is
23. In a closed vessel, 2 moles of SO2(g) and 1 mole of 
2NO2(g)   2NO(g) + O2(g)
O2(g) were allowed to react to form SO3(g) under the
Regarding this which of the following is true?
influence of a catalyst at 1 atm. Then, the reaction
 (1) If the partial pressure of O2 in the equilibrium is
2SO2(g) + O2(g)   2SO3(g)
0.2 atm, then KP = 0.45.
occurred. At equilibrium it was found that 50% of
(2) If the partial pressure of O2 in the mixture is
SO2(g) was converted to SO3(g). Then the pressure of
2 x3
SO3 at equilibrium will be x atm, then K P = .
(1 − 2 x )3
(1) 0.66 atm (2)  0.493 atm
(3) 0.33 atm (4)  0.166 atm (3) If at equilibrium, the decrease in partial pressure of
NO2 is Y atm, the value of KP = (0.5 + Y)2/(2 – 2Y)
24. A mixture of nitrogen and hydrogen in the ratio of (4) None of these
1:3 reached equilibrium to form ammonia when 50%
of the mixture has reacted. If the total pressure is P 30. Equimolar quantities of HI, H2 and I2 are brought to
the partial pressure of ammonia in the equilibrium equilibrium, if the total pressure in the vessel is 1.5
mixture was atm and the KP for the reaction 2HI(g)   
 H2(g)
(1) P/2 (2)  P/3 (3)  P/4 (4)  P/6 + I2(g) is 49. Which of the following is correct for the
equilibrium partial pressure of I2?
25. NO2 associates (or dimerizes) as 2NO2  
 N2O4. (1) 0.4 (2)  0.9
The apparent molecular weight of a sample of NO2
(3)  0.7 (4)  0.5
calculated from the vapour density under certain
conditions was 60, the mole fraction of dimer is 31. Into a 1-litre flask at 400°C 1 mole of N2, 3 moles of
(1) 14/46 (2)  16/46 H2 and 2 moles of NH3 are placed. If KC for the reac-
(3) 28/46 (4)  46/60 tion is about 0.5 at 400°C what reaction, if any, can be
expected to occur
26. At 730°C the vapour density of iodine under a
N2(g) + 3H2(g)   2NH3(g)
­pressure of 1 atm is 97.45% of the theoretical, on the
assumption that the molecule of gaseous iodine is (1) Left to right
diatomic. What is the degree of dissociation of I2? (2)  Right to left
(1) 0.0131 (2)  0.0262 (3) System is at equilibrium
(3) 0.082 (4)  0.0324 (4)  Cannot be predicted

27. If Keq for the dissociation of atomic iodine I2(g) 32. If we start with 1 mole of N2, 3 moles of H2 and

 
 2I(g) is 4 × 10–3 and if the equilibrium con- 2 moles of NH3 in a 1-litre container at 500°C (where
centration of atomic iodine is 4 × 10–3 M, what is the KC = 0.08) at equilibrium
concentration of molecular iodine? (1) the number of moles of N2, H2 and NH3 will be in
(1) 0.8 M (2)  0.4 M (3)  0.3 M (4)  0.2 M the ratio 1:3:2
(2) the number of moles of N2, H2 will be in the ratio
28. 0.2 mole of H2 and 0.5 mole of I2 are mixed in a reac-
1:3
tion vessel and heated until equilibrium is reached,
 (3) the number of moles of N2 will be 1
H2(g) + I2(g)   2HI. Which of the following
statements is true? (4) the total number of moles will be 6.
(1) If x mole of HI is present at equilibrium the 33. For an unknown decomposition of a chemical equilibri-
­quantity of I2 present is 0.5 – x mole. um A  
 nB, operating in gas phase a plot between
(2) If x mole of HI is present at equilibrium the D
­quantity of H2 is present is x – 0.2 mole. and α gives a straight line as shown in the figure
d

Chapter_7a.indd 18 3/26/2014 3:15:03 PM

 Chemical Equilibrium  7A.19

3 9 2
(1)  M 2 (2)  M
4 28
7 1 2
(3)  M 2 (4)  M
28 7
α

3. PCl5 (g)  
 PCl3 (g) + Cl 2 (g). The equilibrium con-
stant, Kc for the dissociation of PCl5 is 4.0 × 10–2 at
250°C in a 3.0-L flask when equilibrium concentra-
tion of Cl2 is 0.15 mol/L. What was the pressure of
45°
PCl3 before any dissociation?
D/d (R = 0.082 L-atm K–1 mol–1)
(1) 37.0 atm (2)  30.59 atm
Find the ratio of the stoichiometric coefficient of the (3) 24.05 atm (4)  6.745 atm
reactant and the product. Here D = inital vapour den- 
4. Na2SO4 ⋅ 10H2O(s)  
 Na2SO4(s) + 10H2O(g)
sity and d = final vapour density at equilibrium. for the equilibrium KP = 4.08 × 10–25. If the vapour
(1) 1:2 pressure of water at 0°C is 4.58 torr, at which relative
(2) 1:1 humidities will Na2SO4 be deliquescent (absorb
(3) 2:1 moisture) when exposed to the air at 0°C essentially?
(4) Data is inadequate to predict. (1) 21.25% (2)  35.3%
(3) 50% (4)  70%
Answers 5. Equilibrium constants are given for the following
­reaction:
  (1) 1   (2) 3   (3) 3   (4) 3   (5) 3
AB2 ⋅ 6H2O(s)    AB2 ⋅ 2H2O(s) + 4H2O(g);
  (6) 4   (7) 4   (8) 2   (9) 3 (10) 1
(11) 1 (12) 1 (13) 3 (14) 1 (15) 2 KP = 6.89 × 10 -12

(16) 2 (17) 3 (18) 4 (19) 4 (20) 4

M2N ⋅ 12H2O(s)  
 M2N ⋅ 7H2O(s) + 5H2O(g);
(21) 1 (22) 4 (23) 3 (24) 2 (25) 1 KP = 5.25 × 10 -13

(26) 2 (27) 2 (28) 3 (29) 1 (30) 3

P2N ⋅ 10H2O(s)    P2N(s) + 10H2O
(31) 1 (32) 2 (33) 3 KP = 4.08 × 10 -25

Which one is the most effective drying agent at 0°C

(the vapour pressure of H2O at 0°C is 4.58 torr)?
(1) AB2 ⋅ 2H2O
 Practice Exercise Level-II
(2)  M2N ⋅ 7H2O
1. A certain amount of N2O4(g) is enclosed in a closed (3) P2N
container at 127°C when following equilibrium got (4)  All are equally effective
set up at a total pressure of 10 atm.
N2O4(g)   
 2NO2(g) 6. Assume that the decomposition of HNO3 can be
represented by the following equation 4HNO3(g)
If the concentration (moles) of NO2(g) in the equilib-

 
 4NO2(g) + 2H2O(g) + O2(g) and that a given
rium mixture be 8 × 105 ppm, the Kc (in mol L–1) for
temperature 400 K and pressure 30 atm the reaction
the above reaction at 127°C is equal to
­approaches equilibrium. At equilibrium partial pres-
(1) 3.189 (2)  2.051 (3) 0.974 (4)  1.842 sure of HNO3 is 2 atm. Find Kc in (mol/lit)3?
2. For the following hypothetical chemical equilibrium (1) 32 (2)  24 (3)  18 (4)  16
A(aq)    2B(aq) + C(aq)
7. LiCl ⋅ 3NH3(s)    LiCl ⋅ NH3(s) + 2NH3(g), Kp
It was found that initially only A and B are present with
1 for the reaction is 9 atm2 at 27°C. A 4.10 litre flask
mole fraction of B equal to . At equilibrium mole contains 0.1 mol of LiCl NH3. How many moles of
3 NH3 should be added to the flask at this temperature
1
fraction of A becomes equal to . So, Kc for the above to drive backward reaction practically to complete?
2
equilibrium is if initial molarity of the “B” is “M”. (1) 0.5 (2)  0.6 (3)  0.7 (4)  0.8

Chapter_7a.indd 19 3/26/2014 3:15:06 PM

 7A.20  Objective Chemistry - Vol. I

8. 0.2 M KCN and 0.06 M AgNO3 solutions are mixed 13. Two solid compounds A and C dissociates into
in equal volumes. At 25°C, KC for the reaction is ­gaseous product at the temperature T.
 Ag + 2CN is 1.6 × 10 . The
+
Ag(CN)–2   
– –19
A(s)   B(g) + D(g)
+
­concentration of Ag present in solution is C(s)   
 E(g) + D(g)
(1) 1.5 × 10–19 M (2)  1.5 × 10–18 M At this temperature, pressure over excess solid A is
(3) 3 × 10 M
–19
(4)  3 × 10–18 M 40 atm and that over excess solid C is 80 atm. The
9. CuSO4 ⋅ 5H2O(s)  
 CuSO4 ⋅ 3H2O(s) + 2H2O (v), total pressure of the gaseous over the solid mixture is
KP for the reaction is 10–4 atm2. Vapour pressure of (1) 67.0 atm (2)  89.4 atm
water at 25°C is 30.4 mm at 25ºC. At what relative (3) 134 atm (4)  178.8 atm
humidities will CuSO4. 5H2O be efflorescent when 14. The equilibrium constant for the reaction A + B → C
exposed to air at 25°C? is 0.9. How much concentration of A should be added
(1) Below 25% (2)  Above 25% to one litre of 0.1 M B solution, so that 60% B is
(3) At 25% (4)  Any ­converted into C?
10. When 1 mole of A(g) is introduced in a closed vessel of (1) 1.67 M (2)  1.73 M
one litre capacity maintained at constant ­temperature, (3) 1.82 M (4)  1.91 M
the following equilibrium is established: 15. 10 g of CaCO3 is taken into a vessel of volume 40
A(g)   
 B(g) + C(g) ; K C1 = ? mL. It comes into equilibrium with CaO and CO2:
  
C(g)  D(g) + B(g) ; K C = ? CaCO3  
 CaO + CO2
2

If the pressure at equilibrium is twice the initial Kp = 0.324 atm at 27°C

K C1 [C]eq Now the vessel is placed in a bigger and evacuated
­pressure, calculate if = 2:1
K C2 [ A ]eq vessel of volume 800 mL. Now a small hole is made
to the smaller vessel. CO2 gas starts effusing into big-
(1) 3:1 (2)  4:1 (3)  2:1 (4)  1:2 ger vessel at a rate of 0.044 g/s. How much time (in
seconds) is required for the effusion of CO2 to stop?
11. CoCl2− 2+
4(aq) is blue in colour while Co(H 2 O)6 (aq) is
(1) 10 s (2)  15 s (3) 5 s (4)  8 s
pink in colour. The colour of the reaction mixture
Co(H 2 O)62+(aq) + 4Cl(aq)
2−


−2
 CoCl 4 (aq) + 6H 2 O(1) 16. Consider the equilibrium HgO(s) + 4I–(aq) + H2O(l)
is blue at room temperature while it is pink when 
 
 Hgl 4 (aq) + 2OH–(aq) which changes will in-
2−

cooled, hence crease the equilibrium concentration of this reaction?

(1) Reaction is exothermic.    (I)  Adding 0.2MHCI
(2) Reaction is endothermic.   (II)  Increasing
(3) Equilibrium will shift in forward direction on (III)  Increasing No. of moles of HgO(s)
adding water to reaction mixture.
(1) I only (2)  II only
(4) The reaction is neither endothermic nor exothermic.
(3) I and II only (4)  II and III only
12. Haber–Bosch process for the manufacture of NH3 is 
based on the reaction
17. For a general gaseous reaction aA(g) + bB(g)  
catalyst cC(g) + dD(g) equilibrium constant Kc, Kp and Kx are
N 2 (g) + 3H 2 (g) 
  2NH 3 (g)∆H = −46.0
0
represented by the following relations
KJ/mol and K op = 14. Which of the following infor-
mation regarding the above reaction is correct? K c =
[C]c [D]d ; KP =
PCc .PDd
and K =
X cC .X dD
x
(1) On adding N2, the equilibrium is shifted to right [A ]a [B]b PAa .PBb X aA .X Bb
side with an increase in entropy. where [A] represents molar concentration of A, PA
(2) The equilibrium constant increases with increase represents partial pressure of A, P represents total
in temperature. pressure and XA represents mole fraction of A.
(3) At equilibrium 2Gm(NH3) = Gm(N2) + 3Gm(H2) On the basis of the above choose the correct option.
n n
where Gm represents the molar Gibbs formation (1) K p = K c ( RT) ∆ g ; K x = K p ( RT) ∆ g
of the species enclosed within the brackets. − ∆ng
(2) K c = K p ( RT) ; K p = K x P
∆ng

(4) The use of catalyst helps increasing the rate of ∆n ∆n

(3) K c = K x P g ; K p = K x P g
forward reaction more than that of backward
− ∆ng ∆ng
­reactions thereby increasing the yield of NH3. (4) K c = K p ( RT) ; K x = K p ( RT)

Chapter_7a.indd 20 3/26/2014 3:15:10 PM

 Chemical Equilibrium  7A.21

18. The activation energies for the forward and reverse condition, when 0.135 mole each of H2 and I2 are
elementary reactions in the system A   B heated at 440 K in a closed vessel of capacity 2.0 L
are 10.303 and 8.000 Kcal, respectively at 500 K. (1) 144 ml (2)  216 ml
­Assuming the pre-exponential factor to be the same (3) 108 ml (4)  192 ml
for both the forward and reverse steps and R = 2cal K–1
25. For the synthesis of NH3 from Haber process starting
mol–1, calculate equilibrium constant of the reaction:
with stoichiometric amount of N2 and H2, the attain-
(1) 1.000 (2)  10.0 (3) 100 (4)  0.1 ment of equilibrium is predicted by which curve?
19. A student determined the value of Ksp for a saturated N2(g) + 3H2(g) → 2NH3(g)
solution of borax at several different temperatures.
The value for DS o for the dissolution of borax in (1)  3   (2)  3
­water can be determined from: 2 2
H2
(1) the slope of the line resulting from a plot of ln Ksp 1 N2
NH3 1
versus (1/T) N2 NH3
(2) the y-intercept of the line resulting from a plot of 0 H2
Reaction 0
in Ksp versus T Reaction
(3) the slope of the line resulting from a plot of Ksp
(3)  3 NH3   (4)  3
versus (1/T) NH3
2
(4) the y-intercept of the line resulting from a plot of 2
in Ksp versus (1/T) 1 H2
N2 1 N2
0 H2
20. N2 and H2 are taken in 1:3 molar ratio in a closed Reaction 0
­vessel to attain the following equilibrium: Reaction
N2(g) + 3H2(g)   2NH3(g) 26. Rate of disappearance of the reactant A at two differ-
Find KP for the reaction at total pressure of 2P. If PN2 ent temperatures is given by A  B
at equilibrium is P/3 −d [A ]
1 4 = 2 × 10 −2 s −1 [ A ] − 4 × 10 −3s −1 [ B] at 300 K
(1)  2 (2)  dt
3P 3P 2
−d [A ]
4P 2 = at 400 k 4 × 10 −2 s −1 [ A ] − 16 × 10 −4 s −1 [ B]
(3)  (4)  None dt
3
Heat of reaction at the given temperature range,
22. “n” mole of a reactant “A” gives one mole each of B when equilibrium is set up is
and C in a reversible reaction. If degree of dissocia-
tion of “A” is independent of initial concentration of 2.303 × 2 × 300 × 400
(1)  log 50 cal
“A” then “n” is 100
(1) 1 (2)  2 (3)  3 (4)  4 2.303 × 2 × 300 × 400
(2)  log 250 cal
23. Consider the following equilibrium for formation of 100
octahedral complex of Co+2 in aqueous medium at 2.303 × 2 × 300 × 400
(3)  log 5 cal
298 K 100
 (4) None
+ 6NH 3  
+2 +2
Reaction (1): Co(aq)  [Co(NH 3 )6 ]
K = 2 × 108 27. At 40°C the vapour pressure in torr, of methyl

Reaction (2): Co +2 + 3en  
 [Co(en)3 ]
+2
­alcohol–ethyl alcohol solution is represented by the
K = 4 × 1017 equation P = 119xA + 135. When xA is mole fraction
P

Assuming ∆H10 = ∆H 02 and ∆S10 = 0, what is the of methyl alcohol, then the value is lim A .
x A →1 X
­approximate value of ∆S02 = A

(1) 95 J/K (2)  –90 J/K (1) 254 torr (2)  135 torr
(3) 180 J/K (4)  150 J/K (3) 119 torr (4)  140 torr

24. The degree of dissociation of HI at a particular 28. In an aqueous solution of volume 500 ml, when the
­temperature is 0.8. Calculate the volume of 1.5 reaction of 2Ag+ + Cu  Cu+2 + 2Ag reached equi-
M sodium thiosulphate solution required to react librium, [Cu+2] was XM. When 500 ml of water is
­completely with I2 present at equilibrium in acidic further added, at the equilibrium [Cu+2] will be

Chapter_7a.indd 21 3/26/2014 3:15:25 PM

 7A.22  Objective Chemistry - Vol. I

(1) 2XM 35. I2 + I –   I3– this reaction set up is in aqueous

(2) XM medium. We start with 1 mole of I2 and 0.5 mole of I–
(3) Between XM and X/2M in the litre flask. After equilibrium is reached, excess
(4) Less than X/2M of AgNO3 gave 0.25 mole of yellow ppt. Equilibrium
constant is
29. For the reaction A + B  C + D, equilibrium con-
centration of [C] = [D] = 0.5 M, if we start with (1) 1.33 (2)  2.66 (3)  2.00 (4)  3.00
1 mole each of A and B. Percentage of A converted to 36. If equilibrium constant of
C if we start with 2 moles of A and 1 mole of B is CH 3 COOH + H 2 O  CH 3 COO − + H 3 O+
(1) 25% (2)  40% is 1.8 10 −5 , the equilibrium constant of
(3) 66.66% (4)  33.33% CH 3 COOH + OH −  CH 3 COO − + H 2 O is
30. The approach to the following equilibrium was (1) 1.8 × 10 −9 (2)  5.55 × 1010
−10
observed kinetically from both directions (3) 5.55 × 10 (4)  1.8 × 109
PtCl −42 + H 2 O  Pt(H 2 O)Cl3− + Cl − 37. 2 moles each of A and B were taken in a con-
tainer and following reaction take place
−d  PtCl 
−2
4 2A(g) + B(g)  2C(g) + D(g). When the system at-
At 25°C, it was found that = 3.9 × 10 −5 s −1
dt tained equilibrium
PtCl −42 – (2.1 × 10–3 s–1)
(1) [A] > [B] (2)  [A] < [B]
 Pt(H 2 O) CI 3−  CI −  (3) [A] = [B] (4)  [A] = [C]
What is the value of equilibrium constant when fourth 38. Zn (Zn +2 (1M) Ag + (1M) Ag. If equilibrium ­constant
Cl– is complexed? is 6.2 × 1052 , calculate DGo at 298 K.
(1) 1.86 × 10–2 (2)  2.1 × 10–3 (1) –301.08 kJ (2)  301.08 kJ

(3) 3.9 × 10 –5
(4)  0.54 × 102 (3) –201.08 kJ (4)  201.08 kJ
31. PCl5 is 40% dissociated when pressure is 2 atm. It will 39. For the following equilibrium N 2 O 4  2NO2 in
be 80% dissociated when pressure is approximately gaseous phase, NO2 is 50% of the total volume when
(1) 0.3 atm (2)  0.5 atm equilibrium is set up. Hence, percentage dissociation
(3) 0.6 atm (4)  0.2 atm of N2O4 is
(1) 50% (2)  25%
32. For N2 + 3H2  2NH3, one mole of N2 and three
(3) 66.66% (4)  33.33%
mole of H2 are at 4 atm. Equilibrium pressure is
found to be 3 atm. Hence, Kp is 40. For a certain equilibrium, over the temperature range
1 1 500 K to700 K. The equilibrium constant Kp con-
(1)  (2)  6.36 × 103
( 0.5)( 0.15) ( 0.5)( 0.15)
2 3
forms to the equation log K p = 30.1 − –5.7
T
3× 3 log T. Calculate at DG at 600 K.
o
(3)  (4)  None
( 0.5)( 0.15)
3 (1) –16.04 Kcal/mole (2)  –14.60 Kcal/mol
(3) –10.064 Kcal/mol (4)  –14.00 Kcal/mol
33. 40% of mixture of 0.2 mole of N2 and 0.6 mole of H2 41. Which of the following statements is incorrect for the
react to give NH3 according to the equation N2 + 3H2 given reaction, 4A + B  2C + 2D ?
 2NH3 at constant temperature and pressure. The (1) The rate of disappearance of B is one-fourth the
ratio of final volume to the initial volume of gases is
rate of disappearance of A.
(1) 4:5 (2)  5:4 (2) The rate of appearance of C is half the rate of
(3) 7:10 (4)  8:5 disappearance of B.
34. The equilibrium constant for the reaction A(g) + B(g) (3) The rate of formation of C and D are equal.
 (4) The rate of formation of D is half the rate of dis-
 
 2C(g) is 3 × 10–4 at 500 K. In the presence of
a catalyst the equilibrium is attained 10 times faster. appearance of A.
The equilibrium constant in the presence of a catalyst 42. The reaction CaCO3 (s)  CaO(s) + CO2 (g) occur-
at 500 K has the value ring in a closed container is at equilibrium. How is
(1) 3 × 10–4 (2)  30 × 10–4 the equilibrium concentration of CO2 affected if mole
(3) 3 × 10 –3
(4)  30 × 10–3 CaCO3 is added at a fixed temperature?

Chapter_7a.indd 22 3/26/2014 3:15:31 PM

 Chemical Equilibrium  7A.23

(1) It decreases If some CO is introduced into the vessel then the new
(2)  It remains unaffected ­equilibrium concentration of
(3) It increases (1) PCl5 is greater
(4)  It cannot be predicted (2) PCl3 remains unchanged
(3) PCl5 is less
43. For the reaction PCl5  PCl3 + Cl 2 in gaseous
(4) Cl5 is greater
phase, Kc = 4. In a 2-litre flask, there are 2 moles
each of PCl3 and Cl2 and 0.5 mole of PCl5. Equilib- 50. A 0.20 M solution of methanol has a degree of ioniza-
rium concentration of PCl5 is tion of 0.032. Its dissociation constant is
(1) 0.25 mol/litre (2)  0.125 mol/litre (1) 2.1 × 10–4 (2)  2.1 × 10–3
(3) 0.75 mol/litre (4)  1 mol/litre (3) 1.1 × 10 –6
(4)  1.1 × 10–3
44. Kp for the equilibrium COCl2(g)  
 CO(g) + 51. For the reaction H2(g) + CO2(g)  H2O(g) + CO(g),
Cl2(g) is 6.7 × 10–9 atm at 100°C. Calculate the the equilibrium constant is 1.8 at 100ºC. If 1.0 mole
­fraction of phosgene dissociated when 1 mole of of CO2 and 1.0 mole of H2 are taken in 1-L flask, the
phosgene is taken in a 100-litre vessel and allowed to final equilibrium concentration of CO at 10 O°C will
reach equilibrium. be
(1) 6.7 × 10–9 (2)  6.7 × 10–7 (1) 0.575 M (2)  0.290 M
(3) 2.48 × 10 –4
(4)  1.48 × 10–4 (3) 0.386 M (4)  0.721 M
K1
52. Consider two gaseous equilibria 2NO(g)  
45. CH3COCH3(g)   CH3 – CH3(g) + CO(g) initial K2
N2(g) + O2(g); 2O2(g) + 2N2(g)  
  4NO(g)
pressure of CH3COCH3 is 100 mm. When equilib-
where K1 and K2 are the corresponding equilibrium
rium is set up mole fraction of CO(g) is 1/3. Hence,
constants at 298 K. The values of the equilibrium
Kp is
constants are related by
(1) 100 mm (2)  50 mm 1
(3) 25 mm (4)  150 mm (1) K 2 = 2 (2)  K1 = 1/K 2z
K1
 1
46. For the reaction A   B + C, the following data (3) K 2 = K12 (4)  K1 = K 2
were obtained at 30°C: 2
53. Solid ammonium carbamate dissociates to give NH3,
Experiment [A] mole/litre Rate in mole l–1 h–1 CO2 according to the reaction NH2COONH4 
1. 0.170 0.05 2NH3(g) + CO2(g). At equilibrium ammonia is added
such that partial pressure of NH3 is equal to the origi-
2. 0.340 0.10
nal total pressure. The ratio of the total pressure now
3. 0.680 0.20 to the original total pressure is
The equilibrium constant for the reaction is (1) 27/31 (2)  31/27 (3) 4/9 (4)  9/4
0.50 mol l–1. Assuming that the reaction proceeds by
a one-step mechanism. Calculate the rate constant for 54. The heat of endothermic reaction at constant volume
the reverse reaction in litre mol–1 h–1. in equilibrium state is 1200 cal more than the heat of
(1) 0.294 (2)  0.588 (3) 0.50 (4)  0.125 reaction at constant pressure at 300 K. The ratio of
the equilibrium Kp and Kc is
47. The following equilibrium is set up at 400°C in a
 (1) 3.296 × 10–2 (2)  3.296 × 10–3
10-litre flask, 2NO(g) + O2(g)   2NO2(g) and its Kc (3) 1.648 × 10 –2
(4)  1.648 × 10–3
= 10. If number of moles of NO and NO2 are equal at
equilibrium, determine number. of moles of O2 ­under 55. The relation between DHq, DSq and equilibrium
­
equilibrium condition. constant K at a given temperature T is
(1) 10 (2)  1 (3)  100 (4)  None ∆H θ ∆S θ
(1) 2.303 log K = − +
48. In the following reaction 3A + B  2C + D initial RT RT
mole of B is twice that of A. At equilibrium mole of ∆H θ ∆S θ
(2) 2.303 log K = −
A and C are equal. Hence, % dissociation of B is RT RT
(1) 10% (2)  20% (3)  40% (4)  45% ∆H θ ∆S θ
(3) 2.303 log K = − +
49. Two systems PCl5(g)  PCl3(g) + Cl2(g) and RT R
COCl2(g)  CO(g) + Cl2(g) are ­simultaneously ∆H θ ∆S θ
(4) 2.303 log K = −
in equilibrium in a vessel at constant volume. RT R

Chapter_7a.indd 23 3/26/2014 3:15:35 PM

 7A.24  Objective Chemistry - Vol. I

56. For the reactions (1) and (2) (1) 12 (2)  4
A  B + C (3)  0.25 (4)  0.0833
D  2E 62. Consider the following equilibria
the ratio K P1 : K P2 = 9:1
   (I)  A(s)  B(s)  (II)  2A(l)  B(l)
If the degree of dissociation of A and D be same then
(III)  A(s)  B(g) (IV)  A(g)  B(g)
the total pressure at equilibrium (1) and (2) are in
Which of the above will not be disturbed by increase
(1) 3:1 (2)  36:1 (3)  1:1 (4)  0.5:1
in pressure?
57. Methane on reaction with steam gives CO and H2 (1) I and IV (2)  I, II and IV
CH4(g) + H2O(g)  → CO(g) + 3H2(g) (3) II, III and IV (4)  IV only
The products of the above reaction are used in the
63. One mole each of A and D is in introduced into a
preparation of methanol at 500 K.
1 litre  container. Simultaneously, two equilibria are
CO(g) + 2H2(g)  CH3OH(g), Kp = 10–2 atm–2 ­established:
What total pressure at equilibrium is required to A  B + C KC = 106 M
­convert 50% of CO to CH3OH at 500 K?
B + D  A, KC = 10–6 M–1
(1) 15 atm (2)  10 atm
Equilibrium concentration of “A” will be
(3)  50 atm (4)  20 atm
(1) 10–6 M (2)  10–3 M
58. The reaction SO2 + Cl2  SOCl2 is exothermic and (3) 10 M –12
(4)  0.5 × 10–3 M
reversible. The mixture is at equilibrium in a closed
container. Now, certain SO2 is added to the container. 64. A reaction at 300 Kwith DGq = –1743 J/mol consists of
Which of the following is correct? 3 moles of A(g), 6 moles of B(g) and 3 moles of C(g). If
(1) The pressure inside the container will not change. A, B and C are in equilibrium in a 1-litre container then
(2) The temperature will not change. the reaction may be (Given 2 = e0.7; R = 8.3 J/k mol)
(3) The temperature will increase. (1) A + B  C (2)  A  B + 2C
(4) The temperature will decrease. (3) 2A  B + C (4)  A + B  2C

59. At the equilibrium of the reaction N2O4(g) 

2NO2(g), the observed molecular weight of N2O4 is
Answers
80 gm mol–1 at 350 K. The percentage of dissociation
of N2O4(g) at 350 K is   (1) 3   (2) 2   (3) 2   (4) 4   (5) 1
(1) 10% (2)  15% (3)  20% (4)  18%   (6) 1   (7) 3   (8) 4   (9) 1 (10) 2
60. Which of the following statements concerning the (11) 2 (12) 3 (13) 2 (14) 2 (15) 1
change in DGq and DG during a chemical reaction is (16) 3 (17) 2 (18) 4 (19) 4 (20) 2
correct? (21) 2 (22) 2 (23) 3 (24) 1 (25) 1
(26) 3 (27) 1 (28) 4 (29) 4 (30) 4
(1) DGq remains constant while DG changes and
(31) 4 (32) 2 (33) 1 (34) 1 (35) 1
­becomes equal to DGq at equilibrium.
(36) 4 (37) 2 (38) 1 (39) 4 (40) 3
(2) Both DGq and DG remain constant during a
(41) 2 (42) 2 (43) 1 (44) 4 (45) 2
chemical reaction.
(46) 2 (47) 1 (48) 1 (49) 3 (50) 1
(3) DGq remains constant if the reaction is carried out
(51) 1 (52) 1 (53) 2 (54) 4 (55) 3
under standard conditions; DG remains constant
(56) 2 (57) 1 (58) 3 (59) 2 (60) 4
if the reaction is carried out under non-standard
(61) 4 (62) 2 (63) 1 (64) 3
conditions.
(4) DGq remains constant while DG changes and
­becomes equal to zero at equilibrium.
61. The equilibrium concentrations of A and B for the
reaction A(g) + 2B(g)  C(g) are 3 M and 4 M, re-  Statement-Type Questions
spectively. When the volume of the vessel is doubled
and the equilibrium is allowed to reestablish the con- In each of the following questions, a statement I is given
centration of B is found to be 3 M. The equilibrium followed by a corresponding statement II just below it.
constant Kc for the reaction is Based on the given statements, mark the correct answer.

Chapter_7a.indd 24 3/26/2014 3:15:39 PM

 Chemical Equilibrium  7A.25

1. B
 oth statement I and statement II are true and 9. Statement I: Ice  Water. If pressure is applied,
­statement II is the correct explanation of statement I. water will evaporate.
Statement II: Increase of pressure pushes the equi-
2. B
 oth statement I and statement II are true but state-
librium towards the side in which number of gaseous
ment II is not the correct explanation of ­statement I.
mole decreases.
3. Statement I is true but statement II is false.
10. Statement I: According to Le Chatelier’s principle
4. Statement I is false but statement II is true. addition of heat to an equilibrium, solid  liquid
results in decrease in the amount of solid.
1. Statement I: A catalyst does not influence the values
Statement II: This reaction is endothermic. So, on
of equilibrium constant.
heating forward reaction is favoured.
Statement II: Catalysts influence the rate of both
­forward and backward reactions equally. 1
11. Statement I: SO2 (g) + O2 (g)  SO3 (g) + Heat.
2
2. Statement I: In dynamic equilibrium, forward and Forward reaction is favoured at high temperature and
backward reactions continue to take place with equal low pressure.
rates. Statement II: The above reaction is exothermic.
Statement II: In dynamic equilibrium, colour and
density changes with time. 12. Statement I: Equilibrium constant has meaning only
when the corresponding balanced chemical equation
3. Statement I: N 2 + 3H 2  2 NH 3 ; ∆H = –92 kJ. is given.
High pressure favours the formation of ammonia. Statement II: Its value changes for the new equa-
Statement II: Increase of external pressure on the tion obtained by multiplying or dividing the original
above reaction at equilibrium favours the reaction in equation by a number.
the direction in which the number of moles decrease.
13. Statement I: Equilibrium constant for the reverse
4. Statement I: ln K = 1, if K1 = 10 ; K2 = 10 . The
10 –10 ­reaction is the inverse of the equilibrium constant for
reaction having K1 = 1010 go farthest completion. the reaction in forward direction.
Statement II: K = 1010 will go farthest completion Statement II: Equilibrium constant depends upon
­because the ratio product/reactant is maximum. the way in which the reaction is written.

5. Statement I: Kp = Kc for all reactions. 14. Statement I: The value of K gives us a relative idea
Statement II: At constant temperature, the pressure about the extent to which a reaction proceeds.
of the gas is proportional to its concentration Statement II: The value of K is independent of the
6. Statement I: Ice melts slowly at higher attitudes. stoichiometry of reactants and products at the point
of equilibrium.
Statement II: The melting of ice is favoured at high
pressure because ice → water shows decrease in 15. Statement I: For the reaction
­volume. 2 NH 3 (g)  N 2 (g) + 3H 2 (g)
7. Statement I: For N 2 (g) + 3H 2 (g)  2 NH 3 (g). The unit of Kp will be atm.
1 3 Statement II: Unit of KP is (atm)Dn.
The equilibrium constant K then for N 2 (g) + H 2 (g)  NH 3 (g)
1 3 2 2 16. Statement I: For the reaction A(g)  B(g) K =
N 2 (g) + H 2 (g)  NH 3 (g) . The equilibrium constant will p
2 2 1 atm. If we start with equal moles of all gases at
be K . 9 atm of initial pressure, than at equilibrium partial
Statement II: If concentrations are changed to half, ­pressure of A increases.
the equilibrium constant will be halved. Statement II: Reaction quotient Qp > Kp hence equi-
librium shifts in backward direction.
8. Statement I: Effect of temperature on K or K c p
d­ epends on enthalpy change. 17. Statement I: According to Le Chatelier’s principle
Statement II: Increase in temperature shifts the addition of heat to equilibrium liquid vapour results
­equilibrium in exothermic reaction and decrease in in decrease in the amount of liquid.
temperature shifts the equilibrium position in endo- Statement II: This reaction is endothermic; so, on
thermic reaction. heating forward process is favoured.

Chapter_7a.indd 25 3/26/2014 3:15:43 PM

 7A.26  Objective Chemistry - Vol. I

18. Statement I: X(g) + Y(g)  A(g) + B(g) at the Answers

­given temperature, there will be no effect by addition
of an inert gas either at constant pressure or at con-   (1) 1   (2) 3   (3) 1   (4) 1   (5) 4
stant volume.
  (6) 1   (7) 3   (8) 3   (9) 1 (10) 2
Statement II: For the reaction where Dng = 0, there is
(11) 4 (12) 1 (13) 1 (14) 3 (15) 4
no effect by addition of the inert gas either at constant
volume or at constant pressure because expression of (16) 1 (17) 1 (18) 1 (19) 1 (20) 1
equilibrium constant in such case does not depend on (21) 1 (22) 1 (23) 2 (24) 1 (25) 4
pressure of volume of container.
O2

19. Statement I: Ag2S + 4 KCN  
 2K [Ag(CN)2]
 + K2S
Statement II: The reaction is carried out in the pres-
ence of air or O2 so that K2S is oxidized to K2SO4
thereby shifting the equilibrium in the forward  Match the Following Type Questions
­direction. 1. Match the following given in List I with those given
20. Statement I: Le Chatelier’s principle is not ­applicable in List II.
to Fe(s) + S(s)  FeS(s)
List-I List-II
Statement II: Le Chatelier’s principle aims to push
the reaction into a stress-free environment. (A)  Law of mass action     (I)  Kp = Kc(RT)
(B) Active mass of   (II)  1
21. Statement I: On opening a sealed soda bottle CaCO3(s)
­dissolved carbon dioxide gas escapes. (C)  2SO2 + O2 → 2SO3   (III)  Kp = Kc(RT)–1
(D) PCl5  PCl3 + Cl2 (IV) Guldberg and
Statement II: Gas escapes to reach the equilibrium
waage
condition of lower pressure.

22. Statement I: The active mass of pure solid is taken as

unity. The correct matching is

Statement II: The active mass of pure solids depends S. No. A B C D

on density and molecular mass. The density and mo-
lecular mass of pure solids are constant. 1. I IV II III
2. IV II III I
23. Statement I: The equilibrium constant does not 3. III IV I II
change on addition of a catalyst. 4. I IV III II
Statement II: A catalyst provides an alternative path
of lower activation energy for conversion of reactants
to products. 2. Match the following given in List I with those given
in List II.
24. Statement I: According to Le Chatelier’s principle
addition of heat to equilibrium, solid  liquid
List-I List-II
­results in decrease of the amount of solid.
(A) N2(g) + 3H2(g) →     (I) Heterogeneous
Statement II: This reaction is endothermic; so, on
2NH3(g) reversible reaction
heating forward reaction is favoured.
(B) CaCO3(s)  CaO(s)  (II) 2HI(g)  H2(g) +
25. Statement I: For every chemical reaction at equilib- + CO2(g) I2(g)
rium standard Gibb’s energy of reaction is zero. (C) KP = KC   (III) Equilibrium state
(D) Rate of forward (IV) Homogeneous
Statement II: At constant temperature and pressure,
reaction = Rate of reversible reaction
chemical reactions are spontaneous in the direction
backward reaction
of decreasing Gibb’s energy.

Chapter_7a.indd 26 3/26/2014 3:15:44 PM

 Chemical Equilibrium  7A.27

The correct matching is hints

x2 p
S. No. A B C D 53. In the equation of KP = neglecting x in the
1− x 2
1. IV I II III 1
2. III II I IV denominator KP = x2p or x ∝
p
3. I IV III II

54. PCl5  PCl3 + Cl 2
4. IV II I III 1.2 0.8 0.8
2 2 2

3. Match the following given in List I with those given 0.4 × 0.4
in List II. KC = = 0.267
0.6
List-I List-II 
55. The calculated QC for the reaction A + B  
Reaction Relation 3× 4
C + D is = 6.
(A) N2 + 3H2  2NH3   (I) Kp = Kc[RT]2 1× 2
(B) PCl5  PCl3 + Cl2   (II) KC = n KP[RT]2 Since QC is less than KC the reaction proceed in the
(C) NH4HS(s)  NH3(g) +   (III) KC = KP RT forward direction.
H2S(g)
(D)  2SO2 + O2  2SO3 (IV)  KP = KC RT 56. 1.0
2HI   H2 + I2
The correct matching is
0.78 0.11 0.11
S. No. A B C D 0.11× 0.11
KC = = 0.0199
1. I IV III II 0.78 × 0.78
2. I II III IV Kf 203
3. II IV I III 57. KC = = Kb   \ = 20.3
Kb 10
4. II IV III I

58. H2 + CO2 
 H2O + CO2
4. Match the following given in List I with those given
1– x 1– x x x
in List II.
x2
= 1.8
List-I List-II (1 − x )2
Reaction Relation
x2 = 1.8 (1 – x) 2
Kp
(A)  = [ RT ]−2
  (I)  N2 + 3H2  2NH3 x = 1.34 – 1.34x
Kc
2.34x = 1.34
(B)  Kp = Kc [RT]0  (II)  PCl5  PCl3 + Cl2
1.34
Kp 1 x = = 0.573
(C)  =  (III) 3Fe(s) + 4H2O(g)  2.34
K c [ RT ]1
Fe3O4(s) + 4H2(g)
Kp 1 [C6 H 6 ] [C H ]
(D)  = (IV) 2SO2 + O2  2SO3 59. KC = ∴ 4 = 6 63
K c [ RT ] [C2 H 2 ]3 [0.5]
The correct matching is [C6H6] = 0.5 M

S. No. A B C D 2
PCO 8×8
60. KC = = = 16 atm
1. IV III II II PCO2 4
2. I III II IV
3. III II I IV [ z ]2
61. = 2.25
[ x] [ y]
2
4. II II IV I

[3]2
Answers = 2.25
[ 2]
2
y
  (1) 2   (2) 1   (3) 3   (4) 2 9
y = =1
4 × 2.25

Chapter_7a.indd 27 3/26/2014 3:15:51 PM

 7A.28  Objective Chemistry - Vol. I

1.0 69. The KC for the reaction

62. 
2SO 3 
 2SO 2 + O 2 PCl3 (g) + Cl 2 (g)  PCl5 (g)
0.4 0.6 0.3
is the reciprocal of KC of the reaction
0.6 × 0.6 × 0.3
K C = = 0.675 PCl5 (g) 
→ PCl3 (g) + Cl 2 (g)
0.4 × 0.4
1
∴ K C = = 4.2 × 10 2
(P )
2
SO3 2.4 × 10 −3
63. KP =
(P ) (P )
2
a 1.5 a
SO2 O2
70. A + 2B 

 2C + D
a− x 1.5 a − 2 x 2x x

K P =
(0.331) 2
Given a – x = 2x
(0.662)2 (0.101) [C ]2 [ D ]
= 2.5 ∴ x = a 3 Now, K C =
3
[ A][ B ]2
 HCO3−   H 3 O +   2a   a 
   
64. KP =  3 3
[CO2 ] =
 a  3a 2a 
2
= 0.32
 a −   − 
Given K P = 3.8 × 10 −7 and  H 3 O +  = 10–6 3 2 3

 HCO3−  3.8 × 10 −7 71. For 100 g of mixture of N2 and H2, the NH3 produced
∴ = = 3.8 × 10 −7 or 0.38 is 20 g. For 340 g of mixture of N2 and H2, the NH3
[CO2 ] 10 −6 produced is
 20
65. For the reaction PCl3(g) + Cl2(g) 
 PCl5(g) 340 × = 68 g
100
26
K P = K C [ RT ]−1 = = 0.605 72. N 2 +3H 2 

 2NH 3
0.0821 × 523
1 vol 3 vol 2 vol

1 3 1 volume of N2 combines with 3 volumes of H2 to

66. 
N 2 + 3H 2 
 2 NH 3
0.8 2.4 0.4
produce 2 volumes of NH3. So, pressure decreases
3 3 3
by 10% when 20% of the mixture reacts and pressure
1 3  decreases to half.
N2 + H2 
 NH3 KC2
2 2 ∴ The pressure will be 90.
K C2 = K C1 or K C1 = K 2C2 73. Increase in the value of KC with increase in tempera-
2 ture indicates that forward reaction is taking place
 0.4  more with increase in temperature. So, the reaction is
 
3  endothermic.
K C1 = 3
= 0.13
 0.8   2.4 
 
3  3 

74. KC =
[ N 2 ][O2 ]
[ NO]2
1.1 2.2
 Given KC = 100 and [NO] = 0.1
67. A + 2B 
 2C + D
1.0 2.0 0.2 0.1
[ N 2 ][O2 ]
100 =
[0.1]
2
(0.2)2 (0.1)
K C = = 0.001
(1.0)(2.0)2 [ N 2 ][ O2 ] = 1 or [ N 2 ] = [ O2 ] = 1

68. 2NO2(g)   2NO(g) + O2(g) KC1
75. K =
[HI ]2
1 
C
[H 2 ][I2 ]
NO(g) + O2(g)   NO2(g) KC2
2 Given KC = 60, [H2] = 2 moles and [I2] = 0.3 moles
1 1 [ HI ] = 60 × 2 × 0.3 = 36
2
K C2 = = = 7.5 × 10 2
K C1 1.8 × 10 −6 ∴ [ HI ] = 6.

Chapter_7a.indd 28 3/26/2014 3:16:02 PM

 Chemical Equilibrium  7A.29

1 1 22. 
A (s ) 
 2B(g) + 3C(g)
76. 
A + B 
 2C a b
1− x 1− x 2x
K C = a 2 b3 ; 
A (s ) 
 2B(g) + 3C(g)
K C =
[C ] 2
x 2b

[ ][B]
A ∴ K = (2b)3; a2b3 = x2(2b)3

(2x ) a2
2
a
81 = x = =
(1 − x ) (1 − x ) 8 2 2
2x 9 2 1
9 = or x = . 23. 
2SO2 + O2 
 2SO3
1− x 11 1 0.5 1
Pressure at equilibrium = p
Cu 2 +  1.8 × 10 −2 1 p 2.5
77. KC = 2
∴ 2 × 1015 = 2 ∴ = p=
 Ag +   Ag +  3 2.5 3
1 2.5 1
PSO3 = × = atm
 Ag +  = 3 × 10 −9 2.5 3 3
600 
24. N 2 + 3H 2 
 2 NH 3
78. 
AB2 
 AB + B
600 − x x x a 3a –  initial mole
∴ Equilibrium pressure 800 = 600 – x + x + x a 3a
a   equilibrium mole
= 600 + x. 2 2
a P
x = 200 PNH3 = P=
3a 3
200 × 200
K p = = 100
400 25. 
2 NO 2 
 N 2 O 4 equilibrium concentration
1− x x
79. Ptotal = PNH3 + PH2S 2

x 46 28
20 1 − = x=
But PNH3 = PH2S = = 10 2 60 60
2 14
Mole fraction of dimer =
K P = PNH3 × PH2S = 100 atm 2 46

26. I 2  2I
2x
1− x

100
Practice Exercise Level-I 1 + x = = 1.026
97.45
[ H 2 ][ X 2 ] α = 0.026.
2. K =
[ HX ]
2

27. 
I2 
 2I
1.2 × 10 −3 × 1.2 × 10 −4
⇒ 1× 10 −5
= I2 ( 4 ×10 )−2 2

[ HI ] K = 4 × 10 −3
=
2

I2 I2
⇒ [ HI ] = 12 × 10 −2 M/litre. I2 = 0.4 M
8. At equilibrium [A] = [B] = [C] = [D] = 2 
28. H2 + I2  2HI
[ C] [ D ] 2 × 2 0.2 0.5 –  initial mole
⇒ K C = = =1
[A ] [B] 2 × 2 0.2– y 0.5 – y 2y  equilibrium mole
The value of KC does not change by the addition or
removal of ingredients. 
29. 2NO2    2NO + O2
1 0.5 –  initial pressure
9. As Dn = 0 for the dissociation of HI there will be no
1 – 2x 0.5 – 2x ×  equilibrium pressure
effect of volume on dissociation.
( 0.9 ) ( 0.2 )
2

10. For the formation of NH3, Dn = –ve. So, decrease in KP = = 0.45

( 0.6 )
2
volume favours forward reaction.

Chapter_7a.indd 29 3/26/2014 3:16:11 PM

 7A.30  Objective Chemistry - Vol. I

30. 2HI   H2 + I2 

2. A   2B + C
1 1 1  initial mole 2M M –  initial
1 – 2x 1 + x 1 + x  equilibrium mole 2M – x M + 2x x  equilibrium
2
 1+ x  2M − x 1
  = 49 =
 1 − 2x  3M + 2 x 2
6 2 4M – 2x = 3M + 2x
1 + x = 7 – 14x x= =
15 5 M
1+ x x =
PI 2 = × P = 0.7 atm 4
2
3  3M   M 
   
31. N2 + 3H2 
  2   4 
  2NH3 KC =
1 2 3 Initial 7M
22 4
Reaction quotient = 3 = 0.148 Q < KC 9
3 KC = M2
28

32. N2 + 3H2    2NH3 
3. PCl5   PCl3 + Cl2
1 3 2  initial mole
a – –  initial
1 – x 3 – 3x 2 + 2x  equilibrium mole
a – x x x  equilibrium

33. A1 
 nB x 2
K C =
1 –  initial mole a−x
n α  equilibrium mole ( 0.15)
2
1 – a
0.04 =
D a − 0.15
∴ 1 – α + nα =
d a = 0.7125
D 1 PV = nRT
α = −
d ( n − 1) n − 1 P = (0.7125) (0.0821) (523)
1 = 30.59 atm
Slope = = Tan 45° = 1
n −1
∴ n = 2. 4. KP = PH102
∴ PH2 O = 3.715 × 10–3 atm
Practice Exercise Level-II = 2.82 Torr
2.82
1. N2O4  2NO2 Humidity (RH) = = 61%
4.58
a –  initial
If relative humidity is more than 61% Na2SO4 acts as
a – x 2x  equilibrium
deliquescent.
2x 8 × 10 5
= 5. Pressure of water vapour in the equilibrium of AB2.
a+ x 106
2x = 0.8a + 0.8x 6H2O is 1.23 Torr.
0.8 2 Pressure of H2O(g) in the equilibrium of M2N.12 H2O
x = a= a is 2.66 Torr.
1.2 3
2 Pressure of H2O(g) in the equilibrium of P2N.10 H2O
4 
 a is 2.82 Torr.
 3  10
KP = × So, the best drying agent is AB2 ⋅ 6H2O.
1 5a
a 3
3 
6. 4HNO3  4NO2 + 2H2O + O2
∴ KP = 32 atm P o – – –
  initial
KP = KC [ RT ]
∆n o
P – 4x 4x 2x ×  equilibrium
32 = KC [ 0.082 × 400 ] Po + 3x = 30; Po – 4x = 2
KC = 0.974 mol/litre x = 4

Chapter_7a.indd 30 3/26/2014 3:16:19 PM

 Chemical Equilibrium  7A.31

(16 ) (8) ( 4 )
4 2
( x + y) y
KP = ∴ K C2 =
(2) x− y
4

K C1
KP = 1.048 × 106 atm = 4:1
K C2
KP = KC [ RT ]
∆n


12. NH4 HS(s) 
 NH3(g) + H2S(g)
2097 = K C [0.082 × 400 ]
3
– 0.5 –   initial
KC = 32 ( mol/litre ) – 0.5 + x x   equilibrium
3

0.5 + 2x = 0.84
7. KP = PNH
2
3 x = 0.17
∴ PNH2
3
= 3 atm KP = PNH3 × PH2S
PV = nRT = 0.67 × 0.17
nNH3 = 0.5 = 0.11 atm2
Mole of NH3 at equilibrium = 0.5
13. A(s) 
 B + D K P1 = 400 atm2
To drive the backward reaction, 0.7 mole of NH3 is
C(s)  
 E + D K P2 = 1600 atm2
required.

K P1 = a(a + b)
8. [ Ag (CN) 2 ] 
−


+
 Ag + 2CN
−
K P2 = b(a + b)
– 0.06 0.2  initial Total pressure = 2(a + b) = 89.4 atm
0.06 x 0.08  equilibrium
[Ag + ] [CN - ]2 14. A + B  → C
KC = a 0.1 –   initial
 Ag(CN) -2 
a – x 0.1 – x x   equilibrium
x × (0.08)2 C
1.6 × 10 −19 = KC =
0.06 A× B
x = 3 × 10 −18 M. 0.06
0.9 =
9. KP = PH22 O 0.04( a − 0.06)
a = 1.73 M
PH2 O = 0.01 atm
7.6 15. KP = PCO2 = 0.324 atm
Relative humidity = = 25%
30.4 Wt. of CO2 present in 40 ml is W
So, relative humidity is below 25%. W
CuSO4 ⋅ 5H2O acts as an efflorescent. PV = RT
M
W

10. A  
 B + C 0.324 × 40 = (82.1) (300)
44
1 – x x + y x – y mole at equilibrium
WCO2 = 0.023 g
C   
 B + D
Wt. of CO2 required to fill 800 ml is 0.23 × 2 = 0.46 g.
x – y x + y y mole at equilibrium
The time required to effuse CO2 is 10 s.
x− y 2
=
1− x 1 18. Heat of reaction ∆H = 10 × 303 × 8
x – y = 2 – 2x = 2.303 kcal −2.303 ×103
3x – y – 2 = 0    (1)
KC = e −∆H / RT KC = e 2 × 500
1 + x + y = 2    (2)
KC = 0.1
x + y = 1
3 1 19. ∆G o = − RT ln Ksp
x = , y =
4 4 ∆H o − T ∆S o = –RT ln Ksp
( x + y) ( x − y) ∆H o ∆S o
∴ K C1 = ln Ksp = − +
1− x RT R

Chapter_7a.indd 31 3/26/2014 3:16:30 PM

 7A.32  Objective Chemistry - Vol. I

20. N2 + 3H2  

 2NH3
2.303 log 25 = ∆H  1 − 1 
P o
3P o –
initial 5 2  300 400 
o o
P – x 3P – 3x 2x equi. 2.303 × 2 × 300 × 400
∆H = log 5
Po – x = P/3 100
4Po – 2x = 2P
27. If XA = 1, then PA = 119 + 135 = 254 Torr
2P 4P
2Po + = 2P 2Po =
3 3 28. 2Ag+ + Cu  
 Cu2+ + 2Ag
2 P P V x equilibrium concentration
Po = ,x=
3 3 x
∴ K C = 2
 2P 
2 y
  4 x
KP =  3 
P 3 KP = Volume is doubled, then concentration of Cu2+ = ;
3
×p 3P 2 y 2
concentration of Ag+ =

22. nA   B + C 2
α α 4x
n(1 – α) Reaction quotient Q = 2 ; Q > KC So, backward
n n ­reaction is favourable. y
α α
× 
n n 29. A + B   C + D
∴ KC =
[ n(1 − α)] 1 1 – – initial
2

1 – x 1 – x x x equilibrium
If n = 2, then KC is independent of concentration of A.
x = 0.5
23. ∆Go = –2.303 RT log. ∴ K C = 1
A + B   
 C + D

24. H2 + I2 
 2HI
2 1 – –
0.135 0.135 – initial
2 – x 1 – x x x
0.135 – x 0.135 – x 2x equilibrium x2 = (2 – x) (1 – x)
4 x2 2 = 3x ∴ x = 2/3
KC =
(0.135 − x )2
K f 3.9 × 10 −5
So, mole of I2 = 0.135 – x. 30. Kc = =
K b 2.1 × 10 −3
But 2HI  
 H2 + I2 Equilibrium constant when Cl– ion is complexed =
1 – x x x
2 2
1
0.4 × 0.4
KC = =4 Kc
(0.2)2 2.1 × 10 −3
2 ∴ K c1 = = 0.54 × 102
1  2x  2x 1 3.9 × 10 −5
∴ =  =
4  0.135 − x  0.135 − x 2

31. PCl5   PCl3 + Cl 2
4x = 0.135 – x 1 – – initial
x = 0.027 1 – x x x equilibrium
Moles of I2 at eq. = 0.108 (0.4) 2
P
1.5V KP = ×
eq I2 = eq hypo (0.108) × 2 = 0.2 1.8
1000
V = 144 ml ∴ P = 0.2 atm
2 × 10 −2 10 32. N2 + 3H2  2NH3
26. KC at 300 K = = =5
4 × 10 −3 2 1 3 – initial
4 × 10 −2 100 1 – x 3 – 3x 2x equilibrium
KC at 400 K = = = 25 4 – 2x = 3
10 × 10 −4 4
x = 0.5 2
K 2 ∆H  1 1  (1)2 3
2.303 log =  −  KP =  
K1 R  T1 T2  (0.5) (1.5)2  3 

Chapter_7a.indd 32 3/26/2014 3:16:40 PM

 Chemical Equilibrium  7A.33

33. N2 + 3H2  2NH3 44. KP = K C [ RT ]

∆n

1.2 0.6 – initial mole

6.7 × 10 −9 = K C [ 0.0821× 373]
1
0.2 – x 0.6 – 3x 2x equilibrium mole.
−10
∴ x = 0.08 mole of N2 = 0.12; mole of H2 = 0.36 K c = 2.18 × 10
mole of NH3 = 0.16 
COCl2  
 CO + Cl2
Mole ratio considered as volume ratio because P and
1 – – initial
T are constant.
Initial mole = 0.8 1 – α α α equilibrium
Equilibrium mole = 0.12 + 0.36 + 0.16 = 0.64 α2 1
K C = ×
0.64 4 1− α v
Ratio = =
0.8 5 α2 1
2.18 × 10 −10 = ×
34. Equilibrium constant does not vary with catalyst. 1 − α 100
α = 1.48 × 10 −4

35. I2 + I–  
 I3–
1 0.5 – initial mole 45. CH3 COCH3  → CH3 – CH3 + CO
1 – x 0.5 – x x equilibrium mole 100 – –
I + AgNO3 
–
→ AgI + NO3– 100 – x x x

0.5 – x = 0.25 x 1
= or 3x = 100 + x or x = 50
x = 0.25 100 + x 3
0.25 ∴ KP = 50.
∴ K C = = 1.33
0.25 × 0.75
46. r = K[A]n
36. CH3COOH   
 CH3COO– + H+
0.05 = K(0.17)n
Ka = 1.8 × 10 −5
0.1 = K(0.34)n ∴ n = 2
CH3COOH + OH–   
 CH3COO– + H2O
0.05
K 1.8 × 10 −5
Kf = = 0.2941

Keq = a = = 1.8 × 109 0.17
kw 10 −14
K 0.29
 Keq = f ⇒ 0.5 =
37. 2A + B   2C + D Kb Kb
2 2 – – initial mole
Kb = 0.588
2 –2x 2 – x 2x x equilibrium mole

47. 2NO + O2   2NO2, KC = 10
38. ∆Go = –2.303 RT log KC. 2
nNO V

39. N2O4   2NO2 KC = 2 2
nNO × nO2
1 – initial
10
1 – x 2x equilibrium 10 =
2x nO2
= 0.5
1+ x nO2 = 1
4x = 1 + x or x = 1/3

49. 3A + B  
 2C + D
6.36 × 10 −3
40. log KP = 30.1 – – 5.7 log 600 a 2a – –  initial
600
a – 3x 2a – x 2x x  equilibrium
∆Go = –2.303 RT log KP.
a – 3x = 2x

43. PCl5 
 PCl3 + Cl 2 a = 5x
a
0.5 2 2 initial mole x =
2×2 5
Reaction quotient, Q = =4 a
0.5 × 2 % dissociation of B = × 100 = 10%
So, it is in equilibrium. 5 × 2a
0.5
[PCl5] = = 0.25 M 50. Ka = ca2 (0.2) (0.032)2 = 2.1× 10 −4
2

Chapter_7a.indd 33 3/26/2014 3:16:53 PM

 7A.34  Objective Chemistry - Vol. I

51. H2 + CO2  

 CO + H2O a
−2
1 1 – – initial mole 2 P
1 – x 1 – x x x equilibrium mole ∴ K P = a  
2  3a 
( 2a)
2 2
 x 
1.8 =   1 9
1− x  10–2 = ⋅
x 4 P2
= 1.34
1− x P = 15 atm
x = 1.34 – 1.34x 58. When SO2 is added then forward reaction takes place.
x = 0.573 M. So, heat is liberated.

53. NH2COO CH4 (s)  
 2NH3(g) + CO2(g) 
59. N2O4  2NO2
– 2P P equi P 1 – α 2α
KP = 4P 3
92
4P 1 + α =
KP = (3P)2x or x = 80
9
4 P 31P α = 0.15
Total pressure now = 3P + =
9 9 
31 61. A + 2B  
 C
∴ Ratio =
27 3 4 x equilibrium concentration
x
54. ∆H – ∆U = ∆nRT ∴ K C =  (1)
3 × 16
−1200
Dn = = −2 If volume is doubled, backward reaction favours thus
2 × 300 
A + 2B  
 C
K
P = [ RT ] = [(0.0821) (300)]
∆n 2
1.5 2 x/2 initial
KC
2 3 x/2 – 0.5 equilibrium
= 1.64 × 10 –3 x
∴ K C = – 0.5/2 (3)2 (2)
α2 P 2
K P1 = × 1
1− α 1+ α From (1) and (2)
4α 2 P x x −1
K P2 = × 2 =
1− α 1+ α 48 36
KP 9 9 P 48
1 = ∴ = 1 x = ∴ KC = 0.0833
K P2 1 1 4 PC 12

P 36 63. In first reaction, Kc = 106. So, a is almost completely

1 = converted to B + C.
PC 1
1× 10 −7
57. CH4 + 2H2  

 CH3OH 100 – 0.1 55.5 – 10–7 ×100
44
a 3a – initial mole
a a
2a equilibrium mole
2 2

Chapter_7a.indd 34 3/26/2014 3:17:02 PM

 7B

Chapter
Ionic Equilibrium

Arrhenius Theory of Ionization • The degree of dissociation (α) can be obtained from
the ratio of equivalent conductivity at certain dilution
  (i) Acids, bases and salts when dissolved in water lc and the equivalent conductivity at infinite dilution λ ∝
split into oppositely charged particles called ions.
λ
Positively charged particles are called cations while α= c
negatively charged particles are called anions. λ∝
(ii) There exists a relationship between ions and non-
ionized molecules.
Factors Affecting the Degree of
Dissociation
MA  M + +A −
[M + ][A − ] • Ionization of electrolytes is more in solvents having
= K (Ionization constant) more dielectric constant.
[MA ]
(iii)  The total charge on the cations is equal but • The degree of ionization increases with increase in the
opposite to that on the ions so that the solution dilution of the solution and ionization is complete at
becomes electrically neutral. infinite dilution.
 (iv)  Substances which ionize in water are called • The more the solvation of ions, the more the degree of
­electrolytes and their properties in solution are ionization.
the properties of the ions. • Increase in temperature increases the degree of ioniza-
  (v) Conductivity of the solution is due to movement tion since the velocity of ions increases and the attrac-
of ions towards the oppositely charged electrodes. tive forces between the ions are broken.
 (vi) Ions behave like molecules in producing colliga-
tive properties. Limitations of Arrhenius Theory

ostwald’s dilution law • Ostwald’s dilution law based on Arrhenius theory is

completely true in the case of strong electrolytes.
• Electrolytes which ionize considerably are called • The degree of dissociation obtained from colligative
strong electrolytes while those which ionize only to a properties and conductance measurements are in good
small extent are called weak electrolytes. agreement in the case of uniunivalent electrolytes
• The extent of ionization or dissociation is called degree like KCl but not at all satisfactory for bi-univalent or
of ionization or degree of dissociation represented by α. ­bi-bivalent electrolytes such as BaCl2or CaSO4.
• The degree of dissociation (α) for weak electrolytes is • Conductivity of molten electrolytes like KCl, NaCl in-
always less than1. dicates that ionization takes place even in the absence
• The degree of dissociation (α) for weak electrolytes of water.
can be calculated from the ionization constant K and • This theory did not take into account about the mobil-
concentration of the solution C for ity of the ions which can be altered by attractive forces
α = ka.C between oppositely charged ions lying side by side.

Chapter_7b.indd 1 3/26/2014 3:15:25 PM

 7B.2  Objective Chemistry - Vol. I

Acids, Bases and Salts • More the Kb value the stronger the base, lesser the Kb
value the weaker the base.
• Boyle’s Theory: According to Robert Boyle, acids
  (i) turn blue litmus to red • Arrhenius acid–base theory is applicable only for
 (ii) are sour to taste and are corrosive in nature aqueous solutions.
(iii) liberates hydrogen gas when reacts with metals • The acidic behaviour of compounds like CO2, SO2,
like zn and Mg etc. and basic behaviour of bases like CaO, NH3, etc.
  (iv)  decompose carbonates and liberate carbon cannot be explained by Arrhenius theory.
­dioxide gas • The behaviour of compounds like CuSO4 and
  
(v)  react with bases to form salts and are good Al2(SO4)3, which can turn blue litmus to red cannot be
­conductors of electricity in aqueous solution explained by Arrhenius theory.
• According to Boyle’s theory, bases
  (i)  turn red litmus to blue
Lowry–Bronsted Theory
(ii)  are bitter to taste
(iii)  react with acids to give salts • According Lowry–Bronsted theory proton donor is
  (iv)  are soapy to touch an acid while proton acceptor is a base.
  (v)  are good conductors of electricity in solution • In the reaction HCl + H2O  H3O+ + Cl–, HCl is an
• Lavoisier proposed that all acids must contain oxygen acid since it donates a proton and H2O is a base since
as a necessary element in them. it accepts a proton.
• Humpry Davy proved that substances like HCl which • In the reaction NH 3 + H 2 O  NH +4 + OH −; NH3 is a
do not contain oxygen can also act as an acid. base since it accepts a proton and H2O is an acid since
• Humpry Davy proved that acids contain hydrogen as it donates a proton.
its constituent element. • The residual part of the acid after losing a proton can
again accept a proton. Thus, it can function as a base.
Arrhenius’ Modified Theory e.g., Cl– formed from HCl by losing a proton behaves
as a base and OH– formed from H2O by losing a proton
• According to Arrhenius an acid is a substance which can function as a base.
increases the hydronium ion concentration in an aque-
ous solution. • The base after gaining a proton from an acid can
function as an acid again since it has a tendency to
• High electrical conductivity of acid solutions is due to
give a proton. e.g., H3O+ formed by H2O after gain-
H+ ions which exchange with water but not travel.
ing a p­ roton and NH +4 formed by NH3 after gaining a
• An acid is strong if it can produce large number of ­proton can function as acids.
H+ ion and it is weak if it produces less number of
• The acid–base pair which differs by a single proton is
H+ ions.
called conjugate acid–base pair.
• The strength of an acid is measured in terms of acid
• Each acid–base reaction involves two conjugate acid–
dissociation constant, Ka, for HX  H + +X −
base pairs.
[H + ][X − ]
Ka = • An acid is strong if it has high tendency to donate elec-
[HX ] tron pair and if its conjugate base is weak or vice versa.
• Higher the Ka value the stronger the acid and lesser the • A base is strong if it has great tendency to accept
Ka value the weaker the acid. ­proton and if its conjugate acid is weak or vice versa.
• According to Arrhenius a base is a substance that • H3O+ is the strongest acid and OH– is the strongest
­increases the hydroxyl ions in its aqueous solution. base that can exist in water.
• The high electrical conductivity of bases in aqueous • The levelling of the strength of strong acids in water
solution is due to OH– ion due to exchange with water to the same level as that of H3O+ or the levelling of the
liberated at anode without travelling. strength of all strong bases in water to the same level
• The strength of bases is measured in terms of dissocia- as that OH– is known as levelling effect of water.
tion constant Kb for BOH  B+ + OH −: • Lowry–Bronsted theory is more generalized theory
[B+ ][OH − ] than that of Arrhenius theory and could explain the

Kb =
[BOH] acid character of SO2, CO2 and basic character of NH3.

Chapter_7b.indd 2 3/26/2014 3:15:26 PM

 Ionic Equilibrium  7B.3

• Lowry–Bronsted theory cannot explain the acidic • Compounds with multiple bonds which can form
character of electron-deficient compounds like BF3, ­coordinate covalent bonds with transition metal ions
BCl3, etc. are Lewis bases, e.g., CO, NO, CH ≡ CH, CH2 = CH2,
pyridine, etc.
Classification of Solvents
Limitations of Lewis Theory
• Solvents which accept proton are called protophilic
solvents, e.g., water, alcohol, ammonia, etc. • Lewis theory cannot explain the strength of acids and
bases. Acids such as HCl and H2SO4 cannot form
• Solvents which can generate protons are called proto-
­coordinate bonds. Acid–base reactions are fast but
genic solvents, e.g., water, liquid HCl, glacial acetic
Lewis acid–base reactions are slow. The catalytic ac-
acid, etc.
tivity of H+ ions and neutralization of normal a­ cids and
• Solvents which can accept and generate protons are bases where coordinate bonds are not formed c­ annot
called amphiprotic solvents, e.g., water, ammonia, etc. be explained by Lewis theory.
• Solvents which can neither donate nor accept protons
are called aprotic solvents, e.g., benzene, carbon
­disulphide, carbon tetrachloride, etc. Influence of Solvent on
Strength of Acids
Lewis Theory • Acetic acid is a weak acid and can also act as a base
but has a little tendency to accept a proton. So, even
• According to Lewis theory, electron pair acceptor is strong acids also ionize feebly in acetic acid. So, the
an acid while electron pair donor is a base. strengths of different acids are compared with acetic
• The neutralization between Lewis acids and bases acid by measuring their conductivities in a­ cetic acid.
is due to the formation of coordinate bond or • Water is a much stronger base than acetic acid. So,
dative bond. all strong acids ionize completely in water and appear
• A Lewis acid must possess a vacant orbital to accept almost equally strong. So, their strength in water can-
the lone pair. not be compared. The strength of weak acids can only
be compared.
• Simple cations like Ag+, Co3+, Al3+, Na+, Cu2+ Zn2+,
etc. which can combine with electron pair donors by • Liquid ammonia has a strong tendency to accept a
accepting lone pair of electrons are Lewis acids. proton and hence weak acids also completely ionize in
ammonia and behave as strong acids.
• Compounds whose central atom has an incomplete
octet or the electron-deficient molecules such as BF3, • HF has a strong acidic character but no basic character.
AlCl3, FeCl3, etc. are Lewis acids. Strong acids such as HNO3 are incapable of ionizing
as an acid when dissolved in HF but ionizes slightly as
• Compounds whose central atom have vacant d-orbit-
a base in HF.
als and can acquire more than an octet in their outer-
most orbit like PF3, PF5, SF4, SeF4, SiCl4, SnCl4, etc. HNO3 + HF  H 2 NO3+ + F −
Acid Base
are Lewis acids. Base
solvent
Acid

• Molecules with multiple bonds between atoms of dis- Similarly, CH3COOH act as a base in HF.
similar electronegativities like O = C = O, O = S = O,
• The strength of bases can be compared in a solvent
SO3, NO2, etc are Lewis acids.
such as water which has a strong basic character but
• Elements with electron sexet like oxygen and sulphur CH3COOH cannot be used to compare the strength of
are Lewis acids. bases because it is acidic.
• All simple negative ions such as F–, Cl–, OH–, CN–,
NH 2− , SO32− , etc. which can donate lone pair of elec- Alkalis,  Acids and Amphoteric
trons are Lewis bases.
Hydroxides
• All the molecules with one or more unshared ­electron
pairs like • Alkalis, acids and amphoteric hydroxides contain one
 ROH,
 ROR,
 RSR,
 RNH 2 , or more OH groups bonded to an element A, which in
:NH 3 H 2 O:, etc. are
   turn is bonded with other atoms.
Lewis bases.

Chapter_7b.indd 3 3/26/2014 3:15:27 PM

 7B.4  Objective Chemistry - Vol. I

• The nature of these hydroxides depends on the point of Strength of HA1 α1

=
ionization. Strength of HA 2 α 2
• When OH is in bond with highly electropositive ­metals • The relative strengths of two acids can be obtained
(IA and IIA group metals), dissociation occurs form- from their dissociation constants
ing A+ and OH– ions and are strongly basic.
Strength of HA1 α1 k
• If OH is in bond with a non metal, electrons are with- = = 1
drawn from oxygen atom towards A and ionization oc- Strength of HA 2 α 2 k2
curs forming AO– and H+, then – behaves as an acid. • Acid catalyzed hydrolysis of esters or the inversion of
• If OH group is in bond with an element of intermediate sugar can be used for comparing the strength two acids
electronegativity ionization may occur on either side HA1 and HA2:
of oxygen producing either OH– or H+ ions ­depending Strength of HA1 k1
on the substance with which it is reacting and behave =
Strength of HA 2 k2
as amphoteric hydroxide.
where k1 and k2 are rate constants for the above reactions.
A – O – H  → A+ + OH–

Metal
A – O – H  → A – O– + H+
Factors Influencing the Strength
of an Acid
Nonmetal
A – O – H  → A+ + OH– or A – O– + H+ • If the conjugate base formed from an acid after giving
Metalloid proton get stabilized by resonance hybridisation and
delocalization of charge makes the acid strong, e.g.,
acetate ion formed from acetic acid.
Determination of Relative • If the conjugate base is insulated by the solvent layer,
Strengths of Acids it will be prevented from combining with H+ ion and
• In Thomson’s method the relative strength of two acids the acid will be strong. Solvents such as water having
can be calculated from the heat evolved, when a mix- more dielectric constant have more insulating power
ture of two acids is neutralized with a base. and ionization of acids will be more in water and thus
Total heat evolved, z = nx + (1 – n) y behave strong acids in water.
z−y • The parent molecule or ion should encourage the loss
∴n =
x− y of proton. For example, in aqua complexes of metal
ions with more amount of positive charge polarizes
Strength of HA1 n
= the water molecules and make it to lose proton. This
Strength of HA 2 1 − n explains the acidic nature of Al3+, Fe3+, etc. ions in
x and y are the heat of neutralizations of two acids HA1 aqueous solutions.
and HA2 and n is the fraction of acid HA1 in the mixture.
• If more electronegative elements or group are present
• In Ostwald’s volume method change in volume is on the atoms to which OH is in bond, the acidic charac-
noted instead of noting the heat evolved: ter increases. Acidic character increases with increase
z−y in the number of electronegative atoms and also with
n=
x− y increase in the electronegativity of an atom.
Strength of HA1 n CCl3COOH > CHCl2COOH > CH2ClCOOH >
=
Strength of HA 2 1 − n CH3COOH
Here Z cc is the change in volume when 1 equivalent CFH2COOH > CClH2COOH > CBrH2COOH >
of NaOH and a solution containing 1 equivalent of CIH2COOH
each HA1 and HA2 and mixed. While x and y are the • Acidic strength decreases with increase in the strength
change in volume when 1 equivalent of each HA1 and of bond holding hydrogen atom e.g., H–F < H–Cl <
HA2 react with NaOH. H–Br < H–I
• In conductivity method the relative strength of two • Acidity increases with increase in positive charge
­acids can be compared from their degree of dissocia- (H3O+ > H2O) and basic character increases with
tions a1 and a2 calculated from their conductivities. ­increase in negative charge (H 2 PO24− > H 2 PO 4− )

Chapter_7b.indd 4 3/26/2014 3:15:30 PM

 Ionic Equilibrium  7B.5

• Increase in the size of an atom with which hydrogen is 1 1

• pH of a weak acid = – log Ka – log C (or)
in bond increases the acidic strength. For example, 2 2
1 1
HF < HCl < HBr < HI pH = pKa – log C
2 2
H2O < H2S < H2Se < H2Fe
• The dissociation constant for a base BOH is given by
• Increase in the electronegativity of the atom with
which the hydrogen is in bond increases the acidic C 0 0 initial concentration
+
strength. BOH  B + OH
CH4 < NH3 < H2O < HF C (1 − α ) Cα C α equilibrium concentration
Also, the acidic strength increases with increase in the [B+ ][OH − ] Cα × Cα
electronegativity of atom to which OH is bound. Kb = =
[BOH] C(1 − α )
HOCl > HOBr > HOI = Cα 2 (neglecting ∝ in the denominator)
• For compounds containing OH group attached to the
central atom, acidic character increases with increase Kb
α=
in the number of electronegative atoms attached to the C
central atom. e.g., • The concentration of OH– ion is given by
O O [OH–] = Kb × C ∵[OH − ] = Cα
HO − Cl < HO − Cl = O < HO − Cl < HO −Cl O
1 1
O O • pOH = pKb – log C
2 2
O 1 1
• pH of a weak base = 14 – ( pKb – log C)
HO − Cl < HO − N = O < HO − N 2 2
O
(HO)2S = O < (HO)2SO2   Objective Questions
• The values of ionization constants for polybasic a­ cids 1. Which of the following statements is false?
decreases with increase in the number of negative (1)  According to Lewis theory electrophiles are
charges, e.g., the ionization constant values of H3PO4, Lewis acids while nucleophiles are Lewis bases.
H2PO4– and HPO42– are in the order Ka1 > Ka2 > Ka3. (2) In Friedel–Crafts reaction, the catalysts used are
Lewis acids.
Degree of Ionization or Degree of Dissociation of (3) In complex compounds, metal ions are Lewis
Weak Acids and Weak Bases bases while ligands are Lewis acids.
(4) Electron-deficient molecules are Lewis acids.
• The extent of ionization or dissociation is called
­degree of ionization or degree of dissociation and is 2. Which statement is universally correct about an acid
­represented by α. and a base?
(1) The number of replaceable H-atoms of an acid is
• The degree of dissociation (α) for weak acids and
called its basicity.
weak bases is always less than one.
(2) Acids burn skin.
• At infinite dilution, the degree of dissociation of weak (3) An acid must contain at least one H–atom.
acids or weak bases approaches unity. (4) An acid turns red litmus to blue.
C 0 0 initial concentration 3. In water the acids HClO4, HCl, H2SO4 and HNO3
+ −
• HA  H + A ­exhibit the same strength as they are completely ion-
C (1 − α ) Cα C α equilibrium concentration ized in water (a base). This is called ........... of the
solvent water.
[H + ][A − ] Cα × Cα
Ka = = = Cα 2 (neglecting α in (1) Strength (2)  Capacity
[HA ] C(1 − α ) (3) Buffer effect (4)  Levelling effect
the denominator)
4. Which is not correct for Lewis acids?
• The concentration of H+ ion is given by
+
(1) They contain at least one vacant orbital.
[H+] = K ac ∵[H ] = Cα (2) They have a tendency to accept electrons.

Chapter_7b.indd 5 3/26/2014 3:15:34 PM

 7B.6  Objective Chemistry - Vol. I

(3) The smaller ion has greater acidic strength. (3) [Al(H2O)3 (OH)3]–

(4) In case of ions, the strength of acid is inversely (4) [Al(H2O)2 (OH)4]–
proportional to its charge.
13. Which of the following is the strongest acid?
5. Arrange H2SO4 (I), H3PO4 (II) and HClO4 (III) in (1) ClO3(OH) (2) ClO2(OH)
­decreasing order of acidic nature. (3) SO(OH)2 (4)  HCOO–
(1) I > III > II (2)  I > II > III
14. Mg(OH)Cl is an example of
(3) III > II > I (4)  III > I > II
(1) Acid salt (2)  Basic salt
6. The increasing order of basic strength of Cl–, CO32–, (3) Neutral salt (4)  Amphoteric salt
CH3COO–, OH–, F– is
15. Which equilibrium can be described as Lewis acid–
(1) Cl − < F − < CH 3 COO − < CO32 − < OH −
base reaction but not Bronsted acid–base reaction?
(2) Cl − < F − < CO32 − < CH 3 COO − < OH −
(1) H 2 O + CH 3 COOH → H 3 O + + CH 3 COO −
(3) CH 3 COO − < Cl − < F − < CO32 − < OH −
(2) 2NH 3 + H 2SO 4 → 2NH +4 + SO24 −
(4) F − < CO32 − < Cl − < CH 3 COO − < OH −
(3) CH 3 COOH + NH 3 → CH 3COONH 4
7. The wrong statement among the following is (4) [Cu(H 2 O) 4 ]2 + + 4NH 3 → [Cu(NH 3 ) 4 ]2 + + 4H 2 O
(1) Conjugate acid–base pair differs by a proton.
(2) The conjugate base of H3BO3 is H2BO3–. 16. The acidic nature of zinc oxide is shown from the
(3) According to Lewis, neutralization is the forma- ­formation of the salt
tion of dative bond. (1) NaZnO2 (2) Na2ZnO2
(4) According to Bronsted–Lowry theory neutraliza- (3) Na2ZnO2 (4) ZnSO4
tion is transfer of proton. 17. A is a weaker acid than B if
8. According to Bronsted–Lowry concept the correct (1) A is more easily decomposed than B when heated
order of strength of bases follows the order (2) A is not corrosive
(1) CH 3 COO − > OH − > Cl − (3) A is less ionized than B when dissolved in a ­solvent
(2) OH − > CH 3 COO − > Cl − (4) A is more ionized than B when dissolved in a
(3) CH 3 COO − > Cl − > OH − solvent
(4) OH − > Cl − > CH 3 COO − 18. Which is correct for equilibrium?
9. Arrange NH4+, H2O, H3O+, HF and OH– in increasing CH3COOH + HF   
 CH3COOH2+ + F–
order of acidic nature –
(1) F is the conjugate acid of CH3COOH
(1) OH − < H 2 O < NH 4+ < HF < H 3 O + (2) F– is the conjugate base of HF
(2) H 3 O + < HF > H 2 O > NH +4 > OH − (3) CH3 COOH is the conjugate acid of CH3COOH2+
(3) NH +4 < HF < H 3 O + < H 2 O < OH − (4) CH3COOH2+ is the conjugate base of CH3COOH
(4) H 3 O + < NH 4+ < HF < OH − < H 2 O
19. The decreasing order of acidic nature of perchloric
10. Hydrochloric acid is a stronger acid than acetic acid acid, sulphuric acid and sodium bisulphate is
because (1) sulphuric acid > sodium bisulphate > perchloric
(1) It can neutralize large quantity of alkali. acid
(2) It can corrode anything it comes in contact. (2) sodium bisulphate > sulphuric acid > perchloric
(3) It ionizes completely into ions in an aqueous acid
­solution. (3) perchloric acid > sodium bisulphate > sulphuric
(4) It ionizes partially into ions in aqueous solution. acid
11. Aqueous solution of acetic acid contains (4) perchloric acid > sulphuric acid > sodium ­bisulphate
(1) CH3COOH, H+ 20. In the dissociation
(2) CH3COO–, H3O+, CH3COOH H2A K 1
→ H+ + HA–
(3) CH3COO–, H3O+, H+
HA– K 2
→ H+ + A2–
(4) CH3COOH, CH3COO–, H+
(1) K1 is equal to K2
12. The conjugate base of [Al(H2O)3 (OH)3] is (2) K1 is smaller than K2
(1) [Al(H2O)3 (OH)2O]– (3) K1 is greater than K2

(2) [Al(H2O)3 (OH)2]+ (4)  K1 is negligible

Chapter_7b.indd 6 3/26/2014 3:15:39 PM

 Ionic Equilibrium  7B.7

21. The decreasing order of the strength of bases OH–, (3) Two conjugate acid–base pairs are formed
NH2–, HC ≡ C– and CH3CH2– (4) One conjugate acid–base pair is formed
(1) CH3CH2– > NH2– > HC ≡ C– > OH–
(2) HC ≡ C– > CH3CH2– > NH2– > OH– Answers
(3) OH– > NH2– > HC ≡ C– > CH3 – CH2–
(4) NH2– > HC ≡ C– > OH– > CH3 – CH2–  (1) 3  (2) 1  (3) 4  (4) 4  (5) 4
 (6) 1  (7) 2  (8) 2  (9) 1 (10) 3
22. Which statement is correct?
(11) 2 (12) 4 (13) 1 (14) 2 (15) 4
(1) An acid and its conjugate base react to form salt (16) 2 (17) 3 (18) 2 (19) 4 (20) 3
and water (21) 1 (22) 2 (23) 4 (24) 3 (25) 2
(2) The conjugate base of a weak acid is a strong base (26) 1 (27) 3 (28) 3
(3) The acid H2O is its own conjugate base
(4) The conjugate base of a strong acid is a strong
base
IoniZation constant of water and
23. Which statement is correct? its ionic product
(1) All Bronsted bases are also Lewis bases
(2) All Lewis acids are not Bronsted acids • The very low electrical conductivity of pure water is
(3) All cations are acids and all anions are bases due to self-ionization of water:
(4) All H 2 O  H + + OH −
24. The dissociation constant values of three acids A, B • The dissociation constant of water
and C are 1.8 × 10 −5 , 1.5 × 10 −4 and 5.2 × 10 −8 respec- [H + ] [OH − ]
tively. ­Correct order of increasing basic character of K=
[H 2 O]
their conjugate bases is
(1) A– > B– > C– (2) B– > A– > C– • Taking the concentration of undissociated water is
(3) B < A < C
– – –
(4) A– < B– < C– nearly constant, the ionic product of water Kw is given
as Kw = [H+] [OH–] and its value is 1 × 10–4 mol2 litre–2
25. The 104 Ka values for the acids acetic, hydrofluoric, at 25°C.
formic and nitrous are 6.7, 4.5, 1.8 and 0.18 but not
• The ionic product of the concentration of H+ and OH–
in the correct order. The correct acid strengths are
ions at any temperature of pure water or an aqueous
(1) HF = 0.18, HNO2 = 1.8, HCOOH = 4.5, solution is known as ionic product of water.
CH3COOH = 6.7
(2) HF = 6.7, HNO2 = 4.5, HCOOH = 1.8, CH3COOH • With increase in temperature, ionic product of water
= 0.18 also increases.
(3) HF = 1.8, HNO2 = 0.18, HCOOH = 4.5, • In pure water or in neutral solutions the concentrations
CH3COOH = 6.7 of H+ and OH– ions are equal. At 25°C
(4) HF = 6.7, HNO2 = 0.18, HCOOH = 4.5,
[H+] = [OH–] = K w = 1× 10 −14 × 1 × 10 −7
CH3COOH = 1.8
• If [H+] = [OH–] in an aqueous solution, it is neutral.
26. An element which can exist as a positive ion in acid
solution and also as –ve ion in basic solution is called • If [H+] > [OH–] in an aqueous solution, it is called an
acidic solution.
(1) Amphoteric (2)  Acidic
(3) Basic (4)  Neutral • If [H+] < [OH–] in an aqueous solution, it is called a
1 basic solution.
27. The ionization constant of a base is . The base is
­described as 10 • If we know the concentration of any one of the H+
and OH– ion the concentration of the other ion can be
(1) Normal base (2)  Strong base
calculated.
(3) Weak base (4)  None of these
Kw 1 × 10 −14
28. According to Bronsted–Lowry theory, in a neutraliza- [H+] = =
[OH − ] [OH − ]
tion reaction
(1) A salt is formed K w 1× 10 −14
[OH–] = =
(2) Two salts are formed [H + ] [H + ]

Chapter_7b.indd 7 3/26/2014 3:15:41 PM

 7B.8  Objective Chemistry - Vol. I

pH scale
  Objective Questions
• pH scale was proposed by S. P. L Sorensen to express
the low concentration of hydrogen ion. It is known as 29. pH of water is 7 at 25°C. If water is heated to 70°C the
pH scale. (1) pH will decrease and solution becomes acidic
• Whether a solution is neutral or acidic or basic is always (2) pH will increase and solution becomes basic
expressed as the reciprocal of H+ ion concentration. (3) pH will remain constant and solution is neutral
1 (4) pH will decrease but solution will be neutral
pH = –log [H+] or log
[H + ] 30. Which of the following statements is wrong?
[H+] = 10–pH (1) pH of rain water is 7.
• Negative logarithms of different terms can be repre- (2) Soda water has a pH greater than 7.
sented as follows: (3) Ionic product of water increases with increase in
pOH = –log [OH–] pKb = –log Kb temperature.
pM+ = –log [M+]    pK = –log K(equilibrium (4) The unit of ionic product of water Kw is mole2
constant) litre –2.
pKa = –log Ka, pKw = –log Kw 31. The OH– ion concentration of a weak base is
pH + pOH = 14, pH = 14 – pOH (1) CKb (2) CK b
• Since in pure water and in neutral aqueous solutions
Kb
[H+] = [OH–] = 1× 10 −7 , pH is equal to 7. (3)  (4) K b
C
• For strong bases the concentration of OH– is equal to
the normality or molarity × acidity of the base. 32. At 90°C pure water has H3O+ = 10–6 mol litre–1. The
value of Kw at 90°C is
• Several industrial processes and biological processes
generally occur at specified pH values only. (1) 10–6 (2) 10–12
–14
(3) 10 (4) 10–8
• In acid solutions, [H+] is greater than1× 10 −7 . So, pH is
less than 7 and for acidic solutions pH varies from 1 to 7. 33. Pure water is kept in a vessel and it remains exposed
• In alkaline solutions, [H+] is less than1× 10 −7 . So, pH to atmospheric CO2 which is absorbed. Then the pH
is greater than 7 and for all basic solutions pH varies will be
from 7 to 14. (1) greater than 7
• Since Kw changes with temperature the pH also (2) less than 7
­changes with temperature. (3) 7
(4) depends on ionic product of water
• With decrease in pH acidic character increases while
basic character decreases. 34. The pH of a solution is defined as
• If acid is added to pure water the pH decreases and (1) Negative logarithm of its hydrogen ion concen-
concentration of H+ ion increases. Similarly if base is tration
added to pure water the pH increases and the concen- (2) Negative logarithm of the reciprocal of its hydro-
tration of H+ ion decreases. gen ion concentration
(3) Logarithm of its hydrogen ion concentration
• If the concentration of H+ ion increases by 10 times, the
(4) Hydrogen ion concentration of the solution
pH decreases by one unit or if pH decreases by 1 unit
the concentration of H+ ion increases by 10 times. 35. The pH of solutions A, B, C and D are 9.5, 2.5, 3.5
• In case of strong acids (which dissociate completely) and 5.5, respectively. The most acidic solution is
the concentration H+ ion is equal to the normality or (1) A (2)  B
molarity × basicity of the acid. (3) C (4) D
• Whenever equal volumes of two different solutions 36. Which of the following would decrease the pH of
having pH between 1 and 6 are mixed, the pH of the 25 mL of 0.01 molar HCl?
resultant solution will be 0.3 more than the lower pH. (1) Magnesium metal
• Whenever equal volumes of two different solutions of (2) Copper powder
pH between 8 and 14 are mixed, the pH of the resultant (3) 25 ml of 0.005 molar NaOH
solution will be 0.3 less than the higher pH. (4) 25 ml of 0.05 M HCl

Chapter_7b.indd 8 3/26/2014 3:15:44 PM

 Ionic Equilibrium  7B.9

37. The ionic product of water changes when 45. The hydrogen ion concentration in a solution of weak
(1) an acid is added to it acid of dissociation constant Ka and concentration C
(2) a base is added to it is nearly equal to
(3) whether a base or acid is added to it Ka C
(4) temperature is changed (1)  (2) 
C Ka
38. The pH of a solution is 5. Its hydrogen ion concentration
is decreased by hundred times, the solution will then be (3) Ka . C (4)  K a ⋅ C
(1) neutral (2)  acidic 46. The extent of ionization or degree of dissociation
(3) basic (4)  more acidic ­increases
39. The pH of a solution is increased from 3 to 6. Its H+ ion (1) with the increase in the concentration of solute
concentration will be (2) on decreasing the temperature of the solution
(3) on adding excess of water
(1) reduced to half
(4) on stirring the solution
(2) doubled
(3) reduced by 1000 times 47. Degree of dissociation of weak acid and weak base
(4) increased by 1000 times are the same. If 0.001 M solution of weak acid has
pH = 5.0 then the pH of 0.001 M weak base is
40. The pH of a 0.01 N solution of monobasic acid is
four. Then the acid involved will be (1) 9 (2) 5 (3) 10 (4) 8
(1) weak (2)  strong 48. A monoprotic acid in 1.00 M solution is 0.01%
(3) strong or weak (4)  cannot be predicted ­ionized. The dissociation constant of this acid is
41. False statement among the following is (1) 1× 10 −4 (2) 1× 10 −6
−8
(3) 1× 10 (4)  10 −5
(1) pH of 10–4 (M) HCl is 4
(2) pH of 10–3 (M) HCl is 3 49. The pH of 1% ionized 0.1 M of a weak monoprotic
(3) pH of 10–6 (M) HCl is 6 acid is
(4) pH of 10–10 (M) HCl is 10 (1) 1 (2) 2 (3) 3 (4) 11
42. Which of the following will have nearly equal H+ 50. One litre of water contains 10–7 moles of H+ ions.
concentration? ­Degree of ionization of water is
(a) 100 ml 0.1 M HCl mixed with 50 ml water (1) 1.8 × 10 −7 % (2)  1.8 × 10 −9 %
(b) 50 ml 0.1 M H2SO4 mixed with 50 ml water −7
(3) 3.6 × 10 % (4)  3.6 × 10 −9 %
(c) 50 ml 0.1 M H2SO4mixed with 100 ml water
(d) 50 ml 0.1 M HCl mixed with 50 ml water 51. The dissociation constants of two acids HA1, and HA2
are 3.6 × 10 −4 and 1.8 × 10 −5, respectively. The relative
(1) a, b (2)  b, c (3)  a, c (4)  c, d
strengths of the acids will be
43. The ionic product of water is defined as (1) 1:4 (2) 4:1 (3) 1:16 (4) 16:1
(1) The product of the concentration of proton and
52. For an acid
hydroxyl ion in pure water
(2) The product of the concentration of acid and CH 3 COOH + H 2 O  CH 3 COO − + H 3 O +; K1
­hydroxyl ion in aqueous solution and for a base
(3)  The ratio of the concentration of dissociated CH 3 COO − + H 2 O  CH 3 COOH + OH; K2
­water to the undissociated water Then
(4) All the above (1) K1 ⋅ K2 = Kw
(2) log K1 + log K2 = log Kw
44. The relation for calculating pH of a weak base is (3) pK1 + pK2 = pKw
1 1 (4) all are correct
(1) pH = pKw – pKb + log C
2 2
53. Which of the following is correct?
1 1
(2) pH = pKw + pKb – log C (1) Ka (weak acid) × Kb (conjugate weak base) = Kw
2 2
1 1 (2) Ka (strong acid) × Kb (conjugate strong base) = Kw
(3) pH = pKw – pKa + log C (3)  Ka (weak acid) × Kb (weak base) = Kw
2 2
(4) None (4) Ka (weak acid) × Kb (conjugate strong base) = Kw

Chapter_7b.indd 9 3/26/2014 3:15:51 PM

 7B.10  Objective Chemistry - Vol. I

54. Consider the following reactions (1) the ionization of HCl is incomplete
   (i)  CO32 − + H 2 O  HCO3− + OH − (2) the ionization of water is negligible
 (ii)  CO2 + H 2 O  H 2 CO3 (3) the ionization of water at such a low concentra-
(iii)  NH 3 + H 2 O  NH 4 OH tion of HCl is significant
 (iv)  HCl + H 2 O  H 3 O + + Cl − (4) the ionization of both HCl and water are negligible
Which pair of reactions proves that water is ampho- 64. HClO is a weak acid. The concentration of H+ ions in
teric? 0.1 M solution of HClO (Ka = 5 × 10 –8) will be equal to
(1) i and ii (2)  ii and iii (1) 7.07 × 10 −5 M (2)  5 × 10 −7 M
(3) iii and iv (4)  i and iii −4
(3) 5 × 10 M (4)  7 × 10 −4 M
55. What is correct about ionic product of an electrolyte? 65. The [H3O+] in the rain water of pH = 4.35 is
(1) it is always equal to solubility product (1) 4.5 × 10 −5 M (2)  6.5 × 10 −5 M
(2) can be < or equal to Ksp −5
(3) 9.5 × 10 M (4)  12.5 × 10 −5 M
(3) always < Ksp
(4) can be < or equal to or > Ksp 66. The [OH–] in 100 mL of 0.015 M HCl (aq) is
(1) 5 × 10 −12 M (2)  3 × 10 −10 M
56. The pH of a solution is 5.0. To this solution sufficient −13
(3) 6.7 × 10 M (4)  2.0 × 10 −9 M
acid is added to decrease the pH to 2.0. The increase
in hydrogen ion concentration is 67. Which solution will have pH closer to 1.0?
(1) 1000 times (2)  5/2 times (1) 100 mL of (M/10) HCl + 100 mL of (M/10)
(3) 100 times (4)  5 times NaOH
(2) 55 mL of (M/10) HCl + 45 mL of (M/10) NaOH
57. Which addition would not change the pH of 10 ml of (3) 10 mL of (M/10) HCl + 90 mL of (M/10) NaOH
dilute hydrochloric acid? (4) 75 mL of (M/10) HCl + 25 mL of (M/10) NaOH
(1) 20 ml of the same hydrochloric acid
(2) 5 ml of pure water 68. The pH of a solution produced when an aqueous solu-
(3) 20 ml of pure water tion of strong acid pH 5 mixed with equal volume of
(4) 10 ml of concentrated hydrochloric acid an aqueous solution of strong acid of pH 3 is
(1) 3.3 (2) 3.5 (3) 4.5 (4) 4.0
58. 0.4 g of NaOH present in 1-litre solution shows
the pH 69. Which of the following when added to 25 mL of a
(1) 12 (2) 2 (3) 6 (4) 10 1.0 M solution of sodium hydroxide would cause the
largest change in pH?
59. The gastric juice in our stomach contains enough
(1) 25 cc of 1.0 M HCl
­hydrochloric acid to make the hydrogen ion concen-
(2) 25 cc of 2.0 M HCl
tration about 0.01 mole/litre. The pH of the gastric
(3) 25 cc of 0.5 M HCl
juice is
(4) 25 cc of distilled water
(1) 0.01 (2) 1 (3) 2 (4) 14
70. The pH of a soft drink is 3.82. Its H+ ion concentra-
60. 0.2 molar solution of formic acid is 3.2% ionized. Its
tion will be
ionization constant is
(1) 1.96 × 10 −2 mol/litre
(1) 9.6 × 10 −3 (2)  2.1× 10 −4
−6 (2) 1.96 × 10 −3 mol/litre
(3) 1.25 × 10 (4)  4.8 × 10 −5
(3) 1.5 × 10 −4 mol/litre
61. The pH of the solution containing 10 mL of 0.1 N (4) 1.96 × 10 −1 mol/litre
NaOH and 10 ml of 0.05 M H2SO4 would be
(1) zero (2)  1 (3)  > 7 (4)  7 Answers
62. An aqueous solution contains a substance which
yields 4 × 10 −3 mol litre –1 ion H3O+. If log 2 is 0.3010 (29) 4 (30) 2 (31) 2 (33) 2 (34) 1
the pH of the solution is (35) 2 (36) 4 (37) 4 (38) 1 (39) 3
(40) 1 (41) 4 (42) 3 (43) 4 (44) 1
(1) 1.5 (2) 2.398 (3) 3.0 (4) 3.4
(45) 4 (46) 3 (47) 1 (48) 3 (49) 2
63. The pH of a 1 × 10 −8 M aqueous solution of HCl is (50) 1 (51) 2 (52) 4 (53) 4 (54) 3
slightly less than 7 because (55) 4 (56) 1 (57) 1 (58) 1 (59) 3

Chapter_7b.indd 10 3/26/2014 3:15:57 PM

 Ionic Equilibrium  7B.11

(60) 2 (61) 3 (62) 2 (63) 3 (64) 1 • The solutions of salts of strong acid and a weak base
(65) 1 (66) 3 (67) 4 (68) 1 (69) 2 hydrolyze in water producing acidic solution due to
(70) 3 cationic hydrolysis. The pH of their solutions is less
than 7. The hydrolysis constant
K
types of salts Kh = w
Kb
• The reaction between an acid and a base to form a salt Degree of hydrolysis, h, for such salts is
and water is called neutralization or the neutralization
is a process of combining H+ from an acid and OH– Kw
h=
from a base to form neutral water. Kb × C
• The salts formed by the loss of all possible protons are pH of such solution can be calculated as
called normal salts, e.g., NaCl, Na2SO4, Na3PO4, etc. 1
pH = [ pK w − log C − pK b ]
• Salts formed by incomplete neutralization of polyba- 2
sic acids are called acid salts. Such salts still contain • Salts of strong bases and acids hydrolyze in water
one or more replaceable hydrogen atoms. For example, producing a basic solution due to anionic hydrolysis.
NaHCO3, NaHSO4, NaH2PO4, Na2HPO4, etc. The pH of their solutions is more than 7. The hydroly-
• Salts formed by incomplete neutralization of p­ olyacidic sis constant
bases are called basic salts. Such salts still contain one K
Kh = w
or more hydroxyl groups. Ka
e.g., Mg(OH)Cl, Fe(OH)2Cl, Bi(OH)2Cl, etc.
Degree of hydrolysis, h, for such a salt is
• Salts formed by the addition of two independent stable
compounds which exist in solid state but ionize com- Kw
h=
pletely in their aqueous solutions and give test for all Ka × C
the ions present in them are called double salts. pH of such a solution can be calculated as
e.g., KCl · MgCl2 · 6H2O, alums, etc. 1
• Salts formed by the addition of two independent stable pH = [ pK w − log C − pK a ]
2
compounds which exist in both solid and in solutions • The nature of the solution of a salt of weak acid and
and do not ionize completely in water are called
weak base depends on their dissociation constant
­complex salts, e.g., K4[Fe(CN)6]; [Co(NH3)6]Cl3, etc.
­values. Their hydrolysis constant
• The salts which furnish more than one cation or more Kw
than one anion when dissolved in water are called Kh =
mixed salts. Ka × K b
e.g., Ca(OCl)Cl; Na(NH4)HPO4, etc. Degree of hydrolysis, h, for such a salt is
• The nature of solution formed during the neutraliza- Kw
tion is not always neutral. It depends on the particular h=
Ka × K b
acid and a particular base involved in the reaction and
the nature of the salt formed in the neutralization. pH of such a solution can be calculated as
1 1 1
pH = pK w + pK a − pK b
Hydrolysis of Salts and the pH of their 2 2 2
Solutions If pKa = pKb, then pH = 7.
• The salt hydrolysis is opposite reaction to neutrali- If pKa > pKb, then pH will be more than 7.
zation reaction of an acid and a base. If pKa < pKb, then pH will be less than 7.
• Salt hydrolysis is the reaction in which anion or cation
or both of a salt react with solvent water to produce
alkalinity or acidity. The alkalinity or acidity produced   Objective Questions
due to salt hydrolysis is very little. 71. The phenomenon of interaction of anions and ­cations
• Salts of strong acids and strong bases do not hydro- furnished by electrolyte with H+ and OH– ions of
lyze. Their solutions are neutral, pH of their solutions ­water to produce acidic nature or alkalinity is known
is 7, e.g., KCl, NaCl, KBr, K2SO4, KNO3, etc. as hydrolysis. In hydrolysis

Chapter_7b.indd 11 3/26/2014 3:16:00 PM

 7B.12  Objective Chemistry - Vol. I

(1) The pH may either increase or decrease (3) No hydrolysis in both
(2) All the salts (except those made up with strong (4) Hydrolysis of the latter but not the former
acid and base) undergo hydrolysis
79. The correct relation for hydrolysis constant of
(3) The variation of pH depends upon the nature of
NH4CN is
salt as well as on the temperature
(4) All Kw Kw
(1)  (2) 
72. The pair of salts that does not hydrolyze Ka Ka × K b
(1) FeCl3, SnCl4 (2) CaCl2, K2SO4 Kh K
(3) CuSO4, AlCl3 (4) NH4Cl, Na2CO3 (3)  (4)  a
C Kb
73. A salt of strong acid and a weak base is dissolved in 80. The correct statement is
water. Its hydrolysis in solution is (1) NH4Cl gives an alkaline solution in water
(1) not affected by heating (2) CH3COONa gives an acidic solution in water
(2) increased by adding a strong acid (3) CH3COOH is a weak acid
(3) suppressed by adding a strong acid (4) NH4OH is a strong base
(4) suppressed by dilution
81. On adding potassium cyanide to water
74. Hydrolysis constant of a salt of weak acid and weak (1) pH will increase
base is inversely proportional to (2) pH will decrease
(1) Dissociation constant of weak acid (3) pH will not change
(2) Dissociation constant of weak base (4) electrical conductance will not change
(3) Ionic product of water
(4)  Dissociation constant of both weak acid and 82. A solution of borax has a pH of approximately
weak base (1) >7 (2)  <7
(3) = 7 (4)  between 4 and 5
75. The aqueous solution of a salt is alkaline. This shows
that salt is made from 83. Which of the following statements is false?
(1) A strong acid and strong base (1) Aqueous solution of sodium bicarbonate is more
(2) A strong acid and weak base basic than sodium carbonate solution
(3) A weak acid and weak base (2) Solution of sodium acetate turns red litmus to blue
(4) A weak acid and strong base (3) If the dissociation constants of a weak acid and
weak base constituting the salt are same its aque-
76. Which salt gives basic solution on dissolution in ous solution has a pH of 7
­water? (4) Acidic nature of copper sulphate solution is due
(1) Salt of weak acid and weak base to cationic hydrolysis
(2) Salt of strong acid and strong base
(3) Salt of strong acid and weak base 84. The pKa of a weak acid HA is greater than the pKb
(4) Salt of weak acid and strong base value of a weak base BOH. An aqueous solution of
the salt AB formed by the neutralization of this acid
77. Which of the following statements is false? by the base will be
(1) Hydrolysis of the salt of strong acid and weak (1) neutral
base is called cationic hydrolysis (2) basic
(2) Hydrolysis of the salt of weak acid and strong (3) alkaline
base is known as anionic hydrolysis (4) acidic if the solution is dilute
(3) Aqueous solution of aluminium chloride is acidic
due to hydrolysis of Al3+ ion 85. Ka and Kb values of formic acid and ammonium hy-
(4) Aqueous solution of sodium carbonate is basic droxide are 2 × 10–4 and 1.8 × 10–5, respectively. An
due to hydrolysis of Na+ ion aqueous solution of ammonium formate is
(1) basic (2)  acidic
78. The pH of solutions of both ammonium acetate and
(3) neutral (4)  cannot be predicted
sodium chloride is 7 due to
(1) Hydrolysis in both cases 86. The hydrolysis constant of a salt of weak acid
(2) The former hydrolyzes and not the latter (Ka = 2 × 10–6) and of a weak base (Kb = 5 × 10–7) is

Chapter_7b.indd 12 3/26/2014 3:16:01 PM

 Ionic Equilibrium  7B.13

(1) 10 (2)  10–2 • To acidic buffer solution if a little acid is added the
(3) 2 × 10 –2 (4) 5 × 10–3 H+ ions are removed by combining with the conjugate
base of the weak acid and thus the pH will not change.
87. The hydrolysis constant Kh of a salt of sodium hy-
droxide and weak acid (HX) if the Ka of the acid is • To acidic buffer solution if a little base is added the
5 × 10–6 is OH– ions are neutralized by the H+ ions of the weak
acid. The number of H+ ions removed by neutralization
(1) 2 × 10–8 (2) 5 × 10–6
is formed by the dissociation of weak acid and thus pH
(3) 2.5 × 10 –7
(4)  5 × 10–9
will not change.
Answers • Example for acidic buffer solution
CH3COOH  CH3COO– + H+
(71) 4 (72) 2 (73) 3 (74) 4 (75) 4 CH3COONa  CH3COO– + Na+
(76) 2 (77) 2 (78) 2 (79) 3 (80) 1
• Basic buffer solutions are made up of mixing a weak
(81) 1 (82) 1 (83) 2 (84) 2 (85) 2
base and its salt of strong acid.
(86) 4
• To basic buffer solution if a little acid is added the H+
ions are neutralized by OH– ions of the weak base.
Common ion Effect on the The number of OH– ions removed by neutralization is
formed by the dissociation of weak base and thus pH
ioniZation of Acids and Bases
will not change.
• If a strong acid or a salt having common anion to weak • To a basic buffer solution if a little base is added the
acid is added to the solution of weak acid, the ioniza- OH– ions are removed by combining with the conju-
tion of weak acid will be suppressed due to common gate acid of the weak base and thus the pH will not
ion effect. Similarly the ionization of a base gives hy- change.
droxide and corresponding cation. If any one of the
• Example for a basic buffer solution is
product is added to the base solution, the ionization of
base will be suppressed. For example, NH4OH  NH4+ + OH–
CH3COOH  CH3COO– + H+ NH4Cl  NH4+ + Cl–
NH4OH  NH4+ + OH– • pH of buffer solutions are calculated by using
If an acid or sodium acetate is added to acetic acid the Henderson–Hesselbalch equations.
ionization of acetic acid will be decreased. Similarly if • pH of acid buffer solution is given by
a base or ammonium chloride is added to ammonium
hydroxide the ionization of ammonium hydroxide will pH = –log Ka + log
[Salt ] = pKa + log
[Salt ]
be suppressed. [ Acid ] [ Acid ]
• pOH = –log Kb + log
[Salt ]
Buffer Solutions [ Base]
• The solution which maintains a fairly constant pH
= pKb + log
[Salt ]
value and resists changes in the hydrogen ion concen- [ Base]
tration on dilution or on adding small amount of acid
or base is called a buffer solution. pH = 14 – pOH
• Buffer solution has a definite pH. Its pH remains unal- • Buffer capacity is the volume of molar acid and molar
tered either on keeping for long time or on dilution. Its alkali to change the pH of one litre of buffer solution
pH is very slightly changed by the addition of a strong by 1 unit.
acid or a strong base. Buffer capacity
• The ability of the buffer solution to resist the changes No. of moles of acid or base added =
in pH value on addition of small amount of an acid or to 1litre of buffer solution 3
a base is called a buffer action. = K sp /4
pH change
• Acidic buffer solutions are made up mixing weak • Buffer capacity depends on pKa or pKb values of a
acid and its salt of a strong base: weak acid or a weak base and also on the concentration
e.g., CH3COOH + CH3COONa of the salt present in a buffer solution.

Chapter_7b.indd 13 3/26/2014 3:16:04 PM

 7B.14  Objective Chemistry - Vol. I

• If pH of a buffer solution is equal to pKa or pKb the 91. Henderson’s equation used to calculate the pOH of a
buffer capacity is maximum. basic buffer is
• Salts of weak acid and weak base will act as buffer [Salt ]
(1) pOH = pKb + log
solution, e.g., CH3COONH4. Addition of little acid [ Base]
or base to KCl or NaCl solution changes pH greatly
(2) pOH = pKb – log
[Salt ]
but the addition of little acid or base to CH3COONH4
­solution its pH does not change.
[ Base]
• The ampholytes or the amphoteric electrolytes are the (3) pOH = pKb + log
[ Base]
substances which can act both as an acid and a base [Salt ]
e.g., proteins, amino acids, etc.
(4) pOH = pKb – log
[ Base]
• NH2CH2COOH + H2O  NH2CH2COO– + H3O+
[Salt ]
 (as acid)
+
NH2CH2COOH + H3O  N H3CH2COOH + H2O
+ 92. The most important buffer in blood consists of
 (as base) (1) HCl and Cl– (2) H2CO3 and HCO3–
–
+ –
The doubly charged ion (N H3 CH2COO ) at a particu- (3) H2CO3 and Cl (4)  HCl and HCO3–
lar pH is known as zwitter ion or amphion or dipolar 93. The following reactions are known to occur in the
ion and can act as a buffer. body
CO2 + H2O  H2CO3  H+ + HCO–3
If CO2 escapes from the system then
  Objective Questions (1) pH will decrease
88. Which of the following statement is false? (2) Hydrogen ion concentration will diminish
(1) If 1 M CH3COONa is added to 1M CH3COOH, (3) H2CO3 concentration will be unaltered
pH of the solution decreases (4) The forward reaction will be promoted
(2) If water is added to a mixture of CH3COOH + 94. A mixture of a weak acid (say acetic acid) and its salts
CH3COONa its pH remain constant with a strong base (say sodium acetate) acts as a buff-
(3) If HCl is added to acetic acid its ionization will er solution. Which other pair has similar ­properties?
be suppressed (1) HCl and NaCl (2)  NaOH and NaNO3
(4) If a crystal of NH4Cl is added to NH4OH solution (3) KOH and KCl (4)  NH4OH and NH4Cl
its pH increases
95. The following equilibrium exists in an aqueous s­ olution
89. The wrong statement among the following is
CH3COOH  CH3COO– + H+
(1) Buffer solutions have reserve pH
If dil. HCl is added to this solution
(2) An acidic buffer mixture can be prepared by mix-
ing a solution of formic acid and sodium formate (1) the equilibrium constant will increase
(3) Buffer solution resist the change in pH by the (2) the equilibrium constant will decrease
­addition of an acid or base (3) H+ ion concentration will increase
(4) Addition of sodium acetate to a buffer solution (4) acetate ion concentration will decrease
of sodium acetate and acetic acid does not affect 96. In a buffer solution consisting of a weak acid and
its pH its salt, the ratio of concentration of salt to acid is
90. The relation for calculating pH of a solution contain- ­increased 10 fold, then the pH of the solution will
ing weak acid and its salt is (1) increase by one
(2) increase by 10 fold
(1) pH = pKa + log
[Salt ] (3) decrease by one
[ Acid ] (4) decrease by 10 fold

(2) pH = pKa – log

[Salt ] 97. Which of the following statements is wrong?
[ Acid ] (1) for an acid buffer solution the pH can be i­ ncreased

(3) pH = pKa + log

[ Acid ] by increasing the concentration of salt
(2) for a basic buffer solution the pH can increased
[Salt ] by decreasing the concentration of base
(4) All

Chapter_7b.indd 14 3/26/2014 3:16:07 PM

 Ionic Equilibrium  7B.15

(3) buffer capacity of a buffer solution is maximum 105. If 50 mL of 0.2 M KOH is added to 40 mL of
when the ratio of salt/acid or base is 1 0.57 M HCOOH, the pH of the resulting solution is
(4) the number of moles of acid or base required by (Ka > 1.8 × 10–4)
one litre of buffer solution to alter its pH by one (1) 3.75 (2) 5.6 (3) 7.5 (4) 3.4
unit is called buffer efficiency
106. A solution prepared by dissolving equal number of
  98. Which one of the pairs given below is best suited to moles of HOCl (Ka = 3.2 × 10–8) and NaOCl is a
prepare a buffer of pH = 9? ­buffer of pH
(1) CH3COOH + CH3COO– (1) 8.0 (2) 3.2 (3) 7.5 (4) 4.8
(2) H2CO3 + HCO3–
(3) NH4+ + NH4OH 107. A buffer solution is prepared by mixing 10 mL of
(4) H2PO4– + HPO42– 1 M acetic acid and 20 mL of 0.5 M sodium acetate
and then diluted to 100 mL with distilled water of the
  99. Which of the following mixture can act as a buffer buffer solution
solution?
(1) 3.84 (2) 4.76 (3) 4.34 (4) 5.21
(1) 1 litre of 0.2 N CH3COOH + 1 litre of 0.2 N NaOH
(2) 1 litre of 0.1 N CH3COOH + 1 litre of 0.2 N NaOH 108. The pH of a buffer solution prepared by mixing
(3) 1 litre of 0.2 N CH3COOH + 1 litre of 0.1 N NaOH 20 mL of 0.1 M NH4OH and 20 mL of 1M NH4Cl is
(4) All the above 8.2. The pKb of NH4OH is
(1) 5.8 (2) 6.8 (3) 4.8 (4) 9.2
100. pH of which of the following buffer will slightly alter
on addition of a strong base 109. The pH of a buffer solution prepared by mixing 50 mL
(1) CH3COOH + CH3COONa of 0.2 M CH3COOH and 250 ml of C ­ H3COONa is
(2) NH4OH + NH4Cl 4.8. What is the concentration of CH3COONa? pKa of
(3) Boric acid + Borax CH3COOH is 4.8.
(4) None (1) 4.0 (2) 0.4 (3) 2.0 (4) 0.2
101. When acid is added to a buffer solution composed of 110. The pKa of certain weak acid is 4.0. What should be
a weak base (B) and its salt with strong acid, then the the salt to acid ratio if we have to prepare a buffer
reaction which occur to maintain the pH is with pH = 5 using the acid and of its salts?
(1) B + H3O+  → BH+ + H2O (1) 4:5 (2) 5:4 (3) 10:1 (4) 1:10
(2) OH + BH 
– +
→ B + H2O
(3) B + H2O  → BH+ + OH– 111. Addition of 0.004 mole of an acid to a litre of a
(4) BH+ + H2O  → B + H3O+ buffer decreases the pH of the buffer by 0.04. Buffer
­capacity is
102. 10 mL of a solution contains 0.1 M NH4Cl + 0.01 M (1) 0.004 (2) 0.04 (3) 0.1 (4) 1
NH4OH. Which addition would not change the pH of
the solution?
(1) Adding 1 mL of water Answers
(2) Adding 5 mL of 0.1 M NH4Cl
(3) Adding 5 mL of 0.1 M NH4OH  (87) 1  (88) 4  (89) 1  (90) 1    (91) 2
(4) Adding 10 mL of 0.1 M NH4Cl  (92) 2  (93) 4  (94) 4  (95) 1  (96) 4
 (97) 2  (98) 3  (99) 2  (100) 1  (101) 1
103. The H+ ion concentration of 0.001 M acetic acid (If (102) 1  (103) 3  (104) 1  (105) 3  (106) 2
Ka = 1.8 × 10–5) is 1.34 × 10–4 g ion/litre. The H+ ion (107) 3  (108) 2  (109) 3  (110) 3
concentration if 0.164 g of CH3COONa is added to
1 litre of 0.001 M CH3COOH will be
(1) 9 × 10–6 (2) 18 × 10–6
(3) 4.5 × 10 –6
(4) 5 × 10–6 Acid–Base Indicator
104. Ka for HCN is 5 × 10–10 at 25°C. For maintaining a • Acid–base indicators are those which exhibit a sharp
constant pH of 9, the volume of 5 M KCN solution colour change at the end point. Acid–base indicators
required to be added to 10 ml of 2 M HCN solution is are either weak organic acids or weak organic bases.
(1) 4 mL (2)  7.95 mL They will exhibit one colour in acid medium and
(3) 2 mL (4)  9.3 mL ­another colour in alkaline medium.

Chapter_7b.indd 15 3/26/2014 3:16:07 PM

 7B.16  Objective Chemistry - Vol. I

• In acid–base titration a sharp pH change takes place coloured. In alkaline medium due to neutralization
at the end point. The range of pH changes at the end of H+ more ionization take place so the solution is
point in acid–base titrations depend on the strength coloured.
and concentration of the acid and base employed in HPh  H+ + Ph–
the titration.
colourless pink coloured
• The range of pH between the lower and higher value • If the indicator is a base, in acid medium more ions
where the colour change of indicator is distinctive is are formed due to neutralization of OH– ions by the
called pH range of the indicator. A suitable indicator acid and so coloured. In alkaline medium the ioniza-
for an acid–base titration must be chosen depending tion is supressed by OH– ions and hence the solution is
upon the pH change at the end point and pH range of ­colourless or slightly coloured.
the indicator. MeOH  Me+ + OH–
• For a successful functioning of an acid–base indicator yellow red
the pH range of the indicator must lie in between the • The colour of the species in a mixture of two coloured
upper and lower limits of the change in pH at the end species will be predominant if the concentration in the
point in an acid–base titration. mixture is above 90%.
• In the titration of a strong acid vs strong base any in- • To exhibit a predominant colour by an indicator at the
dicator whose pH range is in between 3.5 and 10.7 can end point of a titration the pH range of the indicator
be chosen as the pH change at the end point in this must be pKin ±1.
titration is 3.3–10.7. Phenolphthalein or methyl or-
ange or methyl red can be used as an indicator in these Quinonoid   Theory
titrations.
• In the titration of a weak acid vs strong base the indi- • If an indicator has a quinonoid structure it will have
cator which can change colour in a pH range 7.7–9.7 colour and if the indicator has a benzenoid structure it
can be used as an indicator. Methyl orange whose pH will become either colourless or slightly coloured.
range is 3.1 to 4.4 cannot be used but phenolphthalein
(pH range 8.3–10.0) can be used. O O O O
• For a weak base vs strong acid titration (pH range at
the end point 6.3–4.0) phenolphthalein (pH range 8.3– Quinonoid Benzenoid
10) cannot be used but methyl orange (pH range 3.1 to
• Phenolphthalein exists in the benzenoid structure in
4.4) or methyl red (pH range 6.8–8.4) can be used.
acid medium and hence colourless but in alkaline me-
• For a weak acid vs weak base titration no indicator is dium it exists in the quinonoid form. So, it will have a
suitable since pH change is not sharp at the end point. pink colour.
• Universal indicator is a mixture of several indicators • Methyl orange exists in the quinonoid structure in
mixed in fixed proportions. Universal indicator exhib- acid medium, so it is red in colour while in alkaline
its characteristic colours at different pH values. medium it exists in the benzenoid structure. So, it is
yellow in colour.
Theory of Indicators
  Objective Questions
Ostwald Theory
112. The use of methyl orange as an indicator in the volu-
• According to Ostwald, indicators are either weak acids metric determination of the equivalent weight of a
or weak bases and ionize in water forming H+ and In– weak acid would lead to
or In+ and OH– ions: (1) A low value for the equivalent weight
HIn → H+ + In– (2) A high value for the equivalent weight

InOH → In+ + OH– (3) No error in the value
• The In+ or In– ions are coloured while undissociated (4) Improved accuracy
HIn or InOH are colourless or slightly coloured. 113. Phenolphthalein is not a good indicator for titrating
• If the indicator is an acid, in acidic medium the ioniza- (1) NaOH against oxalic acid
tion is suppressed and becomes colourless or slightly (2) Ferrous sulphate against KMnO4

Chapter_7b.indd 16 3/26/2014 3:16:08 PM

 Ionic Equilibrium  7B.17

(3) NaOH against HCl 123. The pKa values of A, B, C and D are 1.5, 4.0, 5.5
(4) NaOH against H2SO4 and 9.4, respectively for a titration at the end point
range if neutralization is in between 6.5 and 10.5. The
114. Which indicator works in the pH range 8–9.8?
best suitable indicator is
(1) Phenolphthalein (2)  Methyl orange
(1) A (2) B (3) C (4) D
(3) Methyl red (4)  Litmus
124. Which one of the following is not a postulate of
115. The best indicator for detection of end point in titra-
­Ostwald’s theory of indicators?
tion of a weak acid and strong base is
(1) The colour of an indicator in solution is due to
(1) Methyl orange (3 to 4)
the ions furnished by it
(2) Methyl red (5 to 6)
(2) The colour of an indicator is due to the ions
(3) Bromothymol blue (6 to 7.5)
­furnished by acidic substance
(4) Phenolphthalein (8 to 9.6)
(3) All indicators are weak acids or bases
116. The alkali not suitable for volumetric determination (4)  Acidic indicators show deep colour in acidic
of HCl using phenolphthalein as an indicator ­solutions and vice versa
(1) NaOH (2)  Ba(OH)2 125. Which one of the following statements is not correct
(3) KOH (4)  NH4OH according to quinonoid theory of indicators?
117. An acid–base indicator has Ka = 3 × 10–5. The acid (1) All indicators are organic compounds, i.e., ­benzene
form of the indicator is red and the basic form is blue. ring derivatives
The [H+] required to change the indicator from 75% (2) One of the benzene rings in the indicator mol-
red to 75% blue is ecules exists in two forms, i.e., benzenoid form
(1) 8 × 10–5 M (2) 9 × 10–5 M and quinonoid form
(3) 1 × 10 M –5
(4) 3 × 10–4 M (3) One form of indicator exists in acidic medium
and the other form exists in the basic medium
1 18. The pKa of an indicator is 4. Its pH range is (4) The benzenoid form has dark colour and quinon-
(1) 1–5 (2)  3–5 oid a light colour
(3) 8–12 (4)  5–8

119. An universal indicator Answers

(1)  consists of a single indicator which changes (111) 1  (112) 2  (113) 1  (114) 4  (115) 4
­colour at different pH ranges (116) 3  (117) 2  (118) 2  (119) 2  (120) 1
(2) consists of a number of indicators which give (121) 3  (122) 4  (123) 4  (124) 3  (125) 4
­different colours at different pH ranges
(3) is used only in the pH range of 0 to 7
(4) is used only in the pH range of 7 to 14
Solubility Product
120. The colour change of an acid–base indicator is due to
the formation of • A solution which remains in contact with undissolved
solute is said to be a saturated solution.
(1) Benzenoid structure
(2) Quinonoid structure • Ionic product is the product of molar concentration
(3) Ionic structure of the ions raised to the power equal to the number of
(4) Covalent bond times each ion occurs in the equation.
• The ionic product of a saturated solution is called its
121. Colour of the indicator is determined by the ratio solubility product (Ksp).
(1) [In–]/[HIn] (2) [HIn]/[In–]
– +
• Solubility is applicable to all solutes, whereas the solubil-
(3) [In ]/[H ] (4)  [In]/[OH–] ity product is only significant in the case of electrolytes.
122. End point in acid–base titration is the point where • Solubility product has a constant value at a given tem-
(1) the base is added to the acid perature, whereas solubility of an electrolyte can be
(2) the base is exactly neutralized with acid varied by the addition of common ion.
(3) the acid is found in slight excess • Solutions are classified into three types based on ionic
(4) none product.

Chapter_7b.indd 17 3/26/2014 3:16:09 PM

 7B.18  Objective Chemistry - Vol. I

1. If ionic product = Ksp the solution is saturated • On saponification of oils and fats (hydrolysis with
2. If ionic product > Ksp the solution is supersaturated NaOH) soap and glycerol will be formed. To ­precipitate
solution and soap NaCl will be added. Due to common ion ­effect
3. If ionic product < Ksp the solution is unsaturated of Na+, soap will be precipitated and this is known as
• The suppression of the degree of ionization of a weak salting out of soap.
electrolyte by the addition of strong electrolyte having Oil + NaOH → Sodium salt + Glycerol
an ion common with the weak electrolyte is known as C17H35COONa  C17H35COO– + Na+
common ion effect.
NaCl → Na+ + Cl–
• Solubility product is useful in knowing (i) the solubil-
• Purification of common salt is based on the precipita-
ity of an electrolyte, (ii) in calculating the solubility
tion of salt by passing HCl gas into saturated solution
of an electrolyte in the presence of a common ion,
of common salt (NaCl)
(iii) ­simultaneous solubility of two electrolytes ­having
common ion, (iv) predicting the direction of ionic NaCl  Na+ + Cl–
­reactions and (v) precipitation of electrolytes.
HCl  H+ + Cl–
• If a solid having general formula AxBy with molar
solubility S is in equilibrium with its saturated solu- ApplicationS of Solubility
tion is represented as product in Analysis
A x B y ( r )  xA y + + yB x − • By using the concept of solubility product and com-
The solubility product for this equilibrium is given as mon ion effect, preferential precipitation of some cati-
Ksp = [Ay+]x [Bx–]y. ons from the mixture under controlled concentrations
• Using the general expression for solubility product, of H+ ion and reagent is carried out.
the solubility product and solubilities (considering the • When HCl is added to a solution containing mixture of
solubility of each compound as S moles/litre) may be cations only AgCl, PbCl2 and Hg2Cl2 are precipitated
expressed as in Ist group since their solubility products are less.
• In the IInd group of qualitative analysis when H2S is
Types of passed in the presence of HCl only second group cati-
electr­ Equation Solubility ons (Pb2+, Hg2+, Cu2+, Cd2+, Bi3+, Sn2+, Sn4+, As3+ and
olyte Example for Ksp product Solubility Sb3+) are precipitated.
AB BaSO4 [Ba2+] [SO42–] Ksp = S2 S = K sp In the presence of HCl the ionization of H2S is sup-
pressed due to common ion effect.
AB2 PbI2 [Pb2+] [I–]2 Ksp = 4S3 S = 3 K sp /4 H2S  2H+ + S2–

HCl → H+ + Cl–
A2B Ag2CrO4 [Ag+]2 [CrO4–]2 Ksp = 4S3 S = 3 K sp /4

In that low concentration of S2– ion, the ionic product
of second group metal ion and the S2– ion exceeds the
AB3 Fe(OH)3 [Fe3+] [OH–]3 Ksp = 27S4 S = 4 K sp /27
solubility product of the second group metal sulphides
and hence they are precipitated. But the values of
A2B3 As2S3 [As3+]2 [S2–]3 Ksp =108S5 S = 5 K sp /108 other group metal sulphides are not exceeded and thus
­remain in solution.
ApplicationS of solubility • In the presence NH4Cl the ionization of NH4OH is
product suppressed due to common ion effect of NH4+ ion
• According to Le Chatelier’s principle if the concentration NH4OH  NH4++ OH–
of any one of the ions in equilibrium state of an electrolyte NH4Cl → NH4+ + Cl–
is increased, it should combine with the oppositely In that low concentration of OH– the ionic product of
charged ion and some electrolyte is precipitated till the OH– ion and third group cation (Fe3+, Al3+ and Cr3+) will
Ksp = Qsp where Qsp is the reaction quotient. exceed the solubility product of their hydroxides and
• If the concentration of one of the ions is decreased hence are precipitated. But the ionic product of other
more salt will dissolve to increase the concentrations group metal hydroxides is less than the solubility prod-
of both the ions till Ksp = Qsp. ucts of their hydroxides and thus remains in solution.

Chapter_7b.indd 18 3/26/2014 3:16:12 PM

 Ionic Equilibrium  7B.19

• In the presence of NH4OH the ionization of H2S (1) a2 (2) 12a2

­increases due to the removal of H+ ions from equilib- (3) 18a3 (4) 2916a8
rium by neutralization.
127. The solubility of AgCl in water at 10oC is 6.2 ×
H2S  2H+ + S2– 10–6 mol/litre. The Kp of AgCl is
NH4OH  NH4+ + OH– 1

In that high concentration of S2– ions the ionic prod- (1) [6.2 ×10 −6 ]2 (2) [6.2 × 10–6]2
uct of S2– ion and IV group cation (Co2+, Ni2+, Zn2+ (3) 6.2 × (10–6 )2 (4) (6.2)2 × 10–6
and Mn2+) will exceed the solubility product of their
128. Ksp of AgCl at 18oC is 1.8 × 10–10. If Ag+ of solution
­sulphides and hence are precipitated
is 4 × 10–3 mol/litre, the Cl– that must exceed before
• In the presence of NH4Cl the ionization of (NH4)2CO3 AgCl is precipitated would be
will be suppressed due to common ion effect (1) 4.5 × 10–8 mol/litre (2)  7.2 × 10–13 mol/litre
(NH4)2CO3  2NH4++ CO32– (3) 4.0 × 10 mol/litre
–3
(4)  4.5 × 10–7 mol/litre
NH4Cl → NH4+ + Cl– 129. In which of the following solutions the solubility of

In that low concentration of CO32– the ionic product of AgCl will be maximum?
CO32– ion and Vth group cation (Ba2+, Sr2+ and Ca2+) (1) 0.1 M AgNO3 (2) water
will exceed the solubility product of their carbonates. (3) 0.1 M NaCl (4)  0.1 M KCl
So, they are precipitated as carbonates. But the ionic
product of CO32– and Mg2+ will not exceed the solubil- 130. The solubility of PbCl2 in water is 0.01 M at 25°C. Its
ity product of MgCO3, thus remain in solution. maximum concentration in 0.1 M NaCl will be
• Solubility of salts of weak acids increases at lower pH (1) 2 × 10–3 M (2)  1 × 10–4 M
due to the decrease in the concentration of anion by (3) 1.6 × 10 M –2
(4)  4 × 10–4 M
protonation until Ksp = Qsp. 131. A saturated solution of calcium fluoride contains 2 ×
ZnS  Zn2+ + S2– 10–4 moles of the salt per litre of the solution. Its Ksp is
S2– + 2H+ → H2S (1) 8 × 10–18 (2) 3.2 × 10–11
H2S gas, being sparingly soluble in water, escapes out. (3) 4 × 10 –6
(4) 1.43 × 10–9
So, ZnS and MnS are soluble in hot dil. HCl. 132. Solubility of AgCl at 20°C is 1.435 × 10–3 g per litre.
• If HCl or HNO3 is added to BaSO4, H2SO4 formed is The solubility product of AgCl is
also a strong electrolyte, ionizes completely and is not (1) 1 × 10–5 (2) 1 × 10–10
removed from the equilibrium (3) 1.435 × 10 –5
(4) 108 × 10–3
BaSO4  Ba2+ + SO42– 133. The solubility product of a sparingly soluble salt

SO42- + 2H+ → H2SO4 AB at room temperature is 1.21 × 10–6. Its molar
Hence, BaSO4 is insoluble in water. ­solubility is
(1) 1.21 × 10–6 (2) 1.21 × 10–3
• If calcium acetate is added to oxalic acid, calcium
(3) 1.1 × 10 –4
(4)  1.1 × 10–3
oxalate will be precipitated completely but if CaCl2 is
added to oxalic acid, precipitation does not take place 134. When equal volumes of the following solutions are
completely. This is because when calcium acetate is mixed, precipitation of AgCl (Ksp = 1.8 × 10–10) will
added to oxalic acid, a weak acid CH3COOH is formed occur only with
but when calcium chloride is added a strong acid HCl (1) 10–4 M (Ag+) and 10–4 M(Cl–)
is formed. So, in the presence of HCl the ionization of (2) 10–5 M (Ag+) and 10–5 M(Cl–)
oxalic acid will be suppressed resulting in the incom- (3) 10–6 M (Ag+) and 10–6 M(Cl–)
plete precipitation.
(4) 10–10 M (Ag+) and 10–10 M(Cl–)
135. The precipitate of CaF2 (Ksp = 1.7 × 10–10) is obtained
when equal volumes of the following are mixed
  Objective Questions
(1) 10–4 M Ca2+ + 10–4 MF–
126. If the solubility of lithium sodium hexafluoro­ (2) 10–2 M Ca2+ + 10–3 MF–
aluminate Li3Na3(AlF6)2 is “a” mol/litre, its solubility (3) 10–5 M Ca2+ + 10–3 MF–
product is equal to
(4) 10–3 M Ca2+ + 10–5 MF–

Chapter_7b.indd 19 3/26/2014 3:16:14 PM

 7B.20  Objective Chemistry - Vol. I

136. Ksp = 1.2 × 10–5 of M2SO4 (M+ is monovalent metal 144. The solubility products of MA, MB, MC and MD are
ion) at 298 K. The maximum concentration of M+ 1.8 × 10–10, 4 × 10–3, 4 × 10–5 and 6 × 10–5, respec-
ions that could be attained in a saturated solution of tively. If a 0.01 M solution of MX is added dropwise
this solid at 298 K is to a mixture containing A, B, C and D ions then the
(1) 3.46 × 10–3 M (2)  7.0 × 10–3 M one to be precipitated first will be
(3) 2.88 × 10 M –2
(4)  14.4 × 10–3 M (1) MA (2) MB (3) MC (4) MD
137. To 100 mL of 0.1 M AgNO3 solution, solid K2SO4 145. A saturated solution of H2S in 0.1 M HCl at 25°C
is added. The concentration of K2SO4 that shows the ­contains a S2– ion concentration of 10–23 mol L–1. The
precipitation is solubility products of some sulphides are: CuS = 10–44,
(Ksp for Ag2SO4 = 6.4 × 10–5 M) FeS = 10–14; MnS = 10–15 and CdS = 10–25. If 0.01 M
(1) 0.1 M (2)  6.4 × 10–3 M solutions of these salts in 1 M HCl are saturated with
(3) 6.4 × 10 M –7
(4) 6.4 × 10–5 M H2S, which of these will be precipitated?
(1) All
138. Ksp = [A]3[B]2 for the salt where A and B are the (2) All except MnS
­cation and anion as the case may be stands true for (3) All except MnS and FeS
(1) Ca3(PO4)2 (2) As2S3 (4) Only CuS
(3) Bi2S3 (4)  All are correct
146. The dissociation constant of H2S for complete
139. If the solubility product of AgBrO3 and Ag2SO4 are dissociation is 1.1 × 10–23 M2. The molarity of
­
5.5 × 10–5 and 2 × 10–5, respectively the relationship saturated solution of a gas is 0.1. The solubility
­
between the solubilities of these can be correctly rep- ­product of CdS is 4 × 10–28 M2. Find the maximum
resented as concentration of cadmium that can remain in a
(1) sAgBrO3 > sAg2SO4 ­solution of 0.1 HCl. Which is saturated with H2S?
(2) sAgBrO3 < sAg2SO4 (1) 0.10 M (2) 3.63 × 10–6 M
(3) sAgBrO3 = sAg2SO4 (3) 2.5 × 10 M –5
(4) 4.23 × 10–6 M

(4) sAgBrO3 ≠ sAg2SO4
147. When NaCl is added to the reaction mixture of an oil
140. The Ksp of PbCO3 and MgCO3 are 1.5 × 10–15 and and caustic soda, the soap is thrown out because
1  × 10–15, respectively at 298 K. The concentration
(1) NaCl is an ionic compound
of Pb2+ ion in a saturated solution containing MgCO3
(2) Soap is insoluble in the presence of chloride ions
and PbCO3 is
(3) The solubility product of NaCl decreases in the
(1) 1.5 × 10–4 M (2) 3 × 10–8 M presence of soap
(3) 2 × 10 M –8
(4) 2.5 × 10–8 M
(4) The solubility product of the soap is exceeded
141. The volume of water needed to dissolve 1 g of BaSO4 due to the increased concentration of Na+ ions
(Ksp = 1.1 × 10–10) at 25°C is
148. Sodium carbonate cannot be used in place of
(1) 820 litres (2)  410 litres ­ammonium carbonate for the identification of the
(3) 205 litres (4)  1220 litres fifth group radicals. This is because the
142. The solubility of BaSO4 in water is 0.00233 g per litre (1) sodium ions will interfere in the detection of the
at 30°C. The solubility of BaSO4 in 0.1 M (NH4)2SO4 fifth group radicals
solution at the same temperature is (2) concentration of carbonate ions is very low
(1) 10–5 mol/litre (2)  10–6 mol/litre (3) sodium will react with acidic radicals

–8
(3) 10 mol/litre (4)  10–9 mol/litre (4) magnesium will be precipitated

143. Let the solubilities of AgCl in H2O, 0.01 M CaCl2; 149. Why only As3+ gets precipitated as As2S3 not Zn2+ as
0.01 M NaCl and 0.05 M AgNO3 be S1, S2, S3 and S4, ZnS when H2S is passed through an acidic solution
respectively. What is the correct relationship between containing As3+ and Zn2+?
these quantities? (1) Solubility product of As2S3 is less than that of ZnS
(1) S1 > S2 > S3 > S4 (2) Enough As3+ are present in the acidic medium
(2) S1 > S2 = S3 > S4 (3) Zinc salt does not ionize in the acidic medium
(3) S1 > S3 > S2 > S4 (4) Solubility product changes in the presence of

(4) S4 > S2 > S3 > S1 an acid

Chapter_7b.indd 20 3/26/2014 3:16:15 PM

 Ionic Equilibrium  7B.21

150. The addition of NaCl to AgCl decreases the solubility (4) A conjugate acid forms a conjugate base by the
of AgCl because loss of a proton and a conjugate base forms a
(1) solubility product decreases conjugate acid by the gain of a proton
(2) due to the common ion effect of Cl–
4. In the system, NH4+ + H2O  NH3 + H3O+ the
(3) solubility becomes unsaturated
­conjugate pairs are
(4) solution becomes supersaturated
(1) NH4+/NH3 and H2O/H3O+
151. The solubility product of barium chromate is 2.4 × (2) NH4+/H3O+ and H2O/NH3
10–10, the maximum concentration of barium nitrate (3) NH4+/H2O and NH3/H3O+
possible without precipitation in a solution of 6 × (4) Only NH4+ and H3O+
10–4 M K2CrO4 is
(1) 4 × 10–7 M (2)  1.2 × 10–10 M 5. When 1 mL of dilute HCl is added to 100 mL of a
(3) 6 × 10 M –4
(4)  3 × 10–4 M buffer solution of pH 4, what is the pH of the solution?
(1) 10–2 moles/litre
Answers (2) 10–1 moles/litre
(3) 10–12 moles/litre
(126) 4  (127) 2  (128) 1  (129) 2  (130) 4 (4) 10–13 moles/litre
(131) 2  (132) 4  (133) 4  (134) 1  (135) 2
6. 20 cc of a solution of HCl exactly neutralizes 40 cc of
(136) 3  (137) 2  (138) 4  (139) 2  (140) 2
0.05 N NaOH solution. The pH of the solution is
(141) 2  (142) 4  (143) 3  (144) 1  (145) 3
(146) 2  (147) 4  (148) 3  (149) 1  (150) 2 (1) 1 (2) 2 (3) 1.5 (4) 2.5
(151) 1 7. The number of H+ ions in 1 mL of solution having a
pH of 13 is
(1) 10–13 (2) 1013
(3) 6.02 × 10
7
(4) 6.02 × 1010
  Practice Exercise Level-I 8. The pH of a buffer solution containing 25 mL of 1 M
1. H2O can act either as an acid or a base which of the CH3COONa and 25 mL of 1 M CH3COOH will be
following reaction best illustrates the behaviour of appreciably affected by
water as a base? (1) 1 M CH3COOH (2)  5 M CH3COOH
(1) HCl + H2O → H3O+ + Cl– (3) 5 M HCl (4)  1 M NH4OH
(2) HCl + NaOH → NaCl + H2O
9. The hydrolysis constant of a salt of a weak acid and a
(3) H2O + NH2– → NH3 + OH–
weak base is inversely proportional to

(4) H2O + NH3 → NH4+ + OH–
(1) dissociation constant of a weak acid
2. A 0.01 M solution of HCN in water ionizes about (2) dissociation constant of a weak base
0.02% while 0.01 M solution of acetic acid ionizes (3) ionic product of water
about 5%. The acid which can donate proton readily
(4) 
dissociation constant of both weak acid and
to water is weak base
(1) HCN
10. The dissociation constant of a weak acid and weak
(2) CH3COOH
base are 1 × 10–5 and 1 × 10–6, respectively. The
(3) Both donates proton to the same extent
­hydrolysis constant of the salt formed by them is
(4) None can donate proton
(1) 10–2 (2) 10–3
3. How a conjugate acid and conjugate base are related? (3) 10 –4
(4) 10–5
(1) A conjugate acid forms a conjugate base by the
11. A solution of X has pH = 2 and another solution of Y
loss of an electron
has pH = 4. Which of the following is correct?
(2)  A conjugate base forms a conjugate acid by
­accepting an electron (1) solution X is twice as acidic as Y
(3) A conjugate acid forms a conjugate base by the (2) solution Y is twice as acidic as X
loss of a proton and the conjugate acid by the loss (3) solution X is 100 times more acidic than Y
of an electron (4) solution Y is 100 times more acidic than X

Chapter_7b.indd 21 3/26/2014 3:16:16 PM

 7B.22  Objective Chemistry - Vol. I

12. If the pH of a solution of NaOH is 12.0, pH of H2SO4 (a) At 348 K the pH of pure water is less than 7.

solution of same molarity will be (b) The pH of 0.1 M HCl is greater than the pH of
(1) 2.0 (2) 12.0 (3) 1.4 (4) 10.0 0.1 M H2SO4.
(c) The pH of a solution whose proton concentration
13. Consider the following statements: is 10–8 M is 6.98.

   (I)  CH3COOH (a weak acid) behaves as a strong (d) The pH range of litmus indicator is from 5.5 to 7.5.
acid in NH3 (1) all are correct (2)  only a, b and d
 (II) HNO 3 (a strong acid) behaves as a base in HF (3) only b, c and d (4)  only c and d
(III) H2SO4 dissociates to a very small extent in
­glacial acetic acid 21. The pH of a solution having double the alkaline
­concentration of water is
Select the correct statements
(1) 14 (2) 0 (3) 8.2 (4) 7.3
(1) I, III (2)  II, III
(3)  I, II (4)  I, II, III 22. The dissociation constant of a weak acid is 1.0 × 10–5,
the equilibrium constant for the reaction with strong
14. When water is heated, then base is
(a) Its Kw increases (b)  Its [H+] increases
–
(1) 1 × 10–5 (2) 1 × 10–9
(c)  Its [OH ] increases (d)  Its pH increases (3) 1 × 10 9
(4) 1 × 1014
The correct statements are
23. Tribasic acid forms ........... anions which exhibit
(1) all (2)  only “a” and “b”
­basic and acidic properties
(3) only “b” and “c” (4)  only a, b and c
(1) 2 (2) 1 (3) 3 (4) 4
15. A certain buffer solution contains equal concentra-
24. The solubility of AgI in NaI solution is less than that
tion of X– and HX. Kb for X– is 10–10. The pH of the
in pure water because
buffer solution is
(1) AgI forms a complex with NaI
(1) 4 (2) 10 (3) 9 (4) 5
(2) of common ion effect
16. Hydrolysis constant for a salt is Kh = Kw (KaKb)–1. (3) solubility product of AgI is less than that of NaI
Then, the hydrolysis equation is (4) the temperature of the solution decreases
(1) A– + H2O → HA + OH– 25. The correct order of increasing [H3O+] in the follow-
(2) B+ + A– + H2O → BOH + HA ing solution is
(3) B+ + H2O → BOH + H+
(1) 0.01 M H2S < 0.01 MH2SO4 < 0.01M NaCl <

(4) HA + H2O → H3O+ + OH–
0.01 M NaNO2
17. 50 mL of 0.1 M Ba(OH)2 solution is added to 10 mL (2) 0.01M NaCl < 0.01 M NaNO2 < 0.01 MH2S <
of 0.5 N HCOOH. Ka of HCOOH is 2 × 10–4. The pH 0.01 M H2SO4
of the resulting mixture is (3) 0.01 M NaNO2 < 0.01 NaCl < 0.01 MH2S < 0.01
(1)  7.7 (2) 3.7 (3) 3.0 (4) 5.3 MH2SO4
(4) 0.01 M H2S < 0.01 M NaNO2 < 0.01M NaCl <
18. 50 mL of a 0.1 M HCl solution on mixing with 0.01 M H2SO4
49.9 mL of a solution of NaOH gave a solution with
pH = 4. The molarity of the NaOH solution is 26. Which one is not an acid salt?
(1) 0.1M (2)  0.2 M (3) 0.5 M (4)  1.0 M (1) NaH2PO4 (2) NaH2PO2
(3) NaH2PO3 (4)  Na2HPO4
19. Which of the following sets are amphiprotic species?
27. A precipitate is formed when
(a) H2O, HPO42–, H2PO3–
(1) the solution becomes saturated
(b) H3O+, HPO42–, HCO3–
(2) the ionic product is less than the solublity ­product
(c) HSO4–, H2PO4–, H2PO3–
(3) the ionic product is nearly equal to the solubility
(d) HSO4–, HCOO–, HSO3–
product
(1) a and b (2)  a and c (4) the ionic product exceeds the solubility product
(3) b and c (4)  a and d
28. Among the following hydroxides, the one which
20. Some statements are given below. Among them, the has the lowest value of Ksp at ordinary temperature
correct statements are (about 25°C)

Chapter_7b.indd 22 3/26/2014 3:16:16 PM

 Ionic Equilibrium  7B.23

(1) Mg(OH)2 (2)  Ca(OH)2 (1) 0.1 M H2CO3

(3) Ba(OH)2 (4) Be(OH)2 (2) 0.1 M Na2CO3
(3) 0.1 M NaHCO3
29. A buffer solution is made by mixing a weak acid HA
(4) 0.1 M Na2CO3 and 0.1 M NaHCO3
(Ka = 10–6) with its salt NaA in equal amounts. What
should be the amount of acid or salt that should be 36. H2S is bubbled into 0.2 M NaCN solution which is
added to make 90 mL of buffer solution of buffer 0.02 M in each [Cd(CN)4]2– and [Ag (CN)2]–. The H2S
­capacity 0.1? produces 1 × 10–9 M sulphide in the solution. Given
(1) 10 m moles (2)  22 m moles Ksp Ag2S = 1 × 10–50 M3; Ksp CdS = 7.1 × 10–28 M2;
(3) 9 m moles (4)  11 m moles
Kinst [Ag(CN)2]– = 1 × 10–20 M and Kinst [Cd(CN)4]2– =
30. The best explanation for the solubility of MnS in dil. 7.8 × 10–18 M4.

HCl is that Identify the correct statement.
(1) solubility product of MnCl2 is less than that of (1) Ag2S precipitates first from the solution
MnS (2) CdS precipitates first from the solution
(2) concentration of Mn2+ is lowered by the ­formation (3)  None of them precipitate under the given
of complex ions with chloride ions ­conditions
(3)  concentration of sulphide ions is lowered by (4) Ag2S precipitates at a sulphide concentration of
­oxidation to free sulphur 1 × 10–15 M
(4) concentration of sulphide ions is lowered by the
37. The pH of 0.2 M NaHCO3 solution at 25°C is 9.2.
formation of the weak acid H2S
When 22 mL of 2.0 M solution of H2CO3 is treated
31. The solubility product of AgCl is 1.8 × 10–10. The with 80 mL of 0.5 M NaOH results in the formation
minimum volume (1 mL) of water required to dis- of H2CO3 + NaHCO3 buffer with pH of 8.6. Hence
solve 1.9 mg of AgCl is approximately pKa of H2CO3 is
(1) 10 (2)  2 (1) 10.8 (2) 7.6 (3) 9.2 (4) 8.6
(3) 1 (4)  0
38. The solubility product of AB is 4 × 10–10 at 18°C. The
32. Consider the following reactions of X loss of weight in the precipitate of AB by washing it
  (I) [Al(OH)3 (H2O)3] + OH–  [Al(OH)4 (H2O2)]– with 5 litres of water is
+ H2O (1) 2 × 10–5 mol (2) 10–4 mol

(II) [Al(OH)3 (H2O)3] + H3O+  [Al(OH)2 (H2O)4]+ (3) 4 × 10 mol –5
(4) 2 × 10–4 mol
+ H2O
39. The ionization constants for H2S are K1 = 1.0 × 107
Select correct statements. and K2 = 1.0 × 10–14. The pH of 0.005 M Na2S solu-
(1) X is an acid in I and base in II tion is
(2) X is a base in I and acid in II (1) 2.3 (2)  11.7
(3) X is a base in I and II both (3) 10.7 (4) 12.7
(4) X is an acid in I and II both
40. Liquid ammonia ionizes to a slight extent at –50°C,
33. pH of a mixture which is 0.1 M CH3COOH and its ionic product is 10–30. The number of anions pre-
0.05 M (CH3COO)2 Ba is [pKa of CH3COOH = 4.74] sent per mm3 of pure liquid ammonia is
(1) 4.74 (2)  5.04 (1) 6 × 102 (2) 17 × 10–15
(3) 4.44 (4) 7.00 (3) 6 × 10 23
(4) 6 × 105
34. Solution S is a mixture of 0.05 M NaCl and 41. A 1-litre solution containing NH4Cl and NH4OH has
0.05 M NaI. The concentration of iodide ion in the hydroxide ion concentration of 10–6 mol/litre. Which
solution when AgCl just starts precipitating is equal to of the following hydroxides could be precipitated
(Ksp AgCl = 1 × 10–10 M2 and Ksp AgI = 4 × 10–16 M2) when the solution is added to 1-litre solution of 0.1 M
(1) 4 × 10–6 M (2)  2 × 10–8 M metal ions?
(3) 2 × 10 M –7
(4)  8 × 10–15 M   (I)  AgOH (Ksp = 5 × 10–3)
35. H2CO3 is a diprotic acid for which Ka1 = 4.2 × 10–7

(II) Ca(OH)2 (Ksp = 8 × 10–6)
 

and Ka2 = 4.7 × 10–11. Which solution will produce a   (III) Mg(OH)2 (Ksp = 3 × 10–11)
pH close to 9?

(IV) Fe(OH)2 (Ksp = 8 × 10–16)

Chapter_7b.indd 23 3/26/2014 3:16:17 PM

 7B.24  Objective Chemistry - Vol. I

(1) I, II, IV (2)  IV (1) 16% (2) 32%

(3) III and IV (4)  II, III, IV (3) 47.2% (4) 62.5%
42. What is the aqueous ammonia concentration of 49. Calculate the ratio of pH of a solution contain-
a solution prepared by dissolving 0.15 mole of ing 1 mole of CH3COONa + 1 mole of HCl per
CH3COONH4 in 1 L H2O? ­litre and of the other solution containing 1 mole of
(Ka of CH3COOH = 1.8 × 10–5 and Kb of NH4OH = ­CH3COONa + 1 mole CH3COOH per litre.
1.8 × 10–5) (1) 1/6 (2) 1/4 (3) 1/8 (4) 1/2
(1) 8.3 × 10–4 (2)  0.15
(3) 6.4 × 10–4 (4)  3.8 × 10–4 Answers
43. Which of the following combinations of weak-acid  (1) 1  (2) 2  (3) 4  (4) 1  (5) 2
dissociation constants and molar concentrations would  (6) 1  (7) 4  (8) 3  (9) 4 (10) 2
correspond to the smallest per cent dissociation? (11) 3 (12) 3 (13) 4 (14) 4 (15) 1
o
(1) Ka = 1.7 × 10–4, c = 0.001 M (16) 2 (17) 1 (18) 1 (19) 2 (20) 1
HA
o (21) 2 (22) 4 (23) 3 (24) 1 (25) 2
(2) Ka = 1.8 × 10–5, c = 0.01 M (26) 2 (27) 4 (28) 4 (29) 4 (30) 4
HA
o (31) 4 (32) 1 (33) 1 (34) 3 (35) 3
(3) Ka = 6.5 × 10–5, c = 0.1 M
HA (36) 3 (37) 1 (38) 2 (39) 4 (40) 1
o (41) 1 (42) 1 (43) 1 (44) 1 (45) 1
(4) Ka = 6.5 × 10–5, c = 0.01 M
HA (46) 3 (47) 1 (48) 1 (49) 4
44. Adding a few drops of hydrochloric acid to a beaker
containing water results in the formation of hydrated
species. Identify which hydrated species can exist in
solution.
  Practice Exercise Level-II
   (I) H3O+    (II) H3O2–
(III) H5O2+ (IV) H2ClO– 1. What is the [HCOO–] in the solution that contains
(1) I only (2)  I and II 0.015 M HCOOH and 0.02 M HCl. Ka of HCOOH =
(3) I, II and III (4)  I, II, III and IV 1.8 × 10–4.
(1) 1.8 × 10–4 (2)  1.35 × 10–4
45. An acid–base indicator has Ka = 3.0 × 10–5. The acid (3) 1.8 × 10
–2
(4)  8 × 10–3
form of the indicator is red and the basic form is blue.
The change in [H+] required to change to indicator 2. Equilibrium constant of the reaction of NH4OH with
from 75% red to 75% blue is a strong acid is 109. Initially, a solution of 0.05 M
(1) 8 × 10–5 M (2)  9 × 10–5 M (NH4)SO4 and 0.1 M NH4NO3 is prepared. If 0.1 M
(3) 1 × 10 M –5
(4)  3 × 10–4 M NaOH is added in equal volumes, the pH of the
­solution is
46. At what molar concentrations of HCl will its aque- (1) 8 (2) 9 (3) 6 (4) 10
ous solution have an [H+] to which equal contribu-
tion come from HCl and H2O at 90°C [Kw of H2O = 3. What volume must 1 L of 0.5 M CH3COOH solu-
10–12 M2 at 90°C]? tion should be diluted with in order to double its pH?
Ka = 1.8 × 10–5.
(1)  50 × 10 −8 (2) 
40 × 10 −7
(1) 3.36 × 104 L
(3) 50 × 10 −7 (4) 
30 × 10 −7 (2)  2.76 × 103 L
47. For an indicator, the value of pH = 2 when half of the (3) 3.1 × 103 L
indicator is present in the unionized form. The pKin of (4)  1.05 × 104 L
the indicator is 4. For the reaction CN − + HAc  HCN + Ac −
(1)  2 (2) 3 (3) 4 (4) 5 which of the following is the correct equilibrium
48. The dissociation constants for aniline, propionic acid ­constant? (Given Ka of HCN = 4.9 × 10–10 and Ka of
and water are 9 × 10–10, 4 × 10–6 and 10–14, respec- CH3COOH = 1.8 × 10–5.)
tively. The degree of hydrolysis of 0.1 N aniline pro- (1) 6.326 × 10–7 (2)  7.84 × 10–15
pionate solution is (3) 3.674 × 10 (4) 
4
5.16 × 103

Chapter_7b.indd 24 3/26/2014 3:16:20 PM

 Ionic Equilibrium  7B.25

5. The solubility of Mg(OH)2 in a buffer of pH = 10 (3) the concentration of both Cd2+ and OH– to ­decrease
is found to be 0.0232 g/litre. Molar solubility of (4) the concentration of both Cd2+ and OH– to ­increase
Mg(OH)2 in pure water would be (in mol/litre)
13. The solubility of CaCO3 = 8 mg/litre. Calculate the
(1) 10–5 (2)  3.2 × 10–8 solubility product of BaCO3 from this information
(3) 3.2 × 10
–5
(4)  10–4 and from the fact that when Na2CO3 is added slowly
6. How many moles of HCl must be removed from 1 ­litre to the solution containing equimolar concentration
of aqueous HCl solution to change its pH from 2 to 3? of Ca2+ and Ba2+, no precipitate of CaCO3 is formed
­until 80% of Ba2+ has been precipitated as BaCO3.
(1) 1 (2) 0.02 (3) 0.009 (4) 0.003
(1) 1.28 × 10–9 (2)  1.28 × 10–10
7. For a sparingly soluble salt NaZn(UO2)3 (CH3COO)9. (3) 1.28 × 10 (4) 
–11
1.28 × 10–12
nH2O dissociates into Na+, Zn2+, UO2+ 2 and CH3
COO–, the relationship of its solubility product (Ksp) 14. For the reaction [Ag(CN)2 ]−  Ag + + 2CN −, the
with its solubility (s) is equilibrium constant at 25°C is 4 × 10–19. If a solution
is 0.1 M in KCN and 0.03 M in AgNO3 originally, at
(1) Ksp = 321 ⋅ S21 (2)  Ksp = 321 ⋅ nn ⋅ S14 + n
equilibrium, the concentration of Ag+ is
(3) Ksp = 3 ⋅ S (4) 
21 14
Ksp = 327 ⋅ S14
(1) 7.5 × 10–16 M (2)  7.5 × 10–18 M
8. pH of 0.1 M BOH (a weak base) is found to be (3) 1.25 × 10 M –19
(4)  1.25 × 10–17 M
12. The solution at temperature TK will display an
­osmotic pressure equal to 15. If 500 mL of 0.4 M AgNO3 is mixed with 500 mL of
2 M NH3 in solution then what is the concentration
(1) 0.01 RT (2) 0.10 RT
of [Ag(NH3)+] in solution? Given K f1 [Ag(NH3)]+ =
(3) 0.11 RT (4) 1.1 RT
103; K f2 [Ag(NH3)2]+ = 104.
9. The solubility of Mg(OH)2 is increased by ­adding (1) 3.33 × 10–7 M (2) 
3.33 × 10–5 M
of NH4+ ion. Mg(OH)2 + 2NH +4  2NH 3 + (3) 3 × 10 M (4) 
–4
10–7 M
2H 2 O + Mg 2 +. If Ksp Mg(OH)2 = 1 × 10 −11 and Kb for
NH4OH = 1.8 × 10–5 then Kc for the reaction is 16. A buffer solution containing 0.04 M Na2HPO4 and
(1) 3.08 × 10–2 (2)  2.71 × 10–2 0.02 M Na3PO4 is prepared. The electrolytic oxida-
(3) 5.10 × 10 (4) 
–3
5.77 × 10–2 tion of 1 millimole of the organic compound RNHOH
is carried out in 100 mL of the buffer. The reaction is
10. In order to prepare a buffer of pH 8.26, the amount RNHOH + H 2 O  RNO2 + 4H + + 4e −
of (NH4)2SO4 required to be mixed with 1 L of 0.1 M
NH3 is (pKb = 4.74) given that for H3PO4 pKa1, pKa2 and pKa3 are 4, 8
and 12, respectively; the dip in pH after electrolytic
(1) 1.0 mol (2)  10.0 mol
­oxidation will be
(3)  0.50 mol (4)  5 mol
(1) 11.7 (2) 8.3 (3) 3.4 (4) 1
11. A 0.1 M solution of fluoride ions is gradually added to
a solution containing Ba2+, Ca2+ and Pb2+ ions, each at a 17. Four species are listed below
concentration of 1 × 10–3 M. In what order, from first to    (I) HCO3–   (II) H3O+
last, will the precipitates of BaF2, CaF2 and PbF2 form? (III) HSO4– (IV)  HSO3F
Solubility product Which one of the following is the correct sequence of
    BaF2 1.8 × 10–7 their acid strength?

    CaF2 1.5 × 10–10 (1) II < III < I < IV (2)  I < III < II < IV
(3) III < I < IV < II (4)  IV < II < III < I

    PbF2 7.1 × 10–7
(1) CaF2, PbF2, BaF2 (2) BaF2, CaF2, PbF2 18. Ksp of PbBr2 is 8 × 10–5. If the salt is 80% dissociated
(3) PbF2, BaF2, CaF2 (4) CaF2, BaF2, PbF2 in solution the solubility of the salt is
(1) 0.016 M (2)  0.024 M
12. Addition of hydrochloric acid to a saturated solution
(3) 0.034 M (4)  0.042 M
of cadmium hydroxide Cd(OH)2, Ksp = 2.5 × 10–14 in
water would cause 19. How many moles of HCl will be required to prepare
(1) the solubility of cadmium hydroxide to decrease 1 litre of buffer solution (containing NaCN + HCN)
(2) the OH– concentration to decrease and the Cd2+ of pH 8.5 using 0.01 g formula weight of NaCN?
concentration to increase pKa of HCN = 9.5.

Chapter_7b.indd 25 3/26/2014 3:16:23 PM

 7B.26  Objective Chemistry - Vol. I

(1) 9 × 10–2 (2) 9 × 10–3 26. 0.2 mole of NH4Cl is dissolved in 1000 g of water
(3) 7 × 10–2 (4) 7 × 10–3 lowered the freezing point by 0.71°C. Degree of dis-
sociation of salt is 0.75. Kb for H2O is 2 K kg mol–1.
20. Solubility product constant (Ksp) of salts of types
The degree of hydrolysis of the salt is
MX, MX2 and M3X at temperature “T” are 4.0 × 10–8,
3.2 × 10–14 and 2.7 × 10–15, respectively. Solubilities (1) 0.033 (2) 0.066 (3) 0.049 (4) 0.099
(moles dm–3) of the salts at temperature T are in the 27. What is the pH of an aqueous solution of 0.1 M
order ­ammonium formate assuming complete dissociation?
(1) MX > MX2 > M3X pKa of formic acid = 3.8 and pKb of ammonia = 4.8.
(2) M3X > MX2 > MX (1) 6.5 (2) 7.5 (3) 8.5 (4) 9.5
(3) MX2 > M3X > MX
(4) MX > M3X > MX2 28. Ksp for SrF2 = 5 × 10–9 at 25°C. How much NaF should
be added to 100 mL of solution having 0.015 M Sr2+
2 ions to reduce its concentration to 0.005 M?
21. 2.5 mL of M weak monoacidic base (Kb = 1 × 10–12
5 2 (1) 0.1764 g (2)  0.0882 g
at 25°C) is titrated with M HCl in water at 25°C.
15 (3) 0.06 61 g (4)  0.0441 g
The concentration of H+ at equivalence point is
29. 25 mL clear saturated solution PbI2 (aq) requires 12.5 ml
(Kw = 1 × 10–14 at 25°C)
of AgNO3 (aq) solution for complete neutralization. Ksp
(1) 3.7 × 10–13 M (2) 3.7 × 10–7 M of PbI2 is 4 × 10–9. So, concentration of AgNO3 is
(3) 3.2 × 10 M
–2
(4) 2.7 × 10–2 M
(1) 2 × 10–3 M (2) 3 × 10–3 M
22. During the titration of 100 mL of a weak monobasic (3) 4 × 10 M –3
(4)  5 × 10–3 M
acid solution using 0.1 M NaOH the solution became
30. pKa value of CH3COOH is 4.78. Now, which of the
neutral at 40 mL addition of NaOH and equivalence
following statements is correct?
point was obtained at 50 mL NaOH addition. The Ka
of the acid is (log 2 = 0.3) (1) pH of 0.1 M CH3COOH is 4.78
(2) pH = 4.78 then degree of dissociation of
(1) 1 × 10–7 (2) 2 × 10–7
CH3COOH is maximum

(3) 3 × 10
–7
(4) 4 × 10–7
(3) pH = 4.78 then degree of dissociation of
23. Equal volumes of the following solutions are mixed. CH3COOH is minimum
In which of the following case the pH of resulting so- (4) pH = 4.78 then 50% CH3COOH is dissociated
lution will be the average of the two solutions. Given
31. One litre of buffer solution of pH = 6.7 can be
Ka of HCN = 10–10 and Ka of acetic acid is equal to Kb
prepared by 0.005 mole NaH2PO4 and X mole of
of ammonia
­Na2HPO4. K2 for H3PO4 = 6 × 10–8. The value of X is
(1) HCl (pH = 3) and NaOH (pH = 12)
(1) 0.1 (2)  0.01
(2) HCl (pH = 2) and HCl (pH = 4)
(3) 0.001 (4)  0.0001
(3) HCN (pH = 2) and NaOH (pH = 12)
(4) CH3COOH (pH = 5) and NH3 (pH = 9) 32. The solubility of the compound Tl2S in pure water is
3 × 10–6 mol/ litre. Assume that the dissolved S–2 ion
24. The solubility product of AgCl is 10–10 at 25°C.
hydrolysis almost completely into HS- and further
A ­solution of Ag+ ion at a concentration of 4 × 10–3 M
hydrolysis to H2S can be neglected. K2 (H2S) = 10–14.
just fails to yield AgCl with a concentration of
The solubility product of the compound is
1 × 10–3 M of Cl– ion when the concentration of NH3
in solution is 2 × 10–2 M. The equilibrium constant of (1) 9 × 10–12 (2) 8.1 × 10–22
Ag+ + 2NH3  [Ag(NH3)2]+ is (3) 8.1 × 10 –12
(4) 3.24 × 10–22
(1) 10–8 (2) 108 33. The self-ionisation constant for pure formic acid K =
(3) 2 × 10 –8
(4) 2 × 108 [HCOOH2+] [HCOO–] has been estimated as 10–6
25. The solubility of silver formate in pure water is at room temperature. The density of formic acid is
10–2 mol/litre. Ka of formic acid is 1 × 10–5. The solu- 1.22 g/cm3. The percentage of formic acid molecules
bility of silver formate in buffer solution of pH = 3 is in pure formic acid converted to formate ion is
(1) 10–1 mol/litre (2)  10–2 mol/litre (1) 0.002% (2) 0.004%
–3
(3) 10 mol/litre (4)  10–4 mol/litre (3) 0.006% (4) 0.008%

Chapter_7b.indd 26 3/26/2014 3:16:24 PM

 Ionic Equilibrium  7B.27

34. 300 mL of saturated clear solution of CaC2O4 (aq) (1) 0.23 (2)  0.46
requires 6 mL of 0.001 M KMnO4 (aq) in acid
­ (3) 0.92 (4)  0.1
­medium for complete oxidation of C2O42– ions. The
41. A weak monoacidic base is titrated against HCl
Ksp of CaC2O4 is
of 0.3 M and the end point has reached on adding
(1) 5 × 10–9 (2) 5 × 10–10 20 mL of the acid. To this solution 120 mg of NaOH
(3) 2.5 × 10 –9
(4)  2.5 × 10–10 if added the pH of the resulting solution would be
35. How many numbers of mole of AgI which may be [pKb of the base is 4.2]
dissolved in 1 litre of 1 M CN– solution? Ksp for
(1) 4.2 (2)  8.4
AgI  = 1 × 10–17 Mz. Ag + + 2 CN − → [Ag(CN )2 ]−;
(3) 9.8 (4)  10.2
Kc = 9 × 1019 M −2
(1) 0.245 (2)  0.3675 42. Solubility of sparingly soluble salt Ba3(PO4)2 in a mix-
(3) 0.491 (4)  0.735 ture of 1/20 M BaCl2 (α = 1) and 1/20 M Ba(NO3)2
(α = 1) is [Ksp of Ba3 (PO4)2 = 10–7 M5. At mass
36. Both AgCNS and Ag Br are dissolved in water. Ksp of
Ba = 137, P = 31, O = 16]
AgBr = 5 × 10–13 and Ksp of AgCNS = 1 × 10–12. The
solubility of AgBr in solution is (1) 300.5 mg/litre (2)  601 mg/litre
(3) 3000.5 mg/litre (4)  6010 mg/litre
(1) 4 × 10–7 M (2)  2 × 10–7 M
(3) 8.16 × 10 M –7
(4)  6.2 × 10–7 M 43. A buffer solution of pH = 6.7 can be prepared by
­employing solutions of NaH2PO4 and Na2HPO4. If
37. It is found that 0.1 M solution of four sodium salts
0.005 mol of NaH2PO4 is weighed out of the no. of
NaA, NaB, NaC and NaD have the following pH
moles of Na2HPO4 must be used to make 1 litre of the
values. Which one of the corresponding acids is the
solution is (K2 for H3PO4 = 6 × 10–8)
strongest?
(1) 0.0015 (2)  0.003
(1) NaD 11.0 (2)  NaC 10.0
(3) 0.0045 (4)  0.006
(3) NaB 9.0 (4)  NaA 7.0
44. The self-ionization of pure formic acid 2HCOOH
38. 100 mL of 0.5 M hydrozoic acid (N3H, Ka = 3.6 × 10–4)
 HCOOH2+ + HCOO– has ionization constant
and 400 mL of 0.1 M cyanic acid (HOCN, Ka = 8 × 10–4)
K = 106 mol2/lit2 at 298 K. If percentage ionization is
are mixed. Which of the following is true for the final
4 × 10–3, then the density of the acid in g/mol is
solution?
(1) 1.15 (2) 1.725 (3) 2.3 (4) 2.875
(1) [H+] = 2 × 10–2 M
(2) [N3–] = 3.6 × 10–2 M 45. Solid BaF2 is added to a solution containing 0.1 mole
(3) [OCN–] = 4.571 × 10–3 M of sodium oxalate (1 litre) until equilibrium is
(4) [OCN–] = 6.4 × 10–3 M reached. If the Ksp of BaF2 and BaC2O4 is 10–6 mol/lit2
and 10–7 mol2/ lit2, then the concentration of C2O42– in
39. When bromocresol green is dissolved in aque-
the solution is
ous solution an equilibrium is established between
­bromocresol green (HIn, a weak monoprotic acid), (1) 7.4 × 10–2 M (2)  3.7 × 10–2 M
the anion (conjugate base) of bromocresol green (In–) (3) 7.4 × 10 M –3
(4)  3.7 × 10–3 M
and H+ ions
HIn (aq, yellow)  H+ (aq, colourless) + In (aq, Answers
blue-green)
If a small amount of bromocresol green is dissolved  (1) 2  (2) 2  (3) 1  (4) 3  (5) 4
in a buffer solution at pH 11, the colour of the result-  (6) 3  (7) 3  (8) 3  (9) 1 (10) 3
ing solution would be close to (11) 4 (12) 2 (13) 1 (14) 2 (15) 2
(16) 2 (17) 2 (18) 3 (19) 2 (20) 4
(1) colourless (2)  yellow
(21) 4 (22) 4 (23) 4 (24) 2 (25) 1
(3) blue-green (4)  red
(26) 1 (27) 1 (28) 2 (29) 3 (30) 4
40. The degree of hydrolysis of 102 M NH4CN in aque- (31) 3 (32) 4 (33) 4 (34) 3 (35) 3
ous solution is 0.46. If the concentration of NH4CN (36) 1 (37) 4 (38) 4 (39) 3 (40) 2
increased fourfold, the new degree of hydrolysis (41) 3 (42) 3 (43) 1 (44) 3 (45) 4
would be given as Ka of HCN = 7.2 × 1010 and Kb
NH4OH = 1.8 × 105 at 25°C.

Chapter_7b.indd 27 3/26/2014 3:16:25 PM

 7B.28  Objective Chemistry - Vol. I

9. Statement I: HCO3– is a conjugate acid of H2CO3.

  Statement-Type Questions
Statement II: HCO3– changes to H2CO3 by accepting
In each of the following questions, a statement I is given a proton.
followed by a corresponding statement II just below it.
10. Statement I: Aqueous solution of NH4NO3 is acidic
Mark the correct answer. If
in character.
1. S
 tatement I and II are true and statement II is the
Statement II: NH4NO3 undergoes anionic ­hydrolysis.
­correct explanation of statement I
11. Statement I: pH of pure water increases with i­ ncrease
2. S tatement I and II are true and statement II is not the in temperature.
correct explanation of statement I
Statement II: Degree of dissociation increases with
3. Statement I is true but statement II is false
increase in temperature.
4. Statement I is false but statement II is true
1. Statement I: H2PO4– can act as a Bronsted base as 12. Statement I: A solution containing CH3COOH and
well as Bronsted acid. CH3COONa can act as a buffer solution.
Statement II: Ion is polybasic which contains at least Statement II: The pH of the above mentioned buffer
one H atom and can act as Bronsted acid as well as could be equal to pKa of acetic acid.
Bronsted base. 13. Statement I: pH of a buffer solution changes with
2. Statement I: An electrophile can act as a Lewis acid. change in temperature.
Statement II: Kw of water changes with change in
Statement II: A substance which can take up an
temperature.
­electron pair is known as a Lewis acid
3. Statement I: According to Lewis concept, NaCl is a 14. Statement I: A solution whose pH is 6.9 must be acidic.
salt. Statement II: In acidic solution H+ ion concentration
must be greater than K w
Statement II: A salt is a compound formed by the
addition of an acid and a base. 15. Statement I: Phenolphthalein is used as an indicator
4. Statement I: According to Bronsted–Lowry theory, during the titration of oxalic acid and sodium h­ ydroxide.
BF3 is an acid. Statement II: pH range of phenolphthalein is
8 to 9.6.
Statement II: BF3 is an electron-deficient compound.
5. Statement I: SF4 can act as a Lewis acid. 16. Statement I: Aqueous solution of CH3COONa is
­alkaline in nature.
Statement II: The compound which contains vacant Statement II: Acetate ion undergoes anionic
d- orbitals can act as a Lewis acid ­hydrolysis.
6. Statement I: The formation of H3N → BF3 is neu-
17. Statement I: The addition of silver ions to a mix-
tralization reaction according to Lewis acid–base
ture of aqueous sodium chloride and sodium bromide
theory
­solution will first precipitate AgBr rather than AgCl.
Statement II: Formation of coordinate covalent bond Statement II: The value of Ksp of AgCl < Ksp of AgBr.
is neutralization.
18. Statement I: A bowler bowling the last crucial over
7. Statement I: Ionic product of water increases with
in India–Pakistan 20-20 match breathes heavily due
temperature.
to excitement and tension, leading to significant
Statement II: Ionization increases with temperature. change in the pH of blood.
8. Statement I: The extent to which a dissolved sub- [HCO3− ]
Statement II: pH of blood = pKa + log
stance can act as an acid or base depends largely on [H 2 CO3 ]
the solvent.
19. Statement I: Aqueous solution of CH3COONH4 is
Statement II: The solute only shows acidic proper-
found to be neutral.
ties if its proton-donating properties exceed those of
the solvent. Statement II: Because this salt does not undergo
­hydrolysis.

Chapter_7b.indd 28 3/26/2014 3:16:26 PM

 Ionic Equilibrium  7B.29

20. Statement I: Addition of a small amount of sodium 30. Statement I: The pH of an aqueous solution of acetic
acetate to a dilute solution of acetic acid does not acid remains unchanged on the addition of sodium
­affect the pH value. acetate.
Statement II: Buffer solutions have a definite pH value. Statement II: The ionization of acetic acid is
21. Statement I: pKa of a weak acid becomes equal to pH ­suppressed by the addition of sodium acetate.
of the solution at the midpoint of its titration.
Statement II: The molar concentrations of proton Answers
acceptor and proton donor become equal at the mid-
 (1) 1  (2) 1  (3) 4  (4) 4  (5) 1
point of titration of a weak acid.
 (6) 1  (7) 1  (8) 1  (9) 1 (10) 3
22. Statement I: To precipitate the cations of the fourth (11) 4 (12) 2 (13) 1 (14) 1 (15) 1
group in qualitative analysis, medium is made alka- (16) 1 (17) 3 (18) 4 (19) 3 (20) 4
line before passing H2S gas. (21) 1 (22) 3 (23) 1 (24) 2 (25) 4
Statement II: This is done to suppress the ionization (26) 1 (27) 1 (28) 1 (29) 3 (30) 4
of H2S in the fourth group analysis.
23. Statement I: Water acts as a levelling solvent for
various acids.
Statement II: Levelling effect of water is due to its  Match the Following Type Questions
high dielectric constant and strong proton-accepting 1. Match the following given in List I with those given
tendency. in List II
24. Statement I: A buffer solution has a capacity to resist
the change in pH value on addition of a small amount List-I List-II
of strong acid or base to it.
(A) NH3    (i)  Salt according to Lewis concept
Statement II: pH value of a buffer solution does not (B) CO2  (ii) Salt according to Bronsted–Lowry
change on dilution or on keeping for a long time. concept
25. Statement I: Na2CO3 does not affect the pH of pure (C) HCO3– (iii)  Lewis base
water on dissociation. (D) NaCl  (iv)  Lewis acid
  (v)  Bronsted acid
Statement II: Salt of a strong acid and a strong base
do not undergo hydrolysis.
The correct matching is
26. Statement I: Equal number of millimoles of
CH3COOH and NaOH when mixed together the S.No. A B C D
­resulting aqueous solution becomes alkaline. 1. I III V II
Statement II: Since the base is stronger, the salt 2. III IV V II
formed undergoes anionic hydrolysis. 3. III IV I II
27. Statement I: Dilution of an aqueous solution of a 4. III IV IV I
salt of a strong acid and a weak base will cause an
increase in pH.
2. Match the following given in List I with those given
Statement II: Degree of ionization of a weak base in List II
will increase with dilution.
28. Statement I: In an acid–base titration involving a List-I List-II
strong acid and a weak base, methyl orange can be (A) Aqueous solution of Na2SO4    (i)  Acidic buffer
used as an indicator. (B) Aqueous solution of  (ii)  Acidic solution
Statement II: Methyl orange changes the colour in CH3COONa
the pH range 3 to 5. (C) Aqueous solution of NH4Cl (iii)  Basic solution
(D) Aqueous solution of   (iv) Neutral
29. Statement I: In acid medium, Zn2+ is not precipitated
CH3COOH along with NaOH solution
by S2– ions.
Statement II: ZnS is soluble in an aqueous solution.

Chapter_7b.indd 29 3/26/2014 3:16:27 PM

 7B.30  Objective Chemistry - Vol. I

The correct matching is 58. 0.4 g of NaOH in 1 litre is 0.01 M

pOH = 2 ∴ pH = 12
S.No. A B C D
1. I II III IV 59. The [H+] ion in gastric juice = 0.01 or 1× 10 −2
2. IV III II I ∴ pH = 2
3. III IV II I
60. HCOOH  HCOO– + H+
4. IV III I II
3.2
[H + ] = × 0.2 = 0.0064 or 6.4 × 10 −3
3. Match the following given in List I with those given 100
in List II [HCOO − ][H + ]
Ionization constant =
[HCOOH]
List-I Reaction List-II Relation 6.4 × 10 −3 × 6.4 × 10 −3
= = 2.1× 10 −4
(A) CH3COONa +    (i) Acidic due to cationic 0.2
CH3COOH hydrolysis 61. Since the concentration of a base is more than an acid,
(B) NH4Cl + NH4OH  (ii) Basic due to anionic the solution is basic and the pH > 7.
hydrolysis
62. [H+] = 4 × 10 −3 = 3 – log 4
(C) AlCl3 (iii) Basic due to buffer action
(D) Na2CO3   (iv) Acidic due to buffer action = 3 – 0.6020 = 2.398
63. Neutral solution contains 1× 10 −7 g ions of H+
The correct matching is
10–8 M HCl = 0.1× 10 −7 g ions of H+
∴ Total concentration of H+ = 1.1× 10 −7
S.No. A B C D
Hence, pH = 6.95
1. I II III IV ∴ The ionization of both HCl and H2O can be
2. IV III I II ­neglected.
3. II III I IV
4. IV III II I
64. [H + ] = K a × C = 5 × 10 −8 × 0.1
= 50 × 10 −10 = 7.07 × 10 −5
Answers 65. pH = 4.35
[H+] = 10–4.35 or 4.5 × 10–5
 (1) 2  (2) 2  (3) 2
66. 6.6 [H+] = 1.5 × 10–2
1 × 10 −4
[OH–] = = 6.7 × 10–13
hints 1.5 × 10 −2

47. pH of a weak base = 14 – 5 = 9 66. When 75 mL of M/5 HCl + 25 ml of M/5 NaOH is

mixed, the concentration of H+ is
(0.0001)2
48. Ka =  1× 10 −8 V N − V2 N 2 75 × 0.2 − 25 × 0.2
(1 − 0.0001) 1 1 = = 0.1
Total volume 100
49. [H+] = 0.001 ∴ pH = 3
67. Whenever equal volumes of acidic solutions having
1000 different pH values are mixed the pH of the result-
50. 1 litre contain = 55.5 moles of H2O
18 ant solution will have 0.3 more pH and hence greater
than the lower pH.
1× 10 −7
Degree of ionization = × 100 = 1.8 × 10 −7 [H+] in pH = 3 solution = 1 × 10–3 or 0.001
55.5
[H+] in pH = 5 solution = 1 × 10–5 or 0.00001
K acid I ∴ [H+] in the mixture is
51. Relative strengths of weak acids =
K acid II 1× 0.001 + 1× 0.00001
−4 = 0.0005 0005
3.6 × 10 4 2
= = 4 :1
1.8 × 10 −5 1 or 5.005 × 10–4
pH = 4 – log 5.005 = 3.3

Chapter_7b.indd 30 3/26/2014 3:16:32 PM

 Ionic Equilibrium  7B.31

69. When 25 mL of 2M HCl is added to 25 mL of 1 M 105. When equal number of moles of HOCl and NaOCl is
NaOH after neutralization the HCl remained is present in a buffer solution, its pH = pKa.
V N − V2 N 2 25 × 2 − 25 × 1 25
1 1 = = = 0.5 M 106. Concentration of CH3COOH = 0.1.
Total volume 50 50
0.5× 20
∴ [H+] = 5 × 10–1 or pH = 0.3 Concentration of CH3COONa = = 0.1
100
The largest change in pH occurs when 25 mL of
pH = pKa + log = 4.774 (∵ pKa = 4.4774)
2.0 M HCl is added to 25 mL of 1.0 M NaOH.
107. pOH = 14 – 8.2 = 5.8
70. pH = 3.82 [H+] = 1 × 10–3.82
5.8 = pKb + log
[H+] = 1 × 10–4 + antilog of 0.18 = 1.5 × 10–4
5.8 = pKb + log 10
83. If pKa is more, acid is weak. The salt formed is of a pKb = 5.8 – 1 = 4.8
strong base and a weak acid. So, the solution is basic.
108. pH = pKa
84. If Ka value is more, acid is stronger. So, the aqueous ∴ [CH3COONa] = [CH3COOH]
solution of ammonium formate is acidic.
50 × 0.2 = 25 × Mz
85. Hydrolysis constant of salt of weak acid and weak Mz = 0.4
Kw 1 × 10 −14
base = = = 10 −2 109. 5 = 4 + log
K a × K b (2 × 10 −6 ) (5 × 10 −7 )
1 = log ∴ = 10
86. Hydrolysis constant of a salt of a strong base and a So, 10:1
K 1 × 10 −14 110. Buffer capacity
weak acid = w = = 10 −2 = 5 × 10–9
Ka 2 × 10 −6 No.of moles of acid to be added to
101. pH of a buffer solution does not change on dilution. 1 litre buffer solution
=
So, addition of 1 mL of water would not change the pH change
pH of the solution.
[H + ] [In − 0] [H + ] × 75
116. Ka = or 3 × 10 −5 =
102. No. of moles of CH3COONa = [HIn] 25
pH = –log 1.8 × 10–5 + log
125. If moles of Li3Na3(AlF6)2 is “a”
= +4.7447 + 0.3010 = 5.0457
[Li ] = 3a; [Na ] = 3a and [AlF6] = 2a
+ + 3–
∴ [H+] = 9 × 10–6
Ksp = [Li+]3 [Na+]3 [AlF63–]2
103. Let x mL of 5 M KCN solution be added = (3a)2 (3a)2 (2a)2 = 2916a8
V1M1 x ×5
Concentration of KCN = = M 126. Ksp of AgCl = [Ag+] [Cl–]
Total volume 10 + x
= (6.2 × 10–6) (6.2 × 10–6)
V2 M 2 10 × 2
Concentration of HCN = = M 127. For precipitation Ksp must be greater than ionic
Total volume 10 + x
­product.
5 x / (10 + x ) ∴ [Ag+] [Cl–] > 1.8 × 10–10
pH = –log 5 × 10–10 + log =
20 / (10 + x ) ⇒ 4 × 10–3 [Cl–] > 1.8 × 10–10
9 = 9.3010 + log log = – 0.3010 or x = 2 mL. ∴ [Cl–] > 4.8 × 10–8 mole/litre

104. When 50 mL of 0.2 M KOH is added to 40 mL of 128. With increase in the concentration of a common
0.5 M HCOOH the concentration of HCOOK formed ion the solubility of the compound decreases. So,
would be the concentration of formic acid left. for maximum solubility common ion must be least
or zero.
40 × 0.5 − 50 × 0.2 10
= =
90 90 129. Solubility of PbCl2 = 0.01 M
10 / 90 [Pb2+] = 0.01 [Cl–] = 2 × 0.01 = 0.02 M
pH = –log 1.8 × 10 + log + log
–4 = 3.75
10 / 90 Ksp = [Pb 2+] [Cl–]2 = (0.01) (0.02)2 = 4 × 10–6

Chapter_7b.indd 31 3/26/2014 3:16:35 PM

 7B.32  Objective Chemistry - Vol. I

Solubility of PbCl2 in 0.1 M NaCl is = a As the solution is saturated with both PbCO3 and
∴[Pb 2+ ] = a ( )
MgCO3 CO32− is same in 1 and 2. Let x moles of
MgCO3 and y moles of PbCO3 are present in the
[Cl− ] = 2a + 0.1 (2a from PbCl2 and 0.1 from NaCl)
­solution.
⇒ a(2a + 0.1) = 4 × 10 −6
[CO32− ]o = x from MgCO3 and y from PbCO3
2a can be neglected when compared to 0.1
= x + y = 2.5x
∴ a = 4 × 10 −5 M/litre
⇒ K sp′ = 1.5x × 2.5x = 1.5 × 10–15
130. Ksp = [Ca 2+ ] [F − ]2 ∵ 2(Ca 2+ ) = F − = 2a x = 2 × 10–8 moles of MgCO3
= (2 × 10 −4 ) (2 × 2 × 10 −4 )2 = 3.2 × 10–11 y = 3 × 10–8 moles of PbCO3.
2 140. Let s be the solubility of BaSO4
 1.435 × 10 −3 
131. Ksp =   = 1 × 10
–10
Ksp = s2 = 1.1 × 10–10
 143 . 5  s = 1.049 × 10–5 mol/litre
132. Ksp = [A+] [B–] = 1.1 × 10–6 Weight of substance per 1 litre = 2.4437 × 10–3 g
But [A+] = [B–] = [AB soluble] ∴ Volume of H2O needed per gram = 409211 ml or
409.211 litre
⇒ [ A+ ] = 1.1 × 10–3 mole/litre
141. Follow the Q. No. 129
133. For precipitation product of ionic concentration must
be greater than Ksp 151. [Ba2+] [CrO42–] = 2.4 × 10–10
10 −4 × 10 −4 = 10 −8 > 1.8 × 10 −10 [CrO42–] = 6 × 10–4
135. Maximum concentration = concentration in saturated ⇒ [Ba2+] = 4 × 10–7
solution
⇒ K sp = [M + ]2 [SO24− ]
Practice Exercise Level-I
= (2a)2 (a) = 4a3 = 1.2 × 10–5

a = 0.0144 6. N1V1 = N2V2
But [M+] = 2a = 2.88449 × 10–2 ⇒ 20 × N = 40 × 0.05
N = 0.1 = [H+]
136. The precipitate that formed is Ag2SO4
pH = 1
So, ionic product must exceed Ksp of Ag2SO4
⇒ 6.4 × 10 −3 ≤ [Ag + ] [SO24− ] ≤ [0.1] [SO24− ] 7. [H+] = 10–pH = 10–13 mole/litre
⇒ [SO24− ] ≥ 0.064 m/litre 10 −13 × N A
⇒ per 1 ml = = 6.02 × 10 7
But for 100 ml = 6.4 × 10 −3 1000
138. The solubility of a compound with higher value of Ksp 8. Change in pH will be maximum if number of [H+] or
is more, if the formula is of the similar. But these two [OH–] ions added are more.
are different forms.
Ksp of AgNO3 = [Ag + ] [BrO3− ] 18. Since the pH of final solution is 4, the [H+] = 1 × 10–4
= (s1) (s2) = 5.5 × 10–5 ∴ Almost all the H+ is neutralized in 1 × 10–1 HCl.
So, the concentration of NaOH is nearly as that of

∴ s1 = 7.416 × 10–3 m/litre
HCl, i.e., 0.1 (volumes being nearly equal).
Ksp = [Ag + ]2 [SO24− ] = (2s)2 (s) = 4s3 = 2 × 10–5
⇒ s = 17.1 × 10 −3 m/litre 21. The [OH–] in water is 1 × 10–7
∴ Solubility of Ag2SO4 > Solubility of AgBrO3. Double the alkalinity means the [OH–] = 2 × 10–7
pOH = 6.7 or pH = 7.3
139. Ksp (PbCO3) = [Pb2+] [CO32–]  (1)
K sp′ (MgCO3) = [Mg2+] [CO32–]  (2) Ka
22.
K sp′′ [Pb ] 1.5 × 10
2+ −15 Kw
= =
K sp′′ [Mg 2 + ] 1 × 10 −5 23. Solubility of alkaline earth metal hydroxides increas-
⇒ [Pb 2+ ] = 1.5[Mg 2+ ] es down the group. So, solubility product increases
[Mg 2+ ] = x [Pb 2+ ] = y = 1.5x from Be(OH)2 to Ba(OH)2.

Chapter_7b.indd 32 3/26/2014 3:16:42 PM

 Ionic Equilibrium  7B.33

29. Buffer capacity = 40. 2NH 3  NH + + NH 2−

No. of moles of acid or base added to 1litre buffer ∴ [ NH 2− ] = 10–15 mol litre.
Change in pH 10 −15 × 6.02 × 10 23
Assume change in pH = 1 ⇒ per mm3 = = 6 × 10 2
1000 × 1000
No. of moles of acid or base added = 0.1
41. If ionic product > Ksp, precipitate will be formed
HA + NaOH  → NaA
a 0.1 a Initial concentration Kw 1× 10 −14
42. Kh = == = 3 × 10 −5
a – 0.1 – a + 0.1 Equilibrium Ka ⋅ K b (1.8 × 10 −5 )(1.8 × 10 −5 )
concentration h
a − 0.1 = K h or h = 3 × 10 −5 neglecting h in d­ enominator
pH = pKa – log 1− h
a + 0.1
[NH4OH] = Ch ⇒ 3 × 10 −5 × 0.15 × 0.15
Change in pH = 1
= 8.3 × 10–4
1 0 − 0.1 11
∴ = ⇒a= moles Ka
10 a + 0.1 9 43. Degree of dissociation α =
C
No. of moles in 90 ml solution = 11 moles
44. Due to hydrogen bonding, all ions exist.
31. Solubility, S = 1.34 × 10–5 mol/litre
HIn
1.9 45. pH = pKin – log
1.9 mg of AgCl = = 1.34 × 10–4 mol In −
143.5 × 1000
So, 1.34 × 10 −4 mol dissolve in 10 litres. 46. Concentration of H+ = 2x
Concentration of OH- = x
32. Proton donor is acid
∴ (2x) (x) = 10–12
0.1
33. pH = pKa – log x = 50 × 10 −7 M
0.1
47. pH = pKin
34. Concentration of Ag+ when AgCl starts precipitation
is 2 × 10 −9 . So, concentration of I– when AgCl starts
h Kw
4 × 10 −16 48. =
precipitation = = 2 × 10 −7 M 1− h Ka K b
2 × 10 −9
pK a1 + pK a2 Neglecting h in the denominator
35. pH =
2  1× 10 −14 
h =  −10 −6 
= 16.7%
36. When ionic product > Ksp, precipitate forms  (9 × 10 )( 4 × 10 ) 
pK a1 + pK a2 49. CH3COO Na + HCl 
→ CH3COOH + NaCl
37. = 9.2
2 1
∴ pH = pKa
H2CO3 + NaOH  → NaHCO3 + H2O 2
4.4 4 – initial mole pH of buffer solution is pKa
0.4 – 4 final mole ∴ [Salt] = [Acid]
0.4
pH = pKa1 – log
4 Practice Exercise Level-II
∴ pKa1 = 7.6
pKa2 = 10.8 1. HCOOH  H+ + HCOO–
0.015 0.02 – initial concentration
38. Solubility = 2 × 10–5
0.015 – x 0.02 + x x equilibrium
∴ Loss in weight of AB by washing with 5 litres of concentration
water = 5 × 2 × 10–5 = 10–4 (0.02 + x ) x
Ka =
1 (0.015 − x )
39. pOH = [ pK w − pK a2 − log C ]
2 [HCOO–] = 1.35 × 10–4 M

Chapter_7b.indd 33 3/26/2014 3:16:53 PM

 7B.34  Objective Chemistry - Vol. I

2. NH4OH + HCl  NH4Cl + H2O 11. CaF2 has low solubility. So, it precipitates first.
K
Keq = b ∴ Kb = 10–5 12. Due to neutralization of OH– by HCl the [OH–]
Kw
­decreases while the [Ca2+] increases.
+
NH 4 + OH −  NH 4 OH
13. Ksp of CaCO3 = [8 × 10 −5 ]2 = 6.4 × 10–9
0.1 0.05 – initial concentration
Assume concentration of CO32– in solution is “x”.
0.05 – 0.05 equilibrium concentration
Concentration of Ca 2+ = a
[NH +4 ] [OH − ]
\ Kb =
[NH 4 OH] Concentration of Ba2+ = 0.2a
[OH ] = 10–5
- ∴ ax = Ksp BaSO4

pOH = 5, pH = 9 ∴ Ksp BaSO4 = 1.28 × 10–9

14. Ag(CN )2 
−
3. pH of 0.5 MCH3COOH is 2.523   Ag+ + 2CN–; Kc = 4 × 10–19
After dilution, pH = 5.046; H+ = 9 × 10–6
– 0.03 0.1 initial
− +
CH 3 COOH  CH 3 COO + H concentration
x2 0.03 x 0.05 equilibrium
∴ K a =
c−x concentration
x ( 0.04 )
2

∴ c = 1.35 × 10 −5 M ∴ Kc =
0.03
M1V1 = M2V2
1 × 0.5 = (1.35 × 10–5) × x 15. Ag+ + NH3  → [Ag(NH3)]+
V = 3.36 × 104 litre 0.2 1 – initial concentration
x 0.8 0.2 equilibrium
4. CN − + HAc  HCN + Ac − concentration
1.8 × 10 −5 [Ag(NH3)]+ + NH3  → [Ag(NH3)2]+
K eq = = 3.674 × 10 4
4.9 × 10 −10 0.2 0.8 – initial concentration
5. Mg(OH)2  Mg 2 + + 2OH − y 0.6 0.2 initial concentration
Solubility in buffer = 4 × 10–4 [Ag(NH3)]+ = 3.33 × 10–5 M
∴ Ksp = (4× 10–4) (10–4)2 = 4 × 10–12 16. In electrolytic oxidation, 4 millimols of H+ is obtained
In pure water, Ksp = 4s3 Na2PO4 + H+  → Na2HPO4 + Na+
∴ s = 10–4 M  
2 y y Initial mol
6. When pH = 2 No. of moles of HCl = 0.01   – 2 2 Final mol
If pH = 3 the no. of moles of HCl = 0.001 Na2HPO4 + H  +
→ NaH2PO4 + Na+
No. of moles of HCl removed = 0.01 – 0.001 = 0.009
6 2 – Initial mole
4 – 2 Final mole
7. NaZn(UO2 )3 (CH 3COO)9  2
pH = pKa2 – log = 8.3
Na + + Zn 2 + + 3UO2+2 + 9CHCOO − 4
∴ Ksp = (s) (s) (3s)2 (9s)9 = 321s14 17. In conjugate acid–base pair if acid is strong conjugate
8. π = CST base is weak.
π = (0.11) RT 18. PbBr2  → Pb2+ + 2Br–

K sp 0.85 1.65
9. KC =
Kb Ksp = (0.85) (1.65)2

∴ 3 = 0.034 M
[NH 4 OH]
10. pOH = pKb – log
[NH +4 ] 19. NaCN + HCl 
→ NaCl + HCN

[NH ] = 1 mole/litre
+ 0.01 a – – Initial mole
4
0.01– a – – a Final mole
[(NH 4 )2SO 4 ] = 0.5 mol/litre

Chapter_7b.indd 34 3/26/2014 3:17:02 PM

 Ionic Equilibrium  7B.35

pH = pKa – log
[HCN ] 10-4 =
10 −5 S 2
CN  −
10 −3
a S = 10–1 M
8.5 = 9.5 – log
0.01 − a 26. NH 4 Cl  → NH +4 + Cl −
a 0.05 0.15(1 – h) 0.15  molarity at
= 10 or a = 9 × 10–3
0.01 − a equilibrium
NH4+ + H2O  
 NH4OH + H+
20. Ksp MX = S12 Ksp MX2 = 4S23

0.15(1 – h) 0.15h 0.15h molarity at
Ksp M3X = 27S3
4
equilibrium

So, order is MX > M3X > MX2
∴ ∆Tf = k f m NH4 Cl + m NH4 + m Cl− + m NH4 OH + m H+
21. At equivalent point, equivalents of base = equivalents ∴ h = 0.033
of acid
1
2 2
∴ 2.5 × = x V = 7.5 mL 27. pH =
2
[ pK w + pK a − pK b ]
5 15
[BCl] = 0.1 M 28. Sr2+ + 2F- → SrF2
K C 2 h2 0.015 Initial concentration
Kh = w = 10–2 Kh =
Kb C (1− h ) 0.005 Final concentration
So, concentration of F- required to precipitate SrF2 =
∴ h = 0.27
(0.01)2 = 0.02
[H+] = Ch = 2.7 × 10-2 M K sp 5 × 10 −9
Concentration of F- in solution = =
Sr 2 +  0.005
22. At equivalent point, M1V1 = M2V2
= 0.001
100 × M = 50 × 0.1
Total concentration of NaF required = 0.021
Molarity of acid = 0.05 M
Wt. of NaF = 0.0882 g
HA + NaOH → NaA + H2O
5 4 – – Initial mole 29. Concentration of PbI2 in solution is 10–3 M
1 – 4 – – Final mole PbI2 + 2AgNO3  
 2AgI ↓ + Pb(NO3)2

pH = pKa – log
[ ]
HA 25 × 2 × 10 = 12.5 M
–3

 A−  M = 4 × 10–3M
1 30. If CH3COOH is 50% dissociated, then pH = pKa
7 = pKa – log ∴ Ka = 4 × 10–7
4
0.005
23. Nature of CH3COONH4 solution is neutral 31. pH = pKa2 – log
x
24. Ag+ + 2NH3   
 [Ag(NH3)2]+ 32. Ksp of Tl2S = (Tl+)2 (S2–)
4 × 10 – 10 2 × 10 4 × 10
–3 –7 –2 –3
Tl2S    2Tl+ + S–2
−3
4 ×10
2s x equilibrium
∴ Kc = = 108
10 × ( 2 ×10 )
−7 −2 2
concentration
- - - -
S + H2O 2 HS + OH concentration at
25. Ksp of silver formate is 10-14
equilibrium
HCOO Ag   HCOO- + Ag+ x – s s
  – x S  equilibrium
K
concentration Kh = w = 1
HCOO– + H+    HCOOH K a2

  x 10-3 S x = s2
∴ Ksp = Sx Ksp = (s)2(2s)2 = 4s4 = 4(3 × 10–6)4 = 3.24 × 10–22
x
Ka = 10-3 5 1.22 1000
×
33. Molarity of HCOOH = = 26.52 M
K S2 46 1
Ksp = a −3 
10 2HCOOH 
 [HCOOH+2] [HCOO–]

Chapter_7b.indd 35 3/26/2014 3:17:13 PM

 7B.36  Objective Chemistry - Vol. I

∴ [HCOO-] = 10–3 39. Forward reaction is favoured.

2HCOOH  
 HCOOH+2 + HCOO– 40. Degree of hydrolysis is independent of concentration
26.52 – 2x x x equilibrium of salt.
concentration
∴ Degree of ionization = 2 × 10 /26.52
–3 41. BOH + HCl → BCl + H2O
∴ Per cent ionization = 8 × 10–3 No. of moles of BCl in solution = 6
+ No. of moles of NaOH added = 3
34. CaC2O4 + KMnO4 = H→ Mn2+ + CO2 + H2O
BCl + NaOH → BOH + NaCl
300 × M × 2 = 6 × 0.01 × 5
6 3 –   initial mole
Molarity of Ca2C2O4 = 5 × 10–5M
3 0 3   equilibrium mole
∴ Ksp = s2 = 2.5 × 10-9
∴ pOH = pKb
 [ Ag(CN )2 ]   Kc = 9 × 1019
−

35. Ag+ + 2CN–  pH = 9.8
a 1 – initial concentration
42. [Ba2+] = 0.1
10 −17
1–2a a final concentration Ba3 (PO4)2 → 3Ba2+ + 2PO43+
a
a ∴ Ksp = (0.1)3(2s)2
∴ 9 × 1019 = −17 ∴ s = 0.5 × 10–4
10
(1 − 2a )
2

a

s = 3005 mg/litre
a
∴ = 30
1 − 2a  H 2 PO 4− 
43. pH = pKa2 – log 
∴ a = 0.491  HPO24− 
36. Assume solubility of AgNCS = a and AgBr = b 44. [HCOOH2+] [HCOO–] = 10–6
∴ a(a + b) = 1 × 10–12 [HCOO-] = 10–3

b(a + b) = 5 × 10–13 2HCOOH   
 HCOOH2+ + HCOO–
∴ b = 4 × 10–7
c – 2x x x
37. pH = 7 indicates that it is a salt of a strong acid and a 2x
∴ α =
strong base. c
2 × 10 −3
 4 × 10-5 =

− +
38. N3H   N +H 3 C
0.1– x x x + y  concentration at ∴ [HCOOH] = 50 M
equilibrium d = 2.3 g/litre
HOCN   
 H+
+ OCN –
  concentration at
45. BaF2 + Na2C2O4 
→ BaC2O4 + 2NaF
equilibrium
– 0.1 – – initial
0.08 – y x + y y
concentration
3.6 × 10 −4 =
(x) (x + y) – 0.1–x – 2x equilibrium
(0.1 − x ) concentration
 
C2 O 4  = 0.1 – x
2−
y (x + y)
8 × 10 −4 = [F–] = 2x
(0.08 − y )
10 −7 0.1− x
3.6 x 0.08 ∴ =
= × 10 −6 ( 2 x )2
8 0.1 y
x
= 56.25
y
∴ y = 64 × 10–3 M

Chapter_7b.indd 36 3/26/2014 3:17:17 PM

 8

Chapter
Redox Reactions

• The reaction that involves gain of oxygen or loss of • In compounds formed by the combination of non-
hydrogen or loss of electrons is called an oxidation metallic atoms, the atom with higher electronegativity
reaction. is given negative oxidation number.
• The reaction that involves loss of oxygen or gain of • Hydrogen is assigned oxidation number +1 in all its
hydrogen or gain of electrons is called a reduction compounds except in metal hydrides.
reaction.
• The oxidation number of fluorine is always -1 in all its
• Reactions involving both oxidation-reduction pro- compounds. For other halogens the oxidation number
cesses are called redox reactions and always oxidation is generally -1, but there are exceptions when these
and reduction take place together in a redox reaction. are bonded to a more electronegative halogen atom or
• In covalent molecules the more electronegative atom oxygen.
which gets partial negative charge is considered as re- • The oxidation number of oxygen is assigned as -2 in
duced while the atom which acquires partial positive most of its compounds; however, in peroxides, super-
charge is considered as oxidised. oxides and in fluorides O2F2 and OF2 it exhibit -1, − 12 ,
• There is competition for release of electrons by differ- +1 and +2 oxidation numbers, respectively.
ent elements. For example, zinc can release electrons
• For neutral molecules, the sum of the oxidation num-
easily than copper and hence electrons can transfer
ber of all atoms is equal to zero.
from zinc atoms to Cu2+ ions.
• The list which shows the order of the tendency to re- • In the case of polyatomic ion the sum of oxidation
lease electrons is known as electrochemical series or numbers of all atoms is equal to the charge on the ion.
metal active series. • If a molecule or ion contains more than one atom of
• Oxidation number of an element is the residual the same element with different oxidation numbers,
charge which its atom has or appears to have when the oxidation number of the element is taken as an
all the atoms from the molecule are assumed to be re- ­average oxidation number.
moved as ions by counting the shared electrons with • The oxidation number of an element cannot exceed its
more electronegative atom. group number. However, if the calculated oxidation
• The oxidation number of an element in the free state number of an element is exceeding its group number it
or elementary state is always zero. may contain peroxy bonds.
• The oxidation number of monoatomic ion is the same • Oxidation state is another way of expressing oxida-
as the charge on the ion. tion number.
• In binary compounds of metal and nonmetal, the oxi- • Unlike oxidation number, valency of an element is
dation number of metal is always positive while that of only a number and do not carry any sign and it is
the non-metal is negative. always a whole number.

Chapter_08.indd 1 3/26/2014 3:17:56 PM

 8.2  Objective Chemistry - Vol. I

• Oxidising agent is a substance which increases the • If an ion/atom in a compound is replaced by an ion/
oxidation number of other substances in a chemical atom of another element, it is called a displacement
reaction. It accepts electrons. Its oxidation number reaction. If a metal in a compound is displaced by
­decreases during a redox reaction. another metal, a better reducing metal can displace a
• Reducing agent is a substance which decreases the weaker reducing metal.
oxidation number of other substances in a chemical • Non-metal displace reactions involve displacement of
reaction. It donates electrons. Its oxidation number hydrogen by metals like Na, Ca from cold water; Mg,
increases during a redox reaction. Fe from steam and by metals from acids.
• More electronegative nonmetal displaces less elec-
tronegative non-metal from their compounds. E.g., F2
Naming of Inorganic Compounds
can displace O2 from water; F2 can displace Cl2, Br2 or
• Binary compounds were named by writing the name of I2; Cl2 can displace Br2(or) I2 and Br2 can displace I2
a electropositive element first and the electronegative from the respective chlorides, bromides or iodides.
element later with a suffix added to the name of the • A disproportion reaction is one by which in an inter-
electronegative element. e.g., NaCl: Sodium ­chloride, mediate oxidation state is converted to a mixture of a
Ca3N2: Calcium nitride, etc. higher and a lower oxidation state.
• If a metal exhibits variable valency the compounds • Comproportion reaction is the reverse of a dispro-
in the lower oxidation state are called as “ous” com- portion reaction. Two species with the same element in
pounds while in higher oxidation state are called as two different oxidation states form a single product in
“ic” compounds. e.g., which the element is in an intermediate oxidation state.
FeSO4 : Ferrous sulphate • If a compound (water) is oxidised by air in the pres-
Cu2O : Cuprous oxide ence of certain substances (phosphorous, metals such
as Zn, Pd and certain unsaturated compounds), it is
Fe2(SO4)3 : Ferric sulphate
called autooxidation reactions. The substances in the
CuO : Cupric oxide presence of which water is oxidised are called activa-
• According Stock notation the oxidation number tors. The intermediate compound formed by the acti-
or oxidation state of the metal should be written as vator combining with oxygen is called an autoxidator.
Roman numeral in parenthesis after the name of the • If the oxidation of one compound induces the oxida-
metal in the name of the compound, e.g., copper (II) tion of another compound, it is called induced oxida-
sulphate and iron (III) chloride. tion reactions.
• Oxidation states are sometimes written for ions that do • If the molecules of a substance is oxidised while the
not contain transition metals. e.g., BrO3− : Bromate (V) molecules of another substance are reduced in a re-
ion. dox reaction, it is called an intermolecular redox
• If the name of a compound ends “ate” it always means reaction.
that the substance contains oxygen, e.g., bromate (v), • If one atom of the same molecule is reduced and
dichromate (vi) and manganate (vii) ion. another atom of the same molecule is oxidised in a
redox reaction, it is called an intramolecular redox
reaction.
Types of Redox Reactions
• Combination reactions are those in which elements
or compounds combine to form new substances. For a   Objective Questions
combination reaction to be a redox reaction either one
or both the reactants should be in the elemental form. 1. Which of the following is a redox reaction?
• If a compound breakdown into two or more compo- (1) AlH 3( g ) + H − ( g ) 
→ AlH 4− ( g )
nents it is called a decomposition reaction. If one of (2) Al 2 Cl6 ( g ) 
→ AlCl3( g )
the product in decomposition reaction is an element
it is a redox reaction and it is an opposite process of (3) Al3+ ( aq ) + OH − ( aq ) 
→ Al(OH)3(s)
combination. (4) 2Al(s ) + 3Cl 2 ( g ) 
→ 2AlCl3( g )

Chapter_08.indd 2 3/26/2014 3:17:57 PM

 Redox Reactions  8.3

2. In which of the following changes there is a transfer of 11. In the ionic compounds the oxidation number of an ion
five electrons? (1) is the same as the charge of the ion.
(1) MnO −4  → Mn 2 + (2) is the same as the charge of the ion with opposite
2−
(2) CrO 4  → Cr 2 + sign
(3) is always zero
(3) MnO −4  → MnO2
2−
(4) cannot be inferred from the formulae of the com-
(4) Cr7 O7  → 2Cr 3+ pounds
3. Oxidation number of carbon in CH2Cl2 is 12. Which of the following statements is not correct?
(1) -4 (2)  +4 (3)  3 (4)  0 (1) oxidation state of O in OH- is +1
4. Which of the following is not a simple displacement (2) oxidation state of O in OF2 is +2
reaction? (3) oxidation state of O in superoxide is -1/2
(1) Mg + FeCl3 → MgCl2 + Fe (4) oxidation state of O in O2- is -2
(2) Al + NiCl2 
→ AlCl3 + Ni 13. The oxidation state of tungsten in Na2W4O13 . 10H2O is
(3) Zn + H2SO4 → ZnSO4 + H2
(1) +12 (2)  +6 (3)  zero (4)  +8
(4) NaCl + AgNO3  → AgCl + NaNO3
14. One mole of N2H4 loses 10 moles of electrons and
5. Which of the following names is wrong?
form y which retain all nitrogen and hydrogen present
(1) Cl2O7: dichlorine heptoxide in the original compound. Assuming that there is no
(2) N2O4: dinitrogen tetroxide change in the oxidation state of hydrogen, the change
(3) NO2: nitrogen peroxide in oxidation state of nitrogen will be from
(4) BaO2: Barium peroxide
(1) +2 to +5 (2)  -2 to +3
6. In which of the following reaction there is change in (3) +3 to +5 (4)  +2 to +4
the oxidation state of chromium?
15. Which of the following statement is false?
(1) 2K2CrO4 + H2SO4  → K2Cr2O7 + K2SO4 +
                  H2O (1) In a conjugate pair of reductant and oxidant the
(2) K2CrO4 + H2SO4 + H2O2  → K2SO4 + CrO5 + reductant has lowest oxidation number.
                  3H2O (2) In a conjugate pair of reductant and oxidant the
(3) K2Cr2O7 + 6H2SO4 + 4NaCl  → 2KHSO4 + oxidant has higher oxidation number.
        4NaHSO4 + 2CrO2Cl2 + 3H2O (3) When an element is oxidised its oxidation number
(4) None increases.
(4) In the reaction with lithium, hydrogen is oxidised.
7. In which of the following pairs the difference in the
positive oxidation numbers of the underlined elements 16. Which is incorrect about oxidation?
is the greatest? (1) deelectronation
(1) PCl3, PCl5 (2)  NO2, N2O4 (2) increased electron density
(3) SO2, SO3 (4)  CO2, C3O2 (3) increase in oxidation state
8. In which of the following reactions the change in oxi- (4) loss of hydrogen
dation state of sulphur is fractional? 17. Reductants are substances which
(1) 2Na2S2O3 + I2  → Na2S4O6 + 2NaI (1) Show increase in their oxidation number during a
(2) Na2SO3 + H2O + I2  → Na2SO4 + 2HI change.
(3) H2S + I2  → 2HI (2) Lose electrons during a change.
(4) PbS + 4H2O2  → PbSO4 + 4H2O (3) Reduce other and oxidise themselves.
9. Which of the following about Fe3O4 is true? (4) All.
(1) The iron in it is trivalent. 18. The oxidation number and covalency of sulphur in the
(2) The iron in it is divalent. sulphur molecule (S8) are respectively
(3) The iron in it has fractional valency of 8/3. (1) 0 and 2
(4) It has both divalent and trivalent iron.
(2)  +6 and 8
10. The oxidation state of Xe in Na4XeO6 is (3) 0 and 8
(1) +2 (2)  +4 (3)  -8 (4)  +8 (4)  +6 and 2

Chapter_08.indd 3 3/26/2014 3:18:00 PM

 8.4  Objective Chemistry - Vol. I

19. Addition of zinc powder to copper sulphate solution 27. Which statement is incorrect?
precipitates copper due to (1) Oxidation of a substance is followed by reduction
(1) Reduction of Cu2+ of another.
(2) Reduction of SO2−
4 (2) Reduction of a substance is followed by oxidation
(3) Reduction of Zn2+ of another.
(4) Hydrolysis of CuSO4 (3) Oxidation and reduction are complimentary reac-
tions.
20. The violent reaction between sodium and water is an
(4) It is not necessary that both oxidation and reduc-
example of
tion should takes place in the same reaction.
(1) Reduction (2) Oxidation
(3) Redox reaction    (4) Neutralisation reaction 28. In the reaction NaH + H2O  → NaOH + H2
-
(1) H is oxidised
21. In which reaction the underlined substance has been
(2) Na+ is reduced
reduced?
(3) Both NaH and H2O are reduced
(1) Carbon monoxide + Copper oxide  → Carbon (4) None
             dioxide + Copper
(2) Copper oxide + Hydrochloric acid → Water + 29. Which statement about oxidation number is incorrect?
             Copper chloride (1) The oxidation number is the number of electrons
(3) Steam + Iron  → Hydrogen + Iron oxide lost (+ve) or gained (-ve) by an atom for the ionic
(4) Hydrogen + Iron oxide  → Water + Iron compounds.
(2) For covalent compounds the oxidation number is
22. In the following reaction
indicated by the change that an atom of element
→ 5BrO3− + 6HCO3−
  3Br2 + 6CO32− + 3H2O  would have acquired if the substance would have
been ionic.

(1)  romine is oxidised and carbonate is reduced
B (3) Oxidation number may have integer or fractional

(2) Bromine is reduced and water is oxidised values.

(3) Bromine is neither oxidised nor reduced (4) None.

(4) Bromine is oxidised and reduced as well
30. In N2 + 2H2O  → NH +4 + NO2; N2 is
23. Which statement is false?
(1) Oxidised (2)  Reduced
(1) All reactions are oxidation and reduction reactions (3) Both 1 and 2 (4)  None
(2) Oxidising agent itself is reduced
(3) Oxidation and reduction always go side by side 31. Nitrogen has fractional oxidation number in
(4) Oxidation number during reduction decreases (1) N2H4 (2)  NH +4 (3)  HN3 (4)  N2F2
24. Magnesium reacts with acids producing hydrogen and 32. What changes in the oxidation numbers occur when
corresponding magnesium salts. In such reactions, copper reacts with concentrated nitric acid to give a
magnesium undergoes blue solution and a brown acidic gas?
(1) Oxidation (1) Cu (0) to cu (II) and N (V) to N (IV)
(2) Reduction (2) Cu (0) to Cu (II) and N (V) to N (III)
(3) Neither oxidation nor reduction (3) Cu (I) to Cu (II) and N (V) to N (IV)
(4) Simple dissolution (4) Cu (II) to Cu (I) and N (V) to N (IV)
25. Which change requires a reducing agent? 33. Oxidation number of Fe in Fe0.94 is
(1) CrO24− → Cr2 O27 − 200 94
(1) 200 (2)  (3)  (4)  None
(2) BrO3− → BrO −
94 200
(3) H 2 O2 → O2
200
Hints: 0.94 × (a + 1) × (-2) = 0 or a =
94
(4) Al ( OH )3 → Al ( OH )4
−

34. Oxidation number of carbon in carbon suboxide is
26. In the reaction H2O2 + Na2CO3  → Na2O2 + H2O + 2 4 4
(1) + (2)  + (3)  + 4 (4)  −
CO2. The substance undergoing oxidation is 3 3 3
(1) H2O2 (2)  Na2CO3 Hint: C3O2 is carbon suboxide. 3a - (2 × 2) = 0 or
(3) Na2O2 (4)  None a = +4/3

Chapter_08.indd 4 3/26/2014 3:18:03 PM

 Redox Reactions  8.5

35. Which of the following is an intramolecular redox • Various steps involved in the balancing of redox
­reaction? ­
reactions by ion-electron method are as follows.
(1) P4 + NaOH → H3PO2 + PH3 The ion electron method is also known as half-reaction
(2) 2Cu+ (aq) → Cu + Cu2+ method.
(3) 2KClO3  → 2KCl + 3O2 (i) F ind the elements whose oxidation numbers are
(4) 4HClO3  → 3HClO4 + HCl changed and choose the substance which acts as an
oxidising agent and one that acts as a reducing agent.
(ii) Separate the complete equation into two half-­
Answers reactions, one for the change undergone by an
­oxidising agent and one that acts as a reducing agent.
  (1) 4   (2) 1   (3) 4   (4) 4   (5) 3
  (6) 4   (7) 4   (8) 1   (9) 4 (10) 4 (iii) Balance the half-reactions by the following steps.
(11) 1 (12) 1 (13) 2 (14) 2 (15) 4 (a)  Balance all atoms other than H and O.
(16) 2 (17) 4 (18) 1 (19) 1 (20) 3 (b) Calculate the oxidation number on both sides
(21) 3 (22) 4 (23) 1 (24) 1 (25) 4 of the equation. Add electrons to whichever
(26) 4 (27) 4 (28) 1 (29) 4 (30) 3 side is necessary to make up the difference.
(31) 3 (32) 1 (33) 2 (34) 2 (35) 3 (c) Balance the half-equation so that both sides get
the same charge.
(d) Add water molecules to complete the ­balancing
Balancing of redox reactions of the equation.
(iv) Add the two balanced half-equations. ­Multiply
• The equation where the equality of the number of one or both half-equations by suitable numbers so
atoms is signified is called a balanced chemical equa- that on adding the two equations, the electrons are
tion. The numericals placed before the formulae of the ­balanced.
reactants and the products in order to balance a chemi-
cal equation are known as stoichiometric. • If H+ ions appear on either side of a redox reaction it
takes place in an acid medium. If OH- ions appear on
• The steps involved in balancing of redox reactions by either side of the equation, the reaction take place in a
oxidation number method are as follows: basic medium. If neither H+ nor OH- ions are present
(i) Assign an oxidation number to each element on the reaction occurs in a neutral medium.
both sides of the given reaction. Identify the ele- • For balancing redox reactions involving acidic and
ment that is oxidised and reduced.
b­ asic media, the method has to be modified as
(ii) Write the oxidation number of the elements par-
ticipating in the reaction. (i) For acidic medium add proper number of H+ ions
(iii) Determine the increase and decrease of oxidation to the side falling short of H atoms.
number per atom multiply the increase and de- (ii) For basic medium add proper number of H2O
crease of ON with number of atoms undergoing molecules to the side falling short of H atoms and
change. equal number of OH- ions to the other side.
(iv) Equalise the increase in ON and decrease in ON • Ion-electron method applies only to those reactions
on the reactant side by multiplying the respective in which ions participate. It gives importance in ex-
formulae with suitable integers. pressing the redox reaction in terms of ions or an ionic
(v) Balance equation w.r.t. atoms other than “O” and equation.
“H” atoms. • The half-equation method gives the information about
(vi) Balance “O” atoms by adding equal number of water
the number of electrons participating in the redox
molecules to the side falling short of “O” atoms.
reaction.
(vii) H atoms are balanced (in case of ionic equations) de-
pending upon the medium in the following manner. • Ion-electron method is not useful for redox reactions
(a) For acid medium add proper number of H+ which take place in the molecular state. For such a
ions to the side falling short of H atoms. r­ eaction oxidation number method can be used.
(b) For basic medium add proper number of H2O • The strength of the solution of reductant/oxidant can
molecules to the side falling short of H atoms be determined by the titration method using redox
and equal number of OH- ions to the other side. s­ ensitive indicator.

Chapter_08.indd 5 3/26/2014 3:18:04 PM

 8.6  Objective Chemistry - Vol. I

Limitations of Concept of Oxidation Number 41. Which of the following change represents dispropor-
tionation reaction?
• Certain reactions which are considered as redox reactions (1) Cl2 + 2OH-  → ClO- + Cl- + H2O
according to classical approach cannot be explained by (2) Cu2O + 2H +  → Cu + Cu2+ + H2O
applying the oxidation number approach. e.g., (3) 2HCuCl2 dilution with water
→ Cu + Cu2+ + 2Cl- +
SiCl4(l) + LiAlH4(s) → SiH4(g) + LiCl(s) + AlCl3(s)                   2H+
According to classical approach, silicon is reduced (4) All of the above
(since it gained hydrogen) while lithium and alumin- 42. In the reaction CH3OH → HCOOH the number of
ium are oxidised (since they lost hydrogen) but their electrons that must be added to the right is
oxidation numbers are not changed.
(1) 4 (2)  3 (3)  2 (4)  1
• Several reactions cannot be interpreted as redox reac-
tions according to any of the three classical, electronic 43. In balancing the half-reaction S2 O32 − ( g ) 
→ S(s ) the
or oxidation number approach. number of electrons that must be added is
  CH3CNO(g) + H2O(l) → CH3NH2(g) + CO2(g) (1) 2 on the right (2)  2 on the left
(3) 3 on the right (4)  4 on the left
44. Which one of the following is correctly represented?
(1) Fe + H2O  → Fe2O3 + H2
  Objective Questions (2) 3Fe + 4H2O  → Fe3O4 + 4H2
(3) 3Fe + 4H2O  → Fe3O4(s) + 4H2(g)
36. A chemical reaction occurs in acid medium while bal- (4) 3Fe(s) + 4H2O(g)  → Fe3O4(s) + 4H2(g)
ancing the ionic equation for such reactions to balance
hydrogen atoms, we add the following to the side defi- 45. Which of the following equations is balanced?
cient in hydrogen. (1) 5BiO3 + 2H+ + Mn2+  → 5Bi3+ + 12H2O +
(1) H2O (2)  OH-  MnO −4
+
(3) H (4)  Any of the above (2) 5BiO3 + 14H+ + 2Mn2+  → 5Bi3+ + 7H2O +
 2MnO 4−
37. A chemical reaction occurs in an acid medium while
balancing the ionic equation for such reaction to bal- (3) 2BiO3− + 4 H + + Mn 2+ 
→ 2Bi3+ + 2H 2 O
ance oxygen atoms we add
+ MnO 4−
(1) O2 (2)  H2O
(3) OH- (4)  H2SO4 (4) 6BiO3− + 12H + + 3Mn 2+ 
→ 6Bi3+ + 6H 2 O

38. A chemical reaction occurs in a basic medium while + 3MnO 4−

balancing ionic equation for such reactions to balance 46. Every redox reaction is made up of ..... that which in-
hydrogen atoms we add volves gain in electrons is called ......
(1) OH- (2)  H+ (3)  H2O (4)  +H2 (1) Reduction half-reaction, two half-reactions
39. For the redox reaction (2) Oxidation half-reaction, two half-reactions
(3) Two half-reactions, oxidation reaction
MnO −4 + C2 O24 − + H + → Mn 2 + + CO2 + H 2 O (4) Two half-reactions, reduction reaction

The correct coefficients of the reactants for the bal- 47. Complete the following equation
anced reaction are
  2CuSO4 + 4HCN → 2K2SO4 + Cu2(CN)2+ ....
MnO −4 C2 O2−
4 H+
(1) 2 5 16

(1) ( CN)2 (2)  CH3CH3
(2) 16 5 2

(3) NH2NH2 (4)  None
(3) 5 16 2 48. 2KClO3 + I2 → 2KIO3 + Cl2
(4) 2 16 5

Which of the following statements is correct regarding
40. In the equation the above reaction?
NO2− + H 2 O → NO3− + 2H + + ne −
(1) It is a simple displacement but not a redox reaction

(2) Chlorine is reduced by iodine

n stands for
(3) Chlorine is oxidised by iodine
(1) H+
(2)  e- (3)  2e- (4)  3e-
(4) It is a metathesis reaction

Chapter_08.indd 6 3/26/2014 3:18:07 PM

 Redox Reactions  8.7

49. Complete the following equation the further deposition. At equilibrium metal acquires
    Cus + HNO3 → Cu(NO3)2 + ..... + ..... + H2O positive charge while the solution acquires negative
charge, e.g., Cu, Hg, Au, etc.

(1) S
 O2, NO (2)  S, NO

(3) SO3, NO2 (4)  SO2, NO2 • Nonmetals also follow the solution pressure theory.
In such cases
50. The number of electrons lost or gained during the
(i) if p > p, the electrode becomes positively charged
change is
while the solution contains negative charges.
Fe + H2O → Fe3O4 + H2 (ii) if p = p, no potential will be set up.
(1) 2 (2)  4 (3)  6 (4)  8 (iii) if p < p, the electrode will be negatively charged
while the solution acquires positive charge.
Answers
• An electrical double layer known as Helmholtz double
(36) 3 (37) 2 (38) 3 (39) 1 (40) 3 layer is set up at the interface of metal and solution.
(41) 4 (42) 1 (43) 4 (44) 4 (45) 2 • The potential developed at the interface of an element
(46) 4 (47) 1 (48) 2 (49) 2 (50) 4 in contact with its own ions is called a single electrode
potential.
• Single electrode potential cannot be measured or de-
redox reactions and electrode termined experimentally.
potentials • The potential difference between two single electrodes
is measured using a potentiometer.
• Electric current is considered as flow of electrons or
flow of electric charge through a conducting medium. • The electrode of known potential used to determine
the potential of another electrode in the potentiometric
• If electron transfer in a redox reaction takes place
method is called a reference electrode.
through a copper wire instead directly from reductant
to oxidant, electric current is generated. • The potential of hydrogen electrode when hydrogen
gas at one atmosphere pressure in contact with H+ ions
• The solutions of oxidant and reductant are taken sepa-
of unit activity in solution is assumed as zero is known
rately in two beakers in which platinum electrodes are
as normal hydrogen electrode (NHE) or standard
dipped and connected by a copper wire through a gal-
hydrogen electrode (SHE). Hydrogen electrode is a
vanometer. Deflection in galvanometer indicates the
reversible electrode.
flow of current.
• Electrons flow from the electrode dipped in a reductant
• Any element in contact with its own ions is called a
single electrode. If two single electrodes are connect-
solution to the electrode dipped in oxidant solution.
ed a galvanic cell will be formed in which electrons
• When a solid substance is kept in water, it tends to flow from oxidation electrode to reduction electrode
pass into solution at a constant temperature and this due to potential difference.
tendency is called solution pressure.
• In this galvanic cell each single electrode is called a
• The pressure exerted by a dissolved solid substance is half-cell. The single electrode potential measured at
called its osmotic pressure. 25°C when an electrode is placed in a solution of its
• When an electrode is dipped into a solution of its own, own ions of unit activity (or concentration) is called
the metal tends to pass into solution (solution pressure, standard electrode potential. If the element is a gas
p) while the ions in solution tend to deposit on the elec- it should be at 1 atom pressure.
trode osmotic pressure, p. The p is opposed by p. • On combining an electrode with SHE, if reduction
• When p > p, the metal continues to dissolve until take place at the electrode the potential of the elec-
the accumulated charge opposes further dissolution. trode is called is called as reduction potential and it
So, the metal becomes negatively charged while the is given +ve sign as reduction potential or -ve sign as
­solution is positive, e.g., Zn, Cd, alkali metals. oxidation potential.
• When p = p no potential will be set up between metal • On combining an electrode with SHE if oxidation
and the solution. Such systems are known as null take place at the electrode the potential of electrode
electrodes. is called as oxidation potential and it is given as a +ve
• When p < π the metal ions from solution deposit on the sign as an oxidation potential or -ve sign as a reduc-
metal electrode until the accumulated charge opposes tion potential

Chapter_08.indd 7 3/26/2014 3:18:07 PM

 8.8  Objective Chemistry - Vol. I

(SRP) (Standard reduction potential) = -SOP solution acquires a charge corresponding to that of the
(Standard oxidation potential) faster moving ion. Thus the junction between the two
SOP (Standard oxidation potential) = -SRP (standard solutions contributes a potential called liquid junc-
reduction potential) tion potential to the cell.
• According to the present convention, the half cell • Salt bridge eliminates the liquid junction potential by
reactions are always written as reduction half reac- neutralising the charges.
tions and their potentials are represented as reduction • Generally potassium chloride is used in a salt bridge
potentials. because both K+ and Cl- ions have the same transport
• The oxidised and reduced forms of a substance taking number. Transport number is the fraction of current
part in an oxidation or reduction half-reaction is called carried by the ion.
redox couple and its standard electrode potential is • As per the IUPAC nomenclature the single electrodes
written as EOox/red are represented as follows:
• The electromotive force (e.m.f.) is the potential gen- (i) M
 etal ion symbol is first written followed by metal
erated by a cell when it draws no current and it is under with a vertical line between the two.
conditions of zero electron flow. Potential difference (a)  zinc electrode Zn2+ /Zn
is responsible for the flow of steady current in the cell (b)  copper electrode Cu2+/Cu
but not related to e.m.f.
(ii) f or non-metal electrodes, the non-metal symbol
• SHE is called the primary standard reference elec- (X2) is first written followed by non-metal ion
trode, but since its construction is difficult some other
symbol (xn–) with concentration and a vertical line
reference electrodes called as secondary reference
between two phases. Platinum symbol Pt is written
electrodes are used.
before non-metal symbol.
• A saturated calomel electrode is a secondary refer- (a)  Hydrogen electrode Pt/H2/H+
ence electrode. It is Hg/Hg2Cl2(s); KCl (saturated) and (b)  Chlorine electrode Pt/Cl2/Cl-
its potential is -0.2422 V.
(c)  Oxygen electrode Pt/O2 /OH-
• The standard electrode potentials are influenced by the
sublimation and ionization energies of the elements • In the IUPAC system the standard potentials given are
and the hydration energies of their ions. standard reduction potentials.
• Though the sublimation and ionisation enthalpies of • The arrangement of various electrodes in the order of
lithium are high, very high heat of hydration energy of increasing reduction potential values is called electro-
its ions leads to easy formation of ions from the metal. chemical series or electromotive series.
So, it will act as a strongest reducing agent not only • The elements which are above hydrogen in e.m.f.
among alkali metals but among all reducing agents. ­series can reduce H+ ions.
• While measuring the single electrode potentials the • The elements which are below hydrogen in emf seris
two half-cells are connected by using a salt bridge. cannot reduce H+ ions and they cannot displace hydro-
A typical salt bridge is made by dissolving potassium gen from acids.
chloride in agar. The charge on the potassium and
• The metals at the top are strongly electropositive and
chloride ions provides electrical contact between the
act as strong reducing agents.
two half-cells.
• When a salt bridge is used sufficient number of Cl- • An element above in the e.m.f. series can displace an
element below to it from its salt solution but not vice
ions migrate from the salt bridge to anode half-cell
versa.
and neutralise the excessive positive charge. Similarly,
to neutralise the excessive negative charge in cathode • Hydroxides of the metals in the upper part of the series
half-cell sufficient number of K+ ions migrate from the are strongly basic and the salts of these metals do not
salt bridge. undergo hydrolysis.
• When two salt solutions of different concentrations are • Hydroxides of metals at the lower part of the series
in contact with one another, due to the difference in are weakly basic and the salts of these metals undergo
the rates of diffusion of the two ions, the more dilute hydrolysis.

Chapter_08.indd 8 3/26/2014 3:18:08 PM

 Redox Reactions  8.9

(3) T he solution becomes blue
  Objective Questions
(4) There is no reaction

51. The calomel electrode is a 58. A student made the following observations in a laboratory
(1) Standard hydrogen electrode (i) Clean copper metal did not react with 1M Pb(NO3)2
(2) Reference electrode solution
(3) Platinum electrode (ii) Clean lead metal dissolved in a 1M AgNO3 solu-
(4) Mercury electrode tion and crystals of Ag metal appeared
(iii) Clean silver metal did not react with 1M Cu(NO3)2
52. In the functions of salt bridge which is incorrect? solution. The order of decreasing reducing charac-
(1) It allows ions to go from one half-cell to another. ter of the three metals is
(2) It provides electrical connection between two (1) Cu, Pb, Ag (2)  Cu, Ag, Pb
half-cells. (3) Pb, Cu, Ag (4)  Pb, Ag, Cu
(3) It keeps the e.m.f. of the cell positive.
(4) It maintains electrical neutrality of the solution in 59. On the basis of position in the electrochemical ­series,
two half-cells. the metal which does not displace hydrogen from
­water and acid is
53. The electrode potential measures the (1) Hg (2)  Al
(1) tendency of the electrode to gain or lose electrons (3)  Pb (4)  Ba
(2) tendency of the cell reaction to occur
(3) difference in the ionisation potential of electrode 60. The standard reduction electrode potential values of
and metal ion the elements A, B and C are + 0.68, -2.5 and -0.5 V,
(4) current carried by an electrode respectively. The order of their reducing power is
(1) A > B > C (2)  A > C > B
54. Which is not true for a standard hydrogen electrode? (3) C > B > A (4)  B > C > A
(1) The hydrogen ion concentration is 1M
61. If the half-cell reaction A + e-  → A- has a large
(2) Temperature is 25°C
negative reduction potential, it follows that
(3) Pressure of hydrogen gas is 1 atmosphere
(4) It contains a metallic conductor which does not (1) A is readily reduced
absorb hydrogen (2) A is readily oxidised
(3) A- is readily reduced
55. Which of the following is not true of electrode poten-
(4) A- is readily oxidised
tials?
(1) They vary with concentration 62. The correct electrochemical series can be obtained
(2) They vary from electrolyte to electrolyte from K, Ca, Na, Al, Mg, Zn, Fe, Pb, H, Cu, Hg, Ag, Au
(3) They are independent of temperature by interchanging
(4) They are dependent on the number of electrons (1) Al and Mg (2)  Zn and Fe
involved in the reaction (3) Zn and Pb (4)  Pb and H
56. Which of the following is not characteristic of the salt 63. When zinc is kept in CuSO4 solution copper gets pre-
bridge? cipitated because
(1) It consists of an electrolyte. (1) Standard reduction potential of zinc is more than
(2) It allows ions to migrate. copper
(3) It prevents the bulk flow of liquids. (2) Standard reduction potential of zinc is less than
(4) It influences the ease of redox reactions in the copper
electrochemical cells. (3) Atomic number of zinc is larger than copper
(4) Atomic number of zinc is lower than copper
57. The position of some metals in the electrochemical
series in decreasing electropositive character is given 64. The correct order of chemical reactivity with water
as Mg > Al > Zn > Cu > Ag. What will happen if a according to electrochemical series is
copper spoon is used to stir a solution of aluminium (1)  K > Mg > Zn > Cu
nitrate? (2)  Mg > Zn > Cu > K
(1) The spoon will get coated with aluminium (3)  Cu > Zn > Mg > K
(2) The alloy of copper and aluminium is formed (4)  Cu > Zn > Mg > K

Chapter_08.indd 9 3/26/2014 3:18:08 PM

 8.10  Objective Chemistry - Vol. I

65. The substance that can reduce Ag+ to Ag but cannot 74. The stronger the oxidising agent, the greater may be its
reduce Ni2+ to Ni is (1) Standard reduction potential
(1) Zn (2)  Pb (3)  Mg (4)  Al (2) Standard oxidation potential
(3) Ionic nature
66. Which defines the standard reduction electrode poten-
(4) None of these
tial of Zn2+ ions?
(1) Zn2+(aq) + 2e- → Zn(s); [Zn2+] = 1M 75. A gas X at atm is bubbled through a solution contain-
(2) Zn(g) → Zn2+ + 2e-; [Zn2+] = 1M ing a mixture of 1M Y- and 1M Z- at 25°C. If the re-
(3) Zn2+(aq) → Zn(s) + 2e-; [Zn2+] = 1M duction potential of Z > Y > X then
(4) Zn2+(g) → Zn(s) - 2e-; [Zn2+] = 1M (1) Y will oxidise X and not Z
67. E° for Fe2+ + 2e- → Fe is -0.44 V and E° for Zn2+ + (2) Y will oxidise Z and not Y
2e- → Zn is -0.76 V. Thus (3) Y will oxidise both X and Z
(4) Y will reduce both X and Z
(1) Zn is more electropositive than Fe
(2) Fe is more electropositive than Zn 76. The order of ease of reduction for the ions H+, Cu2+
(3) Zn is more electronegative and Ag+
(4) None (1) H+ > Cu2+ > Ag+ (2)  H+ > Cu2+ = Ag+
68. A metal having negative reduction potential when (3) Ag > Cu > H
+ 2+ +
(4)  Ag+ > Cu2+ = H+
dipped in the solution of its own ions has a tendency to 77. The reduction potentials increase from -3.04 V for Li
(1) To pass into solution to +2.87 V for fluorine in the table of standard reduc-
(2) To be deposited from the solution tion potentials. This means that
(3) To become electrically positive (1) There is an increasing tendency to lose electrons
(4) To remain neutral from Li to F
69. Standard reduction potential of an element is equal to (2) There is an increasing tendency to gain electrons
(1) +1 × its reduction potential from Li to F
(2) -1 × its standard oxidation potential (3) Fluorine is a powerful reducing agent
(3) 0.00 (4) Lithium is a weak reducing agent
(4) +1 × its standard oxidation potential 78. Copper sulphate solution cannot be stored in an alu-
70. Beryllium is placed above magnesium in the II group. minium vessel because
Beryllium dust therefore when added to MgCl2 (1) Cu2+ ions gets oxidised
­solution will (2) Cu2+ ions gets reduced
(1) have no effect (3) Al gets reduced
(2) precipitate Mg metal (4) Al3+ ions gets reduced
(3) precipitate MgO 79. Four elements A, B, C and D have reduction potentials
(4) lead to dissolution of Be metal -2.71, +0.77, +1.42 and - 0.76 V, respectively. Which
71. The standard hydrogen electrode is written as of the following statements is correct about them?
(1) Pt, H2, H+ (a = 1) (1) A is the strongest reducing agent and it can
(2) Pt, H2 / H+ (a = 1) ­displace B in a chemical reaction.
(3) Pt H2 (g)/atm/H+ (a = 1) (2) C is the strongest reducing agent and it can ­replace
(4) None B in the chemical reaction.
(3) A is the strongest reducing agent and it can be
72. Hydrogen gas will not reduce replaced by C in a chemical reaction.
(1) heated cupric oxide (4) C is the strongest reducing agent and it can be
(2) heated ferric oxide ­replaced by D in a chemical reaction.
(3) heated stannic oxide
80. The standard oxidation potentials of Zn and silver in
(4) heated aluminium oxide
water at 298 K are
73. Which metal does not give the following reaction
→ Zn2+ + 2e–; E° = 0.76 V
Zn 
M + water or steam 
→ oxide + H2 ↑
(1) Iron (2)  Sodium
→ Ag+ + e–; E° = -0.80 V
Ag 
(3) Mercury (4)  Magnesium
Which of the following reactions actually takes place?

Chapter_08.indd 10 3/26/2014 3:18:10 PM

 Redox Reactions  8.11

(1) Z n + 2Ag+ 
→ Zn2+ + Ag
 Practice Exercise
(2) Zn + 2Ag 
2+
→ Zn + 2Ag+
(3) Zn + Ag 
→ Zn2+ + Ag+ 1. In which of the following compounds sulphur exhibit
lowest oxidation state?
(4) Zn2+ + Ag+ 
→ Zn + Ag
(1) Sulphur dioxide
81. From the following data check which of the following (2) Sulphur monochloride
is correct (3) Hydrogen sulphide

→ Ni2+ + 2e-; E° = 0.25 V
  Ni  (4) Oleum
2. OCl- + SO2  → Cl- + SO3

→ Co2+ + 2e-; E° = 0.28 V
  Co 
In the above reaction the oxidation state of chlorine

(1)  i is a better reducing agent
N changes from

(2) Ni2+ is a poor oxidising agent
(1) +1 to -1 (2)  -1 to +1

(3) Co is a better reducing agent
(3) +1 to 0 (4)  -1 to 0

(4) None
3. Oxygen exhibits lowest oxidation state in
82. Given
(1) alkali metal monoxide
→ +0.34 V
A+/A  (2) alkali metal peroxide
→ -1.66 V
B+/B 
(3) alkali metal superoxide
(4) barium peroxide
→ +0.76 V
C+/C 
4. Which of the following reactions depict the oxidising
→ -0.28 V
D+/D  behaviour of H2SO4?

The most reactive metal which displaces other metals (1) 2PCl5 + H2SO4  → 2POCl3 + 2HCl + SO2Cl2
from their salt solution is (2) 2NaOH + H2SO4  → Na2SO4 + 2HCl

(1) C (2)  D (3)  B (4)  A (3) NaCl + H2SO4  → NaHSO4 + HCl
(4) 2HI + H2SO4  → I2 + SO2 + 2H2O
83. Given that
5. In the substance Mg(HXO3)2, the oxidation number

I2 + 2e- 
→ 2I-; E° 0.54 V of X is

Br2 + 2e- 
→ 2 Br-; E° = 1.09 V (1) 0 (2)  +2 (3)  +3 (4)  +4

Which of the following is a true statement? 6. The equivalent weight of MnSO4 is half its molecular

(1) Iodide will reduce bromine to bromide ion. weight when it is converted into

(2) Iodine is a stronger oxidising agent than bromine. (1) Mn2O3 (2)  MnO4-

(3) Bromine will reduce iodine to iodide ion. (3) MnO2 (4)  MnO42-

(4) All are true. 7. The number of electrons lost by Cl- in the reaction
Cl-  → ClO3- is
(1) 1 (2)  3 (3)  5 (4)  6
Answers 8. XCrO42- + YH+ + ZH2O2  → CrO5 + H2O
In the above reaction X, Y and Z, respectively are
(51) 2 (52) 3 (53) 1 (54) 4 (55) 3
(1) 1, 1, 1 (2)  1, 2, 2 (3)  2, 1, 2 (4)  2, 2, 1
(56) 4 (57) 4 (58) 3 (59) 1 (60) 4
(61) 4 (62) 1 (63) 2 (64) 1 (65) 2 9. Identify− the balanced oxidation half-reaction in
(66) 1 (67) 1 (68) 1 (69) 2 (70) 1 P4 OH  → 3H2PO2- + PH3
(71) 3 (72) 4 (73) 3 (74) 1 (75) 1 (1) P4 + 8H2O + 8OH- → 4H2PO2- + 8H2O + 4e-
- → 4H2PO2- + 6H2O + 2e-
(76) 3 (77) 2 (78) 2 (79) 1 (80) 1 (2) P4 + 6H2O + 6OH
(81) 3 (82) 3 (83) 1 (3) P4 + H2O + 12e- → PH3 + 12OH-
(4) P4 + 12H2O + 12e 
-
→ 4PH3 + 12OH-

Chapter_08.indd 11 3/26/2014 3:18:13 PM

 8.12  Objective Chemistry - Vol. I

10. Identify the balanced equation for reduction half-­ 19. The molar ratio of Cl2 to Cl- ion in the following
reaction in ­balanced equation
MnO4- + Cl- + H+  → Mn2+ + Cl2 + H2O is
Cr2O72- + H+ + NO2 
→ Cr3+ + H2O + NO3-
(1) 1:2 (2)  1:1 (3)  2:1 (4)  5:1

(1)  r2O72- + 14H+ + 6e- 
C → 2Cr3+ + 7H2O
20. Regarding oxidation state which of the following is false?

(2) 2Cr2O72- + 14H+ + 10e- → 2Cr3+ + 7H2O

(3) NO2- + H2O  → NO3- + 2H+ + 2e- (1) during oxidation, oxidation state increases

(4) NO2- + 2H2O  → NO3- + 4H+ + 4e- (2) in a redox reaction oxidation state of reductant
­increase
11. What is the oxidation state of hydrogen in LiAlH4? (3) the substance with higher oxidation state may act
(1) 0 (2)  +1 (3)  -1 (4)  none as a reducing agent
(4) in a redox reaction oxidation number of an ­oxidant
12. A sulphur-containing species that cannot be a reducing
decrease
agent is
(1) SO2 (2)  SO32- (3)  H2SO4 (4)  S2- 21. Select the correct statement in the following reaction
NH4NO2  → N2 + 2H2O
13. Which of the following changes require a reducing
(1) Oxidation number of N has changed from -2 to +2
agent?
(2) Oxidation number of N in NH4+ changed from -3
(1) CrO42- 
→ Cr2O72- to 0 and that in NO2- changed from +3 to 0
(2) BrO3- → BrO- (3) Oxidation number of N in NH4+ changed from +1
(3) H2O2  → O2 to 0 and that in NO2- changed from -1 to 0
(4) Al(OH)3 → Al(OH)4- (4) No change
14. In the reaction 2NH4+ + 6NO3- + 4H+ 
→ 6NO2 + 22. If the following is a balanced reaction
N2 + 6H2O, the reducing agent is
  4O2x- + 2H2O 
→ 4OH- + 3O2. Then, x is
(1) NH4+ (2)  NO3- (3)  H+ (4)  NO2

(1) -
 1 and species is superoxide
15. On balancing the selected half-reaction S2O32- 
→

(2) -2 and species is peroxide
S the number of electrons that must be added is

(3) -4 and species is oxide
(1) 2 on the left

(4) -1 and species is peroxide
(2)  2 on the right
(3) 4 on the left 23. More electropositive elements have
(4)  4 on the right (1) Positive reduction potential
16. NO3− + 4H+ + 3e- 
→ NO + 2H2O (2) Tendency to gain electrons
(3) Negative reduction potential
Zn  → Zn2+ + 2e-

(4) Negative oxidation potential
These equations represent a reaction between nitric
acid and zinc. How many moles of NO3- are reduced 24. A KI solution containing starch turns blue on the
by 1 mole of zinc? ­addition of chlorine. Which of the following state-
(1) 2/3 (2)  3 (3)  3/2 (4)  2 ments explain this?
(1) The reduction potential of Cl2 is more than that of I2.
17. Given the reaction (2) The oxidation potential of Cl2 is more than that of I2.
  S2O82- + 2e-  → 2SO42- (3) The reduction potential of Cl2 is less than that of I2.

Mn2+ + 4H2O  → MnO4- + 8H+ + 5e- (4) The product formed when Cl2 combines with
How many moles of S2O82– ions are required to oxidise starch is blue.
1 mole of Mn2+ ions? 25. The oxidation number of carbon is zero in
(1) 0.5 (2)  1.0 (3)  2.0 (4)  2.5  I. HCHO  II. CH2Cl2
18. One mole of hydrazine N2H4 react with one mole of III. C6H12O6 IV. C12H22O11
sulphurous acid (H2SO3) the latter is reduced to sulphur
(1) I, II only
into which of the following is hydrazine is changed to?
(2)  I, II, III only
(1) N2 (2)  2NH3
(3) All
1
(3) NH3 + N2 (4)  2NH2OH
(4)  None
2

Chapter_08.indd 12 3/26/2014 3:18:17 PM

 Redox Reactions  8.13

26. In the unbalanced reaction 32. A solution of 0.1 M KMnO4 is used in the reaction
Al + KMnO4 + H2SO4 → KHSO4 + MnSO4 + H2O. S2 O32 − + 2MnO −4 + H 2 O → MnO2 + SO24− + OH −
The stoichiometric coefficients of Al, H2SO4, MnSO4
The volume of KMnO4 required to react with 0.158 g
and H2O are w, x, y and z respectively the numerical of Na2S2O3 is (Mw = 158) α
x z 
value of  −  will be
(1) 13.33 ml (2)  6.66 ml
y w
(3) 3.33 ml (4)  26.67 ml

(1) 2.0 (2)  2.1 (3)  1.2 (4)  2.4 33. The number of H+ ions in the balanced equation of the
27. Which of the following have been arranged in order of above redox reaction is
decreasing oxidation number of sulphur? (1) 8 (2)  6 (3)  4 (4)  2
 I. H2S2O7 > Na2S4O6 > Na2S2O3 > S8 34. What are the oxidation numbers of nitrogen in
 II. SO2+ > SO42- > SO32- > HSO4- NH4NO3?
III. H2SO5 > H2SO3 > SCl2 > H2S (1) +3, -5 (2)  -3, +5
IV. H2SO4 > SO2 > H2S > H2S2O8 (3) +3, -6 (4)  +2, +2
The correct set is 35. In a reaction 4 mole of electrons are transferred to one
(1) I, IV (2)  I, III mole of HNO3. The possible product obtained due to
(3)  II, IV (4)  II, III reaction is
28. In basic medium, the coefficients of Zn, NO3- and OH- (1) 0.5 mole of N2 (2)  1 mole of NO2
in the following balanced equation respectively are (3) 0.5 mole of N2O (4)  1 mole of NH3
Zn + NO3- 
→ Zn2+ + NH4+ 36. In acid medium the reaction taking place is

(1) 4 , 1, 7 (2)  7, 4, 1 MnO −4 → Mn 2+. This reaction is

(3) 4, 1, 10 (4)  1, 4, 10 (1) oxidised by 3 electrons
(2) reduced by 3 electrons
29. Oxidation states of all the atoms in potassium triiodide
(3) oxidised by 5 electrons
are
(4) reduced by 5 electrons
1 1 1 1
(1) + , − , − −
37. In which of the following compounds transition metal
3 3 3, 3
is in oxidation state of zero?
1 1 1 (1) [Co(NH3)6]Cl2 (2)  [Fe(H2O)6]SO4
(2) +1, + , − , −

3 3 3, (3) [Ni(CO)4] (4)  [Fe(H2O)3](OH)2

(3) +1, − 1, 0, 0
38. The oxidation number of sulphur in S8, S2F2 and H2S
respectively are
(4) +1, − 1, − 1, − 1
(1) 0, +1, -2 (2)  +2, +1, -2
(3) 0, +1, +2 (4)  -2, +1, -2
30. A solution containing Cu2+, C2O42- ions. The solution
requires 22.6 ml of 0.02 M KMnO4 in the presence of 39. In the balanced equation 5H2O2 + xClO2 + 2OH-
H2SO4 for oxidation. The resulting solution is neutral-  → xCl- + yO2 + 6H2O, the reaction is balanced if
ised and add excess KI. The iodine liberated requires (1) x = 5, y = 2 (2)  x = 2, y = 5
11.3 mL of 0.05 M Na2S2O3 solution. The molar ratio (3) x = 4, y = 10 (4)  x = 5, y = 5
of Cu2+, C2O42- in solution is
(1) 1:1 (2)  1:2 (3)  2:1 (4)  1:3 40. In the chemical reaction
Ag2O + H2O + 2e- 
→ 2Ag + 2OH-
31. In a reaction FeS2 is oxidised by O2 to Fe2O3 and SO2.
If the equivalents of O2 consumed are “Y” then the
(1) w ater is oxidised (2)  silver is oxidised
equivalents of FeS2 consumed and moles of Fe2O3 and
(3) silver is reduced (4)  hydrogen is reduced
SO2 produced are respectively 41. The coefficients of I-1 and H+ in the redox reaction
y 2y y y I − + IO3− + H +  → I 2 + H 2 O in the balanced form

(1) y, , (2)  y, ,
22 11 2 5 respectively are

(3) y, y, y (4)  None of these (1) 5, 1, 6 (2)  1, 5, 6 (3)  6, 1, 5 (4)  5, 6, 1

Chapter_08.indd 13 3/26/2014 3:18:19 PM

 8.14  Objective Chemistry - Vol. I

42. In which of the following compounds, the oxidation 48. A 2.5 mole of hydrazine N2H4 loses 25 moles of elec-
number of iodine is fractional? trons to form a new compound x. Assuming that all of
(1) IF7 (2)  I3– (3)  IF5 (4)  IF3 the nitrogen appears in the new compound, what is the
oxidation state of nitrogen in compound x?
43. The false statement about the following reaction is
(1) -1 (2)  -2 (3)  +3 (4)  +4
  NH 4 NO2  → N 2 + 2H 2 O
49. The following facts are available

(1)  is oxidised
N

(2) N is reduced 2A- + B2  → 2B- + A2

(3) it is a disproportionation reaction 2C + B2 
-
→ no reaction

(4) it is comproportionation reaction 2D + A2 
-
→ 2A + D2
44. When KMnO4 acts as an oxidising agent and ultimately
Which of the following statements is correct?
forms MnO −4 , MnO2, Mn2O3 and Mn2+, then the num-
(1) EC− / C2 > E B− / B2 > E A − / A2 > E D− / D2
o o o o
ber of electrons transferred in each case respectively is
(2) EC− / C2 < E B− / B2 < E A − / A2 < E D− / D2
o o o o
(1) 4, 3, 1, 5 (2)  1, 5, 3, 7
(3) 1, 3, 4, 5 (4)  3, 5, 7, 1 (3) EC− / C2 < E B− / B2 > E A − / A2 < E D− / D2

o o o o

(4) EC− / C2 > E B− / B2 < E A − / A2 < E D− / D2

o o o o
45. The oxidation states of the most electronegative ele-
ment in the products of the reaction between BaO2 and
dilute H2SO4 are
(1) 0 and -1 (2)  -1 and -2 Answers
(3) -2 and 0 (4)  -2 and +1
  (1) 3   (2) 1   (3) 1   (4) 4   (5) 4
46. The oxidation state of molybdenum in its oxospecies   (6) 3   (7) 4   (8) 2   (9) 1 (10) 1
[Mo2O4(C2H4)2 (H2O2)]2- is (11) 3 (12) 3 (13) 2 (14) 1 (15) 3
(1) 2 (2)  3 (3)  4 (4)  5 (16) 1 (17) 4 (18) 1 (19) 1 (20) 3
(21) 2 (22) 1 (23) 3 (24) 1 (25) 3
47. A, B and C are three elements forming a part of com- (26) 2 (27) 2 (28) 3 (29) 3 (30) 2
pounds in oxidation states of +2, +5 and -2 respec- (31) 1 (32) 4 (33) 2 (34) 2 (35) 3
tively what could be the compound? (36) 4 (37) 3 (38) 1 (39) 2 (40) 3
(1)  A2(BC)2 (2)  A2(BC)5 (41) 1 (42) 2 (43) 3 (44) 3 (45) 2
(3)  A3(BC4)2 (4)  A(BC)2 (46) 2 (47) 3 (48) 3 (49) 1

Chapter_08.indd 14 3/26/2014 3:18:20 PM

 9

Chapter
Hydrogen and its Compounds

Hydrogen (iv) Similar to halogens it is a nonmetal and exists as

diatomic molecule.
Position of Hydrogen in the Periodic Table
• Electrolysis of fused metal halides liberates halogen at
• Hydrogen is the lightest and simplest of all the elements. anode. Similarly hydrogen is liberated at anode during
• The position of hydrogen in the periodic table is not the electrolysis of fused metal hydrides.
certain. It can be kept in both I group along alkali
­metals and VII group along halogens. Occurrence
• Similarities with alkali metals
• Hydrogen is the most abundant (about 98%) element
(i) Similar to alkali metals it can lose its 1s1 electron in the universe.
and convert into H+ ion.
• Hydrogen is the 9th most abundant element on the
(ii) Similar to alkali metals it contains one electron in
its valence shell. earth’s surface.
(iii) Similar to alkali metals hydrogen is ­monovalent,
electropositive in character and exhibit +1 Isotopes of Hydrogen
­oxidation state.
• Isotopes of hydrogen are ordinary hydrogen or protium
(iv)  Electrolysis of alkali metal halides liberates
alkali metals at cathode. Similarly, electrolysis of ( )
1
( 2 2
) (
3 3
1 H , deuterium 1 H or 1 D and tritium 1 H or 1 T . )
hydrochloric acid or electrolysis of water liberates • The difference in mass percentage of isotopes of hydro-
hydrogen at cathode. gen isotopes when compared with the isotopes of other
(v) Similar to alkali metals hydrogen forms oxides, elements is maximum due to which the ­properties of
halides, etc. hydrogen differ much.
• Ordinary hydrogen is more reactive than deuterium.
Similarities with halogens • Ordinary water decomposes six times faster than
(i)  Because of very high ionisation potential of heavy water during electrolysis.
hydrogen instead of losing electron it shares its • Hydrogen and deuterium can be separated by gas
electron with other elements and form mostly ­diffusion method.
covalent compounds similar to halogens.
• Tritium is the lightest radioactive isotope with half-
(ii) Hydrogen can form H- ion by gaining electron
life period of 12.26 years and emits β-particles during
similar to halogens but only with highly electro-
disintegration.
positive elements like alkali metals, alkaline earth
metals, aluminium, etc. • Tritium is formed by the bombardment of lithium
(iii) Similar to halogens, hydrogen has an electronic nucleus with neutron in nuclear reactions (artificially).
configuration of one electron short of inert gas • Deuterium and tritium are used as tracers in the study
configuration. of the mechanism of complex reactions.

Chapter_09.indd 1 3/26/2014 3:18:59 PM

 9.2  Objective Chemistry - Vol. I

(3) Hydrogen will not be liberated at anode.

 Objective Questions (4) Hydrogen has an oxidation state of +1 and -1

1. Which of the following statement is false? 9. Which of the following about hydrogen is correct?
(1) Hydrogen can be placed in the halogen group (1) It can form bonds in +1 as well as -1 oxidation
­because it forms hydrides like chlorides. state
(2) The best explanation for not placing hydrogen (2) It is collected at cathode
with the group of alkali metals or halogens is that (3) It has a very high ionisation potential
the IP of H2 is too higher than alkali metal but too (4) All of these
low than halogens. 10. Heavy hydrogen is used
(3) The tendency of hydrogen to gain one electron to (1) in filling the balloons
acquire He configuration resembles halogens. (2) in studying reaction mechanism
(4)  Hydrogen molecules are diatomic and form (3) in calculating the heat of formation
H- ions similar to halogens. (4) in oxidation
2. The sum of the number of neutrons and protons in 11. There is an enormous relative mass difference among
one of the isotope of hydrogen is the 3 isotopes of hydrogen. Therefore
(1)  3 (2) 
4 (3) 5 (4) 6 (1) They take part in different types of chemical re-
3. Which of the following statements about tritium is actions
false? (2) They have widely different densities
(1) Tritium emits γ-rays. (3) They show much greater difference in physical
(2) Tritium is obtained by nuclear reaction. properties than the isotopes of other elements
(3) The disintegration product of tritium is 32 He. (4) They have nuclear stabilities
(4) Its physical properties are different from those of 12. Ordinary hydrogen is a mixture of the isotopes H and D.
deuterium. In which of the following properties would the two
4. Hydrogen shows gases H2 and D2 differ?
(1) +1 oxidation state only (1) Number of molecules present in a given volume
(2) -1 oxidation state only at STP
(3) zero oxidation state only (2) Rate of diffusion under the same conditions of
(4) +1, -1 and zero oxidation states temperature and pressure
(3) Colour
5. Deuterium resembles hydrogen in chemical properties (4) Number of orbital electrons
but reacts
(1) slower than hydrogen Answers
(2) faster than hydrogen
(3) more vigorously than hydrogen (1) 2 (2) 1 (3) 1 (4) 4 (5) 1
(4) just as hydrogen (6) 3 (7) 3 (8) 4 (9) 4 (10) 2
(11) 3 (12) 2
6. Hydrogen has 3 isotopes and therefore the possible
number of forms of hydrogen molecule is
(1)  9 (2) 3 (3) 6 (4) 2
types of Hydrogen
7. Molten ionic hydride on electrolysis gives
(1) H+ ions moving towards the cathode
Nascent Hydrogen
(2) H+ ions moving towards the anode • Hydrogen at the moment of its formation is known as
(3) H2 is liberated at anode nascent hydrogen.
(4) H2 is liberated at cathode
• Ordinary hydrogen cannot reduce (decolourise) the
8. Which of the following is correct? acidified permanganate, but the nascent hydrogen
(1)  Hydrogen has same ionisation potential as ­produced by adding zinc to acidified permanganate
sodium. can reduce it.
(2)  Hydrogen has the same electronegativity as • Ordinary hydrogen cannot reduce acidified ferric
­halogens. ­chloride but nascent hydrogen can reduce it.

Chapter_09.indd 2 3/26/2014 3:19:00 PM

 Hydrogen and its Compounds  9.3

• Nascent hydrogen produced by the action of zinc with • It is possible to obtain pure para hydrogen but it is not
dil. HCl can reduce the chlorate to chloride but nascent possible to obtain a sample containing more than 75%
hydrogen produced by the action of sodium amalgam ortho hydrogen.
with water cannot reduce. • The thermal conductivity of para hydrogen is 50%
• At the moment of production nascent hydrogen is present more than that of the ortho hydrogen.
in a very small bubble, where the internal pressure is very • The melting point of para hydrogen is 0.15 K less than
high due to which nascent hydrogen has high reactivity. that of hydrogen containing 75% of orthohydrogen.
• By increasing pressure, reactivity of ordinary hydro-
gen can be increased.

Atomic Hydrogen  Objective Questions

• Bond energy of H2 molecule is very high and is 13. Which of the following statements is wrong?
436 kJ mol-1.
(1) The conversion of atomic hydrogen into ordinary
• At very high temperatures of about 2000  K, H2 hydrogen is endothermic in nature.
molecules convert into atomic hydrogen by about
­ (2) Atomic hydrogen is obtained by thermal decom-
0.081% which increases to 95.5% at 5000 K. position of hydrogen at very high temperatures.
• The life period of atomic hydrogen is only 1/3 of a second. (3) Acidified solution of FeCl3 cannot be reduced by
• Atomic hydrogen is highly reactive and acts as a strong ordinary hydrogen.
reducing agent. (4)  The life period of atomic hydrogen is only
­one-third of a second.
• Conversion of atomic hydrogen into ordinary hydrogen
is highly exothermic. 14. Which statements regarding ortho- and para hydro-
• Atomic hydrogen welding torch is used for cutting and gen is false?
welding the metal plates and rods. (1) Ordinary hydrogen is a mixture of 75% ortho and
25% para hydrogens.
Active Hydrogen (2) Ortho- and para hydrogens are so called due to
• the difference in the nature of spin of protons.
Active hydrogen can be obtained by subjecting a stream
(3) The nuclear spin of ortho hydrogen is zero while
of hydrogen gas at ordinary temperatures to silent elec-
that of parahydrogen is 1.
tric discharge at a voltage of about 30,000 volts.
(4) Percent of para hydrogen in ordinary hydrogen
• Active hydrogen is highly reactive and combines with increases when temperature is lowered.
lead and sulphur directly at ordinary temperatures.
15. The wrong statement among the following is
Ortho- and Parahydrogen (1) Hydrogen produced in contact with a substance
• Hydrogen exists as ortho- and parahydrogen. to be reduced is active hydrogen.
(2) Nascent hydrogen is chemically more reactive
• If the nuclei in a molecule of hydrogen have same spin because it is contained in a tiny bubble under
it is known as orthohydrogen but if they have opposite high pressure.
spin it is known as parahydrogen. (3) The most reactive state of hydrogen is active
• Ortho- and parahydrogens are spin isomers and differ hydrogen.
in physical properties such as boiling points, specific (4) Nascent hydrogen produced by different methods
heats, internal energies, band spectra, etc. has different reactivity.
• The nuclear spin of orthoisomer is 1 while that of para 16. Under what conditions of temperature and pres-
form is 0. sure, formation of atomic hydrogen from molecular
• At absolute zero hydrogen is 100% para in nature but hydrogen will be favoured?
with increase in temperature it slowly converts into the (1) High temperature and high pressure
ortho form. (2) Low temperature and low pressure
• At ordinary temperatures, the ratio between ortho- and (3) High temperature and low pressure
parahydrogens is 3:1. (4) Low temperature and high pressure

Chapter_09.indd 3 3/26/2014 3:19:00 PM

 9.4  Objective Chemistry - Vol. I

17. Ortho- and parahydrogens do not differ in preparation of Hydrogen

(1) Band spectra
• Highly electropositive metals like alkali metals and
(2)  Boiling point
(3) Internal energy alkaline earth metals react with water liberating
(4)  Molecular mass hydrogen.
• In the laboratory hydrogen is prepared by the action of
18. Atomic hydrogen is obtained by passing ordinary zinc with dil. HCl, but pure zinc react only slowly due
hydrogen through to high energy of activation.
(1) a suitable catalyst maintained at high temperature • Pure hydrogen is not obtained by the action of m ­ etals
under high pressure
on acids such as HNO3, H2SO4 and HCl since the
(2) a solution containing zinc and sulphuric acid
hydrogen produced may be contaminated with oxides
(3) an electric arc
of sulphur or nitrogen and HCl vapours.
(4) a silent electric discharge at ordinary temperature
• Large quantities of hydrogen are prepared by passing
19. Which of the following statements is wrong? steam over red hot coke and the process is known as
(1) The most reactive state of hydrogen is atomic coal gasification.
hydrogen. C + H2O → CO + H2
(2)  The poorest reducing form of hydrogen is
• Since the mixture of CO and H2 (water gas) is used for
dihydrogen.
the synthesis of methanol and a number of hydrocar-
(3) Para hydrogen is more stable than ortho hydrogen.
bons, it is also called as synthesis gas or syn gas.
(4) Ortho hydrogen has more internal energy than
parahydrogen. • The water gas mixed with twice the amount of steam
and passed over a catalyst to convert CO to CO2 and
20. Which of the following statement is correct? this reaction is known as water gas shift reaction.
(1) The vapour pressure of ortho hydrogen is more • In Lane’s process, hydrogen is prepared by passing
than that of para hydrogen. superheated steam over red hot iron.
(2) The specific heat of ortho hydrogen is more than
that of para hydrogen.
3Fe + 4H2O → Fe3O4 + 4H2
(3) The conductivity of ortho hydrogen is smaller • In Uyeno’s process, hydrogen is prepared by treating
than that of para hydrogen. scrap aluminium with sodium hydroxide solution.
(4) All are correct. • Electrolysis of acidified or alkaline water using Pt or
Ni electrodes gives hydrogen.
• High pure hydrogen is obtained by the electrolysis of
Answers
warm Ba(OH)2 solution between nickel electrodes.
(13) 1 (14) 3 (15) 1 (16) 3 (17) 4 • Hydrogen is produced as a by-product during cracking
(18) 3 (19) 3 (20) 4 of hydrocarbons and in the manufacture of Cl2 and
NaOH by the electrolysis of brine.

Preparation of Hydrogen
Method Remark
1. Metal + water → Metal hydroxide + H2 Na, K, Rb, Cs, Ca, Sr, Ba (cold)
2. Metal + steam → Metal oxide + H2 Mg, Fe, Zn, Al.
3. Metal + acid → Salt + H2 Metals above hydrogen in e.m.f. series. (pure H2 is not obtained).
4. Metal + base → Salt + H2 Amphoteric metals such as Be, Al, Zn, Sn.
5. Metal hydride + water → Metal hydroxide + H2 NaH, CaH2, etc.
6. Coke + steam → CO + H2 Water gas
7. Hydrocarbons + steam catalyst
→ CO + H 2
8. Electrolysis of acidulated or alkaline water → H2
9. By-product In the manufacture of NaOH and Cl2 by the electrolysis of brine
2NaCl + 2H 2O → 2 NaOH + H 2 + Cl 2 and in cracking of petroleum
CH 3 − CH 3 → CH 2 = CH 2 + H 2

Chapter_09.indd 4 3/26/2014 3:19:01 PM

 Hydrogen and its Compounds  9.5

properties of hydrogen • Methyl alcohol is manufactured by passing a mixture

of water gas and hydrogen over ZnO and Cr2O3
• Hydrogen burns in oxygen forming water. The ­reaction mixture (catalyst) at 300°C and 200 atomic pressure,
between H2 and O2 without igniting is very slow at methyl alcohol will be formed
ordinary temperatures but can be catalysed by Pd and + Cr2 O3
Platinum black. CO + H2 + H2 ZnO

Water gas
→ CH3OH
• Hydrogen reacts with halogens forming hydrogen hal- • In Fischer-Tropsch process, synthetic petrol is
ides or hydraacids and the reactivity of halogens with ­prepared by passing water gas and hydrogen in 2:1
hydrogen decreases in the order of F2 > Cl2 > Br2 > I2. ratio over cobalt catalyst.
• Hydrogen reduces several metal oxides and halides to • Hydrogen is used as a reducing agent in the extraction
their corresponding metals E.g. CuO to Cu and AgCl of metals like molybdenum and tungsten.
to Ag. • Hydrogen is used as a fuel in the form of water gas,
• Hydrogen combines with many unsaturated organic coal gas, etc. which contain hydrogen.
compounds at double or triple bonds converting them • Oxyhydrogen blow torch produces very high temper-
to saturated compounds. atures of about 3000°C at which quartz and several
• H2 combines with CO forming methanol. ­metals can be melted and welded.
• Hydrogen combines with several metals forming ­metal • Liquid hydrogen is used as fuel in the rocket Saturn V
hydrides. through which Neil Armstrong reached the moon.
• Lithium hydride reacts with aluminium chloride • Though heat of combustion of hydrogen is very high, it
­forming lithium aluminium hydride, an important is not much used as a fuel and a reducing agent ­because
reducing agent. (i) preparation of hydrogen is costlier and (ii) storage
and transportation of hydrogen is dangerous.
Reactions of Hydrogen • The cells in which the chemical energy is directly con-
verted into electrical energy are called fuel cells and
1. H 2 + Li 
→ LiH
their efficiency is very high.
2. H 2 + Na 
→ NaH • Hydrogen can be used in fuel cell for the production of
electrical energy.
3. H 2 + Ca 
→ CaH 2
• Hydrogen can be used as a source of nuclear energy.
4. H 2 + La 
→ LaH 2 • When lighter nuclei such as hydrogen, deuterium are
5. H 2 + U 
→ UH 2.87 fused to form heavier nuclei very high amount of
­energy will be released.
6. H 2 + CuO 
→ Cu • To overcome the repulsion between the positively
7. H 2 + WO3 
→W charged nuclei the fusion reactions must be carried at
high temperature. Hence, they are known as thermo-
8. H 2 + Fe3 O 4 
→ Fe nuclear reactions.
9. H 2 + AgCl 
→ Ag • The heat liberated during the fission bomb is used in the
fusion of two isotopes of hydrogen in hydrogen bomb.
10. H 2 + N 2 
→ NH 3 • The energy coming from sun and stars is due to nuclear
11. H 2 + Y2 
→ 2HY (Y = F, Cl, Br or I) fusion reactions between hydrogen nuclei forming
helium.
12. H 2 + CO 
→ CH 3 OH

Uses of hydrogen  Objective Questions

• Hydrogen is used in industries for (i) manufacture 21. Hydrogen is not used
of ammonia by Haber’s process, (ii) manufacture of (1) in the manufacture of vegetable ghee
­hydrochloric acid and (iii) the production of vanaspathi (2) in the production of high temperature
or dalda or margarine by the hydrogenation of (3) as a rocket fuel with kerosene
vegetable oils. (4) as a reducing agent

Chapter_09.indd 5 3/26/2014 3:19:03 PM

 9.6  Objective Chemistry - Vol. I

22. Hydrogen combines with O2 to form H2O. In this 29. Commercial hydrogen is obtained from
­reaction (1) coal gas (2)  water gas
(1) Hydrogen gets reduced (3) air (4)  producer gas
(2) Hydrogen gets oxidised
30. Atomic hydrogen produces formaldehyde when it
(3) Oxygen is oxidised
reacts with
(4) None
(1) water (2)  carbon monoxide
23. In the fuel cells (3) carbon dioxide (4)  formic acid
(1)  The heat energy is directly converted into
31. The most dangerous method of preparing hydrogen
­electrical energy
would be by the action of HCl and
(2)  The heat energy is indirectly converted into
­electrical energy (1) Zn (2) Fe (3) K (4) Al
(3) Electrical energy is directly converted into heat 32. Pure hydrogen can be prepared by
energy (1) the electrolysis of baryta water
(4) Electrical energy is indirectly converted into heat (2) the action of Zn on dil. HCl
energy (3) the action of Zn on dil. HNO3
24. Which of the following is a wrong statement? (4) the action of Zn on dil. H2SO4
(1) Nickel is used as catalyst in the hydrogenation
of oil. Answers
(2) The catalyst used in the manufacture of methyl
alcohol from water gas is CuO + ZnO. (21) 3 (22) 2 (23) 1 (24) 2 (25) 1
(3) The catalyst used in Fischer-Tropsch synthesis (26) 4 (27) 2 (28) 2 (29) 2 (30) 2
of petrol is cobalt. (31) 3 (32) 4
(4) Solar energy is due to nuclear fusion reactions in
sun.
25. Thermo nuclear reactions are hydrides
(1) Fusion reactions • The binary compounds of hydrogen with other ele-
(2) Fission reactions ments are called hydrides and they are of three types.
(3) Both fusion and fission reactions
(4) Artificial disintegration reaction
Saline or Ionic or Salt Like
26. Though heat of combustion of hydrogen is very high, Hydrides
hydrogen is not much used as a fuel because
• These are formed with most of the s-block elements.
(1) hydrogen is not available as an element
LiH, BeH2 and MgH2 have significant covalent character.
(2) preparation of hydrogen gas is costlier
(3)  storage and transportation of hydrogen is • These are prepared by heating s-block elements,
­dangerous ­except Be and Mg, in hydrogen at high temperatures.
(4) all are correct • They have high melting points, insoluble in common
non-aqueous solvents, react vigorously with water and
27. Artificial fats are acids liberating hydrogen.
(1) Saturated vegetable oil converted into ­unsaturated • So, these are used as a source of hydrogen.
oils
• Alkali metal hydrides have rock-salt structure.
(2) Unsaturated vegetable oil converted into satu-
rated oils • Thermal stability of alkali metal hydrides and alkaline
(3) Hydrated vegetable oil earth metals decreases down the group.
(4) Dehydrated vegetable oil • Electrolysis of these fused hydrides liberates hydrogen
28. In Bosch’s process, which gas is utilised for the at anode.
­production of hydrogen? • Densities of these hydrides are greater than that of the
(1) producer gas metal from which they are formed.
(2)  water gas • Fires produced by saline hydrides cannot be extin-
(3) coal gas guished by CO2 as it gets reduced by the hot metal
(4)  natural gas hydrides. Only sand can extinguish the fire.

Chapter_09.indd 6 3/26/2014 3:19:03 PM

 Hydrogen and its Compounds  9.7

• Calcium hydride is called hydrolith, used in the labo- • The presence of lone pairs of electrons on highly
ratory to remove traces of water from solvents and electronegative atoms like F, O and N in e­ lectron-rich
inert gases such as N2 and Ar. hydrides result in hydrogen bond formation which
­
leads to high boiling points, high permittivity
Metallic or Interstitial Hydrides ­(dielectric constants) and aggregation.
• These are formed by the d- and f-block elements.
These are formed by the occupation of hydrogen at-
oms in the interstitial positions of the metal crystals.  Objective Questions
• Metallic hydrides are non-stoichiometric compounds
and show electrical conduction. 33. Which of the following statements is not correct?
• The properties of these hydrides are similar to those of (1) H+ has a unique ability to distort the electron
the parent metal. cloud surrounding other atoms.
• Some metals like Pt and Pd can accommodate a very (2) H- ions exist only in the saline hydrides formed
large volume of hydrogen called occluded hydrogen. by the most electropositive metals.
• The hydrogen absorbed by the metals will be released (3)  All the elements in the periodic table form
when heated and this property is used in the purifi- hydrides.
cation of hydrogen, storing of hydrogen and also for (4) The majority of hydrogen compounds contain
reduction and catalytic hydrogenation. electron pair bond.
• In the chromium group, only chromium forms metallic 34. Which of the following statements regarding saline
hydride. hydrides is false?
• In the periodic table, the region of groups 7 to 9 is (1) Saline hydrides are formed only by those ele-
referred to as the hydride gap because metals in these ments which have very low electronegativity
groups do not form metallic hydrides. values and can transfer electrons to the hydrogen
atom.
(2) Salt-like hydrides are solids with ionic lattices.
Molecular or Covalent Hydrides (3) In fused state, saline hydrides conduct electricity.
• These are formed by p-block elements and consist of (4) The density of salt-like hydrides is lesser than the
individual, discrete covalent molecules. parent metal.
• The molecular formula of covalent hydrides can be 35. Which of the following can absorb large volume of
written as MHn or MH8− n where n = group number of hydrogen gas?
the element in the short form periodic table.
(1) Finely divided platinum
• Covalent hydrides are named from the name of ­element (2) Finely divided nickel
and the suffix “ane”. (3) Colloidal solution of palladium
E.g., phosphane, PH3; oxidane, H2O and azane, NH3. (4) Colloidal magnesium hydroxide
• Molecular hydrides having a less number of electrons 36. The adsorption of large volumes of hydrogen by
for writing the conventional Lewis structure are called ­metal such as palladium is known as
electron-deficient hydrides. E.g., B2H6.
(1) Dehydrogenation
• Molecular hydrides formed by the elements of IV or (2) Hydrogenation
14 group elements in which all the valence electrons (3) Occlusion
are involved in bond formation are known as electron- (4) Adsorption
precise hydrides.
37. Which of the following statements is correct for salt-
• Molecular hydrides which contain more valence
like hydrides?
electrons than required for bond formation are called
electron-rich hydrides. They contain lone pairs, e.g., (1) They have high heat of formation.
NH3, H2O, etc. (2) They are always stoichiometric.
• Only weak Van der Waal’s attractive forces exist (3) They are powerful reducing agents especially at
­between the molecules of covalent hydrides. So, they high temperature.
are volatile with low boiling points. (4) All are correct.

Chapter_09.indd 7 3/26/2014 3:19:03 PM

 9.8  Objective Chemistry - Vol. I

38. Regarding covalent hydrides, which of the following Answers

statement is wrong?
(1) They are formed by elements of high electron- (33) 3 (34) 4 (35) 3 (36) 3 (37) 4
egativity. (38) 4 (39) 4 (40) 1 (41) 1 (42) 4
(2) They are formed by the p-block elements due to (43) 3 (44) 2
sharing of electrons with hydrogen.
(3) They have low melting and boiling points and do
not conduct electricity.
(4) They cannot act as reducing agents. water
39. Which of the following statements is correct? • Water has an abnormally high freezing point, boiling
(1) Hydrides of B, Al, Ga and In are electron defi- point, heat of vaporisation, heat of fusion, etc. due to
cient and polymeric. the association of molecules through hydrogen bonds.
(2) Aluminium hydride is (AlH3)n. • The high heat of vaporisation and high heat capacity
(3) Covalent hydrides are generally volatile. of water are responsible for moderation of the climate
(4) All are correct. and body.
40. Which of the following statements regarding intersti- • Solubility of ionic compounds in water is due to its
tial hydrides is false? polar nature while the solubility of covalent com-
­
(1) In these hydrides hydrogen is present as hydride pounds such as alcohols, carbohydrates, urea, etc. is
ion. due to their ability to form hydrogen bonds with water.
(2) They are less dense than the parent metal. • Under very high pressure and temperature water behaves
(3)  In these hydrides hydrogen is often absorbed like a non-polar solvent in which organic compounds
­reversibly by the metal. are more soluble while inorganic salts are insoluble.
(4) These hydrides are nonstoichiometric. • Purest water is rain water. In water, the ratio of hydro-
41. Ionic hydrides react with water to give gen and oxygen is 2:1 by volume and 1:8 by weight.
(1) a basic solution (2)  an acidic solution • Dipole moment of water is 1.85 D while dielectric con-
(3) a neutral solution (4)  a hydride ion stant is 81.
• Maximum density of water is at 4°C.
42. Which of the following is correct for hydrides of
­lanthanides and actinides? • Structurally, ice has nine different forms, the one which
is formed at atmospheric pressure is normal hexagonal
(1) They are less denser than the parent metal.
form (Ih) but at very low temperatures it condenses as
(2) They have fairly high heat of formation.
a cubic form.
(3) Their electronegativity values are fairly close to
those of Group I and II elements. • Ice has lesser density than water with which it is in
(4) All are correct. equilibrium.
• The water molecules are joined together in a 3D
43. The false statement regarding occlusion is
­network in which each oxygen atom is surrounded by
(1) Occlusion decreases with increase in ­temperature. four water molecules tetrahedrally and bond through
(2) Occlusion depends upon the physical state of the hydrogens two by normal covalent bond and the other
metal. two by hydrogen bonds.
(3)  Occluded hydrogen in palladium is a weak
• Due to the 3D hydrogen bonded structure ice has got
­reducing agent.
open spaces due to which its density is less than water
(4) Occlusion process can be used to purify hydrogen.
and floats over water.
44. The wrong statement among the following is • Many salts crystallise from their aqueous solution as
(1) Ionic hydrides are formed by elements of high hydrated salts and the water molecules associated with
electropositive character. these salts are of five types.
(2)  Phosphine is an example of electron-precise   (i) Coordinated water
­hydride.  (ii)  Hydrogen-bonded water
(3) Titanium hydride is a metallic hydride. (iii)  Lattice water
(4) Metallic hydrides on reacting with water give   (iv)  Zeolite water
­hydrogen.   (v)  Clatharate water

Chapter_09.indd 8 3/26/2014 3:19:03 PM

 Hydrogen and its Compounds  9.9

• In some hydrated salts, water molecules are coordi- H2O + H2O 

→ H3O+ + OH-
nated to a metal ion (aquacomplex compounds). E.g.,
[Ni(H2O)6]Cl2, [Fe (H2O)6]SO4 and [Cr(H2O)6]Cl3. • Halogens oxidise water to oxygen. Solution of ­chlorine
in water is called as chlorine water.
• In some compounds water molecules are hydrogen
bonded to oxygen-containing anions, e.g., in CuSO4·
X2 + H2O 
→ 2HX + 
→ O2 (X = F2 or Cl2)
5H2O four water molecules are coordinated to Cu2+
ion and 1 water molecule is in hydrogen bond with
sulphate ions. • Solutions of basic oxides (Na2O, CaO, etc.) in water
are alkaline while solutions of acidic oxides (CO2,
• In certain compounds water is present as interstitial
N2O5, SO3, etc) in water are acidic.
water, i.e., it occupies the interstices in the crystal
­lattice. E.g., BaCl2 . 2H2O. • Salts undergo hydrolysis in water.
• Water can act both as Bronsted acid and Bronsted base • Water reacts with carbon dioxide in the presence
due to autoprotolysis or self-ionisation and hence of sunlight and chlorophyll to give carbohydrates
water is amphoteric. (photosynthesis).

Reactions of Water Remark

1. H 2 O + M  → MOH + H 2 with water
2. H 2 O + M  → Metal oxide + H 2 with steam and red hot condition
3. H 2 O + C Red
hot
→ CO + H 2
4. H 2 O + F2  → O2 and O3 + HF
5. H 2 O + Cl 2 → HOCl + HCl
6. H 2 O + Metal oxides  → Metal hydroxides Na 2 O, K 2 O, CaO, BaO, etc.
7. H 2 O + Non-metal oxides  → oxoacids N 2 O5 , SO3 , P4 O10 , Cl 2 O7 , etc.
8. Salts + H 2 O  → Hydrolysis Li3 N, Mg3 N 2 , AlN give NH 3
Ca 3 P2 give PH 3
CaC2 give C2 H 4
BeC2 , Al 4 C3 give CH 4 .

48. In the structure of ice, each oxygen atom is ­surrounded

 Objective Questions by four other oxygen atoms.
45. The melting points of most of the solid substances, (1) tetrahedrally
­increases with increase in pressure. However, ice melts (2) octahedrally
at a lower temperature lower than its usual melting (3) square planar manner
point when the pressure is increased. This is because (4)  none of these
(1) ice is less denser than water 49. The low density of ice compared to water is due to
(2) pressure generates heat (1) hydrogen-bonding interactions
(3) the chemical bonds break under pressure (2) dipole-dipole interactions
(4) ice is not a solid (3) dipole-induced dipole interactions
46. The maximum possible number of hydrogen bonds a (4) induced dipole-induced dipole interactions
water molecule can form is 50. Water contracts on heating
(1) 1 (2) 2 (3) 3 (4) 4 (1) to 100°C (2)  from O°C to 4°C
47. At its melting point, ice is lighter than water because (3) to 273 K (4)  from 10°C to 20°C
(1) H2O molecules are more closely packed in solid
state.
(2) Ice crystals have hollow hexagonal arrangement Answers
of H2O molecules.
(3) On melting of ice, the H2O molecules shrink in (45) 1 (46) 4 (47) 2 (48) 1 (49) 1
size. (50) 2
(4) Ice forms mostly heavy water on first melting.

Chapter_09.indd 9 3/26/2014 3:19:07 PM

 9.10  Objective Chemistry - Vol. I

hard water • Calgon reacts with Mg2+ and Ca2+ ions to form inac-
tive complex anions which do not react with soap. This
• Water which gives ready and permanent lather with is known as sequestration (rendering active species
soap is soft water. into inactive species).
• The water which does not give ready and permanent • In the ion exchange method, all the cations and a­ nions
lather with soap is called hard water. present in the hard water are removed.
• Hardness of water is due to the presence of • Resins are giant organic molecules, and the resins
­bicarbonates, sulphates and chlorides of magnesium having acidic group such as -COOH, -SO3H can ex-
and calcium. change the cations with H+ ions and are called cation
• The lather formed by normal sodium or potassium exchange resins while the resins containing basic
soap is coagulated by magnesium or calcium because groups such as -NH3OH can exchange the anions with
they form insoluble salts. OH- ions and are called anion exchange resins.
• • Exhausted cation exchange resins can be regenerated
Temporary hardness is due to the presence of
­bicarbonates of magnesium and calcium. by washing with moderate dilute acids while the ex-
hausted anion exchange resins can be regenerated by
• Permanent hardness is due to the presence of treating with NaOH or Na2CO3 solution.
­chlorides and sulphates of magnesium and calcium.
• The water obtained by passing through ion exchange
• Temporary hardness can be removed by boiling the resin is known as deionised water whose quality is
water or by the addition of calculated amount of slaked equal to distilled water.
lime (Clark’s method) where soluble bicarbonates
• If hard water is used in boilers, the heat resistant and
­convert into insoluble carbonates.
corrosive scales are formed on the inner surface of
M(HCO3)2 ∆ → MCO3 + H2O + CO2 (M = Mg boilers which causes fuel wastage and corrosion of the
or Ca) metal by which the boiler is made.
Mg(HCO3)2 + 2Ca(OH)2 → Mg(OH)2 + 2CaCO3 + • Degree of hardness is the amount of hardness in terms
                  2H2O of calcium carbonate given in units of ppm.
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O 1 CaCO3 ≡ 1 MgSO4 ≡ 1 MgCl2 ≡ 1 CaSO4 ≡ 1 CaCl2
• In the removal of temporary hardness by the addi- 100 ppm 120 ppm 95 ppm 136 ppm 111 ppm
tion of slaked lime, if excess amount of slaked lime is
added the water will get permanent hardness.

Removal of Permanent Hardness  Objective Questions

• By adding washing soda both temporary and perma- 51. Hard water becomes free from ..... ions when passed
nent hardness is removed due to conversion of soluble through ion exchange resin containing R-NH2OH
magnesium and calcium salts into insoluble magne- groups.
sium and calcium carbonates. (1) HCO3− (2) Cl- (3)  SO2−4 (4) All
• In permutit method, permanent hardness of water is 52. Which of the following statement is false?
removed by exchanging the Mg2+ and Ca2+ ion with
(1) Both temporary and permanent hardness can be
sodium ions present in artificially made zeolite.
removed on boiling.
• Zeolite is hydrated sodium aluminosilicate, (2) Hard water is not fit for washing clothes because
Na2Al2Si2O8 ·  H2O. it gives precipitate with soap.
• Exhausted zeolite is regenerated by treating Mg or Ca (3) Hardness of water is due to Mg2+ and Ca2+ ions.
zeolite with 10% NaCl solution. (4) Both temporary and permanent hardness of water
• Artificial zeolite can be prepared by fusing the can be removed by using washing soda.
quartz (SiO2), soda ash (Na2CO3) and china clay 53. Which of the following is not correct?
(Al2O3 . 2SiO2 . 2H2O). (1) Calgon is an industrial name given to sodium
• In Calgon process, permanent hardness is removed by hexametaphosphate, Na2[Na4(PO3)6].
using sodium hexametaphosphate, which is known (2)  Permutit is hydrated sodium aluminosilicate,
as calgon. Na2Al2Si2O8 ⋅ xH2O.

Chapter_09.indd 10 3/26/2014 3:19:08 PM

 Hydrogen and its Compounds  9.11

(3) The main component of the scale that accumu- • The ionic product, dielectric constant and solubility
lates in boilers is calcium carbonate. of salts in heavy water when compared with ordinary
(4) Water softners are used to remove the impurities water are less.
in water. • Since the dielectric constant of heavy water is less
54. Permanent hardness of water can be removed by than ordinary water the solubility of ionic compounds
­adding calgon (NaPO3)n. This is an example of such as NaCl and BaCl2 are less in heavy water than in
­ordinary water.
(1) Adsorption (2)  Precipitation
(3) Sequestration (4) Cleaning • The difference in physical properties of heavy water
from that of ordinary water is due to greater nuclear
55. Hardness of water is commonly expressed in the parts of mass of deuterium and greater degree of association.
(1) Calcium chloride • The D-O bond is stronger than H-O bond so that
(2) Calcium bicarbonate ­reactivity of heavy water is less than ordinary water.
(3) Calcium hydroxide
(4) Calcium carbonate • Ionic product of heavy water is 3.0 × 10-15 mole2 lit-2
at 25°C which is less than that of ordinary water.
56. A sample of water contains 111 ppm CaCl2. Hardness
• Electrolysis of heavy water gives deuterium at cathode
of this sample is
and oxygen at anode.
(1)  111 (2) 50 (3) 100 (4) 55.5
• When metals like Na or Ca react with water, they form
57. Hardness of water is expressed in terms of ppm [parts the corresponding metal deuteroxides such as NaOD
per million (106)]. Mass percentage of CaCO3 in a and Ca(OD)2 with the liberation of deuterium.
sample of water having hardness 200 ppm CaCO3 is
• When metal oxides are dissolved in heavy water alka-
(1) 20 (2)  0.02 line solutions of metal deuteroxides are formed.
(3) 0.002 (4) 0.0002
• When non-metal oxides are dissolved in heavy water
deuteroacids will be formed. E.g., deutero nitric acid
(DNO3) and deutero sulphuric acid (D2SO4).
Answers
• With carbides like CaC2, it gives deutero acetylene
(51) 4 (52) 1 (53) 4 (54) 3 (55) 4 (C2D2) and with Al4C3 it gives deutero methane (CD4).
(56) 3 (57) 2 • Salts which are associated with heavy water molecules
are called deuterates. E.g., CuSO 4⋅5D2O, MgSO4.
7D2O. Deuterates have low vapour pressure than
hydrates.
heavy water • Hydrolysis of salts in heavy water is called
deuterolysis.
• It is deuterium oxide, discovered by Urey. • When heavy water is mixed with compounds contain-
• Ordinary water contains 1 part of heavy water in 6000 ing normal hydrogen, the lighter isotope is exchanged
parts of ordinary water. by heavier isotope deuterium. E.g., NaOH to NaOD;
• On large scale heavy water is prepared by electrolysis NH4Cl to NH3DCl; HCl to DCl, etc.
of ordinary water using steel vessel (electrolytic cell) • Heavy water has different physiological actions on
as cathode and cylindrical nickel sheet as anode. plants and animals.
• When H2S gas is passed through hot water the (1)  The growth of plants is diminished in heavy
outcoming gas is enriched with D2S due to exchange ­water.
of H with D. (2) Seeds cannot germinate in heavy water.
• When H2S gas having more percentage of D2S is (3) In large doses, heavy water is poisonous.
passed into cold water repeatedly D2O will be obtained (4) Aquatic animals die in heavy water.
due to exchange of D in D2S with H in H2O. • Heavy water is used as a moderator in nuclear ­reactors
• Several physical properties like molecular weight, to slow down the fast-moving neutrons.
freezing point, boiling point, density, viscosity, spe- • Heavy water is used as a tracer to study the mechanism
cific heat, latent heat of vaporisation of heavy water of biochemical reactions, electrophilic aromatic sub-
are greater than ordinary water. stitution mechanisms, etc.

Chapter_09.indd 11 3/26/2014 3:19:09 PM

 9.12  Objective Chemistry - Vol. I

• The exchange reaction of heavier deuterium, of heavy 61. The weight percentage of deuterium in heavy water is
water with lighter hydrogen atoms of compounds is (1) 22 (2) 11 (3) 4 (4) 20
used to know the structure of oxoacids. E.g., H3PO2 is
62. The number of protons, electrons and neutrons
a monobasic acid and H3PO3 is a dibasic acid.
­respectively in a molecule of heavy water is
• Deuterium can be prepared either by the electrolysis of (1) 10, 10, 10 (2)  8, 10, 11
heavy water or by the reaction of sodium with heavy (3) 10, 11, 10 (4)  11, 10, 10
water required for making hydrogen bomb.
63. When, e.g., HCl is mixed with D2O the number of
Physical Properties of H2O and D2O types of molecules that would exist in the mixture
would be
(1) 2 (2) 5 (3) 6 (4) 3
Property H2O D2O (Hint: HCl, DCl, D2O, HDO, H2O)
-1
  1. Molecular mass (g mol ) 18.0151 20.0 276
64. Comparing H2O and D2O, which of the following is
  2. Melting point/K 273 276.8
false?
  3. Boiling point/K 373 374.4
  4. Enthalpy of formation/kJ mol-1 -285.9 -294.6
(1) H2O boils at a lower temperature than D2O.
  5. Enthalpy of vaporisation/kJ mol-1 40.66 41.61
(2) D2O unlike H2O is toxic.
  6. Enthalphy of fusion/kJ mol-1 6.01 -
(3) H2O but not D2O can be electrolysed.
  7. Temperature of maximum 276.98 284.2.
(4) D2O but not H2O can be used as a moderator in
density/K
nuclear reactions.
  8. Density (298 K)/g cm-3 1.0000 1.1059 65. The dielectric constants of H2O and D2O are 82 and
  9. Viscosity/centipoise 0.8903 1.107 80.5, respectively. Then, which of the following
10. Dielectric constant/C2/Nm2 78.39 78.06 ­statement is false?
11. Electrical conductivity 5.7 × 10-8 - (1) Solubility of NaCl in D2O is slightly more than in
(293 K/ ohm-1 cm-1 ) H2O.
12. Ionic product, kw, at 298 K 1 × 10-4 3 × 10-15 (2) Dipole moment of both H2O and D2O are not
13. Solubility of NaCl/100 g of water 35.9 30.5 equal.
at 298 K (3) Polarity of both H2O and D2O are not equal.
(4) Structures of both H2O and D2O are same.

Answers
 Objective Questions
(58) 3 (59) 4 (60) 3 (61) 4 (62) 1
58. Heavy water is qualified as heavy water because it is (63) 2 (64) 3 (65) 1
(1) a heavy liquid
(2) an oxide of heavier isotope of oxygen
(3) an oxide of deuterium
(4) denser than water Hydrogen peroxide
59. In the two solvents H2O and D2O, sodium chloride • Hydrogen peroxide can be considered as oxygenated
dissolves water. It was first prepared by Thenard.
(1) equally in both (2)  only in H2O • Commercial name of H2O2 is perhydrol which is 30%.
(3) more in D2O (4)  more in H2O When sunlight falls on water containing d­issolved
60. Which of the following is not correct? oxygen little H2O2 will be formed.
(1)  In nuclear reactors, heavy water is used as a
Preparation of H2O2
­moderator to slow down the fast-moving e­ lectrons.
(2) Heavy water is not useful for drinking because it • In the laboratory, H2O2 can be prepared by the action
is toxic. of ice cold dilute acids on metal peroxides like Na2O2
(3)  Deuterolysis of aluminium carbide gives or BaO2. Anhydrous BaO2 is not decomposed by dil.
­acetylene. H2SO4 due to the formation of a layer of insoluble
(4) The rate of electrolysis of heavy water is less than BaSO4. So, hydrated BaO2.8H2O which easily decom-
ordinary water. poses should be used.

Chapter_09.indd 12 3/26/2014 3:19:09 PM

 Hydrogen and its Compounds  9.13

• Phosphoric acid is preferred in the place of dil. H2SO4 Strength of H2O2

because some SO2 and H2S present in H2SO4 react with
• The strength of H2O2 is expressed in terms of volume
H2O2. But H3PO4 completely precipitate Ba2+ ions.
strength. E.g., 10 vol, 20 vol, 30 vol, etc.
• H2O2 can be prepared by passing CO2 gas through the • 10 vol H2O2 means 1 ml of H2O2 gives 10 cc of O2 at STP.
ice cold BaO2 paste.
• The strength of perhydrol is 30% W/V or 100 vol.
• Commercially H2O2 is manufactured by the
­electrolysis of 50% H2SO4 or autooxidation of 2-ethyl
• 10 vol H2O2 = 3.036% w/v = 1.736 N = 0.893 M
anthraquinol. or 11.2 vol H2O2 = 3.4% w/v = 2N = 1M
• In the electrolysis of 50% H2SO4 or H2SO4 and Physical Properties
(NH4)2SO4 in 1:1 molar ratio for the preparation of
H2O2 anode is platinum and cathode is lead. • Pure H2O2 is colourless, odourless, syrupy liquid. In
thick layers it is light blue in colour, miscible with
• During electrolysis the anion oxidised at anode is
­water in all proportions.
HSO −4 . Distillation of H2S2O8 formed during the elec-
• H2O2 is more hydrogen bonded than water. It is ­slightly
trolysis of 50% H2SO4 or (NH4)2S2O8 formed from the
electrolysis of H2SO4 and (NH4)2SO4 in 1:1 molar ratio acidic but cannot turn the blue litmus to red.
gives H2O2. • The oxidation number of oxygen in H2O2 is -1and
­decomposes to give O2.
• When 2-ethyl anthraquinol is oxidised in air, H2O2 and
2-ethyl anthraquinone will be formed. 2H2O2 → 2H2O2 + O2
• Decomposition of H2O2 is by both oxidation and re-
• 2-ethyl anthraquinone can be reduced with H2 in
duction (disproportionation) because when the oxygen
the presence of catalysts like Pt, Pd or Ni to 2-ethyl
is liberated oxidation number increases from -1 to
anthraquinol.
zero and in another oxygen of H2O oxidation number
decreases from -1 to -2.
Concentration of H2O2
Chemical Properties
• Careful evaporation under reduced pressure gives • H2O2 can function both as an oxidising and a reducing
about 30% H2O2.
agent.
• Dehydration in a vacuum desiccator containing conc. • H2O2 is a very powerful oxidising agent and a poor
H2SO4 gives about 90% H2O2. reducing agent.
• Distillation under reduced pressure gives about 99% • While acting as a reducing agent O2 gas will be evolved
H2O2. and always O2 is liberated from H2O2 without breaking
• Fractional crystallisation using freezing mixtures O–O bond.
gives 100% needle-like crystals of H2O2.
Oxidation Reactions in Acid Medium
• H2O2 oxidises PbS to PbSO4; ferrous salts to ferric
Storage of H2O2
salts; liberates iodine from iodides; oxidises nitrites to
• H2O2 decomposes rapidly on rough surfaces. nitrates; sulphites to sulphates; arsenites to arsenates
and potassium ferrocyanide to potassium ferricyanide.
• Urea, sodium stannate, acetanilide and sodium
• H2O2 gives blue chromium peroxide (CrO5) with
­pyrophosphate inhibits the decomposition of H2O2.
acidified dichromate which has a butterfly structure.
• Dilute solutions of H2O2 are stable in the presence of It contains two peroxy bonds, four oxygen atoms in -1
acids, alcohols or ethers (negative catalysts). oxidation state and one oxygen atom in -2 oxidation
• The decomposition of H2O2 is accelerated by the pres- state while chromium is in +6 oxidation state.
ence of alkalis, sand, MnO2, iron, manganese dioxide • CrO5 is unstable in an acid medium converting into
and alumina (positive catalysts). chromic salt liberating oxygen. It is stable in ether lay-
• H2O2 is stored in a plastic bottle or glass container er in the presence of pyridine forming a blue layer. It is
coated inside with wax and in the presence of a stabi- used for testing the presence of H2O2 or vice versa.
lising agent like glycerol, urea, sodium stannate, etc. • H2O2 oxidises mercury to mercuric oxide.

Chapter_09.indd 13 3/26/2014 3:19:10 PM

 9.14  Objective Chemistry - Vol. I

Oxidation Reactions in Alkaline Medium Uses

• H2O2 oxidises formaldehyde to formic acid in the • H2O2 is a harmless strong antiseptic, so is used to
presence of pyrogallol (1, 2, 3-trihydroxy benzene) clean the wounds. H2O2 in contact with organic matter
with the liberation of hydrogen. liberates oxygen which kills bacteria.
• Oxidation reactions of H2O2 are slow in an acid • H2O2 is used as a mild bleaching agent to bleach silk,
­ edium but faster in an alkaline medium.
m wool, ivory, etc.
• Due to oxidation property H2O2 acts as a mild bleach- • Conc. H2O2 is used as a rocket fuel.
ing agent and used to bleach silk, wool, ivory, and • H2O2 is used in restoring the colour of old and spoiled
hair which are destroyed by the bleaching action of lead paintings.
­chlorine. Ammonical H2O2 bleaches human hair to
golden yellow. Tests for H2O2

Reduction Properties of H2O2 • H2O2 turns starch iodide paper to blue due to liberation
of iodine from iodide by H2O2.
• H2O2 reduces and decolourises acidified potassium • It forms a blue colour in ether layer when reacts with
permanganate, reduces halogens to hydrogen halides, acidified potassium dichromate containing ether.
reduces silver oxide to silver, potassium ferricyanide • H2O2 gives orange coloured pertitanic acid when
to potassium ferrocyanide in basic medium, lead ­reacted with acidified titanium dioxide.
­dioxide to yellow coloured lead monoxide (litharge)
Ti(SO4)2 + H2O2 + 2H2O → H2TiO4 + 2H2SO4
and ozone to oxygen.
Structure of H2O2
Acidic Properties
• H2O2 has a non-linear, non-planar structure with half-
• H2O2 reacts with alkalis and carbonates forming metal open book structure.
peroxides. It liberates CO2 from carbonates.
• The angle between O-H and O-O is 94°48′.
• Since H2O2 is a weak dibasic acid, it forms two series • The angle between the two hydrogen atoms which lie
of salts such as hydroperoxides and peroxides. on the cover pages of an open book (dihedral angle) is
111° 30′.
Formation of Addition Compounds • The bond angles and bond lengths in H2O2 changes
•
with the physical state of H2O2 and the values given
H2O2 forms addition compounds Na2HPO4. H2O2,
above are for gaseous H2O2.
(NH4)2 SO4 H2O2, H2N CO NH2 H2O2. The addition
compounds of H2O2 with urea is called hyperol. These • When H2O2 changes from a gaseous state to solid state
addition compounds release H2O2 when dissolved in the dihedral angle decreases and reaches to 90° in the
water. crystalline state.

Hydrogen Peroxide

Reaction Remark
Preparation
Merck’s process
1. Na 2O2 + H 2SO 4  → Na 2SO 4 + H 2O2
BaSO4 insoluble
2. BaO2 + H 2SO 4  → BaSO4 + H 2O2
Ba3(PO4)2 insoluble
3. BaO2 + H 3PO 4  → Ba 3 (PO 4 )2 + H 2O2
BaCO3 insoluble
4. BaO2 + CO2 + H 2O  → BaCO3 + H 2O
5. 2H 2SO 4 Electrolysis
→ H 2S2O8 + H 2
50%
H 2S2O8 + 2H 2O 
→ 2H 2SO 4 + H 2O2

Chapter_09.indd 14 3/26/2014 3:19:11 PM

 Hydrogen and its Compounds  9.15

Reaction Remark

6. Electrolysis of equimolar mixture of H2SO4

and (NH4)2 SO4
(NH 4 )2SO 4 + H 2SO 4 
→ 2NH 4 HSO 4
2NH 4 HSO 4 Electrolysis
→ (NH 4 )2S2O8 + H 2
(NH 4 )2 S2O8 + 2H 2O 
→ 2NH 4 HSO 4 + H 2O2
Acidic Property:
1. H 2O2 + NaOH  → NaHO2
Metal peroxides are salts of H2O2
2. H 2O2 + 2 NaOH  → Na 2O2
3. H 2O2 + Na 2CO3 → Na 2O2 + H 2O + CO2
Oxidation Properties in acid medium:
1. H 2O2 + FeSO 4  → Fe2 (SO 4 )3
2. H 2O2 + KI  → I2
3. H 2O2 + KNO2  → KNO3
4. H 2O2 + Na 2SO3  → Na 2SO 4
5. H 2O2 + Na 3AsO3  → Na 3AsO 4
6. H 2O2 + PbS  → PbSO 4
7. H 2O2 + Cr2O72 −  → CrO5
Oxidation reactions in alkaline medium
1. H 2O2 + Mn 2+ → MnO2
→ CrO24 −
2. H 2O2 + Cr 3+ 
3. H 2O2 + HCHO  → HCOOH + H 2 Only reaction in which H2O2 is reduced to H2
Reduction reactions in acid medium
→ Mn 2 +
1. H 2O2 + KMnO 4 
purple colourless
→ Cr 3+
2. H 2O2 + K 2Cr2O7 
Orange red green
→ Mn 2 +
3. H 2O2 + MnO2 
Black
4. H 2O2 + O3 → O2
5. H 2O2 + HOCl → HCl

Reduction reactions in alkaline medium

1. H 2O2 + KMnO 4 
→ MnO2
Pink Black
H 2O2 + K 3 [Fe(CN)6 ] 
→ K 4 [Fe(CN )6 ]
H 2O2 + Ag 2O  → Ag (Black)
H 2O2 + PbO2  → PbO (litharge)
H 2O2 + Cl2  → Cl −
H 2O2 + NaOBr  → NaBr
H 2O2 + CaOCl2  → CaCl2
Bleaching
Powder
Addition Reaction
1. H 2O2 + CH 2 = CH 2 
→ HOCH 2 − CH 2OH

Chapter_09.indd 15 3/26/2014 3:19:16 PM

 9.16  Objective Chemistry - Vol. I

74. A given solution of H2O2 is 30 vol. Its concentration

 Objective Questions in terms of molarity is
(1) 9.1 M (2)  2.68 M
66. In the laboratory, H2O2 can be prepared by the action of (3) 2.5 M (4)  26.8 M
(1) Ice cold 20% H2SO4 on barium peroxide.
(2) BaO2 added to CO2 bubbling through cold water. 75. The volume of oxygen liberated by heating 3.4 g of
(3) Excess of Na2O2 with water. H2O2 solution at STP is
(4) All. (1) 2.25 lit (2)  1.12 lit (3)  4.48 lit (4)  0.56 lit
67. The oxide that gives H2O2 on treatment with a dilute 76. Weight of H2O2 present in grams in 10 ml of 20 vol of
acid is H2O2 is
(1) PbO2 (2) MnO2 (1) 1.607 (2) 1.214 (3) 0.306 (4) 0.607
(3) TiO2 (4) BaO2
77. Which of the following statements is not correct?
68. Which of the following will not give H2O2 on hydrol-
ysis? (1) H2O2 is stored in a plastic container after addition
of a stabiliser.
(1) HClO4 (2) H2S2O8
(2) Decomposition of H2O2 is retarded by ­acetanilide.
(3) H2S2O8 (4) H2NO5 (pernitric acid)
(3) The substance that retards the speed of decompo-
69. Pure H2O2 is called sition of H2O2 is alcohol.
(1) Perhydrol (2)  Oxen (4) Decomposition of H2O2 is oxidation.
(3) Peracid (4)  None
78. The bleaching properties of H2O2 are due to its
70. Hydrogen peroxide can be manufactured by (1) reducing property (2)  oxidising property
(1) electrolysis followed by hydrolysis of 50% H2SO4 (3) unstable nature (4)  acidic nature
(2) electrolysis of 1:1 molar mixture of H2SO4 and
(NH4)2SO4 followed by hydrolysis 79. Hydrogen peroxide is not used as
(3) oxidation of 2-ethyl anthraquinol obtained by the (1) Reducing agent (2)  Oxidising agent
catalytic hydrogenation of 2-ethyl anthraquinone (3) Dehydrating agent (4)  Bleaching agent
(4) all
80. Acidified solution of chromic acid on treatment with
71. Partial hydrolysis of one mole of peroxydisulphuric H2O2 yields
acid produces (1) CrO3 + H2O + O2
(1) Two moles of sulphuric acid (2) Cr2O2 + H2O + O2
(2) Two moles of peroxy monosulphuric acid (3) CrO5 + H2O + K2SO4
(3) One mole of sulphuric acid and one mole of (4) H2Cr2O7 + H2O + O2
­peroxy monosulphuric acid
(4) Two moles of sulphuric acid and one mole of 81. The false statement among the following is
­hydrogen peroxide (1) H2O2 reduces K3[Fe(CN)6] in an alkaline
72. When 50% solution of H2SO4 is electrolysed by ­medium.
­passing a current of high density at low temperature (2) H2O2 acts as a strong oxidising agent in an alka-
the main products of electrolysis are line medium.
(1) oxygen and hydrogen (3) H2O2 is reduced to H2 during the oxidation of
(2) H2 and peroxydisulphuric acid HCHO.
(3) H2 and SO2 (4) H2O2 acts as an antiseptic due to its oxidising
(4) O2 and peroxydisulphuric acid property.
73. The method which is not used for concentration of 82. The hair dyes available in the market generally con-
H2O2 is tain two bottles, one containing the dye and the other
(1) Fractional distillation hydrogen peroxide. Before applying the dye, the two
(2) Distillation under reduced pressure solutions are mixed. The hydrogen peroxide
(3) Evaporation in a vacuum desiccator (1) is added to dilute the solution of the dye
(4) Sublimation (2) oxidises the dye to give the desired colour

Chapter_09.indd 16 3/26/2014 3:19:16 PM

 Hydrogen and its Compounds  9.17

(3) reduces the dye to give the desired colour 90. The addition compound of hydrogen peroxide with
(4) acidifies the solution of the dye urea is called as
83. The oxidation states of the most electronegative ele- (1) Perhydrol
ment in the products of the reaction BaO2 and dil. (2) Aldol
H2SO4 are (3) Hyperal
(4) Urotropine
(1) 0 and -1 (2) -1 and -2
(3) -2 and 0 (4)  -2 and +1 91. Metal peroxides are ionic compounds containing
84. Ozone reacts with H2O2 to give oxygen. One volume (1) O2- (2) O2- (3)  O2−
2 (4) O-
of ozone gives 92. H2O2 does not
(1) one volume of oxygen (1) liberate iodine from KI
(2) half-volume of oxygen (2) turn the titanium salt orange yellow
(3) 1.5 volumes of oxygen (3) give silver peroxide with moist silver oxide
(4) two volumes of oxygen (4) turn the mixture of aniline, KClO3 and dil. H2SO4
85. Which is not true in the case of H2O2? to violet
(1) It more stable in a basic solution 93. In the H2O2 molecule
(2) It acts as an oxidising agent in an acidic and a (1) Two hydrogen atoms are connected to one ­oxygen
basic solution (2) All the four atoms are in the same plane
(3) It is decomposed by MnO2 (3) The four atoms are arranged in a non-linear- and
(4) It behaves as a reducing agent towards KMnO4 non-planar manner
86. The false statement among the following is (4) O-H bonds are polar but molecule is nonpolar
(1) H2O2 restores the colour of old lead paintings 94. Titanium salts on treatment with H2O2 form an or-
blackened by the reaction of H2S gas by oxidis- ange yellow colouration due to the formation of
ing PbS to PbSO4.
(1) titanium dioxide
(2) When silver oxide reacts with H2O2, it is reduced (2) titanic acid
to silver. (3) titanium hydroxide
(3) H2O2 oxidises chlorine to chlorine dioxide. (4) pertitanic acid
(4) H2O2 forms two series of salts such as hydro­
peroxides and peroxides because of its dibasic 95. H2O2 does not liberate oxygen when it reacts with
character. (1) NaOCl (2)  MnO2/H+ (3) Cl2 (4) C6H6
87. Two compounds A and B liberate iodine from aque-
ous KI; “A” blackens a clean silver foil unlike “B”. A Answers
can occur in traces in air in some places unlike “B”.
“A” and “B” are respectively (66) 4 (67) 4 (68) 1 (69) 4 (70) 4
(1) O2 and CO (2)  SO3 and H2O2 (71) 4 (72) 2 (73) 4 (74) 2 (75) 2
(3) O3 and H2O2 (4) O3 and NO (76) 4 (77) 4 (78) 2 (79) 3 (80) 3
(81) 2 (82) 2 (83) 2 (84) 4 (85) 1
88. In the reaction represented by the equation
(86) 3 (87) 3 (88) 3 (89) 3 (90) 3
PbO2 + H2O2 → PbO + H2O + O2 (91) 3 (92) 3 (93) 3 (94) 4 (95) 4
(1) The oxidising agent is H2O2
(2) The reducing agent is PbO2
(3)  The reducing agent is H2O2 that itself gets
­reduced   Practice Exercise Level-I
(4) There is no reducing agent
1. The maximum percentage mass difference is found in
89. When H2O2 behaves as a reducing agent the end which of the following pairs?
product is generally 232 238
(1) 92 U, 92 U (2) 16 18
8 O, 8 O
(1) O2 (2) H2O
(3) Both (4) Neither (3) 11 H, 12 H (4) 12 14
6 C, 6 C

Chapter_09.indd 17 3/26/2014 3:19:17 PM

 9.18  Objective Chemistry - Vol. I

2. Hydrogen peroxide is not stored in a glass bottle 8. Which of the following is used to remove hardness in
­because Clark’s process?
(1) SiO2 of the glass reacts with it (1) Baryta water (2)  Slaked lime
(2) Glass dissolves in it (3) Caustic soda (4)  Aluminium hydroxide
(3) Light passes through the glass 9. Which of the following statements is not correct
(4) Alkaline oxides in glass catalyse decomposition about Calgon process to remove hardness?
of H2O2
(1) Calgon is sodium hexametaphosphate
3. Under the same conditions of pressure and tempera- (2)  Calgon reacts with Ca2+ and Mg2+ to form
ture which property is the same for H2 and D2? ­inactive complex anions
(1) reactivity with other substances (3) Calgon process can be used where high pure
(2) rate of diffusion ­water is required
(3) most probable velocity (4) Calgon process is used in laundry purposes
(4) average kinetic energy per mole 10. When heavy water reacts with compounds ­containing
4. The incorrect statement about the manufacture of ordinary hydrogen, the lighter isotope will be
synthetic gasoline is ­exchanged by heavier isotope deuterium. This p­ rocess
is rapid if hydrogen is in
(1) it is manufactured from a mixture of water gas
and hydrogen (1) Ionic or polar bond
(2) iron oxide is used to remove sulphur (2) Covalent bond
(3) in the presence of a cobalt catalyst hydrocarbons (3) Organic molecule
are formed from water gas (4) Any type of bond
(4) in the presence of an iron oxide hydrocarbons are 11. Which of the following physical property of heavy
formed from water gas water is not correctly represented?
5. About nuclear fusion reactions, the false statement is (1) it freezes at higher temperatures (3.8°C) than
­ordinary water
(1) Energy is released due to fusion of lighter nuclei
(2) it boils at higher temperature (101.42°C) than
(2) Solar energy is due to nuclear fusion reactions
­ordinary water
(3) These are called thermonuclear reactions since
(3) it has maximum density at higher temperature
they take place at high temperatures
(11.6°C) than ordinary water
(4) Energy liberated in these reactions is less than in
(4) it has more dielectric constant (82) than ordinary
fission reactions
water (80.5)
6. Identify the false statement 12. In the laboratory H2O2 is prepared by the reaction of
(1)  When water gas mixed with hydrogen gas is metal peroxides with ice cold dilute acids because
passed over ZnO and Cr2O3 methyl alcohol will (1) H2O2 formed at low temperatures only
be formed. (2) H2O2 formed decomposes if the temperature is high
(2) When a mixture of water gas and hydrogen gas is (3) H2O2 formed at high temperature is not pure
passed over cobalt catalyst, synthetic petrol will (4) Reaction cannot take place at high temperatures
be obtained.
(3) When a mixture of water gas and producer gas 13. In the concentration of H2O2, when freezing mixture
is passed over iron catalyst, ammonia will be of solid CO2 and ether is used, the H2O2 formed is
formed. (1) 30% pure (2)  90% pure
(4)  When a mixture of water gas and hydrogen (3) 100% pure (4)  60% pure
is passed over iron catalyst ammonia will be
formed. 14. In Merck’s process the reagents involved in the prepa-
ration of hydrogen peroxide are
7. Which of the following compound is converted from (1) BaO2, HCl (2)  Na2O2, H2SO4
a liquid state to solid state by hydrogen? (3) BaO2, H3PO4 (4) PbO2, H2O
(1) Ethylene
(2) Acetylene 15. In the reaction NaOH + D2O → X + Y, the X and Y are
(3) Oil (1) NaOD and HDO (2)  NaOD and H2
(4) Glycerol (3) NaOD and D2 (4)  all of these

Chapter_09.indd 18 3/26/2014 3:19:17 PM

 Hydrogen and its Compounds  9.19

16. Property of H2O2 indicated by the reaction H2O2 + 24. In nature, tritium formed by which of the following
2e- → 2OH- is nuclear reaction?
(1) 14 7 N + 0n → 6 C + 1H
1 12 3
(1) reduction in acid medium
(2) oxidation in acid medium (2) 3 Li + 0 n → 2 He + 13 H
6 1 4

(3) reduction in alkaline medium (3) 12 H + 11H → 13 H + 0+1e

(4) oxidation in alkaline medium
(4) 12 H + 24 He → 13 H + 32 He
17. Hydrogen peroxide is stored in two separate glass
25. When a mixture of soda ash, alumina and silica are
bottles, one coated inside with wax while the other
fused together the product obtained is
is a n­ ormal bottle. The concentration of H2O2 after
1 month is (1) an artificial zeolite
(2) permutit
(1) same in both bottles
(3) sodium aluminate orthosilicate
(2) more in bottle coated with wax inside
(4) all of these
(3) less in bottle coated with wax inside
(4) more in normal bottle 26. The physical property of heavy water which is more
than that of ordinary water is
18. With which of the following hydrogen peroxide do
not produce characteristic colours? (1) Dielectric constant
(2) Ionic product
(1) Acidified K2Cr2 O7
(3) Latent heat of vaporisation
(2)  Acidified TiO2
(4) Solubility of ionic compounds
(3) Acidified KMnO4
(4)  Starch iodide paper 27. When bromine liquid is added to hydrogen peroxide
the gas coming out is
19. Hydrogen peroxide forms two types of salts, viz.
­peroxides and hydroperoxides. This indicates that (1) HOBr (2)  H2 (3) O2 (4) HBr
(1) in the oxidation reaction it removes two electrons 28. Some inorganic, and organic compounds like Na2HPO4,
(2) in the reduction reaction it supplies two electrons (NH4)2SO4 and urea form addition compounds with
(3) in the bleaching action it gives two oxygen atoms H2O2. These addition compounds when added to water
(4) in the neutralisation reaction it act as a dibasic (1) gets oxidised
acid (2)  gets reduced
20. The type of change associated with the addition (3) release H2O2
of ­silver to hydrogen peroxide in order to liberate (4)  release oxygen
­oxygen is
29. Methyl magnesium bromide and aluminium carbide
(1) decomposition by a catalyst are separately reacted with heavy water. The gases
(2) transfer of electrons from one particle to another evolved are
(3) the assembly of ions into a lattice
(4) the transfer of oxygen from one substance to (1) CH3D, CD4
­another (2) CD4, CH3D
(3) CH3D, CH3D
21. In gaseous hydrogen peroxide the dihedral angle (4) CD4, CD4
­between H atoms is X° but in solid state it is Y°. The
values of X and Y are respectively 30. Electrolysis followed by hydrolysis of an equimolar
solution of ammonium sulphate and sulphuric acid
(1) 94.8, 94.8 (2)  111.5, 90.2
produces a compound “A”. A can turn the chromic
(3) 90.2, 90.2 (4)  111.5, 111.5
salts to yellow in alkaline medium. A is
22. The activation energy in the reaction of halogen with (1) SO2 (2) H2O2
hydrogen when compared to deuterium is (3) (NH4)2S2O8 (4) (NH4)2SO5
(1) less (2)  more
31. Number of millimoles of Ca(OH)2 required for
(3) equal (4)  cannot be predicted
the removal of hardness of a sample of hard water
23. The number of oxygen atoms in -1 oxidation state in ­containing 1 millimole Ca(HCO3)2 and 1 millimole
CrO5 is Mg(HCO3)2 is
(1) 1 (2) 2 (3) 5 (4) 4 (1) 1 (2) 2 (3) 3 (4) 4

Chapter_09.indd 19 3/26/2014 3:19:18 PM

 9.20  Objective Chemistry - Vol. I

32. Consider the following statements about heavy 39. Hard water does not give good lather with soap
­hydrogen. ­because soap is precipitated as
   (i) It is a by-product of the fertiliser industry ob- (1) Magnesium and calcium stearate
tained in the electrolysis of water. (2) Calcium and magnesium carbonate
 (ii) It is used in a nuclear reactor as a moderator. (3) Hydroxides of calcium and magnesium
(iii) It is used for obtaining thermonuclear energy (4) Sulphates of calcium and magnesium
through fusion of these statements.
(1) i, ii and iii are correct 40. The order of heats of fusion of T2, D2 and H2 is
(2) iii only is correct (1) T2 > D2 > H2
(3) i and ii are correct (2) H2 > T2 > D2
(4) i and iii are correct (3) D2 > T2 > H2
(4) D2 = T2 > H2
33. Which of the following physical property is same for
both ordinary hydrogen and deuterium? 41. Which of the following statements is correct for
(1) Bond energy (2)  Bond length ­isotopes of hydrogen?
(3) Molecular mass (4)  Boiling point (1) These isotopes have essentially the same chemi-
34. Which of the following statement is false about cal properties
­hydrogen fuel cell? (2) They show much greater difference in physical
properties than are found between the isotopes of
(1) At anode, H2 reacts with O2 to convert into H2O
other elements
(2) At cathode, reduction of O2 takes place forming
(3) The only difference in chemical properties are
OH-
equilibrium constants and the rates of reactions
(3) At anode, oxidation of OH- takes place reacting (4) All are correct
with H2
(4)  In the fuel cell, chemical energy is directly 42. Which of the following statements regarding H2O2 is
­converted into electrical energy false?
(1) Pure H2O2 and its 65% solution in water are less
35. It is not possible to determine the boiling point of
ionising solvents compared to water
H2O2 at atmospheric pressure because
(2)  In the liquid state H2O2 is even more highly
(1) It is completely miscible with water ­associated via hydrogen bonding than water
(2) It decomposes vigorously on heating (3) H2O2 is a strong oxidising agent in acid or basic
(3) It contains large amounts of impurities medium
(4) It is highly volatile (4) It behaves as a reducing agent towards MnO2 in
an acid medium
36. Deionised water is obtained by passing hard water
through 43. The pH of a solution of H2O2 is 6.0. Some chlorine
(1) Zeolite gas is bubbled into this solution. Which of the follow-
(2) Anion exchanger ing is correct?
(3) Cation exchanger (1) The pH of the resultant solution becomes 8.0
(4)  Both cation and anion exchanger one after (2)  Hydrogen gas is liberated from the resultant
­another ­solution
37. Which of the following statements is not correct? (3) The pH of the resultant solution becomes less
than 6.0 and oxygen gas is liberated
(1) Permutit is an inorganic cation exchanger
(2) Organic cation exchanger contain -COOH groups (4) Cl2O is formed in the resultant solution
(3)  Organic anion exchanger contain -NH3OH 44. Exhausted permutit does not contain ...... ions.
groups (1) Na+ (2) Mg2+
(4) The water coming out of cation exchanger is
(3) Al 3+
(4) Si4+
­neutral
45. 100 mL of 0.01 KMnO4 oxidises 100 mL of H2O2 in
38. The soft water obtained in the permutit process acidic medium. Volume of same KMnO4 required in
­contains alkaline medium to oxidise 100 mL of same H2O2
(1) free Na+ ions (2)  free H+ ions will be (MnO4- changes to Mn2+ in acid medium and
(3) free OH- ions (4)  All of these to MnO2 in alkaline medium)

Chapter_09.indd 20 3/26/2014 3:19:19 PM

 Hydrogen and its Compounds  9.21

100 500 (3) H2O2 gets ionised during chemical reactions

(1)  mL (2)  mL (4) H2O2 gets decomposed during chemical ­reactions
3 3
2. The H-O-O-H bond angles and O-H bond lengths are
300 200
(3)  mL (4)  mL 101.9 and 98.8 pm, respectively in solid phase instead
5 5 of 111°30′ and 95 pm in gaseous phase of H2O2. This
46. 10  mL of H2O2 solution (volume strength = x) indicates that the structure of H2O2 in solid and gase-
­required 10 mL of N/0.56 MnO4- solution in acidic ous phase is different. This is due to
medium. Hence, x is (1) Intermolecular hydrogen bonding
(1) 0.56 (2) 5.6 (3) 0.1 (4) 10 (2) Intramolecular hydrogen bonding
(3) Van der waal’s bonding
47. 10 litres of hard water required 0.56 g of lime (CaO)
(4) All are true
for removing hardness. Hence, temporary hardness in
ppm of CaCO3 is 3. Amongst the following, choose the correct s­ tatements.
(1)  100 (2) 200 (3) 10 (4) 20   (i) Atomic hydrogen is obtained by passing hydro-
gen gas through electric arc
48. At 25°C, the pH of heavy water is  (ii) Hydrogen gas will not reduce heated aluminium
(1) higher than that of water oxide
(2) less than that of water (iii) Finely divided palladium absorbs large amount
(3) equal to that of water of hydrogen gas
(4) not definable   (iv) Pure nascent hydrogen is prepared by reacting
49. As H2O2 solid is brought into liquid and gaseous Na with ethyl alcohol
states the dihedral angle (1) i, ii, iii (2)  ii, iv
(3) i, iii (4)  All of these
(1) decreases (2)  increases
(3) remains unchanged (4)  becomes 180° 4. If x and y are boiling points and dielectric constant of
water, respectively and a and b are that of D2O (heavy
50. Ionic hydrides water) then
(1) conduct electricity in liquid state (1) x > a; y < b (2)  x > a, y > b
(2) formed with elements of high ionisation energy (3) x < a; y < b (4)  x < a, y > b
(3) occupy the vacant spaces in metallic lattice
(4) does not exist 5. To an aqueous solution of AgNO3 some NaOH (aq)
is added, till a brown precipitate is obtained. To this
H2O2 is added dropwise. The precipate turns black
Answers
with the evolution of O2. The black ppt is
(1) 3 (2) 4 (3) 4 (4) 4 (5) 4 (1) Ag2O (2) Ag2O2 (3) AgOH (4) Ag
(6) 4 (7) 3 (8) 2 (9) 3 (10) 1 6. When KI in acidic medium was mixed in 50 ml H2O2
(11) 4 (12) 2 (13) 3 (14) 2 (15) 1 liberated I2 requires 20 mL of 0.1 N hypo. What is the
(16) 4 (17) 2 (18) 3 (19) 4 (20) 1 strength of H2O2?
(21) 2 (22) 1 (23) 4 (24) 1 (25) 4 (1) 6.8 g/lit (2)  0.68 g/lit
(26) 3 (27) 3 (28) 3 (29) 1 (30) 2 (3) 680 g/lit (4)  68.0 g/lit
(31) 2 (32) 4 (33) 2 (34) 1 (35) 2
(36) 4 (37) 4 (38) 1 (39) 1 (40) 1 7. In the following reaction using isotopic 18O in H2O2
(41) 4 (42) 1 (43) 3 (44) 1 (45) 2 2MnO4- + 3H2O218 → 2MnO2 + 3O2 + 2H2O +
(46) 4 (47) 2 (48) 1 (49) 1 (50) 1 2OH- isotopic oxygen goes
(1) Both with O2
(2) Both with MnO2
(3) Both with OH-
  Practice Exercise Level-II (4) One with O2 and one with MnO2
1. The dipole moment of H2O2 is 2.1 D while that of 8. The incorrect statements about hydrogen peroxide
­water is 1.84 D. But water (H2O) is a better solvent    I. It oxidises potassium ferrocyanide to potassium
than that of H2O2 because ferricyanide in basic medium
(1) Its dipole moment   II. It reduces potassium ferricyanide to potassium
(2) It is less corrosive ­ferrocyanide in acidic medium

Chapter_09.indd 21 3/26/2014 3:19:20 PM

 9.22  Objective Chemistry - Vol. I

III. It bleaches coloured matter to colourless matter (1) Hydrogen peroxide; 15 and 15
by oxidation as well as reduction (2) A mixture of hydrogen and oxygen; 20 and 15
 IV. It liberates iodine from KI solution which gives (3) A colourless gas hadrogen; 15 and 20
blue colour with amylose (a straight chain poly- (4) A colourless gas dioxygen; 15 and 21
mer containing many glucose units)
(1) I, II and III only 14. By starting with 0.5 moles of sodium peroxide how
(2)  II, III and IV only many moles of dioxygen can be obtained by dropping
(3) I, II and IV only excess of water on it?
(4)  I, III and IV only (1) 0.5 mole (2)  1 mole
(3) 0.25 mole (4)  0.125 mole
9. There are three samples of H2O2 labelled as 10  V,
15 V and 20 V. Half a litre of each sample is mixed 15. Electrolysis of aqueous NaCl and NaH differs in
and then diluted with equal volumes of water. Then, (1) formation of basic solution at the cathode by
­volume strength of the resultant solution is NaCl only
(1) 7.5 (2) 1.339 (3) 5.6 (4) 15 (2) formation of basic solution at the cathode by
NaH only
10. The incorrect statements about the melting of ice
(3) formation of H2 gas at cathode and anode both by
   I. Ice melts at a temperature lower than its usual NaCl and NaH
melting point, when the pressure is increased. (4) formation of NaOH at cathode and anode
This is because ice is less dense than water.
  II. Ice melts at a temperature higher than its usual 16. The stability of alkali metal hydrides is
melting point, when the pressure is increased. (1) LiH > NaH > KH > RbH > CsH
This is because ice is less dense than water. (2) LiH < NaH < KH < RbH < CsH
III. Ice melts at a temperature lower than its usual melt- (3) LiH = NaH = KH < RbH > CsH
ing point, when the pressure is increased. This is
(4) LiH < NaH > KH > RbH > CsH
because the chemical bonds break under pressure.
 IV. Ice melts at a temperature lower than its usual 17. An aqueous solution of compound (A) is weakly
melting point, when the pressure is decreased. acidic in nature, it can form two series of salts, with
This is because ice is not a true solid. TiO2 in conc. H2SO4 it gives orange colour. Which of
(1) I, II and III only the following pairs cannot give (A) in water?
(2)  II, III and IV only (1) H2S2O8 and KO2
(3) I, II and IV only
(2) HClO4 and PbO2
(4)  I, III and IV only
(3) H2SO5 and Na2O2
11. When a small amount of calcium phosphide Ca3P2 is (4) BaO2 and K2O2
added to water, what are the most likely products?
(1) Aqueous Ca2+ and OH- ions and gaseous PH3 18. The ionisation constant of protium in water (H2O 
(2) Aqueous Ca2+ and OH- ions and aqueous H3PO3 H+ + OH-) is 1 × 10-14 and that in heavy water (D2O
(3) Solid CaH2 and aqueous H3 PO2 D+ + OD-) is 3 × 10-15. H2O dissociates about
(4) Solid CaO and gaseous PH3 (1)  1.8 times as much as D2O does
(2) thirty times as much as D2O does
12. Deuteroammonia (ND3) can be prepared
(3) 0.3 times as much as D2O does
(1) by heating a solution of NH4Cl in NaOD
(4) 300 times as much as D2O does
(2)  by the action of heavy water on magnesium
nitride 19. Acetone exhibit keto-enol tautomerism
(3) by fractionation of ordinary ammonia
(4)  by the exchange of hydrogen in ammonia by O OH
­dissolving in heavy water
CH3 – C – CH3 CH3 – C = CH2
13. Acidified potassium permanganate is dropped over
sodium peroxide taken in a round bottom flask at Which of the following products is obtained when
room temperature, vigorous reactions takes place acetone is treated with an excess of D2O for a suf-
to produce ..... and the sum of the coefficients of ficient time in the presence of small amount of dilute
­reactants and products are respectively NaOH solution?

Chapter_09.indd 22 3/26/2014 3:19:20 PM

 Hydrogen and its Compounds  9.23

OD OH 25. Select the correct statement

(1) CH3 – C = CH2 (2)  CH2D – C = CH2    I. H2O2 reduces MnO4- to Mn2+ in acid medium
  II. H2O2 reduces MnO4- to MnO2 in basic medium
III. H2O2 reduces K3[Fe(CN)6] to K4[Fe(CN)6] in al-
O OD
kaline medium
(3) CD3 – C – CD3 (4) 
CH 3 – C = CHD   IV. H2O2 oxidises Mn2+ to MnO2 in alkaline medium
(1) I, II, III only (2) I, II, IV only
20. Hydrogen molecule differs from chlorine molecule in (3) II, III, IV only (4) I, II, III, IV
the following aspect:
(1)  Hydrogen molecule is polar while chlorine
­molecule is nonpolar Answers
(2)  Hydrogen molecule can form intermolecular
­hydrogen bonds but chlorine molecule does not (1) 4 (2) 1 (3) 1 (4) 4 (5) 4
(3) Hydrogen molecule cannot participate in coordi- (6) 2 (7) 1 (8) 1 (9) 1 (10) 2
nation bond but chlorine molecule can (11) 1 (12) 2 (13) 4 (14) 1 (15) 3
(4) Atomicity of both hydrogen and chlorine is same (16) 1 (17) 2 (18) 1 (19) 3 (20) 1
(21) 4 (22) 4 (23) 1 (24) 4 (25) 4
21. Hydride ion reacts with water liberating hydrogen gas
H- + H2O → H2 + OH-
This reaction indicates that
(1) Hydride ion reduces water to hydrogen   Statement-Type Questions
(2) Hydride ion oxidises water to hydrogen
In each of the following questions, a statement-I is ­given
(3) Hydride ion displaces H+ ion from water
followed by corresponding statement-II just below.
(4) Hydride ion being stronger base than OH- takes Mark the correct answer as indicated.
up H+ ion from water
1. If both Statement I and Statement II are true and
22. A sample of water containing some dissolved table Statement II is the correct explanation of Statement I.
sugar and common salt is passed through an organic 2. If both Statement I and Statement II are true and
cation exchange resin. The resulting solution contain Statement II is not the correct explanation of State-
(1) Both sugar and common salt ment I.
(2) Only sugar 3. If Statement I is true and Statement II is false.
(3) Only pure water 4. If Statement I is false but Statement II is true.
(4) Sugar, glucose and fructose 1. Statement-I: The isotopes of hydrogen show much
greater differences in physical properties than are
23. When formaldehyde is treated with hydrogen perox-
found between the isotopes of other elements.
ide in the presence of alkaline pyrogallol produces
light. This is due to Statement-II: Because of enormous mass difference
between the isotopes of hydrogen.
(1) Reduction of H2O2 forming H2 and chemilumi-
nescence 2. Statement-I: 1H reacts more rapidly with halogens
(2) Oxidation of H2O2 forming O2 and chemilumi- than 2H.
nescence Statement-II: 1H has lower energy of activation than
(3) Oxidation of H2O2 forming H2 and phosphores- 2
H and thus reacts faster.
cence 3. Statement-I: Ionic compounds are less soluble in
(4)  Reduction of formaldehyde forming O2 and D2O than H2O.
phosphorescence
Statement-II: D2O has a lower dielectric constant
24. The hydride having highest electrical conductance is than H2O.
(1) LiH 4. Statement-I: The pink colour of KMnO4 disappears
(2) BeH2 when H2O2 is put in acidic medium.
(3) CaH2
Statement-II: H2O2 has an open book structure hav-
(4) TiH2
ing sp3 hybridised “O” atoms.

Chapter_09.indd 23 3/26/2014 3:19:22 PM

 9.24  Objective Chemistry - Vol. I

5. Statement-I: Tritium is nontoxic. The correct matching is

Statement-II: Tritium emits low energy beta S.No. A B C D
­radiation and gamma radiation.
1. 2 3 1 4
6. Statement-I: Ferricyanide ion oxidises H2O2 to H2O. 2. 2 4 1 3
Statement-II: Oxidation product of H2O2 is O2 3. 4 3 1 2
7. Statement-I: In a reaction of H2O2 and Na2CO3, 4. 4 2 1 3
H2O2 acts as an acid.
2. Match the following.
Statement-II: H2O2 cannot act as an acid.
8. Statement-I: The colour of old lead paintings can be List-I List-II
restored by washing with dil. H2O2. (A)  Potable water   (i) D2O
Statement-II: Black lead sulphide is oxidised by (B)  Temporary hardness  (ii)  CaSO4
H2O2 to white lead sulphate. (C)  Permanent hardness (iii) Mg(HCO3)2
(D)  Heavy water   (iv)  Drinking water
9. Statement-I: H2O2 reacts with PbS to form PbSO4.
Statement-II: H2O2 is a weak acid. The correct matching is
10. Statement-I: D2O and H2O have same chemical S.No. A B C D
properties.
1. i ii iii iv
Statement-II: D2O and H2O are different allotropes 2. iii iv i ii
of water. 3. iv iii ii i
11. Statement-I: Electrolysis of hard water produces O2 4. iv iii i ii
and D2.
3. Match the following.
Statement-II: Ordinary hydrogen is called protium.
List-I List-II
12. Statement-I: The solubility of NaCl in heavy water
is less than that in ordinary water. (A) Zeolite   (i) Na2[Na4(PO3)6]
Statement-II: The dielectric constant of D2O is 80.5 (B) Calgon  (ii)  (RNH3)OH
and that of water is 82 (at 20°C). (C)  Cation exchange resin (iii) Na2Al2Si2O8. x H2O
(D)  Anion exchange resin  (iv)  RCOOH

Answers The correct matching is

(1) 1 (2) 1 (3) 1 (4) 2 (5) 1 S.No. A B C D

(6) 4 (7) 3 (8) 1 (9) 2 (10) 3 1. iii i iv ii
(11) 4 (12) 1 2. iv iii ii i
3. iii ii iv i
4. iii iv ii i

4. Match the given in List I with those given in List II.

 Match the Following Type Questions
List-I List-II
1. Match the following volume strengths given in list I 3
(A)  Heavy water   (i)  H
with the values given. 1

(B) 1 electron, 1 proton (ii)  Fuel cells

List-I List-II and 2 neutrons
(A)  10 volumes   (i) 5.358 N (C)  Rocket fuel (iii)  Trace compound
(B)  20 volumes  (ii)  3.036% (W/V) (D) Fischer-Tropsch  (iv) Synthetic motor pro-
(C)  30 volumes (iii)  3.4 g H2O2/100 mL solution cess fuel
(D)  11.2 volumes   (iv)  1.785 M   (v)  12 H

Chapter_09.indd 24 3/26/2014 3:19:23 PM

 Hydrogen and its Compounds  9.25

The correct matching is The correct matching is

S.No. A B C D S.No. A B C D
1. iii i ii iv 1. ii iii i iv
2. iii v ii iv 2. iv i iii ii
3. ii iii iv i 3. ii iii iv i
4. iv v iii i 4. i ii iii iv

7. Match the following

List-I List-II
5. Match the given in List I with those given in List II.
(A)  Preparation of heavy water   (i) CaCl2
List-I List-II (B)  Hardness to water (ii)  RN+H3OH-
(A)  Hydrogenation of oils   (i) Fe (C)  Anion exchange resin (iii) 10% NaCl (aq)
(B)  Haber’s process (ii)  Hydrogen (D)  Revival of permutit  (iv)  6% KCN
(C)  Nuclear fusion (iii) Ni   (v)  H2S
(D)  Most abundant in the universe  (iv)  Hydrogen bomb The correct matching is
  (v)  Helium
S.No. A B C D
1. v i ii iv
The correct matching is 2. v ii i iv
3. i iv ii iii
S.No. A B C D 4. v i ii iii
1. Iii i iv v
2. Iii i iv ii
3. Iv iii v ii Answers
4. Iv iii ii v
(1) 2 (2) 3 (3) 1 (4) 1 (5) 2
6. Match the property of H2O2 in List I with those given (6) 3 (7) 4
in List II.
List-I List-II
(A) Second most powerful   (i) 
H2O2 oxidises PbS to
oxidising agent PbSO4
(B) H2O2 is stored in wax- (ii)  O3
coated bottles
(C) H2O2 has higher boiling (iii) H2O2 decomposes
point than H2O into H2O and O2
(D) H2O2 is used to restore   (iv) H2O2 is more hydro-
colour of lead painting gen bonded than H2O

Chapter_09.indd 25 3/26/2014 3:19:23 PM

 This page is intentionally left blank.

Chapter_09.indd 26 3/26/2014 3:19:23 PM

 10

Chapter
Group IA Alkali Metals

• Except H2 and Fr, the other elements of Group IA give • Hydration energies of alkali metal ions decrease
strong bases by dissolving their oxides and hydroxides down the group due to increase in size.
in water, so they are known as alkali metals. • Every alkali metal ion has two layers of water
• Since these elements are highly reactive, they do not ­occur molecules of hydration, i.e., primary and secondary
in nature in a free state but occur as their compounds. The ­layers. The water molecules in the primarily layer are
most abundant alkali metal is Na and the least abundant coordinated water while in the secondary layer are in
metal is Cs. Francium is a radioactive metal. ion–dipole attractions.
• All these elements have ns1 electronic configuration in • In the primary layer of Li+ ion only 4 water molecules
their valence shell. are coordinated to Li+ tetrahedrally using its sp3 ­hybrid
orbitals. Similarly, Na+ and K+ ions may also have four
Physical Properties fold primary hydration in aqueous solutions.
• Rb+ and Cs+ ions are surrounded by six water mol-
• In a period alkali metal has highest atomic size and ecules octahedrally in the primary layer using sp3d2
lowest density. hybrid orbitals.
• Density increases from Li to Cs but K is lighter than • The secondary hydration decreases from Li+ to Cs+
Na because of the presence of vacant 3d orbitals and since the ion–dipole attraction decreases with increase
also due to bigger atomic size of K, large gaps between in size.
the atoms in crystalline structure of K occur.
• Ionic mobilities increase from Li+ to Cs+ due to
• Due to larger size of the atoms of alkali metals, their ­decrease in the size of hydrated ions.
outer electron is weakly attracted by the nucleus and
• Tendency to form hydrated salts decreases from Li to
hence their ionisation enthalpies are less and decrease
Cs due to decrease in the attractive force towards ­water.
down the group as the atomic size increases.
Nearly all Li compounds are hydrated commonly as
• Electropositive character increases down the group. ­trihydrates. In these hydrated salts, Li+ is coordinated to
• Alkali metals exhibit a fixed oxidation state of +1. 6H2O molecules octahedrally sharing the faces in chains.
• The second ionisation enthalpy of alkali metals is very Many sodium salts and few potassium salts are hydrated.
high because the second electron to be removed is Rubidium and caesium do not form hydrated salts.
from most stable inert gas configuration. • Alkali metals give flame colours Li-crimson red,
• The compounds of alkali metals are colourless and ­Na-golden yellow, K-Lilac or pale violet; Rb-red
diamagnetic because all electrons are paired. ­violet; Cs-blue violet.
• Alkali metals when irradiated with light emit elec- • The order of oxidation potential is Li > Cs > Rb > K > Na.
trons. This phenomenon is known as photoelectric • Though the heat of sublimation and ionisation energies
effect and hence K and Cs are used as electrodes in of lithium is high, it is the strongest reducing agent due
photoelectric cells. to very large hydration energy in aqueous solution.

Chapter_10.indd 1 3/26/2014 3:19:53 PM

 10.2  Objective Chemistry - Vol. I

(3) In an aqueous solution, lithium is the strongest

 Objective Questions reducing agent.
(4) Alkali metals show abrupt increase in second IP.
1. Sodium reacts with water less vigorously than
11. Which of the following alkali metals has the highest
­potassium because
tendency for the half-reaction?
(1) it has higher atomic weight
M(s) → M ( aq ) + e
+ −
(2) it is less electropositive
(3) it is more electronegative (1) Sodium (2)  Lithium
(4) it is a metal (3) Potassium (4)  Caesium
2. A colourless salt gives violet colour to Bunsen flame 12. Which is wrong regarding the density of alkali ­metals?
and also turns moist litmus paper to blue. It is
(1) Li < Na (2)  Na < K
(1) Na2CO3 (2)  KNO3 (3) K < Rb (4)  Rb < Cs
(3)  K2CO3 (4)  Cu(OH)2
3. Sodium has .................. as compared to potassium. Answers
(1) less electronegativity
(2) more ionisation potential   (1) 2   (2) 3   (3) 2   (4) 2   (5) 2
(3) large atomic radius   (6) 3   (7) 4   (8) 3   (9) 3 (10) 1
(4) lower melting point (11) 2 (12) 2
4. The least density is for
(1) Na (2)  K (3)  Rb (4)  Cs
Chemical Properties
5. Select the largest atom from the following:
(1) 1s22s22p1 (2)  1s22s1 • Chemical reactivity of alkali metals increases from Li
2 2
(3) 1s 2s (4)  1s22s22p2 to Cs.
• When exposed to air alkali metals tarnish due to the
6. The electronic configuration of elements X, Y, Z and
formation of oxides, hydroxides and carbonates at the
J are given below. Which element has the highest me-
surface due to reaction with oxygen, moisture and CO2
tallic character?
in air.
(1) X = 2, 8, 4 (2)  Y = 2, 8, 8
(3) Z = 2, 8, 8, 1 (4)  J = 2, 8, 8, 7 • When burned in air, Li forms monoxide as well as lith-
ium nitride (Li3N). But other alkali metals react only
7. Melting point of alkali metal decreases with with oxygen but not with nitrogen. Li forms monox-
(1) decrease in size ide, Na forms peroxide and other alkali metals form
(2) decrease in density superoxides.
(3) decrease in atomic mass • Alkali metals react with water liberating hydrogen and
(4) increase in size the reactivity towards water increases from Li to Cs.
8. From the trends observed in the alkali metals group • Alkali metals react with hydrogen forming hydrides
the element Francium should be and the reaction of alkali metals with hydrogen
(1) more electropositive than caesium ­decreases from Li to Cs. These alkali metal hydrides
(2) the lightest of these elements when dissolved in water yield hydrogen.
(3) the biggest in size • Stability of superoxides increases from KO2 to CsO2
(4) the least ionisable though lattice energy decreases with increase in size of
cation. This is because when they decompose forming
9. Which of the following gives different flame coloura-
metal oxide which has more lattice energy in K2O (due
tion from the other?
to small sizes of K+ and O2– ions) that compensate the
(1) Caustic soda (2)  Washing soda heat required to decompose KO2 but in the case of CsO2
(3) Caustic potash (4)  Chile salt petre less lattice enthalpy (due to bigger size of Cs+ ion) can-
10. Which of the following statement is false? not compensate the heat required to decompose CsO2.
(1) Among alkali metals, lithium is the softest metal. • Pure oxides and peroxides are colourless but superox-
(2) Ionisation potential of lithium will be greater ides are coloured and paramagnetic due to the pres-
than that of sodium. ence of an unpaired electron.

Chapter_10.indd 2 3/26/2014 3:19:56 PM

 Group IA Alkali Metals  10.3

Solutions of Alkali Metals in Ammonia

 Objective Questions
• All the alkali metals dissolve in ammonia to form met-
astable solutions. When ammonia is pure and if there 13. Which of the following is correct regarding solutions
are no impurities evaporation of these solutions yields of sodium metal in liquid ammonia?
alkali metals. (1) The solutions are generally blue coloured,
• Solutions of alkali metals in ammonia are blue col- good conductors of electricity and conductivity
oured and have electrical conductivity, paramagnetic ­decreases as temperature rises.
character and reducing properties due to the presence (2) The solutions are paramagnetic but paramagnetic
of ammoniated metal ions and ammoniated electrons. character decreases as concentration of solution
+ −
is increased.
M liquid
 NH3
→  M ( NH 3 )x  + e ( NH 3 )y  (3) When NH4Cl solid is added to such a solution,
NaCl is precipitated.
• The solutions of alkali metals in ammonia have more (4) All the above are correct.
volume than the sum of volumes of the metal and sol-
14. A metal from period 4 is added to water and a vigor-
vent probably due the occupation of electrons in the
ous reaction takes place with the evolution of a gas.
cavities of radius 300–400 pm. So, the density of solu-
Which statement is correct?
tion decreases and hence floats.
   (I)  Oxygen is evolved.
• At high concentrations, dimerization of metal ions and   (II)  Hydrogen is evolved.
pairing of electrons takes place due to which the solu-   (III)  The resulting solution is acidic.
tion becomes diamagnetic. (IV)  The resulting solution is basic.
• Solution of alkali metals in ammonia reduces O2 to O2− (1) I and III only (2)  II and III only
and O2−2 ; transition metal complexes to unusual lower (3) II and IV only (4)  I and IV only
oxidation states, e.g., K2[Ni(CN)4] to K4[Ni(CN)4],
15. Which of the following statements is wrong?
i.e., Ni2+ to Ni(0); [Pt(NH3)4] Br2 to [Pt(NH3)4], i.e.,
Pt2+ to Pt(0); Mn2(CO)10 to K[Mn(CO)5], i.e., Mn(0) (1) When sodium burns in air, sodium peroxide is
to Mn–1; Fe(CO)5 to Na2[Fe(CO)4], i.e., Fe(0) to Fe2–. formed.
(2) Potassium when heated strongly in oxygen
• Solutions of alkali metals in liquid ammonia liberate gives KO2.
H2 gas from protonic species like RC ≡ CH; C2H5OH, (3) Among alkali metal ions, the ion having
etc. ­maximum value of hydration energy is Li+.
• Complex forming tendency of alkali metals is very (4) The metal that do not give superoxide is rubidium.
less because of their bigger sizes, less effective nuclear
16. Regarding KO2 which of the following is correct?
charge and less tendency to accept electrons.
(1) It is a superoxide. (2)  It is coloured.
(3) It is paramagnetic. (4)  All are correct.
Principles of Extraction 17. In the formation of superoxide M + O2 → MO2 the
metal M is
• Alkali metals cannot be extracted by the usual meth-
(1) Li (2)  Na (3)  K (4)  Ba
ods because (i) they themselves are strong reducing
agents and stronger reducing agents which can reduce 18. Identify the false statement regarding the solutions of
alkali metal compounds are not available (ii) alkali alkali metals in ammonia.
metals cannot be prepared by the electrolysis of the (1) The blue colour, paramagnetic character and
aqueous solutions of their salts because the discharge ­reduction properties of the solution are due to
potential of alkali metal ions is more than that of H+ ammoniated electrons.
ion and hence H+ ion will be reduced at cathode pref- (2) The conductivity is due to both ammoniated elec-
erentially to alkali metal ion and H2 gas will be liber- trons and ammoniated metal ions.
ated at cathode. (3) Evaporation of the solution in the absence of
• Alkali metals are generally prepared by the electroly- catalyst or impurities gives metal amides.
sis of their fused metal halides after the addition of (4) The conductivity of saturated solutions is nor-
some other salt to decrease their m.pt. mally equal to the metal dissolved in ammonia.

Chapter_10.indd 3 3/26/2014 3:19:57 PM

 10.4  Objective Chemistry - Vol. I

19. When burned in air lithium forms Nitrides

(1) Lithium monoxide and lithium nitride
• Only lithium reacts with nitrogen directly forming
(2) Lithium monoxide and lithium peroxide
nitride Li3N.
(3) Lithium monoxide only
• Sodium and potassium nitrides are prepared by the
(4) Lithium nitride only
action of active nitrogen on metals or heating a ­mixture
20. Identify the false statement about the extraction of of metal oxide and metal.
alkali metals. • Li3N on heating with hydrogen gives ammonia and
(1) They cannot be extracted by thermal decomposi- LiH.
tion because their compounds are stable.
(2) They cannot be extracted by chemical reduction Oxides
because they themselves are strong reducing • Alkali metals when burnt in oxygen, Li forms ­monoxide,
agents. sodium forms peroxide and others form superoxides.
(3) They cannot be extracted by electrolysis of their • Oxides of any required element can be prepared by
aqueous solutions of salts because they are more
dissolving the metal in ammonia and treating the solu-
electropositive than the hydrogen
tion with the required amount of O2.
(4) They cannot be extracted by electrolysis of the
• All the alkali metal oxides are ionic, strongly basic
fused salts because of their high melting points.
and highly soluble in water forming strongly alkaline
solutions of their hydroxides. Solubility increases
down the group.
Answers • There is a trend in increasing colouration, with
(13) 4 (14) 3 (15) 4 (16) 4 (17) 3 ­increase in atomic number. Li2O and Na2O are colour-
(18) 3 (19) 1 (20) 4 less or white, K2O is yellowish, Rb2O is bright yellow
and Cs2O is orange.

Hydroxides
compounds of alkali metals • Alkali metal hydroxides are formed by dissolving their
Hydrides oxides in water, and these are the strongest bases. The
strength of these hydroxides increases regularly from
• All the alkali metals react with hydrogen forming Li to Cs due to increase in electropositive character of
ionic hydrides of the formula M+H–. The reactivity of the metals and bond lengths.
alkali metals towards hydrogen is in the order < i >
Cs > K > Na.
• All the alkali metal hydroxides are white crystalline
and deliquescent in nature. Except lithium hydroxide
• The ionic character of these hydrides increases from all are highly soluble in water and solubility increases
Li to Cs and their stability decreases from LiH to CsH. from LiOH to CsOH.
• These hydrides act as strong reducing agents and liber- • Thermal stability of these hydroxides increases from
ate H2 with protonic solvents such as H2O, NH3 and LiOH to CsOH. LiOH tends to lose H2O on heating
C2H5OH with the formation of hydroxide, amide and converting itself to Li2O.
ethoxide, respectively.
• Except LiOH other alkali metal hydroxides sublime at
• NaH reduces several substances forming another about 673 K without decomposition and their vapours
­hydride or complex hydride, e.g., BF3 to B2H6 or contain (MOH)2.
NaBH4, AlBr3 to NaAlH4 or TiCl4 to Ti.
• The dissolution of alkali metal hyroxides in water is exo-
• NaH reduces SO2 to dithionate (Na2S2O4) and CO2 to thermic due to the formation of hydrates and hydration.
formate.
• LiH forms LiAlH4 with AlCl3 which is used as a Halides
­reducing agent in organic chemistry to reduce carbonyl
compounds to alcohols, reduces several inorganic • Alkali metal halides are colourless solids with high
compounds, e.g., BCl3 to B2H6 PCl3 to PH3, SiCl4 to m.pts and b.pts but they turn yellow (NaCl), violet
SiH4, etc. (KI), etc. owing to non-stoichiometric crystal defects.

Chapter_10.indd 4 3/26/2014 3:19:57 PM

 Group IA Alkali Metals  10.5

• The order of heat of formation for a given metal is Compounds of Carbon

F > Cl > Br > I. For any alkali metal, fluoride is most
stable and iodide is least stable. • Lithium on heating with carbon forms ionic carbide
Li2C2. Other alkali metals react with acetylene or
• The order of Df H° for fluorides of alkali metal is LiF >
by passing acetylene through a solution of the metal
NaF > KF > RbF > CsF. LiF is most stable and CsF is
­liquid ammonia, forming M2C2.
least stable.
• These carbides contain acetylide ion ( C2−
2 ) and on
• For other halides the trend is opposite to fluorides: LiX hydrolysis gives acetylene.
< NaX < KX < RbX < CsX.
• Ionic character of alkali metal halides is in the
­order LiX < NaX < KX < RbX < CsX; MF > MCl >
 Objective Questions
MBr > MI
• M.pts of halides for a given alkali metal will be in the 21. Which one of the following decomposes on heating
order NaF > NaCl > NaBr > NaI. to M2O?
• M.pt. of alkali metal halides for a given halogen will (1) LiOH (2)  NaOH
be in the order Li < Na > K > Rb > Cs. Low m.pts of (3) KOH (4)  Mg(OH)2
lithium halides may be due to covalent character. 22. Which of the following fluorides are sparingly solu-
• The solubility of alkali metal fluorides is in the order ble in water?
LiF < NaF < KF < RbF < CsF. The low solubility of (1) LiF (2)  NaF (3)  CsF (4)  KF
LiF is due to its very high lattice energy because of
small sizes of both Li+ and F–. 23. LiF is less soluble in water than KF because
(1) LiF is more covalent than KF.
• Except fluorides, for the other halides solubility
(2) LiF has more lattice energy than KF.
decreases from NaX to KX and then increases to
(3) LiF has higher enthalpy of hydration than KF.
CsX. The solubility of KX is less than NaX because,
(4) Li+ ions are not extensively hydrated as K+.
the difference in hydration and lattice energies of
potassium salts are positive, whereas in the halides of 24. NaF has higher melting point than those of NaCl,
other metal halides, it is negative. NaBr and NaI because it has a
• Lithium halides (except LiF) have significant covalent (1) minimum ionic character
character and hence soluble in organic solvents. (2) maximum ionic character
• CsCl, CsBr and CsI have bcc structure in which coor- (3) higher oxidising power
dination number (CN) of each ion is 8. All the other (4) lowest polarity
alkali metal halides have fcc structure in which the CN 25. The chloride that can be extracted with ether
of each ion is 6. (1) NaCl (2)  LiCl (3)  BaCl2 (4)  CaCl2
• Theoretically, the CN of Li+ ion must be 4 but
abnormally it adopts CN 6 which is attributed to 26. Which is not correct in the case of lithium?
more favourable lattice energy acquired by achieving (1) It combines directly with N2 to form Li3N.
a higher CN. Hence, the solubility of lithium halides (2) It has great tendency to form hydrates.
is less. (3) It is not affected by air.
(4) It burns in air forming superoxide.
• If two alkali metal halide solutions are mixed, it results
in the formation of a new alkali metal halide, one hav- 27. Lattice energy is lowest for
ing more lattice energy. (1) LiF (2)  NaCl (3)  KBr (4)  CsI
LiI + CsF → CsI + LiF ∆H = –46 kJ mol–1
28. Which among the following statements is not ­correct?
• If excess HF is used in the preparation of fluoride by (1) Lithium is softest among all the alkali metals.
adding HF to NaOH or KOH, solid hydrogen fluorides (2) Lithium possess high m.pt and b.pt.
NaHF2 and KHF2 will be formed which contain (F – H (3) Lithium is the least reactive among alkali metals.
...... F)– ion. (4) Lithium chloride is soluble in alcohol.

Chapter_10.indd 5 3/26/2014 3:19:57 PM

 10.6  Objective Chemistry - Vol. I

29. Which of the following statements is correct? • The size of Li+ is smaller when compared with CO32−
(1) The monoxide formed by lithium contains O2− ion. ion. So, the replacement of larger CO32− ion by the
(2) The peroxide formed by sodium contains O2− ion. smaller O2– will lead to the increase in the lattice
(3) The ozonide formed by potassium contains energy and hence favours the decomposition of
O2− ion. Li2CO3.
(4) The ozonide ion is diamagnetic. • Except Li2CO3 other alkali metal carbonates are stable
up to 1200 K above which they melt and then con-
30. The m.pt of CsCl is lower than that of NaCl. It
verted into oxides.
implies that
• Order of thermal stability of alkali metal carbonate is
(1) two compounds have different ionic nature
(2) two compounds have different polarising power Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
(3) their lattice arrangements are different. • When dissolved in water they hydrolyse in water and
(4) given statement is wrong their aqueous solutions are basic in nature.
31. LiAlH4 is obtained by reacting an excess of (x) with CO32 − + 2H 2 O → H 2 CO3 + 2OH −
an ethereal solution of AlCl3. (x) is • Li2CO3 is only sparingly soluble in water and the solu-
(1) LiCl (2)  LiH (3)  Li (4)  LiOH bility of alkali metal carbonates increases down the
group.
32. Which of the following halides crystallises from its Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
aqueous solution as hydrate?
(1) LiCl (2)  KCl (3)  NaCl (4)  RbCl
Bicarbonates
33. Alkali metal hydrides react with water to give
(1) acidic solution (2)  basic solution • Only bicarbonates of alkali metals (except Li) can be
(3) neutral solution (4)  hydride ion prepared in solid state. LiHCO3 exists only in solution
but cannot be prepared in a solid state.
34. Amongst the alkali metal hydrides, the most stable • The bicarbonates of alkali metals decompose on heat-
one is ing converting into bicarbonates. The heat of decom-
(1) LiH (2)  NaH (3)  KH (4)  RbH position of bicarbonates increases with increase in the
35. Which of the following hydrogen compounds is most size of cation.
ionic? LiHCO3 < NaHCO3 < KHCO3 < RbHCO3 < CsHCO3
(1) LiH (2)  CsH (3)  HF (4)  HI • The bicarbonates of alkali metals hydrolyse in water
forming alkaline solution.
HCO3− + H 2 O → H 2 CO3 + OH −
Answers
• Bicarbonate solutions are less alkaline than carbonate
(21) 1 (22) 1 (23) 2 (24) 2 (25) 2 solutions because more no. of OH– ions are formed
(26) 4 (27) 4 (28) 1 (29) 4 (30) 1 during the hydrolysis of carbonate (per mol).
(31) 2 (32) 1 (33) 2 (34) 1 (35) 2 • Bicarbonate does not give pink colour with phenol-
phthalein but carbonates can turn the phenolphthalein
to pink and this test can be used to distinguish between
carbonate and bicarbonate.
Oxosalts of alkali Metals • Potassium bicarbonate dimerizes due to hydrogen
Carbonates bonding but NaHCO3 forming long chains. Because
of this reason NaHCO3 is very less soluble in water
• Alkali metals form carbonates of the type M2CO3 by and this is the basis of the ammonia-soda process.
passing CO2 gas through their hydroxide solutions or
by the reaction of CO2 with their oxides.
Nitrates and Nitrites
• In the presence of excess CO2 carbonates convert into
bicarbonates. • All the alkali metal nitrates are soluble in water. Solid
• Thermal stability of alkali metal carbonates increases LiNO3 and NaNO3 are deliquescent and because of
with increase in size of the cation though lattice ­energy this reason KNO3 is used in preference to NaNO3 in
decreases with increase in size of cation. gun powder, a mixture of KNO3, sulphur and charcoal.

Chapter_10.indd 6 3/26/2014 3:19:59 PM

 Group IA Alkali Metals  10.7

• Alkali metal nitrates have fairly low melting points (3) Due to loss of CO2 from Li2CO3 and water from
and are the lowest melting points among the most Na2CO3 . 10H2O.
­stable nitrates. On strong heating they decompose into (4) Due to sublimation of Li2CO3
nitrites but at high temperatures to the oxide.
o
40. Aqueous solution of sodium carbonate is alkaline due to
2NaNO3 500  C
→ 2NaNO2 + O2 (1) hydrolysis of Na+
800o C
4NaNO3 → 2Na2O + 5O2 + 2N2 (2) hydrolysis of CO32−
• Similar to Li2CO3, LiNO3 is also least stable among (3) hydrolysis of both Na+ and CO32−
­alkali metal nitrates and the reason is same as ­explained (4) hydration of Na+
in the case of carbonate. 41. (X) is a white solid. A piece of red litmus paper turns
1
2LiNO3 → Li2O + 2NO2 + O2 white when it is dipped into freshly prepared aqueous
2 solution of (X). The (X) is
• LiNO3 is used in fireworks and red coloured distress
flares. Alkali metal nitrates are widely used to carry high (1) Na2O2 (2)  Na2O
temperature oxidations and also heat transfer medium. (3) Na2CO3 (3)  Na2SO4
• Nitrites of alkali metals can be prepared by heating 42. Which of the following statements is correct?
their nitrates or by the reaction of NO with a hydroxide. (1) An aqueous solution of sodium carbonate is nei-
• Nitrites liberate brown fumes of NO2 by reacting with ther acidic nor basic.
acids. (2) An aqueous solution of sodium carbonate is alka-
line because as a base, the carbonate ion picks up
the H+ ion from water releasing a hydroxide ion
making the solution alkaline.
 Objective Questions CO32 − + 2H 2O → HCO3− + OH −
(3) An aqueous solution of sodium carbonate is
36. Which of the following carbonates is sparingly acidic because being very electronegative the
­soluble in water? sodium ion picks up the hydroxide ion from water
(1) Li2CO3 (2)  Na2CO3 to release H+ ion making the solution acidic.
(3) K2CO3 (4)  Rb2CO3 2Na+ + 2H2O → 2NaOH + 2H+
37. In industries caustic potash is used in the place of (4) In an aqueous solution of sodium carbonate, car-
caustic soda to remove acidic oxides like SO2, CO2, bonate ion reacts with water to form carbonic
etc. because acid.
(1) Potassium salts are thermally stable than sodium CO32 − + 2H 2O → H 2 CO3 + 2OH −
salts.
43. Na2CO3 and NaHCO3 may be distinguished by treat-
(2) Potassium salts are more soluble than sodium salts.
ing their solutions with
(3) Caustic potash can react with them but not caus-
tic soda. (1) litmus solution (2)  dil. acetic acid
(4) Caustic potash is cheaper than caustic soda. (3) methyl orange (4)  phenolphthalein

38. Which of the following about compounds of lithium

Answers
is false?
(1) The hydroxide, carbonate and nitrate decompose (36) 1 (37) 2 (38) 3 (39) 3
to give the oxide on heating. (40) 2 (41) 1 (42) 4 (43) 4
(2) It is the most electronegative element of group IA.
(3) The hydrogen carbonate can be isolated in stable
state.
(4) It forms an oxide but not a superoxide. Anomalous properties of Lithium

39. There is loss of weight when a mixture of Li2CO3 and • Anomalous properties of lithium are due to
Na2CO3. 10H2O is heated strongly. This loss is due to    (i)  its small size
(1) Li2CO3 due to decomposition into Li2O and gase-  (ii)  high electronegativity
ous CO2. (iii) presence of only two electrons in its penultimate
(2) Both Li2CO3 and Na2CO3 decompose to Li2O shell
and Na2O losing gaseous CO2.  (iv)  absence of d-orbitals in its valence shell.

Chapter_10.indd 7 3/26/2014 3:20:00 PM

 10.8  Objective Chemistry - Vol. I

• Lithium is the hardest metal with high m.pt. and b.pt

among alkali metals.  Objective Questions
• Except with hydrogen, it is the least reactive metal
among alkali metals. 44. The bicarbonate that cannot be prepared in solid state is
• Unlike other alkali metals it reacts with nitrogen di- (1) NaHCO3
(2)  LiHCO3
rectly. It can be stored by wrapping with wax-coated
(3) KHCO3
paper, whereas other alkali metals are stored under
(4)  RbHCO3
hydrocarbons like kerosene.
• On heating LiOH, Li2CO3, decomposes but other alkali 45. Lithium and magnesium exhibit diagonal relation-
metal hydroxides and carbonates do not decomposes. ship because
• Li2O and LiOH are weak bases. (1) both possess nearly the same size
(2) both possess similar electronic configuration
• Lithium salts like fluoride, phosphate, oxalate and
(3) both occur together in nature
­carbonate are sparingly soluble while the correspond-
(4) both have same number of valence electrons
ing salts of other alkali metals are freely soluble.
• LiCl is highly deliquescent and crystallize as hydrated 46. Lithium the only alkali metal which is not placed in
salt LiCl.3H2O. Other alkali metal chlorides are not kerosene but is wrapped in paraffin wax because
deliquescent and crystallize as anhydrous salts. (1) it reacts with kerosene
• Due to covalent character lithium halides (except LiF) (2) it floats to surface of kerosene because of low
and LiNO3 are soluble in organic solvents while cor- density
responding salts of other alkali metals are not. (3) its reactivity with air moisture is very less
(4) none
• LiNO3 on heating decomposes giving Li2O, NO2 and
O2 while the nitrates of other alkali metals give nitrites 47. Considering greater polarization in LiCl compared
(MNO2) and O2. to that in NaCl which of the following statements is
• Li2SO4 do not form alum but the sulphates of other wrong?
alkali metals forms alums. (1) The m.pt. of LiCl is lower than that of NaCl.
• In aqueous solutions it has least ionic mobility due to (2) LiCl dissolves more in organic solvents than NaCl.
extensive hydration because of its small size. (3) LiCl ionizes in water more than NaCl.
(4) Fused LiCl would be less conducting than fused
NaCl.
Diagonal Relationship of Lithium with
48. Which of the following statements regarding lithium
Magnesium is false?
• The similarities between lithium and magnesium are (1) Anomalous properties of lithium is due to its
due to the similar ionic sizes and similar polarizing small size and its ions.
power. (2) Polarization power of Li+ is the smallest of the
• Both Li and Mg are harder and lighter than the other alkali metal ions.
elements in their respective groups. (3) Polarization power of lithium ion leads to a great
tendency towards solvation and covalent bond
• Both Li and Mg react with water slowly and can react formation.
with N2 directly forming nitrides Li3N and Mg3N2. (4) Lithium is least reactive among all the alkali
• Oxides and hydroxides of both Li and Mg are weak ­metals.
bases, less soluble in water and decompose on heating.
49. Which of the following statements is correct?
• Li and Mg do not form peroxides.
(1) The Li+ ion is very small and so has high charge-
• Carbonates and nitrates of Li and Mg decompose on radius ratio.
heating similarly. (2) Salts of Li+ with small anions are exceptionally
• Solid bicarbonates of Li and Mg cannot be isolated stable.
and are soluble in organic solvents and they crystallize (3) Salts with large anions are relatively unstable.
as hydrated salts. (4) All are correct.

Chapter_10.indd 8 3/26/2014 3:20:00 PM

 Group IA Alkali Metals  10.9

50. Na and Li are placed in dry air. Then, we get • Highly soluble in water with liberation of heat due to
(1) NaOH, Na2O, Li2O formation of hydrates NaOH ⋅ nH2O (n = 1, 2 or 7).
(2)  Na2O, Li2O • NaOH dissociates the proteins of the skin into pasty
(3) Na2O, Li2O, Li3N, NH3 mass and corrosive. Hence, it is called caustic soda.
(4)  Na2O, Li3N, Li2O • NaOH is a strong base, neutralizes almost all acids and
acidic oxides forming salts.
• Amphoteric metals like Zn, Al, Sn, Be, Ge, etc. can
Answers
dissolve in NaOH liberating H2 gas.
(44) 2 (45) 1 (46) 3 (47) 4 (48) 2 • F2 liberates OF2 with cold, dilute NaOH and O2 with
(49) 4 (50) 4 conc. NaOH. Cl2, Br2 and I2 gives halides and hypo-
halites with cold and dilute NaOH but with hot and
concentrated NaOH gives halides and halates.
• When sulphur is boiled with NaOH, hypo and sodium
polysulphides are formed.
Important Compounds of
• When phosphorous is boiled with NaOH, phos-
Sodium
phine gas is liberated with the formation of sodium
Sodium Hydroxide hypophosphite.
• In the reactions of Cl2Br2, I2, S and P with NaOH the
• Solid NaOH is known as caustic soda and aqueous
oxidation numbers of nonmetals both increases and
NaOH is known as soda lye.
decreases. So, these reactions are disproportion reac-
• In causticising process, NaOH is formed by the action tions or redox reactions.
of milk of lime on sodium carbonate. • When silicon is heated with NaOH sodium silicate
• NaOH is manufactured by the electrolysis of brine in known as water glass is formed with the liberation of H2.
different electrolytic processes. • Carbon reduces the NaOH to Na and H2 with forma-
• In Nelson’s Cell method or porous diaphragm method tion of Na2CO3.
cathode is porous, U-shaped steel vessel, whereas • NaOH liberates ammonia from ammonium salts.
anode is a graphite rod separated by asbestos lining.
• Sodium hydroxide precipitates many metals from their
By-products are chlorine and hydrogen.
salts as metal hydroxides. These are of three types.
• The Castner–Kellner method is also known as mer-  (i) Metal hydroxides precipitated from their salts but
cury cathode method. In this method, the electrolytic insoluble in excess of NaOH
cell contains three compartments.   e.g., Fe(OH)2, Fe(OH)3, Ni(OH)2, Cu(OH)2 and
 (i) Mercury in the outer compartment acts as a cath- Mn(OH)2.
ode while in middle compartment acts as an anode  (ii) Metal hydroxides are precipitated from their
due to induction. salts but the precipitates dissolve in excess of
(ii) Graphite rods in the outer compartments act as an NaOH. These are amphoteric hydroxides such as
anode while the iron rods in the middle compart- Al(OH)3, Sn(OH)2, Zn(OH)2, Cr(OH)3, Pb(OH)2
ment act as a cathode. and Be(OH)2.
• Sodium liberated at mercury cathode in the outer (iii) Metal hydroxides are precipitated but are unsta-
­compartments dissolve in mercury forming sodium ble and decompose into metal oxide and water.
amalgam which moves into middle compartment   e.g., Hg(OH)2 to HgO and AgOH to Ag2O
where it reacts with water at cathode forming NaOH, • Amphoteric metal oxides like Al2O3, ZnO, SnO, SnO2,
H2 and Hg. BeO, PbO, PbO2 and Cr2O3 dissolve in sodium hy-
• Cl2 gas is liberated at graphite rods in the outer droxide forming corresponding salts.
compartments. • When CO is passed over solid NaOH under pressure
• Kellner–Solvay cell is a modified Castner–Kellner of 150°–200°C it forms sodium formate.
cell. • Sodium hydroxide is used in the manufacture of soap,
• NaOH is deliquescent white crystalline solid. So, it paper, rayon compounds like NaOH, NaXO3, in petro-
absorbs moisture and CO2 from air and hence cannot leum refining, in mercirization of cotton, in the prepa-
be used as a primary standard. ration of alumina and silica glass.

Chapter_10.indd 9 3/26/2014 3:20:00 PM

 10.10  Objective Chemistry - Vol. I

Reactions of NaOH
Reaction Remark
I. Action of heat
1. NaOH → Na + H2 + O2
II. Basic Character
1. NaOH + Acid → Salt + water All most all acids form salts
2. NaOH + CO2 → Na2CO3
3. NaOH + SiO2 → Na2SiO3
4. NaOH + SO2 → Na2SO3
5. NaOH + NO2 → NaNO2 + NaNO3 Disproportionation
III. Reaction with non-metals
1. NaOH + B → Na3BO3 + H2
2. NaOH + Si → Na2SiO3 + H2
3. NaOH + C → Na2CO3 + H2 + Na
4. NaOH + P4 → NaH2PO2 + PH3 Disproportionation
5. NaOH + S → Na2S + Na2S2O3 Disproportionation
6. NaOH + F2 → NaF + OF2 Cold and dilute condition
7. NaOH + F2 → NaF + O2 Hot and conc. condition
8. NaOH + X2 → NaX + NaOX Cold and dil. condition disproportionation
9. NaOH + X2 → NaX + NaXO3 Hot and dil condition disproportionation
IV. Reaction with metals
1. NaOH + Be → Na2BeO2 + H2
2. NaOH + Al → NaAlO2 + H2
3. NaOH + Sn → Na2SnO2 + H2
4. NaOH + Pb → Na2PbO2 + H2
5. NaOH + Zn → Na2ZnO2 + H2
V. Reaction with compounds
1. Any ammonium salt + NaOH → NH3
2. Certain metal ions ppt as hydroxides insoluble in
excess of NaOH. Fe2+, Fe3+, Ni2+, Cu2+, Mn2+
3. Amphoteric metal ions ppt as hydroxides but
soluble in excess of NaOH Be2+, Al3+, Sn2+, Sn4+, Pb2+, Pb4+, Zn2+, Cr3+
4. Ag+ and Hg2+ ions ppt as hydroxides and
decompose to metal oxides.
5. Amphoteric metal oxides dissolve in NaOH BeO, Al2O3, SnO, SnO2, PbO, PbO2, ZnO
6. NaOH + CO → HCOONa

(2) In Castner–Kellner cell, the anode in the middle

 Objective Questions compartment is mercury.
(3) The products of the electrolysis of concentrated
51. When a crystal of caustic soda is exposed to air a aqueous solution of common salt are NaOH, H2
­liquid layer is deposited because the crystal and Cl2.
(1) melts (2)  loses water (4) The products formed during the electrolysis of
(3) absorbs moisture (4)  Sublimes brine at cathode, anode and in the solution are in
and CO2 the mole ratio 1:1:1.
52. Which of the following statements is wrong? 53. Which of the following is wrong?
(1) In Nelson’s cell asbestos diaphragm is used (1) Sodalime is a mixture of NaOH and CaO.
because it is permeable to ions and prevents the (2) The reagent used in the causticisation of sodium
reaction between NaOH and Cl2. carbonate is Ca(OH)2.

Chapter_10.indd 10 3/26/2014 3:20:01 PM

 Group IA Alkali Metals  10.11

(3) Water glass is hydrated form of a glass. 61. A boy collected the chocolate wrappers of a metal,
(4) The by-products in the manufacture of NaOH are and added washing soda and lime water to the pieces
H2 and Cl2. of chocolate wrappers in a bottle. A gas is liberated.
The gas is
54. The aqueous solutions of A and B on addition to
NaOH “A” gives green precipitate and B gives red (1) CO2 (2)  NH3 (3) H2 (4)  O2
precipitate. So, A and B are respectively 62. When chlorine is passed into hot concentrated caus-
(1) FeSO4, FeCl3 tic soda solution, the oxidation number of chlorine is
(2)  FeCl3, FeSO4 increased in one of the products from
(3) AlCl3, ZnSO4 (1) 0 to +7 (2)  –1 to + 7
(4)  FeSO4, CuSO4 (3) 0 to +5 (4)  0 to –1
55. If NaOH is added to an aqueous solution of Zn2+ ions 63. The ratio of volumes of hydrogen at STP when equal
a white precipitate appears and on adding excess amounts of tin reacts with dilute NaOH and conc.
NaOH the precipitate dissolves. In this solution, zinc NaOH is
exists in the (1) 1:1 (2)  1:2
(1) Cationic part (3) 2:1 (4)  2:3
(2) Anionic part
(3) Both in cationic and anionic parts 64. The compounds X and Y are obtained by the reaction
(4) There is no zinc left in the solution of Cl2 with cold and dilute solution of NaOH and X
and Z are formed with hot and concentrated solution
56. Excess of dilute sodium hydroxide solution is gradu- of NaOH. The Y and Z respectively are
ally added with shaking to an aqueous solution of (1) NaCl, NaClO3 (2)  NaClO, NaClO3
zinc sulphate or aluminium sulphate. What would (3) NaCl, NaClO (4)  NaClO, HCl
you observe?
(1) A permanent white precipitate is formed imme- 65. A standard solution of sodium hydroxide cannot be
diately. prepared by direct weighing of cold sodium hydrox-
(2) A white precipitate appears which dissolves to ide because
give a colourless solution. (1) NaOH is a solid
(3) No change in the beginning but later a white pre- (2) NaOH is a liquid
cipitate is formed on standing. (3) NaOH is easily dissolved
(4) No change takes place and the solution remains (4) NaOH is a deliquescent substance
clear. 66. On addition of aqueous solution of NaOH to a salt
57. Which on heating with NaOH solution gives inflam- ­solution, a white precipitate is formed which dis-
mable gas? solves in excess alkali. The salt solution contains
(1) Zn (2)  P (3)  Si (4)  All (1) Aluminium ions (2)  Zinc ions
(3) Tin ions (4)  Any of these ions
58. Caustic soda under different conditions reacts with
chlorine to give
(1) NaCl (2)  NaClO3 Answers
(3) NaClO (4)  All
(51) 3 (52) 4 (53) 3 (54) 1 (55) 2
59. Caustic soda when heated with which of the follow- (56) 2 (57) 4 (58) 4 (59) 1 (60) 3
ing do not liberate a gaseous product? (61) 3 (62) 3 (63) 3 (64) 2 (65) 4
(1) Sulphur (66) 4
(2) Phosphorous
(3) Silicon
(4) Ammonium chloride
Sodium Carbonate
60. Which of the following do not undergo dispropor-
tionation on heating with caustic soda? • The hydrated sodium carbonate Na2CO3. 10H2O is
(1) Chlorine (2)  Silicon known as washing soda while anhydrous Na2CO3 is
(3) Phosphorous (4)  Sulphur known as soda ash.

Chapter_10.indd 11 3/26/2014 3:20:01 PM

 10.12  Objective Chemistry - Vol. I

• In Le Blanc process Na2CO3 is manufactured by heat- • With excess of CO2 the carbonate converts into
ing the salt cake with coke and lime stone. The salt bicarbonate.
cake is obtained by heating NaCl with conc. H2SO4. • When fused with SiO2 it forms sodium silicate called
• Salt cake is reduced by coke to Na2S which reacts with water glass.
lime stone forming black ash (CaS and Na3CO3) from • When boiled with sulphur and sulphur dioxide it forms
which Na2CO3 is leached. hypo but with only SO2, it forms sodium sulphite.
• In Solvay’s process, first brine is saturated with • Except alkali metal carbonates and ammonium carbon-
­ammonia containing little CO2 in ammonia saturation ate almost all other metal carbonates are ­insoluble. So,
tower when impurities like Mg and Ca are removed in when Na2CO3 is added to soluble metal salts ­insoluble
the form of Mg(OH)2 and CaCO3. metal carbonates will be precipitated.
• In Solvay’s ammonia soda process sodium bicarbonate • With highly electropositive metal salts such as CaCl2,
is precipitated by passing CO2 into a solution of brine BaCl2, etc. it forms normal carbonates CaCO3, BaCO3.
saturated with ammonia. But with less electropositive metal salts it gives basic
• Sodium bicarbonate on heating gives sodium metal carbonates. E.g.,
carbonate.    (i)  With Mg salts give MgCO3 ⋅ Mg(OH)2
 (ii)  With Zn salts give [2ZnCO3 ⋅ 3Zn(OH)2] ⋅ H2O
• Ammonia can be recovered from the filtrate by boiling
(iii)  With Cu salts give CuCO3 ⋅ Cu(OH)2
with lime and can be used again.
 (iv)  With Pb salts give 2PbCO3 ⋅ 3Pb(OH)2
• In Nelson cell method for the manufacture of NaOH,
• Carbonates of metals like iron, aluminium, tin, etc.
if a mixture of steam and CO2 is used, sodium carbon-
when formed hydrolyses to hydroxides immediately
ate will be obtained.
liberating CO2. This reaction is used in foam fire
• Na2CO3 ⋅ 10H2O is efflorescent and convert into mono- extinguishers.
hydrate when exposed to air but converts into anhy- • Sodium carbonate is used in the manufacture of glass,
drous compound on heating. It is soluble in water and
caustic soda, in softening hard water, in petroleum
its aqueous solution is alkaline due to hydrolysis.
­refining, in washing purposes and laundries, in dyeing
• With acids, it liberates CO2 gas. industries and in fire extinguishers.

Reactions of Sodium Carbonate

Reaction Remark
1. Na2CO3 + Acid → CO2
2. Na2CO3 + H2O + CO2 → NaHCO3
3. Na2CO3 + SiO2 → Na2SiO3
4. Na2CO3 + SO2 → Na2SO3 + CO2
5. Na2CO3 + SO2 + S → Na2S2O3 + CO2
6. M2+ + Na2CO3 → MCO3 More electropositive metals
e.g., Ca, Sr, Ba ppt as normal carbonates
7. Na2CO3 + M2+ → Basic metal carbonate Less electropositive metals
e.g., Mg2+, Pb2+, Cu2+, Zn2+
8. Na2CO3 + M3+ → M(OH)3 + CO2 Fe3+, Cr3+, Al3+

Sodium bicarbonate • On heating it decomposes to give sodium carbonate

and CO2.
• Sodium bicarbonate is known as baking soda. In the • The metal salts which gives basic metal carbonates
laboratory it is prepared by passing CO2 into sodium with sodium carbonate gives normal carbonates with
carbonate solution but industrially it is manufactured sodium bicarbonate.
by Solvay’s process.
• Sodium bicarbonate is used as antacid in medicine,
• It is sparingly soluble in water and its aqueous solution in dry fire extinguishers, in baking powders, as mild
is alkaline due to hydrolysis. antiseptic for skin infections.

Chapter_10.indd 12 3/26/2014 3:20:01 PM

 Group IA Alkali Metals  10.13

74. In which of the following sodium carbonate is not

 Objective Questions used?
(1) In soap making
67. The false statement among the following is (2)  In paper making
(1) Acidity of the body fluids is neutralized by (3) In tyre making
­sodium bicarbonates. (4) In baking of bread
(2) Sodium bicarbonate is commercially known as
baking soda. 75. In Solvay’s process the reaction 2NH4Cl + Ca(OH)2
(3) Washing soda is deliquescent solid. → CaCl2 + 2NH3 + 2H2O takes place in
(4) Aqueous solutions of sodium carbonate and (1) Ammonia recovery tower
­sodium bicarbonates are basic in nature. (2) Carbonation tower
(3) Saturation tower
68. In Solvay’s process, the products that are recycled (4) Filtration unit
are
(1) CO2, NH4Cl (2)  NaCl, CaO 76. Na2CO3 can be prepared from Nelson cell method by
(3) CO2, NH3 (4)  CaCl2, CaO passing ........... to react with NaOH.
(1) CO (2)  CO2
69. The useful by-products obtained in Solvay’s process (3) CO and CO (4)  None of these
2
are
(1) NaHCO3 and NH4Cl 77. Which of the following reactions is not involved in
(2) Quick lime and CO2 Solvay’s process?
(3) NaHCO3 and CO2 (1) CaCO3 → CaO + CO2
(4) NH4Cl solution and quick lime (2) NaCl + NH3 + CO2 + H2O → NH4Cl + NaHCO3
(3) CaO + 2NH4Cl → NH3 + CaCl2 + 2H2O
70. The basic raw materials used in the manufacture of
(4) Na2CO3 + CO2 + H2O → 2NaHCO3
sodium carbonate by Solvay’s process are
(1) Lime stone and ammonia 78. A compound of sodium does not give CO2 when heat-
(2) Sodium chloride and ammonia ed but it gives CO2 when treated with dilute acids.
(3) Ammonia, carbon dioxide and sodium chloride A crystalline compound is found to have 37.1% Na
(4) Common salt and lime stone and 14.52% H2. Hence, the compound is
(1) NaHCO3 ⋅ 10H2O
71. Which of the following is not correct?
(2)  NaHCO3 ⋅ 5H2O
(1) Fire extinguishers contain H2SO4, NaHCO3 and (3) Na2CO3 ⋅ 10H2O
Na2CO3. (4)  Na2CO3 ⋅ H2O
(2) Black ash is Na2CO3 and CaS
(3) Raw materials in the manufacture of Na2CO3 by
Le Blanc process are brine, conc. H2SO4, coke Answers
and limestone.
(4) By-products in the manufacture of sodium car- (67) 3 (68) 3 (69) 2 (70) 3 (71) 2
bonate by Le Blanc process are hydrochloric acid (72) 3 (73) 3 (74) 1 (75) 2 (76) 4
and calcium sulphide. (77) 4 (78) 2
72. Some large white transparent crystals are left out in a
bowl for several days. They are then observed to have
changed their form into white powder. The crystals
Sodium Oxide
may have been of
(1) Ammonium chloride (2)  Sodium chloride • Pure sodium oxide is prepared by heating NaNO2 or
(3) Sodium carbonate (4)  Calcium oxide NaNO3 with sodium metal or sodium azide
73. When ammonical solution of common salt is satu- 2NaNO2 + 6Na → 4Na2O + N2
rated with carbon dioxide we get 2NaNO3 + 10Na → 6Na2O + N2
(1) NH4HCO3 (2)  (NH4)2CO3 • At 400° C, it disproportionate into Na2O2 and Na. With
(3) NaHCO3 (4)  MgCO3 liquid ammonia it forms sodamide.

Chapter_10.indd 13 3/26/2014 3:20:03 PM

 10.14  Objective Chemistry - Vol. I

Sodium Peroxide Sodium chloride

• It is obtained by heating sodium metal in excess of air. • It is mainly found in sea water and occur as rock salt.
• At low temperatures when dissolved in water, in ­dilute • Ordinary sodium chloride is hygroscopic due to the
solution gives H2O2 but in concentrated solution presence of magnesium and calcium chlorides.
gives O2. • Its solubility in water changes very little in water with
• With dilute acids it gives H2O2. change in temperature because its lattice energy and
• It absorbs CO and CO2. In the reaction with CO2 hydration energies are almost equal.
­oxygen gas is liberated. So, it is used in breathing
­apparatus of divers, firemen and in submarines.
• Na2O2 oxidizes several compounds, e.g., chromium (III) Sodium sulphate
compounds to chromates, manganese (II) compounds
• Na2SO4 ⋅ 10H2O is known as Gluber’s salt and anhy-
to manganates, sulphides to sulphates, benzoyl
drous Na2SO4 is known as salt cake, manufactured by
­chloride to benzoyl peroxide.
heating NaCl with concentrated H2SO4.
• Na2O2 is used for the production of oxygen under the
• It is used in textile industry, in medicine as purgative
name oxone, for purification of air, to bleach delicate
and in manufacture of glass plate and sodium salts.
articles like wool, silk, etc.

Sodium Nitrate
 Objective Questions
• Sodium nitrate occurs naturally as Chile salt petre. In
the laboratory it is prepared by the action of HNO3 on 79. The hydrated sodium peroxide crystallized from its
NaOH or Na2CO3. aqueous solution contain ............. molecules of water
of crystallization.
• Reduction of NaNO3 with Zn, Pb, etc. gives sodium
nitrite. (1) 4 (2)  6 (3)  8 (4)  2
• It is used as nitrogenous fertilizer in agriculture and in 80. Sodium peroxide reacts with Cr(OH)3 to give
the manufacture of HNO3, NaNO2 and KNO3. (1) Na2Cr2O7 (2)  Na2CrO4
(3) CrO5 (4)  Cr2O3
Sodium Nitrite
81. The species formed in concentrated aqueous solution
• It is manufactured by heating sodium nitrate alone or of Na2O2 is
reduction with lead or a mixture of lime and carbon. (1) H2O2 (2)  O2
• It can be manufactured by passing oxides of nitrogen (3) NaOH (4)  Both 2 and 3
NO and NO2 into an aqueous solution of NaOH or
82. Which of the following will absorb CO2 from atmos-
Na2CO3.
phere and liberate oxygen?
• It is also formed when SO2 is passed into concentrated
(1) NaOH (2)  Na2CO3
solution of NaNO3 to which lime is added.
(3)  Na2O2 (4)  Na2O
• When heated with NH4Cl it gives N2 gas.
• It can act both as oxidizing and reducing agent. 83. Salt cake is anhydrous
• It oxidizes urea to nitrogen in acid medium, liberates (1) Sodium carbonate
iodine from iodides in acid medium and oxidizes stan- (2)  Sodium sulphate
nous chloride to stannic chloride, sulphur dioxide to (3) Sodium tetraborate
sulphuric acid. (4)  Sodium nitrate
• If cobalt nitrite is treated with sodium nitrite and acetic 84. Sodium peroxide is used to purify the air in subma-
acid, sodium cobalt nitrate Na3[Co(NO2)6] is formed. rimes and confirmed spaces because
• It reduces potassium permanganate, potassium dichro- (1) it decomposes to form Na2O and O2
mate, bromine, etc. (2) it removes CO2 and produce O2
• It is used in the manufacture of azo dyes, used as a (3) it reacts with oxygen to form sodium superoxide
food preservative. (4) it kills the bacteria in air

Chapter_10.indd 14 3/26/2014 3:20:03 PM

 Group IA Alkali Metals  10.15

85. By starting with 0.5 moles of sodium peroxide how • K2O3 is obtained when O2 is passed through liquid
many moles of dioxygen gas can be obtained by ­ammonia containing potassium.
dropping excess of water on it? • Potassium superoxide (KO2) is prepared by burning
(1) 0.5 mole (2)  1 mole potassium in excess of oxygen free from moisture.
(3) 0.25 mole (4)  0.125 mole • KO2 is chrome yellow powder, when dissolved in
86. Sodium reacts with excess of oxygen, oxidation num- ­water it forms K2O2 and O2.
ber of oxygen changes from • It absorbs CO and CO2 and liberates O2.
(1) 0 to –1 (2)  0 to –2 • It oxidizes sulphur to potassium sulphate.
(3) –1 to –2 (4) 1 to –1
• It is used as an oxidizing agent in air, as air purifier in
87. Sodium when strongly heated in air forms a yellow submarines, space capsules and breathing masks as it
compound (A). (A) reacts with CO2 to give (B). The produces oxygen and removes CO2.
correct statement about (B) is
(1) Its aqueous solution is basic in nature. Potassium Hydroxide
(2) When (B) is fused with SiO2 liberates CO2.
(3) It is used in textile industry. • Solid KOH is known as caustic potash and aqueous
(4) When (B) reacts with SO2 liberates SO3. KOH is known as potash lye.

88. Pure sodium oxide can be prepared by heating

• Its preparation and properties are similar to those of
NaOH.
(1) NaNO3 with Na (2)  NaNO2 with Na
(3) Na2CO3 with Na (4)  Both 1 and 2 • It is mainly used in making soft soaps. Alcoholic KOH
is used in organic chemistry as it eliminates hydrogen
89. The solubility of which of the following compounds halides from alkyl halides.
does not change much with change in temperature
• It is a better absorber for acidic oxides like CO2, SO2,
(1) NaCl (2)  NaOH etc. than NaOH because potassium salts are more
(3) Na2CO3 (4)  Na2SO4 soluble than sodium salts.
90. Raw sodium chloride directly obtained from sea wa-
ter becomes damp but not the pure sodium chloride. Potassium Carbonate: Pearl  Ash
This is because
• It cannot be manufactured by Solvay’s process because
(1) Raw sodium chloride contains hygroscopic ­calcium KHCO3 is highly soluble in water and does not crystal-
and magnesium chlorides. lize like NaHCO3.
(2) Pure sodium chloride is hygroscopic.
(3) Pure sodium chloride is deliquescent.
• It can be manufactured by Le Blanc’s process by using
(4) Pure sodium chloride hyrolyzes. KCl in the place of NaCl.
• It is now manufactured by magnesia process in which
CO2 is passed into KCl solution at 293 K in the pres-
Answers ence of hydrated magnesium carbonate. Potassium
hydrogen magnesium is precipitated which up on
(79) 3 (80) 2 (81) 4 (82) 3 (83) 2 decomposition with water gives MgCO3, precipitates
(84) 2 (85) 3 (86) 1 (87) 4 (88) 4 K2CO3 solution from which K2CO3 can be prepared in
(89) 1 (90) 1 solid state by evaporation.
• It resembles Na2CO3 and is used in making hard glass,
toilet soaps and potassium compounds.
Important Compounds of Potassium Iodide
Potassium
• Potassium iodide can be prepared by the neutralization
Potassium Oxide of KOH or K2CO3 with HI.
• Potassium forms K2O, K2O2, K2O3 and KO2 of which • It is manufactured by heating iodine with concentrated
K2O and K2O2 can be prepared exactly in a similar way KOH solution. The resulting liquid contains KI and
as that of Na2O2. Their behaviour is also similar to that KIO3. This is evaporated to dryness and heated with
of Na2O and Na2O2. carbon to reduce KIO3 to KI.

Chapter_10.indd 15 3/26/2014 3:20:04 PM

 10.16  Objective Chemistry - Vol. I

• It can also be prepared by treating ferrosoferric iodide Biological Importance of Sodium and
(Fe3I8) formed by the action of iodine on iron filings Potassium
with potassium carbonate.
4K2CO3 + Fe3I8 + 4H2O → 8KI + 4CO2 + Fe(OH)2 + • Sodium and potassium ions balance the negative
                  2Fe(OH)3 charges associated with organic molecules present in
cells.
• Iodine dissolves in potassium iodide which is unstable
and gives up extra iodine easily. • The ion transport activity is known as sodium pump.
• With conc. H2SO4 it gives violet-coloured vapours of • Sodium ions can be pumped out of the cells but not
I2 due to the oxidation of HI formed initially by conc. potassium ion.
H2SO4. • The energy required for pumping out of the sodium
• Several oxidizing agents like Cl2, Br2, KMnO4, ions and taking of K+ ions or the H+ ions is provided
K2Cr2O7, H2O2, etc. liberate iodine from KI. by the hydrolysis of ATP to ADP.
• With CuSO4 first it gives cupric iodide (CuI2) which • The presence of Na+ and K+ ions inside and outside
decomposes to cuprous iodide (white Cu2I2) and iodine. the cell produce an electrical potential across the cell
• It gives yellow precipitate with lead and silver salts. membrane.
• It forms red precipitate of HgI2 with HgCl2 soluble in • Sodium ions are associated with the movement of glu-
excess of KI due to the formation of complex K2HgI4. cose into the cells.
The alkaline solution of K2HgI4 is known as Nessler’s • The potassium ions are essential for metabolism of
reagent used for detection of ammonia. glucose inside the cell, the synthesis of proteins and
• Tincture of iodine is a mixture of KI, I2 and alcohol. the activation of certain enzymes.

Reactions of Potassium iodide

Reaction Remark
Preparation
1. KOH + HI → KI
2. K2CO3 + HI → KI
3. KOH + I2 → KI + KIO3
4 KIO3 + C → KI
Properties
Reduction reactions
1. KI + H2SO4 → SO2 + I2
Ionic
2. KI + HNO3 → NO2 + I2
3. KI + KMnO4 → Mn2+ + I2
4. KI + K2Cr2O7 → Cr3+ + I2
5. KI + H2O2 → I2
6. KI + CuSO4 → Cu2 I2 + I2
Precipitation Reaction
1. KI + Ag+ → AgI Yellow ppt
2. KI + Pb2+→ PbI2 Yellow ppt
3. KI + Hg2+ → HgI2 Red ppt soluble in excess KI
2KI + HgI2 → K2HgI4

 Objective Questions 92. Salt A + S → B  → white ppt. A is paramagnetic

in nature and contains about 55% K. Thus, A is
91. When potassium superoxide is dissolved in water the (1) K2O
products obtained are (2)  K2O2
(1) KOH and H2O2 (2) KOH, H2O2 and O2 (3) KO2
(3) KOH and O2 (4) KOH, H2O2 and O3 (4)  K2SO4

Chapter_10.indd 16 3/26/2014 3:20:05 PM

 Group IA Alkali Metals  10.17

93. 0.242 g sample of potassium is heated in oxygen. The (3) Alkali metals show the typical characteristics of
result is 0.44 of a crystalline compound. What is the representative elements.
formula of this compound? (4) Alkali metal compounds are colourless and
(1) KO (2)  K2O (3)  KO2 (4)  KO3 ­diamagnetic.

94. KO2 reacts with CO2 to produce 2. Which of the following order is not correct?
(1) K2CO3 + O2 (2)  K2CO3 + CO (1) Thermal stability of carbonates LiCO3 < Na2CO3
(3) K2CO3 (4)  K2O + CO < K2CO3< Rb2CO3.
(2) Lattice energy of fluorides LiF > NaF > KF >
95. Which of the following is not known? RbF > CsF.
(1) K2O (2)  K2O2 (3) The radius of hydrated ion Li+ < Na+ < K+ < Rb+
(3) KO4 (4)  KO3 < Cs+.
96. Na2CO3 can be manufactured by Solvay process but (4) Electrical conductivity of hydrated ions Li+ < Na+
K2CO3 cannot be prepared because < K+ < Rb+ Cs+.
(1) K2CO3 is more soluble 3. The structure of superoxide ion is
(2) K2CO3 is less soluble − −
 . ..   .. .. 
(3) KHCO3 is more soluble than NaHCO3 (1) : O : O : (2)  : O
.. : O
.. :
(4) KHCO3 is less soluble than NaHCO3  .. ..   
−
 .. ..

97. An alloy of Na + K is (3) : O :: . O
.. : (4)  All
 
(1) liquid at room temperature
(2) used in specially designed thermometers 4. Which of the following is arranged in the order of
(3) both 1 and 2 increasing solubility?
(4) none of the above (1) CaCO3, KHCO3, NaHCO3
(2) NaHCO3, KHCO3, CaCO3
98. K2CS3 can be called as potassium
(3) KHCO3, NaHCO3, CaCO3
(1) sulphocyanide (2)  thiocarbide (4) CaCO3, NaHCO3, KHCO3
(3) thiocarbonate (4)  thiocyanate
5. Lithium has highest ionization energy but it is the
99. An inorganic compound first melts, then resolidifies strongest reducing agent in solution because of its
and then liberates a gas. It may be
(1) greater sublimation
(1) KClO3 (2)  KMnO4 (2) greater heat of atomization
(3)  Al2O3 (4)  MnO2 (3) covalent nature
100. Aqueous solution of KOH is called (4) greater heat of hydration
(1) Potash lye (2)  Caustic potash 6. Strong solutions of caustic soda are not stored in
(3) Pearl ash (4)  Salt cake glass vessels because
(1) the solution absorbs CO2 from air
(2) caustic soda is reactive towards silica of the glass
Answers (3) concentration of caustic soda changes due to
evaporation
(91) 2 (92) 3 (93) 3 (94) 1   (95) 3 (4) all are correct
(96) 3 (97) 3 (98) 3 (99) 1 (100) 1
7. In the extraction of sodium metal by the electrolysis
of fused NaCl, it is mixed with CaCl2 or a mixture of
KCl and KF to decrease the melting point of NaCl.
Decrease in the melting point of NaCl is advanta-
geous because of the following except
  Practice Exercise
(1) the cost of fuel can be decreased
1. Which of the following statements is wrong? (2) burning of sodium can be prevented due to low
(1) The alkali metal which do not contain an octet in vapour pressure at low temperature
the penultimate shell is Li. (3) solubility of sodium in fused electrolyte can be
(2) The alkali metal in which f-orbital is filled with decreased
electrons is caesium. (4) formation of sodium is fast at low temperature

Chapter_10.indd 17 3/26/2014 3:20:07 PM

 10.18  Objective Chemistry - Vol. I

8. Which of the following is wrong? 17. Which of the following substances react differently
(1) Aqueous NaOH is soda lye. with NaOH?
(2) The catalyst used in the manufacture of rubber is (1) AlCl3 (2)  ZnCl2
sodium. (3) SnCl2 (4)  FeCl3
(3) The reactivity of alkali metal sodium with water
18. The species X and Y are obtained by the reaction
is made use of drying benzene or ether.
of F2 with cold and dilute solution of NaOH and X
(4) To mercirize the cotton the reagent used is Na3CO3.
and Z are formed with hot concentrated solution of
9. The difference in the oxidation numbers of the prod- NaOH. The formula of Y and Z respectively are
ucts formed when chlorine reacts with hot concen- (1) NaF and NaOF (2)  NaF and O2
trated sodium hydroxide is (3) NaF and OF2 (4)  OF2 and O2
(1) 2 (2)  3 (3)  4 (4)  6
19. Which of the following will give metal oxide as a
10. Heat is liberated when sodium hydroxide dissolves in ­precipitate when sodium hydroxide is added?
water. This is due to (1) FeCl3 (2)  ZnCl2
(1) Hydrolysis (2)  Hydration (3) AlCl3 (4)  AgNO3
(3) Ionization (4)  Dissociation
20. Ammonia–soda process is preferred over Le Blanc
11. The products formed when sodium hydroxide is process because
­reduced with carbon are (1) Na2CO3 produced is cheap.
(1) Na, O2 and H2 (2)  Na, Na2CO3 and H2 (2) Na2CO3 produced is pure.
(3) Na, CO2 and H2 (4)  Na2CO3 and H2 (3) The raw materials CO2 and NH3 can be recycled.
(4) All are correct.
12. Aluminium bronze is an alloy of copper and alumin-
ium. The copper from aluminium bronze can be ob- 21. Baking soda can be manufactured by
tained by dissolving it in (1) passing CO2 into an aqueous solution of Na2CO3
(1) dil. H2SO4 (2)  NH4OH (2) passing CO2 into brine solution saturated with
(3)  NaOH (4) dil. HNO3 ammonia
(3) adding slaked lime to washing soda
13. The inflammable gas that can act as Lewis base is
(4) adding lime stone to soda lye
liberated when NaOH reacts with
(1) Al (2)  Si (3)  C (4)  P 22. Which of the following is not correct?
(1) Caustic soda is deliquescent.
14. When sulphur is boiled with NaOH, the product that
(2) Washing soda is hygroscopic.
is not formed is
(3) Brine is concentrated solution of NaCl.
(1) Na2SO3 (2)  Na2S (4) Aqueous solutions of Na2CO3 and NaHCO3 are
(3) Na2S5 (4)  Na2S2O3 basic.
15. In the reaction between hot concentrated sodium 23. When Na2CO3 reacts with sulphur and sulphur
­hydroxide and chlorine which of the following ­dioxide, the compound formed is
­observation is not correct?
(1) Na2S (2)  Na2SO3
(1) Chlorine undergoes both oxidation and ­reduction. (3) Na2S2O3 (4)  All

(2) Chlorine undergoes disproportionation.
(3) The products formed are NaCl and NaClO3 24. False statement about Na2CO3 ⋅ 10 H2O is
(4) The difference in the oxidation numbers of (1) It contains dative, covalent and ionic bonds.
­products is 5. (2) It removes only permanent hardness of water.
(3) It does not give pink colour with ­phenolphthalein.
16. A pungent gas that can react with Nessler’s reagent
(4) All are false.
is evolved when a salt is treated with which of the
­following? 25. Which of the following statements is false?
(1) Conc. H2SO4 (1) Compounds of alkali metals are diamagnetic,
(2)  dil. HCl since all electrons are paired.
(3) Conc. NaOH (2) Sodium chromate is yellow coloured due to the
(4)  All presence of unpaired electrons.

Chapter_10.indd 18 3/26/2014 3:20:07 PM

 Group IA Alkali Metals  10.19

(3) KO2 is yellow due to the presence of an unpaired 33. A deliquescent crystalline hydroxide X reacts with a
electron. nitrate Y to form another hydroxide that decomposes
(4) Potassium permanganate is pink in colour due to to give an insoluble brown layer of its oxide. X is a
anion. powerful cautery and breaks down the proteins of the
skin, flesh to a pasty mass. X and Y are
26. When milk of lime is added to an aqueous solution
of A, CaCO3 is precipitated along with an aqueous (1) NaOH and AgNO3
solution of B. When CO2 is passed into B again A is (2) NaOH and Al(NO3)2
formed. A and B are (3) NaOH and Zn(NO3)2
(4) Ca(OH)2 and Hg(NO3)2
(1) NaOH and NaHCO3
(2)  NaHCO3 and Na2CO3 34. Which of the following compounds are consumed dur-
(3) NaOH and Na2CO3 ing the preparation of Na2CO3 by Solvay’s ­process?
(4)  Na2CO3 and NaOH (1) NH3 + CaCO3 + NaCl
27. The pair of substances that react differently from one (2) NH4Cl + CaO + NaCl
another with NaOH is (3) CaCO3 + NaCl
(4) NaCl + NH4HCO3
(1) FeSO4, FeCl3 (2)  ZnSO4, SnCl2
(2) AgNO3, Hg(NO3)2 (4)  F2 and Cl2 35. Sodium hydroxide is called caustic soda because
28. The pair of substances that react differently with one (1) It produces burning sensation when it falls on the
another with NaOH is skin.
(1) SO2, SiO2 (2)  C, Si (2) It decomposes the proteins of the muscles when
(3) Al, Zn (4)  Cl2, Br2 it falls on the skin.
(3) It produces blisters when it falls on the skin.
29. An aqueous solution of FeCl3 and AlCl3 is heated (4) It acts as a poison when it falls on the skin.
with excess of NaOH and filtered. The materials ob-
tained are 36. Alkalis cannot be stored in glass bottles or porcelain
ware because
(1) a colourless filtrate and green residue
(2)  a colourless filtrate and reddish brown residue (1) They react with glass or porcelain forming ­silicates.
(3) brownish yellow filtrate and white residue (2) They are decomposed by glass or porcelain.
(4) a green filtrate and brown residue (3) They are leaked out of these vessels.
(4) Porcelain or glass vessels are costlier.
30. Metal A reduces silica converting itself into B. B ab-
sorbs moisture from C. When C is heated with am- 37. In the manufacture of ultramarine the substance used is
monium salts, it liberates ammonia. Then A, B and C (1) sodium hydroxide (2)  sodium carbonate
are respectively (3) Epsom salt (4)  Gluber salt
(1) Na, Na2O, NaOH 38. Among the following, the false statement is
(2) Na, Na2O2, NaOH
(1) Peroxide and superoxide ions are larger than
(3) Al, Al2O3, Al(OH)3
­oxide ion.
(4) Be, BeO, Be(OH)2
(2) The stability of peroxide and super oxides in-
31. An alkali metal (A) reacts with CO2, it forms (B). creases as the metal ion becomes larger.
When milk of lime is added to the aqueous solution (3) The bond order of superoxide ion is 3.5.
of (B), (C) is formed. On heating C with white phos- (4) Many peroxides are coloured due to the presence
phorous a gas is liberated along with the formation of of superoxides.
D. In these reactions, A and D are
39. In the Solvay process
(1) Na, neutral salt (2)  K, acidic salt
(3) Rb, basic salt (4)  Li, mixed salt (1) an ammonical brine solution is carbonated with
CO2 forming NaHCO3 which on decomposition
32. The impurities that may be present in caustic soda at 150°C gives Na2CO3.
produced by porous diaphragm method are (2) a sodium amalgam reacts with water to produce
(1) Na2CO3 (2)  NaHCO3 NaOH which gives Na2CO3 upon reacting with
(3) NaCl, NaClO3 (4)  Na2SO4 CO2.

Chapter_10.indd 19 3/26/2014 3:20:08 PM

 10.20  Objective Chemistry - Vol. I

(3) a brine solution is made to react with BaCO3 to C in water. When another substance D reacts with
produce Na2CO3. this solution of C, it also produced the same gas B
(4) Brine is carbonated with CO2 forming NaHCO3 on warming, but D can produce B on reaction with
which on decomposition at 150°C produces dilute sulphuric acid at room temperature A imparts
Na2CO3. golden yellow colour to Bunsen flame. A, B, C and D
respectively are
40. The atomic radii of alkali metals (M) lie in the order
Li < Na < K < Rb, but radii of M+ ions in aqueous (1) Na, H2, NaOH and Zn
solution lie in the reverse order Li+ > Ma+ > K+ > Rb+. (2) K, H2, KOH and Al
What is the reason for the reverse order (on going (3) Ca, H2, Ca(OH)2 and Sn
from Li to Rb)? (4) CaC2, C2H2, Ca(OH)2 and Fe
(1) Gradual increase in ionization energy 46. One mole of fluorine is reacted with two moles of
(2) Increasing weakness of metallic bond hot and concentrated KOH. The products formed are
(3) Increasing electropositive character KF, H2O and O2. The molar ratio of KF, H2O and O2
(4) Decreasing degree of hydration respectively is
41. A solution of sodium in liquid ammonia serves as a (1) 1:1:2 (2)  2:1:0.5
good reducing agent due to the reaction (3) 1:2:1 (4)  2:1:2
(1) 2Na + 2NH3 → 2NaNH2 + H2 47. Sodium metal reacts with Al2O3 at high temperature
(2) NaNH2 + N2O → NaN3 + H2O to give a sodium compound X. X reacts with carbon
(3) 2Na + H2O → 2NaOH + H2 dioxide in water to form Y. Y is ...........
(4) Solvated electron (1) Na2O2 (2)  Na2O
42. Which of the following statements is correct? (3) Na2CO3 (4)  NaAlO2
(1) On descending the group from Li to Cs the reac- 48. The addition of Na2CO3 to the aqueous solution of an
tion with water increases in violence. oxide produces CO2. This indicates that
(2) Alkali metal hydroxides are the strongest bases
(1) Oxide is basic
known.
(2) Oxide is amphoteric
(3) The peroxides and superoxides of these metals
(3) Oxide is that of a metal
are oxidizing agents and react with water and
(4) Oxide is that of a nonmetal
acid giving H2O2 and O2.
(4) All are correct. 49. Consider the following reactions
43. Which of the following statements is correct? (1) 2Na + 2H2O → 2NaOH + H2
(2) 2NaOH + Cl2 → NaCl + NaOCl + H2O
(1) Superoxide of an alkali metal contains a three
(3) 4OH– → O2 + 2H2O + 4e–
electron bond due to which it is paramagnetic
(4) 2Cl– → Cl2 + 2e–
and coloured.
In the diaphragm cell used for the electrolysis of
(2) The peroxides and superoxides are oxidizing
brine, the reactions that occur would include
agents and react with water and acid giving H2O2
and O2. (1) AB and D
(3) Peroxides and superoxides are used in supplying (2)  BC and D
oxygen by absorbing carbon dioxide in subma- (3) A, C and D
rines and at high altitudes. (4)  A, B and C
(4) All are correct. 50. In the electrolysis of NaCl when Pt electrode is taken
44. Sodium hydroxide solution reacts with phosphorous to then H2 is liberated at the cathode while with Hg cath-
give phosphine. To bring about this reaction we need ode it forms sodium amalgam. The reason for this is
(1) White phosphorous and dil. NaOH (1) Hg is more inert than Pt.
(2) White phosphorous and conc. NaOH (2) More voltage is required to reduce H+ at Hg than
(3) Red phosphorous and dil. NaOH at Pt.
(4) Red phosphorous and conc. NaOH (3) Na dissolves in Hg, thus decreasing the discharge
potential of Na+ than H–.
45. When a substance A reacts with water it produces (4) Concentration of H+ ions is larger when Pt elec-
a combustible gas B and a solution of a substance trode is used.

Chapter_10.indd 20 3/26/2014 3:20:08 PM

 Group IA Alkali Metals  10.21

51. Which of the following will precipitate as hydroxide 57. X reacts with aqueous NaOH to form Y and H2.
instead of metal carbonate with liberation of carbon Aqueous solution of Y is heated to 323–333 K and
dioxide? on passing CO2 into it, Na2CO3 and Z were formed.
(1) AlCl3 (2)  CuSO4 When Z is heated to 1200°C, Al2O3 is formed. X, Y
(3)  BaCl2 (4)  MgSO4 and Z respectively are
(1) Al, AlCl3, NaAlO2
52. Cs+ ion imparts violet colour to Bunsen flame. This is
due to the fact that emitted radiations are of (2) Zn, Na2ZnO2Al(OH)3
(3) Al, (OH)3, AlCl3
(1) high energy
(2) lower energy frequencies (4) Al, NaAlO2, Al(OH)3
(3) longer wavelengths 58. The conductivity decreases from Li+ salts to Cs+ salts
(4) zero wave number in an aqueous solution because of
53. When excess of potassium superoxide is placed in a (1) increase in the number of water molecules
container containing CO2, then ­surrounding the ion in their primary shell for
(1) the pressure of the container decreases Li+ to Cs+
(2) the pressure of the container increases (2) decrease in the number of water molecules
(3) the pressure of the container remains constant ­surrounding the ion in the secondary layer from
(4) the pressure of the container first increases and Li+ to Cs+
then decreases (3) the presence of vacant d-orbitals in the valence
shells of K+, Rb+ and Cs+
54. The standard oxidation potential value of Li is greater
(4) decrease in the number of water molecules
than that of K. But K is more reactive towards water
­surrounding the ion in their primary shell from
than Li. This is because
Li+ to Cs+
(1) the m.pt. of K is less than Li, and the heat of reac-
tion is sufficient to make it melt. So, the molten 59. Solubility of NaOH in water
metal spreads out and exposes a larger surface to (1) increases with increase in temperature
water. (2) decreases with increase in temperature
(2) the m.pt. of Li is less than K and the heat of reac-
(3) is not affected by a change in temperature
tion is sufficient to make it melt. So, the molten
(4) first increases and then decreases with temperature
metal spreads out and exposes a larger surface to
the water. 60. Which of the following is true?
(3) The E value is more negative and ∆G is more
(1) Li+ being smallest in size and thus moves faster
positive of Li+ + e– → Li
and hence a good conductor of electricity in aque-
(4) The E value is more positive and ∆G is more
ous solutions among the elements of IA group.
negative for K+ + e– → K
(2) LiClO4 is more soluble than CsClO4.
55. KO2 + CO2 + H2O excess CO2
→ A + O2↑. Correct (3) CH3NH2 is a better Lewis base than CH3CN.
statement about A is (4) Both 2 and 3 are correct.
(1) The anion present in crystalline A exists as a di-
mer due to hydrogen bonds. 61. When hydrogen peroxide and alcohol are added to a
(2) A can be isolated in a solid state. concentrated solution of lithium hydroxide, a white
(3) A is generally called washing soda. precipitate of ............... is formed.
(4) A gives a thermally unstable carbonate on heating. (1) Li2O (2)  Li2O2
(3) LiH (4)  LiAlH4
56. S1: Alkali metals are generally extracted by electroly-
sis of their aqueous salts. 62. Which of the following statements is true?
S2: The electropositive character of alkali metals de- (1) Alkali metal hydride in an aqueous medium is
creases with increasing atomic number. alkaline.
S3: Lithium is the hardest element in alkali metals. (2) BeH2 has more reducing tendency than MgH2.
S4: Potassium carbonate is prepared by Solvay’s (3) The melting points of LiCl, LiI, KF, CsCl and
­process. NaCl can be LiI < LiCl < CsCl < NaCl < KF.
(1) TTFF (2)  TFTF (3)  FTFT (4)  FFTF (4) All the above.

Chapter_10.indd 21 3/26/2014 3:20:09 PM

 10.22  Objective Chemistry - Vol. I

63. When silicon or boron is dissolved in caustic soda, (4) It has an higher m.pt. than both Na2CO3 and
hydrogen gas is liberated. It is K2CO3 and converts the metal salts to carbonates
(1) an intermolecular redox reaction which decompose to metal oxides.
(2) an intramolecular redox reaction
(3) disproportionation reaction 69. A + H2O → NaOH; A + O2 400° C
→ B H 2O
→
at 25° C
(4) not a redox reaction NaOH + O2
Which of the following statements is false regarding
64. Potassium is produced by the electrolysis of fused B?
KCl in a cell similar to one used for Na but the cell (1) B turns green chromic salt solution to yellow.
must be operated (2) B can be used to purify air in submarines.
(1) at a higher temperature since KCl has a lower (3) B can be used as an oxidizing agent.
m.pt. than NaCl. (4) When crystallized from a solution, B is obtained
(2) at a lower temperature since KCl has a lower as anhydrous compounds.
m.pt. than NaCl.
(3) at higher temperature since potassium is more 70. When sodium hydroxide is added dropwise to a mix-
electropositive with a low m.pt. ture of two compounds, a white precipitate appears
(4) at lower temperature since potassium is more but on adding excess of sodium hydroxide the amount
electropositive with an high m.pt. of precipitate decreases. The possible compounds are
(1) ZnSO4 and FeSO4
65. When a concentrated solution of ammonia is saturat- (2) CuSO4 and Al2(SO4)3

ed with sodium chloride in the presence of pieces of (3) AlCl3 and MnCl2
dry ice, a water cloud forms. This is due to (4) ZnSO4 and SnCl2

(1) the formation of solid Na2CO3
(2) the formation of solid NaHCO3 71. Li+ and H– ions have isoelectronic structures. Which
(3) the formation of solid (NH4)2CO3 of the following statements concerning these two
(4) the formation of solid NH4HCO3 ions is true?
(1) Li+ is a strong reducing agent than H–.
66. In the reaction LiH + AlH3→ LiAlH4, AlH3 and LiH
(2) H– is larger than Li+.
acts as (3) More energy is needed in removing electrons
(1) Lewis acid and Lewis base from H– than from Li+.
(2) Lewis acid and Lewis acid (4) The chemical properties of the two ions are
(3) Bronsted base and Bronsted acid identical since they have the same electronic
(4) Arrhenius acid and Arrhenius base configuration.
67. The process that causes nerve signals in animals is
(1) Electrical potential gradient due to transfer of K+ Answers
ions.
(2) Electrical potential gradient due to transfer of   (1) 2   (2) 3   (3) 4   (4) 4   (5) 4
Na+ ions in (Na+ - K+) pumps.   (6) 2   (7) 4   (8) 4   (9) 4 (10) 2
(3) Electrical potential gradient set up due to transfer (11) 2 (12) 3 (13) 4 (14) 1 (15) 4
of Ca2+ ions. (16) 3 (17) 4 (18) 4 (19) 4 (20) 4
(4) No nerve signals exist in animals. (21) 2 (22) 2 (23) 3 (24) 4 (25) 2
68. A mixture of Na2CO3 and K2CO3 is used as a fusion (26) 4 (27) 4 (28) 2 (29) 2 (30) 1
mixture because (31) 1 (32) 3 (33) 1 (34) 3 (35) 2
(1) It has a lower m.pt. than Na2CO3 and converts (36) 1 (37) 2 (38) 3 (39) 1 (40) 4
metal salts to carbonates which decompose to (41) 4 (42) 4 (43) 4 (44) 2 (45) 1
metal oxides. (46) 2 (47) 3 (48) 4 (49) 3 (50) 3
(2) It has an higher m.pt. than K2CO3 and converts (51) 1 (52) 1 (53) 2 (54) 1 (55) 1
metal salts to carbonates which decompose to (56) 4 (57) 4 (58) 2 (59) 2 (60) 4
metal oxides. (61) 1 (62) 4 (63) 1 (64) 2 (65) 2
(3) It has a lower m.pt. than both Na2CO3 and K2CO3 (66) 1 (67) 2 (68) 3 (69) 4 (70) 3
and converts the metal salts to carbonates which (71) 2
decompose to metal oxides.

Chapter_10.indd 22 3/26/2014 3:20:10 PM

 Group IA Alkali Metals  10.23

Statement-II: The metallic bond in alkali metals is

 Statement-Type Questions very weak.
In each of the following questions, a statement-I is given 11. Statement-I: Among the hydroxides of alkali ­metals,
followed by corresponding statement-II just below. Mark LiOH is the weak base.
the correct answer as indicated.
Statement-II: Among alkali metals, lithium has the
1. If both statement-I and statement-II are true and
highest ionization energy.
­reason is the correct explanation of assertion.
2. If both statement-I and statement-II are true but ­reason 12. Statement-I: Sodium ions are discharged in prefer-
is not the correct explanation of assertion. ence to hydrogen at mercury cathode.
3. If statement-I is true but statement-II is false. Statement-II: The nature of the cathode can affect
4. It statement-I is false but statement-II is true. the order of discharge of cations.
1. Statement-I: Sodium is more reactive than ­potassium.
13. Statement-I: The conductivity order of ions is Cs+ >
Statement-II: IP1 of potassium is lesser than sodium Rb+ > K+ > Na+ > Ba2+ > Li+ in an aqueous solution.
because of less effective nuclear charge.
Statement-II: Lithium being small is heavily hydrat-
2. Statement-I: K2CO3 cannot be prepared by Solvay’s ed and hence move slowly and Cs+ the least hydrated
process. moves faster.
Statement-II: KHCO3 is highly soluble. 14. Statement-I: The alkali metals are chemically very
3. Statement-I: Lithium halides are covalent in nature. reactive.
Statement-II: Li+ has more polarizing power towards Statement-II: They have a strong tendency to lose
anion. their single-valence electron and become cations
with a single positive charge.
4. Statement-I: The softness of IA group elements in-
creases down the group with increasing atomic ­number. 15. Statement-I: Alkali metals may cause a fire or even
Statement-II: The metallic bonding increases with be explosive.
increase in atomic size. Statement-II: The reactions of alkali metals with
­water and oxygen produce much heat.
5. Statement-I: Superoxides of alkali metals are col-
oured and paramagnetic. 16. Statement-I: IA group elements are highly electro-
Statement-II: Superoxides contain a three-electron positive.
bond which makes it paramagnetic and coloured. Statement-II: Valence electron present in s-orbital is
6. Statement-I: M.pt. and B.pt. of alkali metals increas- loosely held.
es from Li to Cs. 17. Statement-I: Superoxides of alkali metals are para-
Statement-II: The energy, binding the atoms, in crys- magnetic.
tal lattice decreases from Li to Cs. Statement-II: Superoxides of alkali metals contain
7. Statement-I: Alkali metals lose metallic lustre up on an unpaired electron.
exposure to air.
18. Statement-I: Sodium reacts with oxygen to form
Statement-II: Alkali metals are easily reduced to Na2O2, whereas potassium reacts with oxygen to
form a film of their oxide. form KO2.
8. Statement-I: Alkali metals are kept in kerosene or Statement-II: Potassium is more reactive than KO2.
paraffin.
19. Statement-I: Alkali metals impart colour to a flame.
Statement-II: In alkali metals, the metallic bond
Statement-II: The ionization energies are low.
strength decreases from top to bottom.
9. Statement-I: The hydroxides of aluminium and iron 20. Statement-I: Li+ ion has the least mobility in ­aqueous
are insoluble in water. However, NaOH is used to solution among alkali metal ions.
separate one from the other. Statement-II: Lithium ion has highest ionization
­energy in the group.
Statement-II: Al(OH)3 gets dissolved in NaOH and
forms soluble NaAlO2. 21. Statement-I: Sodium is not produced commercially
10. Statement-I: Alkali metals are soft metals and can be by the electrolysis of brine.
cut easily with the help of a knife. Statement-II: Sodium reacts violently with water.

Chapter_10.indd 23 3/26/2014 3:20:10 PM

 10.24  Objective Chemistry - Vol. I

22. Statement-I: Among alkali metals, lithium is the Correct matching is

strongest reducing agent.
S. No. A B C D
Statement-II: Li+ ions are heavily hydrated in water
and large amount of hydration energy helps in the re- 1. ii iv i v
lease of electrons from lithium atoms. 2. ii iv i iii
3. iii ii iv v
23. Statement-I: Li(+aq ) has large ionic radius than that of 4. I iv v iii
Na+(aq).
Statement-II: Li+(aq) is relatively more extensively
hydrated as compared with Na+(aq). 2. Match the compounds given in X with their uses in Y.
24. Statement-I: In liquid ammonia, Na and K are at-
tracted towards cathode. X Y
Statement-II: Na and K are respectively converted to (A)  Na2CO3    (i)  Glass
Na+ and K+. (B)  Na2SO3  (ii)  Bleach
(C)  NaOH (iii)  SO2 absorber
25. Statement-I: The alkali metals form ionic hydrides
(D)  NaOCl  (iv)  Detergent
which contain the hydride ion, H–.
Statement-II: The alkali metals have low electroneg-
ativity, their hydrides conduct electricity when fused Hence, the correct order is
and liberate hydrogen at the anode.
S. No. A B C D
26. Statement-I: Common salt becomes damp after some
1. iv i iii ii
time up on exposed to air.
2. i iii iv ii
Statement-II: Common salt, which is NaCl, is hygro- 3. ii iv i iii
scopic in nature. 4. iii ii iv i

Answers
3. Match the compounds/metal in X with their uses in Y.
  (1) 4   (2) 1   (3) 1   (4) 3   (5) 1
  (6) 4   (7) 3   (8) 2   (9) 1 (10) 1 X Y
(11) 1 (12) 1 (13) 1 (14) 1 (15) 1
(16) 1 (17) 1 (18) 2 (19) 1 (20) 2 (A)  Sodium metal    (i) Breathing apparatus in
(21) 1 (22) 1 (23) 1 (24) 1 (25) 1 submarines
(26) 3 (B)  Potassium stearate  (ii)  Explosive
(C)  Potassium nitrate (iii) Coolant in nuclear
reactors
(D)  Potassium superoxide  (iv)  Soft soap

 Match the Following  Type Questions

Hence, the correct order is
1. Match the following given in List I with those given
in List II. S. No. A B C D
List-I List-II 1. i iii ii iv
(A) Most negative standard   (i)  Na2SO4 ⋅ 10H2O 2. iii iv ii i
potential of an element in 3. ii i iii iv
the periodic table 4. iv ii iii i
(B) Na/liquid NH3 is a blue- (ii)  Li
coloured solution which has
electrical conductivity
Answers
(C) Gluber salt (iii)  Cs2CO3
  (1) 1   (2) 2   (3) 2
(D) Alkali metal carbonate  (iv)  Solvated electron
decomposes on heating
  (v)  Li2CO3

Chapter_10.indd 24 3/26/2014 3:20:11 PM

 11

Chapter
Alkaline Earth Metals

• Be, Mg, Ca, Sr, Ba and Ra belong to Group IIA and • Since the alkaline earth metals atoms possess smaller
s-block of periodic table. size and more nuclear charge, they have more ionization
• These elements are known as alkaline earth m­ etals since energies than the corresponding alkali metals but de-
these are abundant in earth as their oxides, lime (CaO), creases down the group due to increase in atomic size.
strontia (SrO) and baryta (BaO) which are ­alkaline. • The second ionization energies are almost double to
Hence, these elements are called alkaline earth metals. the first ionization energies of alkaline earth metals.
• Radium is the radioactive metal. • Since the hydration energies of M2+ ions are more
than that of I1 and I2 of alkaline earth metals, their
M2+ ions are easily formed. Hence, they do not exhibit
General Characteristics
+1 ­oxidation state.
• The variations in physical properties are not as regular • The hydration energies decrease from Be2+ to Ba2+
as for the alkali metals because the elements of this with increase in size.
group do not crystallize with the same type of metallic
• The M2+ ions of alkaline earth metals are colourless
lattice. Be and Mg have hcp structure, whereas Ca and
and diamagnetic because all the electrons in them are
Sr have ccp structure.
paired.
• At high temperature Ca and Sr, and at room tem-
• The electropositive character of alkaline earth ­metals is
perature Ba have bcc structures (similar to Group IA)
less than the corresponding alkali metals but ­increases
­instead of the expected hcp structure. This is probably
from Be to Ba.
because at high temperature the paired s-electron is
excited to a ”d” orbital instead of p-orbital and hence • Because of more attraction towards water molecules
there is only one s- or p-electron per atom participat- by alkaline earth metal ions, their solid compounds
ing in metallic bonding. are heavily hydrated than those of alkali metals. e.g.,
MgCl2 . 6H2O, CaCl2 . 6H2 O, etc.
• They are all white lustrous silvery white metals, mal-
leable and ductile but less than alkali metals. This is • Ionic mobilities decrease from Be2+ to Ba2+.
because in these elements metallic bonding is stronger • Standard oxidation potentials of these elements
than in Group I A elements since two electrons partici- increases from Be to Ba and hence reduction power
pate in metallic bonding compared to one electron in increases from Be to Ba.
alkali metals. • Except Be and Mg the other alkaline earth metals give
• Alkaline earth metals are harder than alkali metals and flame colouration. For example, Ca gives brick red; Sr
hardness decreases with increase in atomic number. gives crimson red and Ba gives apple green or yellow
• Atomic radii of these elements is less than those of green.
corresponding alkali metals due to increased effective • Be and Mg atoms are smaller and their electrons,
nuclear charge and hence these elements are harder, ­being strongly bound to the nucleus, are not excited
have higher m. pts and higher densities than alkali to higher energy levels. Therefore, they do not give the
metals. Atomic radii increase down the group. flame colour test.

Chapter_11.indd 1 3/26/2014 3:23:17 PM

 11.2  Objective Chemistry - Vol. I

• Alkaline earth metals are less reactive than the 2. Magnesium form Mg2+ and not Mg+ because
­corresponding alkali metals due to small size, high (1) Magnesium carbonate is insoluble in water.
charge and more ionization energies. (2) Generally higher oxidation states are preferred
• The reactivity increases from Be to Ba as their ioniza- by metals.
tion energies decrease with increase in atomic number. (3) Ionic radius of Mg (II) is smaller than Mg (I).
• Since the alkaline earth metals are more reactive they (4) Hydration energy of divalent magnesium ion is
do not occur in native state but occur in the form of higher.
oxycompounds like carbonates, silicates, etc. 3. A chloride dissolves appreciably in cold water. When
• The important minerals of alkaline earth metals are placed on a platinum wire in bunsen flame no dis-
   (I)  Beryllium minerals tinctive colour is noticed. Based on the information
(a)  Beryl 3 BeO . Al2O3 . 6SiO2 (or) provided, which one is a cation?
Be3Al2Si6O8 (1) Mg2+ (2) Ba2+ (3) Pb2+ (4) Ca2+
(b)  Crysoberyl BeOAl2O3 4. A fire work gave bright crimson light. It is probably
(c)  Phenacite 2BeO . SiO2 (or)
(1) Ca2+ (2)  Sr (3) Ba (4) Mg
Be2SiO4
  (II)  Magnesium minerals 5. Which of the following statement is false?
(a)  Magnesite MgCO3 (1) Beryllium and magnesium will not impart colour
(b)  Epsomite MgSO4 . 7H2O to flame.
(c)  Kieserite MgSO4 . H2O (2) Beryllium compounds are mostly covalent.
(d)  Carnalite KCl ⋅ MgCl2 . 6H2O (3) The activity of alkaline earth metals as reducing
(e)  Asbestos 3MgSiO3 ⋅ CaSiO3 agents increases from Be to Ba.
(4) Ionic mobility of alkali metal ions increases in
(III)  Calcium minerals
the order Be2+ < Mg2+ < Ca2+ < Sr2+ < Ba2+.
(a) Lime stone,
marble, chalk, 6. Beryl is
aragonite CaCO3 (1) 3BeO . Al2O3 . 6SiO2
(b)  Dolamite CaCO3 . MgCO3 (2) BeO . Al2O3
(c)  Gypsum CaSO4 . 2H2O (3) 2BeO . SiO2
(d)  Anhydrite CaSO4 (4) BeO
(e)  Fluorspar CaF2
(f)  Phosphorite Ca3(PO4)2 7. The hydration energy of Mg2+ ion is larger than that of
(1) Al3+ (2)  Na+ (3) BeCl2 (4)  Mg3+
 (IV)  Strontium minerals
(a)  Celestite SrSO4 8. The decreasing order of second ionization energy of
(b)  Strontianite SrCO3 K, Ca and Ba is
   (V)  Barium minerals (1) Ca > Ba > K (2)  Ba > K > Ca
(a)  Barytes BaSO4 (3) K > Ca > Ba (4) K > Ba > Ca
(b)  Whitherite BaCO3 9. Elements of II A group having electronic configura-
  (VI)  Radium minerals tion ns2 are called alkaline earth metals because
(a)  Uranium oxide (1) they occur in earth and their oxides are strongly
(b)  Carnotite K2O, U2O3 . (VO4)2 . 3H2O alkaline
(2) their salts form only alkaline solution
(3) they all form divalent cations only
  Objective Questions (4) their oxides are weakly basic
1. Radium is placed at the bottom of alkaline earth 10. The correct order of hydration energy of alkaline
­metals. The element should earth metal is
(1) have the highest atomic volume (1) Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+
(2) possess the minimum density (2) Ba2+ > Be2+ > Ca2+ > Mg2+ > Sr2+
(3) be less easily ionizable (3) Mg2+ > Be2+ > Ba2+ > Ca2+ > Sr2+
(4) be least electropositive (4) Ca2+ > Sr2+ > Be2+ > Mg2+ > Ba2+

Chapter_11.indd 2 3/26/2014 3:23:17 PM

 Alkaline Earth Metals  11.3

11. The first ionization energies of alkaline earth metals 17. Which of the following statements is correct?
are higher than those of alkali metals. This is because (1) Alkali metals are less electropositive than ­alkaline
(1) there is increase in the nuclear charge of the ­alkaline earth metals.
earth metals (2) The alkaline earth metals are denser and harder
(2) there is decrease in the nuclear charge of alkaline than alkali metals.
earth metals (3) The alkali metals are denser and harder than
(3) there is no change in the nuclear charge ­alkaline earth metals.
(4) none of the above (4) The second IP of alkali metals is less than that of
alkaline earth metals.
12. Which of the following is wrong?
(1) Beryl is BeO 18. Halides of alkaline earth metals form hydrates such
(2) Marble is CaCO3 as MgCl2 . 6H2O, CaCl2 . 6H2O, BaCl2 . 2H2O. This
(3) Dolamite is MgCO3 . CaCO3 shows that halides of group 2 elements
(4) Anhydrite is CaSO4 (1) are hygroscopic in nature
(2) acts as dehydrating agents
13. Which of the following is not correct? (3) can absorb moisture from air
(1) Baryta is BaO (4) all of these
(2) Beryl is 3BeO . Al2O3 . 6SiO2
(3) Calcite is SrCO3 19. The group IIA elements of the periodic table
(4) Whitherite is BaCO3   (I)  are called alkaline earth metals
  (II)  are capable of forming coloured ions M2+
14. Group IIA metals are   (III) are capable of forming colourless ions M2+
(1) harder and have high cohesive energies and ­melting
(IV)  form volatile compounds of these
points than group I metals (1) I, II and III are correct
(2) softer and have lower cohesive energies and ­melting (2) I and IV are correct
points than group I metals (3) I, II and IV are correct
(3) softer and have lower cohesive energies and (4) I and III are correct
­higher melting points than group I metals
(4) harder and have higher cohesive energies and
lower melting points than group I metals Answers
15. Which of the following statement is false?   (1) 1   (2) 4   (3) 1   (4) 2   (5) 4
(1) The ionization energy of Be2+ is high and its   (6) 1   (7) 2   (8) 3   (9) 1 (10) 1
compounds are covalent. (11) 1 (12) 1 (13) 3 (14) 1 (15) 4
(2) The polarizing power of small Be2+ is more and (16) 4 (17) 2 (18) 4 (19) 4
hence its compounds are covalent.
(3) The compounds formed by Mg, Ca, Sr and Ba
are predominantly divalent and ionic. Reactivity of Alkaline Earth Metals
(4) The ionization energy of Be2+ is low and its
­compounds are ionic. • The reactivity of alkaline earth metals increases down
the group. Be mainly forms covalent compounds
16. Which of the following statements is false?
but other alkaline earth metals form mainly ionic
(1) Alkaline earth metals are weaker reducing agents compounds.
than alkali metals because of their comparatively
high ionization energies.
• When burnt in air these elements react with both
(2) The reducing nature of alkaline earth metals fol- ­oxygen and nitrogen in air forming oxides and nitrides.
lows the increasing order as Be < Mg < Ca < • Except Be all the other group IIA elements react with
Sr < Ba. water forming hydroxides with the liberation of H2 . Mg
(3) Compounds of IInd group elements are colourless reacts only with boiling water while other ­elements
and diamagnetic due to the absence of unpaired react even in cold condition but slowly.
electrons. • The inertness of Be and Mg towards water is ascribed
(4) Alkaline earth metals have low electrical and to the formation of a protective thin layer of hydroxide
thermal conductivities than alkali metals. on the surface of the metal.

Chapter_11.indd 3 3/26/2014 3:23:18 PM

 11.4  Objective Chemistry - Vol. I

• These elements readily displace hydrogen from • These elements have less tendency to form ­complexes
p­ rotonic acids forming corresponding salts. but have more tendency to form complexes than ­alkali
• Conc. HNO3 render Be passive due to the formation of metals. In these complexes Be exhibit a ­maximum
a thin oxide film on the surface of the metal. coordination number 4. So Be salts cannot have
more than 4 water molecules of crystallization. Mg
• Only Be react with alkalies forming beryllates with
can exhibit a coordination number 6 by utilizing the
liberation of H2, but other group IIA elements do not
­d-orbitals in its valence shell.
react with bases.
• Like alkali metals, Ca, Sr and Ba dissolve in liquid
• Except Be all the other group IIA elements ­directly
ammonia to give blue-black solutions.
combine with H2 to form hydrides of the type
MH2 . MgH2 has some covalent character but the other • Unlike the solutions of alkali metals in liquid ­ammonia,
hydrides are ionic. evaporation of the solutions of Group II A metals in
liquid ammonia solution gives hexaammoniates which
• When heated with carbon these elements form ionic
gradually decompose to the corresponding amides.
carbides. Be form methanide Be2C, while other
The tendency to form ammoniates decreases down the
­elements form acetylides (MC2).
group.
• On burning in nitrogen these elements form nitrides
(M3N2). The ease of formation of nitrides decreases
down the group. These nitrides react with water liber- Principles of
ating ammonia. Extraction
• All the Group IIA elements except radium form oxides • Similar to alkali metals, alkaline earth metals cannot
with oxygen. Be and Mg form only monoxides. Ca, Sr be prepared by the electrolytic reduction of their aque-
and Ba forms peroxides also in excess of oxygen. ous salt solution.
• All the Group IIA elements react with S, Se, and Te • Alkaline earth metals are prepared by electrolysis of
forming sulphides, selenides and tellurides. their fused anhydrous salts containing alkali metal
• All the Group IIA elements react with halogens form- salts to lower the m.pt and to increase the conductivity
ing halides of the type MX2. of the electrolytic mixture.
Reactivity of Alkaline Earth Metals

Reaction Remark
  1. Action of air. Exposed to air When alkaline earth metals are exposed to air they tarnish due to the formation of
M + O2  → MO basic metal carbonates.
MO + H2O  → M(OH)2
M(OH)2 + CO2  → MCO3
Burning in air
M + O2  → MO When burned in air they react with both nitrogen and oxygen in air.
M + N2  → M3N2
  2. M + H2O  → M(OH)2 + H2 Be do not react with steam, Mg react with hot water and others with cold water.
  3. M + 2HCl  → MCl2 + H2 All metals react with acids. Be becomes passive with conc. HNO3.
  4. Be + NaOH  → Na2[Be(OH)4] + H2 Only Be reacts with bases because it is amphoteric.
  5. M + H2  → MH2 Be and Mg forms polymeric covalent hydrides Ca, Sr and Ba form ionic hydrides.
  6. Be + C  → Be2C Be forms methanide; others form acetylide.
M + C  → MC2
  7. M + N2  → M3N2 All metals form nitrides and phosphides.
M + P4  → M3P2
  8. M + O2  → MO Normal oxides are formed by all metals.
M + O2  → MO2 Ca, Sr and Ba form peroxides with excess oxygen.
M + X  → MX X = S, Se, Te
  9. M + X2  → MX2 X = F, Cl, Br, I
10. 2M + NH3  → M(NH2)2 + H2 All metals form amides at high temperature. Ca, Sr and Ba dissolve in liquid NH3
forming a blue-coloured solution.

Chapter_11.indd 4 3/26/2014 3:23:20 PM

 Alkaline Earth Metals  11.5

29. Alkaline earth metals form carbides of the type MC2.

  Objective Questions But MgC2 on heating converts into X, which on
­hydrolysis give
20. When bright shining magnesium is exposed to wet air
it becomes dull because (1) Methane (2) Acetylene
(3) Propyne (4) Ethane
(1) of the formation of MgO or basic carbonate of
magnesium 30. Which is most stable among the following?
(2) of the formation of Mg3N2 (1) [Be(H2O)4]2+ (2) [Mg(H2O)4]2+
(3) of the formation of Mg(NO3) 
(3) [Ca(H2O)4] 2+
(4) [Sr(H2O)4]2+
(4) the moisture forms as a layer
31. The hydration energies of Group 2 ions are four to
21. Which of the following oxides on heating with mag- five times greater than that of the group 1 ions. This
nesium, instead of reduced to element forms different is due to their
products? (1) smaller size and increased nuclear charge
(1) B2O3 (2) CO2 (3) K2O (4) NO (2) greater size and decreased nuclear charge
22. The value of X is maximum for (3) smaller size and decreased nuclear charge
(4) greater size and increased nuclear charge
(1) Mg SO4 . x H2O
(2) CaSO4 . x H2O 32. Which of the following statements is wrong?
(3) BaSO4 . x H2O (1) Elements of Group 2 are good conductors of
(4) all have the same value of x. electricity and heat.
23. A metal on heating in nitrogen gas gives Y. Y on (2) Compounds of Group 2 elements are ­diamagnetic
treating with H2O gives a colourless gas which when in nature.
passed through CuSO4 solution gives blue colour. Y is (3) The salts of Group 2 elements are more heavily
hydrated than those of elements of group 1.
(1) Mg(NO3)2 (2) Mg3N2
(4) Element of Group 2 are more electropositive than
(3) NH3 (4) MgO
Group 1 elements.
24. Which of the following statements is false?
(1) Beryllium forms covalent compounds due to Answers
small size and high charge of the Be2+ ion.
(2) The maximum coordination number of beryllium (20) 1 (21) 4 (22) 1 (23) 2 (24) 2
is six. (25) 3 (26) 2 (27) 1 (28) 4 (29) 3
(3) Beryllium salts are extensively hydrolyzed. (30) 1 (31) 1 (32) 4
(4) Beryllium can form complexes due to its small size.
25. Identity the false statement.
(1) Beryllium liberates H2 to form HCl or H2SO4.
(2) Beryllium is rendered passive on treatment with Compounds of Alkaline
conc. HNO3. Earth METALS
(3) Magnesium is lighter than calcium. Hydrides
(4) The number of molecules of water of crystalli-
zation decreases with the increase in size of the • The reactivity of alkaline earth metals towards hydro-
metal ions. gen increases down the group.
26. X and Y are two metals. When burnt in air X forms • Expect BeH2, hydrides of other Group II A elements
only oxide while Y forms oxide and nitride also. The can be prepared by heating the metal with hydrogen.
metal X and Y may be • BeH2 and MgH2 can be prepared by the action of
(1) Ca and Mg (2) Na and Mg LiAlH4 on their halides.
(3) Li and Na (4) Na and K • BeH2 is covalent while MgH2 is partially ionic. CaH2,
27. Metal M + air  → A 
A
→ B → white
H2 O HCl
SrH2 and BaH2 are ionic. All these hydrides react with
fumes; Metal M can be water liberating H2.
(1) Li, Mg or Al (2) Li, Al or K • BeH2 and MgH2 are polymeric. (BeH2)n contain 3C-2e
(3) Na, K, or Mg (4) Li, Na or K hydrogen bridge bonds.

Chapter_11.indd 5 3/26/2014 3:23:21 PM

 11.6  Objective Chemistry - Vol. I

Nitrides • Solubility of these hydroxides in water increases down

the group.
• All the elements of Group II A burn in nitrogen
f­ orming nitrides of M3N2. The ease of formation • Be(OH)2 dissolves only in bases containing excess of
­decreases down the group. OH– ions.
• Barium amide on heating decomposes to give Ba3N2. • Basic character of these hydroxides increases down
the group.
• All these nitrides are stable up to 1000° C. Addition of
water causes hydrolysis liberating ammonia. • Mg(OH)2 is weakly basic and used as an antacid in
medicines.
• These nitrides on heating with hydrogen gives metal
hydride and ammonia and decomposed by CO or CO2 • Hydroxides of Group II elements are less basic than
to metal oxide and nitrogen. those of Group I elements because of less electroposi-
tive character.
Oxides
Halides
• Be forms monoxide only which is predominantly
­covalent. The other Group II elements form ­monoxides • Group II A elements form halides of the type MX2..
which are ionic and have NaCl structure. They can be obtained directly by heating the metals
• Except BeO the oxides of other Group II elements are with halogens or by the action of halogen acid on ei-
usually obtained by thermal decomposition of their ther of the metal or carbonate.
carbonates. BeO is obtained by igniting the metal or • These halides crystallize from solution as hydrated
its compounds in oxygen. salts. Anhydrous CaCl2, SrCl2 and BaCl2 can be
• The oxides of Group II elements are extremely ­stable ­prepared by heating their hydrated salts.
and their free energies of formation are highly negative. • Anhydrous beryllium and magnesium halides cannot
• BeO has wurtzite structure with 4:4 coordination be prepared by heating their hydrated salts, because
­number. The radius ratio values of SrO and BaO pre- the hydrated salts on heating gives metal oxides or
dict a coordination number 8 but they are found to hydroxides.
have 6 coordinates because this has the most favour-
• Anhydrous BeCl2 can be prepared by heating BeO
able lattice energy.
in CCl4.
• BeO is insoluble in water. MgO is not very reactive.
CaO, SrO and BaO react exothermally with water
• Anhydrous beryllium halides are covalent having low
forming hydroxides. m.pts as well as low electrical conductivity in fused
state.
• BeO is amphoteric and react with acids and bases. The
amphoteric character is due to strong polarizing power • Beryllium halides are soluble in organic solvents sug-
of small Be2+ ion with large charge to radius ratio. gesting the covalent character which is due to polar-
izing power of small Be2+ ion on the neighbouring
• The oxides of Group II elements are useful refractory
halide ions.
materials because of their high m. pts, low vapour
pressure, high thermal conductivity, chemical ­inertness • BeCl2 exist as linear monomer above 1200°c but at
and electrical insulating property. low temperature the vapours contain dimers of BeCl2.
• MgO and CaO are used as basic fluxes in metallurgy. In solid state it has polymeric (BeCl2)n structure simi-
CaO is used in the production of calcium carbide. lar to (BeH2)n but in (BeH2)n contain 3C-2e bonds,
whereas (BeCl2)n contains halogen bridges in which
Peroxides halogen atom bonded to Be atom with covalent bond.
Be atom is involved in sp hybridisation in monomer,
• The tendency to form peroxides and their stability in- sp2 hybridisation in dimer and sp3 hybridisation in
creases as the metal ion becomes bigger. Be do not polymer and coordination number of Be changes from
form peroxide. 2 to 3 to 4, respectively.
• These peroxides react with water liberating H2O2. • BeF2 and BeCl2 form 4 coordinate complexes like
[BeF4]2– and [BeCl4]2–.
Hydroxides • Fluoride and chloride of magnesium are ionic but
• Hydroxides are formed by the reaction of the oxides of its bromide and iodides have significant covalent
alkaline earth metal with water. ­character and are soluble in organic solvents.

Chapter_11.indd 6 3/26/2014 3:23:21 PM

 Alkaline Earth Metals  11.7

• The halides of alkaline earth metals are hygroscopic. (3) greater hydration energy of Be2+ ion as compared
Due to the strong affinity for water anhydrous CaCl2 is to its lattice energy
used as a dehydrating agent. (4) lesser hydration energy of Be2+ ion as compared
• Ionic character of halides of alkaline earth metals is to its lattice energy
in the order BeX2 < MgX2 < CaX2 < SrX2 < BaX2 and 40. Which among the following statements is correct?
MI2 < MBr2 < MCl2 < MF2. (1) In the solid state BeCl2 has a polymeric chain
• Order of solubility in water structure and contains three centred bonds.
BeF2 > MgF2 > CaF2 < SrF2 < BaF2 (2) In the vapour state BeCl2 exists as a dimer.
BeX2 > MgX2 > CaX2 < SrX2 < BaX2 (3) BeCl2 is a covalent compound soluble in organic
MF2 > MCl2 > MBr2 < MI2 solvents.
(4) All are correct.
41. Which of the following statements is correct?
  Objective Questions
(1) No peroxide of beryllium is known is on date.
32. Which chloride is soluble in ether? (2) The ease with which peroxide is formed ­decreases
(1) BeCl2 (2) CaCl2 (3) CrCl3 (4) BaCl2 with increase in the size of atom.
(3) BaO2 is prepared by passing air over BaO at
33. Which of the following is least ionic chloride?
500°C.
(1) BeCl2 (2) MgCl2 (4) Peroxide of Mg, Ca, Sr and Ba are white ionic
(3) CaCl2 (4) SrCl2 solids containing O2−2 ion.
34. The weakest base among the following 42. Which of the following statements is not correct?
(1) NaOH (2) Ca(OH)2 (1) Alkaline earth metal hydrides are all reducing
(3) KOH (4) Be(OH)2 agents.
35. True peroxide is (2) BeH2 and MgH2 are covalent polymers having
(1) NO2 (2) MnO2 (3) BaO2 (4) SO2 bridge structures.
(3) They react with water and liberate one mole of
36. The correct order regarding the solubility of alkaline H2 for each one mole of metal hydride.
earth metal halide in water is (4) CaH2, SrH2 and BaH2 are ionic hydrides.
(1) BeCl2 > MgCl2 > CaCl2 > SrCl2 > BaCl2
43. In polymeric (BeCl2)n there are
(2) MgCl2 > CaCl2 > BeCl2 > BaCl2 > SrCl2
(3) BaCl2 > MgCl2 > CaCl2 > BeCl2 > SrCl2 (1) three centre and four-electron bonds
(4) CaCl2 > MgCl2 > SrCl2 > BaCl2 > BeCl2 (2) three centre and three-electron bonds
(3) two centre and two-electron bonds
37. The basicity of alkaline earth metal oxides is less than (4) two centre and three-electron bonds
that of alkali metal oxides because
44. The pair of substances that give same products on
(1) Alkali metal oxides are ionic compounds.
­reaction with water is
(2) Alkali metals have high affinity towards oxygen.
(3) Electropositivity of alkali metals is more than (1) Mg and MgO
that of alkaline earth metals. (2) Sr and SrO
(4) Electropositivity of alkali metals is less than that (3) Ca and CaH2
of alkaline earth metals. (4) Be and BeO

38. The correct order of increasing ionic character is 45. Alkaline earth metals form halides of the type MX2.
Which is false about them?
(1) BeCl2 > MgCl2 > CaCl2 > BaCl2
(2) BeCl2 > MgCl2 > BaCl2 > CaCl2 (1) They can be prepared by direct reaction of metal
(3) BeCl2 < MgCl2 < CaCl2 < BaCl2 and halogen.
(4) BeCl2 < CaCl2 < MgCl2 < BeCl2 (2) Beryllium halides are covalent while the halides
of other elements are ionic.
39. BeF2 is soluble in water, whereas fluorides of other (3) Their melting points increases from BeX2 to
alkaline earth metals are insoluble because of BaX2.
(1) ionization nature of BeF2 (4) Except BeF2 the solubility of other halides
(2) covalent nature of BeF2 ­increases from BeX2 to BaX2.

Chapter_11.indd 7 3/26/2014 3:23:22 PM

 11.8  Objective Chemistry - Vol. I

46. Calcium metal is used to produce high vacuum ­because • CaCO3 occur in two different crystalline forms: ­calcite
(1) It can remove water. and aragonite. Calcite is the more stable form in
(2) It can remove O2 and N2. which each Ca2+ ion is surrounded by 6 oxygen atoms
(3) It is a good reducing agent. of CO32–, whereas in aragonite (a meta stable form)
(4) It is highly electropositive. each Ca2+ ion is surrounded by 9 oxygen atoms of
CO32– ion with an unusual coordination number.
47. One mole of substance (X) was heated with an excess
• Though aragonite is less stable and should convert
of water, 2 moles of readily combustible gas were pro-
into calcite, the high activation energy prevents the
duced along with a solution which when reacted with
conversion.
CO2 gas produced a white turbidity. The ­substance
(X) could be
Sulphates
(1) Ca (2) CaH2
(3) Ca(OH)2 (4) Ca(NO3)2 • Sulphates of alkaline earth metals can be obtained by
the action of dil. H2SO4 on metals, oxides, hydroxides
Answers or carbonates.
• Sulphates of Be, Mg and Ca crystallize as hydrated
(32) 1 (33) 1 (34) 4 (35) 3 (36) 1 salts BeSO4 . 4H2O; MgSO4 . 7H2O; CaSO4 . 2H2O.
(37) 3 (38) 3 (39) 3 (40) 4 (41) 1 Sulphates of Sr and Ba crystallize without water of
(42) 3 (43) 1 (44) 3 (45) 4 (46) 2 crystallization.
(47) 2 • Thermal stability increases down the group similar to
carbonates.
• Sulphates decompose into MO, SO2 and O2 on ­heating.
Oxosalts of Group II Elements But when heated with carbon they form sulphides.
Carbonates and Bicarbonates • Solubility of the sulphates in water decreases from
Be to Ba. BeSO4 and MgSO4 are fairly soluble while
• These carbonates occur in nature as solid rock BaSO4 is completely insoluble.
materials.
• These can be prepared by passing CO2 into the aque- Nitrates
ous solutions of alkaline earth metal hydroxides or
by adding sodium carbonate or ammonium carbonate • The nitrates of alkaline earth metals can be prepared
­solution to a soluble salt of these metals. The carbon- by the reaction of nitric acid with oxides, hydroxides
ates of alkaline earth metals precipitate out. or carbonates.
• All these carbonates decompose on heating giving • When crystallized from solution they crystallize as hy-
MO and CO2. drated salts, but anhydrous nitrates cannot be prepared
by heating hydrated nitrates because they decompose
• Thermal stability of these carbonates increases from
to metal oxide.
Be to Ba.
• Anhydrous nitrates can be prepared using N2O4 and
• BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3 decom-
ethyl acetate. Be forms unusual basic beryllium nitrate
position temperature increases.
in addition to normal nitrate.
• Solubility in water decreases from BeCO3 to BaCO3.
• In basic beryllium acetate 4 Be atoms are arranged
• BeCO3 > MgCO3 > CaCO3 > SrCO3 > BaCO3 tetrahedrally and 6NO3– ions act as bridges (between
• All the carbonates are much more soluble in a solu- two Be atoms along 6 edges of tetrahedron). Similar
tion of CO2 than in water owing to the formation of structures occur for Be4O(O2CR)6 where RCOO– be
bicarbonates. acetate, or any carboxylate ion.
• The bicarbonates of alkaline earth metals cannot be • All nitrates decompose on heating into MO, NO2
prepared in solid state. They exist only in solution. and O2.
• All the carbonates of alkaline earth metals are ionic, • Thermal stability and solubility of the nitrates of
but BeCO3 is unusual because it contains the hydrated Group II elements follow the same order as in the case
[Be(H2O)4]2+ rather than Be2+ ion. of carbonates and sulphates but all nitrates are soluble.

Chapter_11.indd 8 3/26/2014 3:23:22 PM

 Alkaline Earth Metals  11.9

Trends in the Solubilities and Thermal Stability • When a small cation like Be2+ combines with a small
of the Compounds of Group II Elements oxide ion the lattice energy is more and the difference
in lattice enthalpies of oxosalt and oxide is little. So it
• The solubilities of oxides, hydroxides and flourides decomposes at low temperatures because less energy
of the Group II A elements increase down the group is required to decompose.
while the solubilities of most of their salts decrease
• When a bigger cation such as Ba2+ combines with a
down the group.
small oxide ion the lattice energy is less and the differ-
• Thermal stabilities of the oxosalts of the elements of ence in lattice enthalpies of oxosalt and oxide is more.
Group II increase down the group though their lattice So it decomposes at high temperature because more
energies decreases. energy (more difference in lattice enthalpies of oxosalt
• The trends in solubilities and thermal stabilities of com- and oxide) is required to decompose.
pounds depend on (lattice) enthalpies and ­hydration
energies.
• Lattice energy is inversely proportional to the bond   Objective Questions
length in ionic solids. 48. Which decomposes on heating?
1
∆H L ∝ (1) K2CO3 (2) Rb2CO3
r+ + r (3) Na2 CO3 (4) MgCO3
• Hydration energy is related to each ion individu-
49. A metal carbonate is sparingly soluble in water and
ally and for a compound it is the sum of individual
evolves CO2 on heating. The metal is
contributions
1 1 (1) An alkali metal
∆ hyd H ∝ + (2) A noble metal
r+ r−
(3) An alkaline earth metal
• Lattice energy rapidly decreases with increase in the (4) None
size of one ion, if the other ion is smaller one but do
not change much with increase in size of one ion, if the 50. Thermal stability of BaCO3, CaCO3 and MgCO3 is
size of other ion is very large. (1) CaCO3 > MgCO3 > BaCO3
(2) MgCO3 > CaCO3 > BaCO3
• Though hydration energies decrease with increase in
(3) BaCO3 > MgCO3 > CaCO3
size of cation, it dominates the lattice energy when the
(4) BaCO3 > CaCO3 > MgCO3
anion is small because the decrease in lattice energy is
more rapid than the decrease in hydration energy. So 51. Which of the following represents marble?
the solubilities of the compounds containing smaller (1) CaSO4 (2)  CaCO3
oxide and hydroxide ions increase down the group (3) CaCl2 (4)  MgSO4
with increase in the size of cation.
52. Whose decomposition temperature is more?
• Since the decrease in lattice energy is less rapid than
the decrease in hydration energy when anion is bigger (1) SrCO3 (2)  MgCO3
one, the solubility of the compounds decreases down (3) BaCO3 (4)  CaCO3
the group with increase in size of cation. Hence the 53. Which of the following compounds is not found in
­solubilities of compounds such as carbonates, ­sulphates, nature?
nitrates, phosphates, oxalates, chlorides, bromides, (1) CaCO3 (2)  BaCO3
iodides, etc. of alkaline earth metals decrease down (3) BeCO3 (4)  SrCO3
the group with increase in the size of cation.
54. The lowest solubility of BaSO4 in water is due to
• When oxosalts decompose one of the products is metal
oxide. (1) ionic bond (2)  low lattice energy
(3) high lattice energy (4)  dissociation energy
• The lattice energy is more when metal ion combines
with the small oxide ion than combined with bigger 55. The carbonates of alkaline earth metals are soluble in
oxoanion such as CO32 − , SO24 − , NO3− , etc. The decom- (1) cold water
position temperature depends on the difference in the (2) hot water
lattice enthalpies of metal oxide and oxosalt and direct- (3) the presence of CO2
ly proportional to the difference in lattice enthalpies. (4) the presence of (NH4)2SO4

Chapter_11.indd 9 3/26/2014 3:23:23 PM

 11.10  Objective Chemistry - Vol. I

56. Thermal stability of the carbonates of alkaline earth 63. A mixture of sodium oxide and calcium oxide is
metals is directly proportional to their ­dissolved in water and saturated with excess of
(1) ionic radius carbon dioxide gas. The resulting solution is ...... and
(2) decomposition temperature contains
(3) atomic number (1) Basic, NaOH and Ca(OH)2
(4) any one of these (2) Neutral, Na2CO3 and CaCO3
(3) Basic, Na2CO3 and CaCO3
57. Which of the following statements is not correct?
(4) Basic, NaHCO3 and Ca(HCO3)2
(1) SrCO3 decomposes readily than BeCO3.
(2) Be(OH)2 is less basic than Ba(OH)2. 64. A metal M readily forms water soluble sulphate
(3) BaCO3 melts at higher temperature than CaCO3. MSO4, water insoluble hydroxide M(OH)2 and oxide
(4) Ba(OH)2 is more soluble in water than Mg(OH)2. MO which becomes inert on heating. The hydroxide
is soluble in NaOH. The M is
58. Property of the alkaline earth metals that will not
­increase with their atomic number (1) Be (2)  Mg (3)  Ca (4)  Sr
(1) Solubility of their hydroxides 65. The compound A on heating gives a colourless gas
(2) Decomposition temperature of their carbonates and residue which dissolves in water to give B. When
(3) Solubility of their sulphates excess of CO2 is passed into B and gently heated, A is
(4) Basic character of their oxides formed. The compound A is
59. Which of the following properties show a reverse (1) CaSO4 2H2O (2) Na2CO3
trend on moving from Mg to Ca within the II group? (3) CaCO3 (4) K2CO3
(1) Density 66. A certain metal is present in the soil, plants, bones,
(2) Solubility of sulphates egg shells, sea shells and coral. It is also used to
(3) Ionization ­remove oxygen from molten steel and its hydroxide
(4) All of the above is used to detect CO2. The metal is
60. Choose the false statement. (1) Mg (2) Al (3) Ca (4) Na
(1) The solubility of II group salts depends upon 67. A substance which gives a brick red flame and breaks
­lattice energy of solid and the hydration energy down on heating to give oxygen and a brown gas
of the ions.
(1) Magnesium nitrate
(2) The solubilities of II group fluoride and ­hydroxides
(2) Calcium carbonate
have opposite trends.
(3) Calcium nitrate
(3) The solubilities of most II group salts decrease
(4) Magnesium Carbonate
with an increase in atomic weight of correspond-
ing salts. 68. Which of the following statements is false?
(4) The solubilities of II group fluorides and hydroxides (1) Strontium decomposes water readily than ­beryllium.
increase with molecular weight. (2) Barium carbonate decomposes at a higher
61. Which of the following statements is not correct? ­temperature than calcium carbonate.
(1) Affinity for oxygen to form basic oxides ­increases (3) Barium hydroxide is more soluble in water than
in the order BeO < MgO < CaO < SrO < BaO. magnesium hydroxide.
(2) Basic strength of oxides and hydroxides ­increases (4) Barium hydroxide is less basic than magnesium
from Be to Ba compounds. hydroxide.
(3) Bicarbonates of alkaline earth metals do not exist
in solid state but they are known in solutions.
(4) All are correct. Answers
62. Property of alkaline earth metals that increases with (48) 4 (49) 3 (50) 4 (51) 2 (52) 3
their atomic number is (53) 3 (54) 3 (55) 3 (56) 4 (57) 1
(1) ionization energy (58) 3 (59) 4 (60) 4 (61) 4 (62) 2
(2) solubility of their hydroxides (63) 4 (64) 1 (65) 3 (66) 3 (67) 3
(3) solubility of their sulphates (68) 4
(4) electronegativity

Chapter_11.indd 10 3/26/2014 3:23:24 PM

 Alkaline Earth Metals  11.11

AnOmalous Behaviour of • Both Be and Al are rendered passive on treatment with

Beryllium conc. HNO3.
• Unlike alkaline earth metals but like aluminium, Be
• The reasons for the anomalous behaviour of beryllium does not get readily attacked by dry air.
is attributed to
• Both Be and Al react very slowly with dilute mineral
  (i)  its small size
acids due to the presence of an oxide layer.
(ii)  its high electronegativity
(iii)  absence of d-orbitals in its valence shell • Both Be and Al react with alkalis liberating H2.
  (iv) presence of only two electrons in its penultimate • Both Be and Al form carbides which on hydrolysis
shell liberate methane.
• Be compounds are predominantly covalent due to • Both form nitrides when heated in nitrogen which give
its high polarizing power and its salts are readily ammonia by the reaction with water.
hydrolyzed. • Both form oxides which are amphoteric.
• Be is an amphoteric metal and dissolves in alkali • Halides of both Be and Al contain halogen bridge bonds.
­solutions forming beryllates. • Both Be and Al do not impart flame coloration.
• BeSO4 is soluble in water, whereas sulphates of Ca, Sr • Both Be2+ and Al3+ have strong tendency to form
and Ba are sparingly soluble. complexes.
• Be and its salts do not respond to flame test while Ca,
Sr and Ba give characteristic flame colours.
  Objective Questions
• Be forms many complexes while the heavier elements
do not show much tendency to form complexes. 69. The electronegativity of aluminium is similar to that of
• Maximum covalency of Be is 4 while other alkaline (1) Barium (2) Beryllium
earth metals can exhibit a covalency of 6. (3) Calcium (4) Strontium
• BeO is covalent and has 4:4 ZnS structure but all the 70. Beryllium and aluminium have similar properties
others are ionic and have 6:6 NaCl structure. ­because
• Be do not react with H2 directly but others can react (1) they belong to the same group
with H2 directly. (2) they have different electronegativities
(3) they have nearly same electronegativities
• Be3N2 is volatile but the nitrides of others are not
(4) they have same ionization potential
volatile.
• With carbon Be forms methanide (Be2C) while other 71. Be shows diagonal relationship with Al. Which of the
form acetylide (MC2). following is wrong?
• Beryllium halides polymerize to form chains contain- (1) Be2C like Al4C3 yields methane on hydrolysis.
ing bridging halogen groups, e.g., (BeF2)n, (BeCl2)n. (2) Be like Al is rendered passive by conc. HNO3.
But halides of other group II elements are ionic. (3) Be(OH)2 like Al(OH)3 is basic.
(4) Be forms beryllates and Al forms aluminates.
72. Both Be and Al become passive on reaction with
Diagonal Relationship between
conc. HNO3 because
Be   and   Al
(1) they are non-reactive metals
• Be and Al have same electronegativity (Be = 1.5; (2) of the non-reactive nature of the acid
Al = 1.5) and their charge/radius ratios are very much (3) of the formation of inert layer of oxide on the
similar indicating similar field strengths (Be = 6.4; surface of metals
Al = 6.0). So, Be and Al resemble each other in several (4) none of these
properties. 73. Which of the following statements is not correct?
• The standard oxidation potential of both Be and Al are (1) Be like Al does not dissolve in alkalies.
of the same order (Be = 1.69 V; Al = 1.7 V). (2) Oxides of both Be and Al are amphoteric.
• Since the polarizing power of both Be and Al are near- (3) BeC2 like Al4C3 is covalent.
ly the same, the covalent character of their compounds (4) Burning of lime stone containing more than 10%
is also similar. aluminium silicates gives hydraulic mortar.

Chapter_11.indd 11 3/26/2014 3:23:24 PM

 11.12  Objective Chemistry - Vol. I

74. Beryllium differs from rest of the members of its ­family • On large scale it is manufactured by fractional crystal-
(II A group) in many ways. The reason for this is its lization of fused carnalite.
(1) small size and high electronegativity. • Anhydrous MgCl2 cannot be prepared by heating
(2) small size and low electronegativity. ­hydrated MgCl2 . 6H2O because it hydrolyzes to form
(3) large size and lower ionization energy. hydroxy chloride or hydroxide or oxide depending on
(4) larger size and large ionic radius. the temperature.
• Anhydrous MgCl2 can be prepared by (i) heating
Answers MgCl2 . 6H2O in vacuum in a current of dry HCl,
(ii)  heating a mixture of MgO and C in a current of
(69) 2 (70) 3 (71) 3 chlorine gas and (iii) passing a mixture of CO and Cl2
(72) 3 (73) 1 (74) 1 over MgO at 1023 K.
• It is a colourless, deliquescent solid soluble in water.
• It is used in making Sorrell’s cement and in lubricating
Important compounds of cotton threads in spinning.
Magnesium Oxide
Magnesium Sulphate (MgSO4 . 7H2O
Magnesium Oxide Epsom Salt)
• It can be prepared by calcination of magnasite. It is • It occurs in the nature in the form of minerals kieserite
called calcined magnesia. MgSO4 . H2O and epsomite MgSO4 . 7H2O.
• It can also be prepared by heating Mg(OH)2, Mg(NO3)2
• It is prepared by dissolving magnesium, or its oxide or
or MgSO4.
hydroxide or carbonate in dil. H2SO4 and evaporating
• It is sparingly soluble in water, less basic in nature and the solution gives heptahydrate Mg . SO4 . 7 H2O.
easily soluble in acids.
• Dolamite when dissolved in dil. H2SO4 gives a mixture
• It dissolves in aqueous solutions of MgCl2 or MgBr2 of MgSO4 and CaSO4. Insoluble CaSO4 is removed by
forming basic salts such as MgBr2 . 9Mg(OH)2 . 5H2O. filtration and the filtrate on evaporation gives epsom salt.
• It is used as an antacid in medicine. When moistened • Anhydrous MgSO4 is obtained by heating the hydrated
with saturated solution of MgCl2 it sets into hard
salt at 473 K.
mass called Sorell’s cement whose composition is
MgCl2 . 5MgO . xH2O. It is used in plaster casting, re- • Epsom salt is manufactured by dissolving kieserite in
pairing of porcelain ware and in filling teeth. boiling water and crystallizing the resulting solution.
• It is used as an adsorbent in the manufacture of • It is colourless efflorescent crystalline solid having a
­dynamite and in vulcanization of rubber. Flocculent bitter taste.
form of MgO is used as a rubber filler. • It has two types of crystalline forms. One is isomor-
phous with rhombic crystals of ZnSO4 . 7H2O and
Magnesium Hydroxide the other is isomorphus with monoclinic crystals of
FeSO4 . 7H2O.
• It occurs in the mineral brucite. It is prepared by
adding NaOH or NH4OH to a solution of soluble • Out of seven water molecules six are coordinated to
magnesium salt. Mg(OH)2 will be precipitated out. Mg2+ ion and the seventh water molecule is in ­hydrogen
• On large scale it is manufactured by treating MgCl2 of bond with sulphate ions.
the potash industry with slaked lime. • It is extensively used as purgative or laxative, in ­dyeing
• It is white powder slightly soluble in water, dissolves and tanning of leather, in the manufacture of fire
in acids decomposes to oxide at 573 K to MgO. proofing fabrics. Platinized MgSO4 crystals are used
as a catalyst in the manufacture of H2SO4 by Grillo’s
• The suspension of Mg(OH)2 in water is called milk of
process.
magnesia and is used as an antacid in medicine.

Magnesium Chloride (MgCl2 . 6H2O) Magnesium Carbonate

• In the laboratory it is prepared by dissolving the metal • It occurs in nature as magnesite. It can be precipitated
oxide, hydroxide or carbonate in dil. HCl and evapo- by adding sodium carbonate solution to hot solution
rating the solution. of magnesium salt. If precipitation is carried out in

Chapter_11.indd 12 3/26/2014 3:23:25 PM

 Alkaline Earth Metals  11.13

the cold condition magnesia alba having ­formula 78. Commercially epsom salt is manufactured from
MgCO3 . Mg(OH)2 . 7/2H2O is obtained. Hot con- (1) Carnallite (2) Dolamite
centrated solutions yield magnesia alba ­ponderosa (3) Magnesite (4) Kieserite
having the approximate formula MgCO3 . Mg(OH)2.
3H2O. Magnesia alba is used in medicine as an antacid 79. In espom salt the number of water molecules bound
and a laxative. Also it is used in tooth powders and to Mg2+ ion is
pastes and silver polishes. (1) 2 (2)  4 (3) 6 (4) 1
• If the solution of the bicarbonate is crystallized at 80. Epsom salt on strong heating gives
325  K heated with MgO crystals of MgCO3 . 3H2O (1) anhydrous salt (2) MgO + SO2 + O2
separate out. (3) MgS + O2 (4) MgSO3 + O2
• The MgCO3 . 3H2O is more reactive than the anhy-
81. Platinized magnesium sulphate is used as a catalyst in
drous salt and is used in the Engel–Precht process.
(1) Haber’s process (2) Contact process
• It is used in glass manufacture, inks, ceramics fertilizers, (3) Decon process (4) Hoopes process
insulation, industrial chemicals and rubber ­products, as
a refractory material and for certain medicinal prepara- 82. Electric cookers have a coating of .......... that protects
tions as a filler for paper, rubber and pigments. them against fire.
(1) Heavy lead (2) Magnesium oxide
Magnesium Ammonium Phosphate (3) Zinc oxide (4) Sodium sulphate
(Mg(NH4) PO4 . 6H2O)
83. Which of the following statements is correct?
• It is the least soluble compound of magnesium and is (1) MgCl2 ⋅ 6H2O is deliquescent and due to its pres-
formed as a white crystalline precipitate when a solu- ence in small amount table salt gets sticky on
tion of Na2HPO4 is added to a solution of ­magnesium ­humid summer days.
salt containing some ammonia and ­ammonium (2) The basic magnesium carbonate is used as an
chloride. ­ingredient in toothpaste.
• The formation of magnesium ammonium phosphate (3) Mg(OH)2 suspension known as milk of magnesia
as white precipitate is used in the detection and is used as stomach antacid.
­estimation of magnesium. (4) All are correct

Answers
  Objective Questions
75. Milk of magnesia used as a medicine for treating (75) 4 (76) 1 (77) 3 (78) 4 (79) 3
­indigestion is a substance that (80) 2 (81) 2 (82) 2 (83) 4
(1) helps in disintegration of food products leading
to their metabolism
(2) combines with gastric hydrochloric acid thereby Important Compounds
enhancing the latter’s efficiency of Calcium
(3) improves the enzymatic activities inside the
stomach Calcium Oxide (CaO)
(4) neutralizes excess acidity, providing a buffered
• It is also known as quick lime or burnt lime; prepared
medium inside the stomach
on large scale by burning lime stone in lime kiln.
76. The mixture of MgCl2 and MgO is called • It is a white solid. When heated in oxyhydrogen flame
(1) Sorrel’s cement a brilliant white light known as lime light is emitted.
(2) Mixed salt • It absorbs moisture from air; so, it is used as a drying
(3) Portland cement agent but cannot be used to dry acidic substances.
(4) Magnesium oxychloride
• It is used in the manufacture of bleaching powder,
77. Epsom salt is ­calcium carbide, cement, glass, lime mortar, etc.
(1) hygroscopic (2) deliquescent Used in the purification of sugar, as a basic refractory
(3) efflorescent (4) None material and basic flux in metallurgy.

Chapter_11.indd 13 3/26/2014 3:23:25 PM

 11.14  Objective Chemistry - Vol. I

Calcium Hydroxide (Ca(OH)2) • Highly concentrated solutions of CaCl2 are used in

­liquid baths for heating purposes.
• It is obtained by the addition of water to quick lime.
• When water is added to quick lime a hissing sound is Calcium Carbonate (CaCO3)
heard and lumps of CaO crack and disintegrate into
powder. This process is called slaking of lime and the • It is widely distributed in nature in huge deposits as
product is called slaked lime. lime stone, chalk, marble and Iceland spar.
• It is a white amorphous powder and sparingly soluble • In the laboratory it is prepared either by passing CO2
in water. through lime water or by adding calculated amount of
• Its solubility in water decreases with increase in sodium carbonate to a solution of CaCl2.
temperature. • It is a white solid, insoluble in water, but dissolves in
• The suspension of lime in water is called milk of lime, the presence of CO2 due to the formation of calcium
whereas the filtered and clear solution is called lime bicarbonate.
water. • Used in the manufacture of cement, lime, washing
• When CO2 is passed through lime water first it turns soda, glass, as chalk in tooth pastes and powders and
milky which disappears by passing excess of CO2 due as flux in metallurgy.
to the formation of soluble bicarbonate.
• Milk of lime when treated with chlorine gives hypo­ Calcium Sulphate (CaSO4 . 2H2O)
chlorite in cold condition and chlorate in hot condition
along with chloride. • In the nature it occurs in the form of gypsum,
• When Cl2 gas is passed over dry slaked lime bleaching CaSO4 . 2H2O, anhydrous calcium sulphate CaSO4
powder is formed. known as anhydrite. The calcium sulphate occurring
as pure fine powder is known as alabaster.
• Milk of lime liberates ammonia gas from ammonium
salts. • Gypsum is used in cement to retard setting time, in the
manufacture of plaster of paris, in agriculture and to im-
• It is used in the manufacture of bleaching powder,
pregnate filter papers. It is also used in the production of
caustic soda, in the production of lime mortar, in glass
SO2 required in the manufacture of sulphuric acid.
making, tanning industry and for purification of sugar.

Calcium Chloride (CaCl2 . 6H2O) 1

Plaster of Paris (CaSO4 . H2O)
• It is obtained as a by-product in Solvay’s process for 2
the manufacture of sodium carbonate. • It is prepared by heating gypsum at 390 K. If tem-
• In the laboratory it is obtained by dissolving CaCO3 in perature of heating is above 390 K setting properties
dil. HCl and crystallizing gives CaCl2 . 6H2O. of plaster of paris are partly destroyed and it is called
dead burnt.
• On heating CaCl2 . 6H2O at about 473 K forms CaCl2 . 
2H2O which finally becomes anhydrous CaCl2 on • It is hemihydrate and when mixed with water sets into
futher heating. It is also called as fused calcium hard mass which is known as setting of plaster of
chloride. paris.
• It is extremely soluble in water. It forms addition com- • During setting of plaster of paris little expansion takes
pounds with ammonia, methyl alcohol like CaCl2 .  place with the liberation of little heat (exothermic).
8NH3 and CaCl2 . 4NH3. • It sets into hard mass into two stages, the first stage
• Anhydrous CaCl2 is hygroscopic and deliquescent, is called setting stage during which it converts into
and hence used as a drying agent in desiccator but it ortho­rhombic gypsum and in the second stage
cannot be used to dry ethyl alcohol or ammonia as it known as hardening stage during which it converts
forms addition compounds with them. into monoclnic gypsum.
• When mixed with ice the freezing point of water • Setting of plaster of paris is due to hydration or uniting
­decreases to 255 K, so it is used to melt ice and snow with water into another hydrate.
on roads. It is also used in making freezing mixtures • It is used in making moulds, statues, in plastering the
and refrigeration. fractured bones and in making black board crayons.

Chapter_11.indd 14 3/26/2014 3:23:26 PM

 Alkaline Earth Metals  11.15

Mortar Biological Importance of Mg and Ca

• It is also known as lime mortar. It is an intimate ­mixture • Mg2+ ions are concentrated in animal cells.
of 1 part of slaked lime, 3 parts of sand and water made • Enzymes like phosphohydrolases and phosphotrans-
into paste. ferases contain Mg2+ ion. These enzymes participate
• Lime absorbs CO2 from air converts into CaCO3 which in ATP reactions and release energy. In this process,
acts as a binding material. Lime also reacts with silica Mg2+ forms a complex with ATP.
forming calcium silicate which gives hardness. Sand • Mg2+ is a constituent of chlorophyll, the green pigment
makes the mass porous which prevents the cracking of plants.
due to excessive shrinkage during drying.
• Ca2+ ion present in bones and teeth as apetite
• Mortar mixed with cement is called cement mortar [Ca3(PO4)2]. Enamel of teeth is fluorapetite
which is harder and more water proof. [3Ca3(PO4)2 . CaF2].
• Mortar obtained by using the slaked lime obtained by • Ca2+ ions are necessary for clotting of blood, to main-
burning lime stone containing 10% aluminosilicate tain regular heart beating and for muscle contraction.
is hydraulic mortar which can set on addition of
water. This is used as an antiseptic and for bleaching
purposes.
  Objective Questions
Cement 84. Gypsum is added to clinker during cement
­manufacture to
• The name Portland cement was given to it by Joseph
(1) decrease the rate of setting of cement
Aspidin because when it is mixed with sand and water
it hardens like the lime stone quarried at Portland in (2) make the cement impervious
England. (3) bind the particles of calcium silicate
(4) to facilitate the formation of colloidal gel
• The composition of cement is CaO – 50 to 60%;
SiO2 – 20 to 25%; Al2O3 – 5 to 10%; MgO – 2 to 3%; 85. Which of the following is correct?
Fe2O3 – 1 to 2% and SO3 – 1 to 2%. (1) Gypsum is CaSO4 . 2H2O
• The ratio between silica and alumina should be (2) Anhydrite is CaSO4
­between 4 and 2.5 and the ratio of CaO and the mix- (3) Naturally occurring fine powder of calcium
ture of SiO2, Al2O3 and Fe2O3 should be close to 2.0. ­sulphate is known as alabaster
(4) All are correct
• If lime is excess the cement cracks during setting but
if it is less, the cement is weak. 86. Which of the following statement is false?
• The raw materials for the manufacture of cement (1) The solubility of gypsum in water increases with
are lime stone and alumino silicates. (clay, sand and increase in temperature.
shales). (2) The solubility of gypsum in water increases
in the presence of ammonium sulphate due to
• When the powdered raw materials are heated in a
­formation of a double salt.
­rotary kiln, sintered clinker will be obtained.
(3) Gypsum on heating to 120°C forms plaster of
• The important compounds in the Portland cement paris.
are dicalcium silicate (Ca2SiO4) 26%; tricalcium (4) Gypsum when heated to 200°C converts into
silicate (Ca3SiO5) 51% and tricalcium aluminate dead burnt.
(Ca3Al2O6) 11%.
87. Plaster of Paris is
• The setting of cement by mixing with water is due to 1
hydration of molecules and their rearrangement and (1) CaSO 4 ⋅ H 2 O
2
also due to hydrolysis. (2) hemihydrate
• About 1% gypsum is added to the cement to slow (3) formed by partial dehydration of gypsum
down the process of setting of the cement. (4) all of these

Chapter_11.indd 15 3/26/2014 3:23:27 PM

 11.16  Objective Chemistry - Vol. I

88. During setting of plaster of paris 96. The role of silica in mortar is to
(1) mass is expanded (2) heat is liberated (1) form slag with lime
(3) hydration takes place (4) all of these (2) make the mass porous
(3) give slight acidic nature
89. Plaster of paris hardens by
(4) make it insoluble in water
(1) combining with water
(2) giving out water 97. Hydraulic mortar which contains aluminosilicate can
(3) giving of CO2 be used for
(4) changing into CaCO3 (1) bleaching
(2) antiseptic action
90. Which of the following is not the use of plaster of (3) building construction
paris? (4) all
(1) Ordinary black board chalk pieces contain ­plaster
of paris. 98. Which of the following statements is false?
(2) Plaster of paris is used for moulds basing on the (1) Calcium oxide is also called quick lime or burnt
property of setting. lime.
(3) Plaster of paris is used in plastering of fractured (2) Slaking is a process of dissolving quick lime in
bones. water.
(4) It is mixed with cement to retard the setting time (3) Suspension of slaked lime in water is called milk
of cement. of lime.
(4) The clear solution of slaked lime in water is
91. Setting of plaster of paris involves called lime water.
(1) Oxidation with atmospheric oxygen
99. The raw materials used for cement are
(2) Combination with atmospheric CO2
(3) Dehydration (1) CaCO3 and SiO2 (2) CaCO3 and clay
(4) Hydration to yield another hydrate (3) CaO and SiO2 (4) Ca(OH)2 and clay

92. During setting of plaster of paris which is incorrect? 100. Concrete is a mixture of
(1) It converts into gypsum (1) Cement, lime and water
(2) Heat is liberated (2) Cement, sand and water
(3) Hydration takes place (3) Cement, gravel, sand and water
(4) Contraction takes place (4) Cement, slaked lime and water
93. Identify the correct statement. 101. The setting of cement under water is essentially
(1) Gypsum contains a lower percentage of calcium (1) an oxidation process
than plaster of paris. (2) a reduction process
(2) Gypsum is obtained by heating plaster of paris. (3) a double decomposition process
(3) Plaster of paris can be obtained by partial oxida- (4) a hydration process
tion of gypsum. 102. Portland cement does not contain
(4) Plaster of paris can be obtained by hydration of
(1) Ca3Al2O6 (2) Ca3SiO5
gypsum.
(3) Ca2SiO4 (4) Ca3(PO4)2
94. Mortar is a mixture of
103. Which of the following is used as a dessicant in the
(1) CaCO3 and CaO laboratory?
(2) Slaked lime and water
(1) Na2CO3 (2) anhydrous CaCl2
(3) Slaked lime, sand and water
(3) H2SO4 (4) Ca3(PO4)2
(4) Gypsum, sand and water
104. A drying agent which absorbs CO2 and react violent-
95. The function of sand in mortar is ly with water is
(1) to decrease the hardness (1) Na2CO3 (2) C2H5OH
(2) to make the mass compact (3) Conc. H2SO4 (4) CaO
(3) to decrease the plasticity of the mass
(4) to prevent the excess shrinkage because of which 1 05. A gas reacts with CaO and not with NaHCO3 is
cracks may be result (1) CO2 (2) Cl2 (3) O2 (4) N2

Chapter_11.indd 16 3/26/2014 3:23:27 PM

 Alkaline Earth Metals  11.17

106. Iceland spar is (1) CaCO3 (2) CaO

(1) CaSiO4 (2) CaCO3 (3) Ca(OH)2 (4) CaHCO3
(3) CaF2 (4) NaAIF6 6. Identify the false statement.
(1) Anhydrous MgCl2 is obtained by heating the hy-
Answers drated salt in a current of dry HCl or with NH4Cl.
(2) Plaster of paris is made by heating gypsum to
  (84)  1   (85)  4   (86)  1   (87)  4   (88)  4 100°C and its formula is CaSO4 . H2O.
  (89)  1   (90)  4   (91)  4   (92)  4   (93)  1 (3) An aqueous solution of BeCl2 is acidic.
  (94)  3   (95)  4   (96)  2   (97)  4   (98)  2 (4) Salts of alkaline earth metals are diamagnetic.
  (99)  2 (100)  3 (101)  4 (102)  4 (103)  2
(104)  4 (105)  1 (106)  2 7. Which of the following statement is wrong?
(1) MgO is used for the lining of furnace for steel
making.
(2) NaCl is added during electrolysis of fused
­anhydrous MgCl2.
  Practice Exercise (3) MgCl2 . 6H2O on heating gives anhydrous MgCl2.
(4) In the electrolysis of CaH2 hydrogen is liberated
1. Which of the following statement about IIA group at the anode.
elements is false?
8. Identify the false statement.
(1) They belong to s-block.
(2) Their atoms are bigger than 1A group elements. (1) The order of basic character of the following
(3) Their outer electronic configuration is ­oxides is NiO < MgO < SrO < K2O < Cs2O.
(n – 1)s2 (n – 1)p6 ns2. (2) Be(OH)2 is a stronger base than Ba(OH)2.
(4) They are all called as alkaline earth metals. (3) The order of the ionic character of the following
chlorides is
2. Magnesium burns in CO2. Which is not true about
BeCl2 > MgCl2 > CaCl2> SrCl2 > BaCl2.
this reaction?
(4) Ca(OH)2 is more soluble in water than Mg(OH)2.
(1) Magnesium acts as a reducing agent and removes
oxygen from CO2. 9. Which of the following statement is not correct?
(2) MgO and CO are formed. (1) Anhydrous MgCl2 is obtained by heating the
(3) Black carbon powder deposits on the walls of the hyrated salt with HCl gas.
vessel. (2) Heating MgCl2 . 6H2O gives MgO.
(4) Magnesium gets oxidized. (3) Be shows covalency and electrovalency.
3. Magnesium burns with a brilliant white dazzling (4) IE of Be is larger than that of Mg.
light. The property is not used in 10. In the hardening stage of plaster of paris, the product
(1) fire works formed is
(2) military signals (1) orthorhombic CaSO4 . 2H2O
(3) in photographic flash bulbs (2) monoclinic CaSO4 . 2H2O
(4) in artificial lighting (3) anhydrous CaSO4
4. Which of the following statement is false? (4) hexagonal CaSO4 . 2H2O
(1) Epsom salt is used as purgative or laxative. 11. The filter papers are impregnated with
(2) The calcium salt used in agriculture is CaCO3.
(1) gypsum
(3) Dead burnt has no setting property.
(2) epsum
(4) The hardness of mortar is due to the formation
of CaSiO3. (3) alumina
(4) plaster of paris
5. Chemical “A” is used for water softening to ­remove
temporary hardness. “A” reacts with sodium 12. Which of the following is used to remove last traces
­carbonate to generate caustic soda. When CO2 is of oxygen in the radio tubes?
­bubbled through “A” it turns cloudy. What is the (1) carbon (2)  silicon
chemical formula of A? (3) boron (4) magnesium

Chapter_11.indd 17 3/26/2014 3:23:28 PM

 11.18  Objective Chemistry - Vol. I

13. In the alkaline earth metals the electrons are more (3) Owing to their great chemical activity, alkaline
firmly held to the nucleus and hence earth metals are not found in the free state in
(1) atoms of these metals are bigger than alkali ­metals ­nature.
(2) ionization energy of these metals is greater than (4) In the reaction of Mg with an acid resulting in
alkali metals the formation of a corresponding Mg salt and the
(3) reactivity of these metals is greater than alkali subsequent liberation of Mg is oxidized.
metals 22. Sodium bicarbonate solution on adding to ­magnesium
(4) these metals are less abundant in nature sulphate solution forms
14. One of the elements present in carnalite shows flame (1) soluble magnesium bicarbonate
colouration. The colour of the flame is (2) insoluble magnesium bicarbonate
(1) orange (2)  green (3)  yellow (4)  lilac (3) insoluble magnesium carbonate
(4) insoluble basic magnesium carbonate
15. Which of the following is best suited to dry crystals
of ammonia salts (complexed) in which NH3 is a 23. Portland cement is
­ligand? E.g., [Ni(NH3)6] Br2. (1) Calcium alumino silicate
(1) anhydrous CaCl2 (2) Calcium aluminate + calcium silicate
(2) anhydrous CaO (3) A mixture of calcium oxide, aluminium oxide
(3) a mixture of CaO and NH4Cl and silica
(4) P2O5 (4) Calcium silicate and gypsum
16. The compound insoluble in acetic acid is 24. Which reagent would enable you to remove SO2−
4
(1) calcium oxide (2) calcium carbonate ions from a solution containing both SO2−
4 and
(3) calcium oxalate (4) calcium hydroxide Cl– ions?
(1) NaOH (2) BaCO3
17. Which of the following is used for taking the X-ray
(3) BaCl2 (4)  MgCl2
spectra of digestive system?
(1) CaSO4 (2) BaSO4 25. A salt on treatment with dil. HCl gives a pungent
(3) BaCO3 (4) MgSO4 smelling gas and a yellow precipitate. The salt gives a
green flame when tested. The salt solution that gives
18. Lithophone is a mixture of a yellow precipitate with potassium chromate is
(1) CaSO4 + BaS (1) NiSO4 (2) BaS2O3
(2) CaS + ZnSO4 (3) PbS2O3 (4) CuSO4
(3) CaSO4 + ZnS
(4) BaSO4 + ZnS 26. Which of the following is false?
(1) Mg burns in air releasing dazzling light rich in
19. Which of the following statements is false? UV-rays.
(1) The solutions of alkaline earth metals in liquid (2) CaCl2 . 2H2O when mixed with ice gives a
ammonia give metal amides on evaporation. ­freezing mixture.
(2) BeCl2 contains sp hybrid Be in gaseous state but (3) Mg has less tendency to form complexes.
sp3 hybrid Be in solid state. (4) Be form complexes due to its very small size.
(3) Calcium carbide reacts with water to give
27. The lattice and hydration energy of Be are not
­acetylene.
­sufficient to provide complete charge separation and
(4) Calcium is also an essential constituent of
the formation of simple Be2+ ions because of
­chlorophyll.
(1) its small size
20. The white enamel of our teeth is (2) high ionization potential
(1) Ca3(PO4)2 (2) CaF2 (3) high heat of sublimation
(3) CaCl2 (4) Both 1 and 2 (4) all are correct
21. Which of the following statement is false? 28. A compound of calcium (X) is used in sugar ­industry
(1) CaCl2 is deliquescent. for the purification of sugar. When exposed to an
1 ­oxyhydrogen flame, it becomes incandescent and
(2) Gypsum is CaSO 4 ⋅ H 2 O. starts emitting white light, on treating with CO2
2

Chapter_11.indd 18 3/26/2014 3:23:30 PM

 Alkaline Earth Metals  11.19

it forms a compound which can be decomposed to 35. Select the incorrect statement about alkaline earth
give back X at very high temperature X is metals.
(1) CaCO3 (2) CaO (1) Solubility of sulphates decrease down the group.
(3) Ca(OH)2 (4) CaSO4 (2) Solubility of hydroxides decrease down the
group.
29. CaCl2 is preferred to NaCl for clearing ice on roads
(3) Thermal stability of carbonates increase down
particularly in very cold countries. This is because
the group.
(1) CaCl2 is less soluble but NaCl is not (4) Basic nature of hydroxides increases down the
(2) CaCl2 is hygroscopic but NaCl is not group.
(3) Eutectic mixture of CaCl2 /H2O freezes at –55°C High temperature
while that of NaCl/H2O freezes at –18°C 36. X + C + Cl 2 Y + CO;
of about 1000 K
(4) NaCl makes the road slippery but CaCl2 does not
Y + 2H2O → Z + 2HCl. Compound Y is found in
30. The use of BaSO4 in having X-ray pictures of the polymeric chain structure and is an electron-deficient
­digestive tract is based on molecule. Y must be
(1) its insolubility in water (1) BeO (2) BeCl2 (3) BeH2 (4) AlCl3
(2) greater scattering of X-rays of Ba2+ ions
(3) both of these 37. Sort the odd one out
(4) its non-poisonous character (1) Ca(HCO3)2
(2) Mg(HCO3)2
31. The correct statement for group 2 metals is (3) NaHCO3
(1) The metal ions become larger on descending the (4) LiHCO3
group. So, the lattice energy as well as hydration
energy decreases. 38. The order of decreasing polarity in the compounds
(2) The solublity of their salts decreases as ­lattice CaO, CsF, KCl, MgO is
­energy decreases slowly compared to the (1) CaO, CsF, KCl, MgO
­decrease in hydration energy. (2) MgO, KCl, CaO, CsF
(3) For a substance to dissolve, the hydration energy (3) KCl, CaO, CsF, MgO
must be more than the lattice energy. (4) CsF, KCl, CaO, MgO
(4) All the above.
39. Beryllium is placed above magnesium in the second
32. Calcium is obtained by group Beryllium. Beryllium dust therefore, when
(1) roasting of limestone added to MgCl2 solution
(2) electrolysis of a solution of calcium chloride in
(1) Have no effect
water
(2) Precipitate Mg metal
(3) reduction of calcium chloride with carbon
(3) Precipitate MgO
(4) electrolysis of molten anhydrous calcium
(4) Lead to dissolution of beryllium metal
­chloride
33. Choose the false statement 40. Which of the following on the thermal decomposition
yields a basic as well as an acidic oxide?
(1) BeCO3 is kept in the atmosphere of CO2 since it
is least thermally stable. (1) KClO3 (2) CaCO3
(2) Be dissolves in alkali forming [Be(OH)4]2–. (3) NH4NO3 (4) NaNO3
(3) BeF2 forms a complex with NaF in which Be 41. A doctor by mistake administers a dilute Ba(NO3)2
goes with action. solution to a patient for radiographic investigations.
(4) BeF2 forms a complex with NaF in which Be Which of the following should be the best to prevent
goes with anion. the absorption of soluble barium and subsequent
34. BaC2 + N2 ∆
→ (A) ­barium poisoning?
CaC2 + N2 ∆ → (B) (1) NaCl (2)  Na2SO4
(3) Na2CO3 (4) NH4Cl
A and B are
(1) BaCN2, CaCN2 42. A sodium salt on treatment with MgCl2 gives a white
(2) Ba(CN)2, Ca(CN)2 precipitate only on heating. The anion of the sodium
(3) Ba(CN)2, CaCN2 salt is
(4) BaCN2, Ca(CN)2 (1) HCO3− (2) CO3− (3) NO3− (4) SO2− 4

Chapter_11.indd 19 3/26/2014 3:23:31 PM

 11.20  Objective Chemistry - Vol. I

50° C
43. Identify the correct order of solubility in IInd group 48. BeCl2 + N2O4 → A Vacuum → B 125
 °C
→ C. The
compounds of modern periodic table. compounds A, B and C are
 I.  CaC2O4 > SrC2O4 > BaC2O4 (1) BeO, Be(NO3)2, Be(NO2)2
 II.  CaSO4 < SrSO4 < BaSO4 (2) BeO, Be(NO2)2, Be(NO3)2
(3) Be(NO3)2 . 2N2O4,Be(NO3)2, Be(NO2)2
III.  Ca(OH)2 < Sr(OH)2 < Ba(OH)2 (4) Be(NO3)2 . 2N2O4, Be(NO3)2, [Be4O(NO3)]6
 IV.  CaF2 < SrF2 < BaF2
49. [Be(H2O)4]Cl2 on heating gives
(1) III, IV only (2) I, III, IV only (1) O2 (2) Be
(3) I, II only (4) I, IV only (3) Be2Cl2 (4) Be(OH)2
44. Lattice energies of the oxides of Mg, Ca, Sr and Ba 50. BeO dissolves in strongly alkaline solutions to form
follow the order (1) Be(OH)2 (2) Be
(1) BaO > SrO > CaO > MgO (3) Be2O3 (4) [Be(OH)4]2–
(2) CaO > BaO > SrO > MgO
51. MgO and CaO are used for lining furnaces because
(3) MgO > SrO > CaO > BaO
(4) MgO > CaO > SrO > BaO (1) they have high m.pts
(2) they are good conductors of heat
45. When a saturated solution of magnesium sulphate is (3) they are electrical insulators
treated with NH4Cl and NH3, followed by the addi- (4) all are correct
tion of disodium hydrogen phosphate, a white pre-
cipitate is formed. This on heating gives 52. Calcium cyanamide on hydrolysis gives a gas “B”
(1) Mg2P2O7 (2) Mg3(PO4)2 which on oxidation with bleaching powder gives an-
(3) Mg(NH4)PO4 (4) Mg(NH4)HPO4 other gas “C”. When magnesium is heated in the gas
C and the resultant compound D on adding to water
46. The solubility of the fluorides and hydroxides of gives the same gas B. The B, C and D are
­alkaline earth metals increases on descending the (1) NH3,N2,Mg3N2
group because (2)  N2,NH3,MgNH2
(1) lattice energy of the compounds increases more (3) N2,NH3,Mg(NO3)2
rapidly than the hydration energy (4) NH3,NO,Mg(NO3)2
(2) lattice energy of the compounds decreases more
rapidly than the hydration energy 53. A metal salt solution forms a yellow precipitate with
(3) size of the metals decreases on descending the K2CrO4 in acetic acid, a white precipitate with dil.
group H2SO4 but gives no precipitate with NaCl or NaI. The
(4) ionization energy of the metals increases on white precipitate obtained when Na2CO3 is added to
­descending the group the metal salt solution contains
(1) CaCO3
47. On descending the group 2, the ions of the
(2) SrCO3
­corresponding metals become larger. Therefore, the
(3) BaCO3
(1) lattice energy and the hydration energy of the (4) Basic magnesium carbonate
compounds decreases but the decrease in lattice
energy is small when anion is larger. 54. To two different samples of magnesium sulphate A
(2) lattice energy and hydration energy of the and B, sodium carbonate solution is added to ­sample
­compounds decreases but the decrease in lattice A and sodium bicarbonate solution is added to
­energy is small when anion is smaller. sample B. In both cases there appears
(3) lattice energy and hydration energy of the com- (1) white precipitate of MgCO3 in both A and B
pounds decreases but the decrease in hydration (2) white precipitate of MgCO3 in A and no
energy is more when anion is smaller. ­precipitate in B
(4) lattice energy and hydration energy of the (3) white precipitate of MgCO3 in A and white
­compounds decreases but the decrease in ­precipitate of MgCO3 . Mg(OH)2 in B
­hydration or lattice energy have no relation with (4) white precipitate of MgCO3 Mg(OH)2 in A and
the size of anion. white precipitate of MgCO3 in B on heating

Chapter_11.indd 20 3/26/2014 3:23:33 PM

 Alkaline Earth Metals  11.21

Answers 5. Statement I: The crystalline salt of alkaline earth

metals contain more water of crystallization than the
  (1)  2 (2)  2 (3)  4 (4)  2 (5)  3 (6)  2 corresponding salts.
  (7)  3 (8)  3 (9)  3 (10)  2 (11)  1 (12)  4 Statement II: Alkaline earth metals act as strong
(13)  2 (14)  4 (15)  3 (16)  3 (17)  2 (18)  4 ­reducing agents.
(19)  4 (20)  4 (21)  2 (22)  3 (23)  2 (24)  3
(25)  2 (26)  3 (27)  4 (28)  2 (29)  3 (30)  3 6. Statement I: Alkaline earth metals have lower
(31)  4 (32)  4 (33)  3 (34)  3 (35)  2 (36)  2 ­density than alkali metals.
(37)  3 (38)  4 (39)  1 (40)  2 (41)  2 (42)  1 Statement II: Atomic size of alkaline earth metals is
(43)  1 (44)  4 (45)  1 (46)  2 (47)  1 (48)  4 smaller than the corresponding metals.
(49)  4 (50)  4 (51)  4 (52)  1 (53)  3 (54)  4
7. Statement I: The elements of IIA Group are more
heavily hydrated than the elements of Group IA.
Statement II: The less electropositive the metal, the
weaker the tendency M → M+ and stronger the degree
 Statement-Type Questions of hydration.
In each of the following questions, a statement-I is given
followed by corresponding statement-II just below. Mark 8. Statement I: Beryllium salts never have more than
the correct answer as indicated. four molecules of water of crystallization.
(1) If both Statement I and Statement-II are true and Statement II: There are only four orbitals available
reason is the correct explanation of Statement I. in the second shell of beryllium.
(2) If both Statement I and Statement-II are true and
Statement-II is not the correct explanation of 9. Statement I: Magnesium gets oxidized when ­heated
Statement I. in CO2 atmosphere.
(3) If Statement I is true and Statement-II is false. Statement II: Magnesium has a strong affinity for
(4)  If Statement I is false but Statement-II is true. oxygen.

1. Statement I: Alkaline earth metals do not form 10. Statement I: BaSO4 is less soluble than CaSO4.
monovalent ions. Statement II: BaSO4 is much heavier than CaSO4.
Statement II: Alkaline earth metals possess
­maximum lattice energy. 11. Statement I: Magnesium does not impart character-
istic colour to the Bunsen burner flame.
2. Statement I: NaCl is added to anhydrous MgCl2 be-
Statement II: Ionization energy of magnesium is
fore electrolysis.
very high.
Statement II: Addition of NaCl to anhydrous MgCl2
during its electrolysis is made to lower the fusion 12. Statement I: Anhydrous CaCl2 cannot be used for
temperature. drying ammonia gas.
3. Statement I: Anhydrous MgCl2 is prepared by heat- Statement II: Ammonia is basic in nature.
ing MgCl2 . 6H2O in a current of dry HCl gas.
Statement II: Presence of HCl gas checks up the hy-
drolysis of MgCl2 by its own water of crytallization. Answers
4. Statement I: Be shows covalence while other ­alkaline   (1) 3   (2) 1 (3)  1 (4) 1   (5)  2
earth metals show electrovalence.
  (6) 4   (7) 1 (8)  1 (9) 1 (10)  3
Statement II: Be2+ shows more polarizing power (11) 1 (12) 2
­towards anion.

Chapter_11.indd 21 3/26/2014 3:23:33 PM

 11.22  Objective Chemistry - Vol. I

2. Match the following given in List I with those given

  Match the Following Type Questions in List II.
List-I List-II
1. Match the following given in List I with those ­given
in List II. (A)  Dolamite (i)  CaC2
(B) Metal carbide which on  (ii)  Mg
List-I List-II hydrolysis gives acetylene
(A) Deoxidizer in metallurgy       (I) MgO (C)  Metal used in flash bulbs (iii)  MgSO4 . 7H2O
(B) Refractory material in    (ii) Mg (D)  Epsom salt (iv)  CaCO3 . MgCO3
furnaces
 (V)  Ra
(C) Aeroplane parts  (iii) CaSO 4 × H 2 O (vi)  Be2C
(D) Absorbing agent for SO2 (iv) Mg + Al
near electrical generators The correct matching is
   (v) NaOH S. No. A B C D
1. IV VI II III
The correct matching is
2. V VI III II
S. No. A B C D 3. IV I II III
1. II II IV V 4. IV I III II
2. III I IV II
3. V II III IV
Answers
4. II V IV I
(1)  1 (2) 3

Chapter_11.indd 22 3/26/2014 3:23:34 PM

 12

Chapter
Group-III (13) Elements:
The Boron Family

• The elements boron, aluminium, gallium, indium • The abrupt increase in the atomic radius of aluminium
and thallium belong to III A group and p-block of the is due to greater screening effect of s- and p-electrons
­periodic table. in penultimate shell.
• The outer electronic configuration of these elements is • The atomic radii of gallium, indium and thallium are
ns2 np1. almost equal because of the poor shielding ­capacity of
• Owing to the difference in the electronic configuration d-electrons of penultimate shell than s- and p-electrons.
in penultimate shell, there is difference in the proper- • Density increases down the group. Comparatively, the
ties of these elements. low densities of B and Al are attributed to their lower
• Boron has two electrons, whereas aluminium has eight atomic weights.
electrons in their penultimate shells. Hence, they differ • Gallium is unusual because the liquid expands when
markedly in their properties. forms solid and thus solid Ga is less denser than
• Aluminium has eight electrons, whereas gallium, indi- liquid Ga.
um and thallium have 18 electrons in their penultimate • The melting points do not change regularly.
shells due to which there is difference in the proper- • The melting point of boron is very high because of its
ties of aluminium and gallium, and again indium and giant covalent polymeric structure in both solid and
thallium. liquid states.
• In III B group elements scandium, yttrium, lanthanum • The very low melting point (29.8°C) of gallium is
and actinium, the differentiating electron enters into ­attributed to the existence of Ga2 molecules. The liquid
(n−1) d-orbital. Therefore, their properties are differ- gallium remains in liquid state up to 2000°C and hence
ent from III A group elements. used in high-temperature thermometers.
• Aluminium is the third most abundant element and • Boiling points follow a regular decrease from boron to
first most abundant metal in the Earth crust. thallium.
• Gallium, indium and thallium are less abundant in nature. • Ionization potentials decrease from boron to alu-
• As thallium exhibits similarities with alkali metals minium but remain almost equal in the remaining
in +1 oxidation state and with the elements of boron elements. This is because of the poor shielding ­­effect
­family in +3 oxidation state, it is nick named as “duck- of d-electrons in gallium and indium, whereas in
billed platypus”. thallium due to the poor shielding effect of d- and
f-electrons.
• Owing to the shielding effect of ns2 electrons on np1
General Characteristics
electron, their first ionization energies are less but the
• Atomic and ionic radii increase from B to Tl. second and third ionization energies are high.
Element B Al Ga In Tl • III A group elements exhibit two types of oxidation
Atomic radius Å 0.80 1.26 1.26 1.50 1.55 states +1 and +3.

Chapter_12.indd 1 3/26/2014 3:21:53 PM

 12.2  Objective Chemistry - Vol. I

• Boron exhibits −3 oxidation state also. For example, • Elements of group III A have some tendency
Mg3B2. to form complexes such as [BF4]−, [AlCl4]-,
• If a pair of electrons are present in the valence shell [GaCl4 ]− , and [InCl4 ]−.
and are reluctant to participate in the bond formation, • The co-ordination number of boron is restricted to 4, as
it is known as inert pair and the effect is known as boron does not contain d-orbitals in its valence shell.
“inert pair effect”. However, the other elements can exhibit a ­covalency of
• Inert pair effect increases from boron to aluminium. up to 6, as these elements consist of vacant d-orbitals
in their valence shell. For example, [ AlF6 ] , [TlF6 ] .
3− 3−
• As the atomic number increases, the atomic size
­increases down the group and also owing to the poor • Tl in + III oxidation state acts as an oxidizing agent
shielding capacity of d- and f-electrons of penultimate because of its instability due to the inert pair effect.
shell, the ns2-electrons are attracted strongly by the • TlI is insoluble water but dissolves in excess of iodide
nucleus and hence remain as inert pair. concentration forming TlI3 which contains Tl+ and I 3−
• Owing to inert pair effect, the stability of +1 oxidation ions. However, in aqueous solution, hydrated Tl2O3 is
state increases, whereas the stability of +3 oxidation very insoluble. Therefore, Tl+ ion is oxidized by I2 of
state decreases from boron to thallium. I 3− ion to Tl3+ precipitating Tl2O3.
• In fact Tl (I) salts resemble alkali metals because ­thallium
is having large size and low oxidation state, for example,
  (i) TlOH is soluble in water yielding strong alkaline   Objective Questions
solution similar to NaOH. 1. A particular element belongs to III A group and II
 (ii) Tl (I) cyanide, perchlorate, sulphate, nitrate, period of the periodic table. It is
phosphate and carbonate are stable and isomor-
(1) Gas, slightly metallic.
phous with alkali metal salts.
(2) Liquid, metallic.
(iii) TlF is having distorted NaCl type structure,
(3) Solid, non-metallic.
whereas other thallous halides crystallize with
(4) Solid, less metallic.
CsCl structure.
  (iv) Similar to alkali metals, thallium (I) is known to 2. Aluminium and gallium have the same covalent radii
form alums. because of
For example, Tl2SO4 ∙ Al2(SO4)3 ∙ 24H2O. (1) Greater shielding power of s-electrons of Ga
• Unipositive ions in aqueous solutions are stable only ­atoms.
in the case of thallium; however, for other elements, (2) Poor shielding power of s-electrons of Ga atoms.
the unipositive oxidation state disproportionate. (3) Poor shielding power of d-electrons of Ga
• Boron never forms B3+ ion because the sum of three ­atoms.
ionization energies is very large. (4) Greater shielding power of d-electrons of Ga
­atoms.
• On account of small size with high charge of B3+, the
compounds of boron are covalent (Fajan’s rule). 3. Which of the following statements is false?
• The +3 oxidation state is largely covalent in other (1) Thallium shows different oxidation states ­because
­elements but the tripositive cations are known in aque- of inert pair effect.
ous solution as the hydration energy of tripositive ion (2) Stable compounds in +1 oxidation state are
exceeds the sum of the three ionization energies. formed by thallium.
• The trivalent hydrated metal ions undergo hydrolysis (3) Inert pair is a pair of outmost electrons which act
as inert.
to form acidic solutions.
(4) Among III A group elements, aluminium is ­present
• The important feature of the III A group elements in cations only.
is that the electronegativity decreases from boron to
aluminium but then increases to thallium an opposite 4. Boron differs from the other members of III A group
trend generally observed in other groups. because it
• The reduction potentials increase from boron to thallium (1) has much lesser radius.
so the reducing nature of the metals decreases down the (2) is non-metal.
group but aluminium has a very low reduction potential (3) is covalent in its compounds.
and hence is a strong reducing agent in the III group. (4) has maximum covalency of 6.

Chapter_12.indd 2 3/26/2014 3:21:58 PM

 Group-III (13) Elements: The Boron Family   12.3

5. Which of the following statements is false? Answers

(1) The most abundant metal in the Earth crust is
aluminium.   (1) 3   (2) 3   (3) 4   (4) 2   (5) 3
(2) Boron never form B3+ ion.   (6) 3   (7) 1   (8) 1   (9) 1 (10) 3
(3) Among III A elements, boron has the lowest
melting point.
(4) Owing to small size and more charge on M3+ ion
of III A group elements, their aqueous solutions Reactivity of Group III A
are acidic, and their acidic nature increases from Elements
Al3+ to Tl3+.
• Amorphous boron is more reactive than crystalline
6. An element R is in III A group. Which is true with boron, as more number of bonds have to be broken in
respect to R? crystalline boron.
(1) It is a gas at room temperature. • Aluminium is stable in air because of the formation of
(2) It has an oxidation state of +4. a protective oxide film.
(3) It forms an oxide of the type R2O3. • In the absence of the oxide layer, aluminium rapidly
(4) It forms a halide of the type RX2. gets oxidized and decomposes water.
7. Which of the following statements is wrong? • Gallium and indium are stable in air and are not
(1) The electronegativity of III A group elements ­attacked by water except when free oxygen is present.
­decreases from aluminium to thallium. • Thallium is a little more reactive and is superficially
(2) Among III A group elements, Ga has the least oxidized in air.
melting point, whereas B has the highest melting • Boron and aluminium react with oxygen in air forming
points. B2O3 and Al2O3.
(3) Liquid gallium expands during conversion into
solid. • The reaction of aluminium with oxygen is highly
(4) Liquid gallium is used in thermometers, as it ­exists exothermic.
in liquid state in a wide range of ­temperatures. • Aluminium in massive form is less reactive because of
less surface area and the oxide layer. However, if finely
8. Boron differs from other members of III A because divided, aluminium explodes when it comes in contact
of its with liquid oxygen, as the extent of reaction is more
(1) small size, high ionization potential and absence and the heat liberated is more because of large surface
of d-orbitals. area.
(2) large size, low ionization potential and presence
• Boron is not affected by water but decomposes steam
of d-orbitals.
at red-hot condition liberating H2.
(3) small size, low ionization potential and absence
of d-orbitals. • Thermodynamically aluminium should react with
(4) large size, high ionization potential and absence water but owing to the presence of oxide layer on the
of d-orbitals. surface, it does not react with cold water.
• Aluminium corrodes in salt water, as the salts remove
9. Which species does not exist?
the oxide layer. Therefore, aluminium vessels should
(1) BF63− (2)  AlF63− not be kept with water overnight. Aluminium decom-
(3) GaF63− (4)  InF63− poses steam.
10. The electropositive character increases from B to Al • Boron does not react with non-oxidizing acids such
and then decreases from Al to Tl because of as HCl but reacts with oxidizing acids such as conc.
HNO3 and conc. H2SO4 forming boric acid.
(1) the decrease in the ionization energy of the
­elements. • Aluminium readily dissolves in dil. or conc. HCl and
(2) the increase in the size of the elements. the reaction becomes vigorous with the increase in the
(3) the ineffective shielding of nuclear charge by concentration of HCl.
d-electrons increases from Ga to In to Tl. • Cold dil. H2SO4 does not attack the aluminium ­because
(4) the decrease in the electronegativity of the of oxide layer but hot dil. H2SO4 liberates H2, as the
­elements. oxide layer dissolves in hot condition.

Chapter_12.indd 3 3/26/2014 3:21:59 PM

 12.4  Objective Chemistry - Vol. I

• Aluminium liberates SO2 with conc. H2SO4. • The meta aluminate ion in solution exists as hydrat-
• Very dilute nitric reacts slowly with impure aluminium ed metahydroxo aluminate ion [Al(OH)4]− (aq) or
forming aluminium nitrate and ammonium nitrate. [Al(OH)4(H2O)2]−, whereas the aluminate ion exists as
Conc. HNO3 makes aluminium passive because of the [Al(OH)6]3−; however, in both cases, the co-ordination
formation thin oxide layer on the surface. number of aluminium is 6.
• Amalgamation with mercury or in contact with solu- • Gallium also dissolves in alkalis forming gallates.
tion of certain salts, which can destroy the oxide layer, • Only boron reacts with metals forming metal borides.
increases the reactivity of aluminium. • At high temperatures, boron reacts directly with all the
• Gallium also rendered passive with conc. HNO3. non-metals except hydrogen.
• Boron does not react with alkalis at low temperatures; • Aluminium combines with most of the non-metals on
however, at high temperatures, borates are formed heating.
­liberating hydrogen. • When heated with ammonia, both boron and alumini-
• Aluminium reacts with strong alkalis forming meta um form nitrides.
aluminates or aluminates liberating hydrogen.

Reactions of Boron

Reaction Remark
1.  B + O2 
→ B2O3 at high temperature
2.  B + S → B2S3 at high temperature
3.  B + N2 
→ BN at high temperature
4.  B + X2 
→ BX3 X = F, Cl, Br, I
5.  B + NaOH → Na3BO3 + H2 Fused with alkali
6.  B + NH3 → BN + 3H2
7.  B + M → MxBy Highly electropositive metals from borides.

Chemical Reactivity of Group III A (Except Boron Elements)

Reaction Remark
1.  Action of air Al corrodes in air, but corrosion is prevented by its oxide layer. When
    M + O2  → M2O3 burnt in air, it forms M2O3. Tl forms some M2O3. Al also forms AlN.
Powdered Al explodes in air because of highly exothermic reaction.
2.  M + H2O 
→ M2O3 + H2 Al does not react with pure H2O because of oxide layer but corrodes easily
in salt water. Al decomposes steam.
3.  M + acid → Al reacts with acids. It becomes passive with conc. HNO3.
4. M + NaOH  → NaMO2 + H2 Only Al and Ga react with alkalis.
          Na3MO3 + H2
5.  M + X2  → MX3 ( )
Al forms trihalides; TlI3 is Tl+ I 3− .

12. Aluminium reacts with nitrogen to form

  Objective Questions (1) AlN (2)  Al2N3 (3)  Al2N (4)  Al4N6
11. When aluminium is added to potassium hydroxide 13. Which of the following cannot liberate hydrogen with
solution acids?
(1) No reaction takes place. (1) Al (2)  In (3)  Tl (4)  B
(2) Oxygen is evolved.
(3) Water is produced. 14. Conc. HNO3 can be stored in a container of
(4) Hydrogen is evolved. (1) Cu (2)  Al (3)  Fe (4)  Zn

Chapter_12.indd 4 3/26/2014 3:22:01 PM

 Group-III (13) Elements: The Boron Family   12.5

15. Which of the following statements is not true for (3) Aluminium vessels should not be washed with
Al and B? washing powders containing washing soda, because
(1) They burn in oxygen to give oxides at high it reacts with aluminium to form soluble aluminate.
­temperature. (4) Aluminium dissolves in ammonium hydroxide
(2) They react with nitrogen to form nitrides. liberating hydrogen.
(3) They react with HCl to give chlorides. 23. In the reduction of sulphate ion to sulphur dioxide
(4) They react with alkalis liberating hydrogen. by aluminium, the number of electrons given by
16. The non-metal character of boron is indicated by ­aluminium atom per each sulphate ion is
(1) reaction with metals forming borides (1) 2 (2)  3 (3)  6 (4)  1.5
(2) liberation of hydrogen with alkalis 24. The co-ordination number of aluminium in meta
(3) basic nature of its oxide ­aluminate and aluminates, respectively, is
(4) reaction with metals forming alloys
(1) 4, 4 (2)  4, 6 (3)  6, 4 (4)  6, 6
17. Aluminium becomes passive because of the forma-
tion of oxide layer by Answers
(1) conc. H2SO4 (2)  conc. HCl
(3) dil. HNO3 (4)  conc. HNO3 (11) 4 (12) 1 (13) 4 (14) 2 (15) 3
(16) 1 (17) 4 (18) 4 (19) 4 (20) 4
18. In the reaction of aluminium with dilute sodium (21) 3 (22) 4 (23) 1 (24) 4
hydroxide solution, which of the following is not
­correct?
(1) Hydrogen gas will be liberated.
(2) Sodium meta aluminate is formed. compounds of group III A (13)
(3) The product exists as [Al(OH)4 . 2H2O]-. elements
(4) Co-ordination number of aluminium in the a comparative study
­product is 4. Hydrides
19. Hydrogen is not liberated when aluminium reacts with
• III A Group elements do not react with hydrogen
(1) boiling water ­directly but form hydrides by indirect methods.
(2) hot conc. NaOH
(3) conc. HCl • Boron forms large number of hydrides called ­“boranes”
(4) conc. H2SO4 with general formula BnHn+4 and Bn Hn+6.
• Indium hydride (InH3)n is a polymeric unstable
20. When concentrated solution of caustic soda is boiled hydride.
in an aluminium container
• Aluminium forms only one polymeric hydride called
(1) NaOH does not crystallize. “alane”.
(2) Na is displaced by Al.
• Gallium hydride gallane GaH3 is unstable.
(3) O2 is liberated.
(4) H2 is displaced. • Indium hydride (InH3)n is a polymeric unstable
hydride.
21. Aluminium is more reactive than iron. However,
• Boron, aluminium and gallium form complex as ionic
­aluminium is less easily corroded than iron because
hydrides, for example, Na[BH4], Li[AlH4]. In these
(1) Aluminium is a metal. complex hydrides, the hydride ion acts as Lewis base
(2) Iron undergoes reaction easily with water. (electron donor) and XH3 group acts as Lewis acid
(3) Oxygen forms a protective layer. (electron acceptor).
(4) Iron forms mono- and divalent ions.
• The stability of these complex hydrides increases with
22. Which of the following statements is false? the increase in the polarizing power of cation. In the
(1) The metal that is protected by its own oxide layer alkali metal, borohydride’s stability decreases with the
is aluminium. increase in the size of cation.
(2) Aluminium vessels are easily corroded in coastal • These are good reducing agents and are mainly used to
areas of sea, because the oxide layer is removed reduce aldehydes and ketones to alcohols and nitrites
by salts present in sea water. to amines.

Chapter_12.indd 5 3/26/2014 3:22:01 PM

 12.6  Objective Chemistry - Vol. I

Oxides • All the group III B elements form trihalides of the

type MX3.
• Group III A elements form sesquioxides of the type
• TlCl3 and TlBr3 are unstable and tend to lose halogen
M2O3.
on heating forming thallium (I) halide.
• These elements except boron also form monoxides
• Owing to oxidizing nature of Tl3+ ion and reducing
which are unstable. Thallium monoxide is stable, but
nature of I− ion, thallium does not form thallium (III)
its sesquioxide is unstable.
iodide but forms TlI3 which contains Tl+ and I3− ions.
• B2O3 is acidic; Al2O3 and Ga2O3 are amphoteric; and
• All the boron trihalides are stable and covalent.
In2O3 though appears as amphoteric, it is mostly basic.
Tl2O and Tl2O3 are purely basic. • Flourides of Al, Ga, In and Tl are ionic and have high
melting points.
• In these oxides, acidic character decreases, whereas
basic character increases down the group. • Chlorides, bromides and iodides of these elements are
largely covalent when anhydrous but ionize in their
• Tl2O behaves similar to alkali metal oxides.
aqueous solutions.
• Ionic character of these halides increases with the
Hydroxides
­increase in the size of action.
• These elements form hydroxides of the type M(OH)3. • The trichlorides, tribromides and triiodides of Al,
• Hydroxides of boron and aluminium are formed when Ga and In can be obtained by direct combination of
their oxides react with water. elements.
• Owing to small size and high charge (+3) of these • These trihalides are relatively volatile and have layer
ions, their hydroxides have some acidic character. lattices containing dimeric molecules.
• The acidic character of these hydroxides decreases • The dimeric molecules exist in the vapour phase and also
from boron to thallium, whereas their basic character in the solutions of the compounds in organic solvents.
increases. • Trihalides hydrolyse in water or in moist air giving
• H3BO3 is acidic; Al(OH)3, Ga(OH)3 and In(OH)3 are fumes.
amphoteric, but the basic character increases from BCl3 + 3H2O  → H3BO3 + 3HCl
Al(OH3) to In(OH)3; and Tl(OH)3 is purely basic. AlCl3 + 3H2O  → Al(OH)3 + 3HCl
Except H3BO3, the remaining hydroxides are insoluble
in water. Lewis Acid Character of  Trihalides
• Thallous hydroxide (TlOH) is a strong base and
­resembles the alkali metal hydroxides. It is soluble in • The trihalides of group III A elements are electron-
water. deficient compounds, as the octet is not completed and
hence they act as Lewis acids.
• The Lewis acidic strength of boron trihalides is found
Halides
to be in the order BF3 < BCl3 < BBr3. This is the re-
• Group III A elements form three types of halides, viz. verse order of what is expected on the basis of elec-
monohalides, dihalides and trihalides. tronegativities of halogens.
• Except thallium monohalides, other monohalides are • This anomalous behaviour is due to the tendency of
unstable. the halogen atom to back donate its lone pair electrons
to the vacant p-orbital of boron.
• Thallium monohalides resemble silver (I) halides. F
TlF is soluble, but other thallium monohalides are F F F B
F B F B F
insoluble. F
F
• The dihalide of boron B2Cl4 exists in two forms • Owing to the back donation of electron pair by the hal-
eclipsed and non-eclipsed because of free rotation ogen, the electron deficiency of boron atom decreases
about B–B bond. partially.
Cl Cl Cl Cl • The lateral overlap of p-orbitals of halogen and boron
B B B B is more effective in the case of BF3 because in both
Cl Cl Cl Cl ­boron and fluorine 2p-orbitals having nearly same
Planar Non-eclipsed ­energy overlap.

Chapter_12.indd 6 3/26/2014 3:22:02 PM

 Group-III (13) Elements: The Boron Family   12.7

• As the size and energy of valence p-orbital of halogen 26. Halides of III A group elements are predominantly
increase, the overlap is less effective and hence back known as
donation decreases. (1) Lewis acids (2)  Lewis bases
• Owing to back bonding, the B–F bond gets double (3) Neutral halides (4)  Arrhenius acids
bond character and its bond length shortens and be-
27. BF3 adducts with NH3 because
comes less than the sum of covalent radii of boron and
fluorine. (1) N contains the highest electronegativity.
(2) N contains the lowest atomic size.
• When boron halides form addition compounds with (3) NH3 contains lone pair of electrons and BF3 is
Lewis bases, such as ethers, amines, phosphines, electron-deficient molecule.
­alcohols, anions and carbon monoxide, the back bond- (4) Boron contains the lowest atomic size.
ing is absent so the B–X bond strength decreases.
• During the formation of addition compounds with 28. Which of the following statements is correct?
Lewis bases, the hybridization of boron changes from (1) The hydroxide of aluminium is more acidic than
sp2 to sp3 disrupting the B–X π dative bond in BX3. that of boron.
(2) The hydroxide of boron is basic, whereas that of
• The enthalpy change for the adduct formation is more
aluminium is ampthoteric.
negative for BBr3 and least for BF3 indicating that
(3) The hydroxide of boron is acidic, whereas of
the energy required to break the B–F π dative bond is
­aluminium is amphoteric.
more.
(4) The hydroxides of boron and aluminium are
• As the B–F π dative bond is stronger, BF3 will have ­amphoteric.
less tendency to form addition compound and act as a
weak Lewis acid. 29. Which of the following statements about BF3 is false?
• The halides of other group III A elements are also elec- (1) It is an electron-deficient compound.
tron deficient and can act as Lewis acid. However, the (2) It is a Lewis acid.
Lewis acid character decreases down the group with (3) It is a solid at room temperature.
the increase in the atomic size of Group III elements. (4) It is a covalent compound.
• The Lewis acidic character also depends on the hard 30. Which of the following statements is false?
and soft nature of Lewis bases. The order towards hard (1) Oxides of Al and Ga are amphoteric.
bases is BCl3 > AlCl3 > GaCl3; however, towards soft (2) TlI3 is a stable compound.
bases, the order will be reversed GaX3 > AlX3 > BX3. (3) Basic character of hydroxides increases on
­moving down the group 13.
Structure (4) The oxide and hydroxide of boron are acidic in
nature.
• Boron trihalides exist as monomers only. BF3 exists 31. Aluminium (III) chloride forms dimer because
only as monomer because of strong back bonding;
(1) higher co-ordination number can be achieved.
however, in other trihalides, boron cannot be co-­
(2) aluminium has high ionization energy.
ordinated with four bigger halogen atoms.
(3) aluminium belongs to III group.
• The trihalides of aluminium, gallium and indium ex- (4) it cannot form a trimer.
ist as dimers which contain halogen bridge bonds, one
with covalent bond another with dative bond and thus 32. AlCl3 is
forming three centre and four electron bonds. (1) anhydrous and covalent.
• As fluorides of the group III A elements (except boron) (2) anhydrous and ionic.
are ionic, they contain ion pairs and not molecules. (3) covalent and basic.
(4) co-ordinate and acidic.
33. Which of the following is the correct order of the
  Objective Questions
strength of Lewis acid?
25. Boron compounds behave as Lewis acids because of (1) BBr3 > BCl3 > BF3
their (2) BCl3 > BBr3 > BF3
(1) Acidic nature (2)  Covalent nature (3) BF3 > BCl3 > BBr3
(3) Electron deficiency (4)  Ionization property (4) BCl3 > BF3 > BBr3

Chapter_12.indd 7 3/26/2014 3:22:02 PM

 12.8  Objective Chemistry - Vol. I

34. Which of the following does not act as Lewis acid? Answers
(1) AlCl3 (2)  AlCl3 . 6H2O
(3) FeCl3 (4)  SiCl4 (25) 3 (26) 1 (27) 3 (28) 3 (29) 3
(30) 2 (31) 1 (32) 1 (33) 1 (34) 2
35. Which of the following statements is correct?
(35) 1 (36) 2 (37) 3 (38) 4 (39) 4
(1) BCl3 and AlCl3 are both Lewis acids and BCl3 is (40) 4
stronger than AlCl3.
(2) BCl3 and AlCl3 are both Lewis acids and AlCl3 is
stronger than BCl3.
(3) BCl3 and AlCl3 are both equally strong Lewis AnOmalous Behaviour of Boron
­acids. Differences
(4) Both BCl3 and AlCl3 are not Lewis acids.
• The reasons for the anomalous properties of boron are
36. TlI3 is an ionic compound which furnishes the fol-
(i) small size (ii) high electronegativity (iii) the
lowing in solution.
­presence of two electrons in the penultimate shell
(1) Tl3+ and I− ions (2)  Tl+ and I3− ions (iv) high IP values
3+ −
(3) Tl , I ions and I2 (4)  Tl+ and I− ions
• Boron is a non-metal but other elements are metals.
37. BCl3 does not exist as a dimer but BH3 exist as a • Small size and high charge make the ion B3+ highly
­dimer (B2H6) because polarizing power. Thus, it does not exist. Therefore,
(1) chlorine is more electronegative than hydrogen. almost all boron compounds are covalent.
(2) there is pπ–pπ back bonding in BCl3 but BH3 • The maximum covalency of boron is 4, as it has no
does not contain such multiple bonding. d-orbitals in its valence shell but other elements can
(3) large-sized chlorine atoms do not fit in between exhibit a maximum covalency of 6.
the small boron atoms, whereas small-sized hy-
drogen atoms get fitted in between boron atoms. • Boron combines with metals forming borides but
(4) None of the above. other elements are metals and form alloys.
• Boron cannot react with non-oxidizing acids such as HCl.
38. Which of the following statements is correct?
• Boron cannot decompose water or steam, whereas
(1) B(OH)3 is acidic but Tl(OH)3 is basic.
other elements can.
(2) The pπ–pπ back bonding occurs in the halides of
boron but not in halides of Al. • Boron is non-conductor, whereas other elements are
(3) Aluminium sulphide gives a foul odour when it good conductors of electricity.
becomes damp. • Boron exhibits allotropy but other elements do not
(4) All are correct. ­exhibit allotropy.
39. Which of the following statements is correct for • Boron forms large number of volatile hydrides which
­halides of Al, Ga and Tl? are electron-deficient compounds. However, other
­elements form only one polymeric hydride. Thallium
(1) In anhydrous state, these halides are largely
does not form hydride.
­covalent.
(2) These halides do not show back bonding. • B2O3 is acidic, whereas the similar oxides of the other
(3) The metal atoms complete their octet by forming elements are either amphoteric or basic.
dimers. • Boron halides are monomeric, whereas the halides of
(4) All are correct. the other elements (except thallium) are dimeric.
40. Fluorine is more electronegative than either boron
or phosphorous. What conclusion can be drawn Similarities between Boron and
from the fact that BF3 has no dipole moment but PF3 Aluminium
does?
(1) BF3 is not spherically symmetrical but PF3 is. • Both B and Al have same outer electronic configuration.
(2) BF3 molecule must be linear. • Both these elements exhibit +3 oxidation state.
(3) The atomic radius of P is larger than that of B. • Both these elements form covalent compounds,
(4) The BF3 molecule must be planar triangular. ­however, Al can also form ionic compounds.

Chapter_12.indd 8 3/26/2014 3:22:03 PM

 Group-III (13) Elements: The Boron Family   12.9

• Both these elements form similar sesquioxides of the 43. Boron differs from the other elements of the group
type M2O3. because it has
• The chlorides of both elements are formed by direct (1) a different configuration in its penultimate shell.
reaction and these are covalent electron deficient and (2) a valence shell electronic configuration of s2 p1.
act as Lewis acids. These chlorides hydrolyse in water. (3) 10 d-electrons in third orbit.
• Both react with nitrogen forming nitrides which on (4) high ionization potential.
hydrolysis liberate ammonia. 44. Which of the following statements is not true for
• Both dissolve in alkalis forming borates and alumi- Al and B?
nates with the liberation of hydrogen gas. (1) Boron is insulator but aluminium is a good
• Both react with conc. H2SO4 liberating SO2. ­conductor.
(2) Boron and aluminium both exhibit allotropy.
Diagonal Relationship of Boron with Silicon (3) Boron always present in anions but aluminium
exists in both cations and anions.
• Both boron and silicon are typical non-metals with high (4) B2O3 is acidic, whereas Al2O3 is amphoteric.
melting points and are bad conductors of electricity.
45. Boron differs from the other members of III A group
• Both exhibit allotropy. because it
• Their electro negativities are almost similar (B = 2.0; (1) has much lesser radius.
Si = 1.8). (2) is a non–metal.
• Their ionization energies are similar. (3) is covalent in its compounds.
• Their oxides B2O3 and SiO2 are weakly acidic. (4) has a maximum covalency of 6.
• Both can be prepared by the reduction of their oxides
with magnesium. Answers
• Both form carbides B4C and SiC, which are very hard.
(41) 4 (42) 2 (43) 1 (44) 2 (45) 2
• Both react with metals forming borides and silicides.
• Both combine with halogens directly forming covalent
halides, which act as Lewis acids.
Boron
• Both form large number covalent hydrides, which are
volatile and inflammable. • Important minerals of boron are
   (i)  Borax or tincol Na2B4O7 ∙ 10H2O
• Both these elements and their oxides react with alkalis
  (ii)  Kernite or rasorite Na2B4O7 ∙ 4H2O
forming borates and silicates.
(iii)  Boracite 2Mg3B8O15 ∙ MgCl2
  (iv)  Colemanite Ca2B6O11 ∙ 5H2O
  Objective Questions    (v)  Pandernite Ca2B6O11 ∙ 3H2O
 (vi)  Borocalcite CaB4O7 ∙ 4H2O
41. Boron differs from the other elements of its own
(vii)  Boric acid H3BO3
group in several properties. The anomalous behav-
iour of boron may be attributed to • Preparation of boron involves two stages
(i)  preparation of boron trioxide
(1) its small size and high ionization energy.
(ii)  reduction of boron trioxide
(2) its high electronegativity.
(3) the presence of only two electrons in the penul- • Borax when treated with conc. HCl or conc. H2SO4
timate shell and the absence of d orbitals in the gives boric acid which on heating gives B2O3
valence shell. Na2B4O7 + 2HCl  → 2NaCl + H2B4O7
(4) All of the above. H2B4 O7 + 5H2O  → 4H3BO3
42. Which of the following is a false statement? 2H3BO3 ∆ → B2O3 + 3H2O
(1) Boron does not form B3+ ion. • Fusion of colemanite with sodium carbonate forms
(2) Boron shows inert pair effect. insoluble CaCO3 and soluble NaBO2 and Na2B4O7.
(3) Aluminium carbide on hydrolysis gives methane. • If CO2 gas is passed into the solution of NaBO2 solu-
(4) Boron nitride gives ammonia on hydrolysis. tion, it converts into Na2B4O7.

Chapter_12.indd 9 3/26/2014 3:22:03 PM

 12.10  Objective Chemistry - Vol. I

Ca2B6O11 + 2Na2CO3  → CaCO3 ↓ + Na2B4O7 + 49. Boron can be obtained by various methods but not by
2NaBO2 (1) Thermal decomposition of B2H6.
4NaBO2 + 4CO2  → Na2B4O7 + Na2CO3 (2) Pyrolysis of BI3.
(3) Reducing BCl3 with H2.
• Reduction of B2O3 with electropositive metals such as
(4) Electrolysis of fused BCl3.
Na, K, Be, Ca, Al and Fe gives boron.
• The boron obtained by the reduction of B2O3 with 50. Which of the following gives boron directly by heating?
magnesium is about 95–98% pure and is called (1) B2H6 (2)  BI3
“Moisan boron”. (3)  BCl3 (4)  Both 1 and 2
• Crystalline boron can be prepared by the reduction of 51. Pure boron is best prepared by
BCl3 with zinc. (1) heating B2O3 with H2.
• Thermal decomposition of boron hydrides at about (2) heating B2O3 with Na or K.
900°C gives amorphous boron. BI3 gives crystalline (3) heating KBF4 with Na or K.
boron. (4) heating BBr3 with H2 in the presence of catalyst.
• Crystalline boron contains the clusters of boron atoms
arranged in regular icosahedron.
• Boron is used Answers
   (i) as a deoxidizer for metals in the form of calcium
boride. (46) 2 (47) 2 (48) 4 (49) 4 (50) 4
 (ii) in making boron steels, which are very hard and (51) 2
used in nuclear reactors as controlling rods.
(iii) as abrasive in the form of metallic borides.
 (iv) as a rocket fuel in the form of boron hydrides.
• Boron steel or boron carbide rods are used to control compounds of boron
the nuclear reactions as boron has very high cross-
sectional area to capture neutrons. 1.  Boron Trioxide or Boric Oxide B2O3
• It is prepared by heating boron or boric acid to red-hot
condition.
  Objective Questions
• It is also obtained by the dehydration of boric acid over
phosphorous pentoxide.
46. A boron carbide rod is used in a nuclear reactor
­because (10B) has very • It is a colourless transparent glassy mass.
(1) low cross-sectional area for capturing neutrons. • It is hygroscopic and when exposed to atmosphere,
(2) high cross-sectional area for capturing neutrons. it converts into metaboric acid and orthoboric acid
(3) low cross-sectional area for removing positrons. ­absorbing moisture.
(4) high cross-sectional area for capturing neutrions. • It can be reduced to boron by the metals such as Na, K,
47. When borax is treated with mineral acids, the product Mg and Al.
formed is • It is acidic and can displace other volatile acids.
(1) Boron oxide K2SO4 + B2O3  → 2KBO2 + SO3
(2) Orthoboric acid CuSO4 + B2O3  → Cu(BO2)2 + SO3
(3) Metaboric acid
The corresponding metaborates of transition metals
(4) Pyroboric acid
are coloured glassy bead and used for the identifica-
48. Borax is converted into crystalline boron by the tion of the metals. This is known as “borax bead test”.
­following steps • It reacts with very strong acidic oxides showing its
Borax X → H3BO3 ∆ → B2O3 ∆y →B feeble basic character. (Recently, these are considered
X and Y are, respectively mixed oxides.)
(1) HCl, Mg (2)  HCl, C B2O3 + 3SO3  → B2(SO4)3
(3) C, Al (4)  HCl, Al B2O3 + P2O5  → 2BPO4

Chapter_12.indd 10 3/26/2014 3:22:05 PM

 Group-III (13) Elements: The Boron Family   12.11

2.  Boric Acids • Boric acid is used

   (i) in making enamels, pottery glazes and glass
• Several boric acids are known industry.
  (i)  Orthoboric acid H3BO3 (or) B2O3 ∙ 3H2O  (ii)  as antiseptic and in medicine (eye-lotion).
(ii)  Metaboric acid HBO2 (or) B2O3 ∙ H2O (iii)  as food preservative.
(iii)  Pyroboric acid H6B4O9 (or) 2B2O3 ∙ 3H2O
  (iv)  Tetraboric acid H2B4O7 (or) 2B2O3 ∙ H2O Summary of the Reactions of
• The simplest acid is “orthoboric acid”. Boric Acid
NaBO2
• It can be obtained by adding conc. HCl or conc. H2SO4
to borax.
NaOH
HBO2 160° C
• It is also formed when sulphur dioxide gas is passed H2B4O7

through a suspension of powdered colemanite. Na2B3O7

100°
Ca 2 B6 O11 + 4SO2 + 11H 2 O 
→ 2Ca(HSO3 )2 Red

HC S O 4
Borate peroxo hydrates

H2
hot

lo
and peroxo borates
+ 6H 3 BO3

r
H
Na 2 O2
2O
• It is formed by passing super heated steam over boron 2
Red hot Na or K or
NH4BF4 Fusion with NH4 HF2 H2BO3 B2O3 Mg or Fe B
nitride or boron sulphide.
r s
2BN + 3H2O  → H3BO3 + 2NH3 ∆ B2O3 ls o ol H C + Halogen
dio lcoh 2O
Cis ric a
d

RCOCl
B2S3 + 6H2O  → 2H3BO3 + 2H2S

n s
yhy

sio de

(R
pol

fu oxi

CO
BF3 BX3
Acidic

) 2O
eta
• It is moderately soluble in cold water, and its solubility

M
chelate
increases with the increase in the ­temperature. complexes Borates B2O(RCOO)4
B(RCOO)3
• It is volatile in steam and imparts green colour to acyl borate
­non-luminous flame.
• On heating, it converts into metaboric acid, tetraboric 3. Metaboric Acid
acid and finally to boron trioxide.
• It is obtained by heating orthoboric acid at 375 K
H3BO3 375
→ HBO2 435
→ H2B4O6 red
 hot
→ B2O3 (100°C).
• It is a very weak monobasic Lewis acid. It cannot • It is a white solid stable below 475 K, above which it
­liberate H+ ion but liberates H+ ion from water by decomposes to boric anhydride.
−
­accepting OH− forming  B (OH )4  . • It converts into B2O3 on heating to red-hot condition that
• As it is weak acid, it cannot be titrated accurately converts into orthoboric acid when dissolved in water.
with sodium hydroxide solution. However, the acidic
strength of H3BO3 increases in the presence of poly 4. Sodium Tetraborate or Borax or Tincol
hydroxy compounds such as mannitol, sorbitol, Na2B4O7 ∙ 10H2O
­glucose, glycerol and glycols because of the forma-
• Borax occurs naturally as tincol.
tion of complex. Then, it can be titrated with NaOH
solution using phenolphthalein as ­indicator. • When the mineral colemanite is boiled with sodium
carbonate, insoluble CaCO3 and soluble Na2B4O7 and
• When boric acid is heated with ethyl alcohol in the
NaBO2 are formed. After removing CaCO3, if CO2 is
presence of conc. H2SO4, the ethyl borate vapours
passed, the metaborate also converts into tetraborate.
formed burns with green-edged flame. This property
is used for the detection of borates. • Borax is sparingly soluble in cold water but highly
soluble in hot water.
• In boric acid, boron is in sp3 hybridization, and in bond
with three OH groups, in planar triangular manner. • If a saturated solution of borax is allowed to crystallize
Such several planar triangular units are joined together at room temperature, “ordinary” or “prismatic borax”
through hydrogen bonds forming two-dimensional Na2B4O7 ∙ 10H2O separates out.
sheets. Thus, boric acid has layered lattice structure. • If crystallization is carried at about 62°C, octahedral
• As the layers in solid boric acid are held by weak Van or “Jeweller’s borax” Na2B4O7 ∙ 5H2O separate.
der Waals forces, boric acid is slippery and can be • When heated to red-hot condition, it loses the water
used as solid lubricant. and swells up into porous mass owing to the expulsion

Chapter_12.indd 11 3/26/2014 3:22:06 PM

 12.12  Objective Chemistry - Vol. I

of water and finally forms clear glass called ­“borax 5.  Boron Halides
glass” which again converts into decahydrate by
•  F3 is prepared by heating a mixture of fluorspar and
B
­absorbing moisture from air.
boron trioxide with conc. H2SO4.
• Its aqueous solution is alkaline because of ­hydrolysis.
3CaF2 + B2O3 + 3H2SO4  → 2BF3 + 3CaSO4 + 3H2O
Na2B4O7 ∙ 7H2O    4H3BO3 + 2NaOH • Other boron trihalides are prepared by heating ­boron
• On heating with ammonium chloride, it gives ­boron trioxide with carbon in the presence of ­halogen.
nitride.
B2O3 + 3C + 3H2   → BX3 + 3CO (x = Cl, Br or I)
Na2B4O7 + 2NH4Cl  → 2BN + B2O3 + 3NaCl +
• BF3 is a gas, BCl3 is a liquid, BBr3 is a viscous ­liquid
 4H2O
and BI3 is a crystalline solid.
• Borax on heating forms a transparent glassy mass
• The melting points and boiling points of boron halides
called “borax bead” which gives characteristic
increase with the increase in the atomic ­number of
­coloured bead on heating with a transition metal ion
halogen.
because of the formation of metal metaborates. This is
known as “borax bead test”. BI3 > BBr3 > BCl3 > BF3

Na 2 B4 O7 ⋅10 H 2 O −
heat
→ Na 2 B4 O7 heat
→ NaBO2 + B2 O3 • All the trihalides of boron hydrolyse in water.
H2 O 
Glassy bead • The hydrolysis products of BF3 are different from
CuSO 4 + B2 O3 
→ Cu(BO2 )2 + SO3 ­others because of the stronger B–F bond. BF3
­hydrolyses incompletely.
Blue.
4BF3 + 3H2O  → H3BO3 + 3H+ + 3[BF4]−
• Borax is used BF4 + H2O 
−
→ [BF3OH]− + HF
  (i) in the manufacturing of optical glass, soap, drying
oils, glazes, enamels, paper, plastic and leather.
 (ii) in the metallurgy, soldering and in welding as flux.
(iii)  for stiffening candle wicks. Reactions of Boron Halides
  (iv)  in the preservation of food.
Reaction Remark
  (v)  as water softening compound
 (vi) as an antiseptic and eyewash under the name Boron trifluoride
­boric lotion. 1. BF3 + H2O  → H3BO3 + HF + + [BF3OH]−
• Boric acid has the following structure. 2. BF3 + B2O3 ∆→ NH4BF4
OH 3. BF3 + RMgBr  → RBF2, R2BF, R3B
 
  4. BF3 + NH3 . NR3 
→ F3B . NH3, F3B . NR3
 HO B O B O
O B OH 8H2O 5. BF3 + Ether → BF3 . OR2
 O B O 
  6. BF3 + NaBH4 Ether
 → B2H6
  7. BF3 + CH3CN  → F3B . NCCH3
OH
Al Cl or Al Br
  (i) In borax, two boron atoms are in sp2 hybridiza- 8. BF3 
2 6 2 6
→ BCl3 or BBr3
tion and the remaining two boron atoms are in sp3 9. BF3 → B2H6
NaH or BF4

hybridization.
(ii) The sp2 hybrid boron atoms are planar, whereas • The degree of hydrolysis increases from BCl3 to BI3.
sp3 hybrid boron atoms are tetrahedral.
(iii) As sp2 hybrid boron atoms contain vacant p-
orbital, there will be back bonding from oxygen
to vacant orbital of sp2 carbon. Therefore, borax   Objective Questions
contains two types of B–O bonds, the shorter sp2 52. Borax bead test depends on the formation of
B–O and longer sp3 B–O bonds. (1) B2O3 (2)  elemental boron
 (iv) Borax contains two six-membered heterocyclic (3) metal boride (4)  metal metaborate
rings.
  (v) In borax, eight water molecules are present as 53. Borax bead test is not given by a/an
water of crystallization, whereas the remaining (1) aluminium salt (2)  cobalt salt
two water molecules are hydrated to boron atoms. (3) copper salt (4)  nickel salt

Chapter_12.indd 12 3/26/2014 3:22:09 PM

 Group-III (13) Elements: The Boron Family   12.13

54. Which of the following statements is wrong about 63. Boric acid is polymeric because of
­borax bead test? (1) its acidic nature
(1) Nickel salts give brown bead. (2) the presence of H bonds
(2) Copper salts give blue bead. (3) its monobasic nature
(3) Cobalt salts give blue bead. (4) its geometry
(4) Chromium salts give yellow bead.
64. Identify the false statement.
55. Borax bead test is used for the detection of (1) Boric acid behaves as a strong acid in the ­presence
(1) alkali metal (2)  alkaline earth metal of catechol.
(2) Boron forms stable [ BF6 ] .
3−
(3) transition metal (4)  p-block metal
(3) Tl(OH)3 is basic.
56. Which of the following statements regarding boric
(4) The first ionization potential of B and Al is lower
acid is false?
than that of Be.
(1) It acts as monobasic acid.
(2) It is soluble in hot water. 65. In borax bead test, which component of the bead
(3) It is formed by the hydrolysis. ­reacts with basic radical to form metaborate?
(4) It acts as a tribasic acid. (1) Na2BO3 (2)  B2O3
57. When orthoboric acid is heated to red hot, the residue is (3)  NaBO2 (4)  Na2B4O7
(1) boron trioxide (2)  boric acid 66. Sodium borate on reaction with conc. H2SO4 and
(3) pyroboric acid (4)  metaboric acid ethyl alcohol gives a compound A which burns with
green flame. The compound A is
58. Borax is not used
(1) H2B4O7 (2)  H3BO3
(1) as an antiseptic
(3) (C2H5)2B2O7 (4)    (C2H5)3BO3
(2) in making enamels and pottery glazes
(3) as a flux in soldering 67. Which of the following statements is false about
(4) in making optical glasses ­boric acid?
59. Boric acid is prepared from the borax by the action of (1) Boron is in sp3 hybridization.
(1) hydrochloric acid (2)  sodium hydroxide (2) It has layer structure in which planar BO3 units
(3) carbon dioxide (4)  sodium carbonate are linked by hydrogen bonding.
(3) It can be used as solid lubricant as the layers are
60. Borax when dissolved in water exhibits slippery.
(1) alkaline nature (4) Different layers are held by weak Van der Waal’s
(2) acidic nature forces.
(3) neutral behaviour 68. Borax on heating strongly above its melting point
(4) amphoteric behaviour melts to a liquid which then solidifies to a transparent
61. Which of the following statements is false about mass commonly known as borax bead. The transpar-
­boric acid H3BO3? ent glassy mass consists of
(1) It is prepared by acidifying an aqueous solution (1) mixture of sodium metaborate and boric anhydride.
of borax. (2) boric anhydride.
(2) It has a layer structure in which planar BO3 units (3) sodium meta borate.
are joined by hydrogen bonds. (4) sodium pyroborate.
(3) It is a strong tribasic acid.
69. Which of the following statements is false?
(4) It does not act as proton donor but act as a Lewis
acid by accepting hydroxide ion. (1) B(OH)3 partially reacts with water to form H3O+
and [B(OH)4]− and behaves like a weak acid.
62. When boron is four co-ordinate, the compound con- (2) B(OH)3 behaves like a strong monobasic acid in
forms a the presence of sugars and this acid can be titrated
(1) tetrahedral geometry against on NaOH solution using phenolphthalein.
(2) square planar geometry (3) B(OH)3 does not donate a proton and hence does
(3) triangular geometry not form any salt of NaOH.
(4) none of these (4) B(OH)3 reacts with NaOH forming Na[B(OH)4]−.

Chapter_12.indd 13 3/26/2014 3:22:10 PM

 12.14  Objective Chemistry - Vol. I

70. B Z LiH (62) 1 (63) 2 (64) 2 (65) 2 (66) 4

X Y + LiBF4
(67) 1 (68) 1 (69) 3 (70) 3 (71) 4
(72) 1 (73) 1 (74) 1 (75) 4

Heat
Which statement is true for the above sequence of 6.  Boron Hydrides
­reaction?
(1) Z is hydrogen. • The hydrides of boron are called “boranes”.
(2) X is B2 H6. • Boranes are “electron-deficient compounds”.
(3) Z and Y are F2 and B2H6, respectively. • Boron forms two series of boranes having the general
(4) Z is potassium hydroxide. formula BnHn+4 and BnHn+6.
71. Which of the following statements is false? BnHn+4 BnHn+4
(1) Boron carbide is used as abrasive. 1. Diborane B2H6 1. Tetraborane B4H10
(2) Boron is used to increase the hardenability of steel. 2. Pentaborane (9) B5H9 2. Pentaborane (11) B5H11
(3) Boron sesquioxide B2O3 is used in the manufac- 3. Hexaborane (10) B6H10 3. Hexaborane (12) B6H12
ture of borosilicate glass. 4. Decaborane (14) B10H14 4. Decaborane (16) B10H16
(4) Orthoboric acid undergoes intramolecular hydro- • The simplest borane is “diborane”.
gen bonding.
• Diborane can be prepared by treating BF3 or BCl3 with
72. Burning of amorphous boron in air at about 973 K LiAlH4 in diethyl ether.
gives which pair of products? 4BF3 + 3LiAlH4  → 2B2H6 + 3LiF + 3AlF3
(1) B2O3 and BN (2)  B2N3 and B2O3 4BCl3 + 3LiAlH4  → 2B2H6 + 3LiCl + 3AlCl3
(3) Borazine and H3BO3 (4)  B2O3 and B2H6 • It is formed by the action of iodine on sodium
73. H3BO3 and HBO2 do not differ in borohydride.
(1) oxidation number. 2NaBH4 + I2  → B2H6 + 2NaI + H2
(2) reacting with water. • On large scale, it is prepared by the reaction of BF3
(3) melting point. with NaH or LiH.
(4) structure.
2BF3 + 6NaH 450 k
→ B2H6 + 6NaF
74. Borax is used as buffer because 2BF3 + 6LiH 450 k
→ B2H6 + LiF
(1) its aqueous solution contains equal amounts of • It is also formed by subjecting a mixture of boron
weak acid and its salt. trichloride and hydrogen to silent electric discharge
(2) it is easily available.
(3) its aqueous solution contains equal amounts of 2BCl3 + 6H2 or
electric discharge
Cu − Al catalyst at 450 ° C
→ B2H6 + 6HCl
strong acid and its salt. • Diborane is a colourless, highly toxic gas with a boil-
(4) statement that borax is a buffer is wrong. ing point 180 K.
75. Aqueous solution of borax reacts with two moles of • In the absence of moisture and grease, it is stable at
acids. This is because of low temperatures; however, at high temperatures, it
slowly converts into higher boranes.
(1) the formation of the moles of B(OH)3 only.
(2) the formation of two moles of [B(OH)4]− only. • Diborane burns or explodes in air with the evolution of
(3) the formation of one mole of each of B(OH)3 and much heat.
[B(OH)4 ]− . • It reacts with water liberating hydrogen with the
(4) the formation of 2 mole of each [ B(OH) 4 ] and
−
­formation of boric acid.
B(OH)3 of which only [ B(OH) 4 ] reacts with acid.
−
• With alkalis, it forms borates with the evolution of
hydrogen.
Answers • Hydrogen halides react with diborane in the presence
of their corresponding aluminium halides to give halo-
(52) 4 (53) 1 (54) 4 (55) 3 (56) 4 gen substituted diborane. The reactivity of diborane
(57) 1 (58) 1 (59) 1 (60) 1 (61) 3 towards hydrogen halides decreases from HCl to HI.

Chapter_12.indd 14 3/26/2014 3:22:12 PM

 Group-III (13) Elements: The Boron Family   12.15

• With diborane chlorine, bromine reacts violently and • The stability sequences of the donor acceptor
gives only controlled yield and with iodine does not ­complexes of boron compounds may be summarized as
react at all. (CH3)3N as donor:
• Diborane reacts with ammonia giving different pro­ BBr3 > BCl3 > BF3 ~ BH3 > B(CH3)3
ducts under different conditions. (CH3)3P as donor:
   (i) At 120°C and in low concentration of ­ammonia, BBr3 > BCl3 ~ BH3 > B(CH3)3
an addition product B2H6 ∙ 2NH3 (diammoniate of CO as donor:
diborane) is formed. BH3 >> BF3 ~ B(CH3)3
 (ii) At 200°C, it forms borazole (B3N3H6), which is • With sodium amalgam, diborane forms addition
known as inorganic benzene. ­compound B2H6–Na2Hg.
(iii) At above 200°C and in excess of ammonia, boron • In diborane, two hydrogen atoms are one type and the
nitride is formed. other four hydrogen atoms are another type, which is
• Diborane forms addition compounds with Lewis confirmed by methylation.
bases as it is electron-deficient compound and acts as • Melthylation of diborane gives (CH3)4B2H2, that is,
Lewis acid. only four hydrogen atoms are substituted.
• If the Lewis base is small without steric strain, unsym- • Diborane contains two “hydrogen bridge bonds”.
metric cleavage takes place.
• In each hydrogen bridge bond in diborane two ­electrons
H H are delocalized on three atoms so it is known as three
H
+ 2NH3 [BH2(NH3)2]+ [BH4]– centre–two electron (3c–2e) bond.
B B
H
• The two hydrogen bridge bonds are also known as
H H
“­banana bond” or “Tau bond” or “protonated bond”.
• If the Lewis base is larger with steric strain, symmetric • The hydrogen bridge bonds in diborane are present one
cleavage takes place. above and the other below the plane of the ­molecule,
whereas the other four hydrogen atoms and two boron
H atoms are in the same plane.
H H
B B + 2NR3 2H3B NR3 • In diborane, each boron is in sp3 hybridization.
H H H • In the hydrogen bridge bond, the orbital overlap is
“sp3–s–sp3”.
• Addition compounds with symmetric cleavage are • The ∠HBH in diborane is 121.5° in the plane of mol-
formed with CO, (CH3)2O, (CH3)2S, NR3 and C5H5N. ecule but 97.5º in the case of bridge bonds.

Reaction of Diborane

Reaction Remark
  1.  B2H6 + O2 → B2O3 + H2O
combustion

  2.  B2H6 + H2O 

→ H3BO3 + H2
  3.  B2H6 + KOH 
→ KBO2 + H2 or K3BO3 + H2
  4.  B2H6 ∆
→ Higher boranes
  5.  B2H6 + Cl2 
→ BCl3 + HCl
B2H6 + Br2 
→ B2H5Br + HBr
B2H6 + I2 
→ No reaction
→ [H2B(NH3)2]+ [BH4]− ∆
  6.  B2H6 + NH3  → B3N3H6(borazole)
B2H6 + CH3NH2 
→ [H2B(CH3NH2)2]+ []
B2H6 + (CH3)2NH −
42° C
→ H3 B − +NH(CH3)2 ∆
→ (CH3)2NBH2
+
B2H6 + (CH3)3N 
→ (CH3)3 N − B H3
  7.  B2H6 + CH3OH 
→ BH(OCH3)2 + B(OCH3) 3 + H2
+
  8.  B2H6 + ROR 
→ R 2O — BH 3
+
B2H6 + RSR 
→ R 2S — BH 3

Chapter_12.indd 15 3/26/2014 3:22:16 PM

 12.16  Objective Chemistry - Vol. I

Reaction Remark
  9.  B2H6 + HCl 
→ B2H5Cl
AlCl3

10.  B2H6 BCl

3 or BBr3
→ B2H5Cl or B2H5Br
11.  B2H6 CO
or PF3
→ H3B ←
 CO or H3B ←
 PF3
12.  B2H6 + LiR 
→ LiBH4 + BR3
→ (CH3)2PH . BH3
13.  B2H6 + (CH3)2PH 

7. Borazole • With two similar substituents, benzene gives three

­isomers but borazole gives four isomers one ortho,
• It is formed by the reaction of diborane with ­ammonia.
two meta and one para. In meta isomers, both similar
• Its structure is similar to benzene and hence is known substituents may be either on boron or on ­nitrogen.
as inorganic benzene.
H H 8. Borohydrides
C C • The metal borohydrides contain tetrahedral complex
ion [ BH 4 ] . It is chemically tetrahydridoborate ion.
−
H C C H H C C H
• Alkali metal borohydrides are white ionic solids and
C H C H react with water with varying ease.
H C C H C C • The beryllium, aluminium and transition metal boro-
H H hydrides become increasingly covalent and volatile. In
them, the [ BH 4 ] group acts as a ligand and forms
−
Benzene
H H covalent compounds with metal ions. One or more
H atoms are in three centre bond with two electrons
B B shared by three atoms.
H N N H H N N H
• In Al(BH4)3 and Zr(BH4)4, each BH4− forms two
B H B H ­hydrogen bridges, whereas in Be (BH4)2, one of each
H B N H B N BH4− forms hydrogen bridges.

H H H H
Borazole H H
B
• The difference in the structures of benzene and H H
Be H H
­borazole is that in benzene the π bonds are covalent, H H
whereas in borazole π bonds are dative bonds by the B Al H
donation of lone pair on nitrogen to boron atom. H
B B H
• On account of the difference in the electronegativity H H
B H
between boron and nitrogen, the π cloud in borazole H
H H
is more with highly electronegative nitrogen than with H
boron. This partial localization weakens the π bonding
in borazole. Be (BH4)2 A (BH4)3
• On account of the above reason, borazole is less
­aromatic and more reactive than benzene, and readily
undergoes addition reactions. 9.  Boron Nitride
• As nitrogen retains some basic character and the boron • When borax is fused with ammonium chloride, ­boron
the acidic character, polar compounds such as HCl can nitride is formed.
attack the double bond and the positive part of polar
molecule will be added to nitrogen, whereas the nega- Na2B4O7 + 2NH4Cl 
→ 2BN + 2NaCl + B2O3 +
tive part to boron.  4H2O

Chapter_12.indd 16 3/26/2014 3:22:18 PM

 Group-III (13) Elements: The Boron Family   12.17

• On large scale, it is prepared by fusion of urea with (3) Common name of borazole is inorganic benzene.
­boric acid. It is also formed by heating diborane with (4) The bonds present in borazole are 6σ and 6π.
ammonia, or boron in nitrogen or boron with ammonia.
79. Which of the following statements is not correct
• Pure boron nitride is obtained by the action of NH3 ­regarding the structure of diborane?
on BCl3.
(1) There are two bridging hydrogen atoms in ­diborane.
• Boron nitride is colourless solid and good insulator. (2) Each boron atom forms four bonds in diborane.
• It gets decomposed when heated in steam under pres- (3) All the hydrogen atoms are not in the same plane
sure to yield ammonia. in diborane.
(4) All B–H bonds in diborane are similar.
• When dissolved in HF, it forms NH4BF4.
• Boron nitride consists of planar sheets of atoms like 80. Identify the false statement regarding diborane.
those in graphite. The planar sheets of alternating B (1) It has B–B covalent bond.
and N atoms consist of edge-shared hexagons and as (2) Boron atom is involved in sp3 hybridization.
in graphite, the B–N distance within the layer (1.45 Å) (3) It has a maximum of six planar atoms.
is much shorter than the distance between the layers (4) It contains two 3c–2e bonds.
(3.33 Å).
81. In diborane molecule, hydrogen bridge bond is due to
• The layers in boron nitride are staked directly over each (1) the shortage of four electrons required for ­bonding.
other with B and N atoms alternating in successive layers. (2) the shortage of two electrons required for ­bonding.
This is because of the partial positive charge on B and the (3) four electrons more than required for bonding.
partial negative charge on N atom attract. (4) two electrons more than required for bonding.
• It can be used as solid lubricant, as the layers are slippery.
82. Which of the following statements is wrong?
• It is an insulator, as there is large gap between the (1) In the formation of tau or banana bond in dibo-
filled and the vacant π bonds. rane, the number of electrons and the number of
• At high pressure and temperatures (60 k bar and atoms involved, respectively, are 2 and 3.
200°C), the layered boron nitride converts into a hard (2) The number of hydrogen bridge bonds in ­diborane
crystalline analogue of diamond. is 2.
• The order of the hardness of different materials is (3) Methylation of diborane gives only tetramethyl
­diamond > sphalerite cubic boron nitride > ­boron diborane.
­carbide > silicon carbride > tungsten carbide > ­alumina. (4) The orbital overlap in hydrogen bridge bond is
sp2–s–sp2.
83. Identify the false statement.
  Objective Questions (1) Borazole is isostructural with benzene.
(2) Borozole contains B, H and N.
76. Which of the following statements is wrong?
(3) Both borazole and benzene are equally aromatic.
(1) Boranes are the compounds of boron halogen. (4) Borazole participate in addition reaction faster
(2) When a mixture of BCl3 and H2 is subjected to than benzene.
­silent electric discharge, the product formed is
diborane. 84. Boron reacts with nitrogen at higher temperatures
(3) Diborane is an electron-deficient compound. and pressures forming boron nitride. It is
(4) Reduction of BF3 or BCl3 with LiH gives ­diborane. (1) a slippery white solid with a layer structure simi-
lar to graphite.
77. Which of the following cannot be obtained from (2) a white solid with diamond-like structure.
­diborane? (3) a liquid and is structurally similar to silicon ­dioxide.
(1) BH3CO (2)  H3BO3 (4) a liquid and is isostructural with benzene.
(3) B2(CH3)6 (4)  B2H6–Na2Hg
85. Boron nitride obtained by heating borazole is
78. Which of the following statements is wrong? (1) white solid with a diamond-like structure.
(1) At low temperatures, B2H6 reacts with NH3 to (2) slippery white solid with layered structure simi-
form diammoniate of diborane. lar to that of graphite.
(2) Diborane on heating with ammonia at high (3) covalent liquid and is structurally similar to CO.
­temperatures forms borazole. (4) soft low-melting solid with rock salt-like ­structure.

Chapter_12.indd 17 3/26/2014 3:22:18 PM

 12.18  Objective Chemistry - Vol. I

Answers • On account of its great hardness, high melting point

(2045°C), non-volatility, chemical inertness and
(76) 1 (77) 3 (78) 4 (79) 4 (80) 1 good electrical insulating properties, it finds many
(81) 2 (82) 4 (83) 3 (84) 2 (85) 2 ­applications in abrasives (including tooth pastes),
­refractories and ceramics.
• Larger crystals when coloured with metal ion impu-
rities are used as gem stones. For example, rubies,
Important Compounds of ­sapphires, emerald green and topaz.
Aluminium
3. Aluminium Hydroxide
1. Aluminium Hydride
• It is obtained as a white gelatinous precipitate by
• It is prepared by the reaction of lithium hydride with the action of ammonium hydroxide solution with
aluminium chloride in dry ether ­aluminium salt solutions.
3LiH + AlCl3  → 3LiCl + AlH3 • It is amphoteric and dissolves in both acids and bases.
• If excess lithium hydride is present, it converts into • In solid state, it is polynuclear complex with layer
LiAlH4. structure that each aluminium atom is associated with
• It is an electron-deficient compound and acts as Lewis six OH groups and each OH is associated with two
acid. aluminium atoms.
• It hydrolyses violently in water liberating hydrogen. • Partial dehydration of aluminium hydroxide gives
• It is an insoluble polymer (AlH3)n containing AlH2 Al. “alumina gel”, which is used as a drying agent and as
an adsorbent.
2. Aluminium Oxide (Alumina) Al2O3 • It is used in making water-proofing cloth, as a mordant
in mordant dyeing.
• It is prepared by the thermal decomposition of
­aluminium salts. 4. Aluminium Chloride
Al2(SO4)3  → Al2O3 + 3SO3
4Al(NO )  → 2Al2O3 + 12NO2 + 3O2 • It is prepared by the action of hydrochloric acid on
3 3
2Al(OH)  
→ Al2O3 + 3H2O a­ luminium metal or its oxide or hydroxide.
3
2Al + 6HCl  → 2AlCl3 + 3H2
• It can be prepared by heating Al(OH)3 precipitate
obtained by the addition of ammonium hydroxide to Al2O3 + 6HCl  → 2AlCl3 + 3H2O
aluminium salts. Al(OH)3 + 3HCl  → AlCl3 + 3H2O
Crystallization from solution gives hydrated AlCl3 ∙
• When it is heated with carbon in a current of ­nitrogen
6H2O.
gas, aluminium nitride (AlN) is formed. This on
­hydrolysis gives ammonia and aluminium hydroxide. • Anhydrous aluminium chloride cannot be prepared by
heating the hydrated salt, as it hydrolyses with its own
• It reacts with carbon or calcium carbide at very high
water of crystallization.
temperatures to form aluminium carbide, which on
hydrolysis gives methane.
2AlCl3 ∙ 6HCl ∆ → 2AlCl3 ∙ 3H2O + 6H2O
2Al2O3 + 9C  → Al4C3 + 6CO 2AlCl3 ∙ 3H2O ∆ → 2Al(OH3) + 6HCl
∆
2Al 2 + 2CaC 2  
→ Al4C3 + 3CaO + 2CO 2Al(OH)3  → Al2O3 + 3H2O
• Anhydrous AlCl3 can be prepared by passing chlorine
Al4C3 + 12H2O  → 4Al(OH)3 + 3CH4
gas or HCl gas over heated aluminium.
• It is used
2Al + 3Cl2  → 2AlCl3
 (i)  for the manufacture of aluminium and its salts.
2Al + 6HCl  → 2AlCl3 + 3H2
 (ii)  as a refractory material.
(iii)  as adsorbent in chromatography. • In Mac Affe method, anhydrous aluminium chloride
 (iv) to fuse “alumina” or artificial corundum at 3275 can be prepared by heating a mixture of Al2O3 and
K in an arc furnace, which is called “alundum” coke in a current of chlorine gas.
and is used as abrasive. Al2O3 + 3C + 3Cl2  → 2AlCl3 + 3CO
 (v) to fuse the mixture of alumina and lime, which • Hydrated aluminium chloride can be converted into
is known as bauxite cement and is resistant to anhydrous AlCl3 by dehydration using thionyl chloride
sea water and sets quickly. or 2, 2-dimethoxy propane.

Chapter_12.indd 18 3/26/2014 3:22:21 PM

 Group-III (13) Elements: The Boron Family   12.19

AlCl3 ∙ 6H2O + 6SOCl2 → AlCl3 + 6SO2 + 12HCl • The terminal Al–Cl bond lengths are shorter than
OCH3 bridge Al–Cl bond lengths probably due to the back
donation of lone pair electrons to the vacant d-orbitals
AlCl3 . 6H2O + 6CH3 C CH3 → of aluminium.

OCH3 5. Potash Alum K2SO4 ∙ Al2 (SO4)3 ∙ 24 H2O
AlCl3 + 6CH3COCH3 + 12CH3OH
• Alums are the double salts.
• Anhydrous aluminium chloride fumes in moist air.
AlCl3 + 3H2O  → Al(OH)3 + 3HCl
• The general formula of alum is M2SO4 ∙M′2 (SO4)3 ∙
24H2O or M, M ′ (SO4)2 ∙12H2O where M is mono-
The HCl liberated collects the moisture and forms as valent cation such as Na+, K+, Rb+, Cs+, NH4+ and Tl+
droplets which appear as fumes. and M ′ is a trivalent cation such as Al3+, Cr3+, Fe3+
• It sublimes at 180°C. It exists as dimer Al2Cl6 in vapour and Co3+.
phase and above 800°C, it converts into monomer. • All alums are isomorphous.
• It is covalent when anhydrous and does not conduct
• In alums, every cation is surrounded by six water mol-
electric current in fused state. ecules octahedrally.
• It is soluble in organic solvents and remains as dimer
• Lithium cannot form alum, as it cannot be surrounded
in them.
by six water molecules because of its small size.
• When dissolved in water, it ionizes and then ­hydrolyses
• The common alum is potash alum.
to give acidic solution.
• It is a white crystalline substance which is soluble in
Al2Cl6 + 12H2O  → 2AlCl3 ∙ 6H2O
water.
AlCl3 + 3H2O  → Al(OH)3 + 3HCl
• Its aqueous solution is acidic because of the hydrolysis
• It is a strong Lewis acid and used as a catalyst in
of aluminium ion.
Friedel–Crafts reactions.
• On heating, it swells up because of the removal of
• Anhydrous aluminium chloride has six co-ordinate
water of crystallization and on further heating gives
layer structures in the solid phase and converts into
alumina.
four co-ordinate dimers at its melting point. Above
350°C, it converts into trico-ordinate monomeric • It is used
AlCl3.    (i)  in the purification of drinking water.
 (ii)  as a styptic to arrest bleeding.
(iii)  as a mordant in mordant dyeing.
 (iv)  in tanning of leather.
Al
 (v)  in sizing the paper.
• The alums formed by replacing two univalent cations
Cl Cl by one bivalent cation are known as pseudoalums. For
180°C
example, MnSO4 ∙ Al2(SO4)3 ∙ 24H2O.
Cl Al Cl
Al   Objective Questions
Al Cl Cl
86. Which of the following is called alum?
(1) (NH4)SO4 ∙ FeSO4 ∙ 6H2O
2.06A° (2) Na2SO4 ∙ Al2(SO4)3 ∙ 24H2O
Cl Cl Cl (3) KCl ∙ MgCl2 ∙ 6H2O
(4) NaAlO2
101°
Al 79° Al 118° 350°C 87. Which of the following statements is not true about
alum?
Cl Cl (1) All alums contain monovalent and trivalent ­
Cl metal ions.
Cl
2.21 A° Cl Al (2) In a molecule of alum, each metal is surrounded
Cl by six water molecules.

Chapter_12.indd 19 3/26/2014 3:22:23 PM

 12.20  Objective Chemistry - Vol. I

(3) All alums are double salts. 96. Which of the following statements about alum is not
(4) The structure of different alums is different. true?
88. Which statement is not true for alum? (1) Lithium cannot form alum because of its small
size.
(1) Its empirical formula is K Al (SO4)2 ∙ 12H2O.
(2) Potash alum is used as styptic to arrest the bleeding.
(2) Its aqueous solution is basic in nature.
(3) It is used in dyeing industries. (3) Acidic nature of aqueous solution of potash alum
(4) On heating, it melts and swells because of the is due to anionic hydrolysis.
loss of water of crystallization. (4) The alum used in sizing the paper is potash alum.

89. Which of the following is pseudoalum (not an alum)? 97. When aluminium chloride is dissolved in pure ­water,
the pH of the resulting solution is not 7. This is
(1) K2SO4 ∙ Al2(SO4)3 ∙ 24H2O
­because
(2) K2SO4 ∙ Cr2(SO4)3 ∙ 24H2O
(3) Na2SO4 ∙ Fe2(SO4)3 ∙ 24H2O (1) Aluminium ions accept protons from water
(4) CuSO4 ∙ Al2(SO4)3 ∙ 24H2O ­molecules leaving free OH− ions in solution.
(2) Aluminium ions donate protons to water
90. Potash alum is water soluble and ionizes in aqueous ­molecules forming H3O+ ions in solution by tak-
solution. The number of ions formed and the type of ing OH– ions from water.
ions that give test for their presence, respectively, are (3) Aluminium ions combine with water molecules
(1) 8 ions, 3 (2)  6 ions, 2 to give complex [Al(H2O)6]3+.
(3) 8 ions, 4 (4)  4 ions, 4
(4) Chloride ions make the solution acidic.
91. Alumina was dissolved by heating with the less 98. Which of the following methods cannot be employed
amount of aqueous KOH. To this solution, dilute for preparing anhydrous aluminium chloride?
­sulphuric acid is added and then allowed to give
(1) Heating hydrated crystals of AlCl3 ∙ 6H2O.
­crystals of
(2) Heating a mixture of alumina and coke in a
(1) aluminium sulphate. ­current of dry chlorine gas.
(2) potassium sulphate. (3) Passing dry chlorine over heated aluminium
(3) aluminium sulphate and potassium sulphate. powder.
(4) potash alum. (4) Passing dry HCl over heated aluminium powder.
92. The empirical formula of alum is   99. Which of the following reactions takes place in the
(1) K2SO4 ∙ Al2(SO4)3 ∙ 24H2O presence of anhydrous aluminium chloride?
(2) KAl (SO4)2 ∙ 12H2O (1) Friedel–Crafts (2)  Cannizzaro’s
(3) 2KAl (SO4)2 ∙ 12H2O (3) Kolbe’s (4)  Hofmann’s
(4) None
100. Which of the following compounds can make cloth
93. Common alum can be prepared by crystallizing a fire proof?
mixed solution of
(1) Aluminium sulphate
(1) Na2SO4 + K2SO4 (2)  Ferrous sulphate
(2) K2SO4 + (NH4)2SO4 (3) Magnesium sulphate
(3) (NH4)2SO4 + Al(SO4)3 (4)  Cuprous sulphate
(4) K2SO4 + Al2(SO4)3
101. The molecules (smallest particles) in aluminium
94. Alum is not used chloride vapour at high temperature
(1) as a mordant in dyeing. (1) have no shape.
(2) as an insecticide. (2) are shaped like a plane triangle.
(3) in the purification of water. (3) are spherical.
(4) in tanning of leather. (4) are like randomly broken bricks.
95. Identify A and B in the following reaction sequence 102. AlCl3 exists as dimer because
AlCl3 excess

NH 4 OH
→ A H 2 SO 4
→ B K 2 SO 4
→ (1) ionization potential of Al is high.
­potash alum (2) atomic size of Al is large.
(1) NH4Cl, Al2(SO4)3 (2)  Al2(SO4)3, Al(OH)3 (3) nuclear charge of Al is more.
(3) Al(OH)3, Al2(SO4)3 (4)  Al(OH)3, NH4Cl (4) p-sub-shell is incomplete.

Chapter_12.indd 20 3/26/2014 3:22:23 PM

 Group-III (13) Elements: The Boron Family   12.21

103. Which of the following statements is false? 4. Which of the following pair of elements has nearly
(1) Anhydrous AlCl3 is covalent, whereas hydrated same electronegativity?
AlCl3 ∙ 6H2O is ionic. (1) In, Tl (2)  B, Al
(2) Dehydration of hydrated AlCl3 ∙ 6H2O with thio- (3) B, Ga (4)  Al, Tl
nyl chloride gives anhydrous AlCl3.
5. Which of the following statements is correct about
(3) Dehydration of hydrated AlCl3 ∙ 6H2O with 2,
IIIA group element?
2-dimethorxy propane gives AlCl3.
(4) Dehydration of hydrated AlCl3 ∙ 6H2O with lime (1) It forms an oxide having the formula MO.
gives anhydrous AlCl3. (2) Its trihalide exists as dimers.
(3) Its trifluoride is a weak Lewis acid.
104. Which of the following statements is wrong? (4) Its hydride is (MH3)n or MnHn + 4.
(1) Anhydrous AlCl3 sublimes at 180°C.
6. The element that cannot form peroxide but can form
(2) The vapour of anhydrous AlCl3 contains dimer
nitride directly is
Al2Cl6.
(3) The dimeric structure of Al2Cl6 is retained in (1) Ca (2)  Ba (3)  Na (4)  Al
­benzene. 7. Diborane reacts with carbon monoxide under ­pressure
(4) The dimeric Al2Cl6 contain 3C–2e bonds. to form
105. The false statement among the following is (1) addition product.
(2) elimination product.
(1) Anhydrous AlCl3 is covalent.
(3) substitution product.
(2) Hydrated AlCl3 ∙ 6H2O is ionic.
(4) double decomposition product.
(3) Anhydrous AlCl3 is a Lewis acid.
(4) Hydrated AlCl3 ∙ 6H2O is Lewis acid. 8. B2H6 undergoes substitution reaction with
(1) Br2 at 100°C
Answers (2)  HCl / anhyd AlCl3
(3) Cl2 at 100°C
  (86)  2   (87)  4   (88)  2   (89)  4   (90)  1 (4)  both 1 and 2
  (91)  4   (92)  2   (93)  4   (94)  2   (95)  3
9. Identify A in the following sequence.
  (96)  3   (97)  2   (98)  1   (99)  1  (100)  1
(101)  2  (102)  4  (103)  4  (104)  4  (105)  4 A NH 
3 120° C
→ (NH4)2B2H4 200°
 C
→ B3N3H6
(1) Na2B4O7 (2)  B2H6
(3) H3BO3 (4)  (BN)2
10. Hydrogen gas is not liberated when diborane reacts
 Practice Exercise with which of the following?
1. Covalency and valency of boron in BF4− are (1) H2O (2)  NaOH
(3) Cl2 (4)  HCl in the presence of AlCl3
(1) 5, 4 (2)  4, 3 (3)  3, 4 (4)  4, 2
11. Which of the following statements about boranes is
2. Which of the following statements is correct for the
correct?
elements of group III A?
(1) They have unusual stoichiometry.
(1) Covalent radii of the atoms increases regularly
(2) They are potentially high energy sources.
from B to Tl.
(3) They have typical structures.
(2) Melting point and boiling point gradation shows
(4) All the above are correct.
a regular trend.
(3) Heat of sublimation decreases regularly in 12. The addition compound of B2H6 with ammonia on
­moving down the group from B to Tl. heating gives
(4) All are correct. (1) Boron nitride (2)  Borazole
(3) Tetraborane (4)  Boron
3. The ionization potential values of Ga, In and Tl
(1) gradually decrease. 13. Choose the wrong statement.
(2) gradually increase. (1) Boron occurs in free state as well as in combined
(3) almost similar because of the poor shielding state.
­effect of d- and f-electrons. (2) Ga, In and Tl occur in traces along with Zn and
(4) increase from Ga to In and then decrease to Tl. PbS ores.

Chapter_12.indd 21 3/26/2014 3:22:24 PM

 12.22  Objective Chemistry - Vol. I

(3) Aluminium occurs in combined state as oxides, 20. When bauxite powder mixed with coke and reacted
fluorides and silicates. with nitrogen at 2075 K, carbon monoxide and X are
(4) Indium has the lowest IP value among boron formed. What is the gas formed when X is reacted
family. with water?
(1) NH3 (2)  N2 (3)  N2O (4)  O2
14. Which of the following statements is correct?
(1) The densities of group 13 elements are lower 21. Aluminium reacts with conc. HCl and conc. NaOH to
than that of group II elements. liberate the gases.
(2) The melting point and boiling point of boron is (1) H2 and O2 (2)  O2 and H2
much higher as compared to the other elements (3) H2 and H2 (4)  O2 and O2
of the group. 22. A colourless gas obtained by the electrolysis of NaCl
(3) The elements of group 13 are less electro­negative in Nelson’s cell is made to react with a compound
than those of groups I and II. X. The resulting compound has low melting point
(4) All the members of group 13 are metals. and boiling point. The compound X forms a weak
15. BF3 is reduced with lithium hydride and the product ­monabasic Lewis acid when dissolved in water. The
formed is treated with caustic potash. The products resulting compound is
formed are (1) AlCl3 (2)  B2H6
(1) B2H6, Li (3) BCl 3 (4)  Ga2Cl6
(2) KBO2, H2 and H2O 23. A compound of boron X reacts at very high
(3) KF, HF and B2H6 ­temperature with ammonia to give a new compound
(4) H3BO3 and KBO2 which is isosteric and isostructural with benzene.
16. The hydrogen bridge structure for diborane was The ­compound (X) with excess of ammonia and at
­suggested because the molecule has still higher temperatures gives boron nitride (BN)n.
The compounds X and Y are, respectively,
(1) 14 electrons available for bonding.
(2) deficiency of electrons. (1) BH3, B2H6 (2)  NaBH4, C6H6
(3) similar formula of C2H6. (3) B2H6, B3N3H6 (4)  B4C3, C6H6
(4) boron atoms with lone pairs. 24. Which of the following statements is incorrect in
­relation to the structure of diborane?
17. Among III A group (boron) elements, gallium has the
lowest melting point because of (1) The terminal B–H bond distance is the same
as the bond distances measured in compounds
(1) weak metallic bond due to inert pair effect.
which are not electron deficient and which have
(2) more interatomic distance due to larger atomic size.
no bridge structure.
(3) simpler molecular structure having Ga2 ­molecules.
(2) The terminal B–H bond is a 2C–3e bond.
(4) polymeric structure.
(3) The terminal B–H bond is a 2C–2e electron bond.
18. The correct order of melting points of group 13 (4) The B–H–B is 3C–2e bond.
­elements is
25. When diborane is passed through water, a white
(1) B > Al > Ga > In > Tl ­precipitate settles down. The precipitate is
(2) B < Al < Ga < In < Tl (1) B3N3H6 (2)  H3BO3
(3) B > Al > Tl > In > Ga (3) NaBO2 (4)  HBO2
(4) B > Al > In > Tl > Ga
26. Which of the following statements is not correct in
19. X reacts with aqueous NaOH solution to form Y and the case of boron nitride?
H2. Aqueous solution of Y is heated to 323–333 K and (1) It is also called borazon.
on passing CO2 into it, Na2CO3 and Z were formed. (2) It is chemically unreactive.
When Z is heated to 1200°C, Al2O3 is formed. X, Y (3) It is hard because it has diamond-like structure.
and Z, respectively, are (4) It has electrical conductivity.
(1) Al, AlCl3, NaAlO2
(2) Zn, Na2ZnO2, Al(OH)3 27. Inorganic graphite is
(3) Al, Al(OH)3, AlCl3 (1) BN (2)  BF4−
(4) Al, NaAlO2, Al(OH)3 (3)  B2H6 (4)  B3N3H6

Chapter_12.indd 22 3/26/2014 3:22:24 PM

 Group-III (13) Elements: The Boron Family   12.23

28. The main factor responsible for the strong B–F bonds 35. Which of the following statements about H3BO3 is
in BF3 is not correct?
(1) large electronegativity of fluorine. (1) It is strong tribasic acid.
(2) three centred two electron bonds in BF3. (2) It is prepared by acidifying an aqueous solution
(3) pπ–pπ back bonding. of borax.
(3) pπ–dπ back bonding. (3) It has a layer structure in which planar BO3 units
29. Borax is the sodium salt of are joined by hydrogen bonds.
(1) tetraboric acid (4) It does not act as proton donor but act as a Lewis
(2)  diboric acid acid by accepting hydroxyl ion.
(3) triboric acid 36. Anodized aluminium is aluminium
(4)  boric acid
(1) obtained at anode,
30. BF3 and boric acid B(OH)3 have the same number of (2) electrolytically coated with aluminium oxide,
electrons. The former is a gas, whereas the latter is a (3) alloy of aluminium containing 95% Al,
solid the reason is (4) None of the above,
(1) BF3 is a Lewis acid, whereas B(OH)3 is not.
(2) in BF3, F− is smaller in size than OH− in B(OH)3. 37. Aluminium chloride catalyses reaction by forming
(3) no molecular association is possible in BF3, carbocations with chloroalkanes as shown in the
whereas it is in B(OH)3. ­following equation.
(4) They have different geometrical structures. RCl + AlCl3  → R+ + AlCl4−

31. Which one of the following method is used to prepare The formation of AlCl4− implies that
borax crystals? (1) AlCl3 is covalent.
(1) A hot concentrated solution of B2O3 is made to (2) AlCl−4 is tetrahedral.
react with calculated quantity of conc. H2SO4. (3) The aluminium atom in AlCl3 has an incomplete
(2) Tincol is dried up and heated to red heat. octet.
(3) Tincol is powdered, treated with water and (4) The chlorine atom in RCl has a vacant p-orbital.
­evaporated.
38. Which of the following properties describes the
(4) An alcoholic solution of boric acid is evaporated
­diagonal relationship between boron and silicon?
and cooled.
(1) BCl3 is not hydrolysed, whereas SiCl4 can be
32. On account of hydrolysis, anhydrous AlCl3 ­hydrolysed.
(1) is deliquescent (2) Both forms oxides, B2O3 is amphoteric and SiO2
(2)  fumes in air is acidic.
(3) is acidic nature (3) Both dissolves in cold and dilute nitric acid.
(4)  All are correct
(4) Borides and silicides are hydrolysed in water.
33. Which of the following statements is correct?
(1) Boron may be regarded as non-conductor, and 39. The solubility of anhydrous AlCl3 and hydrated AlCl3
chemically as a non-metal. in diethyl ether are S1 and S2, respectively. Then,
(2) In general, boron resembles more closely to sili- (1) S1 = S2
con than Al, Ga, In and Tl. (2)  S1 > S2
(3) B2O3 and SiO2 are similar in their acidic nature. (3) S1 < S2
(4) All are correct. (4)  S1 < S2 but not S1 = S2
34. An alkali metal hydride NaH reacts with diborane in
40.   (i)  B2O3 + 6NaOH → (X) + 3H2O
Y to give a tetrahedral compound Z which is exten-
sively used as reducing agent in organic synthesis. (ii)  B2O3 + 2NaOH → (Y) + H2O
The Y and Z in the above reactions are (X) and (Y) are
(1) C2H6, C2H5Na (1) Sodium borate and sodium metaborate.
(2) C2H5OC2H5, NaBH4 (2) Both are sodium borates.
(3) NH3, B3N3H6 (3) Both are sodium metaborates.
(4) C3H8, C3H7Na (4) Sodium metaborate and sodium borate.

Chapter_12.indd 23 3/26/2014 3:22:25 PM

 12.24  Objective Chemistry - Vol. I

41. Borax is Na2B4O7 ∙ 10H2O, consider the following (1) only I, III, IV
statements about borax. (2)  only I, II, III
  (I) Two boron atoms have four B–O bonds, ­whereas (3) only I, II, IV
other two have three B–O bonds. (4)  I, II, III and IV
  (II)  Each boron has one −OH groups. 46. AlCl3 is more volatile than NaCl this is because
  (III)  It is a salt of tetraboric acid.
(1) AlCl3 molecules are held by weak Van der Waal’s
(IV) It is a cyclic metaborate having two six-mem-
forces, whereas the NaCl species are held by
bered heterocyclic rings.
strong ionic forces in giant lattice.
Select the correct statements.
(2) AlCl3 unlike NaCl is dimersed.
(1) I, II, III (2)  II, III, IV
(3) Sodium is more electropositive than aluminium.
(3) I, II, IV (4)  I, I, III, IV
(4) NaCl unlike AlCl3 is a natural product.
42. The structure of aluminium bromide is best repre-
47. Borax structure contains
sented as
(1) two BO4 groups and two BO3 groups.
(1) Br
(2) four BO4 groups only.
Al Br
(3) four BO3 groups only.
Br 120°
(4) three BO4 and one BO3 groups.
(2) [Al Br2]+ [Al Br4]−
48. In the borax bead test for transition metal ­compounds,

(3) Br the fused beads have unique colour is due to the
Al Br ­formation of
Br (1) glass-like metal metaborate.
(4)  Br (2) opaque metal hexaborate bead.
Br Br (3) B2O3.
Al ∼ − 90° Al (4) glass-like metal orthoborate.
Br
Br Br 49. Which of the following reactions is wrong?
+
(1) B2H6 + (CH3)3N  → H 3 B − N (CH 3 )3
43. Which of the following statements regarding the
structure of aluminium chloride is correct? (2) B2H6 + 2LiH 
→ 2Li [BH4]
(1) All the bond angles Cl–Al–Cl and Al–Cl–Al are (3) B2H6 + 6CH3OH → 2(CH3)3 B + 6H2O
identical. (4) B2H6 + 6H2O 
→ 2H3BO3 + 6H2
(2) All the bond lengths Al–Cl in Al2Cl6 are identical.
50. Which of the following statements is not characteris-
(3) All the Al–Cl bond lengths as well as all the bond
tic of boranes?
angles Cl–Al–Cl bond and Al–Cl–Al angles are
equal. (1) They undergo spontaneous combustion in air.
(4) The terminal Al–Cl bond lengths and bridged (2) Their combustion products are water and crystal-
Al–Cl bond lengths are different and also outer line boron.
bond ­angle Cl–Al–Cl and bridged bond angles (3) They form borohydride complexes by reaction
Cl–Al–Cl and Al–Cl–Al have different values. with alkali metal hydrides.
(4) They readily get hydrolysed by liberating H2 gas.
44. When borax is dissolved in water
51. Which of the following reactions is used to prepare
(1) only B(OH)3 is formed.
BF3?
(2) only [B(OH)4]− is formed.
(3) both B(OH)3 and [B(OH)4]– are formed. (1) B2O3 + CaF2 + H2SO4 heat  →
(4) both B(OH)3 and B2O3 are formed. (2) B2O3 + NH4BF4 heat  →
45. Identify the correct statements regarding the structure (3) Na2[B4O5(OH)4] + H2SO4 (conc.) heat →
of Al (BH4)3. (4) All of these
     (I)  Al is sp3d2 and B is sp3 hybridized. 52. What is correct statement amongst the following
  (II)  It has six 3C–2e bonds. about the structure of borax molecule?
  (III)  It has six Al–H–B bonds. (1) All the four boron atoms are sp3 hybridized.
(IV)  It has six 2C–2e bonds. (2) All the four boron atoms are sp2 hybridized.

Chapter_12.indd 24 3/26/2014 3:22:27 PM

 Group-III (13) Elements: The Boron Family   12.25

(3) Two of the four boron atoms are sp3 hybridized (3) Aluminium forms [AlF6]3− ion but boron does
not form [ BF6 ] .
−
and the rest two are sp2 hybridized.
(4) Out of the 10 water molecules generally shown as (4) Cryolite is added to alumina to lower the fusion
water of crystallization in its MF, four molecules of temperature and to make the mass a good con-
H2O are really involved in the structural formation. ductor of electricity.
53. The bond dissociation energy of B–F in BF3 is 646 58. The self-protective oxide film on aluminium can be
kJ mol−1, whereas that of C–F in CF4 is 515 kJ mol−1. removed by
The correct reason for higher B–F bond dissociation (1) boiling aluminium with water.
energy as compared to that of CF is (2) amalgamation with mercury.
(1) Stronger σ bond between B and F in BF3 as com- (3) adding conc. HNO3.
pared to that between C and F in CF4. (4) reacting with chlorine.
(2) Significant pπ–pπ interaction between B and F 59. Which of the following pairs contain molecules with
in BF3, whereas there is no possibility of such different structures?
interaction between C and F in CF4. (1) Borazine and benzene
(3) Lower degree of pπ–pπ interaction between B (2) Diborane and hydrazine
and F in BF3 than that between C and F in CF4. (3) NaCl and NiO
(4) Smaller size of B atom as compared to that of C (4) Graphite and boron nitride
atom.
60. Aluminium chloride ionizes in an aqueous solution
54. 2NH3 + B2H6 ∆ →A because
How many disubstituted (same substituents) isomers (1) its dissociation constant is low.
of A are possible?
(2) it forms a dimer in aqueous solution.
(1) 3 (2)  2 (3)  4 (4)  6
(3) it is a Lewis acid.
55. Aluminium oxide exists in nature as gems with different (4) its total hydration energy exceeds the ionization
colours. The reason for the difference in colour is that energy of the system.
(1) The oxidation states of aluminium in these gems 61. In solid state,
are different. (1) AlCl3 exists as a closely packed lattice of Cl− and
(2) The extent of crystallinity in these gems is ­different. Al3+ occupying octahedral holes.
(3) The Al–O bonding is different in these gem (2) AlCl3 exists as a closely packed lattice of Cl− and
structure. Al3+ occupying trigonal holes.
(4) There are different transition metal ions present
(3) AlCl3 exists as a closely packed layered lattice of
as impurities in these gems.
Cl− and Al3+ occupying octahedral holes.
56. Which of the following statements is false in regard (4) AlCl3 exist as Al2Cl6.
to the B–F bond in BF3?
62. In the structure of solid AlCl3, each Al participates in
(1) All the three B–F bond lengths are equal (1.30Å)
and each of them is shorter than the sum of the co- (1) four bridges (2)  six bridges
valent radii of boron (0.80 Å) and fluorine (0.72 Å). (3) three bridges (4)  twelve bridges
(2) The bond energy of the B–F bond is highest 63. Which is not true about borax?
(646 kJ mol−1).
(1) It is a useful primary standard for titrating against
(3) The unusually short bond length and high bond
acids.
strength of the B–F bond is due to pπ–pπ interac-
(2) Borax forms basic buffer solution.
tion between the boron and the fluorine atoms.
(3) Aqueous solution of borax can be used as buffer.
(4) The short length and high strength of the bonds
(4) It is made up of two six-membered hetero-cyclic
are due to pπ–dπ interaction.
rings.
57. Which of the following statements is wrong?
(1) Anhydrous aluminium chloride cannot be 64. Choose the correct sequence for the geometry of the
­prepared by heating AlCl3 ∙ 6H2O because of the given molecules. Borazan, Borazole, B3O63− and ­Al2Cl6.
hydrolysis of AlCl3 into Al(OH)3. (P stands for planar and NP stands for non-planar)
(2) AlCl3 is a high-melting solid, whereas AlF3 is a (1) NP, NP, NP, P (2)  P, P, NP, NP
low melting volatile solid. (3) NP, NP, P, P (4)  NP, P, P, NP

Chapter_12.indd 25 3/26/2014 3:22:28 PM

 12.26  Objective Chemistry - Vol. I

65. Which of the following amines has little tendency 1. I f both Statement I and Statement II are true and
to show the reaction B2H6 + 2X  → [BH2(X)2]+ + Statement II is the correct explanation of Statement I.
−
[BH4] ? 2. If both Statement I and Statement II are true and
(1) NH3 (2)  CH3NH2 Statement II is not the correct explanation of State-
(3) (CH3)2NH (4)  (CH3)3N ment I.
3. If Statement I is true and Statement II is false.
66. BF3 forms tetrahedral complex with the compounds 4. If Statement I is false but Statement II is true.
which can donate lone pair of electrons. The B–F
bond length in BF3 is 1. Statement I: Gelatinous white precipitate of Al(OH)3
(1) equal to that existing in the tetrahedral complex. dissolves both in HCl as well as in conc. NaOH.
(2) greater than that existing in the tetrahedral Statement II: Al(OH)3 is amphoteric.
­complex.
2. Statement I: B(OH)3 is acidic, whereas Tl(OH)3 is
(3) smaller than that existing in the tetrahedral
basic.
­complex.
(4) greater than, smaller than or equal to that existing Statement II: B(OH)3 has highly hydrogen bonded
in tetrahedral complex depending on the nature network structure.
of the electron-donor compound 3. Statement I: Anhydrous AlCl3 is covalent in nature.
67. Alumina is insoluble in water because Statement II: AlCl3 exists as a dimer AlCl6.
(1) It is a covalent compound. 4. Statement I: B2H6 on methylation gives B2H2 (CH3)4.
(2) It has high lattice energy and low heat of hydration. Statement II: In B2H6, two H atoms are bonded to
(3) It has low lattice energy and high heat of hydration. B atoms by bridge bonds.
(4) Al3+ and O2− ions are not excessively hydrated.
5. Statement I: Al(OH)3 is amphoteric in nature.
68. Chemically borax is Statement II: In Al(OH)3, O–H bond energy and
(1) sodium metaborate. Al–OH bond energy are nearly same.
(2) sodium orthoborate.
6. Statement I: Tl3+ is less stable than Tl+.
(3) sodium tetraborate.
(4) sodium tetrametaborate decahydrate. Statement II: Owing to inert pair effect, electrons
do not participate in reactions.
Answers 7. Statement I: Boron cannot form cation B3+.
  (1) 2   (2) 3   (3) 3   (4) 1   (5) 4 Statement II: Boron is the smallest atom in group
  (6) 4   (7) 1   (8) 4   (9) 2 (10) 3 III A.
(11) 4 (12) 2 (13) 1 (14) 2 (15) 2 8. Statement I: Alloys of “Al” can be used in making
(16) 2 (17) 3 (18) 3 (19) 4 (20) 1 of aircrafts.
(21) 3 (22) 2 (23) 3 (24) 2 (25) 2 Statement II: Density of Al is very low.
(26) 4 (27) 1 (28) 3 (29) 1 (30) 3
(31) 3 (32) 4 (33) 4 (34) 2 (35) 1 9. Statement I: There is large difference between the
(36) 2 (37) 3 (38) 4 (39) 2 (40) 1 properties of boron and aluminium. Boron is non-
(41) 4 (42) 4 (43) 4 (44) 3 (45) 4 metal, always covalent, acidic and high melting.
(46) 1 (47) 1 (48) 1 (49) 3 (50) 2 Statement II: The size of Al3+ ion is about 2.5 times
(51) 4 (52) 3 (53) 2 (54) 4 (55) 4 the size of B3+ ion.
(56) 4 (57) 2 (58) 2 (59) 2 (60) 4 10. Statement I: Tl exhibits oxidation states of
(61) 3 (62) 2 (63) 2 (64) 4 (65) 4 +1 and +3.
(66) 3 (67) 2 (68) 4
Statement II: Tl exhibits inert pair effect.
11. Statement I Among elements of III A, boron has
high melting point.
 Statement-Type Questions Statement II: Boron is metallic in nature.

In each of the following questions, a statement-I is ­given 12. Statement I: AlF3 is ionic compound, whereas BF3 is
followed by corresponding statement-II just below. covalent compound.
Mark the correct answer as indicated. Statement II: BF3 involves back π bonding.

Chapter_12.indd 26 3/26/2014 3:22:29 PM

 Group-III (13) Elements: The Boron Family   12.27

13. Statement I: Boron does not form B3+ ion yet BF3 The correct matching is
exists.
S. No. A B C D
Statement II: Boron cannot lose its valence electrons
because of high values of ionization potentials. 1. IV I II III
14. Statement I: Lithium ion cannot form alum. 2. I IV II II
3. IV III III I
Statement II: Li+ ion is very small ion and cannot 4. IV V II III
­accommodate a co-ordination number six.
15. Statement I: Graphite is used in lead pencils. 3. Match the following given in List I with those given
Statement II: Graphite is black and contains layer in List II
­lattice.
List-I List-II
(A)  Al   (i) Most abundant element in
Answers the earth’s crust
(B)  B   (ii)  Boric acid
  (1) 1   (2) 2   (3) 2   (4) 1   (5) 1 (C)  B(OH)3 (iii) Catalyst in Friedel–Crafts
  (6) 1   (7) 2   (8) 1   (9) 1 (10) 1 reactions
(11) 3 (12) 2 (13) 1 (14) 2 (15) 1 (D)  Anhydrous AlCl3  (iv)  −3
  (v) Most abundant metal in the
earth’s crust

The correct matching is

 Match the Following Type Questions S. No. A B C D
1. Match the following given in List I with those given 1. V IV II III
in List II. 2. IV V III II
3. I IV V II
List-I List-II 4. V III II I
(A)  Potash alum   (i) (NH4)2SO4 ∙ Fe2(SO4)3 ∙ 24H2O
(B)  Ferric alum   (ii) K2SO4 ∙ Cr2(SO4)3 ∙ 24H2O 4. Match the following given in List I with those given
(C)  Chrome alum (iii) K2SO4 ∙ Al2(SO4)3 ∙ 24H2O in List II
(D)  Alunite  (iv) K2SO4 ∙ Al2(SO4)3 ∙ 4Al(OH)3 List-I List-II
The correct matching is (A)  Alum   (i)  Rocket fuel
(B)  Diborane   (ii)  Chocolate wrappers
S. No. A B C D (C)  Borazole (iii)  Styptic
(D)  Aluminium  (iv)  Antichlor
1. III II I IV
  (v)  A planar molecule
2. III I II IV
3. I II IV III The correct matching is
4. IV III I II
S. No. A B C D
2. Match the following given in List I with those given 1. I II IV V
in List II 2. III I V II
3. III I V IV
List-I List-II 4. III V I II
(A)  B3N3H6   (i)  Hexaborane (10)
(B)  B6H12   (ii)  Borax
(C)  Na2B4O7 ∙10H2O (iii)  Diborane Answers
(D)  Two B–H–B bonds  (iv)  Inorganic benzene
  (1) 1   (2) 4   (3) 1   (4) 2
  (v)  Hexaborane (12)

Chapter_12.indd 27 3/26/2014 3:22:29 PM

 This page is intentionally left blank.

Chapter_12.indd 28 3/26/2014 3:22:29 PM

 13

Chapter
The Carbon Family

• The elements carbon, silicon, germanium, tin and • Lead is the densest element in IVA group.
lead belong to IVA or 14 group and p-block of the • Except carbon, density increases with increase in
periodic table. atomic number in other elements.
• Carbon is the seventh most abundant element by mass • Carbon in the form of diamond has more density than
in the earth’s crust. silicon.
• It is widely distributed in nature in free as well as in • The melting points decrease from carbon to tin but
the combined state. there is a slight increase from tin to lead.
• In the elemental state it occurs as coal, diamond and • Boiling points decrease gradually down the group
graphite, however, in combined state it is present in from carbon to lead.
metal carbonates, hydrocarbons and carbon dioxide
• The m.pts and b.pts of IVA elements are higher than the
gas (0.03%) in air.
corresponding group IIIA elements. This is due to
• Naturally occurring carbon contains two stable the formation of four covalent bonds using the four
­isotopes 12C and 13C. Another isotope 14C which is ­valence electrons.
­radioactive is also present.
• Carbon, silicon and germanium have diamond like
• Silicon is the second most abundant (27.7% by mass) structure so they have high m.pts because more
element in the earth’s crust and is mostly present in the ­energy is required to break more number of bonds but
form of silica and silicates. ­decreases with increase in atomic size.
• Germanium exists only in traces. Tin occurs mainly as • Tin and lead are metals but they do not use all the
casseterite, SnO2 and lead as galena, PbS. ­valence electrons in metallic bond.
• Ultrapure germanium and silicon are used to make • Ionization energies decrease from carbon to tin but
transistors and semiconductors. the decrease is not regular.
• The general outer electronic configuration of these • There is large decrease between carbon and silicon
­elements is ns2 np2. but then onwards the decrease is very little because of
the poor shielding effect of d-electrons in germanium
Physical properties and tin.
• Atomic and ionic radii increase from carbon to lead. • Lead has little more ionization energy than tin because
• The small difference in the atomic radii of silicon of the lanthanide contraction.
(1.17 Å) and germanium (1.22 Å) is due to the poor • Electronegativity decreases from carbon to silicon
shielding capacity of d-electrons in the penultimate but remain constant in the remaining elements.
shell of germanium. • Down the group from carbon to lead metallic
• The small difference in the atomic radii of tin (1.41 Å) ­character increases. Carbon and silicon are ­nonmetals,
and lead (1.41 Å) is due to the poor shielding capacity ­germanium has some metallic properties while tin and
of the f-electrons in the antipentimate shell of lead. lead are metals.

Chapter_13.indd 1 3/26/2014 3:25:09 PM

 13.2  Objective Chemistry - Vol. I

• All the elements of IVA group elements exhibit two • Catenation is the combining capacity of the atoms of
types of oxidation states, +2 and +4. the same element to form long chains, branched chains
• From top to bottom in the group the stability of +2 and cyclic compounds.
oxidation state increases while the stability of +4 oxi- • Of all the elements carbon has maximum catenation
dation state decreases due to inert pair effect. power. The reasons are
• In +2 oxidation state these elements act as reducing    (i)  its tetravalency,
agents and their reduction power decreases down the  (ii)  high C–C bond energy,
group due to increase in the stability of +2 oxidation (iii) absence of lone pairs of electron on tetravalent
state. carbon,
  (iv) absence of d-orbitals in its valence shell and
• In +4 oxidation state these elements act as oxidizing   (v)  ability to from multiple bonds.
agents and their oxidation power increases down the
group due to decrease in the stability of +4 oxidation • The catenation power of Group IVA elements is in the
state. order C > > Si > Ge > Sn > Pb.
• All the compounds of IVA group elements in +4 • Allotropy is the occurrence of the same element in two or
oxidation state are covalent. Most of the compounds more different physical forms having more or less simi-
of carbon and silicon in +2 oxidation state are also lar chemical properties but different chemical properties.
­covalent. Ge, Sn and Pb tend to form M2+ ions. The • Different forms of the element are called allotropes
tendency to form ionic compounds increases from Ge and they may be either crystalline or amorphous.
to Pb in +2 oxidation state. • The type of allotropy where at ordinary temperatures
• In Group IVA elements, only carbon can form pπ–pπ and pressures one allotrope is thermodynamically stable
multiple bonds between carbon atoms. But other IVA than the other but can exist together is called monotropy.
group elements do not form pπ–pπ multiple bonds • Except lead all the elements of IVA group exhibit
between their atoms. This is because with increase in allotropy.
atomic size lateral overlap of p-orbitals becomes dif- • Crystalline allotropes of carbon are diamond, graphite,
ficult due to increase in the distance between atoms.
fullerenes and these are monotropic allotropes.
• The maximum covalency of carbon is only 4 as it does • Amorphous allotropes of carbon are coal, coke, wood
not contain d-orbitals in its valence shell, but other
charcoal, animal charcoal, lamp black, carbon black,
elements can exhibit a covalency up to 6 by using the
gas carbon, petroleum coke and sugar charcoal.
vacant d-orbitals in their valence shell.
• If only one allotrope exist at a particular temperature
• Except in carbon, the d-orbitals of valence shell of
but transform into another allotrope when temperature
other elements can participate in pπ–pπ bonding,
changes, then it is called enantiotropy.
e.g., trimethyl amine is pyramidal but trisilyl amine is
planar triangular as the lone pair electrons of nitrogen • Silicon, germanium and tin exhibit enantiotropic
delocalize into the vacant d-orbital of silicon in trisilyl allotropy.
amine. • The temperature at which one allotrope transforms
into another and are in equilibrium at that temperature
SiH3 SiH3 is called transition temperature.
H3Si N H3Si N
SiH3
SiH  Objective Questions
SiH3
1. Which of the following statement is false about IVA
H3Si N group elements?
SiH3 (1) Carbon has maximum catenation power.
(2) Lead shows pronounced inert pair effect.
(3) Germanium is a metal.
• Due to the same reason H3Si = N = C = O is linear
 = C = O is angular. The bond angle (4) Carbon occurs in both native and combined states.
while H3C – N
in (R3Si)2O is more than in (R3C)2O. Silonols such 2. Which statement is correct with respect to the pro­
as SiOH are stronger protonic acids than carbon perty of the elements with increase in atomic number
analogues. of the carbon family?

Chapter_13.indd 2 3/26/2014 3:25:10 PM

 The Carbon Family  13.3

(1) Their metallic character decreases. 10. Germanium (II) compounds are powerful ­reducing
(2) The stability of +2 oxidation state increases. agents while lead (IV) compounds are oxidants.
(3) Their ionization energies increase. It can be due to
(4) Their electronegativities decrease. (1) Lead is more electropositive than germanium.
3. Carbon and silicon belong to IVA group. The maxi- (2) The ionization potential of lead is less than that
mum coordination number of carbon in commonly of germanium.
occurring compounds is 4, whereas that of silicon (3) The ionic radii of Pb2+ and Pb4+ are larger than
is 6. This is due to that of Ge2+ and Ge4+.
(4) More pronounced inert pair effect in lead than in
(1) Large size of silicon
germanium.
(2) Availability of vacant d-orbitals in silicon
(3) More electropositive nature of silicon 11. The maximum catenation power of carbon is because of
(4) Silicon being vulnerable to attack by nucleo (1) Carbon has vacant d-orbitals.
philic reagents (2) C–C bond strength is low.
4. Which is not a characteristic property of carbon? (3) The number of valence electrons is equal to
number of valence orbitals and high C–C bond
(1) Catenation
­energy.
(2) Multiple bond formation
(4) Carbon shows variable valency.
(3) Availability of d-orbitals for bonding
(4) Highest electronegativity in the group 12. Regarding the elements of Group IVA, which of the
following statement is false?
5. Carbon differs from other elements of the group.
Which is the false statement? (1) Lead do not exhibit allotropy.
(2) Element with lowest melting point is tin.
(1) Due to its limitation of coordination number 4.
(3) Carbon in the form of diamond has maximum
(2) Due to d-orbitals in the penultimate shell.
density.
(3) Due to its unique ability to form multiple bonds.
(4) Catenation power of lead is zero.
(4) Due to marked tendency to form long chains
(catenation power). 13. Which of the following statements is false?
6. Identify the false statement regarding Group IVA (1) Electronegativity values of Si, Ge, Sn and Pb are
­elements. equal.
(2) Electronegativity of carbon is greater than silicon.
(1) Lead is the densest element.
(3) Density of silicon is more than that of carbon
(2) Silicon is denser than diamond.
(diamond).
(3) M–M bond energy is highest for carbon.
(4) The atomic radius of Si is greater than that of
(4) Order of catenation power is C > Si > Ge > Sn.
carbon.
7. Which is false about of carbon?
14. Identify the correct statement.
(1) It exhibits catenation.
(2) Its ionization energy is very high. (1) The density of IVA group elements increases
(3) It forms compounds with multiple bonds. with atomic number.
(4) It shows inert pair effect. (2) The density of IVA group elements decreases
with atomic number.
8. The elements of IVA group have 4 electrons in their (3) The density of carbon is least in IVB group
outermost orbit. They ­elements.
(1) form M4+ ions (4) The density of silicon is less than that of carbon.
(2) form M4+ and M4- ions.
15. Which of the following statements is not correct?
(3) exhibit oxidation states of +4 and +2.
(4) exhibit oxidation states of +4. (1) Among IVA group elements only carbon forms
multiple bonds.
9. Carbon exists in (2) The m.pts and b.pts of carbon and silicon are much
(1) free state like coal higher than those of the other elements of group 14.
(2) the form of CO2 (3) The IP of lead is more than that of tin.
(3) combined state as carbonate (4) The elements of group 14 are more electronega-
(4) All of these forms tive than those of group 13.

Chapter_13.indd 3 3/26/2014 3:25:11 PM

 13.4  Objective Chemistry - Vol. I

16. Which one of the following is correct about stability • Lead is less reactive partly due to the presence of an
of the given ions? oxide layer on the surface and partly due to hydrogen
(1) Pb2+ > Pb4+ (2) Pb4+ > Pb2+ overvoltage.
(3) Si > Si
2+ 4+
(4) Sn2+ > Sn4+ • These elements are not attacked by air at ordinary
temperature.
17. The catenation tendency C, Si and Ge is in the order
Ge < Si < C. The bond energies (in kJ mol-1) of C–C, • Though the reaction of carbon with oxygen is highly
Si–Si and Ge–Ge bonds respectively are exothermic, it will not take place because of the high
(1) 167, 180, 348 (2) 180, 167, 348 activation energy.
(3) 348, 167, 180 (4) 348, 180, 167 • On heating, all these elements combine with oxygen
forming dioxides, whereas lead forms monoxide.
18. Carbon shows catenation while silicon shows little
because
• Water has no action on these elements. However, at
red hot condition these elements decompose steam
(1) Silicon is a metalloid and carbon is a nonmetal.
­forming hydrogen.
(2) Silicon forms ionic compounds, whereas carbon
forms covalent compounds. • Lead is not affected by pure water except at the
(3) The Si–Si bond is stronger than C–C bond. boiling point, but dissolves slowly in water containing
(4) The C–C bond is stronger than Si–Si bond. dissolved oxygen. This is known as plumbosolvancy.
2Pb + 2H2O + O2  → 2Pb(OH)2
19. In the last shell of an atom two electrons are present
in s-orbital and two electrons are present in p-orbital, • Carbon is not attacked by non-oxidizing acids such as
but found in very small quantity in the earth crust. HCl. However, it is oxidized to CO2 by oxidizing acids
The element is such as conc. HNO3 and conc. H2SO4.
(1) C (2) Si (3) Ge (4) Pb • Except with HF silicon do not react with other acids.
• Germanium can react with hot conc. HCl forming
20. Two elements A and B of carbon family have very
germanium chloroform and germanium tetrachloride.
close atomic radii. The elements A and B are
It also dissolves in conc. H2SO4.
(1) Pb and Sn (2) C and Si
(3) Ge and Sn (4) Si and Ge
• Tin dissolves slowly in dil. HCl but rapidly in conc.
HCl liberating H2. The slow reaction in dil. HCl is due
21. The elements lead, silicon, germanium, tin and ­carbon to high hydrogen over voltage at the surface.
all lie in the same group of the periodic table. Which • Sn reduces conc. H2SO4 to SO2.
of the following is true?
• Sn reduces dil. nitric acid to ammonium nitrate while
(1) Like carbon, all the elements are nonmetals.
with conc. HNO3 itself is converted to metastannic
(2) Carbon is closer in properties to silicon than tin
acid liberating NO2 gas.
and lead.
(3) Tin is closer in properties to lead than carbon is • Lead dissolves in hot conc. HCl due to the formation
to silicon. of chloroplumbous acid (H2PbCl4).
(4) Like tin, all the elements are metals. • Lead becomes passive with conc. H2SO4 due to the
formation of insoluble lead sulphate on the surface.
Answers • Lead with dil. HNO3 liberates NO while with conc.
HNO3 liberates NO2 converting itself to Pb(NO3)2.
  (1) 3   (2) 2   (3) 2   (4) 3   (5) 2 • Carbon is not attacked by the alkalis. The remaining
  (6) 2   (7) 4   (8) 3   (9) 4 (10) 4 elements react with alkalis forming their soluble alkali
(11) 3 (12) 3 (13) 3 (14) 4 (15) 1 salts and liberate hydrogen.
(16) 1 (17) 4 (18) 4 (19) 3 (20) 1 • Carbon reacts with metals directly at high tempera-
(21) 3 tures forming metal carbides.
• Silicon also reacts with several metals forming silicides.
• Germanium, tin and lead form alloys with other
Chemical Reactivity metals.
• Elements of Group IVA are relatively unreactive, but • At high temperature carbon can react with many non-
reactivity increases down the group. metals including hydrogen.

Chapter_13.indd 4 3/26/2014 3:25:15 PM

 The Carbon Family  13.5

• Carbon in the form of white coke reacts with sulphur 26. With concentrated nitric acid tin forms
forming carbon disulphide. (1) ammonium nitrate (2) metastannic acid
• Carbon reacts with fluorine forming CF4, with boron (3) NO2 gas (4) both 2 and 3
forming boron carbide B4C.
27. Carbon cannot react with oxygen in air at ordinary
• Silicon in massive form does not react with oxygen, temperature because
water and steam but burn in oxygen at high temperature (1) carbon has no reaction with oxygen
forming SiO2 and decompose steam liberating H2 gas. (2) the activation energy of the reaction of carbon
• Silicon reacts with sulphur vapour at 600°C forming with oxygen is very high
SiS2 analogue to CS2 but SiS2 have polymeric structure (3) carbon becomes passive in air
since silicon cannot from pπ–pπ bonds. (4) carbon and oxygen both are nonmetals

S S S 28. Carbon disulphide is a liquid but silicon disulphide is
S=C=S Si Si Si Sr a polymeric solid. This is because
S S S (1) CS2 is nonpolar but SiS2 is polar
(2) carbon can form strong pπ–pπ bonds with ­sulphur
• Silicon can react with almost all halogens forming but silicon cannot
tetrahalides. (3) of strong molecular attractive forces between
• Tin reacts readily with Cl2 and Br2 in the cold and with larger SiS2 molecules
F2 and I2 on warming giving SnX4. (4) CS2 is covalent while SiS2 is ionic
• Lead reacts with fluorine at room temperature, with
chlorine on heating to form PbF2 and PbCl2. Answers
• Group IVA elements can act as good reducing agents.
Carbon is used as a reducing agent in the extraction of (22) 2 (23) 3 (24) 3 (25) 2
several metals. Silicon is also used as a deoxidizer in (26) 4 (27) 2 (28) 2
the manufacture of steel in the form of ferrosilicon.
Tin also act as a good reducing agent.
compounds of elements of
 Objective Questions group IVA comparative study

22. Lead pipes are not suitable for drinking water because 1. Hydrides
(1) lead forms basic lead carbonate • All the elements of Group IVA form covalent hydrides.
(2) lead reacts with water containing air to form • The number of hydrides formed by these elements and
Pb(OH)2 the ease with which these are formed decreases as we
(3) a layer of lead dioxide is deposited over pipes move down the group.
(4) lead reacts with air to form litharge
• Carbon forms a large number of stable hydrides known
23. Plumbosolvancy means dissolution of lead in as hydrocarbons, because of its catenation power.
(1) hot water (2) acids • Silicon forms a limited number of hydrides called
(3) ordinary water (4) alkalis ­silanes due to small Si–Si bond energy.
24. Tin (II) fluoride can be prepared by • Germanes containing up to six Ge atoms are known.
(1) treating tin with F2 • Tin forms only two hydrides, stannane (SnH4) and
(2) treating tin with HF ­distannane (Sn2H6).
(3) dissolving SnO in HF • Lead forms only one hydride called plumbane, PbH4.
(4) none of these • Thermal stability of the hydrides of the type MH4
25. Tin reacts with conc. H2SO4 to give get decreased from carbon to lead as the bond energy
(1) α-stannic acid ­decreases with increase in atomic size.
(2) stannous sulphate • The stability of higher hydrides also decreases from
(3) β-stannic acid carbon to tin. This is (i) due to decrease in M–M bond
(4) stannic sulphate energy and (ii) due to electronegativity differences.

Chapter_13.indd 5 3/26/2014 3:25:16 PM

 13.6  Objective Chemistry - Vol. I

• Carbon is more electronegative than hydrogen and • Carbon and silicon do not form dihalides.
due to its –I effect, the electron density in C–C bonds • The stability of the dihalides increases down the group.
increases and thus strengthens the bond. But in other This is due to inert pair effect.
elements hydrogen is more electronegative than IVA • Dihalides are ionic solids and have more melting
group elements and due to its –I effect the electron
points than the corresponding tetrahalides which are
density in M–M bond decreases, decreasing the sta-
covalent.
bilities of higher hydrides.
• All the tetrahalides and dihalides are colourless but
• Due to decrease in thermal stability of hydrides from
SnI4 is bright orange and PbI2 is yellow because of
top to bottom, their reduction power increase from
charge transfer.
CH4 to PbH4.
• Except CH4 hydrides of other elements hydrolyze in 3. Oxides
alkalis. The order of stability of these hydrides towards
alkali is CH4 > GeH4 > SnH4 > SiH4. • All the elements of Group IVA form mainly two types
• Silanes easily react with alkali because of the Si–H of oxides: monoxides of the type MO and dioxides of
bond polarity and the availability of d-orbitals with the type MO2.
silicon atom. • SiO is least stable because silicon cannot from pπ–pπ
bonds with oxygen.
2. Halides • CO is neutral, GeO is acidic and SnO and PbO are
amphoteric due to increase in electropositive character
• All the Group IVA elements form tetrahalides of the down the group.
type MX4 except PbBr4 and PbI4. • Stability of monoxides increases down the group due
• PbBr4 and PbI4 do not exist because Br2 and I2 can to increase in the stability of +2 oxidation (inert pair
oxidize Pb2+ to Pb4+, i.e., Pb4+ ion is a strong oxidizing effect).
agent and Br- and I- ions are highly reducing agents • Monoxides can act as reducing agents and their reduc-
resulting in the formation of divalent PbBr2 and PbI2.
tion power decreases down the group due to increase
• All the tetrahalides are volatile and covalent except in stability of +2 oxidation state. Reactivity of monox-
SnF4 and PbF4 which are ionic and high meting solids. ides also decreases in a similar manner.
• Thermal stability of tetrahalides of different elements • All the Group IVA elements form dioxides of the
of Group IVA with common halogen decreases with type MO2.
increase in atomic number. • CO2 and SiO2 are acidic, GeO2 is also distinctly
CX4 > SiX4 > GeX4 > SnX4 > PbX4 acidic but less acidic than SiO2. SnO2 and PbO2 are
• With a particular element of Group IVA the stability is amphoteric.
in the order: • All the dioxides dissolve in alkalis giving carbonates,
MF4 > MCl4 > MBr4 > MI4 silicates germanates, stannates and plumbates.
This is due to decrease in bond energy with increase in • GeO2, SnO2 and PbO2 are insoluble in acids but dis-
bond length as the atomic size increases. solve in the presence of complexing agents such as
• Halides of carbon do not undergo hydrolysis in water F- and Cl- e.g., [GeF6]2-, [SnCl6]2- and [PbCl6]2-.
due to the absence of vacant d-orbitals in the valence • Stabilities of dioxides decrease down the group from
shell of carbon. CO2 to PbO2 due to inert pair effect.
• The tertrahalides of all the other elements hydrolyze in • Dioxides will act as oxidizing agents and their
water forming hydrogen halide and M(OH)4. ­oxidation power increases down the group.
• The hydrolysis of SiF4 gives H2SiF6 and Si(OH)4. • CO2 is a gas while other dioxides are solids.
• Except carbon halides the tetrahalides of other Group • CO2 is a linear non-polar molecule. So only weak Van
IVA elements can act as Lewis acids as they contain der Waal’s forces exist between CO2 molecules and
vacant d-orbitals in their valence shells. e.g., [SiF6]2-, hence it is a gas.
[GeF6]2-, and [SnCl6]2-. • Since silicon cannot form pπ–pπ bond with ­oxygen,
• SiCl4 cannot form complex [SiCl6]2- because silicon silicon is involved in sp3 hybridisation and is in bond
cannot be coordinated by bigger six chloride ions. with four oxygen atoms tetrahedrally. Thus  every

Chapter_13.indd 6 3/26/2014 3:25:16 PM

 The Carbon Family  13.7

silicon is in bond with oxygen atoms while every (1) high electronegativity of silicon than hydrogen
o­ xygen atom is in bond with two silicon atoms result- (2) high electronegativity of hydrogen than carbon
ing in a giant polymeric structure. So, SiO2 is a high (3) high electronegativity of carbon than hydrogen
melting solid. (4) equal electronegativity of carbon and hydrogen
• Carbon also forms suboxide C3O2 having the structure 38. SiF4 on hydrolysis gives
O=C=C=C=O (1) SiO2 + H2SiF6 (2) H4SiO4 + SiO2
(3) H2SiF6 (4) H4SiO4 + H2SiF6
39. SiCl4 + H2O 
→ X + HCl
 Objective Questions
X 1000°
 C
→Y
29. The elements which forms neutral as well as acidic
oxide is X and Y in the above reactions are
(1) Sn (2) Si (3) C (4) Pb (1) SiO2 and Si (2) H4SiO4 + SiO2
(3) Si and SiO2 (4) H4SiO4 + Si
30. CCl4 does not show hydrolysis but SiCl4 is readily
­hydrolyzed because 40. In SiO2 the bonds present between silicon and
­oxygen are
(1) Carbon cannot expand its octet but silicon can
expand. (1) single (2) double
(2) Electronegativity of carbon is higher than that of (3) ionic (4) π-bonds
silicon. 41. Which of the following statements regarding CO2 and
(3) IP of carbon is higher than that of silicon. SiO2 is false?
(4) Carbon forms double bonds and triple bonds but (1) At room temperature CO2 is a gas, whereas SiO2
not silicon. is a solid.
31. Silicon hydrides are named as (2) They differ in their structures.
(1) Silicones (2) Silicates (3) Both are acidic oxides.
(3) Silicols (4) Silanes (4) CO2 and SiO2 both contain multiple bonds.

32. Which of the following statement is false? 42. Which of the following can react with cold water?
(1) GeO2 is amphoteric. (1) SiCl4 (2) CCl4
(2) CO is neutral to litmus. (3) SiO2 (4) Silicon
(3) SiO2 is solid at room temperature. 43. Which of the following reactions is not correct?
(4) SiO does not exist because silicon cannot form (1) SiF4 + 2F-  → SiF62-
pπ–pπ bonds with oxygen. (2) GeCl4 + 2Cl - → GeCl62-
-  → SnCl62-
33. Which is not correct? (3) SnCl4 + 2Cl
(1) Ge(OH)2 is amphoteric. (4) SiCl4 + 2Cl -  → SiCl62-
(2) GeCl2 is more stable than GeCl4. 44. Which of the following statements is not correct?
(3) GeO2 is less acidic than SiO2. (1) The dihalides of 14th group elements are more
(4) GeCl4 in HCl forms [GeCl6 ] .
2−
ionic as compared to their tetrahalides.
(2) GeX2 is less stable than GeX4.
34. When SnCl4 is treated with excess of conc. HCl, the (3) PbX2 is less stable than PbX4.
complex SnCl62- is formed. The oxidation state of Sn (4) Silicon cannot form monoxide.
in this complex is
(1) +6 (2)  +4 (3)  –2 (4)  +2 45. Which of the following statements is not correct?
(1) Silicon halides are rapidly hydrolyzed by water to
35. The compound which is not completely saturated is form silicic acid.
(1) CH4 (2)  C4H10 (3)  CCl4 (4)  SiCl4 (2) Carbon halides are Lewis acids.
36. Anhydride of orthosilicic acid is (3) In silicon halides OH- ions may be coordinated
as a first step in hydrolysis.
(1) Si (2) SiO2 (3)  H2SiO3 (4) SiO
(4) In the presence of excess of acid the halides of
37. Greater stability of hydrocarbons when compared to Si, Ge, Sn and Pb increase their coordination
silanes is due to number from 4 to 6 and form complex ions.

Chapter_13.indd 7 3/26/2014 3:25:18 PM

 13.8  Objective Chemistry - Vol. I

46. Which of the following statements is correct? • All the valence electrons in carbon atoms of diamond
(1) Carbon can form double bonds and CO2 contains are involved in covalent bonding, there are no free
discrete molecules. electrons. Hence, diamond is an insulator.
(2) Silicon cannot form double bonds and hence SiO2 • Diamond has the highest known thermal ­conductivity
forms an infinite three-dimensional ­structure. because its 3D structure distributes thermal motion in
(3) CO2 is a gas but SiO2 is a high melting solid. three dimensions very effectively.
(4) All are correct. • When diamond is heated in vacuum at about 1500°C it
47. The reducing character of hydrides of Group IV converts into graphite showing that diamond is chemi-
­elements is cally inert but thermodynamically unstable.
(1) maximum for CH4 and minimum for PbH4 • When burned in air at about 1000°C it converts into
(2) maximum for CH4 and minimum for SnH4 carbon dioxide.
(3) maximum for PbH4 and minimum for SiH4 • Measurement of thermal conductivity is used to
(4) maximum for PbH4 and minimum for CH4 ­identify the fake diamonds.
• Diamonds are used as precious stones.
Answers • Diamond dies are used in making cutting tools such as
glass cutters and rock drilling units.
(29) 3 (30) 1 (31) 4 (32) 1 (33) 2
(34) 2 (35) 4 (36) 2 (37) 3 (38) 4 • By using a diamond die, very thin tungsten wires ­having
(39) 2 (40) 1 (41) 4 (42) 1 (43) 4 a thickness of 1/6 of human hair can be prepared.
(44) 3 (45) 2 (46) 4 (47) 4

Graphite
Allotropes of carbon • Artificially graphite can be prepared by Acheson
method.
Diamond
• In Acheson method when a mixture of sand and coke
• The quality of diamonds is measured in terms of is heated at 3723 K silicon carbide known as carborun-
carats. One carat = 0.200 g or 200 mg.
­
dum will be formed. At high temperatures the silicon
• Kohinoor diamond is 186 carats and pit diamond is carbide decomposes giving silicon and graphite.
136.25 carats. • Graphite is thermodynamically more stable than
• Black diamonds are available in Brazil. ­diamond but chemically reactive than diamond.
• Pure diamonds are colourless and presence of impuri- • Graphite has a layered lattice structure.
ties imparts colour. • In graphite, every carbon is in sp2 hybridisation.
• Diamond is the hardest material known so far. • In each layer the carbon atoms are arranged hexago-
• Density of diamond is 3.5 g/cc. nally like benzene and every carbon is in bond with
three other carbon atoms.
• Diamonds glitter due to high refractive index of 2.45.
• The C–C bond distance in each layer is 1.42 Å while
• Diamond is insoluble in any solvent and is chemically
the distance between the layers is 3.35 Å.
inert.
• The layers in graphite are held together by weak Van
• In diamond every carbon is in sp3 hybridisation.
der Waal’s attractive forces. Hence, they are slippery
• Several tetrahedrons of carbon are joined three one above the other. So, it can be used as a solid
dimensionally. lubricant.
• Diamond is a giant covalent molecule. • Every carbon in graphite contains one p-orbital that
• The C–C bond length in diamond is 1.54 Å and the has not participated in hybridisation in which one
bond angle is 109°28′. unpaired electron is present. Because these electrons
• The high hardness, high density, high melting point move freely in the layer graphite acts as a good con-
and high boiling point of diamond are due to three- ductor of electricity.
dimensional (3D) structure which requires very high • Electrical conductivity occurs in a layer but not from
energy to break all bonds. one layer to another under normal conditions.

Chapter_13.indd 8 3/26/2014 3:25:18 PM

 The Carbon Family  13.9

• The electrical conductivity of graphite perpendicular • The ball-shaped C60 molecule contains 60 vertices and
to the planes is very low and increases with increas- each one is occupied by one carbon atom and it is in
ing temperature. Thus, graphite is a semiconductor both single and double bonds with C–C distances of
­perpendicular to the layers. 1.44 Å and 1.38 Å.
• With increase in temperature conduction decreases • The reduced fullerenes with alkali metals like K3C60,
in the layers and thus it behaves as a metal conductor Rb2CsC60 act as superconductors at about 18 K and
along the layers. 33 K, respectively.
• Graphite is grey-coloured substance having a metallic • Fullerenes are finding many applications in the produc-
lustre. tion of carbon nanometres.
• Since the distance between the layers is more, the • Fullerenes can also form complexes.
­specific gravity of graphite is less than diamond.
• By heating the graphite with conc. HNO3 repeatedly,
yellow coloured graphitic acid (C11H4O5) is formed.  Objective Questions
• Graphite is called black lead and is used in lead 48. Graphite is a good conductor of electricity but ­diamond
­pencils, which contains a mixture of clay and graphite. is nonconductor of electricity because
• Graphite is used (1) Diamond is hard and graphite is soft.
  (i) in making electrodes (2) Diamond and graphite have different atomic
 (ii) in painting the stoves ­configurations.
(iii) in making refractory crucibles used at high (3) Graphite is composed of positively charged ­carbon
­temperature and ions.
  (iv)  in electroplating. (4) Graphite has a hexagonal layer structure with
mobile π-electrons while diamond has a continu-
Fullerenes
ous tetrahedral covalent structure with no free
• Fullerenes are the only pure form of carbon. electrons.
• Unlike diamond and graphite which have a giant 49. Which of the following statements is wrong?
polymeric structure, fullerenes are discrete molecules
(1) The nature of bonding in diamond is only ­covalent
which appear like soccer ball and sometimes called as
while in graphite both covalent and Van der Waal’s
bucky balls or Buckminister fullerene.
forces exist.
• Fullerenes contain even number of carbon atoms such (2) Diamond and graphite are allotropes of carbon.
as C60, C70, C76, C84, etc. and range up to 350. (3) Diamond is a thermodynamically stable allotrope
• When an electric arc is struck between carbon while graphite is thermodynamically unstable
­electrodes in an atmosphere, the soot formed contains ­allotrope.
significant quantities of C60. (4) Diamond is chemically inert while graphite is
• Fullerenes have a smooth structure without having chemically reactive allotropes.
dangling bonds. 50. Difference between diamond and graphite is due to
• Fullerenes contain fused system of five- and six-­ (1) Graphite combines with oxygen to form carbon
membered rings. A six-membered ring is fused either dioxide but diamond does not.
with a six-membered ring or with a five-membered (2) The atoms in each have different masses.
ring but a five-membered ring is always fused with (3) The crystal structure in diamond is different form
six-membered rings only. that in graphite.
• C60 molecule contains twenty 6-membered rings and (4) All
twelve 5-membered rings. 51. Which of the following statements is not correct?
• All the carbon atoms in fullerenes are equal and they (1) Diamond has a 3D polymeric structure while
undergo sp2 hybridisation. graphite has a layered lattice structure.
• Each carbon atom forms three sigma bonds with other (2) Diamond is an insulator while graphite is a good
three carbon atoms. The remaining electron at each conductor of electricity.
carbon is delocalized in molecular orbitals which give (3) Diamond is a good conductor of heat than graphite.
aromatic character to the molecule. (4) Diamond and graphite have same densities.

Chapter_13.indd 9 3/26/2014 3:25:19 PM

 13.10  Objective Chemistry - Vol. I

52. The use of diamond as a gem depends on its (3) All the valence electrons in diamond participate
(1) hardness in sigma bonding while in graphite only three
(2) high refractive index ­electrons are involved in sigma bonding.
(3) purest form of carbon (4) Hybridisation of carbon in diamond and graphite
(4) chemical inertness is sp3 and sp2, respectively.

53. Graphite conducts electricity because of 61. Which of the following statements is false?
(1) weak Van der Waal’s forces between layers (1) Diamond and graphite have different lattice
(2) covalent bonding between carbon atoms of layers structures.
(3) delocalized electrons in each layer (2) Diamond is the purest form and graphite is the
(4) sp2 hybridisation of carbon atom in each layer impure form of carbon.
(3) Diamond can be used as an abrasive while ­graphite
54. Which property is common in diamond and graphite?
can be used as a lubricant.
(1) Electrical conductivity (4) Both on burning in air give CO2.
(2) Relative atomic weight
(3) Crystal structure 62. Graphite is used in nuclear reactors
(4) Density (1) as a lubricant
55. In graphite, electrons are (2) as a fuel
(3) for lining inside walls of the reactors as an ­insulator
(1) localized on each carbon
(4) for decreasing the velocity of neutrons
(2) delocalized along the layers
(3) localized on every third carbon 63. The distance between the layers of graphite is 3.35 Å.
(4) present in anti-bonding orbital Which of the following cannot be attributed as a
56. Diamond is hard because ­consequence of this?
(1) It is made up of carbon atoms. (1) Sigma bond is not possible between carbon ­atoms
(2) All the valence electrons of each carbon atom are in different layers.
involved in bonding. (2) Density of graphite is less than diamond.
(3) It is a giant molecule. (3) Graphite is a good conductor of electricity.
(4) It is colourless. (4) Different layers are held only by Van der Waal’s
attractive forces.
57. When diamond is strongly heated to 2000°C in ­vacuum,
we get 64. The false statement about the manufacture of ­graphite:
(1) amorphous carbon (2) charcoal (1) Graphite is manufactured by Acheson method.
(3) graphite (4) fullerene (2) The raw materials used in the manufacture of
graphite are coke and silica.
58. Which is not the property of diamond? (3) The intermediate formed during the production
(1) It is insoluble in all solvents. of graphite is silicone.
(2) In pure form it is colourless. (4) Graphite is manufactured in electric furnace.
(3) It gives graphitic acid when heated with conc. HNO3.
65. Which one of the following allotropic from of carbon
(4) It is the densest allotrope of carbon.
is isomorphous with crystalline silicon?
59. The melting point of diamond is very high since the (1) Graphite
type of bonding in it is (2) Coal
(1) ionic (3) Coke
(2) Van der Waal’s (4) Diamond
(3) polymeric network
66. The interlayer distance in graphite is
(4) coordinate
(1) very small, the layers being tightly packed
60. Which of the following statements is wrong? (2) many times larger than the covalent radius of
(1) The C–C bond length in diamond is greater than ­carbon
in graphite. (3) about four times more than the covalent radius of
(2) The bond angle in diamond is greater than in carbon
graphite. (4) the same as the covalent radius of carbon

Chapter_13.indd 10 3/26/2014 3:25:19 PM

 The Carbon Family  13.11

Answers • It is a strong reducing agent and reduces several metal

oxides to their corresponding metals.
(48) 4 (49) 3 (50) 3 (51) 4 (52) 2 PbO + CO  → Pb + CO2
(53) 3 (54) 2 (55) 2 (56) 2 (57) 3 Fe2O3 + 3CO  → 2Fe + 3CO2
(58) 3 (59) 3 (60) 2 (61) 2 (62) 4 • Since all valencies of carbon in CO are not satisfied, it
(63) 3 (64) 3 (65) 4 (66) 3
behaves as an unsaturated compound and gives addi-
tion compounds with Cl2, H2 and S.
compounds of carbon CO + Cl2 Sun
 light
→ COCl2
+ Cu
Carbon Monoxide CO + 2H2 ZnO  → CH3OH
CO + S → COS
heat

• It is present in the exhaust fumes of coal furnace and

• Solid caustic soda absorbs CO and forms sodium formate.
automobile.
CO + NaOH pressure
→ HCOONa
• It can be prepared by burning carbon in limited supply
of oxygen at1000°C or more • It combines with Ni at 50°C–80°C to give nickel
2C + O2  → 2CO tetracarbonyl.
• Industrially CO is prepared from water gas obtained
Ni + 4CO  → Ni(CO)4
by passing steam over red hot coke. • When CO is passed through ammoniacal cuprous
C + H2O  → CO + H2 ­chloride solution addition compound is formed.
When water gas is cooled CO liquifies while H2 CuCl + CO + 2H2O  → CuCl ⋅ CO ⋅ 2H2O
escapes. • In CO, carbon is in sp hybridisation.
• Water gas also known as synthesis gas since it is used • In CO there is a sigma bond, a π bond and a dative
in the manufacture of several compounds. bond between carbon and oxygen : C = ←
O:
• If air is used instead of steam producer gas is formed. • Due to the dative bond from oxygen to carbon, CO is
• Producer gas is a mixture of CO and N2. nonpolar.
• Since CO in producer gas and CO and H2 in water • CO can donate the lone pair of electrons on carbon to
gas can burn with liberation of heat they are used as metal atoms and can form metal carbonyls.
­industrial fuels. • CO turns the filter paper dipped in a solution of ­platinic
• In the laboratory CO can be prepared by the action of or palladium chloride to pink, green or black.
conc. H2SO4 on formic acid or oxalic acid. • CO liberates iodine from iodine pentoxide which gives
violet colour in CHCl3, CCl4 or CS2.
HCOOH conc.  H 2 SO4
→ H2O + CO
I2O5 + 5CO  → I2 + 5CO2
(COOH)2 → H2O + CO + CO2
conc. H 2 SO4

• It is used in the purification of Ni by Mond’s process.

When the mixture of CO and CO2 is passed through
caustic potash CO2 is removed in the form of K2CO3. • It is used in metallurgy as a reducing agent.
• It can also be prepared by heating CO2 with coke or • It is used in the preparation of methyl alcohol and
zinc dust. phosgene.
C + CO2  → 2CO
Carbon Dioxide
• Heating the potassium ferrocyanide crystals with
conc. H2SO4 gives CO • Air contains about 0.03% of CO2.
K4[Fe(CN)6] + 6H2SO4 + 6H2O → 2K2SO4 + • It is produced in animal respiration, combustion,
FeSO4 + 3(NH4)2SO4 + 6CO ­fermentation process, etc.
• It is slightly soluble and less soluble than CO2 in water. • It can be prepared by heating carbonates or bicarbonates.
• It is deadly poisonous and neutral to litmus. CaCO3 ∆ → CaO + CO2
• It is a nonsupporter of combustion but itself burns 2NaHCO3  → Na2CO3 + H2O + CO2
with a blue flame. • It can also be prepared by the action of dil. acids on
2CO + O2  → 2CO2 carbonates or bicarbonates.

Chapter_13.indd 11 3/26/2014 3:25:24 PM

 13.12  Objective Chemistry - Vol. I

Na2CO3 + H2SO4  → Na2SO4 + H2O + CO2 • It is a linear molecule.

NaHCO3 + HCl  → NaCl + H2O + CO2 O=C=C=C=O
• In the laboratory it is prepared by the action of dil. HCl
on marble pieces. Carbonic Acid
CaCO3 + 2HCl  → CaCl2 + H2O + CO2
• When carbon dioxide dissolves in water the greater
• It is heavier than air. part of it is loosely hydrated. The hydrated species are
• It is soluble in water and the solubility increases with in equilibrium with carbonic acid, hydrogen ions, and
increase in pressure. hydrogen carbonate and carbonate ions.
• CO2 can be liquefied at 20°C by applying a pressure of CO2 + aq  
 CO2(aq)  
 H2CO3  
50–60 atm. H+ + H CO3−  
 2H +
+ CO 2−
3
• Solid CO2 is known as dry ice. • Pure carbonic acid cannot be isolated but solid
• Solid CO2 is used as refrigerant under the name, ­carbonates are plentiful and group IA metals from
drikold or Cordice. solid hydrogen carbonates.
• Dry ice is manufactured by rapid evaporation of liquid • The properties of carbonic acid can be considered
CO2 at 20°C under a pressure of about 68 atm. as the properties of carbonate ion by taking sodium
• Solid CO2 is harmful to the skin and gives a burning ­carbonate as an example as explained in Group I.
sensation.
• CO2 is noncombustible and nonsupporter of combus- Carbides
tion but active metals like Na, K and Mg continue
burning in CO2. • Carbides are the binary compounds of carbon with less
2Mg + CO2  → 2MgO + C electronegative elements than itself i.e., with ­elements
such as Ca, Al, Be and Si.
• Though CO2 is used as a fire extinguisher it cannot be
used to extinguish metal fires.
• Carbides are classified according to the type of
bonding.
• CO2 is an acidic oxide and its aqueous solution turns
the blue litmus to red.
• Ionic or salt like carbides are formed by strongly
­electropositive elements. These contain ionic bonds.
CO2 + H2O  → H2CO3
These are of three types.
• CO2 is known as carbonic anhydride. • The carbides which liberate acetylene gas on hydrolysis
• It is reduced to CO by red hot carbon of zinc. −
are called acetylides. They contain C2− 2 ( − C ≡ C −)
• When CO2 is passed through lime water first it turns to ion, e.g., Na2C2, CaC2, etc.
milky which disappears by excess of CO2. • The carbides which give methane gas on hydrolysis
Ca(OH)2 + CO2  → CaCO3 + H2O are called methanides. These contain C4- ion, e.g.,
CaCO3 + H2O + CO2  → Ca(HCO3)2 Be2C, Al4C3.
• In CO2, carbon is in sp hybridisation. • Magnesium carbide is the only allylide which gives
• CO2 has non-polar linear structure. propyne on hydrolysis.
• A mixture of 10% CO2 in oxygen is known as Mg2C3 + 4H2O  → 2Mg(OH)2 + CH3–C≡CH2
­carbogen, which is used for artificial respiration to the • Covalent carbides are formed with elements having
victims of CO poisoning. similar electronegativity with carbon. These contain
• CO2 is used in aerated water. covalent bond, e.g., SiC, B4C.
• Silicon carbide is known as carborundum ­having
Carbon Suboxide structure similar to diamond and it is as hard as
diamond. So, it is used for making cutting tools and
• It is prepared by the dehydration of malonic acid.
abrasives.
3CH2(COOH)2 + P4O10  → 3C3O2 + 4H3PO4
• In silicon carbide both carbon and silicon are involved
• It decomposes at 200°C into CO2 and C. in sp3 hybridisation and the tetrahedrons of carbon and
C3O2 ∆ → CO2 + C silicon are arranged alternatively.

Chapter_13.indd 12 3/26/2014 3:25:27 PM

 The Carbon Family  13.13

• Interstitial carbides are formed by transition metals

due to the presence of carbon atoms in the interstitial  Objective Questions
voids of metal crystals, e.g., WC, TiC, ZrC, etc.
67. Which of the following statements is false?
• Interstitial carbides are extremely hard and electrical (1) Carbon monoxide is a neutral gas.
conducting. (2) Carbon monoxide is absorbed by ammonical
• Tungsten carbide is used to make cutting and drilling ­cuprous chloride.
tools. (3) Carbon monoxide combines with haemoglobin
forming carboxyhaemoglobin which does not
have oxygen-carrying capacity.
Carbon–Nitrogen Compounds
(4) Carbon monoxide can be used as a fire ­extinguisher.
• Lime stone on heating with coke forms calcium 68. The correct statement among the following is
carbide. (1) Carbon dioxide can be directly converted into a
CaCO3  → CaO + CO2 solid by applying pressure.
CaO + 3C  → CaC2 + CO (2) Solid carbon dioxide is called dry ice.
(3) Solid carbon dioxide produces a cooling effect
• When calcium carbide is heated with nitrogen at
during sublimation so used as refrigerator under
1373 K, it gives calcium cyanamide.
the name drikold.
• Calcium cyanamide is used as a fertiliser and in the (4) All are correct.
manufacture of melamine plastics.
69. H2SO4 is not used for the preparation of CO2 from
• When calcium cyanamide is fused with carbon, ­sodium
marble chips because
carbonate sodium cyanide is formed.
(1) it does not react
CaCN2 + C + Na2CO3  → CaCO3 + 2NaCN (2) huge amount of heat is evolved
• Sodium cyanide is used for the extraction of gold and (3) the reaction is vigorous
silver. (4) Calcium sulphate is sparingly soluble and gets
• With strong acids NaCN liberates HCN which is a deposited on marble chips and stops the reaction
weak acid.
70. The false statement among the following is
• Industrially HCN is obtained by the reaction of ­ammonia (1) Dry ice is composed of solid CO2.
with methane at high temperature. (2) In dry ice the molecules are held together by
Pt catalyst ­dipole–dipole attractive forces.
CH4 + NH3  → HCN + 3H2
1500 K
(3) Anhydride of carbonic acid is carbon dioxide.
• Cyanides and HCN are extremely poisonous. (4) The hybridisation of carbon in CO2 molecule is sp.
• HCN is used in the manufacture of methyl ­methacrylate
71. Which of the following is not correct about carbon
polymer and adiponitrile (an intermediate for nylon).
monoxide?
• Cynogen (CN)2 is a pseudohalogen due to its resem- (1) In CO carbon is in sp hybridisation.
blance in properties with halogens. (2) CO contains a triple bond.
• Cynogen can be prepared by the oxidation of HCN (3) Both carbon and oxygen contain one lone pair each.
with O2 in the presence of silver catalyst or by the oxi- (4) In the formation of metal carbonyls, oxygen atom
dation of CN- by Cu2+. of CO donate a lone pair to metal.
4HCN + O2  → 2(CN)2 + 2H2O 72. Potassium ferrocyanide crystals on heating with
-  →
2Cu + 4CN
2+
Cu2(CN)2 + (CN)2 conc. H2SO4 produce
• Cynogen is a linear molecule and disproportionates in (1) CO2 (2) CO (3) (CN)2 (4) NO2
a basic solution to cyanide and cyanate ions.
73. Pure carbon monoxide can be obtained from
(CN)2 + 2OH-  → CN- + OCN- + H2O
(1) Sodium oxalate
• Treatment of calcium cyanamide with water gives (2) Nickel tetra carbonyl
cyanamide. (3) Formic acid
CaNCN + H2O  → CaO + H2NCN (4) Oxalic acid

Chapter_13.indd 13 3/26/2014 3:25:31 PM

 13.14  Objective Chemistry - Vol. I

74. Which of the following is not correct? (3) These carbides have chains of carbon atoms
(1) When CO is heated with NaOH under pressure ­running through a distorted metal structure.
forms sodium formate. (4) All are correct.
(2) CO combines with chlorine gives carbonyl ­chloride. 82. Which of the following statement is true for intersti-
(3) CO when heated with hydrogen in the presence tial carbides?
of ZnO and copper powder gives methane.
(1) They are mostly formed by the transition ­elements
(4) CO liberates iodine from iodine pentoxide.
particularly the Cr, Mn and Fe groups.
75. Identify the correct statement. (2) They have typically very high melting point and
(1) Hydrolysis of aluminium carbide gives methane. very hard.
(2) Only one allylide is known. (3) Tungsten carbide is used for cutting tools.
(3) Silicon carbide is a covalent carbide. (4) All are correct.
(4) Interstitial carbides are stochiometric. 83. Which of the following statements is false?
76. In which of the following carbides, the carbon atom is (1) Be2C and Al4C3 yield methane on hydrolysis.
tetrahedrally hybridised? (2) Mg2C3 yields propene on hydrolysis.
(1) SiC (2) Be2C (3) Al4C3 (4) All (3) Salt like carbide contain ( −C = C−)2− ion.
(4) Calcium carbide yields acetylene on hydrolysis.
77. Which of the following cannot be used to separate
CO and CO2?
(1) Conc. H2SO4 Answers
(2) Caustic potash
(67) 4 (68) 4 (69) 4 (70) 2 (71) 4
(3) Ammonical cuprous chloride solution
(72) 2 (73) 2 (74) 3 (75) 4 (76) 4
(4) Iodine pentoxide
(77) 1 (78) 4 (79) 4 (80) 2 (81) 4
78. Dry ice is effective in seeding clouds because (82) 4 (83) 2
(1) CO2 and H2O have similar crystal structure
(2) it increases water content of the cloud
(3) CO2 molecules offer nucleus for condensation Silicon
(4) upon sublimation, it lowers the temperature • Silicon does not occur in the nature in native state.
of water
• Silicon occurs mostly in the form of silica because of
79. Tungsten carbide is its great affinity towards oxygen.
(1) one of the hardest substance known • Aluminium silicate is the main constituent of clay and
(2) an interstitial compound rocks.
(3) a berthalloid compound
(4) all the above • Silicon exists in both crystalline and amorphous
­allotropic forms.
80. Which of the following statements is false?
• Deville first prepared crystalline silicon.
(1) SiC and B4C are covalent carbides.
• Amorphous silicon can be prepared by heating quartz
(2) SiC is widely used as an abrasive called
powder with magnesium powder.
­corrundum.
(3) SiC has a 3D structure of Si and C atoms each SiO2 + 2Mg  → 2MgO + Si
tetrahedrally surrounded by four atoms of other • Amorphous silicon can also be prepared by heating
kind. potassium silicofluoride with potassium.
(4) B4C is harder than SiC and used as an abrasive K2SiF6 + 4K  → 6KF + Si
and also as a shield from radiation. • Crystalline silicon can be prepared by heating ­potassium
fluosilicate with zinc or aluminium.
81. Which of the following statements is correct for inter-
stitial carbides? 3K2SiF6 + 4Al  → 4AlF3 + 6KF + 3Si
K2SiF6 + 2Zn  → 2ZnF2 + 2KF + 3Si
(1) The properties of these carbides are intermediate
between ionic and covalent. • Crystalline silicon can be prepared by passing silicon
(2) They are hydrolyzed by water and acids giving a tetrachloride vapours over molten aluminium.
mixture of hydrocarbons and hydrogen. 3SiCl4 + 4Al  → 4AlCl3 + 3Si

Chapter_13.indd 14 3/26/2014 3:25:36 PM

 The Carbon Family  13.15

• Commercial silicon of 96–98% used for the produc- • Silica can be prepared by heating orthosilicic acid that
tion of ferrosilicon and other alloys is produced by the is obtained by the hydrolysis of silicon tetrafluoride or
reaction of sand with coke in an electric furnace. chloride.
SiO2 + 2C 2273
 − 2773 K
→ Si + 2CO SiCl4 + 4H2O  → H4SiO4 + 4HCl
• Semiconductor grade silicon is prepared by the reduc- SiF4 + 4H2O 
→ H4SiO4 + 4HF
tion of highly pure SiCl4 /SiHCl3 with hydrogen or by H4SiO4 1000°
 C
→ SiO2 + 2H2O
the pyrolysis of SiH4.
• Silica is insoluble in water but slightly dissolves at
• Silicon crystals are light yellow but amorphous silicon high pressures and at 110°C.
is brown in colour with a m.pt. of 1420°C.
• Except with HF silica do not react with other acids.
• Crystalline silicon has the structure similar to
diamond. SiO2 + 4HF  → SiF4 + 2H2
• Silicon is used in making alloys like ferrosilicon and SiF4 + 2HF  → H2SiF6
­silicon bronze. • Silica dissolves in hot concentrated alkalis.
• Ferrosilicon is used as deoxidizer in steel ­industry. SiO2 + 2NaOH  → Na2SiO3 + H2O
Silicon bronze is used in making telephone and • At high temperatures, silica reacts with metal oxides.
­telegraph wires. SiO2 + Na2O  → Na2SiO3
SiO2 + CaO2  → CaSiO3
Silica (SiO2)
• When fused with metal carbonates, silica forms metal
• Silica exhibits polymorphism. Sand is one form of silicates.
silica. Sandstone is sand particles bounded by iron SiO2 + Na2CO3  → Na2SiO3 + CO2
oxide. Flint is amorphous silica associated with SiO2 + CaCO3  → CaSiO3 + CO2
quartz. Kiesulghur is a siliceous rock composed of
the remains of minute, dead marine organisms. • Silica is an acidic oxide. When heated to 1600 °C silica
converts into glass known as silica glass.
• Crystalline silica exists as quartz, tridimite and
crystobalite. These are interconvertible at suitable • Silica glass can withstand sudden changes in tempera-
temperature. ture and used in making laboratory ware.
• Pure silica is quartz. Quartz is known as rock cyrstal
• Silica when heated with carbon in an electric furnace
which contains hexagonal prisms and ends in hexago- converts into silicon carbide known as carborundum.
nal pyramids. SiO2 + 3C  → SiC + 2CO
• UV light can pass through quartz; so, it is used in ­making • Silica is used
optical instruments.    (i) in building construction.
• Pure quartz is colourless but when impurities are    (ii) in making quartz glass used in the preparation
present it is coloured. The quartz stones are used as of laboratory ware.
precious stones.   (iii) in making refractory materials by mixing with
• The ordinary quartz is α-quartz and it converts into clay and lime, to line inside the furnaces of steel
different forms at different temperatures. industry.
   (iv) coloured quartz stones are used as precious stones.
α-Quartz 575°
 C
→ β-Quartz 870°
 C
→ tridimite
   (v) transparent quartz is used in making lenses and
1470°
 C
→ crystoballite
cells of optical instruments.
• All forms of silica converts into liquid at about    (vi) as acidic flux in metallurgy.
1600°C.
 (vii) quartz is extensively used as a piezoelectric
• Amorphous forms of silica are agate, jaspar and onyx.
material in extremely accurate clocks, modern
• Silica is also present in the branches of the trees, radio and televisions.
outer layer of dry grass, claws of animals and quills (viii) silica gel is used as a drying agent and as a sup-
of birds. port for chromatographic materials and catalysts.
• Silica can be prepared by burning silicon in air.    (ix) kieselghur is used in filtration plants.

Chapter_13.indd 15 3/26/2014 3:25:40 PM

 13.16  Objective Chemistry - Vol. I

• Silica has a giant polymeric structure. 89. The product obtained when silica reacts with ­hydrogen
• In silica every silicon atom is in sp3 hybridisation. fluoride is
Every silicon is in bond with four oxygen atoms and (1) SiF4 (2) H2SiF4
every oxygen atom is in bond with two silicon atoms. (3) H2SiF6 (4) SiF2
• Silica has tetrahedral structure and several tetrahedrons 90. Which of the following is not a crystalline form of
are joined to form 3D network polymeric structure. silica?
• Silica is very hard and have high melting point since it (1) Onyx (2) Quartz
requires large amount of energy to break all the bonds (3) Tridimite (4) Crystaballite
in the 3D structure. 91. Which of the following is not an amorphous form of
• Though the structure of silica is similar to diamond silica?
the Si–O–Si bonds in silica are not as strong as in dia- (1) Kieselghur (2) Agate
mond. So both the hardness and melting point of silica (3) Jaspar (4) Crystoballite
are less than diamond.
92. The main constituent of clay and rocks is
Comparison between CO2 and SiO2 (1) sodium silicate (2) calcium silicate
(3) aluminium silicate (4) potassium silicate
  (i) CO2 is a gas while SiO2 is a solid.
93. Silicon has great affinity towards oxygen. So, silicon
 (ii) CO2 is linear while SiO2 is tetrahedral in structure.
occurs in the nature mostly in the form of
(iii) In CO2 carbon is in sp hybridisation while in SiO2
silicon is in sp3 hybridisation. (1) silicates (2) silica
  (iv) CO2 exist as discrete molecules between which (3) silicon (4) orthosilicic acid
only Van der Waal’s attractive forces exist, ­whereas 94. Hydrolysis of silicon tetrachloride gives
silica has a giant polymeric structure due to which (1) orthosilicic acid (2) metasilicic acid
CO2 is gas while SiO2 is solid. (3) parasilicic acid (4) silica
 (v) Both CO2 and SiO2 are acidic in nature but the
acidic character of SiO2 is less than CO2 95. SiO2 + CaCO3 ∆ →X +Y
X and Y in this reaction are
(1) CO2, Si (2) Si, CaCO3
(3) CaSiO3 + CO2 (4) Ca + SiO2 + CO2
 Objective Questions

96. Which of the following statements regarding CO2 and

84. Identify the false statement. SiO2 is false?
(1) Purest form of silica is known as quartz. (1) At room temperature CO2 is a gas, whereas SiO2
(2) Quartz is also known as rock crystal. is a solid.
(3) Quartz contains hexagonal prisms. (2) They differ in their structures.
(4) UV light cannot pass through quartz. (3) Both are acidic oxides.
85. Which is not true about SiO2? (4) CO2 and SiO2 both contain multiple bonds.
(1) It is a network solid. 97. Which of the following properties of silica is used in
(2) It is attacked by molten NaOH. making optical instruments?
(3) It is attacked by HF. (1) Its hardness.
(4) It is the basic structural unit of silicates. (2) Red hot quartz glass does not break when plunged
86. Silica is soluble in into water.
(1) H2O (2) HCl (3) H2SO4 (4) HF (3) Its transparency to UV light.
(4) Both 2 and 3
87. Orthosilicic acid on dehydration gives
98. Which of the following statements is correct?
(1) silicon (2) silica gel
(1) Carbon can form double bonds and CO2 is ­discrete
(3) quartz (4) crystalline forms
molecule.
88. Quartz is made up of silicon and oxygen atoms joined (2) Silicon cannot form double bonds and hence
in a network arrangement that is similar to SiO2 forms an infinite 3D structure.
(1) Diamond (2) Graphite (3) CO2 is a gas but SiO2 is a high melting solid
(3) Dryice (4) NaCl (4) All are correct.

Chapter_13.indd 16 3/26/2014 3:25:41 PM

 The Carbon Family  13.17

  99. In carbonic acid if the carbon atom is replaced by • When SiO4 units share two oxygen atoms with each
­silicon the acid is called as other cyclic and linear single chain silicates having
(1) Silicic acid (2) Orthosilicic acid the empirical formula (SiO32-)n are formed.
(3) Metasilicic acid (4) Hyposilicic acid • Beryl (Be3Al2Si6O18) is a cyclic silicate.
100. Anhydride of orthosilicic acid is • Linear silicate chain is present in pyroxenes, e.g.,
(1) Si (2) SiO2 (3) H2SiO3 (4) SiO Diopside MgCa(SiO3)2 or MgCaSi2O6.
• If two linear chains are cross linked the resulting
Answers double stranded silicates having the composition
(Si4O116-)n are formed. These are called amphiboles,
(84)  4   (85)  4 (86)  4 (87)  2 (88)  1 e.g., asbestos.
(89)  3   (90)  1 (91)  4 (92)  3 (93)  2 • 2D sheet structures are formed when three corners of
(94)  1   (95)  3 (96)  4 (97)  4 (98)  4 each SiO4 tetrahedron are shared.
(99)  3 (100)  2 • Sheet silicate contain (Si2O5)2- units. e.g., Talc
Mg(Si2O5)2. Kaolin [Al2(OH)4 ⋅ Si2O5].
• Sheet silicates are found mainly in clays.
Silicates
• When all the four corners of the SiO4 tetrahedra are
• Silicates are the metal derivatives of orthosilicic acid, shared, a 3D network is formed.
H4SiO4. • When a part of silicon is replaced by aluminium (Al3+),
• The basic structural unit of silicates is the SiO 4− 4 incorporating other cations gives 3D network silicates.
tetrahedron. • Like Na+, K+ and Ca2+ are required to maintain charge
• Depending on the number of corners 0, 1, 2, 3, or 4, in aluminosilicates.
of SiO4 tetrahedra shared, various kinds of silicates are • Feldspars, zeolites and ultramarines are 3D silicates.
formed.
• Zeolites are widely used as catalysts in petrochemical
• Silicates are formed by heating metal oxide or metal industries for cracking of hydrocarbons and isomeriza-
carbonates with sand. tion, e.g., ZSM-5 (a type of zeolite) is used to ­convert
Na2CO3 + SiO2  → Na2SiO3 + CO2 alcohols directly into gasoline.
CaCO3 + SiO2  → CaSiO3 + CO2 • Hydrated zeolites are used as ion exchanges in soften-
• Simple orthosilicates contain discrete SiO4 units, e.g., ing of hard water.
olivine Mg2SiO4; zircon, ZrSiO4; phenacite Be2SiO4, • Glass and cement are man-made silicates.
willemite and Zn2SiO4. • Clay minerals are used for absorbing chemicals.
• Pyrosilicates are formed when SiO4 tetrahedra share a • Micas (i.e., sheet silicates) are used for electrical
corner. Pyrosilicates contain (Si2O7)6- units. insulation.
• Examples of pyrosilicates: Thortevetite (Sc2Si2O7) and • Agate and flint are used for ornaments and jewellery.
hemimorphite (Zn3Si2O7 · Zn(OH)2 · 2H2O).

Structural Units of  Various Silicates

Type of silicate Basic unit No. of  “O” atoms shared
1. Orthosilicate SiO44- 0
2. Pyrosilicate Si2O76- 1
3. Single strand chain silicates (pyroxenes) (SiO3)n2n- 2
4. Double strand chain silicates (amphiboles) (Si2O5)n2n-
(Si4O11)n6n- 2.5
(Si6O17)n10n-
5. Cyclic silicates (SiO3)n2n-
(Si3O9)6- 3
(Si6O18)12- 6
6. Sheet silicates (Si2O5)n2n- 3

Chapter_13.indd 17 3/26/2014 3:25:42 PM

 13.18  Objective Chemistry - Vol. I

Silicones • If some RSiCl3 is added to the starting mixture it will

give cross linkages between the chains because there is
• Silicones are organosilicon polymers containing one more active functional OH group and can produce
Si–O–Si bonds. cross-linked silicones.
• Silicones are formed by the hydrolysis of alkyl or • Hydrolysis of R2SiCl2 under careful conditions
aryl substituted chlorosilicates and their subsequent ­produces cyclic silicones with rings containing three,
polymerization. four, five or six silicon atoms.
• Silicones contain R2SiO repeating units. • Hydrolysis of methyl trichlorosilane (RSiCl3) gives a
• The empirical formula of silicones, R2SiO, is anal­ very complex cross linked polymer.
ogous to that of ketone (R2CO) and hence is named as • Commercial silicone polymers are usually methyl
silicones. ­derivatives and to a lesser extent phenyl derivatives.
• Alkyl- or aryl-substituted chlorosilanes are prepared • Silicones are resistant to heat, oxidation and most
by the reaction of RCl with silicon in the presence of chemicals due to strong Si–C and Si–O–Si bonds.
metallic copper as a catalyst. • Silicones have chemical inertness, water-repelling
Cu powder nature, heat resistance and good electrical insulating
2RCl + Si 
370 K
→ R2SiCl2
properties.
• Alkyl- or aryl-substituted chlorosilanes are also pre- • Silicones are used as scalants, greases, electrical insu-
pared by the reaction of Grignard reagent and silicon
lators and for water proofing of fabrics.
tetrachloride.
• Since silicones are biocompatible they are also used in
RMgCl + SiCl4  → RSiCl3 + MgCl2
making surgical and cosmetic implants.
2RMgCl + SiCl4  → R2SiCl2 + 2MgCl2
3RMgCl + SiCl4  → R3SiCl + 3MgCl2
• Hydrolysis of substituted chlorosilanes yield corre-  Objective Questions
sponding silanols which undergo polymerization.
101. Which of the following is a water repellent?
R Cl + H OH R OH (1) Silicone (2) Polythene
–2HCl
Si Si (3) Teflon (4) Bakelite
R Cl + H OH R OH
1 02. The charge on the cyclic silicate anion [Si3O9]n- is
R (1) –2 (2) –3 (3) –4 (4)  –6

HO Si O H+HO OH 103. The hydrolysis of trialkyl chlorosilane (R3SiCl)

–H2O
yields
R (1) R3Si(OH)  (2) Si(OH)4
(3) RSi(OH)3 (4) R2Si(OH)2
R R
104. Which of the following bonds is present in silicone?
HO Si O Si OH (1) Si–O–Si–O–Si (2) Si–C–Si–O–Si
(3) Si–O–Si–C–Si (4) Si–Si–Si–Si
R R
105. Which of the following is not an orthosilicate?
• Hydrolysis and condensation of R3SiCl gives hexa (1) Phenacite (2) Willimite
alkyl silicone (or siloxane). (3) Thortevetite (4) Forsterite
• Hydrolysis and condensation of R2SiCl2 gives straight
chain polymers, since they have active OH group at 106. Silicates are formed by the replacement of positively
each end of the chain. charged Si4+ in SiO 4−
4  tetrahedra by
(1) Al3+ (2) Na+ and K+
• Addition of R3SiCl will block the end of the straight 2+ 2+
(3) Ca or Mg (4) All
chain produced by R2SiCl2 and thus the chain growth
can be controlled. Thus R3SiCl is a chain-terminating 107. The silicates which do not contain discrete anions are
unit. The ratio R3SiCl and R2SiCl2 in the starting mix- (1) Orthosilicates (2) Sheet silicates
ture will determine the average chain size. (3) Pyrosilicates (4) Cyclic silicates

Chapter_13.indd 18 3/26/2014 3:25:45 PM

 The Carbon Family  13.19

108. A silicate used in talcum powder (1) Density, electrical conductivity

(1) consists of chains which are very long (2) Density, atomic mass
(2) is known as talc and is a pure magnesium silicate (3) Atomic mass, reaction with O2
(3) is a 3D silicate (4) Atomic mass and crystal structure
(4) is a sheet silicate 4. Which of the following is not correct?
109. Silicones have the general formula (1) SiO2 is used as an acid flux.
(1) SiO 4−4 (2) Si 2 O6−
7
(2) The distance between the layers in graphite is
(3) (R2SiO)n (4) (Si 2 O3 )n
2n − 3.35 × 10-3 cm.
(3) SiO2 reacts with Na2CO3 and liberates CO2.
110. Silicones are (4) The hybridisation of carbon in graphite is sp2.
(1) Synthetic polymers containing repeated R2SiO
5. Which of the following pairs liberate a gas when they
units
react with each other?
(2) Silicates with common SiO4 unit
(3) Ketones with silyl group (SiH3) (similar to alkyl) (1) SiO2, Na (2) Fused NaOH, C
(SiH3)2CO (3) Mg, B2O3 (4) Mg, CO2
(4) Zircon (mesosilicates) 6. Which of the following is a set for SiO2?
111. Formula of the following silicate anion is (1) Linear, acidic (2) Linear, basic
(3) Tetrahedral, acidic (4) Angular, basic
7. Largest bond angle is present in
(1) Diamond (2) Graphite

(3) Dry ice (4) Silica
(1) SiO 4−4 (2) Si 2 O6−
7

(3) Si 2 O86− (4) Si3 O96− 8. Often a ground-glass stopper gets stuck in the neck of
a glass bottle containing NaOH solution. The reason
112. The minerals having silicate chains are collectively is that
called
(1) There are particles of dirt in between the glass
(1) olivine (2) zircon stopper and neck of the glass bottle.
(3) pyroxene (4) natrolite (2) A solid silicate formed in between by the ­reaction
of SiO2 of glass with NaOH.
Answers (3) Solid Na2CO3 is formed in between by the ­reaction
of the CO2 of air and NaOH.
(101)  1  (102)  4  (103)  1  (104)  1  (105)  3 (4) Glass contains a boron compound which forms a
(106)  1  (107)  2  (108)  2  (109)  3  (110)  1 precipitate with the NaOH solution.
(111)  2  (112)  3
9. Plumbosolvancy is represented in the reaction
(1) 2Pb + O2  → 2PbO
(2) Pb + 2HCl  → 2PbCl2 + H2O
 Single Answer Type Questions (3) 2Pb + 2H2O + O2  → 2Pb(OH)2
1. Teflon is (4) 2PbS + 3O2  → 2PbO + 2SO2
(1) fluorocarbon (2) hydrocarbon 10. PbCl4 exists but PbBr4 and PbI4 do not because
(3) pesticide (4) insecticide (1) Inability of bromine and iodine to oxidize
2. The tendency of catenation of an element (M) depends Pb2+ to Pb4+.
upon (2) Br- and I- ions are bigger in size.
(1) its nature (3) More electropositive nature of bromine and
(2) its electronegativity ­iodine.
(3) its enthalpy of formation (4) Chlorine is a gas.
(4) the strength of M–M bond 11. Lead becomes passive with
3. Which of the following pairs of properties are ­identical (1) dil. HNO3 (2) Conc. HNO3
to diamond and graphite? (3) Conc. H2SO4 (4) CH3COOH

Chapter_13.indd 19 3/26/2014 3:25:49 PM

 13.20  Objective Chemistry - Vol. I

12. PbCl2 is a solid and PbCl4 is a liquid because 21. Which of the following gases react in the presence of
(1) PbCl2 is ionic and PbCl4 is covalent. sunlight to form a poisonous addition product?
(2) PbCl2 is polymeric and PbCl4 is monomeric. (1) CO, NO2 (2) CO, Cl2
(3) PbCl2 exhibits resonance and PbCl4 does not (3) CO, Cl2 (4) H2, CO
­exhibit resonance. 22. A gas burns with a blue flame and reduces hot iron
(4) PbCl2 is angular and PbCl4 is tetrahedral. oxide to iron metal and when burnt in oxygen, it
13. Which of the following is biocompatible? produces a gas which turns lime water milky. The
colourless original gas is
(1) Silicone (2) Polythene
(3) Teflon (4) Graphite (1) H2 (2) CO (3) CO2 (4) SO2
23. The correct order of decreasing ionic character of
14. Which is formed when SiCl4 vapours are passed over
lead dihalides is
hot magnesium?
(1) PbF2 > PbCl2 > PbBr2 > PbI2
(1) SiCl2 + MgCl2 (2) Si + MgCl2
(2) PbF2 > PbBr2 > PbCl2 > PbI2
(3) Mg2Si + Cl2 (4) MgSiCl6
(3) PbF2 > PbI2 > PbCl2 > PbBr2
15. Carbogen is (4) PbCl2 > PbBr2 > PbF2 > PbI2
(1) mixture of O2 + 5 to 10% CO2 24. What is not true about silicon element?
(2) used by pneumonia patients for respiration (1) Silicon exists in three isotopic forms.
(3) used by victims of CO for respiration (2) Elemental silicon has a structure similar to
(4) all ­diamond.
(3) Most common and abundant isotope of silicon is
16. Which of the following statements about IVA group
Si–30.
elements is not correct?
(4) High pure silicon is used as a semiconductor in
(1) The thermal stability of hydrides decreases from electronic devices.
CH4 to PbH4 as bond enthalpy for M–H bond
­decreases. 25. Which of the following chemical process do not pro-
(2) All form tetrafluorides and tetrachlorides. duce silicon?
(3) Only Sn and Pb form dichlorides. (1) SiO2 + C  → (2) SiC + SiO2  →
(4) All form tetraiodides. (3) SiH4 675K → (4) SiCl4 heat
 →
17. The tendency to form pπ–pπ multiple bond 26. Solid CO2 is produced as white snow by
(1) is prominent for carbon (1) cooling the gas below its inversion temperature
(2) is less prominent for silicon (2) cooling the gas below its Boyle’s temperature
(3) is nonexistent for Sn and Pb (3) expanding the gas below its Boyle’s temperature
(4) all the above (4) the adiabatic expansion of the compressed gas by
allowing it to escape through the orifice in the
18. Which of the following statements is not correct? container
(1) SnO and PbO are more basic and ionic. 27. Which of the following statements is false?
(2) GeO is acidic while SnO and PbO are ­amphoteric. (1) The octahedral SiF62- ion is the only halogen
(3) Ge2+ and Sn2+ are strong oxidizing agents. complex of silicon and in bonding it involves
(4) The mixed oxide Pb3O4 contains Pb2+ and Pb4+ ions. sp3d2 hybridisation.
(2) Silicon is more electropositive than carbon.
19. Colloidal sol of graphite in water is called
(3) Flurosilicic acid (H2SiF6) known only in solution
(1) oil drag (2) aquadrag is a strong acid.
(3) aquagraph (4) peat (4) The formula of tetramethyl silane is (CH3)4SiH4.
20. What is correct about chlorides of tin? 28. When oxalic acid is heated with conc. H2SO4 two
(1) SnCl2 is a solid while SnCl4 is a liquid. gases produced are neutral and acidic in nature
(2) SnCl2 is a liquid while SnCl4 is a solid. ­respectively. Potassium hydroxide absorbs one of
(3) SnCl2 and SnCl4 are both liquids. these two gases. The product formed during this ab-
(4) SnCl2 and SnCl4 are solids. sorption and the gas which absorbed are respectively

Chapter_13.indd 20 3/26/2014 3:25:50 PM

 The Carbon Family  13.21

(1) K2CO3 and CO2 (2) KHCO3 and CO2 (1) SiO2, CO2 (2) SiO2, CO
(3) K2CO3 and CO (4) KHCO3 and CO (3) SiC, CO (4) SiO2, N2
29. PbCl2 is more ionic than PbO2 because 37. In which of the following silicates, only two corners
(1) the radius of Pb2+ is more than that of Pb4+ per tertrahedron are shared?
(2) of inert pair effect    (i)  pyrosilicate
(3) chlorine is more electronegative than oxygen  (ii)  cyclic silicate
(4) chlorine atom is smaller than oxygen atom (iii)  double chain silicate
30. The hydrolysis of dimethyl dichlorosilane gives   (iv)  single chain silicate
  (v)  3D silicate
(1) silicones (2) silicates
  (vi)  sheet silicate
(3) SiO2 (4) silicic acid
(1) i, ii, iii (2) iv and vi only
31. Which of the following statements is incorrect in the (3) i and vi only (4) ii and iv only
context of diamond?
38. Select the false statement about silicates.
(1) Each carbon atom is tetrahedrally surrounded by
four other carbon atoms each at a distance of 1.54 Å. (1) Cyclic silicate having three silicon atoms
(2) The tetrahedral units are linked together into a ­containing six Si–O–Si linkages.
3D giant molecule. 1
(2) 2 corner oxygen atoms per tetrahedron unit are
(3) The unit cell has body-centred cubic structure. 2
shared in a double chain silicate.
(4) Strong covalent bonds extend in all directions.
(3) ( Si 2 O5 )n is the empirical formula of a double
2 n−

32. Even though thermodynamically favourable, the

conversion of diamond into graphite does not occur chain silicate.
normally since (4) SiO4 units polymerize to form silicate because
Si atom has less tendency to form π-bond with
(1) the activation energy of the process is high
­oxygen.
(2) the activation energy of the process is low
(3) the change of entropy is zero 39. The silicate anion in the mineral kaionite is a chain of
(4) the change of enthalpy is zero three SiO4 tetrahedra that share corners with adjacent
tetrahedra. The mineral also contains Ca2+ ions, Cu2+
33. Calcium carbide on heating with nitrogen at 1200°C
ions and water molecules in a 1:1:1 ratio. The mineral
in an electric furnace produces
is represented as
(1) calcium cyanide (2) calcium nitride
(1) CaCuSi3O10 · H2O
(3) calcium amide (4) calcium cynamide
(2) CaCuSi3O10 · 2H2O
34. The silicate minerals are classified on the basis of the (3) Ca2Cu2Si3O10 · 2H2O
manner of linking of (4) None of these
(1) SiO2− 4 tetrahedral units
4− 40. Si2O6−
7 anion is obtained when
(2) SiO 4 tetrahedral units
(1) no oxygen of a SiO4 tetrahedron is shared with
(3) Si2O2− 7 units
another SiO4 tetrahedron
(4) (SiO3 )n triangular units
4 n−
(2) one oxygen of a SiO4 tetrahedron is shared with
35. The structure of silicon (IV) oxide belongs to the type another SiO4 tetrahedron
(1) ionic lattice (3) two oxygen of a SiO4 tetrahedron are shared with
(2) macromolecular, with a layered structure another SiO4 tetrahedron
(3) macromolecular, with a non-layer structure (4) three or all four oxygen of a tetrahedron are
(4) molecular lattice with Van der Waal’s forces shared with other SiO4 tetrahedron
among the molecules 41. PbF4 is good fluorinating agent because
36. An inorganic compound (A) made by two most occur- (1) The Pb–F bond is very weak.
ring elements in the earth crust is having a polymeric (2) It is a fluoride of a heavy metal.
tetrahedral network structure. With carbon, com- (3) It is unstable and dissociates on warming giving
pound (A) produces a poisonous gas (B) which is the fluorine.
most stable molecule. Compounds (A) and (B) will be (4) Fluorine is highly electronegative.

Chapter_13.indd 21 3/26/2014 3:25:52 PM

 13.22  Objective Chemistry - Vol. I

42. In the carbon family, the elements other than carbon (1) planar, pyramidal, planar
do not form pπ–pπ bonds because the (2) planar, pyramidal, pyramidal
(1) atomic orbitals are too small and diffused to (3) pyramidal, pyramidal, pyramidal
­undergo effective lateral overlap (4) pyramidal, planar, pyramidal
(2) atomic orbitals are too large and diffused to 49. H2C2O4 ∆ → gas (A) + gas (B) + liquid (C). Gas (A)
­undergo effective lateral overlap burns with a blue flame and is oxidized to gas (B).
(3) atomic orbitals are too large and less diffused to Gas A + Cl2 → (D) ∆ → (E)
overlap linearly A, B, C and E are
(4) atomic orbitals are too small to overlap with
(1) CO2, CO, H2O, HCONH2
­laterally and linearly
(2) CO, CO2, COCl2, HCONH2
43. Which of the following minerals is classified as an (3) CO, CO2, H2O, NH2CONH2
orthosilicate? (4) CO, CO2, HO, COCl2
(1) CaMg [(SiO3)2)] (2) Na4Si2O7
50. A student prepared a sample of silicon chloride by ­passing
(3) Ca3[Si3O9] (4) Zn2SiO4
chlorine over heated silicon collecting the ­condensed
44. The length of the N–Si bond in (SiH3)3 N is shorter ­silicon chloride in a small specimen tube. He analysed
than what is normally expected for an N–Si single the chloride by dissolving a known mass of it in water
bond. This is due to and titrating the solution with a standard ­solution of silver
(1) sp2–sp2 σ overlap between N and Si atoms nitrate. The formula of the silicon chloride as ­obtained
(2) Localized pπ–pπ bonding between the N atom by this method was SiCl2.6 as against SiCl4. Which of
and one of the three Si atoms. the ­following possible errors could have resulted in this
(3) delocalized four-centred two-electron pπ–dπ bond- wrong formula?
ing spread over the N atom and all the three Si atoms (1) The silicon chloride contained excess dissolved chlo-
(4) Localized pπ–pπ bonding between the N atom rine.
and Si atom (2) More silicon chlorine than the student supposed was
45. The melting point of AlF3 is 104°C and that of SiF4 is actually used owing to inaccurate weighing.
–77°C. Iit sublimes because (3) The small specimen tube was not dry.
(1) There is very large difference in the ionic charac- (4) The reaction between silicon and chlorine stopped
ter of the Al–F and Si–F bonds. prematurely leaving some unreacted ­silicon in the
(2) In AlF3, Al3+ interacts very strongly with the ­reaction tube.
neighbouring F- ions to give a 3D structure but 51. The dehydration of malonic acid
in SiF4 no such interaction is possible. CH2(COOH)2 with P4O10 and heat gives
(3) The silicon ion in the tetrahedral SiF4 molecule (1) carbon monoxide (2) carbon suboxide
is not shielded effectively from the fluoride ions, (3) carbon dioxide (4) All these
whereas in AlF3, the Al3+ ion is shielded on all sides.
Cu
(4) The attractive forces between the SiF4 molecules 52. 2CH3Cl + Si  →A
570 K
are strong, whereas those between the AlF3
“A” on hydrolysis followed by condensation gives
molecules
­ are weak.
46. Sn(II) is a stronger reducing agent than Pb(II) ­because CH 3
(1) Pb(II) is more covalent than Sn(II) (1) Si(CH3)3–Si(CH3)3 (2) O Si O
(2) Pb(II) is more stable than Pb(IV)
(3) Sn(IV) forms more covalent compounds CH 3
(4) Pb(II) forms covalent compounds n
CH 3
47. The silicate anion in the mineral kaionite is a chain of
three SiO 4− O Si O
4 tetrahedra that share corners with adja- CH3 CH3
cent tetrahedra. The charge of the silicate anion is
(3)  O (4) HO – Si – Si – OH
(1) –4 (2) –8 (3) –6 (4) –2
48. The geometry with respect to the central atom of the O Si O CH3 CH3
following molecules is
N(SiH3)3, (CH3)3N; (SiH3)3P CH 3
n

Chapter_13.indd 22 3/26/2014 3:25:54 PM

 The Carbon Family  13.23

53. Select the false statement. 61. Carbon disulphide reacts with chlorine to give
(1) Cyanamide ion (CN2)2- is isoelectronic with CO2 (1) Carbon tetrachloride and sulphur monochloride
and has the same linear structure. (2) Carbon tetrachloride and sulphur tetrachloride
(2) Mg2C3 reacts with water to form propyne. (3) Carbon and sulphur dichloride
(3) CaC2 has C22- and it contains one sigma and two (4) Carbon and sulphur monochloride
π-bonds.
62. In graphite which have several fused hexagonal rings
(4) Al4C3 is an example of methanide and it
of benzene the hybridisation state of each carbon
contains C34−.
atom and the bond order of carbon–carbon bond are
54. Name the structure of silicates in which three oxygen respectively
atoms of (SiO4)4- are shared. (1) sp, 1.5 (2) sp2, 1.5
2
(1) pyrosilicate (2) sheet silicate (3) sp , 1.33 (4) sp3, 1.5
(3) linear silicate (4) 3D silicate
63. The lone pair of electrons in the nitrogen atoms of the
55. Which of the following statements is not correct? molecules (CH3)3N and (SiH3)3N are present respec-
(1) The durability and inertness of silicones is due to tively in the
the high bond enthalpy of Si–O bond. (1) sp3 orbital and sp2 orbital
(2) Silicones are used in water proofing textiles. (2) sp3 orbital and p-orbital
(3) Silicone rubbers are excellent electrical ­insulators. (3) p-orbital and sp2 orbital
(4) The silicones always involve cross-linkage ­between (4) p-orbital in both cases
Si and O atoms.
64. Which of the following statements is correct about
56. (COOH)2 conc. H 2 SO 4
→ A + B + H2O. A can be silicon?
identified by using iodine pentoxide, then incorrect (1) Forms molecular halides that are not hydrolysed.
­statement about “B” is (2) Forms strong but unconjugated multiple bonds of
(1) Solid B is a sublimated compound. the pπ–pπ variety, especially with O and N.
(2) B reacts with ammonia to form urea. (3) Does not undergo coordination number expansion.
(3) Supercritical B is used as a solvent. (4) Forms an oxide that has bonding similar to
(4) It is a linear and a neutral oxide. ­carborundum.
57. Asbestos has composition as 65. Which of the following pairs of ions represent cyclic
(1) CaO · Al2O3 · SiO2 · H2O and double-chain silicates?
(2) CaO · 3MgO · 4SiO2 (1) Si2O7 and (SiO3)2n–  (2) Si3O6−
9 and (Si4O11)
6n–
2n– 7− 2n−
(3) 3MgO · 4SiO2 · H2O (3) Si2O7 and (Si2O5)  (4) Si2O7 and (SiO3 ) n
(4) AlO3 · SiO2 · 2H2O
66. Carborundum on heating with caustic soda in the
58. How many oxygen atoms of SiO 4−4 unit shared in the
presence of air produces
continuous 3D frame work silicates? (1) Na2SiO3 + H2 (2) Na2SiO3 + Na2CO3
(1) 1 (2) 2 (3) 3 (4) 4 (3) Na2SiO2 + H2 (4) Na2SiO4 + O2
59. Trisilyl amine (SiH3)3N is 67. (Si2O5) anion is obtained when
(1) Trigonal pyramidal and acidic (1) no oxygen of SiO 4− 4 tetrahedron is shared with
(2) Trigonal pyramidal and basic another tetrahedron
(3) Trigonal pyramidal and neutral (2) one oxygen of SiO 4− 4 tetrahedron is shared with
(4) Trigonal planar and weakly basic another tetrahedron
(3) two oxygen of SiO 4− 4 tetrahedron are shared with
60. In the equilibrium C(s) (diamond)  
 C(s) SiO 4−
4 tetrahedron
(­graphite)  + heat (density of diamond and graphite (4) three oxygen of SiO 4− 4 tetrahedron are shared with
are 3.5 and 2.3 g/cm3, respectively) the equilibrium SiO 4− tetrahedron
4
will be shifted to the left at
(1) low temperature and very high pressure 68. The silicates having layer and sheet structures involve
(2) high temperature and low pressure (1) the discrete SiO 4− 4 tetrahedra
(3) high temperature and high pressure (2) the sharing of one oxygen atom between two
(4) low temperature and low pressure SiO 4−
4 tetrahedra

Chapter_13.indd 23 3/26/2014 3:25:57 PM

 13.24  Objective Chemistry - Vol. I

(3) the sharing of two oxygen atoms of one SiO 4−4

tetrahedron with two other tetrahedra  Statement-Type Questions
(4) the sharing of three oxygen atoms of one SiO 4−
4 In each of the following questions a statement of ­
tetrahedron with three other tetrahedra statement I is given followed by a corresponding statement
69. An inorganic compound (X) on hydrolysis produces of ­Statement II just below it. Based on the given statements
a gas which on treatment with sodium followed mark the correct answer.
by its reaction with ethyl chloride gives another 1. If both statement I and statement II are true and the
­compound  (Y). Compound (Y) on heating with statement II is the correct explanation of statement I.
Pd catalyst gives (2Z)-pentene as a major product. 2. If both statement I and statement II are true but
Hence, the inorganic compound (X) is ­statement II is not the correct explanation of ­
(1) Tl4C (2) BaC2 statement I.
(3) SiC (4) Mg2C3 3. If statement-I is true but statement-II is false.
70. Which of the following statements is correct? 4. If statement-I is false but statement-II is correct.
(1) C–F bond is stronger than Si–F bond because
1. Statement I: Pb4+ can be reduced easily to Pb2+.
C–F bond length is shorter than that of Si–F.
(2) C–F bond is weaker than Si–F bond because of Statement II: Pb2+ is paramagnetic in nature.
less difference in electronegativity. 2. Statement I: Carbon can form more number of com-
(3) Si–F bond is stronger than C–F bond because of pounds.
double bond character due to back bonding from Statement II: C–C bond energy is more.
F to Si.
(4) Si–F bond is stronger than C–F bond due to more 3. Statement I: Diamond glitters.
difference in electronegativities. Statement II: Diamond is very hard.
71. The wrong statement among the following is 4. Statement I: Graphite can be used as a lubricant.
(1) Diamond is the best conductor of heat so far known. Statement II: In graphite carbon exists as layers and
(2) With increase in temperature electrical conduc- due to weak Van der Waal’s forces.
tivity of graphite decreases parallel to the layers
but increases perpendicular to the layers. 5. Statement I: SiO2 exists as a solid.
(3) C–C bond order in graphite is 1.5. Statement II: SiO2 contains a polymeric network
(4) Graphite acts as a metallic conductor along the structure.
layers but acts as a semiconductor perpendicular
6. Statement I: Pb2+ is more ionic and stable than Pb4+
to the layers.
which is oxidizing.
Statement II: Because the radius of Pb2+ is greater
Answers than Pb4+ and smaller the ion, greater is the tendency
to covalency.
  (1) 1   (2) 4   (3) 3   (4) 2   (5) 2 7. Statement I: Diamond is harder than graphite.
  (6) 3   (7) 3   (8) 2   (9) 3 (10) 1
Statement II: Graphite is more stable than diamond.
(11) 3 (12) 1 (13) 1 (14) 2 (15) 4
(16) 4 (17) 4 (18) 3 (19) 2 (20) 1 8. Statement I: Out of SiCl4 and CCl4 only SiCl4 ­reacts
(21) 2 (22) 2 (23) 1 (24) 3 (25) 4 with water.
(26) 4 (27) 4 (28) 1 (29) 1 (30) 1
Statement II: SiCl4 is ionic while CCl4 is covalent.
(31) 3 (32) 1 (33) 4 (34) 2 (35) 3
(36) 2 (37) 4 (38) 1 (39) 3 (40) 1 9. Statement I: SiO2 is a solid while CO2 is a gas at
(41) 2 (42) 2 (43) 4 (44) 3 (45) 2 room temperature.
(46) 2 (47) 2 (48) 2 (49) 3 (50) 3 Statement II: Si–O bonds are stronger than C–O
(51) 2 (52) 2 (53) 4 (54) 2 (55) 4 bonds.
(56) 4 (57) 2 (58) 4 (59) 4 (60) 3
(61) 1 (62) 3 (63) 2 (64) 2 (65) 2 10. Statement I: Quartz and soda glass are different
(66) 2 (67) 4 (68) 4 (69) 4 (70) 3 names of the same substance.
(71) 3 Statement II: Quartz is a crystalline solid, whereas
glass is an amorphous solid.

Chapter_13.indd 24 3/26/2014 3:25:58 PM

 The Carbon Family  13.25

11. Statement I: Carbon does not form complexes. The correct matching is
Statement II: The valence shell of carbon is the
­second shell which can accommodate four pairs of S. No A B C D
electrons only. Due to the absence of d-orbitals in the 1. III IV I II
valence shell it cannot expand its octet and cannot 2. IV III II I
form ­complexes. 3. IV II I III
4. III IV II I
12. Statement I: CCl4 is not hydrolyzed while SiF4 is
readily hydrolyzed.
Statement II: Carbon halides are not hydrolyzed 3.
­because of the absence of d–orbitals. Carbon cannot
increase its coordination number more than four, but List-I List-II
silicon can expand its coordination number due to (A)  Diamond   (I)  Amorphous allotrope
the availability of d-orbitals and is coordinated by (B)  Lubricant   (II)  Crystalline allotrope
OH- ions. (C)  Sugar charcoal  (III)  Silica
(D)  Acid flux (IV)  Graphite
Answers
The correct matching is
  (1) 3   (2) 1   (3) 2   (4) 1   (5) 1
  (6) 1   (7) 2   (8) 3   (9) 3 (10) 4 S. No A B C D
(11) 1 (12) 1 1. II IV I III
2. IV II I III
3. III I IV II
4. IV III II I
 Match the Following  Type Questions
1. Match the following given List I with those given in 4.
List II.
List-I List-II
List-I List-II
(A)  SiO2     (I)  R2SiO group
(A)  Tridimite     (I) Quartz mixed with amorphous (B)  Graphite  (ii)  SiO 4−
4 Tetrahedra
silica (C)  Silicone  (iii)  Lead pencils
(B)  Flint  (II) Crystalline allotrope of silica (D)  Silicate (iv)  Giant molecules
(C)  Sand  (III) Crushed form of quartz
(D)  Sand stone (IV) Powdered quartz mixed The correct matching is
with sand
S. No A B C D
The correct matching is
1. IV III I ii
S. No A B C D 2. IV II I III
1. IV II I III 3. III II I IV
2. II I III IV 4. II IV III I
3. I II IV III
4. III II I IV 5.

List-I List-II
2.
(A)  CCl4     (i) Liquid, readily hydrolyzed
List-I List-II by water
(A)  Catenation power   (I)  Metalloid (B)  SnCl4  (ii) Liquid, not readily hydrolyzed by
(B)  Si, Ge, Sn and Pb   (II) Not hydrolyzed water
by water (C)  AlCl3  (iii) Solid, readily hydrolyzed
(C)  Germanium  (III)  Bond energy by water
(D)  CCl4 (IV)  Electronegativity is 1.8 (D)  PCl5 (iv) Solid, hydrolyzed by water

Chapter_13.indd 25 3/26/2014 3:25:58 PM

 13.26  Objective Chemistry - Vol. I

The correct matching is The correct matching is

S. No A B C D S. No A B C D
1. II I III IV 1. III I II V
2. II I IV III 2. V I II IV
3. I IV III II 3. V II III I
4. I II IV III 4. II I III IV

6.
Answers
List-I List-II
(A)  Silica     (i)  Refractory crucible   (1) 2   (2) 1   (3) 1   (4) 1   (5) 2
(B)  Graphite  (ii)  Hardest solid
(C)  Carborundum  (iii) Square planar arrangement of
atoms
(D)  Tridmite (iv) Tetrahedral arrangement of
atoms
   (V)  Gem stone

Chapter_13.indd 26 3/26/2014 3:25:58 PM

 14

Chapter
Basic Principles, Nomenclature,
Purification and Characterization of
Organic Compounds

• The first organic compound synthesized in the Classification of hydrocarbons

­laboratory was urea by Wohler.
• Organic compounds are classified into two main types
• Existence of very large number of organic compounds
on the basis of nature of carbon skeleton
is due to
(a) Acyclic- or open-chain compounds
   (i)  Catenation power of carbon
(b) Cyclic- or closed-chain hydrocarbons
 (ii)  Tetravalency of carbon
(iii)  Formation of multiple bonds • Depending on the type of hybridisation of carbon atom
  (iv)  Isomerism aliphatic hydrocarbons are two types.
 (v)  Absence of d-orbitals in its valency shell. (a) Saturated hydrocarbons
(b) Unsaturated hydrocarbons
• The tendency of atoms of an element to unite with
each other forming long chains, branched chains, ring- • In saturated hydrocarbons the carbon atoms involve
structured compound is known as catenation. in sp3 hybridisation and form four single bonds.
E.g., methane, ethane, etc.
• The maximum catenation power of carbon is due to the
more C–C bond energy which is comparable to bond • In unsaturated hydrocarbons the carbon atoms in
strength of carbon with the atoms of other elements. ­involve either sp2 or sp hybridisation.
• The hydrocarbons in which carbon atom is involved in
Bond Energy kJ mole –1 sp2 hybridisation are called alkenes and they contain
double bond. E.g., ethylene.
C–C 348
C–O 351 • The hydrocarbons in which carbon atom involved in sp
C–H 414 hybridisation are called alkynes and they contain triple
C–Cl 326 bond. E.g., acetylene.
C–F 439 • Cyclic- or closed-chain compounds are of two types.
(a) Carbocyclic compounds
• All organic compounds are covalent and are generally (b) Heterocyclic compounds
soluble in non-polar solvents. • Carbocyclic compounds are of two types.
• The solubility of organic compounds in water is due to (a) Alicyclic compounds
formation of hydrogen bonds. (b) Aromatic compounds
• Important sources of organic compounds are p­ etroleum, • In alicyclic compounds, the ring may contain three or
coal, natural gas, plants and animals. more carbon atoms.

Chapter_14.indd 1 3/26/2014 3:24:33 PM

 14.2  Objective Chemistry - Vol. I

• All carbons in alicyclic compounds are involved in sp3 • In aromatic compounds, carbon is involved in sp2
hybridisation and behave like saturated hydrocarbons, hybridisation.
e.g., cyclobutane, cyclopentane. These are known as • Heterocyclic compounds contain oxygen, sulphur or
cycloalkanes. nitrogen along with carbon in the ring, e.g., furan,
• Benzene is the parent compound of aromatic ­pyrrole, etc.
hydrocarbons.

Organic Compounds

Alicyclic or open chain Cyclic or closed chain or ring

compounds compounds

Saturated Unsaturated Carbocyclic Heterocyclic

hydrocarbons hydrocarbons compounds compounds
Alkanes

Alkenes Alkynes Alicyclic Aromatic

compounds compounds

Benzenoid Non-Benzenoid
compounds compounds

• Carbon compounds are classified into different groups depending upon the functional groups present in them.

Name Formula Functional group Name of the functional group

 1. Alkanes R–H – –
 2. Alkenes RCH=CH C=C Double bond
 3. Alkynes RC≡CH –C≡C– Triple bond
  4.  Alkyl halides R–X –X Halogen
 5. Alcohols R–OH –OH Hydroxy
 6. Ethers R–O–R –O– Ether
 7. Amines R–NH2 –NH2 Amino
 8. Aldehydes R–CHO –CHO Aldehyde
|
 9. Ketones R–CO–R C=O Keto
|

10.  Carboxylic acids R–COOH –COOH Carboxyl

11. Esters R–COOR –COOR Ester
12. Amides R–CONH2 –CONH2 Amide
13. Cyanides R–CN –CN Cyanide
14. Nitrocompounds R–NO2 –NO2 Nitro
15.  Sulphonic acids R–SO3H –SO3H Sulphonic acid

State of carbon in carbon • The excited state electronic configuration of carbon is

compounds 1s22s12p1x2p1y 2p1z.
• Energy of excitation is 120 K cal mol–1 or 501.6 kJ mol–1.
• The ground state electronic configuration of carbon is
1s22s22p1x2p1y2p0z. • Tetrahedral nature of carbon was proposed by Vant
Hoff and Label.

Chapter_14.indd 2 3/26/2014 3:24:34 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.3

• In organic compounds carbon atom undergoes sp, sp2 and sp3 hybridisations.

Orbitals % character Nature of Bond Orientation of

Hybridisation involved s p bonds angles orbitals
sp3 one s 25 75 all σ 109° 28′ Tetrahedral
three p no π
sp2 one s 33.3 66.6 3σ 120° Planar
two p 1π
sp one s 50 50 2σ 180° Linear
one p 2π

• sp3 carbon is called saturated carbon. Bond Energy in k cal mol–1

2
• sp and sp carbons are called unsaturated carbons.
sp3–s 104
• For a single C–C or C–O bond the atoms are sp3 sp2–s 106
­hybridised and the carbon atom(s) is tetrahedral. sp–s 121
• For a double C=C or C=O bond the atoms are sp2 sp3–sp3 80–90
­hybridised and the carbon atom(s) is trigonal planar. sp2–sp2 120–164

• For a triple C≡C or C≡N bond, the atoms are sp hybrid- sp–sp 123–199
ised and the carbon atom(s) is linear.
• The shape of organic molecules is therefore deter-
• A single C–C σ bond can undergo free rotation at
mined by the hybridisation of the atoms. room temperature, but a π bond prevents free rotation
around a C=C bond.
• Greater the s-character, the lower the energy and is
near to the nucleus, i.e., orbital is smaller.
• For maximum orbital overlap in a π bond, the two
­p-orbitals need to be parallel to one another. Any rota-
• The order of size of different orbitals is p > sp3 > sp2 > tion around the C=C bond will break the π bond.
sp > s.
• Bond length in carbon compounds Homologous Series
C–C bond length is 1.54 Å
C=C bond length is 1.34 Å • A series of organic compounds containing same func-
C≡C bond length is 1.20 Å tional group and show similar properties but differ
from the preceeding one by CH2 unit.
C–H average bond length is 1.1 A
• Homologues can be prepared by similar methods.
• The shorter the bond length, the stronger the bond. For
C–H bonds the greater the s-character of the carbon • Homologues show similar properties and show grada-
orbitals, the shorter the bond length, because the tion in their physical properties.
­electrons are held closer to the nucleus. • All homologues have the same general formula and the
sp3 sp2 sp successive members differ by CH2 group in ­molecular
formula and 14 in molecular weight.

–C–H > =C–H > ≡C–H Name of General

longest shortest series formula First member
• Hybrid orbitals (i) overlap better and (ii) provide Alkane CnH2n+2 CH4 (methane)
greater bond angles and thereby minimize the repul- Alkene CnH2n C2H4 (ethylene)
sion between electron pairs. Alkyne CnH2n–2 C2H2 (acytelene)
• Bonds formed by hybrid orbitals are more stable than Alkyl halide CnH2n+1X CH3X (methyl halide)
the bonds formed by the pure atomic orbitals. Alcohol CnH2n+1OH CH3OH (methyl alcohol)
Carboxylic CnH2n+1COOH HCOOH (formic acid)
• The C–H bond energy increases with increase in
acid
­s-character sp3–s < sp2–s < sp–s.

Chapter_14.indd 3 3/26/2014 3:24:35 PM

 14.4  Objective Chemistry - Vol. I

9. Among the following orbital bonds, the angle is

 Objective Questions ­minimum between
1. Which of the following statements is wrong? (1) sp3–sp3 bonds (2) px and py orbitals
(3) H–O–H in water (4) sp–sp bonds
(1) The first organic compound synthesized in the
chemical laboratory is urea 10. Alicyclic compounds are
(2) Among C2H2, C2H4 and C2H6 the C–H bond is (1) Aromatic compounds
longest in C2H6. (2) Aliphatic cyclic compounds
(3) Among C2H2, C2H4 and C2H6 the largest HCH (3) Heterocyclic compounds
bond angle is in C2H2. (4) None
(4) Greater the s-character of hybrid orbital greater
the bond length. 11. The C–C bond angle in cyclopropane is
(1) 60° (2) 120°
2. The bond between carbon atom (1) and carbon atom (3) 109° 28′ (4) 180°
(2) in compound N≡1C–2CH=CH2 involves the
­hybrid  as 12. How many σ and π bonds are there in the molecule of
(1) sp2–sp2 (2) sp3–sp (3) sp–sp2 (4) sp–sp tetracyano ethylene (NC)2C=C(CN)2
(1) 9σ and 9π (2) 5σ and 9π
3. Which of the following statements is wrong? (3) 9σ and 7π (4) 5σ and 8π
(1) In general organic compounds have low melting
point and boiling points. 13. The Cl–C–Cl angle in 1, 1, 2, 2-tetrachloroethene and
(2) Isomerism is common in organic compounds. tetrachloromethane respectively will be about
(3) Organic compounds cannot be synthesized in the (1) 120° and 109.5° (2) 90°
laboratory. (3) 109.5° and 90° (4) 109.5° and 120°
(4) The number of organic compounds is very large. 14. The number of σ- and π-bonds in but-1-ene-3-yne are
4. Which hybrid orbitals will form the compound (1) 5σ and 5π (2) 7σ and 3π
CH3–CH=CH–CH2–CH3? (3) 8σ and 2π (4) 8σ and 4π
(1) sp2 and sp3 (2) only sp3
3
15. Allyl isocyanide has
(3) sp and sp (4) sp and sp2
(1) 9σ and 4π bonds
5. The compound in which C uses its sp3 hybrid orbitals (2) 8σ and 5π bonds
for bond formation is (3) 9σ, 3π and 2 non-bonded electrons
(1) HCOOH (2) (H3N)2CO (4) 8σ, 3π and 4 non-bonded electron pairs
(3) (CH3)3COH (4) CH3CHO 16. The Cl–C–Cl bond angle in dichloromethane will be
6. Which of the following statements is wrong? (1) > 109°.28′ (2) < 109°.28′
(1) The overlapping of π electrons in acetylene is (3) 109°.28′ (4) 120°
more than in ethylene. 17. A straight chain hydrocarbon has the molecular for-
(2) The sigma bond energy of C–H bond in C2H6 is mula C8H10. The hybridisation for the carbon atoms
nearly 99 k cal. from one end of the chain to the other are respectively
(3) With increase in s-character of hybrid orbitals the sp3, sp2, sp2, sp3, sp2, sp2, sp and sp. The structural
bond angle decreases. formula of the hydrocarbon would be
(4)  During pyrolysis C–C bond breaks faster
(1) CH3–C≡C–CH2–CH=CH–CH=CH2
than C–H.
(2) CH3–CH2–CH=CH–CH=CH–C≡CH
7. In 2-methyl-1-propanol, the hybrid carbons of sp3, sp2 (3) CH3–CH=CH–CH2–C≡C–CH=CH2
and sp are respectively (4) CH3–CH=CH–CH2–CH=CH–C≡CH
(1) 3, 2, 1 (2) 4, 3, 0
18. In the case of homologous series, which one of the
(3) 4, 0, 0 (4) 1, 2, 3
following statements is incorrect?
8. Which of the following possess an sp hybridised (1) The members of the series have a general f­ormula.
­carbon in its structure? (2) The difference between any two successive mem-
(1) CCl2=CCl2 (2) CH2=C=CH2 bers of the series corresponds to 14 unit of rela-
(3) CH2=CH–CH=CH2 (4) CH2=CCl–CH=CH2 tive atomic mass.

Chapter_14.indd 4 3/26/2014 3:24:35 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.5

(3) The members of the series are isomers of each 27. Which statement is correct about the hybridisation of
other. carbon atoms in HC1≡C2–C3≡C4H
(4) The members of the series have similar chemical (1) C1 and C4 are sp2 hybridised
properties. (2) C2 and C3 are sp2 hybridised
19. The compound having both sp2 and sp3 bonds is (3) All are sp hybridised
(4) All are sp2 hybridised
(1) n-butane (2) isobutane
(3) butene-2 (4) butadiene 28. In which of the following structures the number of
20. Hybridisation concept was necessary to explain sigma bonds is equal to the number of π bonds?
(1) 4 valency of carbon in its compounds (1) 1, 2-propadiene
(2) 4 electrons of carbon (2) 2, 3-dicynobut-2-ene
(3) 4 equivalent non-planar valency bonds of carbon (3) Tetrocynoethylene
(4) 4 non-equivalent planar valency bonds of carbon (4) None of the above

21. Which of the following statement is wrong? 29. Among the following which have more than one kind
(1) Vital force theory of the origin of organic com- of hybridisation?
pounds was discarded by Wohler’s synthesis of    (i)  CH3CH2CH2CH3
urea from ammonium cyanate.    (ii) CH3–CH=CH–CH3
(2) Tetrahedral nature of carbon was proposed by (iii) CH2=CH–C≡CH
Vant Hoff and Label.  (iv)  HC≡CH
(3) The ClCCl bond angle is the same in both CCl4 (1) ii and iii (2) ii and i
and CH2Cl2. (3) iii and iv (4) iv
(4) Bond angle in ethylene and benzene is the same.
30. The enolic form of acetone contains
22. Structural formula of an organic compound describes (1) 9σ bonds, 1π bond and 2 lone pairs
(1) nature of functional group (2) 8σ bonds, 2π bonds and 2 lone pairs
(2) the arrangement of atoms in the molecule (3) 10σ bonds, 1π bonds and 1 lone pair
(3) its characteristics (4) 9σ bonds, 2π bonds and 1 lone pair
(4) all
31. Identify the false statement.
23. In the dehydration reaction CH3CONH2 P 2 O5
→ (1) The angle between the bonds formed by pure
CH3C≡N the hybridisation state of carbon changes
­orbitals in acetylene is 90°.
from
(2) The number of pure orbitals participated in the
(1) sp3 to sp2 (2) sp to sp bonds in acetylene molecule are four.
(3) sp2 to sp (4) sp to sp3 (3) The orbital overlap between two carbon atoms is
24. Which of the following order of decreasing energy of sp-sp.
same energy level atomic orbitals is correct? (4) There are three σ bonds in acetylene.
(1) sp3 > p > sp2 > sp > s 32. Which of the following has a bond formed by the
(2) s > sp > sp2 > sp3 > p overlap of sp3-sp hybrid orbitals
(3) p > sp3 > sp2 > sp > s
(1) CH3–C≡C–H
(4) s > sp3 > sp2 > sp > p
(2) CH3–CH=CH–CH3
25. The hybridisation of carbon atoms in C–C single (3) CH2=CH–CH=CH2
bond HC≡C–CH=CH2 is (4) HC≡CH
(1) sp3–sp3 (2) sp2–sp2
2 33. The number of linear carbon atoms in hexyne
(3) sp–sp (4) sp3–sp
­molecule is
26. The C–C bond length of the following molecules is in (1) 2 (2) 3 (3) 4 (4) 5
the order
(1) C2H6 > C2H4 > C6H6 > C2H2 34. The number of pure and hybrid orbitals in 1, 3-­butadiene
(2) C2H2 < C2H4 < C6H6 < C2H6 are respectively
(3) C6H6 > C2H2 > C2H6 > C2H4 (1) 10 and 12 (2) 12 and 10
(4) C2H4 > C2H6 > C2H2 > C6H6 (3) 10 and 10 (4) 12 and 12

Chapter_14.indd 5 3/26/2014 3:24:40 PM

 14.6  Objective Chemistry - Vol. I

35. Which of the following compounds give only one 43. The structure of H2C=C=CH2 is
monochloro derivative? (1) linear
   (i)  Benzene (2) planar
 (ii)  2-methyl propane (3) nonplanar
(iii)  2, 2-dimethyl propane (4) disymmetric
  (iv)  2, 2, 3, 3-Tetramethyl butane
44. Match list I with list II and select the correct an-
(1) i and iii (2) i, ii and iii swer using the code given below the lists.
(3) i, ii, iii (4) All of these
36. The correct statement/s about HC≡C–CH=CH2 is List I List II
   (i) The molecule lies in the same plane. Compound General formula
  (ii) Bond length between middle carbon atom (A) CH3–CH2–C≡CH    (i)  CnH2nO
is 1.54 Å (B) CH2=CH–CH2-CH3  (ii)  CnH2nO
(iii) The electronegativity of first and second ­carbon (C) CH3COCH3 (iii) CnH2n
atoms is more than that of third and fourth (D) CH3COOH   (iv)  CnH2n–2
­carbon atoms.
(1) i only (2) ii only The correct matching is
(3) i and iii (4) i, ii and iii
S. No. A B C D
37. In which of the following compounds, there is more
than one kind of hybridisation for carbon? 1. i ii iii iv
2. iv iii i ii
   (i)  H3C–CH2–CH2–CH3
3. ii i iii iv
 (ii)  H3C–CH=CH–CH3
4. iv iii ii i
(iii) H2C=CH–CH=CH2
  (iv)  H3C–C≡CH
(1) i and iii (2) i and iv 45.
(3) ii and iii (4) ii and iv List I List II
38. The cylindrical shape of alkynes is due to Formula Functional group
(1) three sigma C–C bonds (A) CH3COOH    (i)  Acid halide
(2) three π C–C bonds (B) CH3COX  (ii)  Ester
(3) two σ C–C and one π C–C bonds (C) CH3COCH3 (iii) Ketone
(4) one sigma C–C and two π C–C bonds (D) CH3COOCH3   (iv)  Acid
39. The bond length between sp3 hybridised carbon and
other carbon atom is minimum in The correct matching is
(1) Propane (2) Propyne
(3) Propene (4) Butane S. No. A B C D

40. Cyclic hydrocarbon “A” has all the carbon and 1. i ii iii iv
­hydrogen atoms in a single plane. All the carbon–­ 2. ii iii i iv
carbon bonds have the same length, less than 1.54 Å 3. iv i iii ii
but more than 1.34 Å. The CCC bond angle will be 4. iii i ii iv
(1) 109°28′ (2) 100° (3) 180° (4) 120°
46.
41. The maximum number of carbon atoms arranged
­linearly in the molecule CH3–C≡C–CH=CH2 List I List II
(1) 5 (2) 4 (3) 3 (4) 2 Compound Number of o bonds
42. In which of the following species all three types of (A) CH3CN   (i) one
hybrid carbons are present? (B) CH3COCH3  (ii)  two
(C) CH3C≡C–CN (iii) three
(1) CH2=C=CH2 (2) CH3–CH=CH–CH2
(D) CH2=CH–CN   (iv)  four
(3) CH3–C≡C–CH2 (4) CH3–CH=CH–CH2

Chapter_14.indd 6 3/26/2014 3:24:41 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.7

The correct matching is • Root word tells about the number of carbon atoms in
the longest chain selected, called the parent chain.
S. No. A B C D
1. i ii iii iv No. of carbon atoms Root word
2. iv i iii ii  1. Meth
3. ii i iii iv  2. Eth
4. ii i iv iii  3. Prop
 4. But
 5. Pent
Answers  6. Hex
 7. Hept
 (1) 4  (2) 3  (3) 3  (4) 1  (5) 3
 8. Oct
 (6) 3  (7) 4  (8) 2  (9) 2 (10) 2
 9. Non
(11) 1 (12) 1 (13) 1 (14) 2 (15) 3
10. Dec
(16) 2 (17) 4 (18) 3 (19) 3 (20) 3
(21) 3 (22) 4 (23) 3 (24) 3 (25) 3
(26) 2 (27) 3 (28) 3 (29) 1 (30) 1 • The root word is followed by appropriate primary
(31) 2 (32) 1 (33) 3 (34) 1 (35) 3 suffixes to represent the nature of C–C bond, i.e.,
­
(36) 3 (37) 4 (38) 4 (39) 2 (40) 4 ­saturation or unsaturation.
(41) 2 (42) 3 (43) 3 (44) 2 (45) 3
Primary General
(46) 4 Nature of bond suffix name
Saturated hydrocarbon –ane Alkane
Unsaturated C=C –ene Alkene
Nomenclature Unsaturated C≡C –yne Alkyne
Group R– –yl Alkyl
• Before 1892 carbon compounds were named based on
the source of occurrence.
• When a hydrogen atom is removed from an alkane,
• Methane is called marsh gas because it is released
this is an alkyl group. The symbol R is used to repre-
from marshy place. Urea is so named since it is present
sent a general alkyl group (i.e., a methyl, ethyl, propyl,
in urine.
etc. group).
• In the IUPAC system of nomenclature of organic
­compounds there are four parts. Name Name
   (i)  Prefix (symbol) Structure (symbol) Structure
 (ii)  Root word
methyl (Me) –CH3 propyl (Pr) –CH2CH2CH3
(iii)  Primary suffix
ethyl (Et) –CH2CH3 butyl (Bu) –CH2CH2CH2CH3
  (iv)  Secondary suffix
When hydrogen atom is removed from benzene ring, this is a phenyl group. The symbol Ph is used to represent this
x

aryl or Ar
Phenyl (C6H5), Ph x = various functional group(s)
• Alkyl substitution
H R R R
| | | |
R–C–H R–C–H R–C–H R–C–R
| | | |
H H R R
A primary (or 1°) A secondary (or 2°) A tertiary (or 3°) A quaternary (or 4°)
carbon is bonded carbon is bonded to carbon is bonded to carbon is bonded to
to another carbon two other carbons three other carbons four other carbons

Chapter_14.indd 7 3/26/2014 3:24:42 PM

 14.8  Objective Chemistry - Vol. I

• Common branched groups have special trivial names. For example,

CH3 – CH – CH3 – CH2 – CH – CH3 – CH – CH2 –
| | |
CH3 CH3 CH3
isopropyl secondary butyl Iso butyl
CH3 CH3
| |
CH3 – C – CH3 – C – CH –
| |
CH3 CH3
Tertiary Butyl Neopentyl
CH3 CH3
| |
CH3 – C CH CH2 CH3 Primary carbon 1°
| Secondary carbon 2°
CH3 Tertiary carbon 3°

Neocarbon 4°

Longest Chain Rule • If two or more identical substituent groups are p­ resent
then the numbers are separated by commas.
• The longest continuous chain of carbon atoms should
be selected. • When there are two identical substituents at one position
1C
same number is given repeatedly.
– 2C – C3 – C4 Wrong
| CH3 CH3
C–C–C | |
4 5 6 Correct CH3 –– C ––– CH –– CH2 –– CH3 2,2,3 – trimethyl
• The numbering is done in such a way that the branched | pentane
carbon atoms get the lowest possible numbers, i.e.,
CH3
starting from the end which results in the lowest sum
• If different alkyl groups are present, they are listed in
of the numbers of substituted carbon atoms.
alphabetical order.
1 2 3 4 5 6 7 8 9
C–C–C–C–C–C–C–C–C Correct • If two substituents are found in equivalent positions
| | the lower number is given to the one coming first in the
C C–C alphabetical order.
7 8 1 2 3 4 5 6 7 8
9 8 7 6 5 4 3 2 1 CH3 – CH2 – CH – CH2 – CH2 – CH – CH2 – CH3
| |
C–C–C–C–C–C–C–C–C Wrong
CH2CH3 CH 3
| |
C C–C 3-ethyl – 6 methyl octane – correct
• If two equally long chains are present then the chain 6-ethyl – 3 methyl octane – wrong
carrying larger number of side chains must be selected.
• The branched alkyl groups can be named by follow-
C ing the above mentioned procedures but numbering
| for branched alkyl group should be started from the
C–C–C–C–C–C–C Correct carbon atom attached to the main chain.
| |
C C • The names of the branched alkyl groups should be
| kept in parenthesis.
C • While writing the trivial names of substituents in
Wrong alphabetical order the prefixes iso- and neo- are
­

Chapter_14.indd 8 3/26/2014 3:24:44 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.9

considered to be the part of the fundamental name • While writing the name of the substituents in
of alkyl group. But the prefixes sec- and tert- are not alphabetical order the prefixes di, tri, etc. are not
­
consi­dered to be the part of the fundamental name. considered.

CH2CH3
4 |3 2 1
CH3 CH2 CH2 CH2 CH2 CH CH2 CH CH2 CH3

10 9 8 7 6 5 1 2 3 4
4
CH2
|
3
CH3 – C – CH3
|
2 1
CH2 CH3

5-(2-Ethyl butyl)-3, 3 – dimethyl decane – correct

5-(2,2-Dimethyl butyl)-3 – ethyl decane – wrong

CH (CH3)2
|
CH3 CH2 CH2 CH CH CH2 CH2 CH2 CH2 CH3
|
CH3 CH CH2 CH3
5-sec-Butyl-4-isopropyl decane

CH3 CH2 CH2 CH2 CH CH2 CH2 CH2 CH3

|
CH – CH3
|
CH – CH3
|
CH3
5-(1, 2-dimethyl propyl) nonane

Nomenclature of Cyclic Compounds

• A saturated monocyclic compound is named by prefix- • When three or more substituents are present,
ing cyclo to the corresponding straight chain alkane. ­numbering should be given so that we get lowest sum
• If only one substituent is present, it is not necessary to of locants.
designate its position. • When the numbering could begin with either of two
• When two substituents are present, numbering is given alkyl groups, begin with the one that is alphabetically
starting with the carbon with the substituent first in first.
alphabet.

Chapter_14.indd 9 3/26/2014 3:24:45 PM

 14.10  Objective Chemistry - Vol. I

OH Cl

cyclo cyclo cyclo isopropyl chloro

propane hexane hexanol cyclo hexane cyclo hexane

CH 3 CH 3
CH 2 CH 3
1 2

4 3

CH 2 CH 3
Cl
1-ethyl-3-methyl cyclohexane 4-chloro-2-ethyl-1-methyl cyclohexane
not 1-ethyl-5-methyl cyclohexane not 1-chloro-3-ethyl-4-methyl cyclohexane

• When a single ring system is attached to a single chain with a greater number of carbon atoms or when more than one
ring system is attached to a single chain, then they are named as cycloalkyl alkane.

– CH 2 – CH2 – CH2 –

1-cyclobutyl pentane 1, 3-dicyclohexyl propane

• Cycloalkanes consisting of two rings only and having two or more atoms in common are named by taking the prefix
bicyclo followed by the name of the alkane. In between bicyclo and alkane, number of carbon atoms representing the
bridge (except bridge head positions) are written within bracket. Bridge head positions are those which join the rings.
C1 and C4 are joined to
7 bridge of one carbons atom
4

5
1
3 C1 and C4 are joined to
2 6 bridge of two carbons

C1 and C4 are joined to

bridge of two carbons
• It is an alicyclic compound with seven carbon atoms, hence it is bicycloheptane. The two rings have two C atoms in com-
mon (numbered 1 and 4) in structural formula. These positions are called bridge head positions. Carbon atoms 1 and 4
are tied together by three bridges two, two and one carbon atoms. Hence, it is bicyclo [2,2,1] heptane norborane.

CH2

bicyclo [2,2,1] heptane bicyclo [2,2,0] hexane bicyclo [4,4,0] decane

• If substituents are present, we number the bridge head proceeding first along the longest bridge head then along the
next longest bridge head back to the first bridge head. The shortest bridge is numbered last.

Chapter_14.indd 10 3/26/2014 3:24:47 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.11

7 1 2
CH2 CH –– CH2 2
| 1 9
3 3
CH3 – CH CH2 CH3
|8 8
4
CH2 CH CH2 6 7
6 5 4 5
8-Methyl bicyclo [3,2,1] octane 8-methyl bicyclo [4,3,0] nonane
• Spiranes are polycyclics that share only one carbon (quaternary) at the apex. These are prefixed by the word spiro
followed by brackets containing the number of carbon atoms in each ring in ascending order and then by the name of
parent hydrocarbon containing total number of carbon atoms in the ring. The numbering starts from the atom next to
spiro atom and proceed through the smaller ring.
4
5 1
Spiro [2,4] heptane
6 3
2
7
• When unbranched identical hydrocarbon units are joined by a single bond, they are named by placing a suitable
­numeral prefix as bi, ter, quater, quinque for 2,3,4,5 respectively before the name of hydrocarbon unit. Starting from
either end, the carbon atoms of each repetitive hydrocarbon unit are numbered with unprimed and primed arabic
­numerals such as 1, 2, 3 ......, 1′, 2′, 3′ ... 1″, 2″, 3″ ......., etc. The connecting points of hydrocarbon units are indicated
by placing the appropriate locants before the name. e. g.,
3 4 4″ 3″
1′ 2′
1,1′ - bicyclopropane 2 1 1″ 2″
4′ 3′
3 2 2′ 3′ 2″ 3″ 1,1′,2′,1″ - tercyclobutane
1 1′ 1″
4 4″
4′
5 6 6′ 5′ 6″ 5″
1,1′,4′,1″ terphenyl

Nomenclature of Organic Compounds Containing Functional Groups

• Organic compounds are classified by functional groups which determine their chemistry.
• The names of organic compounds are derived from the functional group (or groups) and the main chain.
• From the name, the structure of organic compounds can be drawn using Kekule, condensed or skeletal structures.
• A functional group is made up of an atom or atoms with characteristic chemical properties.
• The chemistry of organic compounds is determined by the functional group that are present.
Hydrocarbons (only H and C present)
H H H H
| | | |
H–C–C–H H–C=C–H H – C ≡ C –H
| |
H H
Ethane Ethene Ethyne Benzene (an arene)
(an alkane) (and alkene) (an alkyne) single/double CC bonds
single C – C bond double C = C bond triple C ≡ C bond

Chapter_14.indd 11 3/26/2014 3:24:48 PM

 14.12  Objective Chemistry - Vol. I

• Carbon bonded to an electronegative atom(s). Single bond (R = alkyl group) R–X

Class of compounds Functional group IUPAC group IUPAC group
hydrocarbons structure prefix suffix Example
Alkane C–C – ane Butane CH3(CH2)2CH
Alkene C=C – ene But-1-ene CH2=CH–CH2–CH3
Alkynes C≡C – yne But-1-yne HC≡C–CH2–CH3
Arenes – – – Benzene
Carbon bonded to an electronegative atom(s)
Halides –X X=F, Cl, Br, I halo – 1-Bromobutane CH3(CH2)2CH2 Br
Alcohols –OH hydroxy –ol Butan-2-ol CH3 CH2CHOHCH3
Ethers –O– alkoxy – Ethoxy ethane CH3CH2OCH2CH3
Nitrocompounds –NO2 nitro – 1-nitrobutane CH3(CH2)2CH2NO2
Thiol –SH thiol – Butan-1-thiol CH3(CH2)2CH2SH
Sulphide (thioether) –S– thio –
Amines
Primary –NH2
Secondary –NH–R
Tertiary R–NR2
Quaternary
Ammonium ion R–NR3
Double bond to oxygen
Aldehydes H Formyl or oxo –anal Butanal CH3(CH2)2CHO
|
–C=O
Ketones C=O Oxo –one Butan-2-one CH3CH2COCH3
Acid halide X – –oyl Butanoyl chloride CH3CH2CH2
| COCl
–C=O

Carboxylic acid OH Carboxy –oic acid Butanoic acid CH3(CH2)2COOH

|
–C=O
Carboxylate ions O– – –oate Sodium butanoate CH3(CH2)2
| COONa
–C=O
Esters OR alkoxy carbonyl –oate Methyl propanoate
|
CH3CH2COOCH3
R–C=O
Acid anhydride O O –carbamoyl –amide Butan amide H3(CH2)2CONH2
|| ||
C C
O
Amides O
||
– C – NH
Triple bond to nitrogen
Nitriles –C≡N cyno Nitrile Pentane nitrile CH3(CH2)3CN
Special group
Sulphonic acids –SO3H sulpho sulphonic acid Methyl sulphonic acid CH3SO3H

Chapter_14.indd 12 3/26/2014 3:24:51 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.13

Naming the Carbon Compounds

• The IUPAC name of an organic compound is composed of three parts.
Prefix – Parent – Suffix

Substituents The main The major

(e.g. minor functional carbon chain functional group
groups) on the main chain
and their position

• There are four key steps in naming organic compounds.

  (i)  Identify the longest chain and name this as an alkane. This is the parent name.
    (ii) Identify the major functional group. Replace –ane (in the alkane with a suffix).
 Functional group priorities
 –COOH > –SO3H > –COOR (R = alkyl group) > –COCl > –CONH2 > –CN > –CHO > –C=O > –OH >
–NH2 > –C=C– > –C () C–
(iii) Number the atoms in the main chain. Begin at the end near the major functional group and give this the lowest
number.

 (iv) Identify the substituents (e.g., minor functional group) on the main chain and their number. The substituent
name and position is the prefix.

Minor functional group Prefix Minor functional group Prefix

chloride chloro- aldehyde formyl-
bromide bromo- ketone oxo-
iodide iodo- nitro nitro-
alcohol hydroxy- amine amino-
ether alkoxy- nitrile cyano-

Nomenclature of Substituted Benzene

Compounds
• Monosubstituted derivatives are usually named after The word benzene comes first when functional groups
benzene (C6H6) although some non-systematic or of higher priority (than benzene) are on the ring.
trivial names (in brackets) are still used.
X Name
X Name
CHO Benzene carboxaldehyde
H Benzene
(benzaldehyde)
Br Bromobenzene
COOH benzene carboxylic acid
Cl Chlorobenzene
(benzoic acid)
NO2 Nitrobenzene
CH3 Methyl benzene (toluene) • Disubstituted derivatives are sometimes named using
–CH=CH2 Ethynyl benzene (styrene) the prefixes ortho (or positions 1,2-or 1,6-) meta (or
–OH Hydroxy benzene (phenol) ­positions 1,3- and 1,5-) and para (or position 1,4-)
–NH2 Amino benzene (aniline)
• For trisubstituted derivatives, the lowest possible
–CN Cyano benzene
numbers are used and the prefixes are arranged
(benzonitrile)
alphabetically.

Chapter_14.indd 13 3/26/2014 3:24:51 PM

 14.14  Objective Chemistry - Vol. I

X
(ipso)
ortho (o) 6 2 ortho (o)

meta (o) 5 3 meta (m)

4

para (p)
OH COOH CH3
O2N

Cl
Br OH NO2
p-Bromophenol 3-chloro-4- 2,4-Dinitro-1-methyl benzene
hydroxy benzoic acid (or) 2,4-Dinitro toluene

• Esters are named in two parts. The first part represents the R1 group attached to oxygen. The second represents the
R2CO2 portion which is named as an alkanoate (i.e., the suffix is -anoate; an exception is -oate in benzoate). A space
separates the two parts of the name.
O CH3CH2COOCH3
||
Methyl propanoate
R2 – C – O – R1 First part

Second part COOCH2CH3

Ethyl benzoate
• The R1 group is the prefix, and N- is written before this to show that the group is on nitrogen.
O
||
R2 – C – NH – R1 Prefix
Suffix = – anamide
CH3CH2CONHCH3
N-methyl propanamide

Drawing Organic Structures

• In Kekule structures, every carbon atom and every C–H bond are shown.
• In condensed structures, the C–H bonds, and often the C–C bonds are omitted.
• In skeletal structures, the carbon atoms are not shown, and the bonds to hydrogen are usually also not shown but
the hydrogen atoms within the functional groups, e.g., alcohols, amines, aldehydes and carboxylic acids are shown.
All other atoms are written.
H H O H O
| | |
H–C–C–C–O–C–H → CH3CH2COOCH3 →
| | | O
Condensed Skeletal
H H H
Kekule
H H H H
| | | |
H – C – C = C – C – OH → CH3 CH = CH CH2 OH →
Chapter_14.indd 14 OH 3/26/2014 3:24:53 PM
 H H O H O
| | |
H–C–C–C–O–C–H → CH3CH2COOCH3 →
| | | O
Condensed Skeletal
H H H
Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.15
Kekule
H H H H
| | | |
H – C – C = C – C – OH → CH3 CH = CH CH2 OH →
| | OH
Condensed Skeletal
H H
Kekule
3-methyl octane can be represented as follows.

CH3

CH3CH2CHCH2CH2CH2CH3 Terminals represent methyl groups

 Objective Questions 6. The IUPAC name of the compound

1. IUPAC name of CH3CH(CH3)COOH is CH3
|
(1) Dimethyl acetic acid CH3 – CH2 – CH – CONH2
(2) 2-methyl propionic acid
(3) Propionic acid (1) 2-ethyl butanamide
(4) Butyric acid (2) 2-methyl butanamide
2. IUPAC name of (CH3)3C–CH=CH2 is (3) 1-amino-2-methyl propane
(1) 3,3,3-Trimethyl-1-propene (4) None
(2) 1,1,1-Trimethyl-2-butene
(3) 3,3-dimethyl-1-butene CH 3
(4) 2,2-dimethyl-3-butene |
7. IUPAC name of CH3(CH2)4 –CH C – CH2 –CH3 is
3. IUPAC name of CH2=CH–CH(CH3)2 is

|
| |
(1) 1,1-dimethyl-2- propene CH3 (CH2)2CH3
(2) 3-methyl-1-butene
(3) 2-vinyl propane (1) 3,4-dimethyl-3-n-propyl nonane
(4) 1-isopropyl ethylene (2) 4-ethyl-4,5-dimethyl decane
(3) 6,7-dimethyl-7-n-propyl nonane
4. IUPAC name of CH3CHCl2 is (4) 6,7-dimethyl-7-diethyl decane
(1) 1,2-dichloro ethane
(2) 2,2-dichloro ethane 8. The IUPAC name of the compound having the structure­
(3) 1,1-dichloroethane CH3 – CH – CH2 – CH – CH2 – Cl
(4) Dichloroethane | |
C2H5 OH is
5. IUPAC name of the compound
CH3 (1) 1-chloro-4-methyl-hexanal-2
| (2) 1-chloro-4-ethyl-2-pentanol
CH3 – C – CH2 – CHO is (3) 1-chloro-4-methyl-2-hexanol
| (4) 1-chloro-2-hydroxy-4-methyl hexane
CH3 9. IUPAC name for (CH3)2CHCH2CH2Cl
(1) 3,3,3-trimethyl propanal (1) 1-chloro pentane
(2) 1,1,1-trimethyl propanal (2) isopentyl chloride
(3) 3,3-dimethyl butanal (3) 2-methyl-4-chloro butane
(4) 1,1-dimethyl butanal (4) 1-chloro-3-methyl butane

Chapter_14.indd 15 3/26/2014 3:24:55 PM

 14.16  Objective Chemistry - Vol. I

10. IUPAC name of CH3CH2CH = C–CH2OH 17. 2-methyl-2-butene will be represented as

| (1) CH3 – CH – CH2 – CH3
CH3 |
(1) 2-methyl pentyl alcohol CH3
(2) 4-methyl-3-pentene-1-ol (2) CH3 – CH – CH = CH2
(3) 2-methyl pent-2-en-1-ol |
(4) 4-methyl pentyl alcohol CH3

11. IUPAC name of (3) CH3 – CH2 – C = CH2

|
OHC – CH = CH – CH – CH = CH2 CH3
|
CH2CH2CH2CH3 is (4) CH3 – C = CH – CH3
|
(1) 4-butyl-2,5-hexadiene-1-al CH3
(2) 5-vinyl oct-3-en-1-al
(3) 5-vinyl oct-5-en-8-al 18. IUPAC name of
(4) 3-butyl-1,4-hexadiene-6-al CH3 – C ≡ C – CH – C – CH2 – CH3
| ||
12. The IUPAC name of the compound CH3 CH2
CH = C – CH2 – C ≡ CH is (1) 2-ethyl-3-methyl-hexa-1-en-4-yne
2 | (2) 5-ethyl-4-methyl-hexa-2-yne-5-ene
CH3 (3) 3-methyl-4-methyl hepta-5-ene
(1) 2-methyl pent-1-en-4-yne (4) 5-methylene-5-ethyl-4-methyl hepta-2-yne
(2) 4-methyl pent-4-en-1-yne 19. IUPAC name of (CH3)2N–C2H5 is
(3) 2-methyl pent-2-en-4-yne
(1) Dimethyl ethyl amine
(4) 4-methyl pent-3-en-1-yne
(2) Dimethyl amino ethane
13. Isobutyl chloride is (3) Dimethyl amino methane
(1) CH3CH2CH2 CH2Cl (4) N, N-dimethyl amino ethane
(2) (CH3)2 CHCH2Cl 20. The name of the compound CH3CH2CH2COCH3 is
(3) CH3CH2CHClCH3
(1) 2-pentanone
(4) (CH3)3CCl
(2) pentanone-2
14. The IUPAC name of 4-hydroxy-1-methyl pentanal (3) pentan-2-one
(1) 4-hydroxy-1- methyl pentanal (4) All are correct
(2) 4-hydroxy-2-methyl pentanal 21. Which of the following IUPAC name is correct?
(3) 3-hydroxy-2-methyl pentanal (1) 2-methyl-3-ethyl pentane
(4) 3-hydroxy-3-methyl pentanal (2) 2-ethyl-3-methyl pentane
15. IUPAC name of (3) 3-ethyl-2-methyl pentane
(4) 3-methyl-2-ethyl pentane
CH3 – CH – CH2 – CH – CH2 Cl
| | 22. IUPAC name of the compound
C2H5 CHO
CN CN CN
(1) 2-chloromethyl-4-methyl-hexanal | | |
CH2 – CH – CH2
(2) 1-chloro-4-ethyl-2-pentanal
(3) 1-chloro-4-methyl-2-hexanal (1) 1,2,3-tricyano propane
(4) 1-chloro-2-aldo-4-methyl hexane (2) 2-cyano pentane-1,3-dinitrile
(3) 2-cyano propane
16. IUPAC name of CH3–O–C2H5 is
(4) propane tricarbyl amine
(1) Methoxy ethane
(2) Ethoxy methane 23. Number of tertiary carbon atoms in tertiary butyl
(3) Methyl ethyl ether ­alcohol is
(4) Ethyl methyl ether (1) 1 (2) 2 (3) zero (4) 4

Chapter_14.indd 16 3/26/2014 3:24:58 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.17

24. How many primary carbon atoms are there in the 31. The number of 4° carbon atoms in 2,2,4,4-­tetramethyl
compound pentane is
CH3 CH3 (1) 1 (2) 2 (3) 3 (4) 4
| |
CH3 – C – CH2 – C – CH3 32. The given compound in IUPAC may be called
| | NH2
CH3 CH3 |
(1) 6 (2) 2 (3) 4 (4) 3 (CH3)2 – C – CH2 COCH3
(1) Diacetone
25. The name of the hydrocarbon with the following s­ keleton
(2) Acetone amine
C (3) Diacetone amine
|
(4) 4-amino-4-methyl pentan-2-one
C – C – C – C – C – C – C
|
C 33. The IUPAC name of CH2 – CH – CH2COOH is
| | |
C HOOC COOH
(1) 4-methyl-5-ethyl heptane (1) propane-1,2,3-tricarboxylic acid
(2) 3-ethyl-4-methyl heptane
(2) 3-carboxy-pentane-1,5-dioic acid
(3) 3-isopentyl heptane
(3) Hexane trioic acid
(4) isodecane
(4) propan-1,2,3-trioic acid
26. The IUPAC name of the compound
34. The IUPAC name of the compound CH3–N≡C
OH OH OH
| | | (1) Ethane nitrile
CH2 – CH – CH2 (2) Methane isonitrile
(1) 1,2,3-trihydroxy propane (3) Ethane isonitrile
(2) 3-hydroxy pentane-1,5-diol (4) None
(3) 1,2,3-hydroxy propane
35. Formula of phenyl carbinol and chloral are r­ espectively
(4) propane-1,2,3-triol
(1) C6H5CH2CH2OH and CHCl2CHO
27. IUPAC name of (2) C6H5CH2OH and CCl3CHO
CH3 – CH – CH2 – CH3 (3) C6H5OH and CH2ClCHO
(4) C6H5CHO and CHCl2CHO
36. IUPAC name of urea is
(1) 2-cyclo-hexyl butane (2) 2-phenyl butane (1) Diamino ketone
(3) 3-cyclohexyl butane (4) 3-phenyl butane (2) 1-amino ethanamide
28. The IUPAC name of (3) 1-amino methanamide
(CH3)2CH–CH2–CO–CH2–CH(CH3)2 is (4) amino acetamide
(1) 2,4-dimethyl cyclohexanone 37. The correct IUPAC name of acetonitrile is
(2) 2,6-dimethyl heptanone-4 (1) cyanomethane
(2) 2,6-dimethyl hexanone-6 (2) 2-ketopropane nitrile
(4) 2,6-dimethyl heptanone-5 (3) methane nitrile
29. 3-methyl pent-1,3-diene is (4) ethane nitrile
(1) CH2=CH(CH2)2CH3 38. A student named the compound as 1,4-butadiene
(2) CH2=CHCH(CH3)CH2CH3 (1) The name is correct
(3) CH3CH=C(CH3)CH=CH2
(2) He or she committed an error in the selection of
(4) CH3CHClC(CH3)3
carbon chain
30. The formula of ethane nitrile is (3) He or she committed an error in the position of
(1) C2H5NC (2) C2H5CN double bond
(3) CH3CN (4) None (4) Unpredictable

Chapter_14.indd 17 3/26/2014 3:25:01 PM

 14.18  Objective Chemistry - Vol. I

39. The IUPAC name of CH = CH 45. In which of the following compounds the carbon ­atoms
| | has been correctly numbered?
OHC NH2 (1) 7 6 5 4 3 2 1
(1) 1-Amino prop-2-enal CH3 – CH2 – CH – CH – CH2 – CH2 – CH3
(2) 3-Amino prop-2-enal | |
C2H5 CH 3
(3) 1-Amino-2-formyl ethene
(4) 3-Amino-1-oxoprop-2-ene (2) 1 2 3
CH3 – CH2 – C = CH – CH3
40. An olefin “X” undergoes ozonalysis reaction to |
yield acetone and formaldehyde as the products. The CH2 – CH3
­IUPAC name of the olefin X is 4 5
(1) 1-methyl prop-2-ene (3)  5 4 3 2 1
(2) 2-methyl prop-2-ene CH3 – C H 2 – CH – C ≡ CH
(3) 3-methyl prop-2-ene |
(4) 2-methyl prop-1-ene CH2 – CH2 – CH3
CH3
NH2 |
| (4) 5 4 3 2 1
41. CH3 – CH = CH – CH2 – CH – CH2 COOH CH3 – C – CH = CH – CHO
|
(1) 5-amino-2-heptenoic acid CH3
(2) β-amino-δ-heptenoic acid
(3) 5-amino-hex-2-ene-carboxylic acid 46. Which one is the correct statement?
(4) 3-amino-5-heptenoic acid (1)  IUPAC names are based on the structure of
­compounds.
42. Which is the correct chemical formula for 1,2-­dichloro (2) Common names are based on the structure of
tetrafluoro ethane? compounds.
F F H F (3) IUPAC name of HCOOH is formic acid.
| | | |
(4) Common name of HC≡CH is ethyne.
(1) Cl – C – C – H (2)  H–C–C–F
| | | | 47. IUPAC name of
Cl Cl Cl Cl CH2
||
F F F Cl F CH3 – CH2 – C – C – CH2 – CH3 is
| | | | | ||
(3) Cl – C – C – Cl (4) 
F–C–C–C–F CH2
| | | | | (1) 3,4-dimethyl hexane
F F Cl H F (2) 2-ethyl, 3-methyl, 1-pentene
(3) 2,3-diethyl 1,3-butadiene
CH3 CH3 (4) 2,3-diethyl, 1-butene
| |
43. In the structure CH3 – CH – CH2 – C – CH3 the 48. IUPAC name of neopentyl chloride is
| (1) 2-chloro-2-methyl propane
CH3 (2) 1-chloro-2,2-dimethyl propane
number of carbons are
(3) 3-chloro-2,2-dimethyl propane
(1) one primary, two secondary and one tertiary
(4) 2-chloro-2-methyl pentane
(2) four primary, two tertiary and one secondary
(3) one primary, one secondary, one tertiary and one 49. CH2 = C – CH2 – CH3 has IUPAC name
quaternary |
(4) five primary, one secondary, one tertiary and one CH – CH3
quaternary |
CH3
44. The alkane which contains only primary hydrogen (1) 2-isopropyl butene-1
atom is (2) 2-methyl, 3-ethyl, butene-3
(1) pentane (2) isopentane (3) 2-ethyl, 3-methyl butene-1
(3) neopentane (4) 2,2-dimethyl butane (4) Ethyl isopropyl ethene

Chapter_14.indd 18 3/26/2014 3:25:05 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.19

50. Which of the following is the correct IUPAC name? 57. IUPAC name of the given structure is
(1) 3-methyl-2-ethyl pentane
(2) 3-pentyne
(3) ethyl-1-butene
(4) Hexabromo ethane Cl
51. The decreasing order of the priority of functional Br
groups is (1) 5-bromo-6-chloro-1-cyclohexen-3-yne
(2) 6-bromo-5-chlorocyclohexene-3-yne
(1) –COOH > –COCl > –CHO > –CN
(3) 6-bromo-5-chloro-3-cyclohexen-1-yne
(2) –COOH > –CHO > –COCl > –CN
(4) 4-bromo-3-chloro-1-cyclohexen-5-yne
(3) –COOH > –CHO > –CN > –COCl
(4) –COOH > –CN > –CHO > –COCl 58. IUPAC name of the given compound is
52. Which of the following contains only 1° and 3° ­carbon OH
atoms? Cl CH3
(1) n-butane (2) isobutane
(3) isopentane (4) neopentane

53. The IUPAC name of the given structure is

Br
(1) 4-bromo-2-chloro-6-methyl cyclohexanol
(2) 5-bromo-3-chloro-1-methyl cyclohexanol
(1) 3,3-Dimethyl pentane (3) 1-bromo-5-chloro-3-methyl-3-cyclohexanol
(2) 3,3-Diethyl pentane (4) 5-bromo-1-chloro-3-methyl-3-cyclohexanol
(3) 3-ethyl-3-methyl pentane
(4) 3-ethyl-3-ethyl pentane
59. IUPAC name of
54. IUPAC name of the given structure is
(1) Bicyclo [5,5,0] nonane
(2) Biphenyl
(1) 2,2-dimethyl butane
(3) Cyclopropyl cyclohexane
(2) isohexane
(4) Spiro [5,2] octane
(3) 2,3-dimethyl butane
(4) diisohexane 60. Structure of bicyclo [1,1,0] butane is
55. The IUPAC name of the given compound
(1)  (2) 

(3)  (4) 

(1) octyl cyclopentane 61. When two halogen atoms are linked to same carbon
(2) 3-cyclopentyl octane atom the dihaloalkane is called
(3) cyclopentane octanes (1) alkylidene halide (2) alkylene dihalide
(4) 6-cyclopentyl octane (3) alkyl halide (4) alkane dihalide
56. IUPAC name of the given compound 62. IUPAC name of the compound for

Br Br is

(1) 5,6-diethyl-3-methyl-4-decane (1) 4, 4′-dibromo-1,1′-dicyclohexyl

(2) 7-methyl-2,4,6-triene octanal (2) 4, 4′-dibromo-1,1′-bicyclohexane
(3) 6-methyl heptene (3) 1-bromo-4-(4′-bromo) bicyclohexane
(4) 3,3-diethyl-5-ethyl-4-decane (4) None of these

Chapter_14.indd 19 3/26/2014 3:25:10 PM

 14.20  Objective Chemistry - Vol. I

(1) 3-bromo-1-chlorocyclohexane
63. IUPAC name of HOOC CHO is (2) 1-bromo-3-chlorocyclohexane
(3) 2-bromo-6-chlorohex-1-ene
(1) 4-oxobenzoic acid (4) 6-bromo-2-chlorocyclohexene
(2) 4-formyl benzoic acid
(3) 4-formyl cyclohexane carboxylic acid 70. Names of some compounds are given, which one is
(4) None of these not in IUPAC system

64. Vinyl carbinol is CH3

|
(1) HO–CH2–CH=CH2 (1) CH3 CH2 CH2 CH CH CH2 CH3
(2) CH3CH(OH)=CH2 |
(3) CH3–CH=CH–OH CH2 CH3
(4) CH3–C(CH2OH)=CH2 3-methyl-4-ethylheptane
65. The IUPAC name of acraldehyde is
(2) CH3 – CH – CH – CH3
(1) prop-2-en-1-al | |
(2) propenylaldehyde OH CH3
(3) but-2-en-1-al 3-methyl-2-butanol
(4) propanal
(3) CH3 CH2 CH – CH – CH3
66. IUPAC name for the compound | |
Cl CH 2 CH3 C2H5 CH3

C=C 2-ethyl-3-methyl-1-ene
is
CH 3 I (4) CH3 – C ≡ C – C (CH3)2
(1) trans-2-chloro-3-iodopentene-2 4-methyl-2-pentyne
(2) cis-2-chloro-3-iodo-2 pentene
(3) trans-3-iodo-4-chloro-3-pentene
Answers
(4) cis-3-iodo-4-chloro-3-pentene
67. An organic compound X (molecular formula, C6H7O2N)  (1) 2  (2) 3  (3) 2  (4) 3  (5) 3
has six carbon atoms in a ring system, two double bonds  (6) 2  (7) 2  (8) 3  (9) 4 (10) 3
and a nitro group as substituent X is (11) 1 (12) 1 (13) 2 (14) 2 (15) 1
(1) Homocyclic but not aromatic (16) 1 (17) 4 (18) 1 (19) 4 (20) 4
(2) Aromatic but not homocyclic (21) 3 (22) 1 (23) 1 (24) 1 (25) 2
(3) Homocyclic and aromatic (26) 4 (27) 2 (28) 2 (29) 3 (30) 3
(4) Heterocyclic and aromatic (31) 2 (32) 4 (33) 4 (34) 3 (35) 2
(36) 3 (37) 4 (38) 3 (39) 2 (40) 4
Cl (41) 4 (42) 3 (43) 4 (44) 3 (45) 4
68. The IUPAC name of is (46) 1 (47) 3 (48) 2 (49) 3 (50) 4
O (51) 1 (52) 2 (53) 2 (54) 3 (55) 2
(1) 2,3-dimethyl pentanoyl chloride (56) 1 (57) 1 (58) 1 (59) 4 (60) 3
(2) 3,4-dimethyl pentanoyl chloride (61) 1 (62) 2 (63) 3 (64) 3 (65) 1
(3) 1-chloro-1-oxo-2,3-dimethyl pentane (66) 1 (67) 1 (68) 1 (69) 1 (70) 1
(4) 2-ethyl-3-methyl butanoyl chloride
69. The IUPAC name of the compound
Cl
 Statement-Type Questions
is In each of the following questions, a statement-I is given
followed by corresponding statement-II just below. Mark
Br the correct answer as indicated.

Chapter_14.indd 20 3/26/2014 3:25:17 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.21

1. If both Statement-I and Statement-II are true and Answers

reason is the correct explanation of assertion.
2. If both Statement-I and Statement-II are true and  (1) 1  (2) 2  (3) 3  (4) 3  (5) 2
reason is not the correct explanation of assertion.  (6) 2  (7) 4  (8) 2  (9) 2 (10) 1
3. If Statement-I is true but Statement-II is false.
4. If Statement-I is false but Statement-II is true.
1. Statement-I: IUPAC name of acetic acid is ­ethanoic
acid.
 Match the Following  Type Questions
Statement-II: Acetic acid contains two carbon atoms
including the COOH group. 1. Match the following List I with those given in List II.
2. Statement-I: Glycerol is obtained by hydrolysis of
List I List II
ester of fatty acid.
Statement-II: It contains three –OH groups. (A) CnH2n   (i)  Alcohols and ethers
(B) CnH2n – 2 (ii) Alkenes and cycloalkanes
3. Statement-I: Acetone is the first member of ­alkanone (C) CnH2n + 2O (iii)  Aldehydes and ketones
family. (D) CnH2nO   (iv)  Alkynes and alkadienes
Statement-II: It contains one ketonic group.
4. Statement-I: Formic acid is isolated from red ant. The correct matching is
Statement-II: It is the first member of alkanoic acid S. No. A B C D
family.
1. i ii iii iv
5. Statement-I: Cl3C – CH Cl, DDT is 2. iv iii ii i
an ­insecticide. 3. ii iv i iii
4. iii i iv ii

2. Match the following

Cl List I List II
Statement-II: It contains five chloro and two phenyl (A)  Dimethyl acetylene    (i)  Propanone
groups. (B)  Methyl acetic acid (ii)  Trichloromethane
6. Statement-I: Methyl alcohol is isolated by wood. (C) Chloroform (iii)  Propanoic acid
(D) Acetone   (iv)  But-2-yne
Statement-II: It is called wood spirit.
7. Statement-I: IUPAC name of CH3CHO is ­methanol. The correct matching is
Statement-II: In case of the presence of –CHO
group, the suffix “e” of alkane is replaced by “al”. S. No. A B C D

8. Statement-I: IUPAC name of acetic acid is ­ethanoic 1. iv iii ii i

acid. 2. i ii iii iv
3. iii iv i ii
Statement-II: It is found in vinegar.
4. ii i iv iii
9. Statement-I: CH3COOCH2CH3 is called methyl pro-
panoate. 3. Match the following
Statement-II: Ester is alkyl derivative of alkanoic
acid. List I List II

10. Statement-I: IUPAC name of CH3SO3H is methane (A) Benzene    (i)  Aromatic (bicyclic)
sulphonoic acid. (B) Naphthalene  (ii)  Aromatic (monocyclic)
(C) Anthracene (iii) Alicyclic
Statement-II: The suffix “e” of methane is not re-
(D) Pyridine   (iv)  Heterocyclic
placed by the suffix of functional group as it is not
(E) Cycloalkane  (v)  Aromatic tricyclic
started by vowel.

Chapter_14.indd 21 3/26/2014 3:25:18 PM

 14.22  Objective Chemistry - Vol. I

The correct matching is • In crystallization process large quantity of the organic

compound can dissolve in a solvent at high tempera-
S. No. A B C D E ture and crystallize the same when cooled.
1. i ii iii v iv • Common solvents used for crystallization process are
2. ii i v iv iii water, alcohol, acetone, ether, benzene, etc.
3. iii v ii i v
• Fractional crystallization is used when the impuri-
4. v iv i iii ii
ties are such that they have nearly same solubilities
as the pure organic compound in a solvent, which is
Answers the relatively less soluble component. The mother liq-
uor on further ­crystallization gives other compound
 (1) 3  (2) 1  (3) 2 contaminated with the first one. The process for each
crystallized product is repeated to get two components
with purity.
• Sublimation process can be used for the purification
PURIFICATION AND CHARACTERIZATION of the solids which goes into vapour directly. When
cooled, pure solid will be obtained.
OF ORGANIC COMPOUNDS
• Naphthalene, benzoic acid, camphor, ammonium
• Purification of organic compounds means removal chloride, dry ice, iodine, etc. can be purified by
­
of undesirable impurities associated with a particular sublimation.
organic compound. • Distillation method is used for the purification of
• Purity of an organic compound is checked based on ­organic liquids containing non-volatile impurities.
m.p. and b.p.
• Fractional distillation method is used for the
   (i) impure solid melts at a wide range of tempera-
­purification or organic liquids containing two or more
tures, whereas pure solid completely melts within
liquids having nearly equal boiling points. E.g., water
1° C temperature range.
and ethanol.
 (ii) the m.p. of solids are lowered by the presence of
impurities. • Steam distillation is used if the organic compound is
(iii) the mixed m.p. for impure or a given solid is steam volatile and immiscible with water. For example,
determined and compared with m.p. of pure
­ nitrobenzene, aniline, lemon oil, sandal wood oil, etc.
compounds and if its value and range is same and are purified by steam distillation method.
sharp the compound is pure. • Distillation under reduced pressure is used for the
• Organic solids are purified by filtration, ­crystallization, purification of organic compounds which decom-
sublimation or fractional crystallization. pose at their boiling points. Examples include H2O2,
• Organic liquids are purified by simple distillation, fraction- ­glycerol, formaldehyde, etc.
al distillation, distillation under reduced pressure, steam • Solvent extraction process is used when an organic
distillation, solvent extraction, chromatography, etc. compound is present in aqueous medium and is sepa-
• Filtration is used to separate an insoluble solid rated by shaking it with an organic solvent ­immiscible
­component of the mixture from the soluble component with water in which it is more soluble than in water.
in a given solvent. • If the organic compound is less soluble in the organic
• Soluble urea can be separated from insoluble naphtha- solvent a very large quantity of solvent would be re-
lene by filtration after dissolving in water. quired to extract even for a very small quantity of the
compound.
• Benzoic acid soluble in hot water can be separated
from insoluble anthracene by filtration after ­dissolving • Chromatographic technique involves a stationary
in hot water followed by crystallization of benzoic phase and a mobile phase.
acid by cooling. • Adsorption chromatography is based on the fact that
• Crystallization process depends on the difference in different compounds are adsorbed on an adsorbent
the solubilities of organic compounds and the impuri- to different degrees, when a mobile phase containing
ties present in it in a suitable solvent. different components passes over a ­stationary phase.

Chapter_14.indd 22 3/26/2014 3:25:18 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.23

• In column chromatography the mobile phase con- • When a given organic compound is heated strongly
taining a mixture of compounds in a solvent is passed with dry cupric oxide, the carbon converts to CO2
through a stationary phase like silica gel or alumina while hydrogen converts to water vapour.
packed in long glass tube known as column. C + 2CuO  → 2Cu + CO2
• Thin layer chromatography (TLC) is another type of 2H + CuO  → Cu + H2O
adsorption chromatography. • CO2 can be tested by turning the lime water milky
• In TLC a thin layer of 0.2 mm thick of an adsorbent is and water vapour can be tested with anhydrous copper
spread over a glass plate known as thin layer chroma- ­sulphate which turns blue.
tographic plate. CO2 + Ca(OH)2  → CaCO3 + H2O
• When a small spot of the solution of mixture is ap- 4H2O + CuSO4 ⋅ H2O  → CuSO4 ⋅ 5H2O
plied about 2 cm above one end and hanged in a closed
jar containing solvent, the components of the mixture
     White    Blue
move up as the solvent moves up the plate depend- • Bielstein test is used for the detection of halogens
ing on their degree of adsorption and separation takes ­present in organic compounds.
place. • When an organic compound is heated with copper wire
• The relative adsorption of each component of the mix- in Bunsen flame, appearance of green colour ­indicates
ture is expressed in terms of its retention factor i.e., Rf. the presence of halogens (due to the formation of
copper halides).
Distance moved by the substance
• Bielstein test is not a reliable test since compounds
from baseline ( x)
Rf = like urea also gives this test.
Distance moved by the solvent
• The reliable test for the detection of halogens, ­nitrogen,
from baseline ( y )
sulphur and phosphorous is Lassaigne’s test.
• In TLC method if the spots are colourless they are • In Lassaigne’s test a little organic compound is fused
detected by spraying an appropriate reagent which with sodium metal and dissolved in water. This s­ olution
produces colour. is known as sodium fusion extract.
• In TLC technique amino acids may be detected by Na + C + N 
→ NaCN
spraying the plate with ninhydrin.
Na + C + S + N 
→ NaSCN
• Partition chromatography is based on continuous
differential partitioning of components of a mixture 2Na + X2 
→ 2NaX (X=Cl, Br, I)
between stationary and mobile phases. 2Na + S 
→ Na2S
• Paper chromatography is a type of partition 3Na + P + 4(O) 
→ Na3PO4
chromatography. • While testing for phosphorus the compound should be
• When a strip of chromatography paper is spotted at the heated with an oxidizing agent like Na2O2.
base with a solution of the mixture and suspended in a • When Lassaigne’s filtrate is boiled with ferrous
suitable solvent, the components in the spot are selec- ­sulphate, it gives sodium ferrocyanide Na4[Fe(CN)6]
tively retained by the paper according to their differing which gives deep blue Prussian blue with FeCl3
partition in the two phases while solvent rises up the ­indicating the presence of nitrogen.
paper by capillary action. This is known as elution.
• Prussian blue is ferric ferrocyanide, Fe[Fe(CN)6]3.
• The paper strip with spots of the separated coloured
• When Lassaigne’s filtrate is acidified with nitric acid
compounds is called a chromatogram.
and mixed with silver nitrate, formation of precipitate
indicates the presence of halogens.
DETECTION AND DETERMINATION OF White ppt, soluble in ammonia indicates the presence
ELEMENTS IN ORGANIC COMPOUNDS of Cl.
QUALITATIVE ANALYSIS Pale yellow ppt sparingly soluble in ammonia ­indicates
• The detection and estimation of carbon and h­ ydrogen the presence of Br.
in organic compounds can be made by Liebig’s Yellow ppt insoluble in ammonia indicates the
­combustion method. presence of I.

Chapter_14.indd 23 3/26/2014 3:25:21 PM

 14.24  Objective Chemistry - Vol. I

• If nitrogen or sulphur is also present in the compound, where N is the normality of the sulphuric acid,
Lassaigne’s filtrate first on boiling with conc. HNO3, V is the volume of the sulphuric acid neutralized by
to decompose cyanide or sulphide. NH3 and
• Addition of ammonium molybdate to the Lassaigne’s W is the weight of the sample.
filtrate after boiling with conc HNO3 appearence of • Halogens, sulphur and phosphorous are determined by
canary yellow ppt indicates the presence of Carius method.
phosphorous. • If the sample is heated with fuming HNO3 in the pre­
• Appearance of blood red colour by the addition of sence of AgNO3, the silver halides will be precipitated.
FeCl3 to Lassaigne’s filtrate indicates the presence of From the weight of the precipitate, halogens can be
both sulphur and nitrogen. Blood red colour is due to determined.
the formation of Fe(SCN)3. 35.5 WAgCl
Percentage of Cl2 = × × 100
143.5 Wsample
Quantitative Analysis
80 WAgBr
Percentage of Br2 = × × 100
• Carbon and hydrogen in a compound are oxidized to 188 Wsample
carbon dioxide and water, respectively.
 y y 127 WAgI
CxHy +  x +  O2  → xCO2 + H2O Percentage of I2 = × × 100
 4  2 235 Wsample
• When the sample is heated with fuming HNO3 or
• The mass of water produced is determined by pas­sing
s­odium peroxide in the presence of little BaCl2, the
the mixture of CO2 and H2O over anhydrous CaCl2
sulphur converts into BaSO4.
which absorbs only water vapour.
32 WBaSO4
• The mass of CO2 is obtained by measuring the Percentage of S = × × 100
­increased weight of caustic potash by passing CO2 233 Wsample
through it, which absorbs CO2 completely. • When the sample is heated with fuming nitric acid
• If the mass of organic compound is m g and masses of followed by the addition of ammonium molybdate
water and carbon dioxides produced be m1 and m2g, the phosphorous will be precipitated as ammonium
respectively, then ­phospho molybdate (NH4)3PO4 . 12MoO3.
12 × m2 × 100
Percentage of carbon = Percentage of phosphorous =
44 × m
31 W( NH4 )3 PO4 ⋅12 MOO3
2 × m1 × 100 × × 100
Percentage of hydrogen = 1877 Wsample
18 × m
• Nitrogen can be estimated either by Dumas method or • Phosphorous may also be precipitated as MgNH4PO4
by Kjeldahl’s method. by heating the sample with fuming nitric acid and
magnesia mixture. The MgNH4PO4 on ignition con-
• In the Dumas method the volume of the nitrogen
verts into magnesium pyrophosphate.
formed when the organic compound is heated in the
presence of CuO is measured over an aqueous solution 62 WMg2 P2 O7
Percentage of P = × × 100
of potassium hydroxide which absorbs CO2. 222 Wsample
28 Vol.of N 2 at STP
Percentage of  N2 = × × 100
22, 400 Wt.of the substance DETERMINATION OF MOLECULAR MASS
• In Kjeldahl’s method nitrogen present in the organic
compound is converted into (NH4)2SO4 by heating
• The molecular mass can be determined by using one
with conc. H2SO4 using CuSO4 as a catalyst. The of the following methods.
(NH4)2SO4 when heated with NaOH liberates NH3
   (i)  Victor Meyer method
which is bubbled through known volume of a stan­
 
(ii) Freezing point depression or boiling point
dard acid. The remaining acid after neutralization ­elevation method
with ­ammonia is determined with standard alkali from
(iii) Volumetric method
which N2 is calculated.
  (iv) Silver salt method for acids
1.4 × N × V  (v)  Chloroplatinate salt method for bases (amines)
Percentage of nitrogen =   (vi)  Mass spectrometry
W

Chapter_14.indd 24 3/26/2014 3:25:24 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.25

• In the silver salt method if a known mass of an organic 2. Aniline is purified by

acid is converted into silver salt by using ammonical (1) steam distillation
silver nitrate solution, the ignition of the silver salt (2) simple distillation
leaves metallic silver residue. (3) vacuum distillation
(4) extraction with a solvent
Molar mass of silver salt of a monocarboxylic
WSilver salt 3. Absolute alcohol is prepared from rectified spirit by
acid = 108 × (1) Fractional distillation
WSilver
(2) Steam distillation
Molar mass of RCOOH = Molar mass of RCOOAg – (3) Azerotropic distillation
(At. wt. of Ag + At. wt. of H) (4) Vacuum distillation
Molar mass of monocarboxylic acid = 4. Carbon and hydrogen are estimated by
 WSilver salt  WSilver salt (1) Liebig’s method (2) Carius method
108 × W  – 108 + 1 = 108 × W – 107 (3) Duma’s method (4) None
Silver Silver

• In the case of polycarboxylic acid of basicity, n. 5. In Kjeldahl’s method, nitrogen present is estimated as
(1) N2 (2) NH3
Molar mass of polybasic acid = (molar mass of silver
(3) NO2 (4) None
salt) – (n × at. wt. of H)
6. Petroleum refining involves
WSilver salt 
=  ×108× n  – 108 × n + 1 × n (1) Vacuum distillation
W
 Silver  (2) Steam distillation
 WSilver salt   (3) Fractional distillation
= n  ×108  −107  (4) Passing over activated charcoal
  WSilver  
7. In paper chromatography
• In the chloroplatinate salt method organic bases like
(1) Mobile phase is liquid and stationary phase is solid
amines react with chloroplatinic acid (H2PtCl6) to form
(2) Mobile phase is solid and stationary phase is l­ iquid
salts of chloroplatinates of general formula B2H2PtCl6
(3) Both phases are solids
where B is a monoacidic amine. On heating, these
(4) Both phases are liquids
salts decompose and yield metallic platinum.
8. The most satisfactory method of separating sugars
2RNH + H2PtCl6 
→ (RNH3)2 PtCl6 ignite
 → Pt
from each other is
• The salt formed with H2PtCl6 and diacidic amine B (1) Fractional crystallization
would be B2 (H2PtCl6)2 and with triacidic amine would (2) Sublimation
be B2(H2PtCl6)3 and with amine of acidity n would be (3) Chromatography
B2 (H2PtCl6)n. (4) Benedict solution
Wsalt
Molar mass of chloroplatinate salt = × 195 × n 9. Anthracene is purified by
Wplatinum
where n is the acidity of base. (1) Filtration
1 (2) Crystallization
Molar mass of the base = [molar mass of chloro­ (3) Distillation
2
platinate salt – molar mass of (H2PtCl6)n] (4) Sublimation
1 10. An organic substance from its aqueous solution can
= [molar mass of chloroplatinate salt – (n × 410)]
2 be separated by
410 = molar mass of H2PtCl6 (1) Solvent extraction
(2) Steam distillation
(3) Distillation
(4) Fractional distillation
 Objective Questions 11. Lassaigne’s test for the detection of nitrogen will fail
1. A mixture of acetone and methanol can be separated by in case of
(1) Vacuum distillation (2) Steam distillation (1) NH2CONH2 (2) H2NCONHNH2HCl
(3) Fractional distillation (4) None (3) H2NNH2 . 2HCl (4) C6H5NHNH2 . 2HCl

Chapter_14.indd 25 3/26/2014 3:25:26 PM

 14.26  Objective Chemistry - Vol. I

12. Which reagent is useful in separating benzoic acid (1) Ferric ferrocyanide
from phenol? (2) Ferric sulphocyanide
(1) dilute HCl (2) dilute H2SO4 (3) Ferric cyanide
(3) 5% NaOH (4) 5% NaHCO3 (4) None
22. A mixture of camphor and benzoic acid can be
13. A compound which does not give a positive test in
­separated by
Lassaigne’s test for N is
(1) Sublimation
(1) Glycine (2) Phenyl hydrazine
(2) Chemical methods
(3) Urea (4) Azobenzene
(3) Fractional crystallization
14. In sodium extract test of organic compounds, the (4) Extraction with solvent
­nitrogen of an organic compound is converted into 23. Distillation involves all the following process except
(1) Sodamide (2) Sodium cyanide (1) Change of state
(3) Sodium nitrite (4) Sodium nitrate (2) Boiling
(3) Condensation
15. The most suitable method of separation of 1:1 ­mixture
(4) Evaporation
of ortho- and para-nitrophenols is
(1) Distillation (2) Crystallization 24. In Kjeldahl’s method of estimation of nitrogen, K2SO4
(3) Sublimation (4) Chromatography acts as
(1) Oxidizing agent
16. ClCH2COOH is heated with fuming HNO3 in the (2) Catalytic agent
presence of AgNO3 in Carius tube. After filtration (3) Hydrolyzing agent
and washing, the precipitate obtained is (4) Boiling point elevator
(1) AgNO3 (2) AgCl
25. In Kjeldahl’s method of estimation of nitrogen copper
(3) Ag2SO4 (4) ClCH2COOAg
sulphate acts as
17. In Kjeldahl’s method nitrogen present is q­ uantitatively (1) Oxidizing agent (2) Silver spiral
converted to (3) Catalytic agent (4) Hydrolyzing agent
(1) N2 (2) (NH4)2SO4 26. The function of boiling the sodium extract with conc.
(3) NO2 (4) None HNO3 before testing for halogens is
18. In Lassaigne’s test for N, S and halogens, the organic (1) to make solution clear
compound is (2) to destroy CN– and S2– ions which will otherwise
give ppt.
(1) Fused with sodium
(3) to make the solution acidic
(2) Dissolved with sodamide
(4) to convert Fe2+ to Fe3+
(3) Extracted with sodamide
(4) Fused with calcium 27. Positive Beilstein test shows that
(1) Halogens are surely present
19. In Lassaigne’s test for nitrogen, the blue colour is due
(2) Halogens are absent
to the formation of
(3) Halogens may be present
(1) Ferric ferrocyanide (4) None

(2) Potassium ferrocyanide
(3) Sodium ferrocyanide 28. The sulphur present in an organic compound is o­ xidized
(4) Sodium cyanide by fuming nitric acid into
(1) SO2 (2) H2SO4 (3) H2S (4) S
20. There are several criteria of purity of organic
29. Simple distillation can be used to separate
­compounds. Which is considered to be the best?
(1) A mixture of benzene (b. pt. of 80°C) and toluene
(1) Melting point
(b. pt. of 110°C)
(2) Mixed melting point
(2) 
A mixture of ether (b. pt. of 35°C) and toluene
(3) Colour
(b. pt. of 110°C)
(4) Microscopic examination
(3) A mixture of ethanol (b. pt. of 78°C) and water
21. In Lassaigne’s test when both N and S are present, (b. pt. of 110°C)
blood red colour obtained is due to the formation of (4) None

Chapter_14.indd 26 3/26/2014 3:25:26 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.27

30. For which element, no experimental method is used 39. The presence of nitrogen in the organic compound is
to determine percentage in organic compound tested by
(1) N (2) H (3) C (4) O (1) Flame test (2) Litmus test
(3) Lassaigne’s test (4) None
31. Separation of petroleum into its components is m
­ ostly
done by 40. Which is useful for separating benzoic acid from a
(1) Chromatogaphy mixture of benzoic acid and methyl benzoate?
(2) Sublimation (1) aq. NaHCO3 (2) dil. HCl
(3) Distillation under reduced pressure (3) dil. H2SO4 (4) dil. HNO3
(4) Fractional distillation
41. A bottle containing two immiscible liquids is given to
32. In Duma’s method for determining the nitrogen con- you. These may be separated by
tent of an organic compound, the nitrogen content is (1) Fractionating column
determined in the form of (2) Separating funnel
(1) Gaseous NH3 (2) NaCN (3) Fractional distillation
(3) Gaseous N2 (4) (NH4)2SO4 (4) Steam distillation
33. Simple distillation is used to separate liquids which 42. Which of the following is purified by vacuum
differ in their boiling point by ­distillation?
(1) 5°C (2) 10°C (1) Glycerine (2) Glycerol
(3) 30–80°C (4) Less than 20°C (3) Propane-1,2,3-triol (4) All
34. The presence of carbon in an organic compound can 43. Turpentine oil can be purified by
be shown by
(1) Vacuum distillation
(1) heating with copper which goes black (2) Fractional distillation
(2) burning it to produce green edge flame (3) Steam distillation
(3) heating it with copper oxide to convert it into CO2 (4) Simple distillation
(4) None
44. To determine the weight of a halogen in an ­organic
35. Impure glycerine can be purified by compound, the compound is heated with fuming
(1) Steam distillation HNO3 in the presence of
(2) Vacuum distillation (1) Ag (2) AgNO3
(3) Simple distillation (3) AlCl3 (4) Ag2SO4
(4) Extraction with a solvent
45. Fractional crystallization is carried out to separate
36. For detection of sulphur in an organic compound,
­sodium nitropruside is added to the sodium extract. (1) Organic solids mixed with inorganic solids
A violet colour is obtained due to the formation of (2) Organic solids highly soluble in water
(1) Fe(CN)2 (3) Organic solids having small difference in their
(2) K3Fe(CN)5NS solubilities in a suitable solvent
(3) Na4 [Fe(CN)5NOS] (4) Organic solids having great difference in their
(4) Na4Fe(CN)6 solubilities in a suitable solvent

37. The organic compound which does not give blue 46. A mixture of camphor and NaCl can be separated by
­colour in Lassaigne’s test is (1) Sublimation (2) Evaporation
(1) Aniline (2) Glycine (3) Filtration (4) Decantation
(3) Hydrazine (4) Urea 47. Two substances when separated out on the basis
38. Some organic compounds are purified by distillation of their extent of adsorption by one material, the
at low pressure because the compounds are ­phenomenon is
(1) Low boiling liquids (1) Chromatography
(2) High boiling liquids (2) Paper chromatography
(3) Highly volatile (3) Sublimation
(4) Dissociated before reaching their boiling points (4) Steam distillation

Chapter_14.indd 27 3/26/2014 3:25:27 PM

 14.28  Objective Chemistry - Vol. I

48. A mixture of water and NaCl can be separated by 58. Fractional distillation is used to separate liquids
(1) Sublimation (2) Evaporation which differ in their boiling point by
(3) Filtration (4) Decantation (1) 5°C (2) 10°C
(3) 30–80°C (4) Less than 20°C
49. Fuels from crude oil are separated from one another by
(1) Fractional distillation 59. Distillation under reduced pressure is used to purify
(2) Crystallization liquids which
(3) Steam distillation (1) are explosives
(4) Selective adsorption (2) are highly volatile
(3) decompose below their b. pt.
50. Copper wire test of halogens is known as
(4) have high b. pt.
(1) Beilstein test (2) Liebig test
(3) Lassaigne’s test (4) Fusion test 60. Which can be obtained by crystallization?
(1) Fatty oil (2) Cane sugar
51. An organic compound X contains Y and Z impurities.
(3) Alcohol (4) Essential oils
Their solubility differs slightly. They may be ­separated by
(1) Simple crystallization 61. Which method cannot be used for purification of l­ iquids?
(2) Fractional crystallization (1) Chromatographic (2) Steam distillation
(3) Sublimation (3) Sublimation (4) Distillation
(4) Fractional distillation
62. In Lassaigne’s test the sulphur present in the organic
52. In organic chemistry the element which is estimated compound first changes into
by difference is (1) Na2SO3 (2) CS2
(1) N (2) O (3) S (4) H (3) Na2SO4 (4) Na2S
53. Steam distillation is a better method of purification 63. In organic compounds, phosphorous is estimated as
for ................ compounds. (1) Magnesium pyrophosphate (Mg2P2O7)
(1) liquid (2) steam volatile (2) H3PO4
(3) non-volatile (4) miscible with water (3) Mg3(PO4)2
(4) P2O5
54. Boiling point of a compound does not depend on
(1) Hydrogen bonding in the compound 64. When sodium extract is prepared, generally the
(2) Solubility of the compound in water ­substance ignites
(3) Size of the molecule (1) Na (2) H2
(4) Polarity of the molecule (3) Organic compound (4) O2
55. Chromatographic techniques of purification can be 65. An organic compound is fused with fusion mixture
used for and extracted with HNO3. The extract gives a yellow
(1) Coloured compounds (2) Liquids precipitate with ammonium molybdate. It shows the
(3) Solids (4) All presence of which element?
(1) P
56. Chromatographic technique is used for the separation of
(2) As
(1) small samples of mixtures (3) P and As both
(2) plant pigments (4) may be P or As or both
(3) dyestuffs
(4) all 66. Sodium extract is heated with conc. HNO3 before
testing for halogens because
57. Generally it is more difficult to purify organic
(1) Silver halides are insoluble in HNO3
­compounds than inorganic compounds because
(2) Na2S and NaCN are decomposed by HNO3
(1) They are very unstable (3) Ag2S is soluble in HNO3
(2) Their m.pt. and b.pt. are low (4) AgCN is soluble in HNO3
(3) Organic compounds have low solubility
(4) Physical constants of organic compounds and the 67. Elution is the process for
impurities associated with them are very close to (1) Crystallization of compounds
each other (2) Separation of compounds

Chapter_14.indd 28 3/26/2014 3:25:27 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.29

(3) Extraction of compounds (1) Na2S and NaCN

(4) Distillation of compounds (2) NaSCN
(3) Na2SO3 and NaCN
68. Sublimation method can be used for the purification of
(4) Ns2S and NaCNO
(1) Naphthalene (2) Benzoic acid
(3) Camphor (4) All 78. In the estimation of nitrogen by Duma’s method
0.59 g of an organic compound gave 112 mL nitrogen
69. In Lassaigne’s test sodium metal is used because at NTP. The percentage of nitrogen in the compound
(1) It is very reactive is about
(2) Its melting point is low (1) 23.7 (2) 11.8
(3) Its compounds are soluble in water (3) 20 (4) 47.5
(2) All
79. 13 g of a hydrocarbon contains 1.0 g of hydrogen.
70. A mixture contains four solid organic compounds Its formula is
A, B ,C and D. On heating, only C changes from
(1) C2H2 (2) C2H3
solid to vapour state. C can be separated from others
(3) C3H4 (4) C4H7
­present in the mixture by
(1) Distillation 80. 0.58  g of hydrocarbon on combustion gave 0.9  g
(2) Crystallization ­water. The percentage of carbon is about
(3) Sublimation (1) 75.8 (2) 82.7
(4) Fractional distillation (3) 27.85 (4) 68.8
71. There is no test (direct) for the detection of following 81. 1.4 g of hydrocarbon on combustion gave 1.8 g water.
in an organic compound The empirical formula of hydrocarbon is
(1) Cl (2) N (3) S (4) O (1) CH (2) CH2
72. Separation of two substances by fractional crystalli- (3) CH3 (4) CH4
zation depends upon their difference in 82. An organic compound containing C, H and N have
(1) Densities the percentage 40, 13.33 and 46.67, respectively. Its
(2) Solubility empirical formula may be
(3) Velocity (1) C2H7N (2) C2H7N2
(4) Crystalline shape (3) CH4N (4) CH5N
73. Halogens can be estimated by 83. 0.2 g of an organic compound containing C, H and O,
(1) Duma’s method (2) Carius method on combustion yielded 0.147 g CO2 and 0.12 g water.
(3) Leibig method (4) None The percentage of oxygen in it is
74. Which gives positive Lassaigne’s test for N? (1) 73.29% (2) 78.45%
(1) N2 (2) NaCN (3) 83.23% (4) 89.50%
(3) NH4Cl (4) NaNO3 84. 0.759 g of a silver salt of dibasic organic acid on
75. Which statement applies best to vacuum distillation? ignition left 0.463 g metallic silver. The equivalent
weight of acid is
(1) Distils liquids quickly with decomposition
(2) It is very easy to distil (1) 70.0 (2) 108 (3) 60 (4) 50
(3) Distils liquid to avoid decomposition 85. 0.75 g platinic chloride of a monoacid base on
(4) None ignition gave 0.245 g platinum. The molecular weight
76. Separation of organic compounds by column of the base is
­chromatography is due to (1) 75.0 (2) 93.5 (3) 100 (4) 80.0
(1) Selective adsorption 86. 500 ml of a hydrocarbon gas burnt in excess of o­ xygen
(2) Selective absorption yielded 2500 ml of CO2 and 3.0 litres of water vapour
(3) Solubilities (all volumes measured at the same temperature and
(4) Selective adsorption and selective absorption pressure). The formula of the hydrocarbon is
77. In Lassaigne’s test if both N and S are present in the (1) C3H6 (2) C2H4
organic compound, they are converted to (3) C5H12 (4) CH4

Chapter_14.indd 29 3/26/2014 3:25:27 PM

 14.30  Objective Chemistry - Vol. I

87. 0.5 g of an organic compound containing nitrogen   94. Let a compound contains C, H, S, N and Cl. In the
on Kjeldahlising required 29 ml of N/5 H2SO4 for detection of chlorine, sodium fusion extract is heated
­complete neutralization of ammonia. The percentage with few drops of concentrated HNO3 and then silver
of nitrogen in the compound is nitrate solution is added to obtain a white precipitate
(1) 34.3 (2) 16.24 of AgCl. Addition of HNO is required
(3) 21.6 (4) 14.8 (1) to prevent hydrolysis of NaCN and Na2S
(2) to form S4N4; which prevent the formation of
88. In estimation of nitrogen by Duma’s method 1.18 g of
AgCl
an organic compound gave 224 ml of N2 at NTP. The
(3) to prevent the formation of NO and SO2
percentage of nitrogen in the compound is about
(4) to convert CN– and S2– ions into volatile HCN
(1) 20.0 (2) 11.8 otherwise, they will interfere (by forming AgCN
(3) 47.5 (4) 23.7 and Ag2S)
89. (A) is a higher phenol and (B) is an aromatic
  95. In case nitrogen and sulphur both are present in an
­carboxylic acid. Separation of a mixture of (A) and
organic compound, sodium thiocyanate is formed. If
(B) can be carried out easily by using a solution of
sodium fusion is carried out with excess of sodium,
(1) NaOH (2) lime sodium thiocyanate decomposes. Which of the
(3) NaHCO3 (4) Na2CO3 following compounds is\are present in the extract
90. The technique of gas liquid chromatography is s­ uitable after decomposition?
for compounds which are (1) NaCN (2) Na2S
(1) soluble in water (3) Both (4) None
(2) highly volatile   96. Select the organic compounds which will give red
(3) vaporise with decomposition colour in Lassaigne’s test.
(4) liquids (1) NaCNS (2) NH2CONH2
91. Two substances when separated out on the basis (3) NH2CSNH2 (4) H2NSO-3 Na+
of their extent of adsorption, by one material, the   97. Lassaigne’s test is not shown by diazonium salts
­phenomenon is called ­because they
(1) chromatography (1) form NH3 gas on heating much before the
(2) paper chromatography ­reaction with sodium
(3) steam distillation (2) form N2 gas on heating much before the reaction
(4) sublimation with sodium
(3) they are highly volatile and evaporate before the
92. Select the correct statement about the detection of
reaction with sodium
sulphur in organic compounds
(4) All of these
(1) The sulphur present in the organic compound on
fusion with sodium is converted to Na2S2O3.   98. 0.28 g of nitrogenous compound was Kjeldahlised to
(2) FeCl3 gives a purple colour when added to the produce 0.17 g of NH3. The percentage of nitrogen in
sodium fusion extract. the organic compound is
(3) Sodium nitropruside is used to detect the ­presence (1) 5 (2) 30 (3) 50 (4) 80
of sulphur.
  99. 0.98 g chloroplatinate salt of monoacidic base when
(4) All of these
ignited, left 0.39 g of platinum as residue. The molar
93. Which of the following reactions occur during mass of the base is
the detection of nitrogen in organic substances by (1) 80 g mol–1 (2)  160 g mol–1
­Lassaigne’s test? (3) 40 g mol –1
(4) 240 g mol–1
(1) Na + C + N  → NaCN
100. 0.6 g of silver salt of a carboxylic acid on ignition
(2) FeSO4 + 6NaCN  → Na4[Fe(CN)6] + Na2SO4 gave 0.36 g of pure silver. If molar mass of the com-
(3) 3Na4 [Fe(CN)6] + 2Fe(SO4)3 
→ Fe4 [Fe(CN)6]3 + pound is 219 g mol–1, then the basicity of the acid is
6Na2SO4 (1) 4 (2) 3
(4) All of the above (3) 2 (4) 1

Chapter_14.indd 30 3/26/2014 3:25:29 PM

 Basic Principles, Nomenclature, Purification and Characterization of Organic Compounds  14.31

101. Kjeldhal method cannot be used for estimation of 1. Statement-I: p-NH2C6H5SO3H gives blood red
­nitrogen in colouration while performing Lassaigne’s test for
   (I) CHCONH nitrogen.
 (II) Pyridine Statement-II: Sodium fusion extract containing
 (III) C6H5–N=N–C6H5 ­NaCNS gives blood red colour on treatment with
(IV) C6H5NHCOCH3 FeCl3.
(1) I, II (2) II, III
2. Statement-I: Nitrogen cannot be estimated in
(3) III, IV (4) I, II
­nitrobenzene by Kjeldah’s method.
Statement-II: Nitrogen evolves ammonia gas on acid
Answers treatment.

3. Statement-I: Hydrazine contains nitrogen but does

  (1) 3  (2) 1  (3) 3  (4) 1   (5) 2 not give Lassaigne’s test for nitrogen.
  (6) 3  (7) 1  (8) 3  (9) 4  (10) 1 Statement-II: Hydrazine reacts with fused sodium to
 (11) 3 (12) 4 (13) 4 (14) 2  (15) 1 give H2 gas.
 (16) 2 (17) 2 (18) 1 (19) 1  (20) 2
 (21) 2 (22) 2 (23) 4 (24) 4  (25) 3 4. Statement-I: Lassaigne’s test can be used to detect
 (26) 2 (27) 3 (28) 2 (29) 2  (30) 4 nitrogen in hydrazine.
 (31) 4 (32) 3 (33) 3 (34) 3  (35) 2 Statement-II: During fusion with sodium metal,
 (36) 3 (37) 3 (38) 4 (39) 3  (40) 1 ­nitrogen and carbon of the organic compound combine
 (41) 2 (42) 4 (43) 3 (44) 3  (45) 3 to form sodium cyanide.
 (46) 1 (47) 1 (48) 2 (49) 1  (50) 1 5. Statement-I: Sodium fusion extract of a compound
 (51) 2 (52) 2 (53) 2 (54) 2  (55) 4 gives black precipitate with lead acetate.
 (56) 4 (57) 4 (58) 2 (59) 3  (60) 2 Statement-II: Sulphur containing compounds form
 (61) 3 (62) 4 (63) 1 (64) 2  (65) 4 Na2S in sodium fusion extract.
 (66) 2 (67) 2 (68) 4 (69) 4  (70) 3 6. Statement-I: If sulphur and nitrogen are also present
 (71) 4 (72) 2 (73) 2 (74) 2  (75) 3 in organic compound along with halogen then AgNO3
 (76) 1 (77) 2 (78) 1 (79) 1  (80) 2 solution is added in acidified sodium fusion extract.
 (81) 2 (82) 3 (83) 1 (84) 1  (85) 2 Statement-II: On acidification, NaCN and Na2S
 (86) 3 (87) 2 (88) 4 (89) 3  (90) 3 ­decompose.
 (91) 1 (92) 3 (93) 4 (94) 4  (95) 3 NaCN + HNO3  → NaNO3 + HCN ↑
 (96) 4 (97) 2 (98) 3 (99) 3 (100) 2 Na2S + 2HNO3  → 2NaNO3 + H2S ↑
(101) 2
7. Statement-I: Lassaigne’s test is not shown by
­diazonium compounds.
Statement-II: Diazonium compounds lose N2 on
­heating before they combine with fused sodium.
 Statement-Type Questions
8. Statement-I: Duma’s method is more applic­ able
In each of the following questions, a statement-I is given
to nitrogen containing organic compounds than
followed by corresponding statement-II just below. Mark
­Kjeldhal method.
the correct answer as indicated.
Statement-II: Kjeldah’s method does not give satis­
1. If both Statement-I and S ­ tatement-II are true and factory results.
reason is the correct explanation of assertion.
9. Statement-I: All compounds containing an odd
2. If both Statement-I and S ­ tatement-II are true and number of nitrogen atoms have odd masses and those
reason is not the correct explanation of assertion. which contain even number of nitrogen atoms have
even masses.
3. If Statement-I is true but ­Statement-II is false.
Statement-II: Nitrogen rule can be applied to both
4. If Statement-I is false but Statement-II is true. ­aliphatic and aromatic compounds.

Chapter_14.indd 31 3/26/2014 3:25:33 PM

 14.32  Objective Chemistry - Vol. I

Answers 2. Match the following.

 (1) 1  (2) 3  (3) 1  (4) 4  (5) 2 (A) Equivalent mass of an   (i) Depression in freezing

 (6) 1  (7) 1  (8) 2  (9) 2 organic acid point
(B) Equivalent mass of an (ii) Victor Mayer’s method
organic base
(C) Molecular mass of a (iii) Platinichloride
volatile organic solid
(D) Molecular mass of a   (iv)  Silver salt method
 Match the Following  Type Questions non-volatile organic
1. solid

Method used for The correct matching is

Property to be determined determination
(A) Estimation of carbon and   (i) Lassaigne’s test S. No. A B C D
hydrogen in an organic (a) iv iii ii i
compound (b) i ii iii iv
(B) Estimation of nitrogen in (ii)  Carius method (c) iii i iv ii
aniline (d) ii iv i iii
(C) Estimation of chlorine in (iii)  Liebig’s method
carbon tetrachloride
(D) Detection of nitrogen,  (iv)  Kjeldahl’s method Answers
sulphur and halogens
 (1) 4  (2) 1
The correct matching is

S. No. A B C D
1. i ii iii iv
2. iv iii i ii
3. ii i iv iii
4. iii iv ii i

Chapter_14.indd 32 3/26/2014 3:25:35 PM

 15

Chapter
Fundamental Concepts in Organic
Reaction Mechanism

• In an organic reaction the organic molecule which Covalent Bond Fission (bond
­participates in a reaction is called a substrate. cleavage)
• The species that attacks the substrate is called an
• Organic reactions involve two steps: (i) breaking of
­attacking reagent.
old bonds and (ii) formation of new bonds.
• When the reagent attacks the substrate one or more
• Breaking of covalent bonds is of two types:
intermediate(s) may be formed which finally convert
(i) ­homolytic fission and (ii) heterolytic fission.
into products.
• Symmetric fission of covalent bond is called ­homolytic
Attacking fission or homolysis.
Organic molecule [intermediate] product(s)
(Substrate)
reagent
A:B  → A. + B.
• In homolysis, free radicals will be formed.
• An atom or group of atoms with unpaired electron are
By products called free radicals.
• Free radicals are paramagnetic due to the presence of
• A sequential account of each step, describing details
an unpaired electron.
of electron movement, energetics during bond cleav-
age and bond formation, and the rates of formation of • Free radicals are unstable and highly reactive.
reactants into products (kinetics) is referred to as reac- Reactions involving homolytic fission are known as
tion mechanism. free radical reactions.
• Organic reactions can take place by radical or more • Unsymmetrical breaking of covalent bond is known as
commonly, by ionic mechanism. heterolytic fission or heterolysis.
• The particular pathway of a reaction is influenced by • In heterolysis ions are formed and reactions proceed
the stability of the intermediate radical or ions which via ionic mechanism are called ionic reactions.
can be determined from an understanding of electronic A:|B  → A– + B+
and steric effects. A|:B  → A+ + B–
• The energy changes that occur during a reaction can • The cation with positive charge on carbon is called
be described by the equilibria, i.e., how much of carbenium ion.
⊕ ⊕
the reaction occurs and also by the rate, i.e., how fast the e.g.,: CH 3 , CH 3 CH 2
reaction occurs.
⊕
• The position of the equilibrium is determined by • The unusual cation CH 5 in which eight electrons are
the size of the Gibb’s free energy change, while the shared among five bonds like ammonium (NH+4) ion
rate of the reaction is determined by the activation is called carbonium ion.
energy. • Both type of ions in which positive charge is present
on carbon are called carbocations.

Chapter_15.indd 1 3/26/2014 3:27:48 PM

 15.2  Objective Chemistry - Vol. I

• The organic ion with a pair of available electrons and a • The relative nucleophilic strength (or nucleophilic-
negative charge on the central carbon atom is called a ity) of an anion or a nucleophilic site within a ­neutral

carbanion, e.g., − CH 3 , CH 3CH 2 molecule depends on the availability of the two
electrons.
Nucleophiles and Electrophiles • The more the electronegative the atom, the less
­nucleophilic the atom will be, because the electrons
• Nucleophiles are electron-rich species that can form
are held tighter to the nucleus.
a covalent bond by donating two electrons to an
­electron-deficient site. • The nucleophilic strength of anions within the same
• Nucleophiles are negatively charged (anions) or neu- row of periodic table, follows the same order as
tral molecules that contain a lone pair of electrons. basicity; the more electronegative the atom bearing the
negative charge, the weaker the nucleophile and the
• Electrophiles are electron-deficient species that can
weaker the base.
form a covalent bond by accepting two electrons from   

an electron-rich site. • Nucleophilic strength  RC > RN > RO > F–

(or basicity)
• Electrophiles are often positively charged (cations) or
Electronegativity    C < N < O < F
neutral electron deficient molecules.
Nucleophilic strength   R–NH2 > R–OH > R–F
• The nucleophilic or electrophilic sites within a neutral (or basicity)
organic molecule can be determined by (i) the pres-
ence of lone pairs of electrons, (ii) the type of bonding
(sp, sp2 or sp3) and (iii) the polarity of the bonds. Nucleophilicity =
1. An atom (such as nitrogen, oxygen or sulphur) Basicity = donation
donation of a pair
bearing an electron pair will be a nucleophilic site. of a pair of electrons
of electrons to an
2. Double or triple C–C bonds in alkenes, alkynes and to H (or H+).
atom other than H.
aromatics are of high electron density and hence
are nucleophilic sites.
3. In polar bond, the electrons are held closer to the
more electronegative atom. The electronegative • The pKa values are useful to estimate the nucleophili­
atom will be a nucleophilic site and less electro­ city of atoms within the same row. It is not exact
negative atom will be electrophilic site. because the nucleophilicity is strongly affected by
steric factors while the basicity is not.
Y is more electronegative Y is less electronegative
than carbon than carbon • The nucleophilic strength of anions and neutral atoms
increases on going down a group in the periodic table.
C + ––– Y – C – ––– Y + The electrons are held less tightly to the nucleus as the
atom size increases, and hence they are more available
for forming bonds of larger atoms, with more loosely
Electrophilic site Nucleophilic site held electrons (than smaller atoms) and are said to
Double and Triple bonds have a higher polarizability.
δ+ δ– δ+ δ–
C=Y C≡N  > H O
H 2S 
2
Nucleophilic strength
Electrophilic site Electrophilic site    
I > Br > Cl > F
Relative Strengths of Nucleophiles and
­Electrophiles • The nucleophilic strength of anions depends on the
solvent.
Nucleophiles
• Anions are generally more nucleophilic in aprotic
• A nucleophile with a negative charge is always a more solvents (these contain polar groups but no O–H or
powerful nucleophile than its conjugate acid (which is N–H bonds), such as dimethyl sulphoxide (Me2SO),
neutral).  abbreviated DMSO, than in protic solvents.
Nucleophilic strength OH > H2O

Chapter_15.indd 2 3/26/2014 3:27:52 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.3

• In protic solvents (these contain polar groups and • Ambiphile have both electron-attracting (electrophile)
O–H or N–H bonds) such as methanol (MeOH), and electron-repelling sites (nucleophile), hence have
the solvent can form hydrogen bonds to the anions. dual (amphoteric) nature. E.g., CH3–CN and H2C=O.
This lowers the nucleophilicity because a solvent Since the carbon in each of these species is π bonded to
shell surrounds the anion, and this hinders attack on a very electronegative atom, N and O respectively, C is
the electrophile. Large anions are less solvated and an electrophilic site. The electronegative N and O also
hence are stronger nucleophiles than small anions have unshared electron pairs and are thus nucleophilic
in protic solvents. For example, the smaller F– ion is sites.
more heavily solvated than I– and hence is a weaker
• Ambident nucleophiles may attack in two or more
nucleophile.
different ways to give different products, e.g., anions
from compounds containing reactive methylene group
like malonic ester, β-keto ester, β-diketones, etc. are
Electrophiles resonance stabilized.
• An electrophile with a positive charge is always a more
powerful electrophile than its conjugate base (which is  
O R O O O O O
neutral). || | || | || | |
– C– C– C –C=C–C –C–C=C
⊕ 
| |
Electrophilic Strength OH OH Oδ– R R
|| | ||
C C⊕ Cδ+
• Ambident nucleophiles can attack a saturated carbon
with their carbon atoms (C-alkylation) or with their
• The relative electrophilic strength (or electrophilic) of oxygen atoms (O-alkylation).
a cation depends on the stability of the positive charge.
Inductive (+I), mesomeric (+M) and/or steric effects R′
R′X |
can all lower the reactivity of the cation. –C–C–C– –C–C–C–
• The relative electrophilic strength of an electrophilic || | || || | ||
site within a neutral molecule depends on the size of O R O O R O
the partial positive charge (δ+). Hydrogen or carbon O R OR′
atoms are electrophilic when attached to electronega- || | |
tive atom (–I groups). The more electronegative the – C–C=C–
atoms the more electrophilic the hydrogen or carbon
atom.
• The hydrogen atom in water is more electrophilic than Electron Displacements in
in ammonia as oxygen is more electronegative than Covalent Bond
nitrogen.
Resonance
δ+ δ− δ+ δ−
H − OH > H − NH 2 Electrophilic strength • While writing Lewis diagrams for certain molecules
there is possibility for writing more than one struc-
• The (carbonyl) carbon atom of the acid chloride is ture with the difference in the position of electrons
more electrophilic because both oxygen and chlorine but not in the position of atoms. Such structures
atoms are electronegative. are known as resonance structures or canonical
structures.
Oδ– Oδ–
• The actual structure of the molecule will be the
Cδ+ > Cδ+ ­resonance hybrid of all the canonical forms and this
Electrophilic
strength δ– phenomenon is known as resonance. Examples are
R Cl R R
Acid chloride Ketone

Chapter_15.indd 3 3/26/2014 3:28:00 PM

 15.4  Objective Chemistry - Vol. I

 1
O O O–
⊕ ⊕ 2
CH3 – N CH3 – N CH3 N
 O
O O– 1
2

⊕ ⊕
CH2 = CH – CH2 CH2 – CH = CH2

• The internal energy of the resonance hybrid structure Inductive Effect

is less than those of resonance structures.
• The displacement of electron pair along the carbon
• The energy difference between the resonance hybrid chain due to the presence of an electron-withdrawing
structure and most stable resonance structure is known or electron-repelling group in the carbon chain is
as resonance energy. known as inductive effect.
• The resonance energy of organic compounds can be
δ4+ δ3+ δ2+ δ1+ δ–
calculated from heat of hydration, heat of combustion, C C C C X δ1 > δ2 > δ3 > δ4
heat of formation, etc.
• If resonance energy is more the stability of the com- • A group that attracts electrons from carbon chain is
pounds is more. called as –I group.
• If the number of resonance structures increase stability • A group that releases electrons to the carbon chain is
of resonance hybrid structure also increases. known as +I group.
+I groups: (CH3)3C > (CH3)2CH > CH3CH2 > CH3
Conditions for Writing the Resonance –I groups: –NO2 > –CN > –COOH > –F > –Cl >
Structures –Br > –I > –OR > –OH > –C6H5 > –CH=CH2
• All contributing resonance structures must have same • Inductive effect is a permanent effect and is due to
energy. polarization.
• All resonance structures must have same number of • Inductive effect is neglected beyond C2.
unpaired electrons.
• Only the position of electrons must be changed but not Electromeric Effect
the position of atoms.
• Non-polar structures contribute more to the resonance • Complete shifting of one of the π electron pair to a
hybrid structure than polar structure. more electronegative atom during the reaction for the
formation of +ve and –ve centres for the attacking
• The polar resonance structures having +ve charge less
­reagent is known as electromeric effect.
electronegative atom and –ve charge on more electro­
negative atom are more stable. ⊕ 
C=C C–C
• The polar structure in which the distance between
charges is less, is more stable.
• Electromeric effect takes place in molecules contain-
• All atoms in the molecule should be in the same plane. ing multiple bonds like C=O, –C≡N.
• More stable resonance structure contributes more to • In conjugated systems the electromeric effect is trans-
the actual molecule.
mitted through the chain.
• More is the delocalization, more the stability. ⊕ 
• More the covalent bonds, more the stability. C=C–C=C–C=C 
→ C–C=C–C=C–C

Chapter_15.indd 4 3/26/2014 3:28:03 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.5

• The groups which cause electromeric effect towards Hyper Conjugation

them are called –E groups.
• Shifting of C–H σ bond pair of electrons present in
⊕  the sp3 carbon to sp2 carbon which is in double bond is
C=C C–C
known as hyper conjugation or no bond resonance.
Cl Cl
H H⊕
• The groups which cause electromeric effect away from | 
them are called +E groups. H – C – C = CH2 H – C = C – CH2
| | | |
H3C H3C H H H H
⊕ 
C=C C–C 2 more resonance structures

• Electromeric effect is temporary and occurs during • Due to hyper conjugation, number of resonance struc-
the reaction. tures increase and thus stability increases.
• The resonance stability due to hyper conjugation is
Mesomeric Effect less than the resonance stability due to conjugated
• Mesomeric effect involves the complete transfer of π double bonds.
or lone pair of electrons. • In a system of the type Cl–C–C=C, the p electrons are
• Mesomeric effect is caused by the presence of multiple attracted from the olefinic system, i.e., the ­electron
conjugated bonds or by an atom with lone pair of elec- flow is reversed. This is known as reverse hyper
trons in conjugation with conjugated double bond. conjugation.
⊕
Cl Cl
Θ
CH3–CH=CH–CH=O ←
→ CH3– CH–CH=CH- O | ⊕
– C – CH = CH – C = CH – CH2
• Mesomeric effect is represented by M and it will have | |
both types such as +M and –M effects. H H
 ⊕
C=C–C=C–NH2 ←
→ C –C=C–C=NH2
(+M effect) Polarity of Covalent Bond:
Dipolemoment
Conjugation
• When a covalent bond is formed between unlike
• If single and double bonds are present alternatively, ­atoms, e.g., A:B. The bond pair of electrons will be
they are known as conjugated double bonds. attracted more by electronegative atom towards it.
CH2=CH–CH=CH2 1,3-Butadiene
• If B is more electronegative than A, there develops a
   
partial negative charge on B and an equivalent positive
δ+ δ−
charge in magnitude on A and is represented as A − B.
• The bond polarity is measured by its dipolemoment
Benzene Naphthalene
(µ) defined to be the amount of charge separation
• Due to conjugated double bonds stability of the (δ+ or δ–) multiplied by bond length.
­molecules increases, bond length decreases and bond • The molecular dipolemoment is equal to the vector
energy increases. sum of the individual bond dipolemoments.

Dipolemoments of Molecules

Substance m Substance m Substance m

Inorganic compounds
Hydrogen chloride 1.03 D Ammonia 1.46 D Hydrogen cyanide   2.93 D
Hydrogen bromide 0.78 D Water 1.84 D Sulphur dioxide 1.6 D
Hydrogen iodide 0.38 D Hydrogen sulphide 1.10 D Hydrogen peroxide 2.1 D

Chapter_15.indd 5 3/26/2014 3:28:07 PM

 15.6  Objective Chemistry - Vol. I

Aliphatic Compounds
Alcohols 1.7 Nitriles 3.6 D
Ethers  1.15 Nitrocompounds 3.4 D
Ketones 2.7 Primary amines 1.3 D

Aromatic Compounds
Chlorobenzene 1.73 Phenol 1.7 Benzonitrile 4.37
Bromobenzene 1.71 Diphenyl ether  1.15 Nitrobenzene 4.23
Iodobenzene 1.2 Benzophenone  2.95 Aniline 1.56

Methyl Halides
X CH3X CH2X2 CHX3 CX4
F 1.82 D 1.97 D 1.65 D 0
Cl 1.94 D 1.60 D 1.03 D 0
Br 1.79 D 1.45 D 1.02 D 0
I 1.64 D 1.11 D 1.00 D 0

• Al molecules with centre of symmetry have no resultant dipolemoment since the molecular dipolemoment is equal to
the vector sum of the individual bond moments in a molecule. E.g., CH4.
• The dipolemoment of a bond, e.g., C–X is the resultant of two opposing effects, i.e., larger atoms having longer bonds
but with weaker electronegativities. The overall result is that the bond dipolemoment increase in the order.
C–I < C–Br < C–F < C–Cl
µ 1.29 D 1.48 D 1.51 D 1.56 D
• Dipolemoment (µ) is directly proportional to the electronegativity of central atom or surrounding atoms present on the
central atom of the molecule.
CHF3 > CHCl3 > CHBr3 > CHI3
Electronegativity in decreasing order.
µ is also in decreasing order.
NH3 > PH3 > AsH3 > SbH3
Electronegativity of central atom is in decreasing order and µ is also in decreasing order.
• The dipolemoments of certain bonds are as follows.
H–C C–O C–Cl H–O C=O
0.4 0.7 1.5 1.6 2.3 D
• By the vectorial addition of these bond moments the resultant dipolemoments of various substances can be calculated.
• In several cases it is more convenient to consider resultant moment of a group rather than those of individual bonds.
• The dipolemoments of certain groups in aromatic compounds considering that C–H linkage in benzene has no
­dipolemoment are as follows:
NO2 CN OH Cl H CH3 NH
–3.9 –3.8 –1.7 –1.5 0 +0.4 +1.5 D
• The sign before the group indicates the direction in which the moment operates. Negative sign indicates that the
­moment operates away from benzene, i.e., the group gain negative sign or negative charge.
• The dipolemoment of p-chloronitro benzene will be the difference in the dipolemoments of –Cl and –NO2 groups, i.e.,
3.9 – 1.5 = 2.4. This is because they are operating in opposite direction.

Cl NO2
1.5 3.9

Chapter_15.indd 6 3/26/2014 3:28:07 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.7

• The dipolemoments in p-chloronitro benzene act along • If two identical groups are substituted in the para-
the line joining chlorine or nitrogen atom to the carbon positions the moment of the compound should be zero
atom of the benzene ring. provided the groups are of the type not involving the
• When the groups attached to benzene ring are not direct attachment of oxygen or nitrogen to the ben-
symmetrical about the line of attachment of the
­ zene ring. E.g., p-dichloro, p-dibromo, p-dinitro and
group to the benzene nucleus, the direction of the p-dimethyl benzene.
­dipolemoments should be considered. • The –NO2 and –NH2 groups though appear similar, the
• The –CN and –CH3 groups are symmetrical but –OH dipolemoment of –NO2 groups acts in the plane and
and –NH2 groups are not symmetrical about the line of along the symmetry axis of the benzene ring because
attachment of the group to the benzene nucleus. of the following resonance.
O O–
H + +
N N
O N H C H
H H O– O
H
• The –NO2 group is thus symmetrical and the group mo-
• The dipolemoment of p-chlorophenol is not equal to ment will, therefore, act in the direction of the fourth
the difference in group moments (1.7 – 1.5 = 0.2) as in valence bond of nitrogen atom and the n­itrogroup
p-chloronitrobenzene but it is 2.4 D showing that the ­behave like –CH3, –Cl or similar groups.
moment of –OH group is at an angle 83° with that of • The presence of lone pairs may have a large effect on
the –Cl moment. the dipolemoment of molecules or groups.

H H CH3

H N O C=O CH3 – C ≡ N

H H CH3

µ = 1.5 D µ = 1.9 D µ = 2.9 D µ = 3.9 D

Ammonia Water Acetone Acetonitrite
• Lone pairs of electrons contribute to the dipolemoments of bonds and molecules. Each lone pair corresponds to a
charge separation with the nucleus having a partial positive charge balanced by the negative charge of the lone pair.
• Dipolemoment of disubstituted benzene.
Case - I X X

Or
Y Y

When both groups X and Y are electron-donating- or electron-withdrawing groups (EDGs or EWGs), then
µ = µ12 + µ 22 + 2µ1 µ 2 cos θ
where µ1 = dipolemoment of bond C–X and
µ2 = dipolemoment of bond C–Y
θ = angle between X and Y
If value of θ will be more, then cos θ will be less. Hence, dipolemoment is as follows:
O–>m–>p–
If X = Y, then dipolemoment of paraderivative = 0.

Chapter_15.indd 7 3/26/2014 3:28:10 PM

 15.8  Objective Chemistry - Vol. I

Case II: When one group is electron withdrawing and • The resonance structures due to mesomerism in
the other group is electron donating then ­substituted benzene are as
µ= µ12 + µ 22 − 2µ1 µ 2 cos θ 
⊕ ⊕
Hence, dipolemoment is as p – > m – > o – X ==  X ==
• In the case of ortho derivatives considerable discre­
pancies have been observed between the ­calculated and where X is a halogen. On the other hand, when the sub-
observed dipolemoments, e.g., for ortho-­dinitrobenzene stituent is a nitrogroup the configurations
the observed value is 6.05 D while the ­calculated value
is 6.75 D. This is known as ortho effect. O O ⊕
⊕
• The ortho effect is partly due to repulsion of the N == ⊕ N ==
­adjacent groups, leading to an increase in the angle O O
between the polar groups and thus decreasing ­resultant
dipolemoment but mainly due to induced moment in are possible in addition to the normal structure.
the opposite direction in the other group, thus con­ • In a halogen compound the ionic structures c­ ontribute
siderably decreasing the observed resultant moment.
dipoles acting in the opposite sense to that of the n­ ormal
• Dipolemoments are useful in distinguishing cis- and halogen, while the reverse is true for the nitroderiva-
trans-dihalogeno-ethylene compounds; the trans- tive. Further, in the former case resonance results in
derivatives have a centre of symmetry and consequently the availability of electrons in the ortho- and para-
are nonpolar, whereas the cis-form have relatively positions, but in the latter case there is a ­deficiency of
large moments. electrons in these positions. The assumption of reso-
a b nance, therefore accounts both for the d­ ipolemoment
a a effects and the chemical properties of the two groups
C == C C == C of substituents.
b b b a
µ≠0 µ≈0 Reaction Intermediates
b d Carbocations, Carbanions and
a a Carbon Radicals
C == C C == C
• Carbocations which include carbenium and
d c b a ­carbonium ions contain a positive charge on carbon.
µ≠0 µ≠0
Carbonium ions have three bonds to the positively
⊕
• Halogens (ortho- and/para-groups) when substituted charged carbon, e.g., Me3C while carbenium ions con-
in a benzene ring have smaller moments than when ⊕
attached to saturated aliphatic groups, although the tain five bonds (e.g., H5C carbenium ions are the most
reverse is the case for meta-directing groups, e.g., important).
⊕
–NO2 and –CN. This is because the phenyl group tends • Carbenium ions (R3C) are generally planar and con-
to draw electrons away from the halogen atom, thus tain an empty p-orbital.
decreasing their effective negative moment, whereas
• Carbenium ions are stabilized by EDGs (R = +I, +M)
electrons are repelled by the nucleus towards the
which delocalize the positive charge; +M groups are
–NO2 or –CN group. This is due to electromeric and
generally more effective than +I groups.
­mesomeric effects.

Planar (sp2) Planar (sp2) Pyramided (sp3)

R R

⊕ R –––– C
 C
R –––– C R

R R R R
Carbocation Carbanion

Chapter_15.indd 8 3/26/2014 3:28:13 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.9

• Carbanions have three bonds on the carbon atom which bears the negative charge. Carbanions R3C can be planar
(sp2) or pyramidal (sp3) (or something in between).
• Carbanions are stabilized by
 (i) EWGs (R = –I, –M).
 (ii) An increase in “s” character of the carbon bearing the negative charge.
(iii) Aromatization which delocalize the negative charge.
• Carbon radicals (free radicals) have three bonds on the carbon atom, which contains the unpaired electron. Carbon
radicals (R3C) are generally planar (sp2).
• Similar to carbenium ions carbon radicals are stabilized by EDGs (R = +I, +M) which delocalize the unpaired electron;
+M groups are generally more effective than +I groups.
Planar (sp2)
Planar (sp2)
R 7 valence R 6 valence
R electrons electrons
R –––– C C ⊕C

R R R R R
Carbon radical
• Carbon radicals are similar to carbenium ions because both contain an electron-deficient carbon atom.
• For carbenium ions, the carbon atom is deficient of two electrons and for carbon radicals, the carbon atom is deficient
of one electron.

Order of Stability
• The order of stability of carbocations, carbanions and radicals bearing electron-donating (+I) alkyl groups is as follows.
• Carbonium ions are stabilized by charge distribution and resonance due to hyper conjugation and conjugation.
• Order of stability of carbonium ions is
⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕
CH3 < CH3CH2 < (CH3)2CH < (CH3)3C < CH2=C– CH2 < C6H5CH2 < (C6H5)2CH < (C6H5)3C
• Primary < secondary < tertiary
0° < 1° < 2° < 3°
• Carbanions are stabilized by EWGs and resonance by conjugated double bonds.
       
(CH3)3C < (CH3)2CH < CH3CH2 < CH3 < CH2=CH–CH2 < C6H5CH2 < (C6H5)2CH < (C6H5)3C
Alkyl carbanions: primary > secondary > tertiary
0° > 1° > 2° > 3°
Aromatic carbanions: primary < secondary < tertiary.
• Free radicals are stabilized by resonance due to hyper conjugation and delocalization.
• Order of stability of free radicals is
 3 < CH3CH
CH  2 < (CH3)2CH  < (CH3)3C  < CH2=CH–CH  2 < C6H5CH  2 < (C6H5)2 CH
 < (C6H5)3C 
Primary < secondary < tertiary
0° < 1° < 2° < 3°
• A species which is more stable is less reactive; hence, reactivity order of carbenium ions, carbanions and radicals is in
the reverse order of their stability.

Chapter_15.indd 9 3/26/2014 3:28:21 PM

 15.10  Objective Chemistry - Vol. I

Carbenes
• Carbenes are reaction intermediates in which carbon atom has six electrons, e.g.,
H

C: : CCl2
H
Carbene Dichloro carbene

• The carbon atom is sp2 hybridised in singlet carbene, so it is bent in shape and sp hybridised in triplet carbene which
is linear.
py
pz
sp2 sp
C C
sp2 sp
sp2
Singlet carbene Triplet carbene

• Singlet carbene is less stable (as it is against to Hund’s rule of maximum multiplicity) and is of high reactivity. It is
therefore less selective and highly reactive. It is also known as hot methylene.
• Triplet carbene is diradical. As a result of electronic arrangement it is less reactive compared to singlet methylene.
It is more selective in its reactions and is called cold carbene.
• The order of reactivity of carbene is as follows:
: CH2 > : CF2 > : CCl2 > : CBr2

Nitrenes
• Nitrenes are analogous of carbenes and neutral univalent nitrogen intermediates. These are electron-deficient species
in which N has a sextet of electrons.
• Nitrenes are formed when hydrazoic acid N3H is ­irradiated with UV light. It is trapped in the presence of ethylene as
ethylene imine.
H
N
hν C2H4
N3H HN CH2 ––– CH2
– N2

• Nitrenes can exist in singlet and triplet states. Most of the nitrenes exist in triplet ground state and behave as electro-
philes undergoing cycloaddition and insertion reactions.

Benzyne
• It is a reaction intermediate with a carbon–carbon triple bond in the benzene ring involving the formation of a new
C–C bond by sideways overlap of sp2 orbitals in which sp2 hybrid orbitals participate in p bond.
• This new bond is weak and benzene is a highly reactive molecule.
• It is formed as follows:
Cl Cl Cl

+ NH2 + NH3 + Cl
 
H

Chapter_15.indd 10 3/26/2014 3:28:25 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.11

Steric Effects
• The size as well as the electronic properties (i.e., inductive and mesomeric effects) of the surrounding groups affects
the stability of carbocations and radicals.
• When bulky substituents surround, for example in a carbenium ion, they reduce the reactivity of the cation to nucleo-
philic attack by steric effects. This is because the bulky groups hinder the approach of the nucleophile.
Tertiary Secondary Primary Methyl
R R R H
| | | |
Cation stability C⊕ > C⊕ > C⊕ > C⊕

R R R H H H H H

R R R H
| | | |
Anion stability C < C < C < C

R R R H H H H H

R R R H
| | | |
Radical stability C > C > C > C

R R R H H H H H

• Carbanions can be stabilized by EWGs (–I, –M), whereas carbocations can be stabilized by EDGs (+I, +M).
H H H
| | |

C C C
> >
Anion stability MeOOC COOMe Me COOMe Me Me

two –I, –M groups one –I, –M groups no –I, –M groups

H H
| | |
Cation stability C⊕ > C⊕ > C⊕

Three +I, +M groups Two +I, +M groups One +I, +M groups

• When the size of groups is responsible for reducing the reactivity at a site within a molecule, it is referred as steric
hindrance but when the size of groups is responsible for increasing the reactivity at a site within a molecule it is
referred to as steric acceleration.
Electronic and/or steric effects can affect and can explain the particular pathway for any given reaction.

Chapter_15.indd 11 3/26/2014 3:28:26 PM

 15.12  Objective Chemistry - Vol. I

Types of Organic Reactions

1. Substitution Reactions

• In substitution reactions an atom or group in a compound is replaced by another atom or group.

• Substitution reactions are characteristic of saturated compounds, i.e., as sp3 carbon.
• During substitution reactions the hybridisation of carbon at which substitution takes place does not change.
• Alkanes and aromatic compounds participate in substitution reactions.
• Substitution reactions are of three types.
 (i) Free radical substitution
 (ii) Electrophilic substitution
(iii) Nucleophilic substitution
• Free radical substitution reactions will take place in the presence of light or free radical initiators, e.g.,
CH4 + Cl2 hv → CH3Cl + HCl
CH3Cl + Cl2 hv → CH2Cl + HCl
CH2Cl2 + Cl2 hv → CHCl3 + HCl
CHCl3 + Cl2 → CCl4 + HCl
hv

Polymerization Reactions
• If two or more molecules of the same substance combine repeatedly to give a giant molecule, it is known as
polymerization.
• The simple unit that participates in a polymerization reaction is called a monomer.

nCH2=CH2 
→ CH3–CH2–(CH2–CH2 )n–2 – CH=CH2
Ethylene Polythene

Condensation
• The reactions in which two different molecules of the same or different reactants unite to give a product with or with-
out elimination of another simple molecule is called condensation.
O OH
|| |
dil NaOH
CH3 – C + CH3CHO CH3 – CH – CH2 – CHO
|
H

conc H2SO4
CH3CO OH + H OC2H5 CH3COOC2H5
–H2O

H
| – H2O
CH3 – C = O + H2N – OH CH3CH = NOH
• If polymerization occurs due to condensation, it is known as condensation polymerization and the polymers are
called condensation polymers.

Rearrangement Reactions
• Rearrangement reactions involve the migration of a group or atom from one atom to another in the same molecule.
• The mechanism of these reactions often involves carbocation intermediates, and the first-formed cation (e.g., primary
or secondary) can rearrange to a more stable cation (e.g., tertiary).

Chapter_15.indd 12 3/26/2014 3:28:29 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.13

These groups
H swap positions CH3

⊕ CH3 ⊕
C C

H3C CH2 H3C CH3

Secondary carbocation Tertiary carbocation
(two + I groups) (three + I groups)

Ozonolysis
• Addition of ozone to an unsaturated compound followed by the hydrolysis of the product is called ozonolysis.
• Addition of ozone to alkene or alkyne gives an addition product called ozonide.
• If hydrolysis of ozonide is carried out in the presence of zinc, zinc removes H2O2 formed and prevents the oxidation
of carbonyl compounds. This is known as reductive ozonolysis.
• If hydrolysis of ozonide is carried in the absence of zinc, carbonyl compounds formed are oxidized to carboxylic acids
by H2O2. This is known as oxidative ozonolysis.
• Ozonolysis is useful to detect the position and number of multiple bonds and structure of compounds.

Zn/H2O
CH2 = CH2 + O3 CH2 – O – CH2 2HCHO
| |
O O
O
Zn/H2O CHO
HC ≡ CH + O3 HC – CH |
| | CHO
O –– O
Zn/H2O
CH3 – CH = CH2 CH3 – CH – O – CH2 CH3CHO + HCHO
| |
O O

• Ozonolysis is useful to distinguish branched alkene from n-alkene.

• n-alkenes give aldehydes while branched alkenes give ketones.

Ozonolysis
CH3 – CH = CH – CH3 2CH3CHO

CH3 CH3
| Ozonolysis |
CH3 – C = CH2 CH3 C = O + HCHO

Ozonides can be reduced by Zn/acid, H2 - Raney Ni or triphenyl phosphine to carbonyl compounds.

Ozonides on reduction with LiAlH4 or sodium borohydride give alcohols.

Pericyclic Reactions
• Pericyclic reactions take place in a single step without (ionic or radical) intermediates and involve a cyclic redistribu-
tion of bonding electrons.

Chapter_15.indd 13 3/26/2014 3:28:30 PM

 15.14  Objective Chemistry - Vol. I

The Diels-Alder cycloaddition reaction

2 new σ-bonds
4π-electrons 2π-electrons and 1 π-bond
+
+
+

Diene alkene Cyclic transition cyclohexene

(or dienophile) state (6 delocalised
π-electrons)

Ions vs Radicals
• Heterolytic cleavage of bonds occurs at room temperature in polar solvents. The ions which are formed are solvated
and stabilized by polar solvents.
• Homolytic cleavage of bonds occurs at high temperature in the absence of polar solvents. When a compound is heated
in a non-polar solvent, radicals are formed.
• Radicals are uncharged and hence have little interaction with the solvent. The energy required to cleave a bond homo-
lytically, to give radicals, is called bond dissociation energy or the bond strength.
• The lower the bond dissociation energy, the more stable the radicals (as they are easily formed).
• Ionic reactions occur because of electrostatic attraction, a positive or δ+ charge attracts a negative or δ– charge.
Electron-rich sites react with electron-deficient sites.
• Radical reactions occur because radicals, which have an odd number of electrons in the outer shell, need to “pair” the
electron to produce a filled outer shell.

Reaction Selectivity
• Chemoselectivity is a reaction at one functional group in preference to another functional group(s), e.g., reduction of
a ketoester.
Secondary
Ketone Ester alcohol Ester
O O NaBH4 OH O
|| || then H2O | ||

OMe OMe

Selective reduction of a ketone to a secondary alcohol is an example in this regard.

• Regioselectivity is a reaction at one position within a molecule in preference to others. This leads to the selective
formation of one regioisomer, e.g., addition of HCl to an unsymmetrical alkene.
Me Cl H
H – Cl | |
C = CH2 Me –– C –– CH2
|
Me
Me
Regioselective addition of the H atom onto the carbon
at the end of the double bond and the Cl
atom onto the carbon with the most alkyl substituents.
• Stereoselectivity refers to the formation of one enantiomer, one diastereoisomer or one double bond isomer in
­preference to others, e.g., catalytic hydrogenation of an alkyne.

Chapter_15.indd 14 3/26/2014 3:28:35 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.15

H2 Et Et
Et – C ≡ C – Et C=C
Lindlar catalyst H H
Pd/CaCO3/PbO
Cis or Z-alkene
Formation of Z-rather than an E-alkene

Reaction Thermodynamics and Kinetics

• The thermodynamics of a reaction tells us in what direction the reaction proceeds (and how much energy will be
consumed or released). The kinetics of a reaction tells us whether the reaction is fast or slow.

Thermodynamics
Equilibria

• All chemical reactions can be written as equilibrium processes, in which forward and backward reactions oc-
cur ­concurrently to give an equilibrium position. Drawing arrows pointing in the opposite directions denotes the
­equilibrium, and the position of equilibrium is expressed by the equilibrium constant (K). For simplicity, this is defined
hereunder in terms of concentration rather than activity (as activity is approximately equal to concentration in dilute
solution).

 Concentration of product(s) at equilibrium [ B]eq

A B K = =
Concentration of reactant(s) at equilibrium [ A ]eq
• If K is larger than 1, then the concentration of B will be larger than the concentration of A at equilibrium.
• The equilibrium constant and the free energy change in a reaction are related as ∆G° = –RT lnK.
• If ∆G° is negative, then the products will be favoured at equilibrium (K > 1).
• If ∆G° is positive, then the reactants will be favoured at equilibrium (K < 1).
• If ∆G° is zero then K = 1 and hence there will be the same concentration of reactants and products.
• At a particular temperature, K is constant.

Acids and Bases • The strength of bases is measured in terms of dissoci­

ation constant Kb for
Arrhenius Theory

BOH 
 B+ + OH–
• An acid is a substance which increases the hydronium
 B+  OH − 
ion concentration in an aqueous solution. Kb =   
• An acid is strong if it can produce a large number of [BOH ]
H+ ions and it is weak if it produces a less number of • More the Kb value the stronger the base, and the lesser
H+ ions. the Kb value the weaker the base.
• The strength of an acid is measured in terms of acid
dissociation constant Ka for Lowry–Bronsted Theory
HX   H+ + X– • Proton donor is the acid while proton acceptor is a
base.
H+  X − 
Ka =     • The residual part of the acid after losing a proton can
[HX ] again accept a proton so it can function as base.
• Higher the Ka value the stronger the acid and lesser the • A base after gaining a proton from an acid can function
Ka value the weaker the acid. as acid again since it has a tendency to give a proton.
• A base is a substance that increases the hydroxyl ions • The acid–base pair which differ by a single proton is
in its aqueous solution. called conjugate acid–base pair.

Chapter_15.indd 15 3/26/2014 3:28:41 PM

 15.16  Objective Chemistry - Vol. I

• An acid is strong if it has high tendency to donate an • Liquid ammonia has a strong tendency to accept a pro-
electron and if its conjugate base is weak or vice versa. ton and hence weak acids also completely ionize in
• A base is strong if it has great tendency to accept a ammonia and behave as strong acids.
proton and its conjugate acid is weak or vice versa. • HF has a strong acidic character but no basic character.
Strong acids such as HNO3 are incapable of ionizing
Classification of Solvents as an acid when dissolved in HF but ionizes slightly as
• Solvents which accept a proton are called protophilic a base in HF.
+
solvents, e.g., water, alcohol, ammonia, etc. HNO3 + HF   H 2NO3 + F
−

• Solvents which can generate protons are called

Base Acid solvent Acid Base
­protogenic solvents, e.g., water, liquid HCl, glacial
acetic acid, etc. • Acetic acid acts as a base in HF.
• Solvents which can accept and generate protons are • The strength of bases can be compared in a solvent
called amphiprotic solvents, e.g., water, a­ mmonia, etc. such as water which has a strong basic character but
• Solvents which can neither donate nor accept p­ rotons CH3COOH cannot be used to compare the strength of
are called aprotic solvents, e.g., benzene, carbon bases because it is acidic.
­disulphide, carbon tetrachloride, etc.
Strength of Acids
Lewis   Theory
• Because the dissociation constants of acids are in a
• According to Lewis theory electron pair acceptor is range of many powers of ten, it is useful to express
an acid while electron pair donor is a base. acid strength in a logarithmic manner.
• The neutralization between Lewis acids and bases is pKa = –logKa
due to the formation of coordinate bond or dative Stronger acids have smaller pKa values.
bond. • Acidic character increases as the atom to which the
• Lewis acid must possess a vacant orbital to accept the acidic hydrogen is attached has a greater atomic num-
lone pair. ber within a group of the periodic table. For example,
CH3CH2OH is a weaker acid than CH3CH2SH.
Influence of Solvent on Strength of Acids
• Increase in the electronegativity of the atom with
• Acetic acid is a weak acid and can also act as a base which the hydrogen is in bond increases the acidic
but has a little tendency to accept proton. So, even strength.
strong acids also ionize feebly in acetic acid. So, the CH4 < NH3 < H2O < HF
strengths of different acids are compared in acetic acid
by measuring their conductivities in acetic acid. • Acidic strength increases with increase in the electron-
• Water is a much stronger base than acetic acid. So, egativity of atom to which OH group is attached.
all strong acids ionize completely in water and ­appear HOCl > HOBr > HOI
almost equally strong. So, their strength in water
­ • If the conjugate base formed from an acid after giving
­cannot be compared. The strength of weak acids can a proton get stabilized by resonance, hybridisation and
only be compared. ­delocalization of charge makes the acid strong.

O O
R–C + H2O R–C + H3O+
O–H O–

O O O
R–C R–C R–C 

O O O

Resonance structures of carboxylate ion

Chapter_15.indd 16 3/26/2014 3:28:43 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.17

• Carboxylic acids are more acidic than alcohols or phenols, other compounds with O–H bonds because carbonyl group
is more electronegative than phenyl group in phenols or the alkyl group of alcohols. The polar effect of the carbonyl
group stabilizes the charge in the carboxylate ion.
• Phenols are more acidic than alcohols because the phenoxide ion is stabilized by charge delocalization through reso-
nance. Though phenol also has resonance structures, in the resonance structures of phenol positive charge is present
on more electronegative oxygen and negative charge is present on less electronegative carbon.
⊕ ⊕ ⊕
:O – H O–H O–H O–H :O – H

 

Resonance structures in phenol

O O O O O

 

Resonance structures in phenoxide ion

• If more electronegative elements or groups are present on the atoms to which OH group is attached the acidic character
increases.
• Acidic character increases with increase in the number of electronegative atoms and also with increase in the
­electronegativity of atom.
CCl3COOH > CHCl2COOH > CH2ClCOOH > CH3COOH
CFH2COOH > CClH2COOH > CBrH2COOH > CIH2COOH
• Acidic strength decreases with increase in the size of alkyl group attached to –COOH group since the +I effect of
alkyl group increases with increase in its size.
HCOOH > CH3COOH > CH3CH2COOH > CH3CH2CH2COOH
• Acidic character decreases with increase in the distance of electronegative atom (–I group) from the carboxylic group.
Cl Cl Cl

CH3CH2CHCOOH > CH3CHCH2COOH > CH2CH2CH2COOH > CH3CH2CH2COOH

• More the effect of EWG the compound will be more acidic. NO2CH2COOH > CNCH2COOH
• For compounds containing OH group attached to the central atom acidic character increases with increase in the
­number of electronegative atoms attached to the central atom, e.g., sulphuric acids are more acidic than carboxylic
acids.
O O
|| ||
– S – OH – C – OH
||
O

This is because extra positive charge developed on sulphur (due to two oxygen atoms) stabilizes the negative charge
on oxygen (after giving a proton).

Chapter_15.indd 17 3/26/2014 3:28:44 PM

 15.18  Objective Chemistry - Vol. I

• With increase in the s-character of the hybrid orbital of carbon with which either hydrogen or –OH or –COOH group
is in bond the acidic character increases.
H3C–H < CH2=CH–H < HC≡C–H
CH3–CH2–OH < CH2=CH–OH < HC≡C–OH
CH3–CH2–COOH < CH2=CH–COOH < HC≡C–COOH
• The values of ionization constants for polyprotic acids decrease with increase in the number of negative charges. For
example, dissociation constant values of H2C2O4, HC2O 4− are in the order Ka1 > Ka2.
• Acidic strength of benzoic acid depends upon the substituents attached to the benzene ring.
• The electron-releasing groups decrease the strength of benzoic acid while EWGs increase the strength of benzoic acid.

COOH COOH COOH COOH COOH

> > > >

NO2 Cl CH3 OH

• Orthosubstituted benzoic acids (whether the substituent may be electron releasing or electron withdrawing) are more
acidic among the three isomers, i.e., o-substituted benzoic acid is more acidic than para- and metasubstituted acid. This
is known as ortho effect and it is due to combined effect of steric and electronic factors.
• The order of strength of methyl benzoic acids will be
COOH COOH COOH COOH
CH3
> > >

CH3
CH3

This is because electron-releasing tendency of a methyl group is dominant at para position than the meta position.
Also, the resonance and +I effect both operate in para isomer while in meta isomer it is only +I effect.
• The order of the strength of nitrobenzoic acids will be
COOH COOH COOH COOH
NO2
> > >

NO2
NO2

p-nitro benzoic acid is more acidic due to combined effect (resonance and –I effect) than the m-nitro benzoic acid
having only –I effect.
• The order of the strength of hydroxy benzoic acid is
COOH COOH COOH COOH
OH

OH
OH

Chapter_15.indd 18 3/26/2014 3:28:47 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.19

When –OH group is present in m-position there is only (CH3)2CH– RNH > NH3 > R2NH > R3N
–I effect, no resonance effect. So m-hydroxy benzoic (CH3)3CH –
NH3 > RNH2 > R2NH2 > R3N
acid is stronger than benzoic acid. But when –OH • Aniline is less basic than ammonia. This is due to the
group is present in p-position, the acidic strength is
–I effect of phenyl group.
less than benzoic acid as +M effect dominates.
• Though acetamide contains –NH2 group it is less b­ asic
• The order of the strength of chloro benzoic acids is
than ethyl amine because the lone pair on n­ itrogen parti­
COOH COOH COOH COOH cipate in resonance and is not available for donation.
Cl O O
|| | ⊕
> > > CH3 – C – NH2 CH3 – C = NH2
Cl • The compounds with least s-character (sp3-hybridised)
Cl are most basic and with more s-character (sp-hybrid-
ised) is least basic, e.g.
Here chlorine atom is an electron-releasing group but
 (i) CH3–NH2 > CH3–N=CH–CH3 > CH3–C≡N
with –I effect. So, m-chlorobenzoic acid is stronger than
  (ii) CH3CH2CH2NH2 > H2C=CHCH2NH2 >
p-chloro benzoic acid since in meta isomer –I effect
HC≡CCH2NH2
of chlorine operates while in p-isomer both resonance
(iii) (CH3)2NH > CH3NH2 > NH3 > C6H5NH2
and –I effect operates simultaneously. Because of
–I effect of chlorine all the three acids (o-, m- and EWGs (C6 H 5− ) decrease electron density on nitrogen
p-chlorobenzoic acids) are stronger than benzoic acid. atom and thereby decreasing basicity.
• p-chloro benzoic acid is stronger than p-fluoro benzoic   (iv) (CH3)2NH > CH3NH2 > C6H5NHCH3 > C6H5NH2
acid because 2p-orbitals of both carbon and fluorine   (v) CH3CH2NH2 > HO(CH2)3NH2 > HO(CH3)2NH2
can ­overlap effectively in the mesomeric effect. This Electron withdrawing inductive effect of the –OH
increases the electron density at –COOH group more. group decreases the electron density on nitrogen. This
In p-chloro benzene the 3p-orbitals of chlorine cannot effect diminishes with distance from the amino group.
overlap with 2p-orbitals of carbon. So, compared to  (vi)  CH3CH2NH2 > C6H5CONH2 > CH3CONH2
p-fluoro benzoic acid the +M effect in p-chloro ben-
zoic acid is weaker. • The basic strength of an amine in an aqueous solution
not only depends upon the electron density on N-atoms
• When different groups are present in the para position but also depends upon the stability of conjugate acid
of benzoic acid the strength decreases in the order formed by accepting a proton from water (solvent).
–NO2 > Cl > C6H5COOH > –CH3 > –OCH3 ⊕
RNH2 + H2O 
→ RNH3 + OH–
⊕
Strength of Organic Bases R2NH + H2O 
→ RNH2 + OH–
R3N + H2O 
→ R3NH + OH–
• Amines like ammonia are basic in nature due to the
presence of an unshared pair (lone pair) of electrons on The protonated amines form hydrogen bond with
nitrogen atom. ­water molecules. More the extent of hydrogen ­bonding
• Larger the Kb values or lesser the pKb values stronger in protonated amine, more will be its stabilization,
the base. i.e., compound will be more basic.
⊕
• Due to the +I effect of alkyl groups the electron den- • RN H3 can form hydrogen bonds with 3 water
sity at nitrogen in the aliphatic amines increases. Thus, ⊕
­molecules since it has 3 “H” atoms while RN H2 and
their basic strength increases. ⊕
R3N H can form hydrogen bonds with two and one water
• Due to steric factors, i.e., crowding of alkyl groups,
molecules only, since they contain 2 and 1 “H” atoms.
a proton cannot approach nitrogen in tertiary amines.
Hence, the order of basic character of various amines • Tertiary ammonium ion is less hydrated than second-
is in the order ary ammonium ion which in turn is less hydrated than
­primary ammonium ion. Hence tertiary amines have less
Alkyl group relative strength
tendency to form ammonium ion and finally it will be
CH 3− R2NH > RNH2 > R3N > NH3 less basic. So, the basic strength of amines follows the
C2 H 5− R2NH > RNH2 > NH3 > R3N order

Chapter_15.indd 19 3/26/2014 3:28:53 PM

 15.20  Objective Chemistry - Vol. I

Primary > Secondary > Tertiary C6H5NMe2 > C6H5NHMe > C6H5NH2
RNH2 > R2NH > R3N C6H5NH2 > (C6H5)2NH > (C6H5)3N
• The inductive effect and solvation effects are two • Basic strength of benzyl amine is more than ani-
­opposite factors and they balance each other in case of line due to absence of delocalization of lone pair of
secondary amine and hence it is stronger base among electrons on nitrogen with π-electrons of benzene ring.
amines and the order of basic strength varies. C6H5CH2NH2 > C6H5NH2
Secondary > Primary > Tertiary • Benzyl amine is less basic than alkyl amine because
• In a gas phase or in non-aqueous solvents such as of the less availability of lone pair of electrons on
chlorobenzene the solvent effects (stabilization of
­ nitrogen due to the electron withdrawing effect
­
­conjugate acid due to H-bonding) are absent and hence (–I effect) of aryl group.
the basic strength of amines depend only upon of +I
CH3NH2 > C6H5CH2NH2
effect of the alkyl groups.
Tertiary > Secondary > Primary > NH3
Enthalpy and Entropy
• Aromatic amines are weaker bases than ammonia and
aliphatic amines, because the lone pair of electrons on • The standard Gibbs free energy change of reaction
nitrogen in aniline is delocalized due to +M effect and ∆G° is related to the enthalpy change of reaction ∆H°
is less available for donation. Further the anilinium and the entropy change of reaction DS° as
ion formed by protonation of aniline is less stable due
∆G° = ∆H° – TDS°
to absence of mesomeric effect. In the case of NH3
and aliphatic amines, delocalization of the lone pair of • Enthalpy change of a reaction is the heat exchanged
electrons on nitrogen is not possible. So, they are more with the surroundings (at constant ­temperature) in a
basic than aniline or other aromatic amines. chemical reaction. This represents the difference in
• The basic character of aniline will be decreased by the stability (bond strength) of the ­reagents and products.
presence of EWGs such as –NO2, –CN, –X, etc. where • If ∆H° is negative, then the bonds in the products are
as the EDGs such as –CH3, –OCH3, –NH2 ­enhance the stronger overall than those in the starting material.
basic character of aniline. Heat is released in an exothermic reaction.
• The base strengthening effect of the EDGs and • If ∆H° is positive, then the bonds in the products are
EWGs is more pronounced at para position than at weaker overall than those in the starting material. Heat
meta ­position because the activating or deactivating is absorbed in an endothermic reaction.
groups activate or deactive at ortho or para positions. • Entropy is the change of a reaction which provides
These groups increase or decrease electron density at a measure of the change in molecular disorder or
the nitrogen atom if they are present at ortho or para ­randomness caused by a reaction.
­positions of aniline. Thus p-toluidine > m–toluidine. • DS° is negative when the reaction leads to less ­disorder.
Similarly, p-nitroaniline < m-nitroaniline. This occurs when two reactants are converted to one
• Ortho-substituted anilines are generally weaker bases product.
than aniline regardless of the nature of substituent • DS° is positive when the reaction leads to more
whether electron donating or electron withdrawing ­disorder. This occurs when one reactant is converted
due to ortho effect which is probably due to combina- into two products.
tion of steric and electronic effects.
The order of basic character of toluidine and aniline is
Kinetics
p-toluidine > m-toluidine > aniline > o-toluidine.
Similarly the relative basic character of nitroaniline • Though the negative value of ∆G° predicts the
and aniline is f­easibility of a reaction, the rate at which it occurs is
aniline > m-nitroaniline > p-nitroaniline determined by the activation energy ∆G+ or Ea.
> o-nitroaniline • The energy difference between the reactants and the
• Basic character of arylamines also depends upon the transition state is called as activation energy.
effect of substituents on the nitrogen atom. • A transition state is a structure that represents an
• EDGs enhance the basic strength while EWGs energy maximum or converting starting materials to
decrease the basic strength. For example products and it cannot be isolated.

Chapter_15.indd 20 3/26/2014 3:28:54 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.21

• Transition state is different from intermediate. An ­intermediate occurs at a local energy minimum and can be detected
and sometimes isolated.

Transition state

Ea

Energy Reactants
∆Go
Products

Extent of reaction

• The higher the activation energy, the slower the reaction.

• An increase in temperature increases the rate of ­reaction due to gain of activation energy.
• Activation energy can be calculated from the rate ­constant by using the relation
k = rate constant R = gas constant (JK–1 mol–1)
K = Ae–Ea / RT
A and e = constant T = temperature (K)
• The rate of first-order reactions depend on the ­concentration of only one of the reactant while the rate of second-order
reactions depend on the concentrations of two reactants.
• The slowest step which leads to the highest ­energy transition state is called rate-determining step and thus is the reac-
tion rate that can be determined experimentally.
• Organic reactions with a number of steps will have intermediates. These represent a localized minimum energy in the
reaction profile.
• An energy barrier must be overcome before the ­intermediate forms a more stable product or a second intermediate.
Intermediate I TS = Transition state
Ea = Activation energy

Intermediate II
TS1
TS2

TS3
Energy

Ea

Reactants Products

Extent of reaction

• The conversion of the reactants to intermediate 1 is the rate-determining step in the above reaction.
• The structure of the intermediate can give an idea of the structure of the transition state.

Chapter_15.indd 21 3/26/2014 3:28:56 PM

 15.22  Objective Chemistry - Vol. I

• Hammond postulate states that the structure of a transition state resembles the structure of the nearest stable species.
• In an exothermic reaction (or step of a reaction) the transition state resembles the structure of the reactant since the
energy level of the transition state is closer to the reactant than do the product.

Early transition state

+
[H3C..... H ..... F].+

. Exothermic reaction
CH4 + F The H is closer to C than F in the transition state,
Enthalpy

i.e., more “reactant–like”.

.
H3C + HF
Extent of reaction   

• For an endothermic reaction (or step of reaction) the transition state resembles the structure of the product. This is
because the energy level of the transition state is closer to the product than the reactant.

[H3C..... H ..... I].++

Endothermic reaction
.
Enthalpy

H3C + HI The H is closer to I than C in the transition state, i.e.,

more “product-like”.

.
CH4 + I

Extent of reaction   
• Catalysts increase the rate of a reaction by allowing the reaction to proceed by a different pathway, which has lower
energy transition state, but catalysts do not affect the equilibrium position though equilibrium is achieved quickly.

Transition state of uncatalysed reaction

Transition state of catalysed reaction

Energy

Reactants

Products

Extent of reaction

Chapter_15.indd 22 3/26/2014 3:28:58 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.23

• A homogeneous catalyst is in the same phase as the starting materials of the reaction that it is catalyzing.
• A heterogeneous catalyst is in a different phase from the starting materials of the reaction that it is catalyzing.

Kinetics vs Thermodynamic Control

• For a reaction that can give rise to more than one product, the amount of each of the different products can depend on
the ­reaction temperature. This is because, although all reactions are reversible, it can be difficult to reach equilibrium
ratio of products.
• At low temperatures, reactions are more likely to be irreversible and equilibrium is less likely to be reached. Under
these conditions, the product that is formed at the farthest rate predominates. This is kinetic control. The kinetic
product is therefore formed at the fastest rate, i.e., this product has the lowest activation energy barrier.
• At high temperatures, reactions are more likely to be reversible and equilibrium is likely to be reached. Under these
conditions the energetically more stable product predominates. This is thermodynamic control. The thermodynamic
product is therefore the most stable product, i.e., this product has the lowest energy.

Thermodynamic control

Kinetic control
Energy

Reactants
Kinetic product

Thermodynamic product

Extent of reaction

 Objective Questions (3) A carbenium ion contains only three pairs of

electrons.
1. The phenomenon that involves the union of two or
(4) Free radicals are paramagnetic in nature.
more molecules to form a new molecular aggregate
is known as 4. Hyper conjugation is
(1) polarization (2)  polymerization (1) σ-π conjugation
(3) photosensitization (4)  pasteurization (2) noticed due to delocalization of σ and π bonds
2. Heterolysis of propane gives (3) No bond resonance
(1) Methyl and ethyl free radicals (4) All
(2) Methylium cation and ethyl anion 5. The stability of 2,2-dimethyl but-2-ene is more than
(3) Methyl anion and ethylium cation 2-butene. This can be explained in terms of
(4) Methylium and ethylium cations
(1) Resonance (2)  Hyper conjugation
3. Which of the following statements is false? (3) Electromeric effect (4) Inductive effect
(1)  Homolytic and heterolytic bond dissociation + +
­energies are same. 6. (CH3)4N and NH4 are
(2) Reactions involving heterolytic fission are said to (1) Electrophiles (2)  Nucleophiles
proceed via either ionic or polar mechanism. (3) Ambiphile (4)  None

Chapter_15.indd 23 3/26/2014 3:28:59 PM

 15.24  Objective Chemistry - Vol. I

7. Ease of abstraction of hydrogen is greater when 15. Free radicals can undergo
­attached to (1) Disproportion to two species
(1) 1° carbon (2) 2° carbon (2) Rearrangement to more stable free radical
(3) 3° carbon (4) Neocarbon (3) Decomposition to give another free radical
(4) Combination with other free radical
8. What information is provided by a reaction
(5) All are correct
­mechanism?
(1) the bonds are broken and formed 16. Carbonium ion can undergo
(2) the reaction intermediates (1) Loss of a proton
(3) the relative rates of discrete steps especially the (2) Addition to multiple bond
slowest one (3) Combination with anions
(4) All (4)  Rearrangement to form more stable
9. Which of the following is a singlet carbene? carbonium ion
⊕ (5) All
(1) (CH3)3C 
(2)  C2H5–C–H
⊕
 17. The total number of isomeric carbocations possible
(3) CH3CHCH3 (4) CH2=CH– CH2
for the formula C4 H 9+ is
10. The structure remaining after one H is removed from (1) 3 (2) 4 (3) 2 (4) 5
hydrocarbon is
18. CH2=CHCH2CH=CH2 NBS
 → A, A is
(1) Alkyl group (2)  Alkenyl group
(3) Alkynyl group (4)  All (1) CH2 = CHCHCH = CH2
|
11. Why is light necessary to bring in chlorination Br
­reactions of alkene? (2) CH2=CHCH=CHCH2Br
(1) The dissociation of Cl2 gives Cl free radical (3) CH2=CHCH2CH=CHBr
(2) The Cl2 molecule absorbs light to show ­homolytic (4) None is correct
bond fission 19. Most stable free radical is
(3) The formation of Cl free radical propogate the CH3
chain reaction
(4) All (1) (2) 
12. An organic compound C5H11X on dehydro
­halogenation gives pentene-2 only. What is the h­ alide?
(1) CH3CH2CHXCH2CH3 (3) (4) 
(2) (CH3)2CHCHXCH3
(3) CH3CH2CH2CHXCH3
(4) CH3CH2CH2CH2CH2X

13. The reaction CH2=CHCHO HX

→ gives 20. Relative stabilities of the following carbocation will
(1) CH3CHXCHO be in order
(2) CH2XCH2CHO ⊕
(I)  CH3O CH2
(3) CH2=CHCHX2
(4) All
⊕
14. Which of the following statements is not correct?  (II)  CH2
(1)  Primary carbonium ions are more stable than
secondary ones. ⊕
(2)  Secondary free radicals are more stable than (III)  CH3 CH2
­primary free radicals.
(3)  Tertiary free radicals are more stable than ⊕
(IV) CH3–CH2
­secondary ones.
(4)  Tertiary carbonium ions are more stable than (1) I < II < III < IV (2)  IV < III < II < I
­primary ones. (3) IV < II < III < I (4)  II < IV < III < I

Chapter_15.indd 24 3/26/2014 3:29:08 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.25

Cl (1) VI < V < III < II < IV < I

(2) I < II < III < VI < V < IV
21. NaOH A; A is
Cl (3) I < III < V < II < IV < VI
Cl (4) Cannot be predicted
(1)  (2)  27. Which of the following alkenes will react fastest with
OH H2 under catalytic hydrogenation conditions?
OH OH R
R
(3)  (4)  (1) 
OH Cl
H H
22. The most stable free radical among the following is
R H
(1) C6H5CH2CH  2 
(2) C6H5CHCH
 
3 (2) 
(3) CH3CH2 (4) CH3CHCH3 R H
Cl CH3OH R R
23. H2O
(3) 
In this reaction we get ........ types of substituted R H
a­ lcohols (geometrical isomers not considered) R R
(1) one (2)  two (4) 
(3) three (4)  four R R
24. The order of decreasing stability of the carbanions 28. Polarization of electrons in acrolein may be written as
– – δ− δ+
 (I) (CH3)3C  (II)  (CH3)2C H (1) CH 2 = CH − CH = O
– –
(III) CH3CH 2 (IV)  C6H5C H2 is
(1) I > II > III > IV (2)  IV > III > II > I δ− δ+
(2) CH 2 = CH − CH = O
(3) IV > I > II > III (4)  I > II > IV > III
δ− δ−
25. The most unlikely representation of resonance (3) CH 2 = CH − CH = O
­structures of p-nitrophenoxide ion is δ+ δ−
–O O– O– (4) CH 2 = CH − CH = O
+ +
N =O N 29. –
:CH2 – C – CH3 and CH2 = C – CH3 are
|| |
(1)  (2)  O O
(1) Resonating structures
(2) Tautomers
– (3) Geometrical isomers
O O (4)  Optical isomers
O O –O O 30. The arrangement of (CH3)3C–, (CH3)2CH–, CH3CH2–
+ + when attached to benzene or an unsaturated group in
N N increasing order of inductive effect is
(3)  (4)  (1) (CH3)3C– < (CH3)2CH– < CH3CH2–
(2) CH3CH2– < (CH3)2CH– < (CH3)3C–
(3) (CH3)2CH– < (CH3)3C– < CH3CH2–
(4) (CH3)3C– < CH3CH2– < (CH3)2CH–
O– O 31. Which of the following compounds posses the C–H
26. Leaving tendency of the following in increasing bond with the lowest bond dissociation energy?
­order  is (1) Toluene
 (I) Cl–  (II) CH3COO– (2) Benzene
–
(III) OH (IV) H3C SO3– (3) n-pentane
–
(V) RO (VI) NH–2 (4) 2,2-Dimethyl propane

Chapter_15.indd 25 3/26/2014 3:29:19 PM

 15.26  Objective Chemistry - Vol. I

32. Consider the following structures 39. In triplet carbenes, the two electrons
+ +
 (I) CH2=CH  (II) CH3–CH2 (1) are paired in one orbital
+ + (2) are present in different orbitals
(III) CH2=CH–CH2 (IV) C6H5–CH–C6H5 (3) have the same spin
The correct sequence of these carbocations in the (4) both b and c
d­ ecreasing order of their stability is
40. The reaction C6H6 + Br2 FeBr
 3
→ C6H5Br + HBr is
(1) IV, III, II, I
(2)  I, II, III, IV (1) an electrophilic addition reaction
(3) IV, II, III, I (2) a nucleophilic substitution reaction
(4)  I, III, II, IV (3) an electrophilic substitution reaction
(4) a free radical substitution reaction
33. Which of the following statements is false about an
electrophile? 41. Which of the following statements is false about
­resonance contribution structures?
(1) Electron-deficient species
(2) An acidic reagent (1) Contributing structures contribute to the resonance
(3) A reagent which attacks an electron-deficient site hybrid in proportion of their relative energies
in a molecule (2)  Equivalent contributing structures make the
(4) A species which seeks a pair of electron ­resonance very important
(3)  Contributing structures represent molecules
34. Out of the following the one containing only ­having no real existence
­nucleophile is (4) Contributing structures are less stable than the
(1) AlCl3, BF3, NH3 resonance hybrid
(2) NH3, CN–, CH3OH
42. Acetaldehyde is the rearrangement product of
(3) AlCl3, NH–2, H2O
(4) RNH2, :CX2, H– (1) Methyl alcohol (2)  Alkyl alcohol
(3) Vinyl alcohol (4)  All are correct
35. Inductive effect involves
43. Which behaves both as a nucleophile as well as an
(1) delocalization of σ electrons
electrophile?
(2) displacement of σ electrons
(3) delocalization of π electrons (1) CH3NH2 (2) CH3Cl
(4) displacement of π electrons (3) CH3CN (4) CH3OH

36. Which of the following correctly represents the 44. Which of the following is least reactive in a
+I effect of the substituents? ­nucleophilic substitution reaction?
(1) O– > COO– > CR3 (1) (CH3)3C–Cl (2) CH2=CHCl
(2) COO– > O– > CR3 (3) CH3CH2Cl (4) CH2=CHCH2Cl
(3) O– < COO– < CR3 45. Rate of the reaction
(4) COO– < O– < CR3
O O
37. The dipolemoment of vinyl chloride is lower than that R – C + Nu R–C + Z
of methyl chloride. This is due to
(1) Resonance effect Z Nu
(2) Inductive effect is fastest when Z is
(3) Electromeric effect (1) Cl (2)  NH2
(4) Hyper conjugation effect (3) OC2H5 (4) OCOCH3
38. Hyper conjugation involves 46. Which one of the following has all the effects, namely
(1) delocalization of σ electrons into an adjacent inductive, mesomeric and hyper conjugation?
π-bond (1) CH3Cl
(2) delocalization of π electrons into an adjacent (2) CH2CH=CH2
double bond (3) CH3 – CH = CH – C – CH3
(3) delocalization of π electrons into an adjacent ||
π-bond O
(4) All the above are true (4) CH2=CH–CH=CH2

Chapter_15.indd 26 3/26/2014 3:29:22 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.27

47. What is the decreasing order of strength of the bases 55. Which of the following arrangement is the true with
OH–, NH–2, HC≡C– and CH3CH–2? respect to acidic strength
(1) CH3CH–2 > NH–2 > HC≡C– > OH– (1) CH3COOH < HCOOH < CH3CH2COOH
(2) HC≡C– > CH3CH–2 > NH–2 > OH– (2) FCH2COOH < F2CHCOOH < F3CCOOH
(3) OH– > NH–2 > HC≡C– > CH3CH–2 (3) C6H5OH < CH3COOH < CH2 = CH–OH
(4) NH–2 > HC≡C– > OH– > CH3CH–2 (4) None of these is correct
48. Increasing order of basic nature of NH3(I),
CH3NH2(II) and C6H5NH2(III) is 56. Benzyne contain
(1) III < II < I (2)  I < II < III
(3) III = II < I (4)  III < I < II (1) Six-sp2 hybridised C-atoms
 
(2) Four-sp2 hybridised and two sp-hybridised
49. CH 
3 , NH 2 ,O H and F in increasing pKb values are
C-atoms
    (3) Two-sp2 hybridised and four sp-hybridised
(1) CH3 < N H2 < OH < F C-atoms
    (4) None of these
(2) F < OH < N H2 < CH3
   
57. Pyridine is
(3) OH < NH2 < CH 3 < F (1) more basic than pyrole
   
(2) less basic than aniline
(4) CH 3 < N H2 < F < OH
(3) more basic than methyl amine
50. The order of ease of heterolysis of the following (4) None of these
t-­butyl compound is (I) (CH3)3C–OH
58. Which of the following will not have dipolemoment
(II) (CH3)3C–OAg (III) (CH3)3C–Cl is as zero?
(1) I < II < III (2)  III < II < I (1) p-dichlorobenzene
(3) I < III < II (4)  II < I < III (2) p-xylene
51. Acidic nature of (I) CH3OH (II) CH3SH and (3) p-quinol
(III) CH3NH2 is in the order (4) p-dinitrobenzene
(1) III < II < I 59. Picric acid is
(2) III < I < II (1) Less acidic than carbolic acid
(3) I < II < III (2) More acidic than hydroiodic acid
(4) II < I < III (3) More acidic than acetic acid
52. Which of the following statements is correct? (4) Less acidic than phenol
(1) +I effect stabilizes a carbocation 60. Which of the following have maximum dipole-
(2) +I effect stabilizes a carbanion moment?
(3) –I effect stabilizes a carbocation (1) CH3I (2) CH3Br
(4) –I effect destabilizes a carbanion (3) CH3Cl (4) CH3F
53. The electron displacement effect in which fractional 61. Which of the following has least nucleophilicity?
polarization occurs due to difference in electrone­  
gativities is (1) (CH3)3 C : (2)  (CH3)2CH

(1) Mesomeric effect  2
(3) CH3–CH (4)  : CH3
(2) Inductive effect
(3) Monomeric effect 62. Which of the following is more acidic?
(4) Inductomeric effect (1) γ-Butyric acid (2)  β-Buteric acid
(3) isobuteric acid (4)  α-Buteric acid
54. Which of the following is correct?
(1) Alkanoic acid is more acidic than carbolic acid 63. Which of the following statements is wrong?
(2)  Trimethylamine is more basic than dimethyl (1) Alkyl carbocation is a six-electron system.
amine (2) Carbon free radical is paramagnetic in nature.
(3) Acetylene is more acidic than phenol (3) Carbene is an amphile.
(4) Aniline is more basic than methyl amine (4) Singlet carbene is sp2-hybridised.

Chapter_15.indd 27 3/26/2014 3:29:28 PM

 15.28  Objective Chemistry - Vol. I

64. Identify the false statement. The decreasing order of stability is

(1) Carbanion is an 8-electron system. (1) III > II > I (2)  III > I > II
(2) Nitrene is a nucleophile. (3) I > II > III (4)  II > I > III
(3) Carbene is a six-electron system.
71. Pick out the wrong statement about resonance.
(4) Triplet carbene contains two unpaired electrons.
(1) Resonance structures should have equal energy.
65. The four C–H bonds of methane are broken one at a (2)  In resonance structures, the constituent atoms
time. The cleavage of which of the following bonds must be in the same position.
has the minimum bond dissociation energy? (3) In resonance structures, all the electrons may be
(1) CH3–H (2) CH2–H paired or may be arranged in pairs or unpaired
(3) CH–H (4)  C–H electrons.
(4) Resonance structures should differ only in the
66. The false statements among the following are
­location of electrons around the constituent a­ toms.
  (I)  A primary carbocation is less stable than a
­tertiary carbocation. 72. Nucleophilicity order is correctly represented by
 (II) A secondary propyl carbocation is less stable (1) CH–3 < NH–2 < OH– < F–
than allyl carbocation. (2) CH–3  NH–2 > H2O  F–
 (III) A tertiary free radical is more stable than a (3) CH–3 > NH–2 > OH– > F–
­primary free radical. (4) NH–2 < F– < OH– < CH–3
(IV) Isopropyl carbanion is more stable than ethyl
73. In which of the following, homolytic bond fission
carbanion.
takes place
(1) I and II (2)  II and III
(3) I and IV (4)  II and IV (1) Alkaline hydrolysis of ethyl chloride
(2) Addition of HBr to double bond
67. A less stable carbonium ion rearranges to more (3) Photochlorination of methane
­stable carbonium ion. During this rearrangement, the (4) Nitration of benzene
­migrating atom or group leaves as a
74. The typical reaction of olefinic bond is
(1) Free radical
(2) Carbene (1) Electrophilic substitution reactions
(3) Positively charged ion (2) Electrophilic addition reactions
(4) Negatively charged ion (3) Nucleophilic substitution reactions
(4) Nucleophilic addition reactions
68. Which behave both as a nucleophile as well as an
electrophile? 75. Which of the following statements regarding the
(1) CH3NH2 (2) CH3Cl ­resonance energy of benzene is correct?
(3) CH3CN (4) CH3OH (1) The energy required to break the C–H bond in
benzene
69. In which of the following pairs of carbocations, the
(2) The energy required to break the C–C bond in
first carbocation is more stable than the second?
+ +
benzene
 (I) CH2=CH– CH2 and CH2=CH–CH2– CH2 (3) The energy is a measure of stability of benzene
+ + (4) The energy required to convert
 (II) CH3–NH– CH2 and CH2–OH
+ +
(III) CH3OCH2CH2 and CH3OCH2
+ +
(IV) CH3CHCH2CH2 and CH3CH2CHCH2CH3
(1) I, II and III 76. In which of the following resonance will be possible?
(2)  I, II and IV (1) CH2=CH–CH2–CHO
(3) II and III (2) CH2=CH–CH=O
(4)  III and IV (3) CH3COCH3
70. Among the following alkenes (4) CH2=CH–CH2–CH–CH2
 (I) 1-butene 77. Which of the following represents decreasing order
 (II) cis-2-butene of reactivity of given organic compound towards
(III) trans-2-butene ­nitration?

Chapter_15.indd 28 3/26/2014 3:29:29 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.29

 (I)  terephthalic acid  (II)  toluene 83. Carbocation is the reaction intermediate in which of
(III) p-toluic acid (IV) p-xylene the following reactions?
(V)  m-xylene (1) E1 reactions
(1) IV > V > II > III > I (2) Electrophilic addition reactions of alkenes and
(2) I > II > III > V > IV alkynes
(3) III > I > II > V > IV (3) SN1 reactions
(4) V > IV > II > III > V (4) All of the above

78. Electromeric effect 84. The decreasing order of nucleophilicity among the
nucleophiles is
(1)  comes into play at the demand of attacking O
­reagent ||
(2) involves displacement of electrons in a sigma   (I) (CH3)3 C – O  (II)  CH3O
bond O
||
(3) comes into play in the molecule when at least one (III) CN– (IV)  H3C – –S – O –
atom has unshared pair of electrons ||
(4) involves the distortion of the electron cloud O
(1) I, II, III, IV (2)  IV, III, II, I
79. In which of the following compounds, the carbon (3) II, III, I, IV (4)  III, II, I, IV
marked with an asterisk is most electronegative?
* 85. Which one of the following resonating structures of
(1) CH3–CH2–CH=CH2
* 1-methoxy-1, 3-butadiene is least stable
(2) CH3–CH2–C≡CH  ⊕

(3) CH3–CH=CH–CH3
*
(1) CH2–CH=CH–CH=O–CH3
* ⊕
(4) CH3–CH2–CH2–CH3 
(2) H2C=CH–CH–CH=O–CH3
80. Addition of HI on the double bond of propene yields  ⊕
(3) CH2–CH–CH=CH–O–CH3
isopropyl iodide and not n-propyl iodide as the ma-
 
jor product. This is because the addition proceeds (4) H2C=CH–CH–CH–O–CH3
through
86. Which of the following represents the correct order of
(1) a more stable carbonium ion
the acidity in the given compound?
(2) a more stable carbanion
(1) BrCH2COOH > ClCH2COOH > FCH2COOH >
(3) a more stable free radical
CH3COOH
(4) None of the above is a correct statement
(2) FCH2COOH > ClCH2COOH > BrCH2COOH >
81. Which is dehydrated to a maximum extent using CH3COOH
conc. H2SO4? (3) CH3COOH > BrCH2 COOH > ClCH2COOH >
O O FCH2COOH
OH (4) FCH2COOH > CH3COOH > BrCH2COOH >
(1)  (2)  ClCH2COOH

OH 87. Which one of the following is correct? Formic acid

has lower pKa than that of CH3COOH because
O
O (1) formic acid does not dissociate
(2) formic acid does not have alkyl group
CH3
(3)  (4)  (3) formic acid is smaller in size than acetic acid
(4) formic acid is a strong reducing acid
OH 88. The rate of the reaction
OH
82. Nucleophilic part of the reagent attacks the substrate R– – CH2Br + N
CH3CH2COCH3 on the
(1) carbon atom of carbonyl group
(2) oxygen atom of carbonyl group
(3) methyl group R– – CH2 – N Br–
(4) CH2 group

Chapter_15.indd 29 3/26/2014 3:29:33 PM

 15.30  Objective Chemistry - Vol. I

is influenced by the hyper conjugation effect of group (1) (CH3)3C– > (CH3)2CH– > CH3CH2– > CH3–
R- sequentially is (2) CH3– >CH3CH2– > (CH3)2CH– > (CH3)3C–
 (I)  CH3–   (II)  CH3CH2– (3) CH3CH2– > CH3– > (CH3)3C – > (CH3)2CH–
(III) (CH3)2CH– (IV) (CH3)3C– (4) (CH3)2CH– > (CH3)3C– > CH3– > CH3CH2–
the increasing order of speed of the above reaction is 95. The order of the –I effect orbitals is
(1) IV, III, II, I (2)  I, II, III, IV (1) sp3 > sp2 > sp
(3) I, IV, III, II (4)  III, II, I, IV (2) sp2 > sp3 > sp
89. Hyper conjugation involves overlap of the following (3) sp > sp2 > sp3
orbitals

(4) sp3 > sp > sp2
(1) σ–σ (2)  σ–p 96. The hyperconjugative effect of the group R in
(3) p–p (4)  π–π R–CH=CH2, where R is CH3, CH3CH2–, or (CH3)2CH
follows the order
90. Which among the following statements are true with
(1) CH3– >CH3CH2– > (CH3)2CH–
respect to electronic displacement in a covalent bond?
(2) (CH3)2CH– > CH3CH2– > CH3–
(I) Inductive effect operates through a π-bond (3) CH3– > (CH3)2CH– > CH3CH2–
 (II) Resonance effect operates through a σ-bond (4) (CH3)2CH– > CH3– > CH3CH2–
(III) Inductive effect operates through a σ-bond
(IV) Resonance effect operates through a π-bond 97. The product obtained in the reaction
(V) Resonance and inductive effects operate through CH3
π-bond | H2SO4
CH3 – C – CH – CH3 is
(1) I and II (2)  I and V | | δ
(3) II and III (4)  III and IV H OH
91. The correct stability order of the following species is CH3
|
 (I)   (II)  ⊕ (1) CH3 – C – CH = CH2
|
H
⊕
(III)  (IV)  CH3
⊕ |
(2) CH3 – C = CH – CH3
(1) II > IV > I > III (2)  I > II > III > IV
(3) II > I > IV > III (4)  I > III > II > IV CH3
|
92. The order of reactivity of alkyl halides is (3) CH2 – C – CH2 – CH3
(1) tertiary alkyl halides > allyl halides > secondary (4) None
alkyl halides > primary alkyl halides
(2) primary alkyl halides > secondary alkyl halides > 98. Arrange the acids CH3CH2COOH (I), CH2=CH–
tertiary alkyl halides > allyl halides COOH (II) and HCC–COOH (III) in the order of
(3) allyl halides > primary alkyl halides > secondary decreasing acidic character.
alkyl halides > tertiary alkyl halides (1) I > II > III
(4) secondary alkyl halides > primary alkyl halides > (2) III > II > I
tertiary alkyl halides > allyl halides (3) II > I > III
(4) III > I > II
93. Arrange NO2, F, COOH, Cl, OH, OR, and C6H5 in
order of electron-withdrawing effect. 99. The conjugation of electron-withdrawing groups
(1) F > NO2 > COOH > OH > Cl > OR > C6H5 –CHO, –COR, –COOR, –CN and –NO2 activates
(2) COOH > NO2 > F > Cl > OH > C6H5 > OR ­nucleophilic addition. In the order of reactivity of
these groups
(3) C6H5 > OR > Cl > OH > COOH > NO2 > F
(4) NO2 > F > COOH > Cl > OH > OR > C6H5 (1) –NO2 > –CN > –COOR > –COR > –CHO
(2) –CHO > –COR > –COOR > –CN > –NO2
94. Arrange the groups CH3–, CH3CH2–, (CH3)2CH– and (3) –CN > –NO2 > –CHO > –COR > –COOR
(CH3)3C– in order of electron-releasing effect. (4) –CHO > –NO2 > –CN > –COOR > –COR

Chapter_15.indd 30 3/26/2014 3:29:37 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.31

100. The addition of KI increases the rate of the reaction possible products can be
CH3CH2Cl + H2O  → CH3CH2OH + HCl CH3
This is because I– is a
 (I) CH3 – C – O – CH2 – CH3
(1) good nucleophile and a good leaving group
(2) a poor nucleophile and a poor leaving group CH3
(3) a poor nucleophile and a good leaving group
CH3
(4) a good nucleophile and a poor leaving group |
(II) CH3 – C = CH2
Answers A and B respectively
(1) I, II (2)  II, I
 (1) 2  (2) 3  (3) 1   (4) 4  (5) 2  (6) 4 (3) II in both cases (4)  I in both cases
 (7) 3  (8) 4  (9) 2 (10) 4 (11) 4 (12) 3
(13) 2 (14) 1 (15) 5 (16) 5 (17) 2 (18) 2 CH3
(19) 3 (20) 3 (21) 2 (22) 2 (23) 4 (24) 2 | (CH3)3CO–
(25) 3 (26) 1 (27) 1 (28) 4 (29) 1 (30) 1 3. PhCH2 – CH – CH – CH3 A,
(31) 1 (32) 1 (33) 1 (34) 2 (35) 2 (36) 1 | BuOH
OTs
(37) 1 (38) 1 (39) 4  (40) 3 (41) 1 (42) 3
predominant A is
(43) 3 (44) 2 (45) 1  (46) 3 (47) 1 (48) 4
(49) 1 (50) 1 (51) 2  (52) 1 (53) 2 (54) 1 (1) PhCH = CHCH – CH3
|
(55) 2 (56) 1 (57) 1  (58) 3 (59) 3 (60) 3
CH3
(61) 1 (62) 4 (63) 3  (64) 2 (65) 4 (66) 4
(67) 4 (68) 3 (69) 2  (70) 1 (71) 3 (72) 2 (2) PhCH2CH = C – CH3
(73) 3 (74) 2 (75) 3  (76) 2 (77) 1 (78) 1 |
(79) 2 (80) 1 (81) 3  (82) 1 (83) 4 (84) 3 CH3
(85) 3 (86) 2 (87) 2  (88) 1 (89) 2 (90) 4 (3) PhCH2CH2C = CH2
(91) 4 (92) 1 (93) 4  (94) 1 (95) 3 (96) 1 |
(97) 2 (98) 2 (99) 2 (100) 1 CH3
(4) None is correct

OH
4. + OH– O
 Practice Exercise Level-I
Cl
1. Which is dehydrated to a maximum extent using This reaction is possible when A is
conc. H2SO4? (1) cis (2)  trans
O
O (3) both (a) and (b) (4)  none of these
OH OH
(1) (2) 

5. 1 K2CO3
OH A, A is
2 CH3I
O O CH2OH
CH3
(3) (4)  OCH3
OH
OH OH (1)  (2) 
CH3 CH2OCH3 CH2OH
| CH3CH2OH
2. CH3 – C – Br + CH3CH2OH CH3 CH3
A (Major)
(3)    (4) 
CH3CH2ONa
B (Major)
(CH3CH2OH) CH2OH CH2OCH3

Chapter_15.indd 31 3/26/2014 3:29:43 PM

 15.32  Objective Chemistry - Vol. I

CH2Br 10. Which reacts quickly with conc. HCl?

6. EtOH
products (1) CH2 – CH2OH
∆
The expected products are (2) CH – CH3

 (I)  (II)  OH
CH3
OEt
CH2OEt (3) CH3 – C – OH
(III) 
CH3
(4) CH2=CHCH2OH
Select the correct alternatives
(1) I, II, III (2)  I, III 11. Dehydration of the following in increasing order is
(3) II, III (4)  I, II (I)  OH (II)  OH
7. Which of the following will give precipitate readily
with alcoholic AgNO3? (III)  OH (IV)  OH
CH3
(1) I < II < III < IV (2)  II < III < IV < I
 (I)  CH3
CH2Cl (II)  C Cl
(3) I < III < IV < II (4)  I < IV < II < III
CH3 12. Dehydrobromination of the following in increasing
order Br
(III)   (I)  Br (II) 
Cl
(1) I, II, III (2)  I and II (III)  Br
(3) II and IV (4)  I and III (1) I < II < III (2)  III < II < I
(3) I=II < III (4)  III < I=II
8. + NBS A, A is
13. Increasing order of the following for SE reaction is
Br
Br   (I)  CH3 (II) 
(1)  (2) 

(III)  COOH
(3)  (4) 
Br (1) I < II < III (2)  III < II < I
(3) II < III < I (4)  I < III < II
9. CH3 – CH – CH = CH2 + HBr
⊕
 product (major). 14. Electrophile NO2 attacks the following
CH3
The product is CCl3 NO2
(1) CH3 – CH – CH – CH3   (I)  (II) 
CH3 Br
(2) CH3 – CH – CH2 – CH2Br ⊕
NH2 O–
CH3 (III)  (IV) 
Br
(3) CH3 – C – CH2 – CH3 ⊕
In which cases NO2 will be at meta-position?
CH3 (1) II and IV (2)  I, II and III
(4) None is correct (3) II and III (4)  I only

Chapter_15.indd 32 3/26/2014 3:29:55 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.33

O NH2
15. O–C + NO2 ⊕ (3) (4) 
N
Product of the reaction by single SE reaction
NO2 19. Among the following resonating structures
O 
O O
(1) O–C || | ⊕
 (I)  H – C – O – H  (II)  H – C = O – H
O  ⊕
(2) O O
O–C | |
(III)  H – C – O – H (IV) 
H–C–O–H
⊕ 
NO2 The correct order of stability is
O (1) III < II < IV < I (2)  II < III < IV < I
(3)  O2N (3) III < IV < II < I (4)  IV < III < II < I
O–C
20. Which of the following carbocation is most stable?
O (1) (CH3)3C⊕ (2)  (Ph3)3C⊕
(4) O–C ⊕ ⊕
NO2
(3) (4) 

16. CH2OH on dehydration with conc. H2SO4

21. Arrange the stability of the carbocation in decreasing
forms predominantly order.
+ ⊕
(1) (1) CH3O CH2 (2) HO CH2
= CH2 (2) – CH3
⊕
(3) – CH3 (4) – CH3 (3) H2N CH2 (4) 
Cl CH2

17. Pair of a related chemical species is given below. 22. Which of the following compounds is resistant to
Which pair is not related through resonance? ­nucleophilic attack by OH– ions?
(1) methyl acetate (2)  acetonitrite
(1) CH3COCH2COOC2H5; CH3C(OH)=CHCOOC2H5
(3) dimethyl ether (4)  acetamide
O O–
23. The reaction of CH3 CH = CH OH with
(2) CH3 – C CH3 – C HBr gives
O O (1) CH3CHBrCH2 OH
⊕ ⊕
(3) O O
(2)  CH3CH2CHBr OH

O O O O
O O (3) CH3CHBrCH2 Br
(4) 
(4)  CH3CH2CHBr Br

18. Which of the following is most basic? 24. In the following groups
 (I)  –O–Al  (II)  OMe
(III) –OSO2Me (IV) –OSO2CF3
(1) N (2)  The order of leaving group ability is
| N (1) I > II > III > IV (2)  IV > III > I > II
H (3) III > II > I > IV (4)  II > III > IV > I

Chapter_15.indd 33 3/26/2014 3:30:09 PM

 15.34  Objective Chemistry - Vol. I

25. Examine the following two structures for the anilin- (1) X = dil. aqueous NaOH, 20°C, Y = HBr
ium ion and choose the correct statement from the (2) X = conc. alcoholic NaOH, 80°C, Y = HBr,
ones given below. CH3COOH, 20°C
⊕ (3) X = dil. aqueous NaOH, 20°C, Y = Br,
NH3 NH3 CHCl3, 0°C
⊕ (4) X = conc. alcoholic NaOH, 80°C, Y = Br2,
CHCl3, 0°C
Ι ΙΙ 31. Which of the following statements is true about ­hyper
conjugation?
(1) II is not an acceptable canonical (resonating or
contributing) structure because carbonium ions (1) Transmittance of substituent effect through σ-π
are less stable than ammonium ions. conjugation is called hyper conjugation.
(2) II is not an acceptable canonical structure (2) Like resonance hyper conjugation also leads to
because it is not aromatic. delocalization of electrons.
(3) II is not an acceptable canonical structure (3) Canonical structures due to hyper conjugation
because nitrogen has no 10 valence electrons. are imaginary; in other words, they do not exist.
(4) II is an acceptable structure. (4) Through hyper conjugation, an alkyl group acts
as an EWG.
26. 1,3-Butadiene reacts with one equivalent Br2 to form
1,2 and 1,4 addition products simultaneously due to 32. Among the following compounds the correct order
for no bond resonance is
(1) resonance stabilization of carbocation
(2) resonance stabilization of carbanion CH2 CH3
(3) conjugate effect of diene  (I)  (II) 
(4) hyperconjugative effect in the diene
27. Which of the following statement(s) is (are) true?
(1)  –I effect decreases the carbon–halogen bond CH2
CH3
length in the alkyl halides. (III) 
(2)  The dipolemoment of CH3Cl is greater than
CH3F.
(3) In gaseous state, a tertiary amine is more basic (1) I > II > III
than a primary amine. (2) III > II > I
(4) Cyclohexyl amine is more basic than aniline. (3) II > I > III
(5) All are correct (4) II > III > I
28. Which one of the following has the smallest heat of 33. Which of the following statements is correct about
hydrogenation? methyl group?
(1) 1-butene (1)  It stabilizes both carbocation and free radical
(2) trans-2-butene equally.
(3) cis-2-butene (2)  It stabilizes a free radical more than a
(4) 1, 3-diene carbocation.
29. Overall, functional groups in the α-position stabilize (3)  It stabilizes a carbocation more than a free
the carbanion in the following order ­radical.
(1) NO2 > RCO > SO2 > COOR > CN ≈ CONH2 (4) None of these.
(2) CN > COOR > SO2 > RCO > NO2 34. Which of the following statements is false?
(3) RCO > COOR > CN > SO2 > NO2 (1) Since hyper conjugation increases stability of the
(4) None of these molecule heat of combustion decreases.
30. Identify the set of reagents/reaction conditions “X” (2) Since hyper conjugation increases stability of the
and “Y” in the following set of transformations. molecule heat of hydrogenation increases.
CH3CH2CH2Br X → Product Y → (3) Inductive effect is transmitted through σ-bonds.
(4)  Inductive effect is distance dependent. It de-
CH3 – CH – CH3 creases in magnitude as the distance from group
Br increases.

Chapter_15.indd 34 3/26/2014 3:30:11 PM

 Fundamental Concepts in Organic Reaction Mechanism  15.35

35. The wrong statements among the following is Answers

(1) +I effect originates due to low electronegativity
of the group or atom.  (1) 4  (2) 1  (3) 1  (4) 2  (5) 2
(2) –I effect originates due to high electronegativity  (6) 1  (7) 2  (8) 1  (9) 3 (10) 2
of the group or atom. (11) 1 (12) 1 (13) 2 (14) 2 (15) 3
(3) An alkyl group has +I effect because carbon atom (16) 2 (17) 1 (18) 1 (19) 3 (20) 4
is slightly more electronegative than H atoms. (21) 3 (22) 3 (23) 2 (24) 2 (25) 3
(4)  Inductive effect of alkyl groups stabilizes the (26) 1 (27) 5 (28) 4 (29) 1 (30) 2
­carbanion. (31) 4 (32) 3 (33) 3 (34) 2 (35) 4
(36) 3 (37) 1 (38) 4 (39) 4
36. Regarding mesomerism which of the following
­statements is wrong?
(1)  Mesomeric effect only when resonance is
­possible
(2) Mesomeric effect is transmitted through π bonds  Statement-Type Questions
(3) If an atom or group withdraws a pair of electrons In each of the following questions, a statement of
in resonance then it is said to +M effect ­Statement I is given followed by a corresponding statement
(4) All conditions required for resonance to occur of S
­ tatement II just below it of the statements; mark the
are also required for the operation of mesomeric correct answer.
effect 1. If both statement I and statement II are true and
37.  (I)  NO2 (II)  statement II is the correct explanation of assertion.
2. If both statement I and statement II are true and
NO2 statement II is not the correct explanation of­
(III)  CH3 statement I.
3. If statement I is true and statement II is false.
Which of the following orders is correct about the 4. If statement I is false but statement II is true.
magnitude of –M effect among the following 1. Statement I: Nucleophiles attack the regions of high
(1) I > II > III (2)  II > I > III electron density.
(3) II > I > III (4)  III > II > I Statement II: Nucleophiles act as Lewis bases.
38. Which of the following statements is correct about 2. Statement I: –NO2, –CN, –CNO act as ambident
carbocations? ­nucleophiles.
(1) A less stable cation can rearrange itself into a Statement II: These consist of atoms of the same
more stable carbocation, if structure permits. ­period.
(2)  In rearrangement, an atom or group migrates
from the adjacent carbon to positive centre. 3. Statement I: Inductive and electromeric effects
(3) This rearrangement, can lead to contraction of ­require polar nature in the molecule.
larger rings and expansion of smaller rings. Statement II: Polar nature in inductive effect is a
(4) All are correct. must but not necessary in electromeric effect.
39. Which of the following is wrong? 4. Statement I: Singlet carbenes have opposite spin
⊕
(1) Due to hydride shift (CH3)2CHCH2 carbocation (antiparallel).
⊕ Statement II: They have a bent structure.
changes to (CH3)3C
⊕ ⊕ 5. Statement I: Carbenes act as free radicals.
(2) (CH3)3C– CH2 changes to more stable (CH3)2C Statement II: Only triplet carbenes act as biradical
CH2CH3 by methyl shift (divalent free radical).
⊕
(3) (C6H5)3C– CH2 carbocation rearranges to (C6H5)2 6. Statement I: Tertiary carboncations are generally
⊕ formed more reactive than primary carbocations.
C –CH2(C6H5) by phenyl shift
Statement II: Hyper conjugation as well as inductive
(4) Stability methyl carbocation is more than ethyl effect due to additional alkyl groups stabilize tertiary
carbocation carbocations.

Chapter_15.indd 35 3/26/2014 3:30:13 PM

 15.36  Objective Chemistry - Vol. I

7. Statement I: Alkyl free radical is more stable than 14. Statement I: Dipolemoment of CH3Cl is more than
simple alkyl free radical. CH3F.
Statement II: The alkyl free radical is stabilized by Statement II: Since Cl has less –I effect tendency
resonance. than F.
8. Statement I: Heterolytic fission involves the b­ reaking 15. Statement I: CH3COOH is more acidic than phenol.
of a covalent bond in such a way that both the elec- Statement II: The carboxylate ion is more stable than
trons of the shared pair are carried away by one of the phenoxide ion since, carboxylate ion has an equally
atoms. contributed resonating structure but phenoxide ion
Statement II: Heterolytic fission occurs readily in has not.
­polar covalent bonds.
9. Statement I: Tertiary butyl carbanion is less stable Answers
than methyl carbanion.
Statement II: +I effect of three methyl groups in  (1) 4  (2) 1  (3) 4  (4) 4  (5) 4
­tertiary butyl carbanion tends to make it more stable  (6) 1  (7) 1  (8) 2  (9) 3 (10) 2
than methyl carbanion. (11) 1 (12) 1 (13) 1 (14) 2 (15) 1
–
10. Statement I: CH3 contains a –ve charge with an
eight-electron system.
Statement II: It acts as nucleophile, since the octet of  Match the Following  Type Questions
carbon is completed.
1.
11. Statement I: The stability of carbocation depends on
inductive effect as well as hyper conjugation. List-I List-II
Statement II: More the number of alkyl groups more (A) Carbene  (i) Nucleophile
will be the +I effect tendency hence more will be the (B) Nitrene (ii) Electrophile
stability. More the number of α-H atoms more will (C) Carbanion (iii) Free radical
be the delocalization of charge therefore, more will (D) Carbocation  (iv) Ambiphile
be the stability.
Correct code is
12. Statement I: Free radical has no charge but highly
S. No A B C D
reactive.
1. ii ii i ii
Statement II: It is reactive because it has a tendency
2. i ii iii iv
to complete the octet.
3. ii iii i iv
13. Statement I: The H atom of acetylene is more ­acidic 4. i iv iii ii
than ethylene.
Statement II: sp-hybridised carbon is more electron- Answers
egative than sp2-hybridised carbon.
(1) 1

Chapter_15.indd 36 3/26/2014 3:30:14 PM

 16

Chapter
Isomerism

• Existence of two or more compounds with same mo- • “Structural isomerism” arises due to the difference
lecular formula, but with different properties is known in the structural arrangement of atoms or groups in a
as isomerism; these compounds are called isomers. molecule.
• Isomerism is due to the difference in the arrangement • “Chain isomerism” is due to the difference in the
of atoms in the molecule. ­carbon skeleton.

Isomerism

Structural isomerism Stereo isomerism

Chain Positon Functional Metamerism Tautomerism Geometrical Optical conforma-

isomerism isomerism group isomerism isomerism isomerism tional isomerism

• To exhibit chain isomerism, a compound must contain minimum four carbon atoms.
• Butane has two isomers.
CH3

CH3 – CH2 – CH2 – CH3 CH3 – CH – CH3

n-butane    isobutane   
• Pentane has three isomers.
CH3 CH3

CH3 CH2 CH2 CH2 CH3 CH3 CH2 CH CH3 CH2 C CH3

n - pentane    isopentane    CH3

neopentane

Chapter_16.indd 1 3/26/2014 3:27:21 PM

 16.2  Objective Chemistry - Vol. I

• Hexane has 5, heptane has 9, octane has 18, nonane • 1-Butene has two chain isomers.
has 35 and decane has 75 chain isomers. CH3
• Butanol has two chain isomers.
CH3
CH3 – CH2 – CH = CH2  CH3C = CH2
• Ethyl benzene and xylenes are chain isomers.
CH3 CH2 CH2 CH2OH  CH3CHCH2OH • “Position isomerism” is due to the difference in the
n-butanol isobutyl alcohol position of substituent or C=C or –C≡C– or function
group in carbon chain.

For example,
Cl
CH3 CH2 CH2 Cl CH3 CH CH3
1-chloro propane
2-chloropropane

CH3 CH2 – CH = CH2 CH3 – CH = CH – CH3

1-butene 2-butene

CH3 CH2 CH2 OH OH

1-propanol (or)
n-propyl alcohol CH3 – CH – CH3
2-propanol (or)
isopropyl alcohol

NH2 NH2

CH3 CH CH2 CH2 CH3 CH3 CH2 CH CH2 CH3

2-Amino propane 3-Amino propane

• “Functional group isomerism” is due to the difference in the functional groups.

• Functional group isomerism is exhibited by
(i) Alcohols and ethers CH3CH2OH Ethyl alcohol
CH3OCH3 Dimethyl ether
(ii) Acids and esters CH3COOH Acetic acid
HCOOCH3 Methyl formate
(iii)  Aldehydes, ketones, enols and cyclic ethers
   CH3CH2CHO Propanal
   CH3COCH3 Propanone
   CH2=CH–CH2OH Prop-2-enol
(iv)  Cyanides and isocyandes CH3CN Ethane nitrile
CH3NC Methane isonitrile
   (v)  Nitroalkanes and alkyl nitriles CH3NO2 Nitromethane
CH3ONO Methyl nitrite
(vi) Diene and yne CH2=CH–CH=CH2 1,3-Butadiene
CH3–C≡C–CH3 2-Butyne

Chapter_16.indd 2 3/26/2014 3:27:24 PM

 Isomerism  16.3

(vii)  Primary, secondary and tertiary amines

    CH3CH2CH2NH2 1-Amino propane
     CH3CH2NHCH3 N-methyl, amino ethane
    (CH3)3N N,N-Dimethyl amino methane
(viii)  Phenols and aromatic alcohols

CH2OH CH3
OH

Phenyl methanol 2-methyl phenol or cresol

(ix)  Glucose and fructose are functional group isomers.

• “ Metamerism” is due to the difference in the alkyl groups joined with the same divalent functional group present in
the molecule, for example, ethers, thioethers, ketones, esters, secondary and amines.
CH3

(i) CH3CH2OCH2CH3 CH3OCH2CH2CH3 CH3OCH – CH3

Diethyl ether methyl n-propyl ether methyl isopropyl ether
CH3

(ii) CH3CH2SCH2CH3 CH3SCH2CH2CH3 CH3SCH – CH3

Diethyl thioether methyl n-propyl thioether methyl isopropyl thioether
CH3

(iii) CH3CH2COCH2CH3 CH3COCH2CH2CH3 CH3COCH – CH3

Diethyl ketone methyl n-propyl ketone methyl isopropyl ketone

CH3

(iv) CH3CH2COOC2H5 CH3COOCH2CH2CH3 CH3COOCH – CH3

Ethyl propanoate n-propyl ethanoate isopropyl ethanoate

CH3

(v) CH3CH2NHCH2CH3 CH3NHCH2CH2NH3 CH3NHCH – CH3

Diethyl amine Methyl n-propyl amine Methyl isopropyl amino

• “Ring-chain isomerism” is due to different ways of linking of carbon atoms and the isomers may have either open
chain or closed chain structure, for example, alkenes and cycloalkanes.

CH3 – CH = CH2
Propene Cyclopropane

Butene Cyclobutane Methyl cyclo 2-Butene 2-methyl

propane propene

Chapter_16.indd 3 3/26/2014 3:27:25 PM

 16.4  Objective Chemistry - Vol. I

• “Tautomerism” is a special type of functional isomer- H–C ≡ N H–N C

ism. This is due to the oscillation of a hydrogen atom
I II
between two polyvalent atoms.
• The isomers are readily interchangeable and maintain Alkyl derivatives of (I) are called cyanides, whereas
a dynamic equilibrium with each other and hence those of (II) are called isocyanides.
known as “dynamic isomerism”. • Triad system: In this case, H atom oscillates among
• The type of isomerism in which a substance behaves three polyvalent atoms.
as if two different structures is known as “tautomer- • Keto-enol tautomerism: In this case, the polyvalent
ism” and the different forms are called “tautomers”. atoms are one oxygen and two carbon atoms, for
• Tautomerism is also known as “desmotropism”. example, acetoacetic ester, acetyl acetone, benzoyl
• Tautomerism is of different types, two of them are ­acetone, acetaldehyde, acetone and phenol.
dyad and triad systems. • The form containing keto (oxo) group is called “keto
(i)  Diad system: It involves the oscillation of  H ­atoms form”, whereas that having –C=C– (ene) and –OH (ol)
between two polyvalent atoms, for example, groups is called “enol form”.

O H OH

CH3 – C – CH – COOC2H5 CH3 – C = CHCOOC2H5

keto enol
  
• The conversion of keto into enol forms is known as “enolization”.
• Enolization is catalysed by the presence of acid or alkali.
• Aldehydes, ketones or esters which contain one labile α-hydrogen atom can only show tautomerism.
• Benzaldehyde and benzophenone which do not contain α-hydrogen do not show tautomerism.
• Enolization is more in the case of molecules containing –CH2– group between two carbonyl groups (called β-dicarbonyl
compounds).
O O OH O

CH3C – CH2 – C – CH3 CH3 – C = CH – C – CH3

24 %    76 %

This is due to the resonance stabilization of the conjugated double bonds and hydrogen bonding (in cyclic form),
H H
O O +O O–
| || || |
CH3 – C C CH3 CH3 – C C CH3
C C

H H
• The order of enolization in different compounds is in the order CH3COCH3 < CH3COCH2COOC2H5 <
C6H5COCH2COOC2H5 < CH2COCH2COCH3 < CH3COCH2CHO.
• Triad system containing nitrogen
(i) Nitrous acid exists in two tautomeric forms.
O
H–N H–O–N=O
O
Nitro (keto) form Nitro (enol) form

Chapter_16.indd 4 3/26/2014 3:27:28 PM

 Isomerism  16.5

• Primary and secondary nitroalkanes containing labile α-H atom exhibit tautomerism.
O OH

CH3 – CH2 – N CH3 – CH = N

O O
Nitro (keto) form Aci (enol) form
• The aci form dissolves in alkalies forming salt, whereas the nitro form does not form salt.
• As t-nitroalkanes (for example, (CH3)3CNO2) do not exhibit tautomerism and hence cannot form salt with alkalies.

Some Important Points about Keto-Enol OH O OH

Tautomerism CH2 = C – CH2CH3 CH3 – C – CH2CH3 CH3 – C = CH – CH
1 - Butene - 2 - ol 2-Butanone 2-Butene - 2 - ol
• Tautomerism is a reversible intramolecular change in
which a single substance behaves like two different • In such cases, at equilibrium, keto form exists in
compounds. large quantities, whereas enol forms are in very small
• The less stable tautomer is called “labile form”. concentrations.
• The enol form with the more highly substituted double
• Separation of tautomeric forms is very difficult; how-
ever, they can be separated by some special methods. bond is the more stable of the two enol forms.
•  The percentage of enol content ∝ - Conjugation
• If any reagent that can react with a particular tautomer ∝ - 1/Temperature
is added to the equilibrium mixture of tautomers, one ∝ - 1/Hydrogen bonding
tautomer can be converted completely into another.
∝ - 1/Base strength
For example, if acetyl chloride is added to keto-enol
system, then all the keto forms convert into enol forms.
• Phenyl group conjugated with the enol favours   Objective Questions
enolization.
1. The total number of structural isomers of C4H10O is
• Tautomerism effects the reactivity of a compound.
(1) 5 (2) 7 (3) 2 (4) 4
A ketone that can undergo tautomerization can be
­oxidized by a strong oxidizing agent at the ­carbon– 2. Which pair represents chain isomers?
carbon double bond of the enol tautomer. (1) CH3CHCl2 and ClCH2CH2Cl
• As C=O is stronger than C=C bond, the keto form is (2) Propyl alcohol and isopropyl alcohol
stable for most of the simple aldehydes not for ketones. (3) 2-Methyl butane and neopentane
Therefore, the equilibrium of keto-enol system lies far (4) Diethyl ether and methyl propyl ether
on the side of the keto form. 3. The number of isomers for the aromatic compound of
the formula C7H8O is
Mechanism of T
  automerism (1) 2 (2) 3 (3) 4 (4) 5
• In acid-catalysed mechanism, protonation at the car- 4. A compound not isomeric with diethyl ether is
bonyl oxygen and deprotonation from the α-carbon (1) n-Propyl methyl ether (2) Butan-1-ol
take place. (3) 2-Methyl propan-2-ol (4) Butanone
O OH
5. Which are isomers?
Fast
CH3 – C – CH3 + H+ CH3 – C – CH3 (1) Ethanol and methoxy ethane
+ (2) Methanol and methoxy methane
(3) Propionic acid and ethyl acetate
• With unsymmetrical ketones, enolization may occur in
(4) Propanal and acetone
either of two directions.
6. Amines exhibit
OH OH (1) Chain isomerism (2) Position isomerism
(3) Functional isomerism (4) Metamerism
CH3 – C – CH2 – H + Base CH3 – C = CH2 + H Base
⊕ (5) All are correct

Chapter_16.indd 5 3/26/2014 3:27:30 PM

 16.6  Objective Chemistry - Vol. I

7. The molecular formula of a saturated compound is 18. Acetone and propene-2-ol are
C2H4Br. This formula permits the existence of (1) position isomers
(1) functional isomers (2) optical isomers (2) keto-enol tautomers
(3) position isomers (4) cis–trans isomerism (3) geometrical isomers
(4) chain isomers
8. The isomerism exhibited by n-butyl alcohol and
isobutyl alcohol is 19. o-Hydroxy toluene and benzyl alcohol are
(1) metamerism (2) positional (1) position isomers (2) functional isomers
(3) functional (4) chain (3) chain isomers (4) None
9. The number of possible alcohol isomers for C4H10O is 20. Structural formula of an organic compound describes
(1) 4 (2) 3 (3) 2 (4) 5 (1) the nature of the functional group.
(2) the arrangement of atoms in the molecule.
10. Isomers are compounds having
(3) its characteristics.
(1) same structure but different molecular formulae. (4) All.
(2) same molecular formula but different properties.
(3) same empirical formulae but different molecular 21. The pair of structures given below represents
formulae. CH3 CH3
(4) different molecular formulae and different H Cl
­structures. C C
11. The compound having molecular formula C4H10O H H
shows CH3 CH2Cl

(1) metamerism
(1) enantiomers (2) position isomers
(2) functional isomerism
(3) conformers (4) None of these
(3) position isomerism
(4) All 22. The isomerism exhibited by 2-methyl-1-butene and
2-methyl-2-butene is
12. Isomerism exhibited by acetic acid and methyl for-
mate is (1) chain (2) position
(3) functional (4) tautomerism
(1) Functional (2) Chain
(3) Geometrical (4) Central 23. An alkane of molecular weight 72 gives on mono-
chlorination only one product. Name the alkane
13. On mono chlorination of n-pentane, the number of
isomers formed is (1) 2-methyl butane
(2) n-pentane
(1) 4 (2) 3 (3) 2 (4) 1
(3) 2,2-dimethyl propane
14. How many types of functional groups can be present (4) None of these
in an amine with the formula C3H9N?
24. A hydrocarbon with formula C8H18 gives only one
(1) 1 (2) 2 (3) 3 (4) 4
monochloro derivative. The hydrocarbon is
15. The maximum number of alkyl groups which C8H18 (1) n-octane
can have is (2) 2-methyl heptane
(1) 6 (2) 5 (3) 4 (4) 2 (3) 2,2,4-trimethyl pentane
(4) 2,2,3,3-tetramethyul butane
Hint: (CH3)3 C–C (CH3)3 contains six alkyl groups.
25. Which of the following statements is false?
16. Only two isomeric monochloro derivatives are
­possible for (1) Nitroethane can exhibit functional group
­isomerism.
(1) n-butane (2) 2,4-dimethyl pentane
(2) Alkyl cyanides and alkyl isocyanides are
(3) benzene (4) 2-methyl butane
­tautomers.
17. The isomeric monosubstitution products ­theoretically (3) An alkane can form isomer on monosubstitution
possible for the structure if the number of carbon atoms is ≥ 3.
CH2=CH–CH2–CH2–CH=CH2 are (4) Primary and secondary amines are functional
(1) 3 (2) 2 (3) 4 (4) 6 group isomers.

Chapter_16.indd 6 3/26/2014 3:27:30 PM

 Isomerism  16.7

Answers • Stereoisomerism is two of types: (i) configuration

isomerism and (ii) conformational isomerism.
  (1)  2   (2)  3   (3)  4   (4)  4   (5)  4 • Configuration isomers can be interconverted from one
  (6)  5   (7)  2   (8)  4   (9)  1 (10)  2 another by “bond breaking” and “bond reforming” of
(11)  4 (12)  1 (13)  2 (14)  3 (15)  1 covalent bonds.
(16)  1 (17)  1 (18)  2 (19)  2 (20)  4 • Conformational isomers can be simply interconverted
(21)  2 (22)  2 (23)  3 (24)  4 (25)  2 by “rotation” about bonds.

Geometrical Isomerism

STEREOISOMERISM • Configurational isomers arising due to different

­arrangements of atoms or groups around carbon–car-
• The foundations of organic stereochemistry were laid bon double bond are known as “geometrical isomers”.
by “Jacobus Van’t Hoff ” and “Charles Le Bel”. • Geometrical isomerism is due to “restricted rotation”
• Molecules that have same constitution but differ in of the “carbon–carbon” double bond.
the spatial arrangement of their atoms or groups are • When two groups attached to a carbon atom which are
called “stereoisomers” and the phenomenon is called same, geometrical isomerism is not possible.
“stereoisomerism”.
a–c–a a–c–a a–c–a a–c–a
or or or
b–c–d d–c–b a–c–b b–c–a
• Geometrical isomerism is possible in alkenes containing carbon–carbon double bond when both double bonded
­carbons are in bond with different groups or atoms.
b–c–a b–c–a b–c–a b–c–a
or or
b–c–a a–c–b d–c–e e–c–d
cis trans
b–c–a b–c–a
or
d–c–a a–c–d
• The isomer which has similar groups on the same side of the carbon–carbon double bond is called “cis” isomer and
the isomer which has similar groups on the opposite side of the double bond is known as “trans” isomers.
• In cases where all the four groups are different (abC=Cde), it is not possible to decide the cis and trans isomers.
• The compounds such as 1,2-disubstituted alkenes and unsaturated dicarboxylic acids are capable of showing geometri-
cal isomerism.
Examples:
(i) 1,2 - dichloroethane:
H H H Cl
C=C C=C
Cl Cl Cl H
cis trans

(ii) 2 - Butene:
CH3 CH3 H
CH3
C=C C=C
H H H CH3
cis trans

(iii) Maleic and fumaric acids:

HOOC COOH HOOC H

Chapter_16.indd 7 3/26/2014 3:27:31 PM
 (ii) 2 - Butene:
CH3 CH3 H
CH3
C=C C=C
H H H CH3
16.8  Objective Chemistry - Vol. I
cis trans

(iii) Maleic and fumaric acids:

HOOC COOH HOOC H

C=C C=C
H H H COOH

cis trans

Maleic acid Fumaric acid

(iv) Crotonic acids:
H H H COOH
C=C C=C
CH3 COOH CH3 H

cis trans
Isocrotonic acid Crotonic acid
(v) 2 - pentene:
CH3 C2H5 CH3 H
C=C C=C
H H H C2H5
cis trans
(vi) 3 - Hexene:
C2H5 C2H5 C2H5 H
C=C C=C
H H H C2H5
cis trans
(vii) Cinnamic acid:
C6H5 COOH C6H5 H
C=C C=C
H H H COOH
cis trans

Geometrical Isomers in Compounds

Containing C=N and N=N Bonds
(i) C6H5 – C – H    C6H5 – C – H
In addition, the compounds containing C=N (aldoxime
and ketoxime) and N=N (azo compounds) bonds also N – OH HO – N
show geometrical isomerism. However, in these cases,
Syn benzaldoxime Anti benzaldoxime
“syn” and “anti” are used instead of cis and trans.
m.pt = 35 ºC m.pt = 30 ºC
In aldoximes when –H and –OH groups are on the
same side of the double bond, the isomer is known as In case of ketoximes, it will be considered that the
“syn” (analogous to cis) and when these groups are on group which is syn to –OH or anti to –OH group. Syn
opposite sides of the double bond, the isomer is known and anti indicate the relationship of first group named
as “anti” (analogous to trans). with respect to –OH group.

Chapter_16.indd 8 3/26/2014 3:27:33 PM

 Isomerism  16.9

C6H5 – C – CH3 C6H5 – C – CH3

N – OH HO – N

Syn methylphenylketoxime Syn phenylmethylketoxime

Anti phenylmethylketoxime Anti methylphenylketoxime
(ii) CH3 H3C

C C
|| ||
N – OH HO – N
Syn phenyl p-tolylketoxime Syn-p-tolyl phenylketoxime
Anti-p-tolyl phenylketoxime Anti-phenyl p-tolylketoxime

Number of Geometrical Isomers

(i) I n compounds containing n double bonds and the ends of a polyene are different, the number of geometrical
isomers = 2n.
Example: R–CH=CH–CH=CH–R has four isomers.
H H H R
C=C C=C
R R R H
C=C C=C
H H H H
cis, cis cis, trans

R H R H
C=C H C=C R
H C=C H C=C
H R H H
trans, trans trans, cis
(ii) When the ends of the polyene are same
(a) When the number of double bonds (=n) is even, then the number of geometrical isomers = 2n−1 + 2p−1.
n
p = when n is even.
2
Example: Cl–CH=CH–CH=CH–CH=CH–CH=CH–Cl
n = 4 (even number)
The number of geometrical isomers = 2n−1 + 2p−1
= 23 + 21
= 8 + 2 = 10
(b) When the number of double bonds (n) is odd
The number of geometrical isomers = 2n−1 + 2p−1

Chapter_16.indd 9 3/26/2014 3:27:35 PM

 16.10  Objective Chemistry - Vol. I

n +1
where p = (when n is odd number)
2
Example: C6H5–CH=CH–CH=CH–CH=CH–C6H5
n = 3 (odd number)
The number of geometrical isomers = 2n−1 + 2 p−1
n +1
p=
2
= 23−1 + 2[(3+1)/2] −1 = 22 + 22−1

= 22 + 21 = 6
Polyenes containing the odd number of cumulative double bonds also exhibit geometrical isomerism.
C6H5 C6H5 C6H5 H

C=C=C=C C=C=C=C

H H H C6H5
cis trans

Nomenclature of Geometrical Isomers: The E,Z System

• “cis” and “trans” designation cannot be used for highly substituted alkenes if three or four different groups are ­attached
to the carbon atoms of a double bond.
• For alkenes having three or four different groups attached to the carbon atoms of a double bond, “E,Z system” was
introduced by Cahn-Ingold-Prelog, also known as “Cahn-Ingold-Prelog” system.
• The “E,Z system” involves the alignment of relative priorities to the two groups on each carbon of the double bond
according to a set of sequence rules.
• If the groups of higher priority are on the same side of the double bond, the compound is said to have the “Z-configuration”
[Z from German word Zusammen meaning together].
• If the groups of higher priority are on the opposite side of the double bond, the compound is said to have the
“E-configuration” [E from German word Entgegen meaning “across”].

high priority high priority high priority low priority

C=C C=C

low priority low priority low priority high priority

(Z) (E)

For a compound with more than one double bond, the configuration of each double bond is specified independently.
To assign relative priorities, proceed through each of the following steps in order until a decision is reached.
Step I: Examine the atoms directly attached to a given carbon of the double bond and then follow the first rule that
applies.
Rule Ia: Assign higher priority to the group containing the atom of “higher atomic number”.
Rule Ib: Assign higher priority to the group containing the “isotope” of higher atomic mass.
Step II: If the atoms directly attached to the double bond, which are the same, then, working outwards from the double
bond, consider within each group the set of attached atoms. You will have two sets – one for each group on the double bond.

Chapter_16.indd 10 3/26/2014 3:27:37 PM

 Isomerism  16.11

Rule II: Arrange the attached atoms within each set Example 1:
in descending priority order and make a pairwise 1 2
­comparison of the atoms in the two sets. The higher
Cl Br
priority is assigned to the atom of higher atomic
­number (or atomic mass in the case of isotopes) at the C=C
first point of difference.
Step III: If the sets of attached atoms are identical, H F
move away from the double bond within each group First consider the relative priorities of the atoms at-
to the next atom following the path of highest priority tached to carbon-1 applying Rule Ia. The two atoms
and identify new sets of attached atoms. Then, apply directly attached to carbon-1 are Cl and H. As Cl has
Rule II to these new sets. Keep following this step higher atomic number (17) than H (1), the Cl atom is
until a decision is reached. Remember that a priority assigned the higher priority. Now, consider the groups
decision must be made at the first point of difference. attached to carbon-2. As per Rule Ia, bromine having
By following the above rules, one can learn how to higher atomic number (35) gets the higher priority
name alkene isomers. than fluorine having atomic number (9).

Atom of higher Atom of higher

priority of carbon-1 Cl Br priority at carbon-2

C=C
Atom of lower H F Atom of lower
priority at carbon-1 priority at carbon-2
(Z) configuration

As the groups of like priority are on same side of the double bond, it is the Z configuration. If the groups of like priority
are on opposite sides of the double bond, it will be the E-configuration.

Higher priority atom Lower priority atom

at carbon-1 at carbon-2
Cl F
C=C
Lower priority atom H Br Higher priority atom
at carbon-1 at carbon-2
(E) configuration

Example 2:

Higher atomic number Higher atomic number

(higher priority) (higher priority)
Br CH3
C=C
Cl H
Lower atomic number Lower atomic number
(lower priority) (lower priority)

(Z) configuration

Chapter_16.indd 11 3/26/2014 3:27:38 PM

 16.12  Objective Chemistry - Vol. I

Higher atomic number Lower atomic number

(higher priority) H (lower priority)
Br
C=C

Lower atomic number Cl CH3 Higher atomic number

(lower priority) (higher priority)

(E) configuration

Example 3:
Higher atomic number 1 2 Low priority at carbon-2
m
(higher priority) Br CH3

C=C

Lower atomic number

(lower priority) Cl eCH2CH3 High priority at carbon-2

When the groups attached to carbon-2 are considered, Step I leads no decision, because in both groups, the atom
directly attached to the double bond is the same. Following Step II represents the atoms attached to these carbons as
a set in descending priority order; for carbon e, the set is (C, H, H), whereas for the carbon m, set is (H, H, H). Now,
make a pairwise comparison of (C, H, H) with (H, H, H). The first point of difference occurs at the comparison of
the first atoms of each set C and H. As ‘C’ has higher priority, the group containing the atom – the ethyl group – has
higher priority. The priority pattern, therefore, is shown above. As the groups of like priority are on opposite sides
of the double bond, it is E-configuration. When the groups of like priority are on same sides of the double bond, it is
Z-configuration.
Higher atomic number High priority
High priority Br CH2CH3

C=C
Lower atomic number Cl CH3 Low priority
Low priority
Example 4:
2 3

mCH
H3C 3
C=C
H
eCH2CH3

First, consider the relative priorities of the groups attached to carbon-2. Applying Rule Ia, the two atoms directly
attached to carbon-2 are C and H. As C has a higher atomic number (6) than H(1), the CH3 group is assigned higher
priority. Now, consider the groups attached to carbon-3, Step I leads no decision, because in both groups, the atom
directly attached to the double bond is the same following Step II represents the atoms attached to these carbons as
a set in descending priority order. For carbon e, the set is (C, H, H); notice that the carbon of the double bond is not
included in the set. For carbon m, the set is (H, H, H). Now, make a pairwise comparison of (C, H, H) with (H, H, H).
The first point of difference occurs at the comparison of the first atoms of each set, C and H. As C has higher priority,
the group containing the atom – the ethyl group – has higher priority. The priority pattern is, therefore,

Chapter_16.indd 12 3/26/2014 3:27:40 PM

 Isomerism  16.13

High priority H3C CH3 Low priority

C=C
Low priority H CH2CH3 High priority
(E)
As the groups of like priority are on opposite sides of the double bond, this alkene is the E isomer; its complete name
is (E)-3-methyl-2-pentene.
If the groups of like priority are on same side of the double bond, then it is called as Z isomer; its complete name will
become (Z)-3-methyl-2-pentane.
High priority H C CH CH High priority
3 2 3
C=C
Low priority H CH3 Low priority
(Z)

Example 5:
CH3

CH2 – CH – CH3

CH3 – CH = C – CH2 – CH2 – CH2 – CH3

The above compound can be represented as follows:
2 3 a1 a2
H CH2 – CH2 – CH2 – CH3
C=C b1 b2
H3C CH2 – CH – CH3

CH3

At carbon-2, the methyl group has higher priority, by Rule Ia. At carbon-3, Rule Ia allows no decision, because atoms
a1 and b1 are identical, both are carbons proceeding to Step II; the set of atoms attached to either carbons a1 and
b1 can be represented as (C, H, H); again no decision is possible. Step III says that we must now consider the next
atoms in each chain along the path of higher priority. We, therefore, move to the next carbon atom (a2 and b2) rather
than the hydrogen in each chain, because carbon has higher priority than hydrogen. The set of atoms attached to a2 is
(C, H, H); the set of atoms attached to b2 is (C, C, H). Notice that carbons a1 and b1 considered in the previous step are not
considered to be the members of these sets, because we always work outwards, away from the double bond, by Step II.
The difference in the second atom of each set C- versus H-dictates a decision. As the set of atoms at carbon b2 has
higher priority, the group containing carbon b2 (the isobutyl group) also has the higher priority. The process used can
be summarized as follows.
(C, H, H) (C, H, H)
H CH2 –– CH2 –– CH2 CH3
C=C a decision is made here
H3C CH2 –– CH(CH3)2
(C, H, H) (C, C, H)

Chapter_16.indd 13 3/26/2014 3:27:41 PM

 16.14  Objective Chemistry - Vol. I

As the groups of like priority are on the same side of the double bond, it has Z-configuration.
group of low priority H CH2 – CH2 – CH2 – CH3 group of low priority
at carbon-2 at carbon-3

C=C

group of high priority H3C CH2 – CH – CH3 group of high priority

at carbon-2 at carbon-3
CH3

(Z) - 3 - isobutyl - 2 - heptene

As the groups of like priority are on opposite sides of the double bond, then it is called E isomer.
group of high priority H3C CH2 – CH2 – CH2 – CH3 group of low priority
at carbon-2 at carbon-3

C=C

group of low priority H CH2 – CH – CH3 group of high priority

at carbon-2 at carbon-3
CH3
(E) - 2 - isobutyl - 2 - heptene

Rule III:
Sometimes, the groups to which we must assign priorities themselves contain double bonds. Double bonds are treated
by a special convention, in which the double bond is rewritten as a single bond and the atoms at each end of the double
bond are duplicated.
– CH = CH2 is treated as – CH – CH2 and – CH = O is treated as – CH – O

C C O C
Notice that the duplicated atoms bear only one bond (the developers of this scheme preferred to say that each of these
duplicated carbons bears “phantom, that is, imaginary atoms of priority zero”). The treatment of triple bonds requires
triplicating the atoms involved.
C C N C

– C ≡ CH is treated as – C – C – H and – C ≡ N is treated as – C – N

C C N C

This convention allows us to establish, for example, the relative priorities of the vinyl and isopropyl groups.
H3C
C– H2C = CH – = CH2 – CH –
H3C
vinyl C C
Isopropyl

The higher priority of the vinyl group is decided by the application of Rule II at carbon-2 of each group.
The following examples illustrate the E,Z nomenclature of compounds with more than one double bond.

Chapter_16.indd 14 3/26/2014 3:27:43 PM

 Isomerism  16.15

H3C CH2 H H CH2 H

C=C C=C C=C C=C

H H H CH2CH3 H H H CH2CH3
(2Z, 5E) - 2, 5 - octadiene (E) - 1,4 - heptadiene
In the second example, no number before E is required because the E,Z designation is only relevant to one of the
double bonds.

Properties of Geometrical Isomers

• cis and trans isomers have different physical properties such as melting points, boiling points, solubilities, dipole­
moments, stability and densities.
• In the compounds such as abC=Cab, if C–a bond has strong bond moment but C–b has not, the “cis isomer” should
have a considerable “overall dipolemoments”.
• In the centrosymmetrical “trans isomer”, the bond moments are opposed and the overall moment is “zero”.
• cis-1,2-dichloro, cis-1,2-dibromo and cis-1,2-diiodo ethylenes have dipolemoments, whereas the dipolemoments of
the corresponding trans isomers are zero.
• As the “trans isomer” has in general greater symmetry than the cis, it fits into the crystal lattice more easily and,
therefore, usually have ‘higher melting point”.
• cis isomers are “more soluble in water” because of their dipolemoments.
• There is no relation to the boiling point to configuration.
• cis and trans isomers have similar but not identical chemical properties.
• Maleic acid (cis isomer) forms anhydride on heating, whereas fumaric acid (trans isomer) does not give anhydride,
because in cis isomer, the two COOH groups are on the same side of double bond.
• The formation of anhydride can be used to distinguish the configuration of maleic acid and fumaric acid.
H – C – COOH ∆ H – C – CO
O + H2O
H – C – COOH H – C – CO
Maleic acid Maleic anhydride

(3) Both (a) and (b)

  Objective Questions (4) None

1. Geometrical isomerism is possible in 4. Which of the following structures permits cis–trans

(1) Butene-2 (2) Ethene isomerism?
(3) Propane (4) Propene (1) X2C=CY2 (2) XYC=CZ2
(3) X2C=CXY (4) XYC=CXY
2. Which of the following compounds will exhibit
cis–trans isomerism? 5. Geometrical isomerism is caused
(1) 2-Butene (2) 2-Butyne (1) by restricted rotation around C=C bond.
(3) 2-Butanol (4) Butanol (2) by the presence of one asymmetric=carbon atom.
(3) by the swing of hydrogen atom between two
3. Dichloroethylene shows poly valent atoms.
(1) Geometrical isomerism (4) due to the different groups attached to the same
(2) Position isomerism functional group.

Chapter_16.indd 15 3/26/2014 3:27:44 PM

 16.16  Objective Chemistry - Vol. I

6. Two geometrical isomers are given by which of the 14. Which of the following pairs represents stereoiso­
following compounds? merism?
(1) Ethlidine bromide (1) Geometrical isomerism, position isomerism
(2) Acetylene tetrachloride (2) Geometrical isomerism, metamerism
(3) Acetylene tetrabromide (3) Optical isomerism, geometrical isomerism
(4) Acetylene dibromide (4) Optical isomerism, tautomerism
7. Of the following compounds, which will have a zero 15. Geometrical isomerism is shown by
dipolemoment?
(1) H Br (2) H I
(1) 1,1-Dichloro ethylene
(2) trans-1,2-Dichloroethylene C=C C=C
(3) cis-1,2-Dichloroethylene
H I H3C Br
(4) None
8. Maleic and fumaric acids are (3) CH3 Cl (4) H Cl
(1) Tautomers C=C C=C
(2) Geometrical isomers
(3) Chain isomers CH3 Br CH3 Cl
   
(4) Functional isomers
9. Geometrical isomerism is shown by 16. How many geometrical isomers are possible for the
given compound?
(1) Alkynes
(2) Suitably substituted alkynes C6H5–CH=CH–CH=CH–COOH
(3) Suitably substituted alkenes (1) 3 (2) 4 (3) 2 (4) 1
(4) Compounds of the type (1) and (2)
17. Priority sequence of which alkyl group is maximum?
10. Which of the following has zero dipolemoment? (1) Tertiary (2) Secondary
(1) cis-2-Butene (3) Primary (4) Methyl
(2) trans-2-Butene
18. Which compound has maximum melting point?
(3) 1-Butene
(4) trans-2-Pentene (1) 1-Butene (2) Butane
(3) cis-2-Butene (4) trans-2-Butene
11. Correct IUPAC name of the structure is
19. In which compound cis–trans nomenclature cannot
CH3– C – H be used?
   is
(1) CH3–CH=CH–COOH
H – C – CH3
(2) C6H5–CH=CH–C6H5
(1) Unsym-dimethyl ethylene (3) C6H5–CH=CHD
(2) Sym-dimethyl ethylene CH3
(3) 1,2-Dimethyl ethylene (4) C  6H5 – CH = C
(4) trans-2-Butene
Cl
12. The isomeric cis-2-butene and trans-2-butene can be
distinguished on the basis of 20. Which is a pair of geometrical isomers? (DPMT
(1) their physical properties. 2002)
(2) their reduction products. (I) Cl Br (II) Cl Br
(3) the products they give on ozonolysis.
(4) the products they give on the addition of ­ C=C C=C
bromine. H Br H CH3
13. Which of the following compounds exhibits (III) Cl CH3 (IV) H Br
­geometrical isomerism?
C=C C=C
(1) C2H5Br (2) (CH)2(COOH)2
(3) CH3CHO (4) (CH2)2(COOH)2 Br H Cl CH3

Chapter_16.indd 16 3/26/2014 3:27:46 PM

 Isomerism  16.17

(1) i and ii (2) i and iii 29. IUPAC name of the following compound is
(3) ii and iii (4) iii and iv Cl CH2CH3
21. Which of the following compounds will exhibit C=C    is
­geometrical isomerism? CH3 I
(1) 1-Phenyl-2-butene (1) trans-2-Chloro-3-iodo-2-pentene
(2) 3-Phenyl-1-butene (2) cis-2-Chloro-3-iodo-2-pentene

(3) 2-Phenyl-1-butene (3) trans-3-Iodo-4-chloro-3-pentene
(4) 1,1-Diphenyl-1-propene (4) cis-3-Iodo-4-chloro-3-pentene
22. The molecule having dipolemoment is 30. The correct structure of trans-2-hexenal is
(1) 2,2-Dimethyl propane CHO
(1)
(2) trans-2-Pentene
(3) Hexane CHO
(4) 2,2,3,3-Tetra methyl butane (2)
23. Geometrical isomerism is shown by
(1) CH2=C (Br) I (3) CHO
(2) CH3 CH=C (Br) I CHO
(3) (CH3)2C=C (Br) I
(4)
(4) CH3CH=CCl2
31. Geometrical isomers are possible for
24. Which of the following statements is wrong?
(1) CH3CH2 – C – CH2CH3
(1) trans-2-Butene has zero dipolemoment.
(2) Maleic acid is less soluble in water than fumaric
NOH
acid.
(3) cis-2-Butene and trans-2-butene are diastereoi- (2) CH3 – CH2 – C – CH3
somers.
(4) Maleic acid and fumaric acid are geometrical O
isomers. (3) CH3CH2 – C – CH3
25. Among the following compounds, the one which can
NOH
show geometrical isomerism is
(1) CH2=CH–CH=CH2 (4) C6H5 – C – C6H5
(2) CH3CH=CH–CH=CH2
(3) CH2=CHCH2CH=CH2 NOH
(4) CH3CH=C=CH2 32. Among of the following compounds, the one which
26. Which of the following compounds does not have does not show geometrical isomerism is
geometrical isomers? (1) C6H5N = NC6H5
(1) 2-Pentenoic acid (2) C6H5CH = CHC6H5
(2) 2-Butenoic acid
(3) 3-Pentenoic acid (3) C6H5 – C = N – OH
(4) 3-Butenoic acid
CH3
27. Geometrical isomerism is not shown by
(1) CH3CH=CH–C≡CCH=CH2 (4) C6H5 – C = N – CH3
(2) CH2=CHC≡CCH=CH2
C6H5
(3) HC≡CCH=CH C≡CH
(4) CH2=CH CH=CH CH=CH2 33. Which of the following compounds has no geometri-
28. Geometrical isomers are possible for cal isomer?
(1) 3-Butenoic acid (1) 1-Phenyl propene
(2) 2-Phenyl propenoic acid (2) 1,2-Diphenyl ethene
(3) 3,3-Diphenyl propenoic acid (3) 1,2-Diphenyl propene
(4) 3-Phenyl propenoic acid (4) 1,1-Diphenyl propene

Chapter_16.indd 17 3/26/2014 3:27:48 PM

 16.18  Objective Chemistry - Vol. I

34. Among the following compounds, the one which can 40. The total number of geometrical isomers of
exhibit geometrical isomerism is ­2,4-hexadiene is
(1) 1,3-Butadiene (1) 2 (2) 3 (3) 4 (4) 5
(2) 1,2-Butadiene
41. The total number of geometrical isomers of 2,4-hexa-
(3) 1,3-Pentadiene
dienoic acid is
(4) 1,4-Pentadiene
(1) 2 (2) 3 (3) 4 (4) 5
35. Which of the following pairs of compounds are geo-
metrical isomers? 42. According to the CIP sequence rule, the correct
­arrangement in order of decreasing priority is
(1) Crotonic acid and cinnamic acid
(2) Maleic acid and malonic acid (1) –OH > –CH2OH > –CHO > –COOH
(3) Ethylene dichloride and ethylidene dichloride (2) –OH > –COOH > –CHO > –CH2OH
(4) Maleic acid and fumaric acid (3) –COOH > –OH > CHO > CH2OH
(4) –COOH > –CHO > –CH2OH > –OH
36. The total number of constitutional isomers having the
molecular formula C2BrCl F I is Answers
(1) 2 (2) 3 (3) 4 (4) 6
  (1) 1   (2) 1   (3) 3   (4) 4   (5) 1
37. Which of the following pairs of compounds are geo-
  (6) 4   (7) 2   (8) 2   (9) 3 (10) 2
metrical isomers?
(11) 4 (12) 1 (13) 2 (14) 3 (15) 2
(1) I Cl F I (16) 2 (17) 1 (18) 4 (19) 4 (20) 3
C=C and C=C (21) 1 (22) 2 (23) 2 (24) 2 (25) 2
(26) 4 (27) 2 (28) 4 (29) 1 (30) 2
F Br Cl Br (31) 3 (32) 4 (33) 4 (34) 3 (35) 4
(36) 2 (37) 4 (38) 2 (39) 4 (40) 2
(2) Br F Cl I
(41) 3 (42) 2
C=C and C=C
Cl I Br F
OPTICAL ISOMERISM
(3) I F Br I
C=C and C=C • An object that is not superimposable on its mirror
­image is called “asymmetric” object.
Br Cl F Cl • In stereochemistry, the word used for disymmetric is
(4) I Cl Br I “chiral”.
C=C and C=C • The opposite word for chiral is “achiral”.
Br Cl • The molecule which is superimposable on its mirror
F F
image is called “achiral”.
38. Geometrical isomerism is possible for the compound • If the four groups attached to the carbon atom are dif-
ferent, then the carbon atom is known as “asymmetric”
(1) 1,1-Dichloropropene
or “chiral centre”.
(2) 1,3-Dichloropropene
(3) 2,3-Dichloropropene • The stereoisomers that are related as an object and
(4) 3,3-Dichloropropene its nonsuperimposable mirror image are called
“enantiomers”.
39. Which of the following statements is not true regard-
• Enantiomers possess “same physical properties” such
ing the cis and trans isomers of an alkene?
as melting point, boiling point and refractive index but
(1) They are configurational isomers. differ in their action towards plane-polarized light.
(2) They are diastereomers.
(3) The cis isomer has higher dipolemoment than the
• Isomers which differ only in the rotation of plane-
trans isomer. polarized light are called “optical isomers” and this
(4) The cis isomer usually has a lower boiling point phenomenon is called “optical isomerism”.
than the trans isomer. • Optical activity is measured using “polarimeter”.

Chapter_16.indd 18 3/26/2014 3:27:49 PM

 Isomerism  16.19

• “Nicol prism” is made with “calcite” a special crystal- • Equimolar mixture of dextro- and laevorotatory
line form of calcium carbonate. ­isomers which has zero optical rotation due to external
• Nicol prism “polarizes” the light, that is, it makes the cancelation is known as “recemic mixture” designated
light vibrating in all directions to propagate in only by “dl” or “±”.
one perpendicular direction and it is called “plane- • The process of conversion of an enantiomer into a
polarized light”. ­recemic mixture is called “recemization”.
• The isomer that rotates the plane-polarized light to the • The separation of optical isomers from recemic
right side is called “dextrorotatory” and designated by ­mixture is known as “resolution”.
“d or (+) sign”. • Optical isomers which are not mirror images, that is,
• The isomer that rotates the plane-polarized light to the not super imposable are called “diastereo isomers”.
left side is called “laevorotatory” and designated by • When “recemic mixture” is allowed to react with an
“l or (−) sign”. enantiomer of some other compound gives a mixture
• The extent of the rotation of plane-polarized light by of “diastereoisomers”.
an optically active compound depends on the wave- • “Diastereoisomers” have different melting points,
length of light, the number of optically active mol- boiling points solubility etc.
ecules in the path of light, that is, the concentration • Depending on the difference in the physical proper-
of the sample, the length of the polarimeter tube, the ties, diastereoisomers are separated and broken down
nature of the solvent and the temperature. to give pure enantiomers.
• The optical activity of different compounds is mea­
sured in terms of specific rotation α. Configurations and Fischer Projection
α obs Formulae
[α ]λ =
T

length of the tube × conc.of the solution gmL−1  • The arrangement of atoms that characters a particular
stereomer is called “configuration”.
T = temperature; λ = wavelength, their values to be
mentioned. • The simplest method of writing the configuration is
“Wedge formula”.
• In the wedge formula, a tetrahedral molecule with
Conditions for Optical Activity four atoms or groups a, b, c and d bonded to it can be
­represented by wedge formula.
• The necessary condition for chirality is not just the
a
presence of asymmetric carbon atoms but the “asym-
metry of the molecules as a whole”.
• A molecule as a whole is asymmetric if it does not d C
possess any element of symmetry such as (i) plane of b
symmetry, (ii) centre of symmetry, (iii) axis of sym-
metry and (iv) alternating axis of symmetry. C
• “A plane of symmetry” of a molecule represents a A solid wedge (or thick line) represents a bond pro-
plane bisecting the molecule such that each half of the jecting above the plane of paper (i.e., bonds pointing
molecule is the mirror image of the other half and is towards observer) and a dashed wedge (or dashed line)
known as “sigma (σ) plane or mirror plane”. represents a bond below the plane (i.e., bond pointing
• “Centre of symmetry” is defined as that point (atom) away from the observer). Solid lines (or continuous
in a molecule from which if a single line is drawn from lines) represent bonds in the plane of the paper.
any part of the molecule through that point (atom) and • Simplification of wedge formula is “Fischer projection
extended to an equal distance by a straight line on the formula”.
other side, a like point is encountered and is known as • Fischer projection formula is a convenient way of de-
“centre of inversion (ci)”. picting three-dimensional structures in two dimensions.
• “Axis of symmetry or axis of rotation” is the imagi- • In the Fischer projection formula, the molecule should
nary line passing through the molecule such that when be drawn in the form of “cross” with chiral carbon at
the molecule is rotated about this line, it presents the the intersection of the horizontal and vertical lines and
same appearance more than once in one complete the four groups attached to the chiral carbon on the
revolution, that is, in a rotation through 360°. four ends of the cross.

Chapter_16.indd 19 3/26/2014 3:27:50 PM

 16.20  Objective Chemistry - Vol. I

• “Horizontal lines” represent the bonds directed towards the viewer and the “vertical lines” away from the viewer.
• If the carbon chain is more than one carbon atom, the chain is written vertically.

COOH COOH COOH

H C ≡ H C OH ≡ H OH

HO CH3 CH3 CH3

• For molecules containing several carbons, it is customary to orient the molecule in such a way so that the carbon chain
is vertical with carbon-1, the most highly oxidized carbon at the top.
Example:

Glyceraldehyde Most oxidized carbon

CHO CHO CHO
visualise the structure such
that the main carbon
H C Η C OH H OH
chain is vertical
HO
CH2OH CH2OH CH2OH

• For writing the Fischer projection formula, rotate the molecule so that horizontal bonds are facing the observer and
two vertical bonds are going away from the observer, and press the molecule flat into the paper, indicating the carbon
of the intersection of two crossed lines.

CH3 CH3
CH3

H C ≡ H C OH ≡ H OH

HO CH2CH3
CH2CH3 CH2CH3

• A single molecule may be represented by different Fischer projection formulae.

• To identify whether the given Fischer projections are same or different, follow the procedure give below.
• To identify the Fischer projections, they should be moved around on the paper, but the structures must not be lifted out
of the plane of the paper and flipped over only two types of motions are allowed.
(1) A Fischer projection can be rotated on the page by 180° but not by 90° or 270°. This does not change the configu-
ration of the molecule.

Chapter_16.indd 20 3/26/2014 3:27:52 PM

 Isomerism  16.21

Example:
COOH COOH CH3 CH3

180º rotation
H C (or) H OH HO H (or) C
HO
HO H
CH3 COOH
CH3 COOH

(I) (II)
In this case, the groups going into and coming out of paper remain the same. Therefore, I and II are identical molecules.
(2) A Fischer projection can have one group steady, whereas the other three rotate in either clockwise or anticlockwise
direction. For example, hold the COOH group steadily and rotate the other three groups anticlockwise or clockwise.
COOH (Hold steady) COOH

H OH same as HO CH3

CH3 H

Nomenclature for Stereoisomers

• The commonly used nomenclature systems for stereoisomers are (i) D and L system, (ii) Erythro and Threo system
and (iii) R and S system.
• In the D and L system, the main chain of the carbon containing the chiral centre is arranged vertically on the page with
the carbon in the higher oxidation state (the one with more C–O bonds at the top). The vertical bonds extend behind
the plane of the page and the horizontal bonds towards the observer.
Carbon is the more oxidised state
– C – –C – (bonded to more oxygen)

H–C–X X–C–H

– C – –C – Carbon is the less oxidised state

(bonded to less oxygen)

• In the molecule projected as above, if the hydrogen is on the left side and another group (x) is on the right side, it is
designated as “D-stereoisomer” and if the hydrogen is on the right side and (x) is on the left side, it is designated as
“L-stereoisomer”.
CHO CHO

H OH HO H

CH2OH CH2OH
D-glyceraldehyde L-glyceraldehyde

Chapter_16.indd 21 3/26/2014 3:27:59 PM

 16.22  Objective Chemistry - Vol. I

• For D and L system of absolute configuration, the D- and L-glyceraldehydes are taken as the standard reference
compounds.
• D-series of sugars are those which have –OH group on the highest number stereo centre on the right and L-series of
sugars have –OH group on the left in the Fischer projection formulae.

CHO CHO

H OH
H OH HO H
H OH
H OH
CH2OH CH2OH
D(+) - glyceraldehyde D – (+) – Glucose
(OH group on right side of chiral carbon)

CHO CHO

HO H
HO H H OH
HO H
HO H
CH2OH CH2OH

L (–) glyceraldehyde L – (–) – Glucose

(OH group on left side of chiral carbon)

• All the compounds that can be prepared starting from D-glyceraldehyde or all the compounds that can be converted
into D-glyceraldehyde belong to D-series of stereoisomers.
• All the compounds that can be prepared starting from L-glyceraldehyde or all the compounds that can be converted
into L-glyceraldehyde belong to L-series of stereoisomers.
• “Erythro and Threo system of nomenclature” is used only in those compounds which have (i) only two chiral carbons
and (ii) compounds having the structure R′–Cab–Cbc–R″, that is, out of six substituents on two asymmetric carbons
“at least two should be same”.
• When two like groups in Fischer projection formula are drawn on the same side of the vertical line, the isomer is called
“erythro form”. If these are placed on the opposite sides, the isomer is said to be “threo form”.
R R CH CH
| | | |
a–c–b a–c–b H – C – OH H – C – OH
| | | |
c–c–b b–c–c H – C – Cl Cl – C – H
| | | |
R11 R11 CH3 CH3

Erythro form Threo form Erythro form Threo form

Chapter_16.indd 22 3/26/2014 3:28:02 PM

 Isomerism  16.23

CH3 CH3 CH3 CH3

| | | |
H – C – OH HO – C – H H – C – OH HO – C – H
| | | |
H – C – Cl Cl – C – H Cl – C – H H – C – Cl
| | | |
CH3 CH3 CH3 CH3

These are enantiomers also known These are enantiomers also known
as Erythro enantiomers as Threo enantiomers
• “R,S-Nomenclature (absolute configuration) system” which indicates the absolute configuration was given by
R.S. Cahn, C.K. Ingold and V. Prelog and known as Cahn-Ingold-Prelog system.
• The three-dimensional arrangement of substituents at a stereogenic centre is called its “absolute configuration”.
• Neither the sign nor the magnitude of rotation of an optically active compound gives its absolute configuration.
• To represent the optical isomers in R,S–system, the steps given below should be followed.
 (i) Identify the chiral centres and the four different groups bound to them.
(ii) Assign priorities to the four different groups according to the rules given in E- and Z-configurations to alkenes.
(The convention used in this text is that the highest priority = 1.)
(iii) View the molecule along the bond from the asymmetric carbon to the group of lowest priority, that is, with the
asymmetric carbon nearer and the low priority group farther away.
 (iv) Consider the clockwise or anticlockwise order of the remaining group priorities. If the priorities of these groups
decrease in the “clockwise direction”, the asymmetric carbon is said to have “R-configuration”. If the priorities of
the groups decrease in the “anticlockwise direction”, the asymmetric carbon is said to have “S-configuration”.
1 1
Br Br
4
4
H H
C C
3
2 2
Cl CH3 H3C Cl
3

S-Configuration R-Configuration
• If a molecule contains more than one chiral carbon atom, then the above procedure may be applied to each chiral
carbon atoms are one by one. For example, 3-bromobutan-2-ol contains two chiral carbon atoms 2 and 3.
4CH
3
H Br

3C

2C

H3C1 H
OH

Chapter_16.indd 23 3/26/2014 3:28:04 PM

 16.24  Objective Chemistry - Vol. I

After assigning the priorities, the configuration around C2 can be predicted as shown below.
CH3 CH3

H Br Br
H
2 2
C C
4
H
C C

3 4 1 3
H3C H HO CH3
OH
1 R-Configuration
Designation of configuration of C-3

3
CH3 CH3

4
H Br Br
H

C C

1
Br
2
C C

H3C H H3C H
OH OH

The molecule is 2R, 3S-3-bromobutan-2-ol S-Configuration

Prediction of the R- or S-configuration from Fischer projection formula:

• The R- or S-configuration for a Fischer projection formula can be assigned by following the simple procedure.
 (i) Assign priorities to four atoms or groups attached to the chiral centre.
 (ii) Observe the order of priority of other groups or atoms leaving the lowest priority group or atom and if the pri-
ority order is in clockwise direction, it is R-configuration. If the priority order is anticlockwise direction, it is
S-configuration. These are observed configuration.
(iii) If the atom or group of the lowest priority occupies horizontal position (right or left) in Fischer projection, then
the actual configuration of the Fischer projection will be opposite to the observed configuration. If the observed
configuration is R, the actual configuration will be S or vice-versa.

Chapter_16.indd 24 3/26/2014 3:28:05 PM

 Isomerism  16.25

Examples:
2
COOH

3
H CH3 The observed configuration is R. As H lies on horizontal position, the actual ­
configuration is S.

1
NH2

1
Br

2 3
H3C D The observed configuration is S. As H lies on vertical position, the actual configuration is
same, that is, S.

1
NH2

3
H3C H The observed configuration is R. As H lies on horizontal position, the actual
configuration is S.

COOH
2

Similarly for the molecules containing more than one chiral carbon.
3CH
3
1
HO H
2′

1′ 2
Cl H
3′
CH3

For the upper asymmetric carbon, the priority order of atoms or groups 1, 2 and 3 is in anticlockwise direction.
Therefore, the observed configuration of upper carbon is S as H is on horizontal line, it is R-configuration. For the
lower asymmetric carbon, the priority of atoms or groups 1′, 2′ and 3′ are in clockwise direction. Therefore, the ob-
served configuration is R. As the H lies on horizontal line, it is S-configuration. Therefore, the molecule is (2R, 3S) 2
chloro-2-butanol.

Chapter_16.indd 25 3/26/2014 3:28:07 PM

 16.26  Objective Chemistry - Vol. I

Molecules with Two or More Chiral Centres

• If a molecule contains two chiral carbon atoms, the different stereoisomers are related as follows.
COOH COOH

H –– C – OH Enantiomers HO –– C – H

H –– C – OH HO –– C – H

CH3 CH3
1 2

Diastereoisomers Diastereoisomers Diastereoisomers

|
COOH COOH

HO –– C – H H –– C – OH

H –– C – OH Enantiomers HO –– C – H

CH3 CH3
3 4
(1), (2), (3) and (4) are stereoisomers; (2) is the mirror image of (1) and not superimposable, so they are enantiomers;
(3) and (4) are enantiomers.
• “Diastereomers are stereoisomers that are not enantiomers”, that is, they are not mirror images and not superimposable.
• In the above figure, 1,3; 1,4; 2,3 and 2,4 are diastereoisomers.
• Stereoisomers with an internal plane are called “meso compounds” and are not chiral.
Example:
CH3 COOH
| |
H –– C –– OH H –– C –– OH
| Plane of symmetry |
H –– C –– OH (mirror plane) H –– C –– OH
| |
CH3 COOH

2,3 dihydroxy butane Tartaric acid

• Meso compounds do not rotate the plane of polarized light due to “internal compensation”.
• For a compound to become meso compound, it should have at least two structurally asymmetric carbon atoms.

The number of optical isomers of a compound having more than one asymmetric atom

• The number of optical isomers of a compound depends on its structure and the number of asymmetric atoms present
in the molecule.
• The number of optical isomers can be calculated by applying the following rules.
• When the molecule cannot be divided into two equal halves, that is, the molecule has no symmetry and n is the
number of asymmetric carbon atoms, then

Chapter_16.indd 26 3/26/2014 3:28:08 PM

 Isomerism  16.27

The number of d- and l- (enantiomeric) forms a = 2n.

The number of mesoforms m = 0.   Objective Questions
The total number of optical isomers = a + m = 2n. 1. Two crystalline forms of a substance, one being a
a mirror image of the other is called
The number of recemic forms r = .
2 (1) Metamer
Example:
(2) Chain isomer
CHO (3) Stereoisomer
(4) Functional isomer
H – C – OH 2. Optical isomerism arises because of the presence of
(1) an asymmetric carbon atom.
HO – C – H (2) a centre of symmetry.
a = 24 = 16
(3) a line of symmetry.
H – C – OH r=8 (4) a plane of symmetry.
  m = 0 3. The total number of optical active isomers for CH2OH
H – C – OH
          Total stereoisomers = 16 + 0 = 16. (CHOH)3CHO is
(1) 16 (2) 8 (3) 4 (4) 2
CH2OH
4. Which of the following has asymmetric carbon atom?
Cl Br H Cl
• When the molecule can be divided into two
equal halves, that is, the molecule has symmetry
and the number (n) of asymmetric carbon atoms is (1) H – C – C – H (2) H – C – C – Cl
even then,
The number of d- and l-forms a = 2n−1. H H H H
The number of mesoforms m = 2(n/2)−1. H Cl H H
The total number of optical isomers
= a + m = 2n−1 + 2(n/2)−1. (3) H – C – C – D (4) H – C – C – CH3
a
The number of recemic mixtures = .
2 H H Br CH3
Example:
CH2OH
| a = 2n−1 = 24−1 = 8 5. Stereoisomers (geometrical or optical) which are nei-
H –– C –– OH a 8 ther superimposable nor mirror image to each other
r= = =4 are called
| 2 2
H –– C –– OH m = 2(n/2)−1 = 2(4/2)−1 = 2
(1) Enantiomers
| (2) Mesomers
H –– C –– OH Total stereoisomers = 8 + 2 = 10. (3) Tautomers
| (4) Diastereoisomers
H –– C –– OH
| 6. Optically active compound is
CH2OH H H

• When the molecule can be divided into two equal (1) HO – C – COOH (2) CH3 – C – COOH
halves (symmetrical) and the number (n) of asym-
metric carbon atoms is odd. H NH2
The total number of d- and l-forms
CH3 CH3
a = 2(n−1) − 2(0.5n− 0.5).
The number of mesoforms m = 2(0.5n− 0.5).
(3) CH3 – C – COOH (4) CH3 – C – COOH
The total number of optical isomers = a + m = 2n−1.
a
The number of recemic mixtures = . H Cl
2

Chapter_16.indd 27 3/26/2014 3:28:11 PM

 16.28  Objective Chemistry - Vol. I

7. The angle of rotation of plane-polarized light 16. The process of the separation of racemic mixture into
depends on d- and l-enantiomer is called
(1) the nature of the light beam. (1) Revolution (2) Resolution
(2) the number of the molecules. (3) Hydration (4) Dehydration
(3) the number of asymmetric carbon atom in the
17. An organic compound will show optical isomerism is
molecule of the substance.
(4) All. (1) Four groups attached to C-atom are different.
(2) Three groups attached to C-atom are different.
8. Rotation of plane-polarized light can be measured by (3) Two groups attached to C-atom are different.
(1) Manometer (2) Calorimeter (4) All the groups attached to C-atom are same.
(3) Polarimeter (4) Viscometer
18. The property by virtue of which, a compound can
9. Which of the following is an optically active turn the plane-polarized light is known as
­compound? (1) Photolysis (2) Phosphorescence
(1) CH3CH2COOH (3) Optical activity (4) Polarization
(2) CH3CHOHCOOH
19. Which of the following may exist in enantiomorphs?
(3) HOOCCH2COOH
(4) CH3COCOOH (1) CH3 – CH – COOH
|
10. Which of the following would be optically active or CH3
possess a chiral structure?
(2) CH3 = CHCH2CH2CH3
(1) Tertiary-butanol
(2) Sec-butanol (3) CH3 – CH – CH3
(3) n-Butanol |
(4) 1-Chloro-4-hydroxybutane NH2
11. Addition of Br2 on cis-butene-2- gives (4) CH3 – CH2 – CH – CH3
(1) a racemic mixture of 2,3-dibromobutene. |
(2) mesoform of 2,3-dibromobutane. NH2
(3) dextro form of 2,3-dibromobutane.
(4) laevo form of 2,3-dibromobutane. 20. Which of the following is optically active?
(1) n-Propanol (2) 2-Chlorobutane
12. The compound which exhibits optical isomerism
(3) n-Butanol (4) 3-Hydroxy pentane
(1) CH3CHOHCH3
(2) (CH3)2CHCH2CH3 21. A compound contains two dissimilar asymmetric car-
(3) CH3CHClCH2CH3 bon atoms. The number of optically active isomers is
(4) CH3CCl2CH2CH3 (1) 2 (2) 3 (3) 4 (4) 5
13. Addition of Br2 to trans-butene-2 gives 22. Which of the following compounds can exhibit
(1) a racemic mixture of 2,3-dibromo butane. ­optical isomerism?
(2) meso form of 2,3-dibromo butane. (1) CH3 H (2) CH3 H
(3) dextro form of 2,3-dibromo butane.
(4) laevo form of 2,3-dibromo butane. C C

14. Meso tartaric acid is optically inactive because of the CH3 COOH COOH
C2H5
presence
(1) molecular symmetry. (3) CH3 (4) H H
H
(2) molecular asymmetry.
(3) external compensation. C C
(4) two asymmetric carbon atoms.
H COOH HO COOH
15. Which of the following compounds can exist in opti-
cally active form? 23. Mesotartaric acid is
(1) 1-Butanol (2) 2-Butanol (1) Optically active (2) Racemic mixture
(3) 3-Pentanol (4) 4-Heptanol (3) Optically inactive (4) Geometrical isomer

Chapter_16.indd 28 3/26/2014 3:28:13 PM

 Isomerism  16.29

24. d-Tartaric acid and l-tartaric acid are (3) structural change occurs.
(1) Structural isomers (4) spatial arrangement is changed.
(2) Diastereoisomers 34. Lactic acid shows optical activity in
(3) Tautomers
(1) solution state (2) liquid state
(4) Enantiomers
(3) crystalline state (4) all states
25. An optically active compound has three different
35. A racemic mixture is a mixture of
asymmetric carbon atoms. The number of possible
isomers is (1) meso and its isomers.
(2) d- and its l-isomers in equal proportions.
(1) 2 (2) 4 (3) 6 (4) 8
(3) d- and its l-isomers in different proportions.
26. Lactic acid CH3CH(OH)COOH molecule shows (4) meso and d-isomers.
(1) Geometrical isomerism 36. The production of an optically active compound from
(2) Metamerism a symmetric molecule without resolution is called
(3) Optical isomerism
(1) Walden inversion.
(4) Tautomerism
(2) Asymmetric synthesis.
27. Two optically active isomers of a substance which are (3) Partial racemization.
related to each other as plane mirror image of each (4) None.
other are called
37. How many optically active forms are possible for a
(1) Enantiomers (2) Metamers compound of the formula CHO ∙ CHOH ∙ CHOH ∙
(3) Diastereomers (4) None CHOH ∙ CH2OH?
28. Optically active isomers are called (1) 2 (2) 4 (3) 3 (4) 8
(1) Epimers (2) Anomers 38. Which one of the starred carbons is the asymmetric
(3) Conformers (4) Enantiomers one?
29. Which is optically active? *
(1) CH3 CH2 – CH – CH2 – CH2OH
(1) Isobutyric acid |
(2) β-Chloropropionic acid Cl
(3) Propionic acid *
(4) α-Chloropropionic acid (2) CH3 CH2 CH2 CH2 CH2OH
30. Which is incorrect about enatiomorphs? *
(3) CH3 CH2 CH2 CH2 CH2OH
(1) They rotate the plane of polarized light in
*
­different directions. (4) CH3 CH2 CH2 CH2 CH2OH

(2) They have mostly identical physical properties.
(3) They have same configuration. 39. The structure CH3 H shows
(4) They have different biological properties.
31. An important chemical method to resolve a racemic C=C H
mixture makes use of the formation of
(1) meso compound CH3 C – COOH
(2) enantiomer
|
(3) racemers
CH3
(4) diastereoisomers
(1) geometrical isomerism.
32. The number of asymmetric carbon atoms in a mol-
(2) optical isomerism.
ecule of glucose is
(3) geometrical and optical isomerism.
(1) 6 (2) 4 (3) 5 (4) 3 (4) tautomerism.
33. The reason of the loss of optically activity of lactic 40. Lactic acid in which a methyl group, a hydroxyl
acid when OH group is exchanged by H is that group, a carboxylic acid group and a hydrogen atom
(1) asymmetry of the molecule is destroyed. are attached to a central carbon atom shows optical
(2) symmetry of the molecule is destroyed. isomerism due to molecular geometry at the

Chapter_16.indd 29 3/26/2014 3:28:14 PM

 16.30  Objective Chemistry - Vol. I

(1) carbon atom of the methyl group. 46. Stereoisomerism can be exhibited by compounds
(2) carbon atom of the carboxylic acid group. possessing
(3) central carbon atom. (1) one chiral centre
(4) oxygen of the hydroxyl group. (2) two chiral centres
41. Which of the following compounds is chiral and (3) unsymmetrical molecule
hence optically active? (4) All of these
Cl Br 47. If optical rotation produced by the compound (i) is
| | +52° then that produced by the compound (ii) is
(1) CH3 – C – Br (2) CH3 – C – H
| | CH3 CH3
I H Cl H H Cl
CH3 Br H Cl Cl H
| |
(3) CH3 – C – Cl (4) CH3CH2 – C – CH3 CH3 CH3
| |
CH3 Br (i) (ii)

(1) −52°
42. Which of the following is optically active? (2) +52°
(1) Alanine (2) 2-Butanol (3) 0°
(3) Lactic acid (4) All (4) unpredictable
43. The number of asymmetric carbon atoms and the 48. The number of stereoisomers of 2,3,4-trichloro­
number of optical isomers CH3(CHOH)2 COOH are, pentane is
respectively, (1) 6 (2) 5 (3) 4 (4) 3
(1) 3 and 4 (2) 1 and 3
(3) 2 and 4 (4) 2 and 3 49. Which of the following does have a meso isomer?
(1) 2,3-Butanediol
44. Which of the following will show stereoisomerism? (2) 2,3-Dibromobutane
Br (3) 2,3-Dibromopentane
|
(4) tartaric acid
(1) CH3 – CH2 – C – CH3
| 50. The number of asymmetric carbons in 3-bromo-2-­
Cl butanol is
Br (1) 1 (2) 2 (3) 3 (4) 4
|
51. Which is a chiral molecule?
(2) CH3 – CH2 – C – CH3
| (1) 3-Methyl pentanoic acid
Br (2) 3,3-Dimethyl butanoic acid
CH3 (3) 2,2-Dimethyl butanoic acid
(3) CH3 – CH = C (4) 1-Methyl pentanoic acid
CH3
H 52. The number of possible enantiomeric pairs that can
| be produced during monochlorination of 2-methyl
(4) CH3 – CH2 – C – Br butane is
| (1) 2 (2) 3 (3) 4 (4) 1
H
53. The conversion of enantiomer into racemic mixture is
45. Optically active compound among the following is known as
(1) 2-Ethylbutanol-1 (1) Resolution
(2) n-Butanol (2) Recemization
(3) 2,2-Dimethyl butanol (3) Revolution
(4) 2-Methyl butanol-1 (4) Inversion

Chapter_16.indd 30 3/26/2014 3:28:18 PM

 COOH CHO
(3) H OH (4) HO H
H OH H OH
HO H
Isomerism  16.31
CH2OH CH2OH
54. First member of optically active alkene is 57. Which configuration is erythro?
CH3
| CHO CHO
(1) C2H5 – C – CH = CH2 (1) H Br (2) H D
|
H H Br H H
C2H5 C6H5 C6H5
|
CHO COOH
(2) C3H7 – C – CH = CH2
| (3) H Br (4) H D
H
Br H HO H
C2H5
| C6H5 CH3

(3) C3H7 – C – CH = CH2
|
58. Consider the following statements.
CH3
(I) Meso form is optically inactive because of the
C2H5 ­absence of disymmetry in the molecule.
|    (II) Compound will be optically active if it is
(4) C6H11 – C – CH = CH2 ­disymmetric molecule.
|  (III) Geometrical isomers are stereoisomers.
CH 3 (IV) Physical properties of stereoisomers are
­different.
55. Consider the following pair of compounds
Select the correct answer from the codes given below.
CHO CH3 (1) Only IV is correct
H OH HO H (2) I, II, III and IV are correct
H (3) I, II and IV are correct
HO H OH
(4) II, III and IV are correct
C6H5 C6H5
59. Which among the following pairs are diastereomers?
(I) (II)
(I) CH CH CH H
Which among the following statements are ­correct?
(i) Both are enantiomers. (ii) Both are in threo C=C and C=C
form. (iii) Both are diastereomers. (iv) Both are in
H H H CH3
erythro form.
(1) i, ii (2) i, ii, iii COOH COOH
(3) ii, iii (4) iii, i
(II) H OH HO H
56. Which among the following compounds has (l) con-
figuration? HO H H OH
CHO CH3 CH2OH
CH2OH
(1) H OH (2) H NH2
CHO CHO
CH2OH COOH
(III) H OH HO H
COOH CHO
CH2OH CH2OH
(3) H OH (4) HO H
(IV) Br I I Br
H OH H OH
HO H C=C and C=C
CH2OH CH2OH Cl F F Cl

CHO CHO
(1) H Br (2) H D
Chapter_16.indd 31 3/26/2014 3:28:21 PM
 CH3 CH3
CH3 CH3
(3) H OH H OH
and
HO H H OH
16.32  Objective Chemistry - Vol. I
CH3 CH3
Select the correct answer from the codes given below. CH3 CH3
(1) only II (2) only I
(4) HO H HO H
(3) I and II (4) I, II and IV and
60. Which among the following compounds shows H OH HO H
­geometrical isomerism? CH3 CH3
 (I) 1-Butene  (II)  2-Butene
(III) 2-Methyl-2-butene (IV)  2-Pentene 64. The absolute configuration of the following com-
(1) II, III (2) II, III, IV pounds is (AIIMS 2003)
(3) II, IV (4) I, II, IV CH3
H Cl
61. Correct statement about the compounds A, B and C is
COOCH COOH COOH Cl H
3
H OH H OH H OH CH
2 5
(1) 2S, 3R (2) 2S, 3S
H OH H OH HO H
(3) 2R, 3S (4) 2R, 3R
COOH COOCH3 COOCH3
65. Among the following structures I to IV
(A) (B) (C)  (AIIMS 2003)
(1) A and B are identical. CH3 O CH3
(2) A and B are diastereomers.
(3) A and C are enantiomers. C2H5 – CH – C3H7 CH3 – C – CH – C2H5
(4) A and B are enantiomers.
I II
62. An enantiomerically pure acid is treated with racemic
H CH3
mixture of an alcohol having one chiral carbon. The
ester formed will be (IIT JEE Screening 2003)
H – C+ C2H5 – CH – C2H5
(1) Optically active mixture.
|
(2) Pure enantiomer.
(3) Mesocompound. H
(4) Racemic mixture. III IV
63. Which of the following pairs of compounds are enan- It is true that
tiomers? (CBSE 2003) (1) only II and IV are chiral compounds.
CH3 CH3 (2) all four are chiral compounds.
(3) only I and II are chiral compounds.
(1) H OH and HO H (4) only III is a chiral compound.
HO H H OH 66. A compound whose molecules are superimposable on
their mirror images even though they contain asym-
CH3 CH3 metric carbon atom is called (Kerala MEE 2003)

CH3 (1) a meso compound. (2) an erythro isomer.
CH3
(3) a threo isomer. (4) a glycol.
(2) H OH HO H (5) an electric compound.
and
HO H HO H 67. The two optical isomers given below namely
CH3 CH3  (Kerala EEE 2003)
CH CH3
CH3 CH3 3

(3) H OH H Cl H Cl
H OH and
and
HO H H OH Cl H H Cl
CH3 CH3 C2H5 C2H5

CH3 CH3
(4) HO H HO H
and
Chapter_16.indd 32 H OH HO H 3/26/2014 3:28:26 PM
 Isomerism  16.33

(1) enantiomers a mixture of 25% (−) mandelic acid and 75% (+)
(2) geometrical isomers ­mandelic acid? (SCRA 99)
(3) diastereomers (1) +118.5° (2) −118.5°
(4) structural isomers (3) −79° (4) +79°
(5) conformational isomers
76. The optically active tartaric acid is named as D-(+)-
68. A similarity between optical and geometrical isomer- tartaric acid, because it has a positive (IIT 99)
isms is that (AIEEE 2002) (1) optical rotation and is derived from D-glucose.
(1) each forms equal number of isomers for a given (2) pH in organic solvent.
compound. (3) optical rotation and is derived from D-(+)-­
(2) if in compound, one is present then so is the glyceraldehyde.
­other. (4) optical rotation only when substituted by
(3) both are included in stereoisomerism. ­deuterium.
(4) they have no similarity. 77. IUPAC name of the compound is  (CBSE 98)
69. A compound with molecular formula C7H16 shows Cl CH2CH3
optical isomerism, the compound will be C=C
 (CBSE 2001)
CH I
(1) 2,3-dimethyl pentane. 3
(2) 2,2-dimethyl pentane. (1) trans-2-chloro-3-iodopentene-2
(3) 2-methyl hexane. (2) cis-2-chloro-3-iodo-2pentene
(4) None of these. (3) trans-3-iodo-4-chloro-3-pentene
(4) cis-3-iodo-4-chloro-3-pentene
70. Consider the following organic compound
78. An important chemical method to resolve a racemic
1 2 3 4 5 6 7
mixture makes uses of the formation of (CBSE 94)
CH3 – CH2 – CH2 – CH2 – CH2 – CH2 – CH3
(1) a mesocompound (2) enantiomers
To make it chiral compound, the attack should be on (3) diastereomers (4) racemates
carbon (CEE Delhi 2001) 79. An organic compound C4H8O is found to be ­optically
(1) 1 (2) 3 (3) 4 (4) 7 active. Which of the following could it be?
71. The (R)- and (S)-enantiomers of an optically active  (ISM Dhanbad 94)
compound differ in (CBSE 2000) (1) CH3COCH2CH3
(1) their reactivity with achiral reagents. (2) CH3CH2CH2CHO
(2) their optical rotation of plane-polarized light. (3) (CH3)2CH–CHO
(3) their melting points. (4) CH2=CH–CH(OH)–CH3
(4) their solubility in achiral reagents. 80. Which of the following will have a mesoisomer also?
 (AIEEE 2004)
72. HO – – CH = CH – CH – COOH will
show | (1) 2-Chlorobutane
OH (2) 2,3-Dichloro butane
(3) 2,3-Dichloro pentane
 (CEE Delhi 2000)
(4) 2-Hydroxy propanoic acid
(1) Geometrical isomerism
(2) Optical isomerism 81. Two isomeric alkenes A and B having molecular for-
(3) Geometrical and optical isomerisms mula C5H9Cl on adding H2, A gives optically inactive
(4) Neither geometrical nor optical isomerism compound, whereas B gives a chiral compound. The
two isomers are
73. The number of stereoisomers for pent-3-en-2-ol is (1) A is 4-chloro-2-pentene and B is 4-chloro-1
(1) 2 (2) 4 (3) 3 (4) 5 ­pentene.
74. The number of stereoisomers of the compound (2) A is 3-chloro-2-pentene and B is 2-chloro-2
2-chloro-4-methylhex-2-ene is (Hen CEET 2000) ­pentene.
(3) A is 2-chloro-3-methyl-2-butene and B is
(1) 1 (2) 2 (3) 4 (4) 16
1-­chloro-3-methyl-1butene.
75. (+) Mandelic acid has a specific rotation of +158°. (4) A is 3-chloro-1-pentene and B is 1-chloro-2­
What would be the observed specific rotation of ­pentene.

Chapter_16.indd 33 3/26/2014 3:28:28 PM

 16.34  Objective Chemistry - Vol. I

82. An optically active alkene with molecular formula 89. In which of the following structures is the central car-
C6H12 which upon hydrogenation gives optically bon (C-3) not a chiral centre?
­inactive alkane is CH3 CH3
(1) 2-methyl-2-pentene
(2) 3-methyl-2-pentene (1) H OH (2) H Br
(3) 2-hexene
(4) 3-methyl-1-pentene H Br H OH
83. The total number of optically active and mesoforms H Br H Br
possible for the compound
HO2C–CHOH–CHOH–CHOH–COOH CH3 CH3
(1) 3,2 (2) 4,4
(3) 2,3 (4) 2,2 CH3 CH3
84. Select the S-isomer from the following (3) Br H (4) Br H
Cl CH3
(1) Br F (2) Cl H H OH HO H
H CH2CH3 Br H H Br

CH2CH3 COOH CH3 CH3

(3) H CH3 (4) H OH
90. Which of the following compounds does not have
CH2OH CH3 ­diastereoisomers?

(1) 2,3-Butanediol
85. The necessary and sufficient condition for a molecule (2) 2,3-Dibromo pentane
to be optically active is that (3) 2-Butene
(1) it must contain asymmetric carbon atoms. (4) 2-Butanol
(2) it must be asymmetric. 91. Fischer projection indicates (Gate 1996)
(3) it must be identical with its mirror image.
(1) Horizontal substituents above the plane.
(4) it must be nonidentical with its mirror image.
(2) Vertical substituents above the plane.
86. A molecule is said to be chiral only if (3) Both horizontal and vertical substituents below
(1) it is superimposable on its mirror image. the plane.
(2) it is nonsuperimposable on its mirror image. (4) Both horizontal and vertical substituents above
(3) it possess stereogenic centres. the plane.
(4) it can have different configurations.
87. Which of the following compounds has an achiral Answers
stereoisomer known as mesoisomer?
(1) 3-Bromo-2-butanol   (1)  3   (2)  1   (3)  2   (4)  3   (5)  4   (6)  2
(2) 2,3-Pentanediol   (7)  4   (8)  3   (9)  2 (10)  2 (11)  1 (12)  3
(3) 2,3-Dibromobutane (13)  2 (14)  1 (15)  2 (16)  2 (17)  1 (18)  3
(4) 2,3-Dibromobutanoic acid (19)  4 (20)  2 (21)  3 (22)  2 (23)  3 (24)  4
(25)  4 (26)  3 (27)  1 (28)  4 (29)  4 (30)  3
88. The observed rotation of 2.0 g of a compound in (31)  4 (32)  2 (33)  1 (34)  4 (35)  4 (36)  2
10 ml solution in a 25-cm-long polarimeter tube is (37)  4 (38)  1 (39)  2 (40)  3 (41)  1 (42)  4
+13.4°. The specific rotation of the compound is (43)  3 (44)  1 (45)  4 (46)  4 (47)  1 (48)  4
(1) +30.2° (49)  3 (50)  2 (51)  1 (52)  1 (53)  2 (54)  1
(2) −26.8° (55)  1 (56)  3 (57)  1 (58)  2 (59)  4 (60)  3
(3) +26.8° (61)  4 (62)  1 (63)  1 (64)  2 (65)  3 (66)  1
(4) +40.2° (67)  3 (68)  3 (69)  1 (70)  2 (71)  2 (72)  3

Chapter_16.indd 34 3/26/2014 3:28:29 PM

 Isomerism  16.35

(73)  2 (74)  4 (75)  4 (76)  3 (77)  1 (78)  3 H H H

H
(79)  4 (80)  2 (81)  2 (82)  4 (83)  4 (84)  2
(85)  4 (86)  2 (87)  3 (88)  3 (89)  4 (90)  4
(91)  1
H H
H
H H H HH
Sawhorse projection views Newman projection views the
CONFORMATIONAL ISOMERISM the C–C bond from an C–C bond directly and shows
• When different shapes of the same molecule are in- oblique angle and shows the front carbon atom and shows
terconvertible on rotating a bond, they are known as all C–H bonds. that the second carbon is behind
conformational isomers. the first carbon and cannot be
seen; only H-atoms are visible.
• Conformational isomers can be represented by
Sawhorse representations or Newman projections. • Staggered conformation C–H bonds on each carbon
atom are as far apart as possible.
H
H H H H
Conformations of Ethane H
• Rotation around the C–C bond produces two distinc-
tive conformations. H
H H H H
• Eclipsed conformation C–H bonds on each carbon H
atom are as close as possible. Sawhorse projection Newman projection

• The staggered conformation is more stable as the C–H bonds are further apart. The energy difference between them
(12 kJ mol−1) is known as the “torsion strain”.
• The energy difference is relatively small and hence there is free rotation about the C–C bond at room temperature.
• The angle between the C–H bonds on the front and back carbons is known as the “dihedral” or “torsional” angle.
Rotate rear carbon atom S = Staggered conformer
HH E = Eclipsed conformer
H
H T = Torsional energy
dihedral H Rotation
E
angle
HH
H H HH T
S
H
High energy
Low energy 0 60 120 180 240 300 360
Dihedral angle
• “Eclipsed” bonds are characters by torsion angle of 0°. When the torsional angle is 60°, the conformer is “gausche”,
whereas when it is 180°, the conformer is known as “anti” or “staggered”.
• Torsional strain in eclipsed ethane is due to the repulsion of electron pairs of adjacent C–H bonds.
• Each pair of electrons (C–H bond pair) when eclipsed show a torsional strain that leads to an energy cost of about
1 k.Cal/mol (4.2 kJ/mol) for rotation. Thus, in ethane, the total torsional strain is about 3 k.Cal /mol (12 kJ/mol).

Conformations of Butane
• In butane and related compounds (A–CH2–CH2–A, a 1,2-disubstituted ethane), there are four extremes.
 (i) A fully eclipsed conformation, that is, “syn-periplanar”.
 (ii) A partly eclipsed conformation, that is, “anticlinal”.
(iii) A fully staggered conformation, that is, “anti-periplanar”.
 (iv) A staggered conformation, that is, gauche or “syn-clinal”.

Chapter_16.indd 35 3/26/2014 3:28:34 PM

 16.36  Objective Chemistry - Vol. I

• The anti-periplanar conformation is the most stable as the two methyl groups are as far apart as possible (180°
separation).
• The gausche (or synclinal) conformation is higher in ­energy (by 4 kJ mol−1) as the two methyl groups are nearer each
other (60° separation) resulting in “steric strain”.
• The eclipsed conformations not only have torsional strain but also have additional Van der Waal’s repulsion because of
eclipsed CH3, H; H, H and CH3, CH3 groups.
• If the interconversion is sufficiently slow under a given set of conditions and can be separated, the two conformers are
called “atrope isomers”.

steric strain
CH3 CH3
H H
H H H CH3 H CH3
Rotation
C CH3 C CH3
H3C C H H C
H H H H H
H H
CH3 H
anti-conformation gauche conformation
(more stable) (less stable)

Conformations of Cycloalkanes
• The shape of cycloalkane is determined by torsional strain (Pitzer strain), steric strain and angle strain.
• “Angle strain” is the extra energy that a compound has because of non-ideal bond angles, for example, for an sp3
­hybridized carbon atom, the ideal bond angle is 109.5° (tetrahedral). Angles above or below 109.5o produce angle
strain. This is also known as “Baeyer strain”.
• A three-membered ring has the highest and a five-membered ring has the lowest angle strain. Above five, the angle
strain increases as the ring gets larger.
• Total strain = angle strain + steric strain + torsional strain
• A three-membered ring has the highest total strain which reaches a minimum for a six-membered ring.
• Cycloalkanes can adopt different conformations (or shapes) cyclopropane is flat; cyclobutane can form butterfly shape,
whereas cyclopentane can form an open-envelop shape.

H H H H H H
H H
H H
H H H H
H H
H H
H H
H H
H
H
Cyclobutane
Cyclopropane Butterfly Cyclopentane
C – C angle 60º open envelop

• Cyclopropane has to be planar and, therefore, has very strained bond angles of 60° and a great deal of torsional energy.
• Cyclobutane and cyclopentane can adopt non-planar (puckered) shapes, which decrease the torsional strain by
­straggered the C–H bonds. However, this is at the expense of angle strain, and the butterfly and open envelop shapes
­represent the best compromise between the two opposing effects.

Chapter_16.indd 36 3/26/2014 3:28:39 PM

 Isomerism  16.37

Cyclohexane
• Cyclohexane adopts the chair or boat conformation, which are both free of angle strain.
H H
H H H H
H 5 H H
H H H H 3 H
H 5
H H H
H H H H
1 H H 3 1 4 H 1
H H H H
H
H H H H H H
Chair Steric strain Chair
(strain free) Boat (strain free)
Newman projections
H H
H H
H H H H
H 4
H H 1
2
H
6 2 6
4
6 2 H HH
H H H
1 H
1 H 4
H H H H
Chair Boat Chair
• The chair conformation has six axial and six equatorial hydrogens. On ring flipping, the axial hydrogens become
equatorial hydrogens become axial.
Ha
Ha He Ha
He
He Ha = axial hydrogen (point up and down)
He He = equatorial hydrogen (point sideways)
He
He Ha   
Ha Ha

• The boat conformation is less stable because of steric strain between C1 and C4 (flag pole) hydrogens.
• The two chair forms can interconvert via the boat form in a process known as ring-flipping.
• If a substituent (X) is present, then this prefers to sit in an equatorial position.
• The equatorial conformer is lower in energy because steric strain (or 1,3- diaxial interactions) raised the energy of the
axial conformer.
• With the increase in size of the X group, the proportion of the equatorial conformer at equilibrium also increases.
X
X % eq % axial
H
Me 95 5
X
t-Bu >99 <1
H
axial conformer equatorial conformer
X
Ha
Ha

1,3 - diaxial interactions (unfavourable)

Chapter_16.indd 37 3/26/2014 3:28:42 PM

 16.38  Objective Chemistry - Vol. I

• For disubstituted cyclohexanes, both should occupy in equatorial position. When this is not possible, then the largest
group (e.g., a t-Bu group rather than an Me group) will occupy the equatorial position.

X
X tBu
X
Me
X The bulkier t-Bu group prefers
diaxial conformer diequatorial conformer   the equatorial position
When the two substitutes on the ring are both pointing up (or both pointing down), these cyclic compounds are
designated “cis” stereoisomers. When one substituent is pointing up and the other down, these cyclic compounds are
designated “trans” stereoisomers.
H
Br Up
Br Down
H
Me Up
Me up
H
cis - 1 - Bromo - 2 - methyl trans - 1 - bromo - 2 - methyl
cyclohexane cyclohexane

• In the case of ethylene glycol, CH2OH CH2OH and related compounds R CHOH CH(R)OH exist in considerable
amounts of gausche form in equilibrium because of hydrogen bonding between two OH groups, despite the steric and
dipolar repulsions of the hydroxyl groups. (Repulsions outweigh the energy gained by hydrogen bond).
H H
H | R |
R
H O H O
H OH
H H

HO R O H O
H
R R
R
anti gausche dl- form R groups anti
(no hydrogen bonding) (hydrogen bonding) (hydrogen bonding)
 (i) When R is methyl or n-amyl, both the meso and dl forms exist to a considerable extent in the conformation in
which the hydroxyl groups are gausche to each other even though, in the meso form, this requires the alkyl groups
to be gausche also.
 (ii) When R is isopropyl, and even more, that is, when R is t-butyl, the conformational isomer of the meso form in
which the butyl R groups are gausche contributes little or nothing.
(iii) As the R groups become bulkier, the hydrogen bond becomes stronger presumably because the hydroxyl groups
(one in the case of the meso form, both in the dl form) bend away from the bulky gausche alkyl group on the
adjacent carbon thus move towards each other.

  Objective Questions 2. The number of conformations of ethane is

(1) 1 (2) 2 (3) 3 (4)  infinite
1. Isomers which can be interconverted through rotation
around a single bond are 3. The most stable conformations of ethane is
(1) position isomers (2) enantiomers (1) boat form (2) chair form
(3) metamers (4) conformers (3) eclipsed form (4) staggered form

Chapter_16.indd 38 3/26/2014 3:28:45 PM

 Isomerism  16.39

4. At room temperature, the eclipsed and staggered CH3

forms of ethane cannot be isolated because H H
(1) both the conformers are equally stable.
(2) they interconvert rapidly. 2
(3) there is a large energy barrier of rotation about H
H
the σ bond.
CH3
(4) the energy difference between conformers is
large. (1) Fully eclipsed conformation.
5. Most stable form of cyclohexane is (2) Partially eclipsed conformation.
(3) Gausche conformation.
(1) boat
(4) Staggered conformation.
(2) chair
(3) skew 10. Which of the following rings is most strained?
(4) eclipsed (1) cyclohexane
(2) cyclopentane
6. What are the types of isomers in following pairs?
(3) cyclobutane
H
(4) metamer
H CH3 H CH3
11. The carbon–carbon bond angles in chair and boat
conformations of cyclohexane, respectively, are
H (1) 109.5°, 109.5°
H H (2) 109.5°, 120°
H
H CH3 CH3 (3) 120°, 109.5°

(1) conformers (2) position (4) 120°, 120°
(3) optical (4) geometrical 12. The most stable conformation of chlorohydrin at
7. Which type of conformation is shown by I and II? room temperature is
H (1) fully eclipsed
H H HH (2) partially eclipsed
(3) gausche
(4) staggered
H H H 13. In the following structures, which two forms are stag-
H
H H H gered conformation of ethane?
I II H
(1) I is eclipsed, II is staggered. H H
(2) II is eclipsed, I is staggered. H
H H
(3) Both are eclipsed.
(4) Both are staggered.
H
8. The correct order of stability of different conformers H H H H
H
of n-butane is
I II
(1) eclipsed < skew < antiform < completely eclipsed
(2) completely eclipsed < eclipsed < skew < HH
H
­antiform H
(3) completely eclipsed < skew < eclipsed <
­anti form
(4) eclipsed < completely eclipsed < skew < H H H H
H H H H
­antiform
III IV
9. In a given conformer C2 is rotated about C2–C3 bond
anticlockwise by an angle of 120°, then the formation (1) I and IV (2) II and III
obtained is (3) I and II (4) I and III

Chapter_16.indd 39 3/26/2014 3:28:48 PM

 16.40  Objective Chemistry - Vol. I

14. Torsional strain in eclipsed form of ethane is due to (1) 2 and 2 (2) 4 and 2
(1) the repulsion of electron pairs of adjacent C–H (3) 2 and 4 (4) 2 and 1
bonds of the two different carbon atoms. 5. The number of possible enantiomeric pairs that can
(2) the repulsion of electron pairs of adjacent C–H be produced during monochlorination of 2-methyl
bonds of the same carbon atom. butane is
(3) the repulsion of electron pairs of C–C bond and
(1) 2 (2) 3 (3) 4 (4) 1
C–H bonds.
(4) the attraction between the atoms on both carbon 6. The percentage of enol content is greatest in
atoms. (1) acetone (2) butane
OH OH (3) diethyl ketone (4) 3-oxobutanal
15. About the conformers of R – CH – CH – R, the 7. Energy barrier between staggered and eclipsed
­correct statement is ethane is
(1) the gausche conformer is more in equilibrium (1) 0.6 k.cal/mole (2) 2.9 k.cal/mole
because of hydrogen bonding between the OH (3) 12 k.cal/mole (4) 11 k.cal/mole
groups.
(2) with the increase in the size of R groups, the 8. Chair form of cyclohexane is more stable than that of
strength of hydrogen bonding increases, boat form because
(3) the strength of hydrogen bond outweighs the (1) in chair form, all the six carbons are in staggered
­steric and dipolar repulsions. form, whereas in boat form, two carbons are in
(4) hydrogen bonding is not possible in anti-­ eclipsed form.
conformation with respect to R-groups. (2) in chair form, all the six carbons are in staggered
form, whereas in boat form, all the carbons are in
eclipsed form.
Answers (3) Bond angle in chair form is 111°, whereas bond
angle in boat form is 109.5°.
  (1)  4   (2)  4   (3)  4   (4)  2   (5)  2   (6)  1 (4) Bond angle in chair form is 109.5°, whereas in
  (7)  2   (8)  2   (9)  3 (10)  3 (11)  1 (12)  3 boat form is 111°.
(13)  3 (14)  1 (15)  2
9. Flag pole interaction is present in
(1) boat form of cyclohexane.
(2) chair form of cyclohexane.
  Practice Exercise Level-1 (3) anti form of n-butane.
(4) fully eclipsed form of n-butane.
1. 2-Pentene adds to bromine to give 2,3-dibromo pen-
tane. The number of stereoisomers of the dibromo 10. Conformational isomers are due to
compound is (1) free rotation about C, C single bond.
(1) 1 (2) 2 (3) 3 (4) 4 (2) frozen rotation about C, C single bond.
(3) frozen rotation about C, C double bond.
2. Which of the following may exhibit conformational
(4) restricted rotation about C, C single bond.
isomerism?
(1) H2O2 (2) NH2NH2 11. Which pair of isomerism is not possible together?
(3) CH3 CH2 OH (4) All of these (1) Functional and position
3. Which of the following does not have a meso isomer? (2) Ring-chain and functional
(1) 2,3-Butane diol (3) Metamerism and functional
(2) 2,3-Dibromo butane (4) Chain and functional
(3) 2,3-Dibromopentane 12. Which among the following compounds will show
(4) Tartaric acid tautomerism?
4. The number of constitutional and configurational iso- (1) 2,2-Dimethyl propanal
mers of a bromo compound C5H9Br formed by the (2) 2,2-Dimethyl-1-nitropropane
addition of one mole of HBr to 2-pentyne, respec- (3) Acetyl acetone
tively, are (4) Benzophenone

Chapter_16.indd 40 3/26/2014 3:28:51 PM

 (1) CH2 (2) CH2

Isomerism  16.41

13. According to Baeyer’s strain theory, which cycloal- (3) CHCl (4) CHCl
kane is most stable?
(1) Cyclopropane (2) Cyclopentane
(3) Cyclohexane (4) Cyclobutane
14. Which pair of isomerism is not possible together?
(1) Chain and position 22. The most stable conformation of ethylene glycol is
(2) Functional and position (1) anti (2) gausche
(3) Tautomerism and functional (3) partially eclipsed (4) fully eclipsed
(4) All of these
23. The two compounds shown in the figure below are
15. The energy barrier between chair and boat form of
cyclohexane is O
O
(1) 6 k.cal/moleq (2) 11 k.cal/mole
(3) 0.6 k.cal/mole (4) 16 k.cal/mole and
16. Arrange priority sequence of given groups in
­decreasing order
  (I) OH  (II) COOH (1) Diastereomers (2) Enantiomers
(III) CHOH CH3 (IV) CH2OH (3) Epimers (4) Regiomers
(1) I > II > III > IV (2) IV > III > II > I
24. In the boat conformation of cyclohexane, the most
(3) II > III > IV > I (4) IV > I > II > III
destabilising interaction is
17. Priority sequence of which alkyl group is maximum? (1) eclipsed (2) 1,3-diaxial
(1) Tertiary (2) Secondary (3) 1,3-diequatorial (4) flag pole-flag pole
(3) Primary (4) Methyl
25. The compounds given below are
18. Increasing order of stability among the three main
conformations (i.e., eclipse, anti, gausche) of HO COOH
2-fluoroethanol
(1) eclipse, anti, gausche
HO COOH
(2) anti, gausche, eclipse
(3) eclipse, gausche, anti (1) enantiomers (2) identical
(4) gausche, eclipse, anti (3) regiomers (4) diastereomers
19. The molecular formula of diphenylmethane 26. Fischer projection indicates
CH2 is C13H12 (1) horizontal substituents above the plane.
(2) vertical substituents above the plane.
How many structural isomers are possible when one (3) both horizontal and vertical substituents below
of the hydrogen is replaced by a chlorine atom? the plane.
(1) 6 (2) 4 (3) 8 (4) 7 (4) both horizontal and vertical substituents above
the plane.
20. The dipolemoment is highest for
(1) trans-2–butane 27. The total number of acyclic isomers including the
(2) 1,3-dimethyl benzene stereoisomers (geometrical and optical) with the
(3) acetophenone ­molecular formula C4H7Cl is
(4) ethanol (1) 10 (2) 12 (3) 9 (4) 11
21. Geometrical isomerism is shown by 28. cis-2-Butene and trans-2-butene can be distinguished
(1) CH2 (2) CH2 on the basis of
(1) the products they give on addition of bromine.
(2) the products they give on ozonolysis.
(3) their reduction products.
(4) their optical products.
(3) CHCl (4) CHCl

Chapter_16.indd 41 3/26/2014 3:28:54 PM

 16.42  Objective Chemistry - Vol. I

29. An optically active alkene with the M.F. C6H12 which H O Cl SH

NH2
upon hydrogenation gives optically inactive alkane is
(1) 2-methyl-2-pentene CH2CH3
(2) 3-methyl-2-pentene C CH2OH
H
(3) 2-hexene H HO
(4) 3-methyl-1-pentene CH3
I II III
30. In keto- enol tautomerism of dicarbonyl compounds,
(1) I and III have R-configuration.
the enol form is preferred in contrast to the keto-
(2) Only III has S-configuration.
form, this is due to
(3) Both (b) and (d) are correct.
(1) the presence of carbonyl group on each side of (4) I and II has R-configuration.
–CH2 group.
(2) the presence of methylene group. 36. Which of the following statements is correct?
(3) the resonance stabilization of enol form. (1) Addition of Br2 to cis-2-butene gives meso-2,3-
(4) rapid chemical exchange. dibromo-butene.
(2) Addition of Br2 to trans-2-butene gives
31. (S)-2-methyl butanol on oxidation with chromic acid
­meso-2,3-dibromo-butene.
gives
(3) KMnO4 hydroxylation of fumaric acid gives
(1) (S)-2-methyl butanoic acid. ­meso-tartaric acid.
(2) (R)-2-methyl butanoic acid. (4) OsO4 hydroxylation of maleic acid gives racemic
(3) (RS)-2-methyl butanoic acid. acid.
(4) No reaction.
37. The IUPAC name (including the stereochemical nota-
32. Which of the following statements is correct? tion for the chiral carbon) of
(1) Functional isomerism is a kind of stereoisomerism. H O
(2) The presence of chiral carbon is an essential
­condition for enantiomerism.
(3) Diastereomers are always optically active.
(4) Compounds containing one chiral carbon atom Br H
are always optically active. (1) (S)-2-Bromo-(Z)-hex-3-en-4-one
33. Enantiomers have (2) (R)-2-Bromo-(E)-hex-3-en-4-one
(3) (R)-2-Bromo-(Z)-hex-3-en-2-one
(1) identical melting point/boiling point and
(4) (S)-5-Bromo-(E)-hex-3-ene-2-one
­refractive indices but rotate plane-polarized light
in ­opposite directions but to the same extent. 38. Out of the following, the alkene which exhibits opti-
(2) identical melting point/boiling point but different cal isomerism is
refractive indices. (1) 2-methyl-2-pentene (2)  3-methyl-2-pentene
(3) different refractive indices and rotate plane-­ (3) 4-methyl-1-pentene (4) 3-methyl-1-pentene
polarized light in the same direction but to
39. The compound CHCl=CH CH OH COOH with mo-
­different extents.
lecular formula C4H5O3Cl can exhibit
(4) different melting point/boiling point but rotate
plane of polarized light in different directions but (1) geometrical, optical, position and functional
to the same extents. isomerisms.
(2) position and functional isomerisms only.
34. Which of the following statements is wrong? (3) geometrical, optical and functional isomerisms.
(1) trans-2-Butene has zero dipolemoment. (4) geometrical isomerism only.
(2) Maleic acid is less soluble in water than fumaric
40. At room temperature, the eclipsed and the staggered
acid.
forms of ethane cannot be isolated because
(3) cis-2-Butene and trans-2-butene are diastereo­
mers. (1) both the conformers are equally stable.
(4) Maleic and fumaric acids are geometrical (2) they interconvert rapidly.
­isomers. (3) there is a large energy barrier of rotation about
the σ-bond.
35. Consider the following structures and pick up the (4) the energy difference between the conformers is
right statement. large.

Chapter_16.indd 42 3/26/2014 3:28:56 PM

 Isomerism  16.43

41. Enantiomers can be better separated by (1) H H (2) H

(1) salt formation method.
C–C HC ≡ C – C
(2) mechanical separation.
(3) fractional crystallization. H2C CH2 CH2
(4) fractional distillation.
(3) H2C = C = C – CH3 (4) H2C = C = CH2
42. Pickout the correct statement.
 (i) If a compound has no asymmetric carbon atom, it
is always achiral. Answers
(ii) If a compound has just one asymmetric carbon
atom, it is chiral.   (1)  4   (2)  4   (3)  3   (4)  3   (5)  1   (6)  4
(iii) If a compound has more than one asymmetric   (7)  2   (8)  1   (9)  1 (10)  4 (11)  3 (12)  3
carbon atoms, it may or may not be chiral. (13)  2 (14)  1 (15)  2 (16)  1 (17)  1 (18)  1
(1) (i), (ii) and (iii) are correct. (19)  2 (20)  3 (21)  4 (22)  2 (23)  1 (24)  4
(2) (i) and (ii) only are correct. (25)  2 (26)  1 (27)  2 (28)  1 (29)  4 (30)  3
(3) (ii) and (iii) only are correct. (31)  1 (32)  4 (33)  1 (34)  2 (35)  4 (36)  2
(4) Only (ii) is correct. (37)  4 (38)  4 (39)  1 (40)  2 (41)  1 (42)  3
(43)  3 (44)  4 (45)  3 (46)  4 (47)  2
43. The absolute configuration of
CO2H
HO2C

OH
  Statement-Type Questions
HO In each of the following questions, a statement of
H H statement I is given followed by a corresponding statement
(1) S, R (2) S, S of statement II just below it of the statements; mark the
(3) R, R (4) R, S correct answer.
1. If both statement I and statement II are true and
44. The compound is formed by substitution of two chlo-
statement II is the correct explanation of assertion.
rine atoms for two hydrogens in propane. The number
of possible isomeric compounds is 2. If both statement I and statement II are true and
­statement II is not the correct explanation of ­
(1) 2 (2) 3 (3) 4 (4) 5
statement I.
45. The number of stereoisomers possible for a com- 3. If statement I is true and statement II is false.
pound of the molecular formula CH3CH=CH
4. If statement I is false but statement II is true.
CH(OH)CH3 is
(1) 2 (2) 3 (3) 4 (4) 6 1. Statement I: Cl–CH=CH–Cl will show geometrical
isomerism and cis–trans isomers are ­stereoisomers.
46. The correct statement about the compound
Statement II: cis–trans isomers are diastereomers
CH3 CH(OH)–CH=CH–CH(OH) CH3 (X) is
­because they are not enantiomers.
(1) The total number of stereoisomers possible for
(X) is 7. 2. Statement I: Alkene of the type abC=C=Cab can
(2) The total number of diastereomers possible for show geometrical isomerism because of non-planarity.
(X) is 3. Statement II: Non-planarity in this case causes
(3) If the stereochemistry about the double bond in
­molecular dissymetry.
(X) is trans, the number of enantiomers possible
for (X) is 4. 3. Statement I: Cyclohexanone can show tautomerism.
(4) If the stereochemistry about the double bond in
Statement II: It contains α-hydrogen with respect to
(X) is cis, the number of enantiomers possible for
carbonyl group.
(X) is 2.
47. Amongst the given options, the compound in which 4. Statement I: m-Tartaric acid is optically inactive.
all the atoms are in one plane in all the possible con- Statement II: It is due to the external compensation
formations of rotation of plane-polarized light.

Chapter_16.indd 43 3/26/2014 3:28:57 PM

 16.44  Objective Chemistry - Vol. I

5. Statement I: The dipolemoment of trans- 2.

1-­chloro-1-propene is more than cis form.
List-I List-II
Statement II: In case presence of +I and −I groups,
(A) CH3=CH–CH=CH2 and   (i) Chain isomer
the dipolemoment in case of trans form is added by
HC≡C–CH–CH3
vector.
 (B) CH2=C=CH–CH3 and (ii) Functional
6. Statement I: Recemic mixture is equimolar ­mixture
CH2=CH–CH=CH2 group isomer
of eantiomeric pair.
(iii) Position
Statement II: Recemic mixture is optically inactive. (C) HC≡C–CH2–CH3 and
isomer
7. Statement I: The boiling point of cis form is more (D) CH3=CH–CH2–CH2 and  (iv) Ring chain
than trans form. CH3 isomer

Statement II: It is due to more polarity. CH – C = CH3

8. Statement I: Tartaric acid contains three ­stereomers.
Statement II: m-Tartaric acid is optically inactive.
S. No. A B C D
(a) ii i iii iv
Answers
(b) ii iii iv ii
  (1)  1   (2)  4   (3)  1   (4)  3   (5)  1   (6)  2 (c) ii i iii iv
  (7)  1   (8)  2
(d) ii iii i iv

3.
  Match the Following T
  ype Questions
List-I List-II
1. M
 atch List-I with List-II and select the correct an-
swer using code given below the lists. (A) CH3 CH2 COO C2H5 and CH3COO  (i) Functional
CH2CH2CH3 group isomer
List-I List-II
(B) CH3 COOH and HCOOCH3  (ii)  Metamer
(A) CH3 CO CH3 and CH3 CH2 CHO   (i) Metamers
(ii) Ringchain OH (iii) Chain
O
(B) CH3 C=CH and isomer
isomeris
(C) and
(C) CH3 CH2 CH2 CH3 and (iii) Functional
group isomer
CH3
|  (iv) Tautomer
CH3 – CH – CH3 (D)
and
(D) CH3 OCH2 CH2 CH3 and (iv) Chain isomer

CH3CH2 O CH2CH3
S. No. A B C D
S. No. A B C D (a) ii i iii iv
(a) ii i iii iv (b) i ii iv iii
(b) iii ii i iv
(c) i ii iii iv
(c) iii ii iv i
(d) ii iii iv i (d) ii i iv iii

Chapter_16.indd 44 3/26/2014 3:29:00 PM

 Isomerism  16.45

4. A B C D
List-I List-II (a) ii i iii iv
Compound No. of geome­ (b) ii iv i ii
trical isomers
(c) iv iii i ii
(i) 10
(A)
(d) i ii iii iv
(B) (ii) 8

(iii) 6
(C) Answers
(iv) 16 (1)  3 (2)  2 (3)  4 (4)  4
(D)

Chapter_16.indd 45 3/26/2014 3:29:02 PM

 This page is intentionally left blank.

Chapter_16.indd 46 3/26/2014 3:29:02 PM

 17

Chapter
Alkanes

• Alkanes are saturated open-chain hydrocarbons. From Alkyl Halides

• General molecular formula of alkanes is CnH2n+2. • Reduction of alkyl halides with nascent hydrogen
• Alkanes are called paraffins due to their less reactivity ­obtained from Zn – Cu couple and alcohol, m ­ agnesium
(Latin: parum = little; affinis = affinity). amalgam + H2O, Zn + CH3COOH, Zn + HCl etc.,
• Each carbon in alkanes is sp3 hybridised and has yields alkane.
tetrahedral shape with a bond angle 109° 28i. R – X + 2[H]  → CnH2n+2 + HX
• 3 3
C – C bond length in alkanes (sp – sp overlap) is • High-pure alkanes are produced by this method.
1.54 A°. • It is now believed that reduction of alkyl halide is not
• 3
C – H bond length in alkanes (sp – s overlap) is due to nascent hydrogen but due to the transfer of elec-
1.112 A°. trons from metal to substrate followed by the addition
of protons from the solvent.
• C – C bond energy in alkanes is 82.76 k. cal mol–1.
Zn 
→ Zn2+ + 2e–
• C – H bond energy in alkanes is 98.67 k. cal mol–1.
RX + e– 
→ X– + R.
• Carbon–carbon chains in alkanes are not linear but
zig-zag. R + e– 
→ R :–

R:– + C2H5OH  → R – H + C2H5O–
Preparation • Alkyl iodides may be reduced with hot conc. HI at
150°C in the presence of red P.
Reduction of Unsaturated Hydrocarbons
• Primary and secondary alkyl halides can be reduced by
• Alkenes and alkynes can be reduced to alkanes with LiAlH4, while NaBH4 reduces secondary and ­tertiary
dihydrogen in the presence of catalysts such as Ni and alkyl halides into alkanes.
Pd at 200°C. If Raney nickel is used, the reaction can • Tertiary alkyl halides get dehydrohalogenated to
be carried at room temperature. ­alkene by LiAlH4.
CH2 = CH2 + H2 Ni → CH3–CH3 • Among the halogens, the order of reactivity is
CH3 – CH = CH2 + H2 Ni → CH3CH2CH3 iodides > bromides > chlorides.
HC ≡ CH + H2 Ni → CH2 = CH2 H 2 /Ni
→ CH3–CH3 • Wurtz reaction: If two moles of alkyl halide in
• Catalytic hydrogenation of alkenes and alkynes is ­ethereal solution is treated with sodium, an alkane
known as Sabatier–Senden’s reaction. having double the number of carbon atoms in alkyl
halide will be formed.
• Methane cannot be prepared by this method.
2R – X + 2Na ether
→ R – R + 2NaX
• Cyclohexene and hydrazine can also reduce the
­alkenes. The driving force in the case of c­ yclohexene is • In the product formed, a new C – C bond is formed.
the gain in aromatic stabilisation energy when ­benzene • Only one type of alkane will be formed with same type
is formed. With hydrazine, the strongly bonded N2 alkyl halide molecules but a mixture of three alkanes
­molecule is formed. with different alkyl halides.

Chapter_17.indd 1 3/26/2014 3:30:20 PM

 17.2  Objective Chemistry - Vol. I

• CH3Cl alone gives ethane and C2H5Cl alone gives • The R part of the Grignard reagent is converted to RH.
butane, but a mixture of CH3Cl and C2H5Cl gives
­ • If heavy water D2O is used, then product is RD, that is,
ethane, propane and butane. deuteroalkane.
• If zinc is used in the place of sodium metal in Wurtz R–Mg–X + D2O  → RD + Mg(OD)X
reaction, it is called Frankland reaction. • Grignard reagent reacts as carbanion (formed by
breaking C – Mg bond).
 ⊕
Decarboxylation of Fatty Acids – C–MgX 
→ – C: + MgX
• The process of elimination of CO2 from a fatty acid is • The reaction of carbanion with the proton of an acid
known as decarboxylation. (even H2O) is Bronsted–Lowry Acid–Base reaction.
• Decarboxylation of a sodium salt of a fatty acid is – C + H – OR 
→ – C – H + R – O
⊕
­carried with soda lime (CaO + NaOH). R – O– + MgX 
→ R – OMgX
• Decarboxylation of a carboxylic acid gives an alkane
having one carbon atom less than the parent fatty acid.
• This reaction is an example of protonolysis, which
is the reaction with the proton of an acid that breaks
RCOONa ( Soda lime
CaO + NaOH)
→ RH + Na2CO3 chemical bonds.
CH3COONa (
Soda lime
→ CH4 + Na2CO3 • Hydroboration method is used for preparing long
CaO + NaOH)
chain alkanes.
• Preparation of alkanes by the electrolysis of • Coupling of alkyl boranes by means of silver nitrate in
­concentrated aqueous solution of sodium/potassium
the presence of sodium hydroxide at 298 K gives long
salts of ­monocarboxylic acids is known as Kolbe’s
chain alkanes.
electrolytic reaction. R – CH = CH2 B 2 H6
→ (RCH2 – CH2)3B AgNo
NaOH
3
→
2RCOONa + 2H2O Electrolysis
→ R – R + 2CO2 + H2 RCH2CH2CH2CH2R
 + 2NaOH • Propionic acid can also be used to decompose alkyl
2CH 3 COOK + 2H 2 O 
→ CH 3 − CH 3 + 2CO2 + boranes.
 
at anode

H 2 + 2KOH Physical Properties


at cathode
• The normal alkanes C1 to C4 are colourless gases; C5
• Kolbe’s reaction gives good results for alkanes having to C17 are colourless liquids; and from C18 onwards
even number of carbon atoms. colourless solids at 298 K.
• Methane cannot be prepared by this reaction. • Alkanes are almost non-polar molecules because of
• Alkyl groups in the α position decrease the yield of the covalent nature of C – C and C – H bonds and due
alkanes. to very small difference in the electro-negativities of
• The yield of alkanes is increased by using dimethyl carbon and hydrogen.
formamide as solvent. • In a group of isomeric alkanes, melting point and
• If a mixture of acids is electrolysed, the correspond- boiling point decrease with increase in the number of
ing symmetrical and unsymmetrical hydrocarbons are branches.
obtained. • Increase in the number of branches makes the
• Hydrolysis of beryllium and aluminium carbides gives ­molecule spherical; thus decreasing the surface area
methane. due to which Van der Waals forces decrease.
Be2C + 4H2O  → 2Be(OH)2 + CH4 • The boiling point increases regularly with increase in
Al4C3 + 12H2O  → 4Al(OH)3 + 3CH4 the molecular weight of alkane.
• Melting points of alkanes with even number of carbons
are higher than the adjacent hydrocarbons having odd
Decomposition of Grignard Reagent
number of hydrocarbons.
• Grignard reagent on treatment with water or dilute • The hydrocarbons having even number of carbon
acid or alcohol is decomposed to alkanes. ­atoms can be packed more closely in solid state than
R – Mg – X + H2O  → RH + Mg(OH)X those having odd number of carbon atoms and hence
(R is alkyl or aryl; X is Cl, Br, I) they have high melting points.

Chapter_17.indd 2 3/26/2014 3:30:22 PM

 Alkanes  17.3

• Alkanes being non-polar are almost insoluble in water • Bond energy of extraction is of the order 1° H > 2°
but readily soluble in non-polar solvents, but the solu- H > 3° H. Therefore, the reactivity order is 1° < 2° <
bility decreases with increasing molecular weight. 3° H because of the stability of alkyl free radicals is
• Alkanes having equal molecular weight with alkyl in the order.
­halides have more boiling points, for example, the  3 < CH3CH
CH  < (CH3)2CH
 < (CH3)3C 
boiling point of C10H22 (MW = 142) has boiling point
• Based on the relative reactivity of different types of
447 K while CH3I (MW = 142) has 315.5 K. This is
H, percentage of each in the product mixture can
because of stronger Van der Waal’s forces in alkane
be ­calculated. Consider the halogenation of butane,
with more surface area.
which contain six 1° H and four 2° H atoms.
Chemical Properties CH3–CH2–CH2–CH3 CH3CH2CH2CH2Cl +
• Alkanes are relatively stable to most of the common 6 × (reactivity 1.0)
reagents at room temperature since the C – C and C – H = 6.0 relative amount
bonds are non-polar. Cl
• Because of the lack of reactivity, alkanes are also
CH3–CH–CH2–CH3
known as paraffins (meaning little affinity).
4 × (reactivity 3.8)
= 15.2 relative amount
Substitution Reactions
• One or more hydrogen atoms of alkanes can be sub- Total amount = 21.2
stituted by halogens, nitro group and sulphonic acid
6.0
group. Per cent of A = × 100 = 28.3
21.2
• Lower alkanes do not undergo nitration and sulphona-
tion reactions. 15.2
(i)  Halogenation of alkanes takes place in the pre­ Per cent of B = × 100 = 71.7
21.2
sence of ultraviolet light or at high temperature
(573–773 K). • Since it is easier to form more stable secondary
CH4 + Cl2 hv→ CH3Cl + HCl alkyl radicals, 2-chlorobutane is formed faster than
1-chlorobutane.
CH3Cl + Cl2 hv→ CH2Cl2 + HCl
• Bromine is less reactive towards alkanes in general
CH2Cl2 + Cl2 hv→ CHCl3 + HCl
than chlorine, but bromine is more selective in the site
CHCl3 + Cl2 hv→ CCl4 + HCl of attack when it does react.
• For a given type of substitution of H (say 1°), ­reactivity
CH3
of halogen is in the order F2 > Cl2 > Br2 > I2.
• For a given halogen, substitution of 1°, 2° and 3° H’s is Br2 (CH3)3C – Br + CH3 – CH – CH2Br
in the order 1° < 2° < 3°. > 99% trace
light/400K
• For chlorination, reactivity of 1°, 2° and 3° H’s is in the
ratio
Tertiary > secondary > primary (CH3)3C – H
 5.0   3.8    1.0
CH3
• Halogenation of alkanes proceeds by free radical
mechanism. Cl2, hv
(CH3)3C – Cl + CH3 – CH– CH2Cl
Cl : Cl hv→ Cl .  + Cl .  Chain initiation reaction
37% 63%
 
H 3 C − H + Cl  + HCl  Chain
→ CH 3
propagating
CH + Cl : Cl  → CH 3 Cl + C l  • Iodination is reversible, but it may be carried out in the
3  reactions presence of an oxidising agent, such as HIO3, HNO3
Cl ⋅ + Cl ⋅ → Cl2  and HgO which isolates HI formed in the reaction.
CH + CH   Chain terminating
3 3 → CH 3 − CH 3  CH4 + I2 
→ CH3I + HI
 reactions

CH 
3 + Cl  → CH 3 Cl 5HI + HIO3 
→ 3I2 + 3H2O


Chapter_17.indd 3 3/26/2014 3:30:26 PM

 17.4  Objective Chemistry - Vol. I

  (ii) Nitration of alkanes gives nitroalkanes. formed which is used in the manufacture of printer ink,
• Nitration also leads to chain fission of alkanes; hence black pigments and filters.
other products are nitromethane, nitropropane and CH4(g) + O2(g)  → C(s) + 2H2O(l)
nitroethane. • Controlled oxidation of alkanes in a regulated ­supply
(iii) Sulphonation of alkanes replaces H of alkane by of dioxygen or air at high pressure and in presence
–SO3H group. Sulphonation is carried out by of suitable catalyst gives a variety of oxidation
­using oleum. products.
R – H + H2SO4/SO3  → R – SO3H + H2SO4 (i) 2CH4 + O Cu/532
 K100 atm
→ 2CH3OH
Ease of replacement of H atoms is 3° > 2° > 1° Methanol
(ii) CH4 + O2 Mo
2 O3
→ HCHO + H2O
Combustion Methanal
(iii) 2CH3CH3 + 3O2 (CHCOO)
2 Mn
→ 2CH3COOH + H2O
• Alkanes readily burn in excess of air (oxygen) to form ∆

CO2 and H2O. It is known as combustion.    Ethanoic acid

 3n + 1 • Generally alkanes resist oxidation but alkanes ­having
CnH2n + 2 +  O ∆ → nCO2 + (n + 1) H2O + heat
 2  2 tertiary H atom can be oxidised to corresponding
• ­alcohols by potassium permanganate.
Due to evolution of large amount of heat during
­combustion, alkanes are used as fuels. (CH3)3CH Oxidation

KMnO 4
→ (CH3)3COH
• During incomplete combustion of alkanes with Isomerisation is a process of conversion of one ­isomer
­insufficient amount of air or dioxygen, carbon black is into one or more other isomers.

AlCl3 AlCl3 – HCl

573 K 298 K

AlCl3 – HCl
298 K

• Isomerisation involves 1, 2 - shift of hydride or methyl in the presence of catalysts such as Pt, Pd, Ni or
group. Rearrangement probably occurs via carbocations Cr2O3 – Al2O3.
which are generated by the acidic catalyst.
• Reforming is a process in which compounds are isom-
Aromatisation is a process of converting ­saturated
erised and dehydrogenated to aromatic compounds
n-alkanes containing six to ten carbon atoms into
usually with the same number of carbons.
benzene and its homologues at high temper­ ature

Cr2O3 – Al2O3
873 K (–H2) –3H2

n - hexane Cyclohexane Benzene

Cr2O3 – Al2O3
873 K (–H2) –3H2

n - heptane methyl cyclohexane Toulene

Chapter_17.indd 4 3/26/2014 3:30:28 PM

 Alkanes  17.5

• On heating with steam at 1273 K, a mixture of CO and • Quality of diesel fuel is represented with cetane number.
H2 will be formed. • Hexadecane C16H34 (cetane) ignites rapidly and has
CH4 + H2O Ni 
∆
→ CO + 3H2 been given a rating of 100.
• Pyrolysis is a process of breaking down of the less • 1-methyl naphthalene ignites badly and is given a
­volatile hydrocarbons of higher molecular mass into ­rating 0.
different fragments of lower alkanes having lower
­ • Cetane number is defined as the percentage of c­ etane
­molecular mass by heating in the presence of a catalyst. by volume in a mixture of cetane and 1-methyl
C12H26 973
K/cat
→ C7H16  + C5H10 ­naphthalene which has same ignition quality as the
Dodecane Heptane  Pentene sample of fuel under study.
• Pyrolysis of alkanes is a free radical reaction. • The minimum temperature at which an oil gives enough
• Preparation of oil gas or petrol gas from kerosene oil vapours to form a momentary flash of light when a
or petrol involves the principle of pyrolysis. flame is brought near its surface is called flash point.
• Safety of oils in different countries is decided by f lash
Knocking and Octane Number point. The flash point fixed in cold countries is low,
whereas in hot countries it is high.
• The quality of alkanes as motor fuel depends on
knocking power.
• A sharp metallic rafting sound is produced in an internal  Objective Questions
combustion engine during premature ignition is called
1. The compounds which on reaction with CH3MgI do
knocking.
not give methane are
• There is considerable loss of energy during knocking,
(1) CH3CH2NH2 (2) C2H5OH
and there are also chances of engine damage.
(3) (CH3)3N (4) NH3
• The tendency of knocking decreases in the following
order. 2. What is the chief product obtained when n-butane is
n-alkanes > branched chain alkane > alkene > treated with Br2 in the presence of light at 130°C?
­cycloalkane > aromatic hydrocarbons (1) CH3CH2CHBrCH3 (2) (CH3)2CHCH2Br
• The knocking quality of an automobile fuel is (3) (CH3)3C – Br (4) CH3CH2CH2CH2Br
­measured in terms of Octane number. 3. Why does an oil slick form on the surface of the
• 2,2,4-trimethyl pentane (iso-octane) having least ocean after a spill?
knocking power is given the octane number 100. (1) Arenes, the chief constituents of petroleum are
• Heptane having maximum knocking power is given insoluble and have higher density than water
octane number 0. (2) Heterocycles, the chief constituents of petroleum
• Octane number of a gasoline is the percentage of iso- are insoluble and have a lower density than water
octane present in a mixture of iso-octane and heptane (3) Alkanes, the chief constituents of petroleum are
when the mixture has same knocking efficiency in the insoluble and have a lower density than water
engine as gasoline under study. (4) None of the above
• Higher the octane number, the better the gasoline. 4. Which of the following is/are correct for the conversion
• Gasoline used in automobiles should have an octane of alkyl halide into an alkane with the same skeleton?
number of 80 or higher. The gasoline used in aero- (1) Reduction using Zn, H+
planes has an octane number 100 or even higher.
(2) Reduction using LiAlH4
• During cracking, the octane number of fuel increases (3) Mg/anhydrous ether followed by H2O
due to isomerisation, polymerisation, reforming, etc.
(4) All of the above
• Knocking can be reduced by adding anti-knocking
agents such as tetraethyl lead (TEL). 5. In the reaction CH3MgBr + D2O 
→
• The free radical C2H5 produced from TEL converts the Br
n-alkanes to branched chain alkanes.
Mg + (A)
• Nowadays, tert-butyl methyl ether (MTBE) is used as
anti-knocking agent since lead is toxic. OD

Chapter_17.indd 5 3/26/2014 3:30:29 PM

 17.6  Objective Chemistry - Vol. I

The product (A) is (3) 2 (CH3)3 C – Br + 2Na Ether

 → (CH3)3 C – C(CH3)3
(1) CH3D (2) CH3H (4) None of the above
(3) CH2I2 (4) None of these 13. Bromination of an alkane compared to chlorination
6. Which of the following alkenes on catalytic proceeds
­hydrogenation yield 2-methyl pentane? (1) at a slower rate
(1) 4-methyl-1-pentene (2) at a faster rate
(2) 4-methyl pentene-2 (3) with equal rate
(3) 2-methyl pentene-2 (4) with equal or different rate depending upon the
(4) 2-methyl pentene-1 temperature
(5) All of the above 14. Alkanes can be iodinated in the presence of
7. Isobromyl bromide on reaction with Mg/ether ­followed (1) HI (2) I2 and P
by treatment with heavy water gives (3) HIO3 (4) only I2
(1) (CH3)2 CH – CH(CH3)2 15. Wurtz reaction converts alkyl halide into alkane when
(2) (CH3)2 CH2 it is made to react with
(3) (CH3)2 CD2
(1) Na in alcohol (2) Na in dry ether
(4) (CH3)2 CHD
(3) Zn in alcohol (4) Zn in dry ether
8. Which of the following alkanes cannot be synthesised
16. Vapour phase nitration of propane yields
by the Wurtz reaction in good yield?
(1) 1-nitropropane
(1) (CH3)2 CH CH2 CH(CH3)2
(2) 2-nitropropane
(2) (CH3)2 CH CH2 CH2 CH(CH3)2 (3) 1-nitropropane + 2-nitropropane + nitroethane +
(3) CH3 CH2 C (CH3)2 CH2 CH3 nitromethane
(4) (CH3 )3 C CH2 CH2 CH3 (4) None of the above
9. Which of the following is correct order of reactivity 17. (CH3)3CMgCl on reaction with D2O molecule
of H atoms of alkanes? ­produces
(1) Primary H < secondary H < tertiary H (1) (CH3)3CD (2) (CH3)3OD
(2) Secondary H > primary H > tertiary H (3) (CD3)CD (4) (CD3)3OD
(3) Tertiary H > primary H > secondary H 18. Which of the following is not an endothermic
(4) Tertiary H > secondary H > primary H ­reaction?
10. The reaction conditions giving best yield of (1) Combustion of CH4
C2H5Cl are (2) Decomposition of H2O
(1) C2H6 + Cl2 UVlight
→ (3) Dehydration of C2H6 to C2H4
excess (4) Conversion of graphite to diamond
(2) C2H6 + Cl2 room

dark
temp
→ 19. Aldehydes and ketones can be reduced to alkanes by
(3) C2H6 + Cl2 UVlight
→ (1) Clemensen’s method
(2) Wurtz reaction
excess
(3) Meervim–Pondorf–Verley reaction
(4) C2H6 + Cl2 UVlight
→ (4) Bouveault Blanc reduction
11. When 2-methyl propane is brominated, the 20. A mixture of ethyl iodide and n-propyl iodide is
per cent of (CH3)2 C CH3 is ­subjected to Wurtz reaction. The hydrocarbon which
Br will not be formed is
(1) 0.6 % (2) 100% (1) butane (2) propane
(3) 0% (4) 99.4 % (3) pentane (4) hexane
12. Which of the following reactions occur? 21. The reagent used for the conversion CH3CH2COOH
(1) C2H5Br + 2Na Ether
 → C4H10 + 2NaBr → CH3CH2CH3 is
(2) C2H5Br + 2Na + Br – C(CH3)3 Ether
 → (1) LiAlH4
(CH3)3CC2H5 + 2NaBr (2) Soda lime

Chapter_17.indd 6 3/26/2014 3:30:39 PM

 Alkanes  17.7

(3) Red P and concentrated HI 28. To prepare a pure sample of n-hexane using sodium
(4) Amalgamated zinc and concentrated HCl metal as one reactant, the other reactants will be
22. Pure methane can be produced by (1) ethyl chloride and n-butyl chloride
(2) methyl bromide and n-pentyl bromide
(1) Wurtz reaction
(3) n-propyl bromide
(2) Kolbe’s electrolytic method
(4) ethyl bromide and n-butyl bromide
(3) Soda lime decarboxylation
(4) Reduction with H2 29. Indicate the expected structure of the organic product
when ethyl magnesium bromide is treated with heavy
23. In the free radical chlorination of methane, the chain
water (D2O)
initiating step involves the formation of
(1) C2H5 – C2H5 (2) C2H5OD
(1) chlorine atom
(3) Sodium benzoate (4) C2H5D
(2) hydrogen chloride
(3) methyl radical 30. For preparing an alkane, a concentrated solution of
(4) chloromethyl radical sodium or potassium salt of saturated carboxylic acid
is subjected to
24. Consider the following reaction
(1) hydrolysis (2) oxidation
CH3 – CH – CH – CH3 + Br X + HBr (3) hydrogenation (4) electrolysis
D CH3 31. During the preparation of alkanes by Kolbe’s

­electrolytic method using inert electrodes, the pH of
Identify the structure of the major product X
the electrolyte
(1) CH3 – CH – CH – CH2
(1) decreases progressively as the reaction proceeds
(2) increases progressively as the reaction proceeds
D CH3
(3) remains constant through the reaction
(2) CH3 – CH – C – CH3 (4)  may decrease if the concentration of the
­electrolyte is not very high
D CH3
(3) CH3 – C – CH – CH3 – CH5 – C 32. The compound which produces propane on heating
with HI in the presence of red phosphorous is
D CH3 (1) CH3CH2CH2I (2) CH3CH2CHO
(3) CH3CH2CH2OH (4) All of these
(4) CH3 – CH – CH – CH3
33. CH3CH2CH2CH3 C l2 hv
→ A+B
CH3 (Monochlorination products)
   The approximate ratio of percentage yields of A and
25. On mixing a certain alkane with chlorine and irradi- B formed in the above reaction is
ating it with UV light, it forms a ­monochloroalkane. (1) 50 : 50 (2) 72 : 28
This alkane could be (3) 45 : 55 (4) 60 : 40
(1) neopentane (2) propane
34. Converting n-hexane into benzene in the presence of
(3) pentane (4) isopropane
chromium oxide on alumina support is an example of
26. Which of the following will not produce ethane? (1) hydrogenation reaction
(1) reduction of CH3COOH with HI and red P (2) isomerisation reaction
(2) reduction of CH3COCH3 with HI and red P (3) aromatisation reaction
(3) soda lime decarboxylation of sodium propionate (4) substitution reaction
(4) hydrogenation of ethene in the presence of Raney
35. The molecular formula of diphenyl methane
nickel
(C6H5)2CH2 is C13H12. How many structural isomers
27. Which of the following compounds will form a are ­possible when one of the hydrogen is replaced by
hydrocarbon on reaction with Grignard reagent? chlorine atom?
(1) CH3CH2OH (2) CH3CHO (1) 6 (2) 4
(3) CH3COCH3 (4) CH3COOH (3) 8 (4) 7

Chapter_17.indd 7 3/26/2014 3:30:40 PM

 17.8  Objective Chemistry - Vol. I

36. Which of the following has the minimum boiling (1) to increase the rate of reaction
point? (2) to decrease the rate of reaction
(1) n-butane (2) 1-butyne (3) to change the rate of reaction
(3) 1-butene (4) Isobutene (4) none is correct

37. Amongst the following compounds, the optically active 43. Which of the following is the correct sequence of
alkane having the lowest molecular mass is steps in the halogenation of an alkane?
(1) CH3 – CH2 – CH2 – CH3 (1) Propagation, initiation, termination
(2) Initiation, termination, propagation
CH3 (3) Initiation, propagation, termination
(4) Propagation, termination, initiation
(2) CH3 – CH2 – CH – CH3 44. Which of the following alkane on monochlorination
H gives racemic mixture?
(1) neopentane
(3) CH3 – C (2) n-butane
(3) 2, 3-dimethyl butane
(4) 2, 2, 3, 3-tetramethyl butane
C2H5
45. Which C6H14 gives five types of C6H13Cl ?
  (4) CH3 – CH2 – C ≡ CH
38. Which of the following is reduced with zinc and (1) (2)
­hydrochloride to give the corresponding h­ ydrocarbon?
(1) Ethyl acetate (2) Acetic acid
(3) Acetamide (4) Butan-2-one
(3) (4)
39. Which of the following statement is wrong?
(1) Both methane and ethane may be obtained by a
suitable one-step reaction from methyl bromide
(2) Formation of alkane by the action of zinc and 46. C6H12 (A) has two types of alkenes that can be
alkyl halide is called Frankland reaction ­reduced to one type of C6H14 (B). B is
(3)  Methane on heating with steam gives carbon (1) (2)
black
(4) Kerosene is a mixture of aliphatic hydrocarbons
40. Which of the following statement is false? (3) (4)
(1) Knocking sound is produced in the engine when
the fuel contains water
(2) Knocking will be minimum when the mixture of
fuel is branched and unsaturated hydrocarbons 47. Which has maximum melting and boiling points out
of n-pentane (I) isopentane (II) and neopentane (III)?
(3) Iso-octane is added to petrol as an anti-knocking
agent (1) I, II (2) II, I
(3) III, I (4) II, III
(4) Octane number of a fuel can be increased by
isomerisation and reforming 48. Consider the following statements.
41. Decarboxylation of isobutyric acid gives n-alkane but  (I) Melting points tend to increase with increasing
its reduction with phosphorous and hydrogen iodides molecular mass within a series
gives  (II) Many symmetrical molecules have unusually
high melting points
(1) n-propane (2) isobutane
(III)  Boiling points tend to be lower for highly
(3) n-butane (4) none of these
branched molecules that approach spherical
42. The function of soda lime (a mixture of solid NaOH ­proportions, because they have less molecular
and solid CaO) in the decarboxylation reaction is surface ­available for Van der Waal’s attractions

Chapter_17.indd 8 3/26/2014 3:30:43 PM

 Alkanes  17.9

Select correct statements. 55. Zinc–copper couple that can be used as a reducing
(1) I, II (2) I, III agent is obtained by
(3) II, III (4) I, II, III (1) mixing zinc dust and copper gauze
49. Which of the following statements is wrong? (2) zinc coated with copper
(1) In the halogenation of alkanes, 3° H is more (3) copper coated with zinc
­
reactive (4) zinc and copper wires welded together
(2)  Abstraction of 3° H in alkane leads to the 56. 2.84 g of methyl iodide was completely converted
­generation of most stable 3° radical into methyl magnesium iodide, and the product was
(3) 3° alkyl radical is generated slower than 1° and decomposed by excess of ethanol. The volume of the
2° radicals gaseous hydrocarbon produced at NTP will be
(4) Bromination of alkanes is most selective (1) 22.4 litre (2) 22400 mL
50. Which of the following orders is correct for the reac- (3) 0.448 litre (4) 0.224 litre
tivity of the indicated H atoms in monochlorination?
57. Consider the IUPAC name of alkane obtained in the
(3)
H (2) H reaction of 2-chloropropane + sodium in dry ether is
(1) H (1) 2, 3-dimethyl butane
(2) 2-isopropyl propane
(3) n-hexane
(4) 2, 2-dimethyl butane
58. A fuel has the same knocking property as a mixture
of 70 per cent iso-octane (2,2,4-trimethyl pentane)
(1) H1 > H2 > H3 (2) H3 > H2 > H1
and 30 per cent n-heptane by volume. The octane
(3) H1 > H3 > H2 (4) H2 > H3 > H1 number of the fuel is
51. Pick out the false statement from the following. (1) 70 (2) 40 (3) 100 (4) 50
(1) The name ‘fire damp’ is given to methane 59. Butane can be converted into 2-methyl propane, if
(2) Marsh gas mainly contains methane heated with
(3) Carbon black is obtained by heating methane in (1) Al2Cl6 (2) Cr2O3
the absence of air (3) CrO2Cl2 (4) Na/ether
(4) The simplest alkane that can be prepared by
Wurtz reaction is methane 60. An alkane with a molecular formula C6H14 reacts
with chlorine in the presence of light and heat to
52. Which of the following compounds can yield only give two constitutionally isomeric monochlorides
one monochlorinated product upon free-radical of ­molecular formula C6H13Cl. What is the most
­chlorination? ­reasonable starting alkane?
(1) 2, 2-dimethyl propane (1)  n-hexane       (2) 2, 2-dimethyl butane
(2) 2-methyl propane (3) 2, 3-dimethyl butane  (4)  3-methyl pentane
(3) 2-methyl butane
(4) Propane 61. Consider the following reaction.
CH3 – CH – CH – CH3 + Br X + HB
53. The wrong statement among the following is
(1) The knocking will be minimum when the ­mixture
of fuel is on neocarbonation D CH3
(2) Iso-octane is added to petrol as an anti-knocking
Identify the structure of major product X.
agent
(1) CH3 – CH – CH – CH2
(3) Kerosene is a mixture of aliphatic hydrocarbons
(4) Hydrogenation of coal is done for the production
D CH3
of synthetic petrol in Sabatier process
(2) CH3 – CH – C – CH3
54. The reaction of ROH with R′MgX produces
(1) RH (2) R′H (3) R – R (4) R′ – R′ D CH3
(3) CH3 – C – CH – CH3

D CH3
(4) CH3 – CH – CH –CH3
Chapter_17.indd 9 3/26/2014 3:30:48 PM
 (1) CH3 – CH – CH – CH2

D CH3
(2) CH3 – CH – C – CH3
17.10  Objective Chemistry - Vol. I
D CH3
(3) CH3 – C – CH – CH3
  Statement-Type Questions
D CH3
In each of the following questions, a statement of
(4) CH3 – CH – CH –CH3 ­statement I is given followed by a corresponding statement
of statement II just below it of the statements; mark the
CH3 ­correct answer.
62. 2-methyl butane on reacting with bromine in the 1. If both statement-I and statement-II are true and
­presence of sunlight gives mainly statement I is the correct explanation of statement II.
(1) 1-bromo-2-methyl butane 2. If both statement-I and statement-II are true and state-
(2) 2-bromo-2-methyl butane ment I is not the correct explanation of statement II.
(3) 2-bromo-3-methyl butane 3. If statement-I is true and statement-II is false.
(4) 1-bromo-3-methyl butane 4. If statement-I is false but statement-II is true.
63. The treatment of CH3MgX with CH3 – C ≡ CH 1. Statement I: The octane number of branched-chain
produces hydrocarbon is higher than that of the unbranched-
(1) CH4 (2) CH3CH = CH2 chain hydrocarbon.
(3) CH3C ≡ CCH3 (4) CH3CH = CHCH3 Statement II: The branched-chain hydrocarbons are
more volatile as compared to the unbranched-chain
64. Which of the following statements is wrong? hydrocarbons.
(1) The preparation of an alkane from an alkyl halide
2. Statement I: The boiling point of n-alkanes ­increases
by reaction with zinc is known as the Franckland
with increase in number of carbon atoms.
reaction
(2) The boiling point of a branched alkane as com- Statement II: Van der Waal’s force of attraction
pared to that of a straight-chain isomer is high increases with increase in number of carbon and
­
­molecular mass.
(3) The halogenation of alkanes is an example of
free-radical substitution 3. Statement I: Wurtz reaction is not useful for the
(4) A liquid hydrocarbon is converted to a mixture of preparation of methane.
gaseous hydrocarbons by cracking Statement II: Wurtz reaction is useful for the
­preparation of higher alkanes only.
4. Statement I: In cracking of alkanes C – C bond is
broken but not C – H bond.
Answers
Statement II: C – C bond energy is less than C – H
bond energy.
  (1)  3 (2)  1 (3)  3 (4)  4 (5)  1 (6)  5
 (7) 4 (8) 2 (9) 4 (10) 1 (11) 4 (12) 1 5. Statement I: Melting point of neo-pentane is great-
(13) 1 (14) 3 (15) 2 (16) 3 (17) 1 (18) 1 er than that of n-pentane but the boiling point of
n-pentane is more than that of neo-pentane.
(19) 1 (20) 2 (21) 3 (22) 3 (23) 1 (24) 2
Statement II: Melting point depends upon packing
(25) 1 (26) 2 (27) 1 (28) 3 (29) 4 (30) 4
in crystal lattice whereas boiling point depends upon
(31) 2 (32) 4 (33) 2 (34) 3 (35) 2 (36) 2 surface area of the molecule.
(37) 4 (38) 3 (39) 3 (40) 1 (41) 2 (42) 2
(43) 3 (44) 2 (45) 2 (46) 2 (47) 3 (48) 4
(49) 3 (50) 4 (51) 4 (52) 1 (53) 4 (54) 2 Answers
(55) 2 (56) 3 (57) 1 (58) 1 (59) 1 (60) 3
(61) 2 (62) 2 (63) 1 (64) 2   (1)  2 (2)  1 (3)  1 (4)  1 (5)  1

Chapter_17.indd 10 3/26/2014 3:30:48 PM

 Alkanes  17.11

Correct code is
  Match the Following  Type Questions
S. No A B C D
1. 1. i iii ii iv
List-I List-II 2. iv i ii iii
3. iii ii iv i
(A)  Wurtz reaction  (i)  Ni
4. i iv ii iii
(B)  Sabatier–Sender’s reaction (ii)  Zn
(C)  Frankland reaction (iii) CaO + NaOH
(D) Decarboxylation  (iv)  Na Answer

(1) 2

Chapter_17.indd 11 3/26/2014 3:30:48 PM

 This page is intentionally left blank.

Chapter_17.indd 12 3/26/2014 3:30:48 PM

 18

Chapter
Alkenes

• Alkenes are unsaturated hydrocarbons which contain a • Except terminal alkynes, all the other alkynes on
double bond. ­partial reduction yield cis or transalkenes depending
• Alkenes are also called as olefins (olefiant = oil upon the nature of catalyst used.
forming); because C2H4 forms oily product with
­ • If the catalyst used is Lindlar’s catalyst (or) nickel
Cl2 or Br2. boride, (P–2) catalyst (or) hydroboration followed by
• General formula of alkenes is CnH2n. protolysis gives almost cis alkene.
• The carbon atoms in double bond are sp2 hybridised. • If the catalyst used is Wilkinson catalyst [(PPh3)3 RhCl],
sodium or lithium in liquid ammonia or sodamide in
• Due to the presence of double bond, alkenes are more
liquid ammonia or sodium in ethyl alcohol, metal amine
reactive than alkanes.
and metal ammonia systems yield trans isomer.
• The double bond contains one sigma bond and one
pi bond. Example:
Na in liquid CH3 H
• The pi electrons are easily available to reagents and
NH3
hence alkenes undergo addition reactions. C=C
H CH3
Preparation
CH3 – C ≡ C – CH3
1.  From Alkynes
Lindlar’s
H H
• Partial reduction of alkynes with calculated amount of
catalyst C=C
dihydrogen in the presence of catalysts gives
H3C CH3
CnH2n – 2 Catalyst
H2
→ CnH2n
Cis - 2 - butene
• Palladised charcoal partially deactivated with poisons • In the formation of cis alkene (Z alkene), the metal
such as sulphur compounds or quinoline is known as catalyst ensures that the two hydrogen atoms add to the
Lindlar’s catalyst. same face of the alkene in a syn-addition.
• Raney nickel is precipitated nickel from Ni-Al alloy R–C≡C–R
with NaOH. H2 H H
• Adam’s catalyst is brown platinum oxide (PtO2). R–C≡C–R
Lindlar’s
• Adkin’s catalyst is copper chromite CuO.Cr2O4. catalyst

• Terminal alkynes on partial reduction give only one

R R
type of alkene.
CH ≡ CH + H2 Lindlar’s
→ CH2 = CH2
Catalyst
C=C

CH3 – C ≡ CH + H2 Lindlar’s
→ CH3 – CH = CH2
Catalyst H H

Chapter_18.indd 1 3/26/2014 3:30:48 PM

 18.2  Objective Chemistry - Vol. I

• In the formation of trans alkene (E alkene), the two h­ydrogen atoms add to the opposite faces of the alkene.
The solvated electrons of the Na in liquid NH3 reduce the alkyne to radical anion. The bulky R groups in the radical
anion and subsequently in the vinyl anion lie as far apart as possible.
R R H
R – C ≡ C – R + e–
low Θ NH3
temp C≡C C = C. + NHΘ
2
R R
Radical anion Vinyl radical
electron repulsion
forces the R groups
H apart (trans)
R e–
Θ C=C NH3 H
NH2 + R
C=C
H R Θ R
Vinyl anion

2.  From Alkyl Halides

• (1) Dehydrohalogenation of monohalo alkanes gives alkenes. This involves the b-elimination since hydrogen atom is
eliminated from the b-carbon atom, that is, next to the carbon to which halogen is attached.
H H H H
β |α
alco KOH
H –– C –– C –– H C=C
∆
| |
H X H H
(X = Cl, Br, I)
• Except 2-halopropane, all other higher 2-alkyl halides on heating with alcoholic KOH yield a mixture of two isomeric
alkenes, the more substituted are predominates.
alco KOH +
∆ 2–Butene 1–Butene
Br (Major) (Minor)

alc. KOH
+
∆ 71% 29%
Br
• Saytzeff’s rule states that hydrogen is preferentially eliminated from the carbon having less number of hydrogen
atoms (poor becomes poorer).
• In dehydrohalogenation the more stable the alkene, the more easily it is formed.
• Decreasing order of stability of alkenes is as follows.
R2C = CR2 > R2C = CHR > R2C = CH2 > RCH = CHR > RCH = CH2 > CH2 = CH2.
• The dehydrohalogenation reactivity of alkyl halides is 3° (tertiary) > 2° (secondary) > 1° (primary) halide Iodine >
bromine > chlorine
• The OH– ion (base) removes a proton from carbon, simultaneously a halide ion separates and a double bond is formed.
H Br2 H
| | |
H – C ––– C – H H – C = C – H + Br– + H2O
| |
H H
–
OH

Chapter_18.indd 2 3/26/2014 3:30:50 PM

 Alkenes  18.3

• It is an example of E2 reaction as it follows second 3.  Dehydration of Alcohols

order kinetics. • Dehydration of an alcohol by
• The energy required for breaking the C – H and C – X (i) heating alcohol with conc. H2SO4 or P2O5 or H3PO4
bonds comes from (i) the bonds formed between H+ at 200°C.
and OH– ions (ii) the formation of π bond between car- (ii) passing alcohol vapours over alumina (Al2O3) at
bon atoms and (iii) the solvation energy of halide ion. 350–400°C; Al2O3 acts as Lewis acid.
• More substituted alkenes formed are known as CnH2n+1OH H
2 SO 4
∆
→ CnH2n + H2O
Saytzeff’s product, whereas less substituted alkenes
are termed as ‘Hofmann product’. RCH2CH2OH H
2 SO 4
∆
→ RCH = CH2 + H2O
(2) Dehydrohalogenation of dihaloalkanes (vic and
gem) • The ease of dehydration of different type of alcohols
Dehalogenation of vicinal or gem dihalides with zinc follows the order t-alcohol > s-alcohol > primary
dust and methanol gives alkenes.
due to
CH2Br OH >
CH3OH/CH3COOH OH > OH conjugate
| + Zn → CH2 = CH2 + ZnBr2
CH2Br stabilisation.

CH OH/CH COOH
• Dehydration of alcohols is an example of b-elimination.
CH3 – CHBr2 + Zn →
3 3
CH2 = CH2 + ZnBr2 • When the formation of isomeric alkenes is possible,
the more stable alkenes predominate. This is because
3 CH OH
CH3 – CH – CH2 + Zn →CH
∆ 3 – CH = CH2 + ZnBr2 the reaction proceeds through the formation of carbe-
| | nium ion which converts into the most stable one.
Br Br
• The conversion of less stable carbenium ion to more
• If Na is used in the place of Zn, gem dihalides give stable carbenium ion takes place due to 1, 2-hydride or
alkenes having double the number of carbon atoms. methyl or phenyl shift. The ease of 1,2-shift is in the
order
2CH 3CHBr 2   +   4Na    Ether
 →    CH 3CH   =   CHCH 3
 + 4NaBr C6H5– < CH –3 < H–

For example:
CH3 H CH3 H
| | –H2O | |
1,2 methyl shift
CH3 –– C –– C –– CH3 + H⊕ CH3 – C – C – CH3
| | | ⊕
CH3 OH CH3

CH3 H CH3 CH3

| | + | |
–H
CH3 –– C –– C –– CH3 CH3 – C = C – CH3
⊕ |
CH3
• Anhydrous oxalic acid or anhydrous ZnCl2 can also be used as dehydrating agents.
4. By heating quaternary ammonium hydroxides gives alkenes. This is known as Hofmann elimination, and it is an E2
reaction in which leaving group is an amine.
+
(C2H5)4NOH ∆ → CH2 = CH2 + (C2H5)3N + H2O
⊕
NR3
| – ∆
R – C – CH2 + OH R3N + R2C = CH2 + H2O
| |
R H

Chapter_18.indd 3 3/26/2014 3:30:52 PM

 18.4  Objective Chemistry - Vol. I

The product formed is alkene with fewer alkyl groups on π-bonded carbons and is known as Hofmann product.
⊕
This is due to the steric hindrance in the transition state due to the bulky R3 N group.
5.  Cope Reaction
   Amine oxides on heating at 150°C yield alkene. These Ei eliminations (elimination, intra molecular) proceed via cyclic
transition states, which require a synperiplanar arrangement of the leaving group (i.e., the leaving groups lie in the same
plane on the same side of the molecule). This can be compared to E2 elimination, which requires an anti-periplanar
­arrangement of leaving group.
R R R R R R
H heat H
H C –– C H C ––– C C=C
H H
H NR2 H NR2 +

O O HO – NR2
Tertiaryamineoxide 5-membered cyclic
transition state

Physical Properties
• Alkenes resemble alkanes in physical properties except in types of isomerism and difference in polar nature.
• First 3 members are gases, the next 14 are liquids and the higher members are solids.
• Except ethene, all other alkenes are colourless, odourless and insoluble in water. Ethene has faint sweet smell.
• They show a regular increase in boiling point with increase in size, that is, for every –CH2 group added, boiling point
increases by 20–30 K.
• Similar to alkanes, straight chain alkenes have higher boiling point than isomeric branched chain compounds.
• Since the sp2 orbitals of double-bonded carbon atoms are near to the nucleus than sp3 orbitals, sp2 orbitals are more
electronegative than sp3 orbitals. As a result, any sp2-sp3 carbon–carbon bond has a small dipolemoment in which sp3
carbon is the positive end and sp2-carbon is the negative end.
• Cis–2–butene (in general cis) alkenes have dipolemoment, since it is vector sum of H3C–C bond moments whereas
it is zero in trans isomer.
H3C CH3 H CH3

C=C C=C

H H H3C H
Net Dipole moment

Chemical Properties
• Except ethene, all other alkenes contain two parts in their molecule, that is, alkyl part and the functional group C = C.
R ––– CH = CH2

Alkyl part Functional group

• Alkyl part is inert and does not give usual substitution reactions of alkanes. However, it undergoes alkylic substitution
by halogens at high temperature or with the brominating reagent N-bromosuccinimide (NBS).

Chapter_18.indd 4 3/26/2014 3:30:54 PM

 Alkenes  18.5

• Alkenes are nucleophiles as they are electron rich due to the double bond and react with electrophiles. These reactions
lead to the introduction of two new substituents at the expense of the π-bond.
• For unsymmetrical alkenes, with different substituents at either end of the double bond, the electrophile adds regiose-
lectively, so as to form the more substituted (and therefore the more stable) carbocation.
R R R R R
⊕
Θ
C + E C⊕ + Nu R –– C –– Nu
|| Electrophile
C H C E H –– C –– E
R H
Nucleophile R R
The most stable (tertiary)
carbocation is formed.
• The more alkyl groups on the double bond, the faster the rate of electrophilic addition. This is because the electron
donating (+I) alkyl groups makes the double bond more nucleophilic, for example, Me2C = CMe2 is more reactive
to electrophiles than H2C = CH2. The presence of electron withdrawing (–I, – M) reduces the rate. For example,
H2C = CH – CH3 is much more reactive to electrophiles than H2C = CH – CF3.
• Substitution Reactions of Alkenes: Allylic substitution takes place in gas phase by free radical mechanism.
• N-Bromosuccinimide (NBS) is used for brominating alkenes in allylic positions or at 500–600o C with low concentra-
tion of halogen.
CH2 – CO Br CH2 – C
+ NBr → + NH
CH2 – CO CH2 – CO
• The ease of substitution of H atoms is, allylic > 3° > 2° > 1° > vinylic
• Substitution proceeds by the same radical substitution mechanism in alkanes.
• When a mixture of ethene, HCl and air vapours is passed over red-hot cupric oxide, vinyl chloride is formed.
1
CH2 = CH2 + HCl + O2 250° 
CuO
C
→ CH2 = CH – Cl + H2O
2
• The selective bromination at allylic position by NBS is due to the fact that it supplies low concentration of Br2, since
free radical reaction rate is faster than the addition reaction.

Addition Reactions
1.  Addition of Hydrogen (Reduction)
• The alkene double bond can be hydrogenated by hydrogen in the presence of a platinum or palladium catalyst (Sabatier–
Senderen’s reaction). The hydrogenation occurs with syn- stereochemistry as the two hydrogen atoms are added to the
same face of the alkene on the surface of the catalyst.
R′ R′ R′ R′ R′ R′
Pd/C
C=C C=C R C –– C R
H2 R
H H R H H
R R
Metal catalyst surface
• The terminal C = C may be reduced by Na in liquid ammonia in the presence of CH3OH or C2H5OH to alkane. This is
known as Birch reduction.
+ C2 H5 OH
R – CH = CH Na

2[ H − ]
→ RCH2CH3

Chapter_18.indd 5 3/26/2014 3:30:56 PM

 18.6  Objective Chemistry - Vol. I

2.  Addition of Hydrogen Halides

• The addition of HX (X = Cl, Br, I) to alkene to form alkyl halides occurs in two steps. The first step involves the
­addition of a proton (i.e., the electrophile) to the double bond to make the most stable intermediate carbocation.
The second step involves nucleophilic attack by the halide anion. This gives a racemic alkyl halide product because
the carbocation is planar and hence can be attacked equally from either face (these addition reactions are the reverse
of alkyl halide elimination reaction).

R
R R |
R –C – X
C⊕
| + X |
H –– C –– H H –C – H
| |
R R
The proton
adds to the less tertiary carbocation
R substituted
R
carbon atom
C
δ+ δ–
+ H – X The tertiary rather than
C secondary carbocation
is formed because this
R H is more stable
R

R –– C –– H
C⊕
R H
secondary carbocation

• The regioselective addition of HX to alkenes produces the more substituted alkyl halide, which is known as the
Markonikov (Markonikoff) product.
• Markonikov’s rule states that on addition of HX to an alkene, H attaches to the carbon with fewest alkyl groups and X
attached to the carbon with most alkyl groups. This can be explained by the formation of the most stable intermediate
carbocation.
• The intermediate carbocation undergoes structural rearrangements to form more stable carbocations.
• A hydrogen atom (with its part of electrons) can migrate into an adjacent carbon atom in ‘hydride shift’. This will only
occur if the resultant cation is more stable than the initial cation.
R R
R
H C
H CHR2 H C R
+ – C⊕ H ⊕
C δ δ hydride C
–X shift H
+ H X H C H
C H C H
H X
H H H

Regeoselective addition of This produces

a proton to give the secondary a more stable
rather than primary carbocation tertiary carbocation

Chapter_18.indd 6 3/26/2014 3:30:57 PM

 Alkenes  18.7

• Alkyl groups can also migrate to a carbocation centre in Wagner–Meervin rearrangements (or shifts).
R R R
H CR3
+ –
C δ δ H C H C R
–X R migration ⊕
|| + H– X C⊕ R C
C | | R
H C H H C H X

|
H H

|
| |
H H
Secondary carbocation Tertiary carbocation

3. Addition of HBr to Alkenes in the Presence of Peroxide

• In the presence of a peroxide (ROOR), HBr adds to alkenes to give the alternative regioisomer. This is the
­anti-Markonikov product.
• The change in regioselectivity occurs because the mechanism of the reaction changes from an ionic mechanism in the
absence of peroxide to a radical mechanism in the presence of peroxide.
• Initiation by peroxide leads to the formation of bromine radicals which add to the less-hindered end of the alkene. This
gives the more substituted radical, which in turn produces the less-substituted alkyl halide (more substituted radicals
are more stable similar to more substituted carbocations).

heat or light
RO – OR RO• + •OR (initiation step)

RO• + H Br RO – H + •Br

A strong O – H bond is formed at the expense of a weaker H – Br bond.

R
The bromine atom adds to the The bromine atom is regenerated
R C Br
less hindered carbon because with another molecule of alkene
this is more accessible in a chain reaction
C
•
R H
R R
secondary radical
C
|| •Br
C
R H
R
R R
•
C• Br
R C H
The tertiary radical + H – Br
is more stable than the H C Br H C Br
secondary radical. R
R

tertiary radical Anti-Markonikov

product

Chapter_18.indd 7 3/26/2014 3:30:58 PM

 18.8  Objective Chemistry - Vol. I

4.  Addition of Bromine

• The electrophilic addition of bromine produces 1,2-dibromide (or vicinal dibromide).
• The addition of bromine to double bond is stereospecific because of the formation of an intermediate bromonium ion.
The bromine atoms add to the opposite sides of the alkene in an anti-addition.

H R H

C δ+ δ– ⊕ C R
+ Br – Br → Br
+ Br
C C
H
R H
R

cyclic bromonium ion

The bromine molecule becomes
polarised as it approaches the alkene.
The Br atom near the double bond (cf. SN2 reaction)
becomes electrophilic (as the electrons
in Br – Br bond are repelled away
from the electron - rich double bond) H
Br

C R
|
R C
Overall anti-addition as the two bromine atoms
ends up on opposite sides of the planar alkene. H Br

• The anti-addition explains the formation of different diastereoisomers when using E- or Z-alkenes.
Recimic mixture of
enantiomers
(no plane of symmetry)
⊕ Br H
Br
H H Me
Br2
C=C C C C –– C
Me Me H H H
Me Br
Me Br Me
Z-but-2-ene
diastereoisomers

+ Me
Br Br
H Me H
Br2
C=C C–C C –– C
Me H H Me H
Me H Me Br
Br
E-but-2-ene meso compound-achiral
(has a plane of symmetry)

• As Br– can attack either carbon atom of the bromonium ion, reaction with Z-but-2-ene produces a 1:1 mixture of
enantiomers (only the 2R, 3R isomer is shown above).
• For E-but-2-ene the attack of Br– at either carbon atom of the bromonium ion produces the same compound. This
compound has a plane of symmetry and hence is an achiral meso compound.

Chapter_18.indd 8 3/26/2014 3:30:59 PM

 Alkenes  18.9

5.  Addition of Bromine in the Presence of   Water

• The addition of bromine to an alkene in the presence of water can lead to the formation of a 1,2-bromo-alcohol
(or ­bromohydrin) in addition to a 1,2-dibromide. This is because water can act as nucleophile and compete with the
bromide ion for ring opening of the bromonium ion.
• The opening of the bromonium ion is often regioselective. The nucleophile attacks the more substituted carbon atom
of the ring. Because this carbon atom is more positively polarised.
• Even though Br– is a better nucleophile than H2O, if H2O is present in excess, then 1,2-bromoalcohol will be formed.

6. Addition of Water (Hydration): Markonikov Addition

• The addition of water to alkenes to produce alcohols requires the presence of either (i) a strong acid or (ii) mercury
acetate (in an oxymercuration reaction). In both cases, the reactions involve the Markonikov addition of water (i.e., the
OH becomes attached to the more substituted carbon).
Acid catalysis (requires high temperatures)
R
R R R R
H
⊕
C δ+ δ–
C ⊕
R C O
H – Cl H2O
H
H2O
H C H H C H
C 
H + Cl
H H H
The most stable carbocation
Cl
is formed.
R

R C OH
HCl +
(regenerated)
H C H

H
Oxymercuration
R R
Mercurinium ion R
R δ– R
R OAc δ+C
δ+ –
C δ C ⊕
Hg – OAc ⊕
AcO – Hg AcO – Hg C
H2O
H
C C H
H H nucleophilic attack at H2O
H
+  OAc H the most substituted
carbon atom with the
greatest δ+ character
R R
R
| | ⊕
H
R C OH Reduction of the R – C – OH R– C –O
C–Hg bond to a
C – H bond H
NaBH4 AcOHg – C – H AcOHg – C – H
H C H
(sodium
borohydride) H
H H AcO
Overall anti addition

Chapter_18.indd 9 3/26/2014 3:31:00 PM

 18.10  Objective Chemistry - Vol. I

7. Addition of Water (Hydration): Anti-Markonikov Addition

• The anti-Markonikov addition of water is achieved using borane (B2H6 which reacts as BH3) in hydroboration reaction.
The reaction involves the syn-addition of boron–hydrogen bond to the alkene via a four-membered transition state,
that is, the boron atom and hydrogen atom add to the same face of the alkene.
• Hydroboration is a highly regoselective reaction, and steric factors are important. The boron atom adds to the least
hindered end of the alkene to give an organoborane (regioselectively) which is then oxidised to alcohol.
• Bulkier boranes can enhance the regioselectivity of hydroboration. Hydroboration (regioselective and stereoselective)

R R R R R H
– R
Hδ
C | C
BH2 δ+ C H
C δ+ C
borane C BH2 H BH2
H H H
δ–
H H
The boron atom adds 4-membered Syn-addition : the H and BH2
to the less hindered transition state add to the same face of the alkene
carbon atom

• Boron is more electropositive than hydrogen, and hence the double bond will attack the boron atom to give a partial
positive charge on one of the (alkene) carbon atoms in the four-membered transition state. The partial positive charge
will present on the more substituted carbon atom as this is more stable.
• Alkenes react rapidly with diborane to form trialkyl boranes

RCH = CH2 BH

 3
→ (RCH2–CH2)3B
• Terminal alkenes give primary alkyl boranes which on oxidation with alkaline H2O2 gives primary alcohols.

(RCH2–CH2–)3 B NaOH

H 2 O2
→ 3RCH2CH2OH + H3BO3

8. Oxidation by Peroxycarboxylic Acids (RCO3H) and Hydrolysis of Epoxides to give Anti-Dihydroxylation

• The reaction of alkenes with peroxy carboxylic acids (or peracids) leads to the formation of epoxides in a concerted
addition reaction. The peroxy carboxylic acid donates an oxygen atom to the double bond in a syn-addition reaction.

δ– H
R H
O O R
R
C R C C
O δ+ C O +
C C O
H O
R H R H
H
peroxycarboxylic epoxide
acid
The addition is stereospecific, so the cis- epoxide is formed from the cis -alkene.
A trans alkene would give a trans -epoxide.
• Epoxides can be hydrolysed under acid- or base-catalysed conditions to form 1,2-diols. These reactions lead to the
opening of the strained three-membered (epoxide) ring.
• The formation and hydrolysis of an epoxide lead to the stereoselective anti-addition of two OH groups.

Chapter_18.indd 10 3/26/2014 3:31:01 PM

 Alkenes  18.11

Base Catalysis
δ– H – OH
anti-addition
H
O 
H HO
SN2 attack by O
δ+ R R
C C hydroxide
C C C C
H H
H OH H
OH
R R
R R +


OH OH (regenerated)
Even though hydroxide is a poor nucleophile
it will open the strained epoxide ring on heating
• Though hydroxide is a poor nucleophile, it will open the strained epoxide ring on heating.
Acid Catalysis
H
O ⊕ H
O HO
SN2 attack
H⊕ R
by water
C C C C C ––– C
H –H⊕ H H ⊕
H O
R H
R R R O H
R
protonation makes the OH2
epoxide a better electrophile H
HO
R
⊕
H + C C
(regenerated)
H
OH
R

9. Syn-Dihydroxylation and Oxidative Cleavage of 1,2-Diols to form Carbonyls

• The reaction of alkenes with potassium permanganate at low temperature or osmium tetroxide leads to the syn-­addition
of two OH groups to the same face of the double bond.
   Potassium permanganate (low temperature)
syn-adddition
H
R H R O R H
O
O OH
C O low C 

temp Mn C
HO
C
Mn K⊕ C
O O H2O
R C
 O O K⊕
R H H OH
R
+ H
The two C–O bonds are formed on cyclic manganate ester MnO2
the same face of the alkene
The formation of the cyclic ester leads to the
reduction of manganese, from Mn(VII) to Mn(V)

Chapter_18.indd 11 3/26/2014 3:31:02 PM

 18.12  Objective Chemistry - Vol. I

   Osmium Tetroxide
H
H
R H R
R O O C OH
O O H2O reducing agent
C C
Os (e.g. NaHSO3)
Os C
C C OH
O O O O
R R
R H H H

The two C–O bonds are formed cyclic osmate ester +

on the same face of the alkene H2OsO4

The formation of the cyclic ester leads to the

reduction of osmium, from Os(VIII) to Os(VI)
• 1,2-diols can be oxidised further to form carbonyl compounds. This results in the cleavage of the C – C bond.
• When potassium permanganate is reacted with alkenes at room temperature or above, the intermediate 1,2-diol can be
further oxidised to form carboxylic acids.
R R R R
KMnO4
C=C C=O+O=C
H2O

H H HO OH
• 1,2-diols can also be oxidised to aldehydes or ketones by reaction with periodic acid (HIO4)
OH OH

RCH – CHR + HIO4 2RCHO + HIO3

10.  Oxidative Cleavage by Reaction with Ozone
• The reaction of alkenes with ozone at low temperature produces an intermediate mol ozonide which rapidly rearranges
to form an ozonide. This leads to the cleavage of the C = C double bond.
H H
R H R
O
low C O
C O C
temp. R
O⊕ O
⊕

O
C  O C R C
O O
R H R H H

This is know as a 1,3-dipolar molozonide

addition (ozone is a 1,3-dipole) (or primary ozonide) flip-over aldehyde

H R The rearrangement leads to formation H

δ– δ+
C of two C–O bonds at the expense of O C
O a C–C bond and a very weak O–O bond R
O
⊕ O
R C R C
O
O
H H
ozonide

Chapter_18.indd 12 3/26/2014 3:31:04 PM

 Alkenes  18.13

• The intermediate ozonide can then be reduced to aldehydes/ketones or be oxidised to carboxylic acids.
M e 2S
H H n or 2RCHO aldehydes or ketones
c t i on Z h 3
u P
Red or P

R –– C –– O –– C –– R
Ox
ida
tion
H O
O O 2
2 2RCOOH carboxylic acids

• Ozonolysis reaction is highly useful in detecting the position of the double bond in alkenes or other unsaturated
compounds.
• To determine the product by ozonolysis of alkenes, break C = C bond and place oxygen on either side at break-
­ing point.
H H

Ozonolysis
CH3 – CH = CH – CH3 CH – C = O + O = C – CH3

CH3 CH3 H
|
Ozonolysis
CH3 – C = CH2 CH3 – C = O + O = C – H

• To decide the structure of alkene from ozonolysis products, bring the products together in such way that O atoms are
facing each other and replace ‘O’ atoms by C = C bond.
H H

CH3 – C = O + O = C – CH3 CH3 – CH = CH – CH3

• If only one type of product with number of carbon atoms half of the alkene is given, it means that alkene is symmetrical
and two mol of the products are taken to decide the structure as given above.
• Cycloalkenes give the product containing equal number of carbon atoms as present in parent compound.
• If there are more than one double bond in alkenes or cycloalkenes, ozonolysis will takes place at all the double bonds.
11.  Reaction with Carbenes
• Carbenes will add to alkenes to form cyclopropane.
• The mechanism of insertion of carbene reaction depends on whether singlet carbene or triplet carbene adds to the
double bond.
• Singlet carbene insertion is stereospecific syn addition, whereas triplet carbene insertion is stepwise mechanism and
non-stereospecific.
R H H
R

C X C The C–C bonds are formed

C CX2 at the same time and the reaction
is stereospecific i.e. a Z-alkene gives
C X C a cis-cyclopropane

R H R
H
the two electrons have opposite
spins and are in the same orbital

Chapter_18.indd 13 3/26/2014 3:31:05 PM

 18.14  Objective Chemistry - Vol. I

12.  Reaction with Dienes

• Alkenes containing an electron-withdrawing substituent can add to electron-rich conjugated dienes in the
Diels–Alders cyclo-addition reaction.
• This is a concerted reaction leading to the formation of two new C – C bonds in one step, and it is a pericyclic reaction.
• Pericyclic reaction is a concerted reaction that involves flow of electrons.

(–I, –M) +
COCH3 COCH3 COCH3
Heat

1,3 diene The alkene is

cyclic transition state
known as the
dienophile

• The alkene is known as the dienophile.

• The s-cis (or cisoid) conformation of the diene is required, and the reaction is stereospecific (i.e., only syn addition).
Groups that are cis in the (alkane) dienophile will therefore be cis in the product; conversely, groups that are trans in
the dienophile will be trans in the product.
13. Polymerisation
• Simple alkenes and conjugated dienes polymerise to form very large molecules. The large molecules thus obtained are
called polymers.
• Polymerisation of alkenes takes place at high pressure, at high temperature and in the presence of catalyst.
• The simple compounds from which polymers are made are called monomers.
• Polymerisation of alkenes takes place by free radical mechanism.

nCH2 = CH2 Opressure


2 , heat
→ –– (CH2 – CH2)n

14. Addition of sulphuric acid to alkenes takes place with cold concentrated sulphuric acid according to Markonikov rule
to form alkyl hydrogen sulphate by the electrophilic addition reaction.
O

CH2 = CH2 + HO – S – OH → CH3 – CH2 – OSO2OH or C2H5HSO4

Ethyl hydrogen sulphate
O
CH3 – CH = CH2 + HOSO2OH → (CH3)2 CHOSO2OH
Propyl hydrogen sulphate

 Objective Questions
1. Ethylene forms ethylene chlorohydrin by the 2. Which of the following is an elimination reaction?
action of (1) CH3CH2OH  → CH2 = CH2 + H2O
(1) dry chlorine gas
(2) CH3CH2Br  → CH2 = CH2 + HBr
(2) dry hydrogen chloride gas
(3) solution of chlorine gas in water (3) Br – CH2 – CH2 – Br Zn
→ CH2 = CH2 + ZnBr2
(4) dilute hydrochloric acid (4) All are correct

Chapter_18.indd 14 3/26/2014 3:31:07 PM

 Alkenes  18.15

3. Two jars A and B are filled with hydrocarbons. Br2 in 11. Which of the following reactions will yield 2, 2-
CCl4 is added to these jars. A does not decolourise the dibromopropane?
Br2 solution but B decolourises. What are A and B? (1) HC≡CH + 2HBr  →
(1) Alkane and alkene (2) CH3–C≡CH + 2HBr  →
(2) Alkene and alkane (3) CH3–CH=CH2 + HBr  →
(3) Alkene and alkyne (4) CH3 – CH=CHBr + HBr  →
(4) None of the above
12. The product of the reaction
4. Which of the following is an unsymmetrical alkene? (CH 3 )3 CCH = CH 2 (i(ii
) Hg ( OA C )2 ; THF
→
) NaBH 4 + NaOH
(1) 1-Butene (2) 2-Hexene
(3) 1-pentene (4) All of these (1) (CH3)3C–CH2–CH3
(2) (CH3)3C CH2CH2OH
5. Ozonolysis can be used to detect
OH CH3
(1) 1-butene and 2-butene
(2) branched alkene and unbranched alkene (3) (CH3)2C – CH – CH3
(3) location of double bond/triple bond in c­arbon
CH3
chain
(4) all are correct
(4) HOCH2 – C – CH2 – CH3
6. The olefin which on ozonolysis gives CH3CH2CHO
and CH3CHO is
CH3
(1) 1-butene
(2) 2-butene 13. A hydrocarbon of formula C6H10 absorbs only one
(3) 1-pentene molecule of H2 upon catalytic hydrogenation. Upon
(4) 2-pentene ­ozonolysis the hydrocarbon yields
O = CH – CH2 – CH2 – CH2 – CH2 – CHO
7. Ethylene reacts with sulphur monochloride to form The hydrocarbon is
(1) Cl – CH2 – S – CH2Cl (1) cyclohexane
(2) Cl – CH = CH – S – CH = CH – Cl (2) benzene
(3) Cl – CH2 – CH2– S – CH2– CH2 – Cl (3) cyclohexene
(4) Cl – CH2 – CH2– S – S – CH2– CH2 – Cl (4) cyclobutane
8. A alc.KOH
 → B Zn
O3
+ H2O
→ H − CHO ←O2
M oO3 /350° C
C 14. An alkene obtained by the dehydration of an a­ lcohol
In the above sequence, ‘A’ and ‘C’ are (A) on ozonolysis gives two molecules of a­ cetaldehyde
for every molecule of alkene. The ­alcohol (A) is
(1) Ethyl bromide, ethane
(2) Ethyl chloride, methane (1) CH3CH2CH2OH
(3) Ethyl alcohol, ethane (2) CH3CH2OH
(4) Ethyl alcohol, methane (3) CH3CH = CHCH2OH
(4) CH3CH2CH(OH)CH3
450° C
9. CH 3I Na/ether
 → A absence
 of O2
→ B HBr
 →C
15. Identify Z in the sequence.
alc
KOH
→ D
CH 3 − CH 2 − CH = CH 2 HBr
 / H 2 O2
→ Y C
2 H 5ONa
→Z
In the above sequence, B and D are
(1) B = ethane, D = ethylene (1) CH3 – CH –CH2 –O – CH2 – CH3
(2) B = ethylene, D = acetylene
(3) both B and D are ethane
CH3
(4) both B and D are ethylene
10. When HCl gas is passed through propene in the CH3
­presence of benzoyl peroxide, it gives
(1) n-propyl chloride (2) CH3 – CH2 – CH –O – CH2 – CH3
(2) 2-chloropropane
(3) CH3 – (CH2)3 – O – CH2 – CH3
(3) allyl chloride
(4) no reaction (4) CH3 – (CH2)4 – O – CH3

Chapter_18.indd 15 3/26/2014 3:31:10 PM

 18.16  Objective Chemistry - Vol. I

16. Addition of HI on double bond of propene yields (3) OH– in the first step
­isopropyl iodide and not n-propyl iodide as the major (4) Cl+ and OH– in a single step
product, because addition proceeds through
24. In the preparation of alkene from alcohol using Al2O3
(1) a more stable carbonium ion
which is an effective factor?
(2) a more stable carbanion
(3) a more stable free radical (1) porosity of Al2O3
(4) none (2) temperature
(3) concentration
17. Anti-Morkonikov addition of HBr is not observed in (4) surface area of Al2O3
(1) propene (2) butene-1
(3) butane-2 (4) pentene-2 25. Select the major product formed from the treatment
of 2-bromobutane and alcoholic KOH.
18. A hydrocarbon X adds on one mole of hydrogen to
(1) CH2 = CHCH2CH3
give another hydrocarbon and decolourised bromine
(2) cis CH3CH = CHCH3
water. X reacts with KMnO4 in the presence of acid
to give two moles of the same carboxylic acid. The (3) trans CH3CH = CHCH3
structure of X is (4) CH2 = CHCH3
(1) CH3CH = CHCH2CH2CH3 26. Alkene which upon acid-catalysed hydration ­produces
(2) CH3CH2CH = CHCH2CH3 tertbutyl alcohol is
(3) CH3CH2CH2 – CH = CHCH3 (1) CH3CH2 CH = CH2
(4) CH2 = CH – CH2CH2CH3 (2) CH3CH = CHCH3
19. Reactivity of alkenes towards HX decreases in the (3) (CH3)2CH = CH2
­order (4) CH3CH = CH2
(1) Butene > propene > ethene
27. Addition of HCl to 2-methyl-2-butene mainly gives
(2) Butene > ethene > propene
(3) Ethene > propene > butene (1) 1-chloro-2-methyl butane
(4) Propene > ethene > butene (2) 2-chloro-2-methyl butane
(3) 2-chlorobutane
20. Ozonolysis of 2,3-dimethyl-1-butene followed by (4) 1-chlorobutane
­reduction with zinc and water gives
(1) methanoic acid and 3-methyl-2-butanone 28. The addition of HCl in the presence of peroxide does
(2) methanal and 2-methyl-2-butanone not follow anti-Markonikov’s rule because
(3) methanal and 3-methyl-2-butanone (1) HCl bond is too strong to be broken homolytically
(4) methanoic acid and 2-methyl-2-butanone (2) Cl atom is not reactive enough to add on to a
­double bond
21. Which of the following is the predominant product in
(3) Cl atom combines with H atom to form HCl
the reaction of HOBr with propene?
(4) HCl is a reducing agent
(1) 2-Bromo-1-propanol
(2) 3-Bromo-1-propanol 29. Addition of HBr to 2-methyl 1-propene in the
(3) 2-Bromo-2-propanol ­presence of hydrogen peroxide mainly forms
(4) 1-Bromo-2-propanol (1) 1-Bromobutane
22. 2.8 gm of pure alkene containing only one double (2) 2-Bromobutane
bond per molecule reacts completely with 8 gm of (3) 2-Bromo-2-methyl propane
bromine (in inert solvent). What is the molecular (4) 1-Bromo-2-methyl propane
­formula of the alkane? 30. Which of the following alkene on oxidation with hot
(1) C2H4 (2) C4H8 KMnO4 will give only
(3) C3H4 (4) C6H12 CH3 CO (CH2)4 CO CH3?
23. The reaction of propene with HOCl proceeds via the (1) cyclohexene
addition of (2) 1-methyl cyclohexene
(1) H+ in the first step (3) 1,2-dimethyl cyclohexene
(2) Cl+ in the first step (4) 1,2-dimethyl cyclopentene

Chapter_18.indd 16 3/26/2014 3:31:10 PM

 Alkenes  18.17

31. Which of the following reagent would you prefer to 36. Identify the false statement.
find out whether the hydrocarbon C3H4 contains one (1)  When ethyl iodide is treated with alcoholic
triple bond or two double bonds? ­potash, the product formed is ethylene
(1) Fehling’s solution (2) When ethyl alcohol vapours are passed over hot
(2) Ammoniacal AgNO3 and CuCl solution alumina, the product formed is ethylene
(3) Baeyer’s reagent (3) When ethyl alcohol is heated with conc. H2SO4 at
(4) Br2/CCl4 170°C, the product formed is diethyl ether
(4)  Electrolysis of potassium succinate gives
32. Indicate the organic structure for product expected
­ethylene
when 2-methyl propene is heated with acetyl chloride
in the presence of anhydrous ZnCl2? 37. Which of the following statement is wrong?
CH3 (1) Alkenes decolourises alkaline KMnO4 solution
| but does not give precipitate with silver nitrate
(1) CH3 CO – C = CH2 (2) Oxidation of alkenes with cold and dilute ­alkaline
CH3 KMnO4 gives 1,2-diols (glycols)
| (3)  Hydroxylation of alkenes with alkaline
(2) CH3 – CO – C –– CH3 ­permanganate is always syn-addition
(4)  During oxidation of alkenes by alkaline
|
CH3 ­permanganate, the oxidation state of Mn changes
from +7 to +6
CH3
| 38. The false statement among the following is
(3) CH3 – C – CH2COCH3 (1)  Hydroxylation of cis alkenes with alkaline
| KMnO4 always gives erythro form
Cl (2)  Hydroxylation of trans alkenes with alkaline
H KMnO4 always gives racemic (dl) mixture
| (3) Hydroxylation of alkenes is always anti-addition
(4) CH3 – C – CH2COCH3 (4)  Hydroxylation using I2/CH3COOAg is always
| syn-addition producing 1,2-diols or glycols
CH3 39. Which of the following statement is not correct?
(1) Acidified KMnO4 or K2Cr2O7 oxidises alkenes to
33. The product of acid-catalysed hydration of 2-phenyl
carbonyl compounds finally to carboxylic acids
propene is
(2) Terminal alkenes give CO2 as one of the product
(1) 3-phenyl-2-propanol when oxidised with acidified KMnO4 or K2Cr2O7
(2) 1-phenyl-2-propanol (3) Acidified KMnO4 or K2Cr2O7 oxidises 2-bu-
(3) 2-phenyl-2-propanol tene to acetic acid but 2,3-dimethyl-2-butene to
(4) 2-phenyl-1-propanol ­acetone
34. Which of the following is used for the conversion of (4)  Oxidation of 2-methyl propene with a­cidified
2-hexyne into trans 2-hexene? KMnO4 or K2Cr2O7 gives acetone and
(1) H2/Pd/BaSO4 ­formaldehyde
(2) H2, PtO2 40. Which of the following reaction is correct?
(3) NaBH4
(1) CH2 = CH2 + PdCl2 + H2O 50°
C
→
(4) Li - NH3/C2H5OH
CH3CHO + Pd + 2HCl
35. B ←
Lindlar / H 2
 R − C ≡ C − R Na
/ NH3
→A (2) CH3CH = CH2 + PdCl2 + H2O 50° 
C
→
A and B are geometrical isomers CH3COCH3 + Pd + 2HCl
(R – CH = CH – R) (3) CH2 = CH – CH2 – CH3 SeO
2
→
(1) A is cis, B is trans CH2 = CH– CH – CH3
(2) A is trans, B is cis |
(3) A and B both are cis OH
(4) A and B both are trans (4) All are correct

Chapter_18.indd 17 3/26/2014 3:31:12 PM

 18.18  Objective Chemistry - Vol. I

41. Identify the wrong statement about alkenes. (3) CH2 = CH – CH3 + Hg(OAc)2
(1) The boiling points, melting points and s­pecific CH3 – CH – CH2CH2OAc + CH3COOH
gravities show a gradual increase with the |
­increase in molecular mass OH
(2) These are less volatile and have more melting
points and boiling points than corresponding R–O–O–R
(4) CH3CH = CH2 + HBr
­alkanes CH3CH2CH2Br
(3) Cis isomers have lower boiling points than trans
48. The Markonikov addition of HCl to propene
isomers
involves the
(4) Cis isomers have lower melting points than trans
isomers (1) initial attack of chloride ion
(2) isomerisation of 1-chloropropane
42. Which of the following statement is correct? (3) formation of an n-propyl cation
(1) Cis alkenes are polar and hence have more b­ oiling (4) formation of an isopropyl cation
points than trans isomers but trans ­isomers are
non-polar with low boiling points 49. Which of the following is a cumulated diene?
(2) Trans isomers are symmetrical and hence pack (1) 1,3-pentadiene (2) 1,4-pentadiene
more closely in crystal lattice causing more (3) 2,3-pentadiene (4) 1,5-hexadiene
­melting points than cis isomers 50. Which of the following has the lowest heat of
(3) Alkenes are insoluble in water but soluble in ­hydrogenation per mole?
­organic solvents
(1) cis-2-butene (2) trans-2-butene
(4) All are correct
(3) 1-butene (4) 1,3-butadiene
43. But-2-ene can be obtained by reacting
51. On heating with alcoholic potassium hydroxide,
(1) 1,2-dibromopropane with zinc
­neopentyl bromide gives mainly
(2) Ethyl bromide with sodium
(3) Ethylidine bromide with zinc (1) 2-methyl-2-butene
(4) n-butyl alcohol with alcoholic KOH (2) 2-methyl-1-butene
(3) 2-butene
44. The only alcohol that can be prepared by the indirect (4) 2,2-dimethyl-1-butene
hydration of alkene is
52. Identify the false statement.
(1) ethyl alcohol (2) propyl alcohol
(3) isobutyl alcohol (4) methyl alcohol (1)  Sodium ethoxide is a specific reagent for
­dehydration
45. Among the alkenes which one produces tertiary butyl (2) Alkanes and alkenes can both be obtained by
alcohol on acid hydration? Kolbe’s electrolytic method
(1) CH3CH2 CH = CH2 (2) CH3CH = CHCH3 (3)  The major product of the reaction of
(3) (CH3)2C = CH2 (4) CH3CH = CH2 CH3CH2CHBrCH3 with alcoholic KOH is
2-butene
46. Ozonolysis of an organic compound gives
(4) Butadiene is a conjugated diene
­formaldehyde as one of the products. This confirms
the presence of 53. The number of enantiomeric pairs that can be
(1) a vinyl group produced by the monochlorination of 2-methyl
­
(2) two ethylenic bonds ­butane is
(3) an isopropyl group (1) one (2) two (3) three (4) four
(4) an acetylinic triple bond
54. The addition of HI in the presence of a peroxide does
47. In which of the following reactions are free-radical not lead to anti-Markonikov behaviour because
intermediates obtained?
Br (1) the iodine free radicals formed readily combine
| with each other to give an I2 molecule
(1) CH3CH = CH2 + HBr CH3CHCH3 (2)  the HI bond is too strong to be broken
­homolytically
(2) CH3CH–CH3 + H2SO4 CH3CH = CH2 (3) HI is a reducing agent
| (4) Iodine combines with H to give back HI
OH

Chapter_18.indd 18 3/26/2014 3:31:14 PM

 Alkenes  18.19

55. In the sequence of reactions (3) equal in both reactions

CH3CH2CH2OH PC 
l5
→ A alc
 KOH
→B (4) zero in both reactions
The product B is 64. Isobutylene reacts with HBr to give t-butyl bromide.
(1) propyne (2) propylene The intermediate formed in this reaction is
(3) propane (4) propanol (1) a t-butyl cation
56. In the sequence of reactions (2) an isobutyl cation
CH3CH2CH2OH PC 
l5
→ A aq
KOH
→B (3) a mixture of t- and isobutyl cations
(4) the addition does not take place through a cation
The product B is
intermediate
(1) propylene (2) propane
(3) propyne (4) propanol 65. Tri-n-propyl borane can be converted into propyl
­alcohol by reaction with
57. The reaction of RCH = CH2 with B2H6 followed by
(1) a hydrogen peroxide at 25–30°C
oxidation with alkaline H2O2 gives
(2) a dilute acid at reflux temperature
(1) RCH(OH) CH2OH (2) RCOCH3 (3) a dilute alkali at reflux temperature
(3) RCH2CH2OH (4) RCH2CHO (4) none of these
58. The product of the debromination of meso-­ 66. Propene is more reactive than ethene towards HBr
dibromobutane is ­because
(1) n-butane (2) 1-butene (1) propene can more readily undergo a free radical
(3) trans-2-butene (4) cis-2-butene chain reaction
59. The conversion of 3-hexyne into trans-3-hexene can (2) propene gives rise to more stable carbonium ion
be effected by (3) the double bond in the case of propene is unstable
(1) Na/liquid NH3 (2) H2/Lindlar’s ­catalyst (4) the methyl groups attached to double bond
(3) Clemmensen reduction (4) LiNH2 ­withdraw’s electrons and facilitates the attack

60. The reduction of 3-hexyne with H2/Lindlar’s catalyst 67. Propene CH3CH=CH2 can be converted into
gives predominantly 1-propanol by oxidation. Indicate which set of
­reagents amongst the following is ideal to bring the
(1) n-hexane
above conversion.
(2) trans-3-hexene
(3) cis-3-hexene (1) O3/Zn dust
(4) a mixture of cis and trans 3-hexene (2) B2H6 and alkaline H2O2
(3) alkaline KMnO4
61. A compound C4H8 decolourises a KMnO4 solution. (4) OsO4 followed by NaHSO3/alcohol
How many structures are possible for this compound?
68. Cyclopentene on treatment with alkaline KMnO4
(1) 3 (2) 4 (3) 2 (4) 5
gives
62. In the formation of cyclohexane from 1-hexene, the (1) cyclopentanol
entropy of cyclohexane is (2) trans-1,2-cyclopentane diol
(1) more than that of 1-hexene (3) cis 1,2-cyclopentane diol
(2) less than that of 1-hexene (4) mixture of (2) and (3)
(3) equal to that of 1-hexene 69. A hydrocarbon of formula C6H10 absorbs only one
(4) more or less than that of 1-hexene depending molecule of H2 upon catalytic hydrogenation. Upon
upon the conditions of the reaction ozonolysis, the hydrocarbon yields OHC CH2 CH2
CH2 CH2 CHO. The compound is
63. (A) CH3CH2CH2CH2CH = CH2 
→
(1) cyclohexene (2) cyclohexane
(B) 3CH2 = CH2 
→ (3) benzene (4) cyclobutane
70. Diels–Alder reaction is used to synthesise a ring of
Consider the reactions (A) and (B). The entropy (1) four carbon atoms
change will be (2) five carbon atoms
(1) more in reaction A than in reaction B (3) three carbon atoms
(2) more in reaction B than in reaction A (4) six carbon atoms

Chapter_18.indd 19 3/26/2014 3:31:15 PM

 18.20  Objective Chemistry - Vol. I

71. In the presence of platinum catalyst, hydrocarbon (A) (1) 1-butene (2) Ethene
adds hydrogen to form n-hexane. When hydrogen (3) Propene (4) 2-methyl propane
bromide is added to (A) instead of hydrogen, only 78. Reaction of one molecule of HBr with one molecule
a single bromo compound is formed. Which of the of 1,3-butadiene at 40°C gives predominantly
­following is (A)?
(1)  3-bromobutene under kinetically controlled
(1) CH2 = CH – CH2CH2CH2CH3 ­conditions
(2) CH3CH = CHCH2CH2CH3 (2)  1-bromo-2-butene under thermodynamically
(3) CH3CH2CH = CHCH2CH3 controlled conditions
(4) CH3CH2CH2CH = CHCH3 (3)  3-bromobutene under thermodynamically
72. Addition of bromine to buta-1,3-diene gives ­controlled conditions
(1) 1,2 addition product only (4)  1-bromo-2-butene under kinetically controlled
(2) 1,4 addition product only conditions
(3) both 1,2 and 1,4 addition products 79. Which of the reagents on reaction with cyclohexanol
(4) no reaction gives best yield of cyclohexene?
(1) Conc. H3PO4
73. The reaction of CH3CH = CH – OH with (2) Conc. HCl
HBr gives (3) dil. HCl
(4) Conc. HCl with ZnCl2
(1) CH3 CHBr CH2 OH
80. Acid-catalysed hydration of alkenes except ethene
leads to the formation of
(2) CH3 CH2 CHBr OH (1) primary alcohol
(2) secondary or tertiary alcohol
(3) CH3 CHBr CH2 Br (3) mixture of primary and secondary alcohols
(4) mixture of secondary and tertiary alcohols
81. Elimination of bromine from 2-bromobutane results
(4) CH3 CH2 CHBr OH
in the formation of
(1) equi-molar mixture of 1-and 2-butene
75. In the presence of peroxide, hydrogen chloride and
(2) predominantly-2-butene
hydrogen iodide do not give anti-Markonikoff’s
(3) predominantly-1-butene
­addition to alkenes because
(4) predominantly-2-butyne
(1) both are highly ionic
(2) one is oxidising and other is reducing 82. Addition of Br2 to Z but-2-ene gives
(3) one of the steps is endothermic in both the cases (1) (R, R)-2,3-dibromobutane only
(4) all the steps are exothermic in both the cases (2) (S, S)-2,3-dibromobutane only
(3) (R, S)-2,3-dibromobutane only
76. Identify the set of reagents/reaction conditions ‘X’
(4)  a mixture of (R, R) and (S, S)-2,3-dibromo­
and ‘Y’ in the following set of transformation
butanes (50% : 50%)
Br
83. An alkene on reductive ozonolysis gives two
X Y
CH3CH2CHBr → product → CH3CHCH3
­molecules of CH2(CHO)2. The alkene is
(1) X = dilute aqueous NaOH, 20°C (1) 2,4-hexadiene
Y = HBr/acetic acid, 20°C (2) 1,3-cyclohexadiene
(2) X = conc alcoholic NaOH, 80°C (3) 1,4-cyclohexadiene
Y = HBr/acetic acid, 20°C (4) 1-methyl-1,3-cyclopentadiene
(3) X = dilute aqueous NaOH, 20°C 84. Which cycloalkane has the lowest heat of combustion
Y = Br2/CHCl3, 0°C per –CH2 group?
(4) X = conc. alcoholic KOH, 80°C (1) cyclopropane
Y = Br2/CHCl3, 0°C (2) cyclobutane
77. Which of the following alkenes will give an optically (3) cyclopentane
active alcohol when treated with H2O/H2SO4? (4) cyclohexane

Chapter_18.indd 20 3/26/2014 3:31:17 PM

 Alkenes  18.21

85. HBr reacts with CH2 = CHOCH3 under anhydrous (1) RCH2 CH CH2I
conditions at room temperature to give |
(1) CH3 CHO and CH3Br Cl
(2) Br CH2 CHO and CH3OH (2) RCH2 CH CH2Cl
(3) Br CH2 = CH2OCH3 |
(4) CH3CHBrOCH3 I
86. Reaction of trans 2-phenyl-1-bromo cyclopentane on (3) RCH2 CH = CH2
|
reaction with alcoholic KOH produces I
(1) 4-phenyl cyclopentene (4) RCH = CCH2I
(2) 2-phenyl cyclopentene
(3) 1-phenyl cyclopentene 90. The per cent composition of an organic compound
(4) 3-phenyl cyclopentene A is carbon = 85.71 % and hydrogen = 14.29 %. Its
vapour density is 14. Consider the following reaction
87. CH3CH = CH2 + NOCl 
→ P sequence
Identify the product.
A C
l2 /H 2 O
→ B i)
KCN/EtOH
ii) H3 O
→ C Identify C
(1) CH3 – CH – CH2
| | (1) CH3 CHCOOH
Cl NO |
OH
(2) CH3 – CH – CH2 (2) HOCH2CH2COOH
| | (3) HOCH2COOH
NO Cl (4) CH3CH2COOH
(3) CH3 – CH2 – CH – NO
91. One mole of a symmetrical alkene on ozonolysis
|
gives two moles of an aldehyde having molecular
Cl mass 44u. The alkene is
(4) ON – CH2 – CH2 – CH2 – Cl
(1) ethene (2) propene
(3) 1-butene (4) 2-butene
88. CH3 – CH – CH = CH2 + HBr A
| 92. The major product formed when 2-bromobutane is
CH3 treated with alcoholic KOH is
A is predominantly (1) 2-butanol
(1) CH3 – CH – CH – CH3 (2) trans-2-butene
| | (3) 1-butanol
Br CH3 (4) iso-butyl alcohol

(2) CH3 – CH – CH – CH3 93. The expected increasing order of hydration of ethene,
| | propene and 2-methyl propene is as
CH3 Br (1) propene < ethene < 2-methyl propene
(2) ethene < propene < 2-methyl propene
(3) CH3 – CH – CH2 – CH2Br (3) 2-methyl propene < ethene < propene
|
(4) 2-methyl propene < propene < ethene
CH3
94. Which of the following reactions have negative DS
Br value?
| (1) H2 + CH3CH = CH2  → CH3CH2CH3
(4) CH3 – C – CH2 – CH3
| (2) CH2 – CH2 CH3 – CH = CH2
CH3
CH2
89. In the following reaction (3) CH3 COO– (aq) + H3O+(aq) 
→ CH3COOH
RCH2 CH = CH2 + ICl  → (A) + H2O
Markonikoff’s product A is (4) All of the above

Chapter_18.indd 21 3/26/2014 3:31:25 PM

 18.22  Objective Chemistry - Vol. I

95. A hydrocarbon reacts with HI to give (X) which on H CH3

reacting with aq. KOH forms (Y). Oxidation of (Y) H2O
100. Product of the reaction R′ – C – O – C – R
gives 3-methyl-2-butanone, the hydrocarbon is
O O
(1) CH3 – CH = C – CH3 (1) R′ CHO + RCOCH3
CH3 (2) R′ COOH + RCOCH3
(3) R′ COCH3 + RCHO
(2) CH2 = CH – CH – CH3
(4) R′ COCH3 + RCOOH
CH3
(i) slow
(3) CH3 CH2 – C – CH2 101. +A–R
(ii) fast
CH3 In the above reaction, the product is
(4) HC ≡ C – CH – CH3 (1) d - isomer
(2) l - isomer
CH3 (3) meso isomer
(4) recemic mixture
96. The predominant product formed when 3-methyl
- 2-pentene reacts with HOCl 102. Which of the following is correct for the reaction
Cl CH3
(1) CH3 CH2 – C – CH(OH) CH3 HOBr
?
CH3
CH3 CH3
Cl OH Br OH
Br
(2) CH3 CH2 – C – CH – CH3 (1)  (2) 

CH3Cl
OH Br CH3
(3) CH3 CH2 – C – CH CH3 (3)  OH (4) none of these
CH3Cl
CH3 103. CH3CH = CHCH3 + CH2N2 
→ A; A is
(4) CH3 – C – CH – CH3 (1) CH3 – CH – CHCH3
CH3 OH | |
CH3 N2
97. When an alkene reacts with a peracid, the product is
(2) CH3 – CH – CH – CH3
(1) alkane (2) alkyne
(3) epoxide (4) none of these
CH2
98. The reaction between 1,3-butadiene and ethene gives (3) Both are correct
cyclohexene. It is known as (4) None is correct
(1) Diels–Alder reaction
104. CH3CH = CHCH3 + CHCl3+ t BuOK 
→ A; A is
(2) Perkin’s reaction
(3) Sabatier–Senderns reaction (1) CH3 – CH – CHCH3
(4) Hydrogenation
CH2
99. Which of the following can be used to prepare pure
cis (Z)-2-butene from 2-butyne? (2) CH3 – CH – CH – CH3
(1) Nickel boride (p-2) catalyst
(2) Lindlar’s catalyst C
(3) Hydroboration followed by protolysis
(4) All of the above Cl Cl

Chapter_18.indd 22 3/26/2014 3:31:36 PM

 Alkenes  18.23

(3) CH3 CH –– CH CH3 R

H+
108. 2HCHO + R A; A is
OBuO Cl R
(4) CH3 – CH – CH – CH3 R R
R R
O (1) (2) 

O HO OH
KMnO4
1 05. Alkene (A)
∆ R R R
OH; A is (3) (4) 
+ R
O
109. Which is correct statement?
(1) (1) meso - 1,2-dibromobutane on reaction with NaI/
acetone gives trans-2-butene
(2) d or l - 1,2-dibromobutane on reaction with Na/I
(2) acetone gives cis-2-butene
(3) both statements are correct
(3) (4) none of the statements is correct

110. H2/Pt
(4) A; A is
1 mol

106. H2O/H+ (1) (2) 

– CH = CH – CH3
A(predominant), A is

– CH2 = CH – CH3 (3) (4) 

(1)
OH

– CH – CH2 – CH3
(2) Answers
OH
  (1) 3   (2) 4   (3) 1   (4) 4   (5) 4   (6) 4
(3)   (7) 3   (8) 2   (9) 4  (10) 2  (11) 2  (12) 1
– CH = CH – CH3
 (13) 3  (14) 4  (15) 3  (16) 1  (17) 3  (18) 2
 (19) 3  (20) 3  (21) 4  (22) 2  (23) 2  (24) 1
OH  (25) 3  (26) 3  (27) 2  (28) 1  (29) 4  (30) 3
 (31) 2  (32) 3  (33) 4  (34) 4  (35) 2  (36) 3
(4) HO OH CH = CH – CH3  (37) 4  (38) 3  (39) 4  (40) 4  (41) 3  (42) 4
 (43) 3  (44) 1  (45) 3  (46) 1  (47) 4  (48) 4
 (49) 3  (50) 4  (51) 1  (52) 1  (53) 2  (54) 1
AlCl3  (55) 2  (56) 4  (57) 3  (58) 3  (59) 1  (60) 3
107. Cl + CH2 = CH2 A; A is  (61) 4  (62) 2  (63) 2  (64) 1  (65) 1  (66) 2
 (67) 2  (68) 3  (69) 1  (70) 4  (71) 3  (72) 3
(1) (2)   (73) 2  (74) 4  (75) 3  (76) 2  (77) 1  (78) 2
Cl
 (79) 1  (80) 2  (81) 2  (82) 4  (83) 3  (84) 4
(3) (4)   (85) 4  (86) 4  (87) 1  (88) 4  (89) 1  (90) 2

Chapter_18.indd 23 3/26/2014 3:31:45 PM

 18.24  Objective Chemistry - Vol. I

 (91) 4  (92) 2  (93) 2  (94) 1  (95) 2  (96) 3 5. Statement I: Reduction of but-2-yne by Na/liq
 (97) 3  (98) 1  (99) 4 (100) 2 (101) 4 (102) 2 ­ammonia gives ‘trans’ but-2-ene.
(103) 2 (104) 2 (105) 1 (106) 2 (107) 1 (108) 2 Statement II: It is an example of anti-addition.
(109) 3 (110) 1
6. Statement I: Addition of bromine to trans
but-2-ene yields meso 2, 3-dibromobutane.
Statement II: Bromine addition to an alkene is an
electrophilic addition.
  Statement-Type Questions
7. Statement I: Dimethyl sulphide is commonly used
In each of the following questions, a statement of
for the reduction of an ozonide of an alkene to get the
­statement I is given followed by a corresponding s­ tatement
carbonyl compounds.
of ­statement II just below it of the statements; mark the
correct answer. Statement II: It reduces the ozonide giving w ­ ater
1. If both statement I and statement II are true and soluble dimethyl sulphoxide and excess of it
­
­statement II is the correct explanation of statement I. ­evaporates.
2. If both statement I and statement II are true and
8. Statement I: Propene is more reactive than ethene
statement II is not the correct explanation of­
­
towards electrophilic addition reactions.
statement I.
3. If statement I is true and statement II is false. Statement II: Electron density of double bond
4. If statement I is false but statement II is true. ­increases due to hyperconjugation of methyl group.

1. Statement I: Addition of HBr on 2-butene gives only 9. Statement I: Moist ethylene can be dried by ­passing
one isomeric product. it through concentrated H2SO4.
Statement II: Addition of HBr on 2-butene follows Statement II: Addition of sulphuric acid takes place
Markonikoff’s rule. on alkene.

2. Statement I: Addition of HBr to 1-butene in the 10. Statement I: 1-chlorobutane on heating with KOH
presence of peroxide produces 1-bromobutane. undergoes dehydrohalogenation to yield but-1-ene.
Statement II: It involves the formation of primary Statement II: It is an elimination reaction involving
radical. carbonium ion intermediate.
3. Statement I: Addition of HBr to 1-butene gives two
optical isomers.
Statement II: The product contains one asymmetric
Answers
carbon.
  (1) 3   (2) 3   (3) 1   (4) 4   (5) 1   (6) 2
4. Statement I: Addition of HCl to propene in p­ resence   (7) 1   (8) 1   (9) 4  (10) 1
of peroxide gives 1-chloropropane.
Statement II: The reaction occurs by carbonium ion
intermediate.

Chapter_18.indd 24 3/26/2014 3:31:46 PM

 19

Chapter
Alkynes

• Alkynes are unsaturated hydrocarbons which contain a • The use of alcoholic KOH gives rise to side reactions
triple bond (–C≡C–). and causes the migration of the C=C bond to the centre
• The triple bond in acetylene contains one sigma and of the molecule.
two “pi” bonds. • Sodamide (NaNH2) in liquid ammonia should be used
in the place of alcoholic KOH.
• The hybridisation of carbon atoms in triple bond is sp
NaNH2
and the C–C bond length in C≡C is 1.20 Å. The C≡C R – CH CH R R– C C – R + 2NaBr + 2NH3
bond energy is 827.64 kJ mol–1.
• The angle between the two pi bonds in acetylene is 90°. Br Br
• Electron cloud between two carbon atoms is
­cylindrically symmetrical about the internuclear axis. Mechanism
Step I
Preparation Br H R Br

(1) From calcium carbide: On heating lime stone with  E2

R – C – C – R + NH2 C= C + NH3 + Br–
coke gives calcium carbide which on treating with
­water gives ethyne. H Br H R
CaCO3 ∆→ CaO + CO2
CaO + 3C 
→ CaC2 + CO Step II

R Br
CaC2 + 2H2O 
→ Ca(OH)2 + C2H2 H2N E2
C=C R– C ≡ C – R + NH3 + Br–
(2)  Dehydrohalogenation of dihalides
• 1,2-dihalides (vicinal) when treated with alcoholic H R
KOH give alkynes. • After the removal of first molecule of HX, in the
Br H ­product vinyl halide formed, C–X becomes stronger

due to mesomerism. So, a strong base like NH 2 can
Alcoholic KOH
R C C R R C C R make step II easier.
– HBr (fast)
• Dehydrohalogenation of 1,1-dihalides (gemical) with
H Br Br H alcoholic KOH or NaNH2 in liquid ammonia gives
Alcoholic KOH alkynes.
H C≡C H R–CH2–CHBr2 Alcoholic
 KOH or
→ R–C≡CH
– HBr (fast) NaNH 2 in NH3

Chapter_19.indd 1 3/26/2014 3:33:36 PM

 19.2  Objective Chemistry - Vol. I

(3) Dehalogenation of tetrahalides with zinc in alcohol gives alkynes.

X X

R–C–C–R R – C ≡ C – R + 2ZnX2

X X
CHX3 + 6Ag + X3CH 
→ HC≡CH + 6AgX

(4) Alkylation of ethyne: Ethyne on treating with sodium in liquid ammonia gives sodium acetylyde. This on treating with
alkyl halides gives higher alkynes.
HC≡CH + Na liquid
 NH3
→ HC≡CNa RX
→ HC≡CR
HC≡CR + Na liquid
 NH3
→ NaC≡CR RX
→ RC≡CR
In this reaction, primary alkyl halides should be used. If secondary or tertiary alkyl halides are used, they themselves
convert into alkenes by giving up hydrogen to sodium salt.
(5)  Kolbe’s method: Electrolysis of concentrated solution of sodium or potassium salt of maleic acid gives acetylene
at anode.
CHCOONa +2H2O CH
+ 2CO2 + 2NaOH + H2
CHCOONa Electrolysis CH

Physical Properties
• Acetylene is a colourless gas with ethereal smell in pure state.
• Liquefied acetylene or when compressed is ­explosive. It burns with luminous smoky flame due to high ­carbon content
and hence used for lighting purpose.
• First three members are gases, the next eight are ­liquids and higher ones are solids.
• Alkynes are weakly polar in nature, lighter than water, insoluble in water but are soluble in organic solvents like ethers,
carbon tetrachloride and benzene.
• The heat of formation of alkynes is less than those of corresponding isomeric dienes.

Chemical Properties
1. Acidic nature: Due to the small size of sp hybrid ­ orbital the bond pair of electrons in C–H bond of
triple-bonded carbon are near to the nucleus. So, sp hybrid orbital is more electronegative than sp2 and sp3 hybrid o­ rbitals
of carbon. Thus in ethyne, hydrogen atoms can be l­iberated as protons more easily compared to alkenes and alkanes.
• Only the hydrogen atoms attached to triple-bonded carbons are acidic but not all the hydrogen atoms of alkynes.
• Ethyne and terminal alkynes react with ammoniacal AgNO3 or alcoholic AgNO3 forming white precipitates.
R–C≡CH + AgNO3 + NH4OH  → R–C≡CAg↓ + NH4NO3 + H2O
White
• Ethyne and terminal alkynes react with ammoniacal cuprous chloride forming a red precipitate.
R–C≡CH + Cu2Cl2 + 2NH4OH 
→ R–C≡CCu↓ + 2NH4Cl + 2H2O
Red
• Ethyne and terminal alkynes react with sodium in liquid ammonia forming sodium salts of alkynes.
1
R–C≡CH + Na  → R–C≡CNa + H2
2

Chapter_19.indd 2 3/26/2014 3:33:43 PM

 Alkynes  19.3

2.  Addition Reactions

• Alkynes contain a triple bond, so they add up two ­molecules of H2, X2, HX, etc.
• Addition reactions of alkynes take place via electrophilic addition reaction mechanism. Alkynes, like a­ lkenes, act as
nucleophiles and react with ­eletrophiles. The electrophiles add in the same way as they add to alkenes.
• The addition product formed depends on the stability of the vinylic cation formed as an intermediate.
• Addition in asymmetrical alkynes takes place ­according to Markonikov’s rule.
• Addition of hydrogen to alkynes may be either cis ­addition or anti addition.
• Addition of hydrogen to alkynes in the presence of Lindlar’s catalyst gives cis-alkene by syn addition.
• When alkynes are reduced with Li or Na metal in NH3 at low temperature anti addition of hydrogen takes place.
(Details and mechanism are discussed in the section on “preparation of alkenes from alkynes”).
• Addition of halogens: Acetylene combines with gaseous chlorine or bromine in the dark to form di or tetrahalides.
• Dihalide derivatives are trans-isomers and the addition of halogens to acetylene is stereoselective.
• Alkynes are less reactive than alkenes towards ­addition of halogens because alkynes form a less ­stable intermediate.
Br2
H – C ≡ C– H H – C = C – H (less stable intermediate)
⊕
Br
• Liquid bromine gives tetrabromo derivative while ­bromine water or Br2/CCl4 forms dibromo derivative.
H H
Bromine liquid Br2

CHBr = CHBr water HC ≡ CH CBr2 CBr2
• The order of reactivity of halogens towards alkenes is Cl2 > Br2 > I2.
• Addition of hydrogen halides: The addition of hydrogen halides to alkenes follow Markonikoff’s rule. Addition of
one mole of hydrogen halide gives vinyl halide, which then adds another molecule of hydrogen halide to give gem
dihalide.
→ CH2=CHBr HBr
CHCH + HBr   → CH3–CHBr2
• In the presence of peroxides, addition of HBr follows anti-Markonikoff’s rule.

→ CH2=CHBr HBr
CH–CH + HBr   → CH2Br–CH2Br
• In the presence of mercuric ion (catalyst) at 60–65°C acetylene combines with HCl forming vinyl chloride.
• Polymer of vinyl chloride, poly vinyl chloride (PVC) is used in making PVC sheets, water pipes, etc.
• Order of reactivity of hydrogen halides with alkynes follows the order HI > HBr > HCl > HI. HI adds only under
pressure.
• Addition of hypochlorous acid to acetylene gives dichloro acetaldehyde but with propyne gives 1,1-dichloroacetone.
OH Cl HO
HOCl –H2O
HC ≡ CH + HOCl CH = CH CHCl2 – CHO CHCl2 ⋅ H2O

HO
• Addition of sulphuric acid to acetylene gives ethylidene hydrogen sulphate which on boiling converts into
acetaldehyde.

HC≡CH + H2SO4 
→ CH2=CHHSO4 Conc.
 H 2 SO4
Conc
→ CH3–CH(HSO4)2 H
2O
→ CH3–CH(OH)2 ∆
→ CH3CHO
• Addition of water molecule to alkynes takes place with difficulty when compared to alkenes. Addition of water takes
place in the presence of 40% H2SO4 ­containing 1% HgSO4 at 80°C forming acetaldehyde.

Chapter_19.indd 3 3/26/2014 3:33:45 PM

 19.4  Objective Chemistry - Vol. I

HC≡CH + H2O 40%

 H 2 SO4
1% HgSO4
→ [CH2=CHOH] Tautomerisation

Unstable
→ CH3–CHO

Higher alkynes give ketones

OH
|
RC≡CH + H2O 40%
 H 2 SO4
1% HgSO4
→ R – CH = CH2 Tautomerisation
→ RCOCH3
Unstable

In the case of asymmetrical alkyne a mixture of two isomeric ketones is formed in which methyl ketone predominates.

CHCHC≡CCH + HO 40% H 2 SO4

1% HgSO4
→ CH3CH2CH2COCH3 + CH3CH2COCH2CH3
(Major) (Minor)
• Addition of HCN in the presence of barium cyanide or CuCl/HCl (catalyst) gives vinyl cyanide which is an important
starting material (monomer) such as orlon (polyacrylonitrite or PAN) and buna-N rubber.
HC≡CH + HCN 
→ CH2=CHCN
Vinyl cyanide (Acrylonitrile)
• Addition of acetic acid to acetylene in the presence of HgSO4 or zinc acetate or BF3 (as catalyst) at 160oC gives vinyl
acetate and then ethylidene acetate.
2+
HC≡CH + CH3COOH 80°

Hg
C
→ CH2=CH(OOCH3) CH
3COOH
Hg2+ 80 ° C
→ CH3CH(OOCCH3)2

Vinyl acetate on polymerization gives polyvinyl acetate plastic and ethylidene acetate on heating at 300–400°C gives
acetaldehyde and acetic acid.
• Addition of alcohol in the presence of NaOH or KOH or mercury salt as catalyst acetylene forms ethyl vinyl ether.
HC≡CH + C2H5OH HgSO
∆
4
→ CH2=CHOC2H5 H
2O
→ CH3CHO + C2H5OH
• Ozonolysis of acetylene gives glyoxal. Higher alkynes form diketones.
Ozonolysis
CHO H2O
HC ≡ CH 2HCOOH
CHO

CH3C≡CCH3 Ozonolysis
 → CH3COCOCH3 H
2 O2
→ 2CH3COOH
• Self addition or polymerization
 (i) When acetylene is passed through red hot metallic tube, it forms benzene. If propyne is used mesitelene
(1,3,5-­trimethyl benzene) is formed.
CH3

3CH3C ≡ CH Red hot iron tube

600°C

H3C CH3

 (ii) In the presence of Ni(CN)2 and high pressure in tetrahydrofuran acetylene forms cyclooctatetraene.
(iii) In the presence of cuprous chloride solution containing NH4Cl linear polymerization occurs forming monovinyl
acetylene and divinyl acetylene.
HC ≡ CH
2HC ≡ CH Cu
 2 Cl 2
NH 4 Cl
→ CH 2 = CH − C ≡ CH Cu

2 Cl 2 /NH 4 Cl
→ CH 2 = CH ≡ C − CH = CH 2
vinyl acetylene divinyl acetylene

Reduction of vinyl acetylene with H2/Pt in the presence of BaSO4 forms buta-1,3-diene. This on polymerization with
vinyl cyanide gives buna-N-synthetic rubber.

Chapter_19.indd 4 3/26/2014 3:33:48 PM

 Alkynes  19.5

Addition of HCl to vinyl acetylene gives chloroprene (1) Br2/CCl4, then KOH (2) Na, then CH3CH3I
which on polymerization gives neoprene rubber. (3) Na, then CH3I (4) CH2N2
• Addition of arsenic trichloride to acetylene in the 3. Which of the following statements is true for ethane,
presence of anhydrous AlCl3 gives a poisonous gas ethene and acetylene?
called lewiste (ClCH=CHAsCl2). (1) Acetylene is the weakest acid and has the longest
• Oxidation of Alkynes C–H bond distance.
 (i) Alkynes burn in air or oxygen with liberation of (2)  Acetylene is the strongest acid and has the
heat forming CO2 and H2O. strongest C–H bond distance.
(ii) Cold dilute alkaline KMnO4 oxidizes a­cetylene (3) Ethane is the strongest acid and has the longest
to oxalic acid, propyne to pyruvic acid C–H bond distance.
(CH3COCOOH), 2-butyne to butan-2,3-dione. (4) Ethene is the strongest acid and has the shortest
(iii) Acidified permanganate oxidizes acetylene to C–H bond distance.
formic acid and other alkynes to carboxylic acids
to corresponding acids with the breaking of triple 4. On oxidation with hot aqueous KMnO4 a compound
bond. X gives 2-methyl propionic acid and propionic acid.
Which of the following is the structure of X?
RC≡CR 100

KMnO 4
− 110° C
→ RCOOH + HOOCR
(1) HOOC C CH2 CH2 CH2 COOH
Terminal alkynes give carboxylic acids and CO2 |
CH3
RC≡CH → RCOOH + CO2
KMnO 4
100 − 110° C

These reactions are useful for the detection of the (2) CH3 . CH . CH2 . C ≡ C . CH3
­position of triple bond. |
CH3
• Selenium dioxide also oxidizes acetylene to glyoxal.
• Chromic acid oxidizes acetylene to acetic acid. (3) CH3 . CH . C ≡ C . CH2 . CH3
|
• Hydrogen atoms in acetylene can be substituted with CH3
chlorine by treating with sodium hypochlorite at 0°C
in the absence of light. (4) CH3 . CH . CH = CH . CH2 . CH3
HC≡CH NaOCl  → ClC≡CCl
|
0° C
CH3
• Isomerization
 (i) Heating the terminal alkyne with alcoholic KOH 5. On catalytic hydrogenation, a compound X(C7H12)
or NaNH2 in inert solvent, the triple bond of ­absorbs 2 mol of hydrogen and yields 2-­methylhexane.
1-alkyne is shifted towards the centre to form an On treatment with Ag(NH3)2OH, X gives a p­ recipitate
isomeric 2-alkyne. which contains silver and which regenerates X on
treatment with dilute HNO3. The structure of X is
CH3CH2C≡CH alcoholic
 ∆
KOH
→ CH3C≡CCH3
(ii) On heating with sodamide (NaNH2 in liquid NH3) (1) CH2CH2CH2CH2CH2C≡CH
the triple bond shifts towards the end. (2) CH3 C ≡ C CH2 CH . CH3
|
CH3C≡CCH3 NaNH

− NH3
2
→ CH3CH2–C≡CNa H
2O
→ CH3
CH3CH2C≡CH
(3) CH2 = CHCH = CH CH CH3
|
CH3
 Objective Questions
(4) CH3 – CH CH2 CH2 C ≡ CH
1. Using which of the following reagents one can per- |
form a simple test that can be used to differentiate CH3
between C6H5C≡CH and C6H5CH=CH2?
(1) NaOH/H2O (2) Br2/CCl4 6. Among the following, which has the shortest­
(3) Ag(NH3)2OH (4) CrO3/H2SO4 carbon–carbon single bond?
2. By using which of the following can the conversion (1) CH3CH3 (2) CH2=CHCH3
of PhC≡CH  → PhC≡CHCH3 be achieved? (3) HC≡C–C≡CH (4) CH2=CH–C≡CH

Chapter_19.indd 5 3/26/2014 3:33:52 PM

 19.6  Objective Chemistry - Vol. I

7. On ozonolysis, a compound C7H12 gives acetone and (3) HC≡CH 

Cl2
→
carbon dioxide. The structure of the compound can be
(4) HC≡CH Oxidizing
 Cl2
agent
→
(1) CH3CH2C  ≡  CCH2CH2CH3
CH3 14. In which of the following conditions does the ­reaction
CH3
HC≡CH + CH3OH  → CH3OC≡CH takes place?
(2) C=C=C
(1) HC≡CH + CH3OH 160

KOMe
→
CH3 CH3 − 200° C

(3) CH3 C ≡ C – CH2CH CH3 (2) HC≡CH + CH3OH conc.

 H 2 SO4
→

(3) HC≡CH + CH3OH anhydrous

 ZnCl 2
→
CH3
(4) None of these (4) HC≡CH + CH3OH ClHC

dil.HCl
= CHCl
→

8. The reaction of ethyne with bromine water gives

15. In the reaction HC≡CH X
→ Cl2CH–CHCl2, X is
(1) cis-1,2-dibromoethene
(2) trans-1,2-dibromoethene (1) NaOCl (2)  Cl2/CCl4
(3) 1,1,2,2-tetra bromoethane (3) chlorine water (4)  NaCl
(4) None of these 16. Which of the following will not react with ammonical
9. The final product obtained in the reaction silver nitrate solution?
CH3CH2CH=CH2 2. 1.Br2 /CCl 4
→ is (1) CH3C≡CH (2) (CH3)2CH–C≡CH
NaNH 2 110 −160° C
(3) CH3C≡CCH3 (4) HC≡CH
(1) CH3CH2CH=CHBr
17. The addition of HCN to acetylene in the presence of
(2) CH3 CH2C = CH2
Ba(CN)2 as catalyst gives
Br (1) ethyl cyanide
(3) CH3CH2C≡CH (2) 1,1-dicyanoethane
(4) None of these (3) divinyl cyanide
(4) vinyl cyanide
10. The reduction 4-octyne with H2 in the presence of
Pd/CaCO3-quindine gives 18. Which reagent is used to distinguish 1-butyne from
(1) trans- 4-octene 2-butyne?
(2) cis-4-octene (1) HCl
(3) a mixture of cis- and trans-4-octene (2) Br2/CCl4
(4) a completely reduced product C8H18 (3) Baeyer’s reagent
(4) Ammonical cuprous chloride
11. The major product obtained by the treatment of
propyne with aqueous H2SO4 in the presence
­ 19. A compound decolourises an alkaline KMnO4
of HgSO4 is ­solution but does not react with an ammonical AgNO3
(1) propanal solution. It is
(2) acetone (1) benzene (2)  butyne-1
(3) propanal (3) butyne-2 (4)  acetylene
(4) propyl hydrogen sulphate
20. A compound (C5H8) reacts with ammonical AgNO3
12. Which of the following reactions will yield to give a white precipitate and reacts with an excess
2,2-­dibromopropane? of KMnO4 solution to give (CH3)2CH –COOH. The
(1) HC≡CH + 2HBr  → compound is
(2) CH3CH=CHBr + HBr  → (1) CH3=CH–CH=CH–CH3
(3) CH3C≡CH + 2HBr  → (2) (CH3)2CH–C=CH
(4) CH3CH=CH2 + HBr  → (3) CH3(CH2)2C≡CH
13. In which of the following conditions does the ­reaction (4) (CH3)2C=C=CH2
HC≡CH  → CHCl2CHO takes place? 21. The decreasing order of bond enthalpies is
(1) HC≡CH HOCl
 → (1) sp3 > sp2 > sp (2)  sp > sp2 > sp3
(2) HC≡CH peroxide

HOCl
→ (3) sp > sp > sp
2 3
(4)  None

Chapter_19.indd 6 3/26/2014 3:33:55 PM

 Alkynes  19.7

22. How many isomeric alkynes of molecular formula 32. Which of the following alkyne give aldehyde on
C6H10 are there? ­reaction with dil. H2SO4 in the presence of HgSO4?
(1) 2 (2) 3 (3) 
5 (4) 7 (1) propyne (2)  1-butyne
(3) ethyne (4)  all of these
23. In the reaction
CH3CH2C≡CH KOH 
(alc)
→ (A); (A) is 33. Br CH2 –C≡CH ( ( i) Mg
ii) Br CH 2 C ≡ CH
→ ABrCH2C≡CMgBr.
(1) 2-butene (2)  2-butyne The compound (A) in the given reaction is
(3) 1-butyne (4)  All (1) propyne (2)  1-butyne
(3) 2-butyne (4)  ethyne
24. A war gas lewisite is formed by reaction of arsenic
chloride with 34. Dry heavy metal alkynides are
(1) CH4 (2) C6H6 (3) C2H2 (4) C2H4 (1) reducing agents (2)  poisonous
(3) oxidizing agents (4)  explosive
25. CH3C≡C–CH3 ( ( i) X
ii) Zn + H 2 O
→ CH3COCOCH3
In the above reaction X is 35. Which of the following type of reaction occurs when
1-butyne reacts with HBr?
(1) HNO3 (2) O2 (3) O3 (4) KMnO4
(1) an electrophilic addition
26. The electrolysis of aqueous solution of sodium (2) Markownikoff’s electrophilic addition
maleate yields (3) anti-Markownikoff’s radical addition
(1) ethyne (2)  ethanal (4) None of the above
(3) propyne (4)  ethanoic acid
36. When 1-butyne reacts with one equivalent of HBr in
27. Which of the following reagents can be used to the presence of peroxide we get
­separate a mixture of ethene and ethyne? (1) CH3CH2CH=CHBr
(1) charcoal powder (2) CH3CH2CBr=CH2
(2) ammonical AgNO3 (3) CH3CH2CBr=CHBr
(3) ammonical cuprous chloride (4) All the above
(4) 2 and 3
37. The addition of water to propyne in the presence of
28. The ozonolysis of a triple bond produces HgSO4–H2SO4 gives
(1) a mixture of aldehyde/ketone and carboxylic acid (1) CH3CH=CHOH
(2) a mixture of aldehyde/ketone OH
(3) a mixture of carboxylic acids
(2) CH3C = CH2
(4) CO2 and H2O
(3) CH3CH2CH2OH
29. Ethyne reacts with chlorine gas in presence of a (4) CH3COCH3
­catalyst to give
38. When ethyne reacts with selenium dioxide we get
(1) lewisite (2)  vinyl chloride
(3) westron (4)  westrosol (1) methyl glyoxal (2)  dimethyl glyoxal
(3) glyoxal (4)  ethanal
30. The products obtained via oxymercuration
(HgSO4 + H2SO4) of 1-butyne would be 39. When two moles of ethyne are passed through
­Cu2Cl2 dissolved in ammonium chloride solution the
(1) CH3CH2COCH3
product is
(2) CH3CH2CH2CHO
(3) CH3CH2CHO + HCHO (1) 1-butyne (2)  vinyl acetylene
(4) CH3CH2COOH +HCOOH (3) divinyl acetylene (4)  chloroprene

31. Alkynes are less reactive than alkenes towards 40. Vinyl acetylene reacts with one equivalent of HCl to
­addition of Br2 because of the formation of produce
(1) HC = CH (2)  H2C – CH2 (1) chloroprene (2)  neoprene
(3) lewisite (4)  mesitylene
+ +
Br Br 41. Ethyne reacts with acidified potassium dichromate
(3) HC = CH (4)  H2C – CH2 solution to produce
(1) oxalic acid (2)  glyoxal
Br Br (3) formic acid (4)  acetic acid

Chapter_19.indd 7 3/26/2014 3:33:58 PM

 19.8  Objective Chemistry - Vol. I

42. Passing two moles of acetylene and one mole of (1) methyl alcohol (2)  ethyl alcohol
­hydrogen cyanide through a red hot tube yields (3) acetaldehyde (4)  ethylene
(1) pyrole (2)  pyridine 49. Acetylene is not used in the preparation of
(3) ethyl amine (4)  diethyl amine
(1) Westron (2)  Westrosol
43. 1,1-Dibromopentane on treatment wtih sodamide (3) Lewisite (4)  Mustard gas
­followed by reaction with H3O+ gives
50. Butyne on reaction with hot alkaline KMnO4 gives
(1) 2-pentyne
(1) CH3CH2CH2COOH
(2) 3-methyl butyne-1
(2) CH3CH2COOH
(3) 1-pentyne
(3) CH3CH2COOH + CO2
(4) n-propyl ethyne
(4) CH3CH2COOH + HCOOH
44. Which of the following statements is correct?
51. When C2H2, CH4 and C2H4 pass through a test tube
(1) alkynes are more reactive than alkenes towards which contains ammonical Cu2Cl2, find out which
halogen addition gas comes out unaffected from the test tube.
(2) alkynes are less reactive than alkenes towards
(1) C2H2 and CH4
halogen addition
(2) C2H2 and C2H4
(3) both alkynes and alkenes are equally reactive
(3) C2H2
­towards halogen addition +
(4) C2H4 and CH4
(4)  primary vinylic cation (RCH    =    CH) is
more r­eactive than secondary vinylic cation 52. Structural formula for lewisite is
+
(RC = CH2) (1) CHCl (2)  CHCl
45. CH3CH2CH2C≡CH Base → CH3CH2CH=C=CH2 CHAsCl3 CHAsCl
→ (A). The final product (A) is (3) CHCl (4)  CH2
(1) 2-pentyne
(2) 3-methyl-1-butyne CHAsCl2 CHAsCl2
(3) 1, 3-pentadiene 53. Acetylenic hydrogens are acidic because
(4) none of the above
(1) sigma electron density of C–H bond in acetylene
46. Identify the wrong statement. is nearer to carbon which has 50% s-character
(1)  The hydrocarbon that decolourises ­ alkaline (2) acetylene has only one hydrogen on each carbon
KMnO4 and gives a red precipitate with (3)  acetylene contains least number of hydrogen
­ammoniacal cuprous chloride is ethyne. among the possible hydrocarbons having two
(2) Chloroform or iodoform on heating with silver carbons
powder gives ethyne. (4) acetylene resembles acetic acid
(3) Benzene is a polymer of ethene. 54. Sample of 2,3-dibromo-3-methyl pentane is h­ eated
(4) Addition of HOCl to ethyne gives dichloroace­ with zinc dust. The resulting product is isolated
taldehyde. and heated with HI in the presence of phosphorous.
47. The false statement among the following is Indicate which structure represents the final product
(1) heating 1,1,2,2-tetrabromoalkane is heated with in the reaction.
zinc powder in alcohol gives alkyne (1) CH2 = CH – CH – CH2 – CH3
(2)  1-alkynes liberate hydrogen with sodium in
­liquid ammonia CH3
(3) Acetylene when treated with Cl2 in CCl4 forms
(2) CH3 – CH2 – CH – CH2 – CH3
lewisite
(4)  Terminal dihalides on heating with zinc or CH3
­sodium forms cycloalkanes
(3) CH3 – CI – CH2 – CH2 – CH3
48. The end product of the following sequence of
­operations is CH3
CaC2 H2O
→ (A) HgSO

H 2SO4
4
→ (B) LiA/H
H
4
→ (C) (4) None of the above

Chapter_19.indd 8 3/26/2014 3:34:01 PM

 Alkynes  19.9

55. Which of the following reactions will yield (3) CH3 – CH – CH2 CH2I
2,2-­dibromopropane?
Cl
(1) CH2=CHBr + HBr
(2) CH3C≡CCH3 I
(3) CH3C≡CH + 2HBr
(4) CH3 CH2 CH2 – C –H
(4) CH3CH=CHBr + HBr
Cl
56. Two organic compounds X and Y on analysis gave
 12  61. Identify the alkyne in the following sequence of
the same percentage composition, namely C =   ×
 13  ­reactions:
 1 Alkyne Lindlar’s
H2
→ (A) Ozonolysis
→ (B)
100% and H =   × 100%. However, compound catalyst
 13 
“X” decolourises bromine water while compound Wacker

process
→ CH2=CH2
“Y” does not. Two compounds “X” and “Y” may be (1) CH3–C≡C–CH3
respectively (2) CH3–CH2–C≡CH
(1) ethylene and benzene (3) CH2=CH–C≡CH
(2) acetylene and ethylene (4) HC≡C–CH2–C≡CH
(3) toluene and benzene
62. 2-butyne when treated with lithium in the presence of
(4) benzene and styrene
liquid ammonia gives
57. If CH3COOH is reacted with HC≡CH in the presence (1) cis-2-butene (2) trans-2-butene
of Hg2+, the product is (3) n-butane (4) None of these
(1) CH2 (OOC CH3)
63. Which reaction produces acrylonitrile CH2=CHCN?
CH2 (OOC CH3) (1) Ethyne HCN  →
Ba 2+
(2) CH3CH(OOCCH3)2
(2) Acrylic acid KCN
 →
(3) CH3CH2(OOCCH3)
(4) None of these (3) Ethyne KCN
 →
58. One mole of an unsaturated hydrocarbon on (4) Ethyne HOCl
 →
­ozonolysis gives one mole each of CH3CHO, HCHO
and OHC–CHO. The hydrocarbon is 64. Identify (B) in the following sequence of reactions
(1) CH3CH2C≡CCH3 HC ≡ CH Cu 2 Cl 2 + NH 4 Cl
 → (A) HC
l→ (B)
(2) HC≡CCH2CH2CH3 (1) CH3CH2Cl
(3) CH2=CH–CH2–CH=CH3 (2) CH2=CH–CH2–CH2Cl
(4) CH2=C=CHCH2CH3 (3) HC ≡ C – CH – CH3
59. Reaction of acetylene and propylene with HgSO4 in Cl
the presence of H2SO4 produces respectively
(4) CH2 = CH – C = CH2
(1) acetone and acetaldehyde
(2) acetaldehyde and acetone Cl
(3) propanaldehyde and acetone 65. In the following sequence of reactions identify the
(4) acetone and propanaldehyde product (D)
60. Predict the product “C” obtained in the following HC ≡ CH HBr
 → (A) HBr
 → (B) alc
 KOH
→(C)
­reaction of 1-butyne
CH3CH2C≡CH + HCl HI → (B)  → (C) NaNH
 2
→ (D)

I (1) Ethanol (2)  Ethyne

(3) Ethanal (4)  Ethene
(1) CH3 CH2 – CH – CH2Cl
66. Ozonolysis of a triple bond produces
I (1) a mixture of aldehyde/ketone and carboxylic acid
(2) CH3 CH2 – C – CH3 (2) a mixture of aldehyde/ketones
(3) a mixture of carboxylic acids
Cl (4) CO2 and H2O

Chapter_19.indd 9 3/26/2014 3:34:10 PM

 19.10  Objective Chemistry - Vol. I

67. The reduction of an alkyne to alkene using Lindlar’s 73. The alkene C6H10 producing OHC(CH2)4CHO on
catalyst result in ozonolysis is
(1) cis addition of hydrogen atoms (1) Hexene-1
(2) trans addition of hydrogen atoms (2) Hexene-2
(3) a mixture obtained by cis and trans additions of (3) Cyclohexene
hydrogen which are in equilibrium with each (4) 1-methyl cyclohexane-1
other
74. Which of the following will convert
(4) a mixture obtained by cis and trans additions of
hydrogen atoms which are not in equilibrium HC≡CCH2 CH3 to CH3COCH2CH3?
with each other (1) H2O/H+
(2) Hg2+/H2SO4
68. From the following reactions (3) H2SO4 (conc)/H3PO4
HC≡CH + LiNH   NH + HCCLi (4) K2Cr2O7/KMnO4
HC≡CLi + H2O     HC≡CH + LiOH
Predict which of the following orders regarding base 75. The product formed when vinylacetylene is passed
strength is correct? through concentrated hydrochloric acid in the
­presence of cuprous and ammonium chloride is
(1) HC≡C– < OH– < NH–2
(2) HC≡C– < NH–2 < OH– (1) ClCH2 –CH2–C≡CH
(3) OH– < NH–2 < HC≡C– (2) CH3–CHCl–C≡CH
(4) OH– < HC≡C– < NH–2 (3) CH2=CH–CH≡CHCl
(4) CH2=CH–CCl=CH2
69. HC≡CH + 2CH3COOH  → (A) ∆ → (B) + (C)
(X) (Y) HgSO4/H2SO4
X
B can be obtained from (X) by hydration and (C) can 76. 1 – pentyne
be obtained from (Y) by heating with P2O5. Hence, BH3. THF/H2O2, OH–
Y
(A) is X and Y can be distinguished by
O
(1) silver mirror test (2)  iodoform test
(1) CH2 = CH – O – C – CH3 (3) both of these (4)  none of these
O 77. CH3CH2 C≡CH  A


B
 CH3C≡CCH3, A and B are
(2) CH3 CH (O – C – CH3)2 (1) alcoholic KOH and NaNH2
(2) NaNH2 and alcoholic KOH
(3) CH3CH2COOCH3
(3) NaNH2 and Lindlar’s catalyst
(4) None of these
−
(4) Lindlar’s catalyst and NaNH2
70. HC≡CH + 2HCHO CH
 3O
→ X, X is
O
(1) HOH2CC≡CCH2OH C ≡ CH
(2) HOH2CC≡CCH2OCH3 BH3.THF
(3) both are true 78. A; A is
H2O2/OH
(4) none is true
O O O
71. A H
A can be (1) (2)  CH3
 (I) Li/NH3 O
 (II) LiAlH4
(III) H2Pd/CaCO3 (IV) H2/Ni2B
O O O O
(1) I, II, III, IV (2)  I, III
(3) II, III (4)  I, II OH (4)  H
(3)
72. The compound X (C5H8) reacts with a­mmonical
AgNO3 to give a white precipitate and on
­oxidation with hot alkaline KMnO4 gives the acid
(CH3)2CHCOOH. Therefore, X is 79. C≡C–C≡C
(1) CH2=CHCH=CHCH3 (2) CH3(CH2)2 C≡CH Li/NH3
(3) (CH3)2CH–C≡CH (4) (CH3)2C=C=CH3 A; A is

Chapter_19.indd 10 3/26/2014 3:34:14 PM

 Alkynes  19.11

(66) 3 (67) 1 (68) 4 (69) 2 (70) 1

(1) (71) 4 (72) 3 (73) 3 (74) 2 (75) 4
(76) 3 (77) 1 (78) 2 (79) 2 (80) 1
(81) 1

(2)

(3) Both (a) and (b)

  Statement- Type Questions
(4) None of these
In each of the following questions, a statement of­
80. HC≡CH 2H
 CHO
→ Li/
 NH3
→ A; A is
CH O− 3 statement I is given followed by a corresponding statement
HOH2C of ­statement II just below it of the statements; mark the
(1) correct answer.
CH2OH 1. If both statement I and statement II are true and
statement I is the correct explanation of statement II.
(2) 2. If both statement I and statement II are true
HOH2C CH2OH and statement I is not the correct explanation of
statement II.

(3) 3. If statement I is true and statement II is false.

HOH2C CH2OH 4. If statement I is false but statement II is true.
1. Statement I: Alkynes are less reactive than ­alkenes.
(4)
OHC CHO Statement II: The bond energy of C C bond is –
higher than that of C=C bond.
+
81. (I) CH2=C=CH2 H
3O
→
2. Statement I: H atoms of ethyne are acidic in ­nature.
 (II) CH3C≡CH H
2SO 4 /HgSO 4
→
Statement II: The “sp” hybridisation of carbon
(III) CHC≡CH H
BH.THF
2 O2 /OH −
→ atoms makes carbon atoms more electronegative.
Acetone is the major product in
(1) I, II (2)  I, III Answers
(3) II, III (4)  I, II, III
 (1) 2  (2) 1
Answers

 (1) 3  (2) 3  (3) 2  (4) 3  (5) 4

 (6) 3  (7) 2  (8) 2  (9) 3 (10) 2
(11) 2 (12) 3 (13) 1 (14) 1 (15) 2   Match the Following Type Questions
(16) 3 (17) 4 (18) 4 (19) 3 (20) 2
(21) 2 (22) 4 (23) 2 (24) 3 (25) 3 1.
(26) 1 (27) 4 (28) 3 (29) 3 (30) 1
(31) 1 (32) 3 (33) 1 (34) 1 (35) 2 List-I List-II
(36) 1 (37) 4 (38) 3 (39) 2 (40) 1 (A) C2H5OH + KOH (i) Dehydration
(41) 4 (42) 2 (43) 3, 4 (44) 2 (45) 3 (B) H2SO4/170°C (ii) Hydration
(46) 3 (47) 3 (48) 2 (49) 4 (50) 4
(C) HgSO4/H2SO4 (iii) Dehalogenation
(51) 4 (52) 3 (53) 1 (54) 2 (55) 3
(56) 3 (57) 3 (58) 3 (59) 2 (60) 2 (D) Zn dust  (iv) Dehydrogenation
(61) 1 (62) 2 (63) 1 (64) 4 (65) 2  (v) Dehydrohalogenation

Chapter_19.indd 11 3/26/2014 3:34:16 PM

 19.12  Objective Chemistry - Vol. I

Correct code is 3.

S. No. A B C D List-I List-II

1. ii iii iv i (A) Red precipitate (i) Polythene
2. v i ii iv (B) White precipitate (ii) Cuprous acetylide
3. iii v ii i (C) Poisonous gas (iii) Silver acetylyde
4. iv v i ii (D) Plastic  (iv) Mustard gas

2.
Correct code is
List-I List-II
(A) Bayer’s reagent  (i) Ni S. No. A B C D
(B) Tollen’s reagent (ii) Zn 1. i ii iii iv
(C) Lindlar’s catalyst (iii) MnO–4 2. ii iii iv i
(D) Metal associated with ozonolysis  (iv) Ag+ 3. iv iii ii i
 (v) Pd 4. i iv iii ii

Correct code is

S. No. A B C D Answers
1. i ii iii iv
2. iii iv v ii (1) 2 (2) 2 (3) 2
3. i iii ii iv
4. v iv ii iii

Chapter_19.indd 12 3/26/2014 3:34:17 PM

 20

Chapter
Aromatic Hydrocarbons

• These hydrocarbons have a pleasant odour (in Greek • The structure proposed by Kekule must give two
“aroma” means “pleasant smelling”). So, they are isomeric 1,2-dibromobenzenes one with bromine
­
named as aromatic compounds. atoms attached to the doubly bonded carbon atoms,
• Simply, these hydrocarbons are also known as a whereas in the other, the bromine atoms are attached
arenes. to singly bonded carbons.
• The most important aromatic hydrocarbon is benzene. Br Br
Br
Br
Structure of Benzene
• As per the carbon and hydrogen ratio, benzene is the
most unsaturated molecule.
• Since benzene is forming only one orthodisubstituted
• Like unsaturated compounds (alkenes, alkynes)
product Kekule proposed the resonance structures to
benzene do not participate in addition reactions but
benzene.
participates in substitution reactions like saturated
compounds.
• Benzene cannot be oxidized by alkaline p­otassium
permanganate (Baeyer’s reagent); so, it cannot
­decolourise pink colour of permanganate.
• Benzene was found to form a triozonide which • To explain the unusual stability of benzene and pre­
­indicates the presence of three double bonds. ference to substitution than addition reactions reso-
• Benzene forms only one monosubstituted derivative nance was proposed.
indicating that all the six carbon and six hydrogen • Benzene is a resonance hybrid of various resonance
­atoms of benzene are identical. structures.
• Kekule proposed the cyclic arrangement of six carbon
atoms with alternate single and double bonds and one
hydrogen atom attached to each carbon atom.
H

C Kekule
H C C H
Or
H C C H
C

H Dewar

Chapter_20.indd 1 3/26/2014 3:34:24 PM

 20.2  Objective Chemistry - Vol. I

• The resonance hybrid structure of benzene is

­represented as


Naphthalene Cyclopentadienyl
(10 π-electrons) anion (6 π-electrons)
• Kekule structures are the main contributing structures
to the resonance hybrid structure.
• Resonance energy of benzene is 150.48 kJ mol–1 or
36 k cal mol–1. ⊕
N
• In benzene all carbon atoms are equal and are in sp2 Cycloheptatrienyl
hybridisation. cation (6 π-electrons) Pyridine
(6 π-electrons)
• In benzene each carbon atom uses two sp2 hybrid
orbitals to form bonds with two carbon atoms in
­ • Aromatic compounds containing benzene ring are
the ring and one hybrid orbital to form bond with known as benzenoids and those not containing a
hydrogen. ­benzene ring are known as nonbenzenoids.
• In benzene every carbon has one pure p-orbital
­perpendicular to the plane of the ring and form 3π Preparation of Benzene
bonds.
• The π electron cloud is delocalized above and below • When acetylene gas is passed through a red hot tube, it
the plane of the ring. polymerizes to benzene.
• The C–C bond length in benzene is 1.39 Å which 3C2H2 500°
 C
→ C6H6
is in between the single bond length (1.54 Å) and • Decarboxylation of sodium benzoate with soda lime
­double bond length (1.34 Å) due to delocalization of π gives benzene.
+ NaOH
­electron cloud. C6H5COONa CaO  → C6H6 + Na2CO3
• The C–H bond length in benzene is 1.09 Å, bond • Reduction of phenol with zinc dust gives benzene.
angle is 120°. C6H5OH + Zn  → C6H6 + ZnO
• The shape of benzene molecule is planar hexagonal. • Benzene is formed by the hydrolysis of benzene
The average bond order in the benzene ring is 1.5. ­sulphonic acid.
C6H5SO3H + H2O HCl → C6H6 + H2SO4
Aromaticity
Physical Properties
• Aromatic character is that though the compounds are
unsaturated, they behave as saturated compounds, i.e., • Aromatic hydrocarbons are non-polar molecules
they participate in substitution reactions instead of and are usually colourless liquids or solids with
­addition reactions and resist oxidation. ­characteristic aroma.
• All the aromatic compounds must be cyclic and p­ lanar. • Aromatic hydrocarbons are immiscible with water but
There is complete delocalization of the π electrons in are readily miscible with organic solvents. They burn
the ring. with a sooty flame.
• According to Huckel’s rule, only cyclic planar
­molecules with 4n + 2π electrons can be aromatic. Chemical Properties
• Systems with 4nπ electrons such as cyclobutadiene • As benzene contains six π electrons, it can act as a
are described as antiaromatic. ­nucleophile and react with electrophiles in ­electrophilic
• Aromatic systems contain conjugated double bonds. substitution reactions.
• Aromatic compounds can be monocyclic or ­polycyclic, • The electrophilic substitution reactions in benzene
neutral or charged. Atoms other than carbon can also ­involve the substitution of a hydrogen atom on the
be part of the ring. Examples benzene ring for an electrophile.

Chapter_20.indd 2 3/26/2014 3:34:26 PM

 Aromatic Hydrocarbons  20.3

• The initial electrophilic attack on the benzene ring leads to the formation of a positively charged i­ ntermediate (known
as a Wheland intermediate which is readily deprotonated).
slow (rate- H E H E H E
determining) ⊕ ⊕
E⊕ step

Nucleophile ⊕
fast step Non-aromatic carbocation
⊕ stabilised by resonance
–H
E
Deprotonation
to regain H E
Substituted aromaticity
benezene ⊕ Wheland
intermediate

1. Halogenation
• The reaction of benzene with bromine or chlorine in the presence of a Lewis acid catalyst (such as FeBr3, FeCl3 or
AlCl3) leads to the formation of b­ romobenzene or chlorobenzene, respectively.
• Lewis acid which is an electron-deficient acid forms a complex with bromine or chlorine. This polarizes the halogen–
halogen bond (making the halogen more electrophilic) and attack occurs at the positive end of the complex.
H X
δ+ δ− ⊕
X – X ...... FeX3 
FeX4

X = Br or Cl The Lewis acid can accept

a lone pair of electrons
from the halogen
X

FeX3 + HX +
(regenerated)

• No reaction occurs in the absence of a Lewis acid. This contrasts with the halogenation of alkenes/alkynes which
does not require activation by a Lewis acid. This is because alkenes/alkynes are not aromatic and hence they are more
­reactive than benzene.
2. Nitration
• Nitration of benzene can be carried using a mixture of concentrated nitric acid (HNO3) and sulphuric acid (H2SO4).
These acids react to form an intermediate nitronium ion, which acts as the electrophile.
O O
|| H ⊕ O ||  ⊕ ⊕ O
HO – S – O HO –– N HO – S – O + H2O – N
|

||  || 
O O O O

O
⊕ O || ⊕
⊕
H2O ––– N H2O + N
||

O O
Nitronium ion
NO2
O2N H
O
|| ⊕
Chapter_20.indd 3 – H⊕ 3/26/2014 3:34:31 PM
⊕
 O O O

O
⊕ O || ⊕
⊕
H2O ––– N H2O + N
||
20.4  Objective Chemistry - Vol. I 
O O
Nitronium ion
NO2
O2N H
O
|| ⊕
– H⊕
N ⊕
||
O
Nitrobenzene

3. Sulphonation
• The reaction of benzene with fuming sulphuric acid or oleum (a mixture of conc. sulphuric acid and sulphur trioxide)
leads to the formation of benzene sulphonic acid.
• This sulphonation is reversible, and this makes it a useful tool in organic synthesis for blocking certain positions on a
benzene ring.
• The sulphonation is favoured using strong sulphuric acid but desulphonation is favoured in hot, dilute ­aqueous acid.
O :O O ⊕
H O HO O
|| ||
HO – S – O S HO – S – O + S
|| || ||
O O O O
Electrophile

⊕ HO3S H SO3H
HO O
S ⊕ –H⊕

• Sulphur trioxide (rather than protonated sulphur trioxide) could also act as the electrophile in these reactions.
4. Alkylation: Friedel–Crafts Alkylation
• The reaction of benzene with alkyl bromides or chlorides in the presence of Lewis acid catalyst such as FeBr3, FeCl3
or AlCl3 leads to the formation of alkyl benzenes.
• Aryl or vinyl halides (ArX, R2C = CHX) do not react.
• The Lewis acid increases the electrophilicity of the carbon atom attached to the halogen. This can lead to the formation
of a carbocation which then reacts with the electron-rich benzene ring.
R R R
|δ+ δ– ⊕ 
R – C –– X + FeX3 C FeX4
|
R R

R3C CR3
H
R
⊕C
 ⊕ 
+ FeX4 FeX4 + HX + FeX3
R R (regenerted)

• Intermediate primary or secondary carbocations may rearrange to give more stable secondary or tertiary carbocations,
before the carbon–carbon bond formation can take place.

Chapter_20.indd 4 3/26/2014 3:34:32 PM

 Aromatic Hydrocarbons  20.5

• In general, the higher the reaction temperature, the greater is the amount of rearranged product.
H
AlCl3 ⊕ hydride shift ⊕
CH3(CH2)3Cl 
CH3CH2 – CH – CH2 CH3CH2 – CH – CH3
–AlCl4
Primary cation Secondary cation

The primary carbocation

rearranges to give the
more stable secondary
carbocation
CH2 CH2 CH2 CH3 H3C CH2CH3

CH
Carbocation rearragements
can also occur by
the migration
of alkyl groups
Unrearranged product Rearranged product

• Carbocation rearrangements can occur by the hydride shift or migration of alkyl groups.
5. Acylation: Friedel–Crafts Acylation
• The reaction of benzene with acid chlorides in the presence of Lewis acid catalyst such as AlCl3 or FeCl3 leads to the
formation of acyl benzenes.
• Lewis acid increases the electrophilicity of the carbon atom attached to the chlorine. This leads to the formation of an
acylium ion, which reacts with the electron-rich benzene ring.
⊕
O O O
|| δ+
C δ−
AlCl3 C⊕ C

R Cl AlCl4
R Acylium ion R

R O
R
C
O

C H
C⊕ AlCl4 R + HCl + AlCl3
⊕
 (regenerated)
R AlCl4

• Unlike carbocations, the intermediate acylium ion does not rearrange and is attacked by the benzene ring to give
exclusively the non-rearranged product.
• The Gattermann–Koch reaction (which uses CO, HCl and AlCl3) can be used to produce an aromatic aldehyde, rather
than a ketone.
δ– δ–  ⊕  ⊕
Cl3Al + Cl – H + C ≡ O Cl4Al + H – C ≡ O

H O
O
Chapter_20.indd 5 C 3/26/2014 3:34:33 PM
O
 δ– δ–  ⊕  ⊕
Cl3Al + Cl – H + C ≡ O Cl4Al + H – C ≡ O
20.6  Objective Chemistry - Vol. I

H O
O
C
O
C H
C⊕ H ⊕ 
H AlCl3

Benzaldehyde

Addition Reactions
• Under vigorous conditions, i.e., at high temperature and/or pressure in the presence of nickel catalyst, hydrogenation
of benzene gives cyclohexane.

Ni
+ 3H2
∆

• Under UV light, three chlorine molecules add to benzene to produce benzene hexachloride C6H6Cl6 which is called
gammaxene.
Cl
UV - 500K Cl Cl
+ 3Cl2

Cl Cl
Cl
• Combustion: Benzene burns with a sooty flame producing CO2 and H2O.

Reactivity of Substituted Benzenes

• The introduction of substituents on the benzene ring affects both the reactivity of the benzene ring and also the
­regiochemistry of the reaction, i.e., the position in which the new group is introduced on the benzene ring.
• Reactivity of Benzene rings: Activating and deactivating substituents.
• Substituents that donate electron density towards the benzene ring are known as the activating groups.
• The activating groups have positive inductive (+I) and/or mesomeric effects (+M) and make the substituted benzene
ring more reactive to electrophilic substitution than benzene itself.
• The activating groups stabilize the carbocation intermediate by donating electrons.
• Substituents that withdraw electron density away from the benzene ring are known as the deactivating groups.
• The deactivating groups have negative inductive (–I) and/or mesomeric effects (–M) make the substituted benzene ring
less reactive to electrophilic substitution than benzene itself.
• The deactivating groups can destabilize the carbocation intermediate by withdrawing electrons.
• The reactions that take place during the depletion of ozone layer by freons are
EDG(+I, +M) EDG
More reactive ⊕ E
than benzene
E⊕ H EDG stabilises the
carbocation

EDG = Electron – donating group

EWG (–I, –M) EWG

Chapter_20.indd 6 ⊕ E 3/26/2014 3:34:34 PM
Less reactive
 than benzene EDG stabilises the
E⊕ H
carbocation

EDG = Electron – donating group

Aromatic Hydrocarbons  20.7

EWG (–I, –M) EWG

⊕ E
Less reactive
than benzene
E⊕ H EWG destabilises the
carbocation
EWG = Electron – withdrawing group
• The greater the + M and/or +I effect, the more activating the group and the more reactive the benzene ring is to
­electrophilic attack.
• Positive mesomeric effects are generally stronger than positive inductive effects.
• The greater the –M and/or –I effect, the more deactivating the group and the less reactive the benzene ring to
­electrophilic attack.
Activating groups Most reactive Deactivating groups
NHR, NH2 (+M, –I) Cl, Br, I (+M, –I)
OR, OH (+M, –I) CHO, COR (–M, –I)
NHCOCH3 (+M, –I) COOH, COOR (–M, –I)
Aryl (Ar) (+M, +I) SO3H (–M, –I)
Alkyl (R) (+I) NO2 (–M, –I) Least reactive

Orientation of Reactions
• Electrophilic substitution can occur at the ortho (2–/6–), meta (3–/5–) or para (4–) position of the benzene ring.
• The inductive and/or mesomeric effects the existing substituent determine to which position the new substituent is
introduced on the ring.
• By introducing a new substituent, the formation of the carbocation intermediate is the rate-determining step.
• If the existing substituent can stabilize the carbocation, then this will lower the activation energy leading to attack at
this position.
• Substituents can be classified as: (i) ortho-/para-directing activators; (ii) ortho-/para directing deactivators and or
(iii) meta-directing deactivators.

Ortho-/para-activators Ortho-/para-deactivators Meta-deactivators

NHR, NH2 Cl, Br, I CHO, COR
OR, OH COOH, COOR
NHCOCH3 SO3H
Aryl (Ar) NO2
Alkyl (R)

• The reactive ease of attack (by an electrophile) at the ortho-/para positions can be determined experimentally from
partial rate factors.
• The partial rate factors compare the rate of attack at one position in benzene. The higher the partial rate factor at a
given position, the faster the rate of electrophilic substitution.

Ortho-/Para-Directing Activators
• Electron-donating +I and/or +M groups (EDGs) which make the ring more nucleophilic than benzene will stabilize the
intermediate carbocation most effectively when new substituents are introduced at the ortho- or para-position.
• For the meta-isomer, the positive charge in the carbocation intermediate does not reside adjacent to the EDG in any of
the resonance forms.

Chapter_20.indd 7 3/26/2014 3:34:34 PM

 20.8  Objective Chemistry - Vol. I

EDG EDG EDG EDG

⊕ E ⊕
2 ⊕
+ E⊕ H + + E

4
H
Ortho- H E meta-
EDG = electron- para-
donating group Least stable
Most stable
The EDG can stabilise both of these cations more
effectively than the cation derived from meta-attack
• The EDG can stabilize the both ortho- and meta-substituted cations more effectively than the cation derived from
meta-attack.
• Additional resonance structure can be drawn for intermediate carbocations bearing the +M but not +I groups (at 2- or
4-position).
Ortho-attack Ortho-attack Para-attack
(Inductive (Mesomeric (Mesomeric
stabilisation) stabilisation) stabilisation)
⊕ ⊕
+↓ Me(+I) NH2 (+M) NH2 OH OH
⊕ E ⊕ E E
H H H
⊕

H E H E

Ortho-/Para-Directing Deactivators
• Halogen groups are unique in that though they are deactivating groups, they direct ortho-para positions of benzene
group.
• The +M effect of Cl, Br and I is weak because these atoms are all larger than carbon.
• The orbitals containing lone pair electrons (e.g., 3p-orbitals of Cl) do not overlap well with 2p orbital of carbon. Hence
the mesomeric effects are not transmitted well between the atoms of different rows of the periodic table.
• The weak +M effect does, however, ensure that the halogens are ortho-/para-directing but the strong –I effect (which
deactivates the ring) is more significant in terms of the reactivity of halobenzenes.
⊕
X X
E E
ck H H
X atta
Ortho
⊕
+E ⊕
X X
Para
atta
ck
X = Cl, Br or I

⊕
H E H E

Chapter_20.indd 8 3/26/2014 3:34:35 PM

 Aromatic Hydrocarbons  20.9

Meta-Directing Deactivators
• Electron-withdrawing –I/–M groups (EWGs) which make the ring less nucleophilic than benzene will deactivate the
­meta-position less than the ortho-/para-positions. The carbocation produced from attack at the meta-position will
therefore be the most stable because this does not reside adjacent to the EWG in any of the resonance forms.
EWG EWG
EWG EWG
1
⊕ E ⊕ ⊕
2
+ E⊕ H + + H

4
E
meta-
EWG = electron- Ortho- H E Most stable
withdrawing group para-
Least stable

EWG can destabilise both of

these cations more effectively
than the cation derived from
meta-attack.

Examples:

Ortho-attack Para-attack
NO2 (–I, –M) CHO (–I, –M) CHO

⊕ ⊕
E
H
⊕
H E H E
Unstable Unstable

Steric Effects vs Electronic Effects

• With activating groups, the ratio of attack at the ortho- and para-positions can be expected as 2:1 since there are two
ortho-positions to one para-position in the benzene ring.
• Substitution at ortho-position is often less than at para-position due to steric hindrance.
• As the size of the group increases, substitution at para-position increases.

R Large alkyl group R R

E
+ E⊕ +

The large group E

ortho- para-
shields the ortho- disfavoured favoured
positions from attack

Chapter_20.indd 9 3/26/2014 3:34:37 PM

 20.10  Objective Chemistry - Vol. I

Identifying the Ortho-/Para- and • N-Bromo succinimide (NBS) can brominate at the
Meta-­Directing Groups benzylic position via a radical mechanism (i.e., at
the carbon atom attached to benzene ring). This is
• Let XY is a host group in benzene nucleus where X is ­because the intermediate benzylic radical is stabilized
the atom linked to benzene ring. by resonance since the radical can interact with the
X–Y π-electrons of the benzene ring.
H
| NBS
CHR CHR
Peroxide
initiator

 (i) If Y is in the higher group of periodic table or if Benzylic radical

in the same group but with lower atomic weight
than X, the group XY is meta-directing. Br
 (ii) In all other cases (whether XY is single atom or |
Y in lower group, XY is ortho-/para- directing). CHR
(iii) The presence positive charge on XY makes it
meta-directing (while the presence of negative
charge on XY makes it ortho-/para-directing). Synthesis of substituted benzenes
Group X Y Nature
• The introduction of an activating group into benzene
–NH2 N Vgr H Igr o- and p- ring makes the product more reactive than the starting
–CN C IVgr N Vgr m- material. So, further substitution continues in other
–NC N Vgr C IVgr o- and p- positions also and cannot be stopped after the first
–CCl3 CI Vgr Cl VIIgr m- substitution.
–SO3H S VIgr O VIgr m-
less at weight CH2R CH2R
–OH O VIgr H Igr o- and p-
Further
RCH2Cl/AlCl3 alkylation
Nucleophilic Aromatic Substitution
• The reaction of nucleophile with a benzene ring is More reactive
very rare and can take place when strongly electron- than benzene CH2R
withdrawing substituents (e.g., NO2) are at ortho- and/
or para-positions of aryl halides.
• The introduction of a deactivating group into a benzene
ring makes the product less reactive than the starting
• The nucleophilic substitution reactions in benzene material. So, further substitution does not take place.
proceed by an addition elimination mechanism and
the electron-withdrawing groups can stabilize the
• To get monoalkylated benzene, it is better to prepare
intermediate carbanion (called a Meisenheimer
­ first ketone by Friedel–Crafts acylation and then
­complex) by resonance. ­reduce it to alkyl group with Zn/Hg and HCl.
• To get an ortho-/para-substituted benzene, the first
Transformation of Side Chains group to be introduced in the ring should be ortho-/
para-directing.
• Oxidation of alkyl side chains with strong o­ xidizing • For a meta-substituted benzene ring, the first group to
agents (e.g., KMnO4) gives only benzoic acid be introduced on the ring should be meta- directing.
­irrespective of whatever the length of the side chain.
• In the case of aniline, the orientation of substitution
R COOH
depends on the pH of the reaction. At low pH, aniline is
KMnO4 protonated and the protonated amine is meta-directing.
• Making the activating group larger in size can increase
the proportion of para- over ortho- substitution (as
R = alkyl group
steric hindrance minimizes ortho-attack).

Chapter_20.indd 10 3/26/2014 3:34:38 PM

 Aromatic Hydrocarbons  20.11

• Conversion of an amine to a bulkier amide by treating with an acid chloride leads to para- substitution. The amide
group is referred to as a blocking group.
• Amide group is not as strong an activating group as the amine and thus multiple substitutions is less possible.
• Removable aromatic substituents, typically SO3H or NH2 can be used to direct or block a particular s­ ubstitution. By
using this, aromatic products with unusual substitution patterns can be prepared.
NH2 NH2
(1) H2SO4 Br2 Br Br (1) NaNO2
Br Br
HNO3 FeBr3 HCl
(2) Sn HCl (2) H3PO2

Ortho-/para directing Br Br

• Deactivating groups can be converted to ­activating groups (and vice versa) by functional group interconversion.
CH3 COOH NO2 NH2

KMnO4 Sn, HCl

Ortho-/para meta- meta- ortho-/para

directing directing directing directing
• For the formation of trisubstituted benzenes, the ­directing effects of two groups on the benzene ring must be ­compared.
When these groups direct to ­different positions, the more powerful activating group usually has the dominant ­influence.
Substitution in b­ etween two meta-disubstituted groups is rare of steric hindrance.
Ortho-/para- Ortho-/para- Ortho-/para-
directing directing directing
CH3 OH Attack at CH3
E⊕ E⊕ this site is E⊕
hindered

Cl
COOH CH3 Ortho-/para
meta-directing ortho-/para-directing directing E⊕
OH is more powerful
activating group

2. The C–C bond length in benzene is

 Objective Questions (1) less than in ethylene
1. Among the following the wrong statement is (2) less than in acetylene
(1) aromatic hydrocarbons are the derivatives of (3) less than in ethane
­benzene (4) equal to C–C bond length in ethylene
(2) benzene contains 9 sigma and 3 pi bonds
(3) aromaticity of benzene is due to delocalization of 3. Identify the wrong statement.
p-electrons (1)  All the six carbons in benzene are of the
(4) all carbon atoms in benzene are involved in sp2 same type
hybridisation (2) The ratio of s to p bonds in benzene is 4.

Chapter_20.indd 11 3/26/2014 3:34:39 PM

 20.12  Objective Chemistry - Vol. I

(3) Each p-electron in benzene is associated with (3) Though benzene is unsaturated but does not give
two carbon atoms. addition reactions since resonance lowers the
(4) According to Huckel, aromatic compounds ­energy of benzene molecule and leads to greater
should contain (4n + 2) p-electrons. stabilization
(4)  Benzene always forms only one disubstituted
4. Which of the following is a false statement?
product
(1) The name benzene was given to it by M ­ itcherlich.
(2)  The correct structure for benzene was first 10. Benzene can be prepared directly from
­proposed by Kekule. (1) HC≡CH (2) C6H5OH
(3)  The orbital overlap between carbon atoms in (3) C6H5COONa (4) All
­benzene is sp-sp.
(4) Benzene molecule is plane hexagonal. 11. Which of the following is not correct?
(1) Benzene can be obtained by the cyclisation of
5. Which of the following is not correct? ethene
(1) The bond angle in benzene is 120° (2) Benzene reacts with H2 in the presence of Ni at
(2) The C–C bond length in benzene is 1.39 Å 200°C to give cyclohexane
(3) Benzene was discovered by Faraday (3) C6H6Cl6 can be obtained from C6H6 + Cl2 + light
(4)  Benzene is an unsaturated hydrocarbon and (4)  Benzene reacts with ozone to form benzene
­participate in addition reactions easily ­triozonide
6. Which of the following is represented incorrectly? 12. Benzene is a resonance hybrid mainly of two Kekule
(1) C6 H 6 + Cl 2 anhydrous

Sun light
AlCl3
→ C6 H 6 C6 structures. Hence
(2) C6H6 + CH3Cl  → C6H5CH3 + HCl is an (1) Half the molecules correspond to one structure
­example of Friedel–Crafts reaction and half to the structure
(3)  Distillation of phenol with zinc dust gives (2) At low temperatures benzene can be separated
­benzene into two structures
(4) Benzene reacts with CH3COCl in the presence of (3)  Two structures make equal contribution to
AlCl3 to give C6H5COCl ­resonance hybrid
(4) An individual benzene molecule changes back
7. The wrong statement in the following is and forth between two structures
(1) Sulphonation of benzene takes place only with
hot concentrated sulphuric acid. 13. Benzoic acid gives benzene on being heated with X
(2) In the nitration mixture concentrated sulphuric and phenol gives benzene on being heated with Y.
acid is used for the formation of nitronium ion. Therefore, X and Y are respectively
(3) Because of unsaturation benzene easily u­ ndergoes (1) Soda lime and copper
addition reactions. (2) Zinc dust and sodium hydroxide
(4) Benzene burns with a sooty flame. (3) Zinc dust and soda lime
(4) Soda lime and zinc dust
8. In the reactions,
Phenol distillation

Zn
→ A conc.HNO

conc.H2SO4
→B 14. Two organic compounds A and B have sp2 ­hybridised
3 ,60° C

The compounds A and B are carbon atoms. A can decolourise alkaline KMnO4
while B cannot. A and B could be
(1) Benzene, aniline
(2) Benzene, benzene sulphonic acid (1) Ethylene and acetylene
(3) Benzene, nitrobenzene (2) Propylene and acetylene
(4) Benzene, toludine (3) Benzene and acetylene
(4) Ethylene and benzene
9. The false statement among the following is
(1)  Ozonolysis of benzene gives three moles of 15. Catalytic hydrogenation of benzene gives
­glyoxal (1) another aromatic compound
(2) Aromatic compounds burn with a sooty flame (2) an aliphatic compound
since they have relatively high percentage of (3) an alicyclic compound
­carbon (4) alkyne

Chapter_20.indd 12 3/26/2014 3:34:40 PM

 Aromatic Hydrocarbons  20.13

16. HC≡CH + H2 Lindlar’s

 → X HCl
 → Y A6 6C H
→Z CH3 OCH3
Catalyst lCl 3

Regarding X, Y and Z some statements are given (3)  (4) 

A: “X” can decolourise Br2 water
B: “Y” can give white precipitate with AgNO3
­solution 23. Among the following compounds (I–III) the correct
C: X, Y are aliphatic compounds, but Z is an aromatic order in reaction with electrophile is
compound OCH3
D: In “Z” the number of hybrid orbitals is 26  (I)  (II) 
The correct statements are
(1) A, B, C (2) A, C, D
(3) A, B, D (4) B, C, D NO2
(III) 
17. CHCl3 + Ag 
→ X
CHCl3 + Ag hot
 Cu tube
→Y
(1) II > III > I
CHCl3 + Ag Controlled

Pd + Quinoline
→ Z
hydrogenation (2) III < I < II
Among X, Y and Z the pair of substances which give
(3) I > II > III
the same ozonolysis products are
(4) I=II > III
(1) X, Y (2) X, Z
(3) Y, Z (4) X, Y and Z 24. The ortho/para-directing group among the following is
(1) COOH (2) CN
18. In which of the following new carbon–carbon bond is
not formed? (3) COCH3 (4) NHCOCH3
(1) Wurtz reaction 25. Among the following compounds, the decreasing
(2) Friedel–Crafts reaction ­order of reactivity towards electrophilic substitution is
(3) Passing benzene through hot iron tubes  (I)  CH3  (II) 
(4) Sabatier–Sender’s reaction

19. Which are among the following gives a dicarbonyl

compound with O3 followed by reduction with zinc (III)  OCH3 (IV)  CF3
and water?
(i)  C2H4   (ii) C6H6
(iii) C2H2 (iv) C3H6 (1) III > I > II > IV
(1) i and iii (2) i, ii and iii (2) IV > I > II > III
(3) i, ii and iv (4) ii and iii only (3) I > II > III > IV
(4) II > I > III > IV
20. Amongst the following compounds which can be
most easily sulphonated? 26. Identify the correct order of reactivity in electrophilic
(1) Benzene (2) Nitrobenzene substitution reaction of the following compounds.
(3) Toluene (4) Chlorobenzene  (I)   (II)  CH3

21. Which of the following will undergo meta-­substitution

on monochlorination?
(1) Ethoxy benzene (2) Chlorobenzene (III)  Cl (IV) NO2
(3) Nitro benzene (4) Phenol

22. Which of the following will have fastest rate of

­reaction with Br2/FeBr3? (1) I > II > III > IV
NO2 (2) IV > III > II > I
(1)  (2)  (3) II > I > III > IV
(4) II > III > I > IV

Chapter_20.indd 13 3/26/2014 3:34:46 PM

 20.14  Objective Chemistry - Vol. I

27. Which of the following represents the correct ­decr-­ 31. Consider p-amino phenol
easing relative reactivity towards an electro­phile, E+? O– OH OH
(1) C6H5CH3, p-CH3C6H4CH3,
β OH– H+ Y
p-CH3C6H4NO2, p-NO2C6H4NO2
(2) p-CH3C6H4CH3, p-CH3C6H4NO2, α X
p-NO2C6H4NO2, C6H5CH3 NH2 NH2 NH3
(3) p-CH3C6H4NO2, C6H5CH3, ⊕
B A
p-CH3C6H4CH3, p-NO2C6H4NO2
Which positions are activated in acidic and basic
(4) p-CH3C6H4CH3, C6H5CH3, ­media for coupling?
p-CH3C6H4NO2, p-NO2C6H4NO2
(1) X in A and b in B (2) X in A and a in B
28. The compound (3) Y in A and a in B (4) Y in A and b in B
X
( where X is an o-p-directing group and Y OH
is a ­m-­directing group) NO+2
Y 32. A; A can be
is subjected to electrophilic substitution reaction for
introduction of Z. The compound formed would be CH3
(1) X (2)  X
(1) OH (2) OH
NO2

Z Y Y
NO2
Z CH3 CH3
(3) X (4) both (2) and (3) (3) (4) No SE reaction is possible
OH
Z

Y NO2
29. The molecular formula of diphenyl methane C13H12 is
Br2/Fe
33. A; A is
CH2

How many structural isomers are possible when one Br

of the hydrogen is replaced by chlorine atom?
(1) 6 (2) 4 (3) 8 (4) 7 (1)

∆
B (2) Br
CCl4, KOH ∆ CH3 COCl
30. OH A C (3) Both are correct
(4) None is correct
CH3 OH
D Cl
*
A, B, C and D respectively are 34. NaOH, H2O
Product
(1) Salicylic acid, salol, aspirin and oil of winter 395°C
green The product is
(2) Salicylic acid, aspirin, salol and oil of winter (1) OH (2) *
green *
(3) Salicylic acid, oil of winter green, salol and
­aspirin OH
(4) None is correct (3) Both (4) None

Chapter_20.indd 14 3/26/2014 3:34:52 PM

 Aromatic Hydrocarbons  20.15

35. Which separates by sulphonation? 40. Why does 1,3-cyclohexadiene undergo dehyd­
(1) o-xylene (2) m-xylene rogenation readily?
(3) p-xylene (4) All (1) It can be easily reduced
(2) It has no resonance energy
H2O/H+ (3)  It gains considerable stability by becoming
36. CH = CH – CH
A(predominant) .A is ­benzene
(4) It cannot undergo dehydrogenation
(1)  CH2 – CH – CH3 41. How many different tetrachlorobenzenes are
| ­possible?
OH
(1) two (2) three (3) four (4) five
(2)  CH – CH2 – CH3
| 42. How many isomers can tribromobenzene have?
OH (1) one (2) two (3) three (4) four

(3)  CH = CH – CH3 43. The major product obtained in the reaction

COOH
OH HNO3
A; A is
H2SO4
(4) 
HO CH = CH – CH3
COOH
(1)  COOH (2)  COOH
H2/pt
37. A; A is NO2
1 mol

COOH O2N COOH

(1) (2)  (3)  COOH (4)  COOH
NO2

(3)  (4)  COOH COOH

NO2 NO2

44. The major product obtained in the reaction

CH2 CH2 CH3
38. The conversion Cl
SO3
is
CH2 CH2 CH3 H2SO4
Cl
Br (1)  Cl (2)  Cl
can be effected using Cl
SO3H
(1) Br2/CCl4 (2) Br2/H2O
(3) Br2/Fe (4) Br2/benzoyl peroxide
Cl HO3S
39. Which of the following is expected to be aromatic?
(3)  Cl (4)  Cl
(1)  (2)  SO3H

H HO3S Cl Cl
(3)  (4)  ⊕
H SO3H SO3H

Chapter_20.indd 15 3/26/2014 3:35:00 PM

 20.16  Objective Chemistry - Vol. I

45. The major product obtained in the reaction 48. The sulphonation of chlorobenzene gives exclusively
O (1) an o-product
|| Br2 (2) an m-product
C – CH2
FeBr3 (3) a p-product
(4) an o-, p-disubstituted product
is expected to be
(1) Br CO – CH2 49. When an aromatic compound undergoes ­ozonolysis
followed by treatment with H2O/Zn, it produces
­glyoxal, monomethyl glyoxal and dimethyl glyoxal.
(2) CO – CH2 Br It could be
(1) benzene (2) toluene
(3) o-xylene (4) m-xylene
(3) CO – CH –
| 50. Which of the following is the most reactive towards
Br electrophilic nitration?
(1) Benzene (2) Toluene
(4) CO – CH2 Br (3) Benzoic acid (4) Nitrobenzene

51. Which form of xylene is most easily sulphonated?

Br
(1) ortho-
46. The final product obtained in the reaction (2) meta-
(3) para-
CH3 CH2 COCl CH3 NH2
X is (4) All are sulphonated at the same rate
AlCl3 H2, Ni
52. Which form of xylene has only one monobromo
(1) H3C NH CH2 CH2 COCl ­derivative?
(1) ortho- (2) para-
(3) meta- (4) None of these
(2) CH CH2 CH3
| 53. Arrange C6H5CH3 (I), C6H6 (II), C6H5COOH (III),
NH CH3 C6H5NO2 (IV) in order of decreasing reactivity to
ring monobromination.
(3) CH2 CH2 CONHCH3 (1) I > III > II > II (2) III > II > IV > I
(3) I > II > III > IV (4) II > I > III > IV

(4) COCH2 CH2 NHCH3 54. Iodobenzene can be obtained by

(1) C6H6 + I2  →
47. The major product obtained by Friedel–Crafts (2) C6H6 + I2 HNO
 3
→
­reaction of n-butyl bromide with benzene in the (3) C6H6 + KI  →
­presence of anhydrous AlCl3 is
(4) C6H6 + HI  →
(1) CH2 CH2 CH2 CH3 55. m-dinitrobenzene can be converted into
­m-nitroaniline by reduction with
CH3 (1) Raney nickel (2) LiAlH4
|
(2) (3) (NH4)2S (4) Na/C2H5OH
CH – CH2 CH3
56. A Friedel–Crafts reaction of benzene with ­chloroform
CH3 produces
|
(3) C – CH3 (1) C6H5CHCl2 (2) C6H5CHClC6H5
| (3) C6H5 – CH – C6H5 (4)  All of these
CH3 |
(4) None of these C6H5

Chapter_20.indd 16 3/26/2014 3:35:06 PM

 Aromatic Hydrocarbons  20.17

57. Toluene can be converted into benzaldehyde by ­ -dichlorobenzene (II), ortho-chlorobenzene (III)
m
­oxidation with and p-dichlorobenzene (IV).
(1) KMnO4/alkali (2) CrO2Cl2 (1) IV < I < II < III (2) I < IV < II < III
(3) K2Cr2O7/H2SO4 (4) O2/V2O5 (3) IV < II < I < III (4) IV < I < III < II
58. Which of the following is a Wurtz–Fittig reaction? 64. Which of the following are produced when a ­mixture
of benzene vapour and oxygen is passed over the
(1) Br + 2Na + BrCH2CH3 ­catalyst V2O5 at 775 K?
(1) Oxalic acid (2) Glyoxal
(3) Fumeric acid (4) Maleic anhydride
CH2 CH3 + 2NaBr
65. Which of the following is the end product of the
­treatment of benzene with an excess of Cl2 in the
(2) AlCl3 presence of I2?
+ BrCH2 CH3
anhyd (1) Monochlorobenzene
(2) Dichlorobenzene
CH2 CH3 + HBr (3) Trichlorobenzene
(4) Hexachlorocyclohexane
130–150°C 66. Arrange the following in order of decreasing boiling
(3) SO3H + H2O
HCl point.
CH3
+ H2SO4 CH3
CH3 H3C CH3

(4) MgBr + CH3 CH2COCl

II H3C
I CH3C CH3
COCH2 CH3 III IV

(1) I > II > III > IV (2) IV > III > II > I
59. The stability of the free radicals allyl, benzyl, 3°, 2°, (3) I > III > IV > II (4) II > III > I > IV
1° and CH3 is of the order 67. The alkylation of benzene with n-propyl chloride in
(1) allyl=benzyl > 3° > 2° > 1° > CH3 the presence of anhydrous AlCl3 produces
(2) allyl > benzyl > 3° > 2° > 1° > CH3 (1) n-propyl benzene (2)  isopropyl benzene
(3) 3° > 2° > 1° > CH3 > allyl > benzyl (3) o-dipropyl benzene (4)  a mixture of all these
(4) 3° > 2° > 1° > CH3 > allyl=benzyl
68. Which of the following do not undergo a Friedel–
60. The final product of the nitration of toluene is Crafts reaction?
(1) o-nitrotoluene (1) Benzene (2) Toluene
(2) m-nitrotoluene (3) Nitrobenzene (4) Naphthalene
(3) 2,4-dinitrotoluene
(4) 2,4, 6-trinitrotoluene 69. The directing power of the groups –NH2, –OCH3,
–C6H5 and –NO2 follows the order
61. Which of the following can be easily nitrated?
(1) –NH2 > –OCH3 > –C6H5 > –NO2
(1) Benzene (2) Phenol (2) –NO2 > –C6H5 > –OCH3 > –NH2
(3) Nitrobenzene (4) Chlorobenzene (3) –OCH3 > –NH2 > –C6H5 > –NO2
62. Which of following reacts slower than benzene in (4) –OCH3 > –NO2 > –NH2 > –C6H5
electrophilic substitution? 70. The reactivities of C6H5CH3 (I), C6H5CH2Cl (II),
(1) C6H5CH3 (2) C6H5NO2 C6H5CHCl2 (III) and C6H5CCl3 (IV) towards n­ itration
(3) C6H5OH (4) C6H5NH2 are in the order
63. Arrange the following compounds in o­ rder (1) I > II > III > IV (2) II > I > III > IV
of ­increasing dipole moment. Toluene (I), (3) IV > III > II > I (4) III > I > II > IV

Chapter_20.indd 17 3/26/2014 3:35:08 PM

 20.18  Objective Chemistry - Vol. I

71. Which of the following groups would enhance the (3) OH > Cl > COOH > NO2
­reactivity of electrophilic aromatic substitution? (4) NO2 > COOH > OH > Cl
(1) –CN (2) –CHO 78. Friedel–Crafts reaction of benzene with propene
(3) –CH3 (4) –NO2 ­proceeds through the formation of
+
72. Which of the following will be obtained by the (1) CH3CH2CH2
+
­bromination of ethylbenzene in the presence of light? (2) CH3CHCH3
CH2 CH3 (3) CH3CH2CH2
(1) (4) CH3CHCH3
Br
79. Arrange the following groups in order of decreasing
o- and p-directing strength.
(2) Br CH2 CH3
–NH2, –OH, –Cl, –R
Br (1) –Cl > –R > –OH > –NH2
(2) –NH2 > –OH > –R > –Cl
(3) CH – CH3
(3) –OH > –NH2 > –R > –Cl
(4) –R > –Cl > –NH2 > –OH

80. Arrange the following groups in order of increasing

(4) CH2 CH2 Br m-directing strength.
–NR3, –CN, –NO2, –COOH
73. Which is the major product formed in the following
(1) –NR3 > –NO2 > –CN > –COOH
reaction?
(2) –COOH > –CN > –NO2 > –NR3
C6H6 + (CH3)2CHCH2OH H 2SO 4
→? (3) –CN > –NO2 > –NR3 > –NR3
(1) C6H5CH2CH(CH3)2 (4) –NO2 > –CN > –NR3 > –COOH
(2) C6H5C(CH3)3
(3) C6H5C(CH3)2C6H5 81. The nitration of isopropyl benzene exclusively
(4) A mixture of all these gives a/an
74. Which of the following is a wrong statement? (1) o-isomer
(2) m-isomer
(1) The reacting species in sulphonation is H2SO4
(3) p-isomer
(2) In Friedel–Crafts reaction of benzene with an
(4) 2,4-disubstituted product
acid chloride the electrophilic reagent is RCO
(3) In the nitration of toluene by electrophilic sub­ 82. The reactivity of p-nitrochlorobenzene (I), 2,4-
stitution the electrophile is nitronium ion dinitrochlorobenzene (II) and 2,4,6-trinitroc­ hloro-
(4) Reaction of benzene with chlorine in the ­presence benzene (III) towards alkali is of the order
of sunlight is an addition reaction (1) I > II > III (2) III > II > I
75. Which of the following is the least reactive in (3) II > I > III (4) III > I > II
­electrophilic substitution?
83. The function of anhydrous aluminium chloride in
(1) Aniline (2) Nitrobenzene
Friedel–Crafts reaction is
(3) Aniline hydrochloride (4) Acetanilide
(1) to absorb water
76. Arrange toluene (I), benzyl chloride (II), benzalchlo- (2) to absorb hydrochloric acid
ride (III) and benzotrichloride (IV) in order of the (3) to produce an electrophile
inductive effect of the group attached to the benzene (4) to produce nucleophile
nucleus.
(1) I < II < III < IV (2) IV < III < II < I 84. In a set of reactions, ethyl benzene yielded a
(3) III < IV < II < I (4) II < I < III < IV product (D)
KMnO4 Br2
77. Arrange the following groups in order of decreasing CH2 CH3 (B) (C)
electron attracting capacity. KOH FeCl3
C2H5OH
(1) COOH > NO2 > OH > Cl (D) would be
(2) NO2 > COOH > Cl > OH H+

Chapter_20.indd 18 3/26/2014 3:35:10 PM

 Aromatic Hydrocarbons  20.19

Br 91. The position least nitrated, when m-bromochloro­

| benzene is nitrated is
(1) CH2 – CH – COOC2H5
(1) position ortho to bromine
(2) position ortho to chlorine
Br (3) position ortho to bromine and chlorine
(4) position meta to chlorine
(2) Br CH2 COOC2H5
92. Benzene on reaction with conc. HNO3 in the presence
of conc. H2SO4 followed by the treatment of Cl2 in
HOOC
the presence of FeCl3, it gives
(3) (1) 2-chloro-1-nitrobenzene
OCH2 CH3 (2) 3-chloro-1-nitrobenzene
(3) 4-chloro-1-nitrobenzene
Br (4)  a mixture of 2-chloro and 4-chloro-
1-­nitrobenzene
(4) COOC2H5 93. When nitrobenzene is treated with Br2 in the presence
of FeBr3, the major product formed is m-bromoni-
trobenzene. Statement which is related to obtain the
85. Which one of the following is not aromatic? m-isomer is
(1) cyclopentadienyl anion (1) the electron density on meta-carbon is more than
(2) cyclohepta trienyl cation that on ortho- and para-positions
(3) cyclooctatetraene (2) loss of aromaticity when Br+ attacks at the ortho-
(4) triophene and para-positions and not at meta-position
86. Chlorination of toluene in the presence of light and (3)  easier loss of H+ to regain aromaticity from
heat followed by treatment with aqueous KOH gives the meta-position than from ortho- and para-
(1) o-cresol positions
(2) p-cresol (4) None of the above
(3) 2,4-dihydroxy toluene 94. The replacement of chlorine from chlorobenzene to
(4) benzoic acid give phenol requires a drastic condition, but the ­chlorine
87. The compound with molecular formula CH which of 2,4-dichloro-nitro-benzene is readily ­replaced since
will give only two isomers on electrophilic sub­ (1) nitro groups make the aromatic ring electron rich
stitution with Cl2/FeCl3 or with HNO3/H2SO4 is at ortho/para-positions
(1) p-dimethyl benzene (2) nitro groups withdraw electrons from the meta-
(2) m-dimethyl benzene position of the aromatic ring
(3) o-dimethyl benzene (3) nitro groups donate electrons at meta-position
(4) ethyl benzene (4)  nitro groups withdraw electrons from ortho/
para-positions of the aromatic ring
88. The reaction least likely to occur is
95. Identify the false statement about the nitration of
(1) C6H6 + HNO3 H 2 SO 4
→ C6H5NO2
­aromatic compounds.
(2) C6H6 + H2SO4  Heat
→ C6H5SO3H
(3) C6H6 + Cl2 UV → C6H5Cl (1) The rate of nitration of benzene is almost the
(4) C6H6 + Br2  → C6H5Br same as that of hexa deuterobenzene.
(2) The rate of nitration of toluene is greater than
89. Which of the following is the most reactive towards that of benzene.
ring nitration? (3) The rate of nitration of benzene is greater than
(1) Benzene (2) Toluene that of hexa deuterobenene.
(3) m-Xylene (4) Mesitylene (4) Nitration is an electrophilic substitution reaction.
90. Toluene on treatment with CH3Cl and AlCl3 at 80°C 96. In the reaction p-chlorotoluene with KNH2 in liquid
gives the major product as NH3 the major product is
(1) o-xylene (2) p-xylene (1) o-toludine (2) m-toludine
(3) m-xylene (4) ethyl benzene (3) p-toludine (4) p-chloroaniline

Chapter_20.indd 19 3/26/2014 3:35:12 PM

 20.20  Objective Chemistry - Vol. I

97. A set of compounds in which the reactivity of h­ alogen OH

atom is in the ascending order is
NO2
(1) chlorobenzene, vinyl chloride, chloroethane
(2) chloroethane, chlorobenzene, vinyl chloride (3)
(3) vinyl chloride, chlorobenzene, chloroethane CH3
(4) vinyl chloride, chloroethane, chlorobenzene NO2
98. Nitrobenzene is used as a solvent for Friedel–Crafts OH
alkylation of bromobenzene because
(1) nitrobenzene cannot be used in alkylation
(2) nitrobenzene is less reactive than bromobenzene (4)
(3) nitrobenzene is more reactive than bromoben- O2N CH3
zene NO2
(4) none of the above
99. Amino group is ortho, para-directing for aromatic 102. The compounds P, Q and S
electrophilic substitution. On nitration of aniline, a COOH OCH3 O
good amount of m-nitroaniline is obtained. This is ||
due to C–O
(1) in nitration mixture, ortho, para-activity of –NH2 HO H3C Q S
group is completely lost P
(2) –NH2 becomes –NH3 which is m-directing were separately subjected to nitration using
(3) –NH2 becomes –NHSO–4 which is m-directing HNO3/H2SO4 mixture. The major product formed in
(4) –NH2 becomes –NHNO+2 which is m-directing each case respectively are
100. In electrophilic aromatic substitution reaction, the COOH OCH3 O
­nitro group is meta-directing because it ||
(1) , , C–O
(1) decreases electron density at meta-position
(2) increase electron density at meta-position HO H3C O2N
(3)  increase electron density at ortho- and para-­ NO2 NO2
positions
(4)  decreases electron density at ortho- and COOH OCH3 O
||
­para-positions , , C–O
(2)
101. In the reaction for dinitration HO H3C NO2
OH NO2 NO2
conc.HNO3 COOH OCH3 O
(X) ||
(3) , , C–O NO2
CH3
HO H3C NO2
The major dinitrated product NO2
OH
COOH OCH3 O
O2N ||
(4) , , C–O
(1)
CH3 HO H3C NO2 NO2
NO2
NO2
OH 103. Which xylene is most readily nitrated?
(1) o-xylene
(2) O2N NO2 (2) p-xylene
(3) m-xylene
CH3 (4) all at the same rate

Chapter_20.indd 20 3/26/2014 3:35:16 PM

 Aromatic Hydrocarbons  20.21

104. Which of the following structures corresponds to the 107. Which of the following on reaction with benzene in
product expected, when excess of C6H6 reacts with the presence of anhydrous AlCl3 gives cumene?
CH2Cl2 in the presence of anhydrous AlCl3? (1) CH3CH=CH2 (2) CH3CH2CH2Cl
Cl (3) (CH3)2CHCl (4) All
|
(1) CH 108. Which of the following compounds on reaction with
benzene in the presence of anhydrous AlCl3 gives
t-butyl benzene?
(2) CHCl2 OH
(1) (2)  OH
Cl
| (3) (4) Cl
(3) C Cl
| (5) All of these
Cl
109. For two identical substituents and one different there
(4) CH2 are ................. trisubstituted products.
(1) 2 (2) 4
(3) 6 (4) 3
105. Which of the following is correct for the mononi­
tration of phenyl benzoate? 110. Which of the following is not a criterion for
­aromaticity?
COO (1) An aromatic compound is cyclic and planar
(2) Each atom in aromatic ring has p-orbital. These
p-orbitals must be parallel so that a continuous
overlap is possible around the ring
(1) COO NO2 (3) The cyclic p-molecular orbital (electron cloud)
formed by overlap of p-orbitals must contain
O2N (4n + 2) p-electrons
(4)  It should decolourise Br2/CCl4 and alkaline
(2) COO KMnO4 solution
111. The end product of the reaction
NO2
AlCl3 Cr2O3/Al2O3
+ CH2 = CH2 A B;
(3) COO ∆ 600°C

(1) C6H5CH = CH2 (2) C6H5CH2CH3
(4) (3) C6H5CH3 (4) C6H5CHO
COO

NO2 Answers

106. The products A and B in the following reaction  (1) 2  (2) 3  (3) 3  (4) 3  (5) 4
CH CH = CH Br 2 → (A) (i)
NaNH 2 3equi
→ (B)  (6) 4  (7) 3  (8) 3  (9) 4 (10) 4
(ii)CH3I
(11) 1 (12) 3 (13) 4 (14) 4 (15) 3 
(1) C6H5CHBrCH2Br, C6H5CCCH3 (16) 2 (17) 1 (18) 4 (19) 4 (20) 3
(2) C6H5 CHBrCH2Br, C6H5CHCH2Br (21) 3 (22) 4 (23) 3 (24) 4 (25) 1 
(26) 3 (27) 4 (28) 4 (29) 2 (30) 1
NH2 (31) 1 (32) 1 (33) 1 (34) 3 (35) 2
(36) 2 (37) 1 (38) 3 (39) 4 (40) 3
(3) BrC6H4 CH = CH2, BrC6H3CH = CH2
(41) 3 (42) 3 (43) 2 (44) 1 (45) 2
(46) 2 (47) 2 (48) 3 (49) 3 (50) 2
NH2 (51) 2 (52) 2 (53) 3 (54) 2 (55) 3
(4) None of the above (56) 3 (57) 2 (58) 1 (59) 1 (60) 4

Chapter_20.indd 21 3/26/2014 3:35:22 PM

 20.22  Objective Chemistry - Vol. I

 (61) 2  (62) 2  (63) 1  (64) 4  (65) 4 5. Statement I: In strongly acidic solution, ­ aniline
 (66) 1  (67) 2  (68) 3  (69) 1  (70) 1 ­becomes more reactive towards electrophilic r­ eagents.
 (71) 3  (72) 3  (73) 2  (74) 1  (75) 2 Statement II: The amino group being completely
 (76) 1  (77) 2  (78) 2  (79) 2  (80) 1 ­protonated in strongly acidic solution, the lone pair
 (81) 4  (82) 2  (83) 3  (84) 4  (85) 3  of electrons on the nitrogen is no longer available for
 (86) 4  (87) 3  (88) 3  (89) 4  (90) 2 resonance.
 (91) 4  (92) 2  (93) 1  (94) 4  (95) 1
 (96) 3   (97) 1  (98) 2  (99) 2 (100) 4 6. Statement   I: Rates of nitration of benzene and
(101) 1 (102) 3 (103) 3 (104) 4 (105) 1 ­hexadeuterobenzene are different.
(106) 1 (107) 4 (108) 5 (109) 3 (110) 4 Statement  II: C–H bond is weaker than C–D bond.
(111) 1
7. Statement   I: Styrene on reaction with HBr gives
2-bromo-2- phenyl ethane.
Statement   II: Benzyl radical is more stable than
alkyl radical.
  Statement- Type Questions
8. Statement I: Aromatic compounds burn with a sooty
In each of the following questions, a statement of­ flame.
statement I is given followed by a corresponding statement
Statement   II: Aromatic compounds contain higher
of ­statement II just below it of the statements; mark the
percentage of hydrogen.
correct answer.
1. If both statement I and statement II are true and 9. Statement I: Benzene is a solvent for Friedel–Crafts
­statement I is the correct explanation of statement II. alkylation of bromobenzene.
2. If both statement I and statement II are true and state- Statement   II: Friedel–Crafts reaction is used to
ment I is not the correct explanation of statement II. ­introduce an alkyl group in benzene.
3. If statement I is true and statement II is false.
4. If statement I is false but statement II is true. 10. Statement I: Benzene does not undergo addition
­reactions.
1. Statement I: Phenol is more reactive than benzene
Statement II: Benzene has lower heat of hydration.
towards electrophilic substitution.
Statement II: In the case of phenol, the intermediate 11. Statement I: Benzene reacts with chlorine in the
carbocation is more resonance stabilized. presence of light to give BHC.
2. Statement I: Friedel–Crafts reaction between ben- Statement II: BHC is called as gammaxene.
zene and acetic anhydride in the presence of ­anhydrous
12. Statement I: C6H6 decolourises Br2 water.
AlCl3 yields acetophenone and not ­polysubstitution
product. Statement   II: All the six carbon atoms have
­delocalized p-electrons.
Statement   II: Acetophenone formed, poisons the
­catalyst preventing further reaction.

3. Statement I: o-phenol sulphonic acid on heating at

100°C changes to p-phenol sulphonic acid. Answers
Statement II: Sulphonation of phenol is a reversible
process. (1) 1 (2) 3 (3) 2 (4) 4 (5) 4
(6) 1 (7) 3 (8) 3 (9) 4 (10) 2
4. Statement I: Nitrobenzene undergoes Friedel–Crafts
(11)  2 (12) 4
reaction.
Statement   II: Friedel–Crafts reaction is an
­electrophilic substitution reaction.

Chapter_20.indd 22 3/26/2014 3:35:22 PM

 21

Chapter
Environmental Chemistry

• The surroundings in which we are living is called • Secondary pollutants are formed by the chemical
environment. reactions from primary pollutants, e.g., the primary
• Environment constitutes air, water, soil, and atmos- pollutants such as hydrocarbons and nitrogen oxides
phere and the plants around us. react in the presence of sunlight to form a secondary
pollutant, peroxyacetyl nitrate.
• Environmental study deals with the sum of all social,
economical, biological, physical and chemical inter- • Basing on ecosystem, pollutants are classified into
relations with our surroundings. biodegradable and non-biodegradable pollutants.
• Environmental chemistry deals with the study of the • Animal and plant debris, domestic sewage, etc. are
origin, transport, reactions, effects and fates of chemi- biodegradable pollutants. Inorganic compounds like
cal species that takes place around us and adversely mercury and lead salts, aluminium cans, some organic
affects the environment. compounds such as DDT, plastic materials, etc. are
non-biodegradable pollutants.
• Environmental pollution is the effect of undesirable
changes in our surroundings that have harmful effects • A substance which is not present in the nature,
on living organisms. but released during human or natural activity into
­environment is called as a contaminant.
• A substance, which causes pollution, is known as a
pollutant. • The medium which is affected by the pollutant is
called a receptor.
• The addition of any foreign material like organic,
­inorganic, biological, radiological, etc. or any change • The medium which reacts with pollutants is called a
in nature which may harm or effect badly the living sink. E.g., Microorganisms are sink to dead plants and
organism directly or indirectly, immediately or slowly animals. Sea water is a sink for carbon dioxide.
is called pollution. • Dissolved oxygen (DO) is the amount of oxygen
• Pollutants can be solid, liquid and gaseous substances present in water.
present in greater concentration than in natural abun- • The optimum value of good quality water is 4–6
dance and are produced due to human activities or due mg/litre. Lower DO values indicate water pollution.
to natural happenings. • Chemical oxygen demand (COD) is the amount of
• Pollutants which degrade slowly accumulate in the oxygen required to oxidize organic substances present
environment, e.g., DDT, plastic materials, heavy
­ in water.
­metals, several chemicals nuclear wastes, etc. • COD is the index of the organic content of water. It can
• Basing on the form, pollutants may be classified into be determined by oxidizing the organic matter with
primary and secondary pollutants. acidified (50% H2SO4) potassium dichromate solution.
• Primary pollutants are directly released into the • Biochemical oxygen demand (BOD) is the amount of
environment from an identifiable source and exist
­ oxygen required by bacteria to break down the ­organic
as such in the environment, e.g., oxides of carbon, matter present in a certain volume of a sample of
­nitrogen and sulphur. water.

Chapter_21.indd 1 3/26/2014 3:32:28 PM

 21.2  Objective Chemistry - Vol. I

• BOD is a parameter for measure of water pollution. • SO2 bleaches the chlorophyll and thus prevents
Clean water would have BOD value of less than photosynthesis.
5 parts per million (ppm), whereas highly polluted • SO2 is oxidized to SO3 slowly but in the presence of
­water would have a BOD value of 17 ppm or more. particulate matter and ozone oxidation takes place
rapidly.
Environmental Segments
(b) Oxides of nitrogen
• Environment consists of four segments: (i) atmosphere, • Oxides of nitrogen (N2O, NO and NO2) are liberated
(ii) hydrosphere, (iii) lithosphere and (iv) biosphere. into air during the combustion of fossil fuels.
• Atmosphere is the layer of air present around the earth. • Upto 10 ppm the oxides of nitrogen have no e­ffect
It maintains the heat balance on the earth by ­absorbing on plants beyond which plants cannot perform
electromagnetic radiations coming from sun and photosynthesis.
­transmitting UV, visible and infrared (IR) radiations.
• The irritant red haze in the traffic and congested places
• Hydrosphere includes all types of water resources
is due to oxides of nitrogen.
like oceans, seas, rivers, lakes, reservoirs, polar ice
caps, ground water, etc. Further, 97% water is present • NO2 damages various textile fibres and metals.
in oceans and seas and about 3% is in the form of polar (c) Hydrocarbons are released into the atmosphere due
ice caps. to incomplete combustion of fuel used in ­automobiles.
• Lithosphere is the land leaving hydrosphere of the Hydrocarbons are carcinogenic.
earth space. It is occupied by plants and animals.
Inner layer contain minerals and the deep inner layers (d) Oxides of Carbon
­contain natural gas and oil. (i) Carbon monoxide is released into the ­atmosphere
• Biosphere includes all living organisms and their due to incomplete combustion of carbonaceous
interactions with the environment viz. atmosphere,
­ fuel, due to degradation of organic substances, the
hydrosphere and lithosphere. methane gas, liberated will be oxidized to CO
2C + O2 
→ 2CO
Atmospheric Pollution
2CH4 + 3O2 
→ 2CO + 4H2O
• The four parts of atmosphere are (a) troposphere,
(b) stratosphere, (c) mesosphere and (d) thermosphere. Carbon monoxide combines with haemoglobin to
form carboxyhaemoglobin due to which the haemo-
• Troposphere extends up to the height of 10 km from
globin loses the oxygen-carrying capacity. Thus, CO
sea level in which the human beings along with other
acts as a poisonous gas.
live organisms.
(ii) Carbon dioxide is released into the atmosphere
• Stratosphere is the region of atmosphere above
due to respiration of animals and plants, fermenta-
­troposphere between 10 and 50 km above sea level.
tion process, burning of fuels and decomposition
• Troposphere is turbulent, dust zone containing air, of lime stone during the manufacture of cement.
much water vapour and clouds. It is the region of
strong air movement and cloud formation. • Atmosphere contains about 0.03% CO2 and its level
is balanced by green plants which utilize CO2 for
• Stratosphere contains dinitrogen, dioxygen, ozone
photosynthesis.
and water vapour.
• Deforestation and increase in population, transpo­
Tropospheric Pollution rtation, industries, etc. disturb the balance of CO2 in
atmosphere.
• Tropospheric pollution occurs due to the presence of
undesirable solid or gaseous particles in the air.
Green House Effect
1. Gaseous Air Pollutants • The phenomenon of heating up of the surface of the
(a) Oxides of sulphur earth is called green house effect.
• Oxides of sulphur are released into atmosphere ­directly • CO2 is the main green house gas.
by burning sulphur or by roasting sulphide ores or by • Other green house gases are chlorofluorocarbons,
burning fossil fuels containing sulphur. ozone, methane, water vapour and nitrous oxide.

Chapter_21.indd 2 3/26/2014 3:32:29 PM

 Environmental Chemistry  21.3

• If the temperature on earth surface increases it results • Lead is the major air pollutant emitted by vehicles
in (a) melting of polar ice caps, (b) decrease in ground which use leaded petrol.
water, (c) unseasonal rains and (d) great effect on • Smog is formed due to mixing of smoke with fog.
­agriculture sector due to fast evaporation of surface
• Classical smog is a mixture of smoke, fog and sulphur
water.
dioxide formed in cool humid climate. It is reducing in
nature and called reducing smog.
Acid Rains • Photochemical smog is formed by the action of sun-
light on unsaturated hydrocarbons and nitrogen oxides
• The oxides of nitrogen and sulphur dissolve in rain
produced by automobiles and factories in warm, dry
water forming nitric acid and sulphuric acid resulting
and sunny climate. It is oxidizing in nature and is
in acid rains.
called oxidizing smog.
4NO2 + 2H2O + O2 
→ 4HNO3 • NO combines with oxygen converting into NO2 which
inturn breaks up into NO and free oxygen atom that
SO2 + 1/2O2 
→ SO3 combines with dioxygen to form ozone.
SO3 + H2O  → H2SO4 2NO + O2 
→ 2NO2
• The pH of the acid rains will be less than 5.6 (4 to 5).
NO2 
→ NO + O
• Due to acid rains (i) life of buildings will be consi­
derably reduced, (ii) the glassy nature of Taj Mahal is O2 + O  → O3
affected due to reaction between acid rain and ­marble • The NO2 and O3 oxidizes unburnt hydrocarbons in the
(CaCO3), (iii) Due to acid rains the pH of the soil pollutant air converting them into toxic substances such
changes affecting the fertility and (iv) Aquatic animals as formaldehyde (HCHO), acrolein (CH2=CHCHO)
and plants die in acid water. and peroxyacetyl nitrate (PAN).
• Photochemical smog causes irritation of eyes, throat,
2. Particulate Pollutants nose and cause headache, chest pain, dryness of throat,
cough, etc.
• Particulate pollutants are the minute solid particles or
liquid droplets in air. • Photochemical smog causes damage of plant life,
­corrosion of metals, stones, building materials, rubber
• The particulates in the atmosphere may be viable or
and painted surfaces.
nonviable.
• Formation of photochemical smog can be prevented in
• The viable particulates such as bacteria, fungi, moulds
controlling the release of primary pollutants such as
algae, etc are minute living organisms. These are
NO2, hydrocarbons and thus preventing the formation
­allergic to human being and can cause plant diseases.
of ozone and PAN.
• The non-viable particulates are smoke, dust, mist and
• Using catalytic converters in automobiles prevents the
fumes.
release of nitrogen oxide and hydrocarbons into the
• Smoke particulates consist of solid or liquid droplets atmosphere.
formed during the combustion of organic matter. E.g.,
cigarette smoke, smoke from industries, burning of
garbage, fossil fuels, etc. Stratospheric Pollution
• Dust is composed of fine solid particles (over 1 mm • The upper stratosphere consists of mainly ozone
in diameter) produced during crushing, grinding, which protects the living organisms from the harmful
sand blasting, saw dust from wood works, coal dust, UV radiations coming from the sun.
­cement, fly ash, etc.
• Ozone is formed by the absorption of UV light by
• Mists contain liquid droplets produced from spray oxygen
liquids, condensation of vapours in air, e.g., sulphuric
acid mist, herbicides, insecticides, etc. O2(g) UV
light
→ O(g) + O(g)
• Fumes are obtained during sublimation, distillation, O(g) + O2(g) UV
→ O3(g)
boiling and several other chemical reactions generally • A dynamic equilibrium exists between the production
consist of organic solvents, metals and metal oxides. and decomposition of ozone.

Chapter_21.indd 3 3/26/2014 3:32:30 PM

 21.4  Objective Chemistry - Vol. I

• The release of chlorofluorocarbons known as freons • Sewage from domestic, commercial, food processing
into atmosphere causes the depletion of ozone layer. and industrial effluents consumes dissolved oxygen in
• The reactions that take place during the depletion of water for their degradation.
ozone layer by freons are i • Organic pollutants include plastics, fibres, detergents,
i
CF2Cl2(g)  → C l(g) + CF2Cl(g) paints, pesticides, fungicides, weedicides, insecticides,
i i
dyes and pharmaceuticals.
C l(g) + O3(g)  → ClO(g) – O2(g)
i i
ClO(g) + O(g)  → Cl(g) + O2(g) • The pesticides and insecticides like malathion,
DDT, carboryl, chlorophenoxy group compounds,
• These reactions take place continuously and ­repeatedly compounds of dithiocarbamate, phenyl mercury
­
damaging the ozone layer. ­acetate, etc. are water pollutants.
• In winter season the polar stratospheric clouds
• Bioamplification is a process of increasing the
­provide surface on which chlorine nitrate formed gets
­concentration of pollutants like pesticides in higher
­hydrolyzed forming hypochlorous acid. The chlorine
animals and human beings through lower animals.
nitrate also reacts with hydrogen chloride produced
during the following sequence of reactions. • The carriers like plants, fish, animals and birds through
i
which bioamplification takes place are called food
ClO(g) + NO2(g) 
→ ClONO2(g)
i i chains.
C l(g) + CH4(g)  → CH3(g) + HCl • Eutrophication is the overnutrition of ponds and
ClONO2(g) + H2O(g)  → HOCl(g) + HNO3(g) lakes by the organic substances coming from agricul-
ClONO2(g) + HCl(g)  → Cl2(g) + HNO3(g) tural waste and industrial waste.
• In the spring (summer) season the HOCl and Cl2 • Due to eutrophication the unwanted algae and other
breaks up due to photochemical reaction which initiate plants grow much and the ponds and lakes are filled
chain reaction for ozone depletion. with sediment and become dry.
i i
HOCl(g) 
→ OH(g) + Cl(g) • If the fluoride content in drinking water is greater
i than 3 ppm it is harmful and cause a disease known as
Cl2(g) 
→ 2Cl(g) fluorosis.
• If ozone layer depletes the UV light from sun d­ irectly • The fluoride reacts with calcium present in teeth and
fall on the earth, causing skin cancer, cataract of the bones to form calcium fluoride due to which the teeth
eyes. Also, efficiency of photosynthesis in plants becomes yellow and the bones become weak.
decreases. The UV light also cause the mutation
­
Ca + F2 
→ CaF2
of cells, evaporation of surface water, decrease the
­moisture content of the soil, damage paints and fibres. • If the fluoride content is up to 1 ppm or 1 mg dm–3,
the hydroxy apatite [3Ca3(PO4)2 . Ca(OH)2], i.e., the
Water Pollution enamel on the surface of the teeth converts into much
harder fluorapatite [3Ca3(PO4)2 . CaF2].
• The phenomenon by which the quality of water in the • Excessive sulphate (>500 ppm) in drinking water
hydrosphere decreases is called water pollution. causes laxative effect.
• Easily identifiable source or place of water pollution
• Excessive nitrate (>50 ppm) causes disease such as
is called as point source, e.g., municipal and industrial
methemoglobinamia (blue baby syndrome).
discharge.
• If the source of water pollution cannot be easily iden-
tifiable it is called a non-point source, e.g., agricultural Soil Pollution
runoff, acid rain, storm-water drainage, etc. • Insecticides, pesticides and herbicides cause soil
• Pathogens are living organisms, such as bacteria that pollution.
enters into water from domestic sewage and animal • Pesticides are synthetic toxic chemicals with ecologi-
excreta, and are the disease-causing agents. cal repercussions.
• Human excreta contain bacteria such as Escherichia • Repeated use of same or similar pesticides increases
coli and Streptococcus faecalis which cause gastroin- the resistance in pests. So, more powerful pesticides
testinal diseases. should be used. E.g., due to the repeated use of DDT

Chapter_21.indd 4 3/26/2014 3:32:33 PM

 Environmental Chemistry  21.5

resistance towards DDT increases in insects. So, pow- • The use of tetrachloroethene (Cl2C = CCl2) in dry
erful organic toxins such as aldrin and dieldrin were cleaning contaminates the ground water and it is a
introduced. ­suspected carcinogen.
• Organophosphates and carbamates are biodegradable • Replacement of halogenated solvent by liquid CO2
toxins. These are severe nerve toxins and are more will result in less harm to ground water.
harmful to humans. • Use of H2O2 as a bleaching agent in laundry ­purpose
• Sodium chlorate, sodium arsenite and many such and in bleaching of paper pulp in the place of
­compounds are herbicides. ­chlorinated substances decreases the pollution.
• Most herbicides are toxic to mammals and decompose
in a few months.
• Herbicides also become concentrated in the food web,
 Objective Questions
i.e., bioamplification through food chain.
1. Which is incorrect regarding pollution?
Industrial Waste (a) The presence of anything in the environment in
excess of the required.
• Industrial wastes are also biodegradable and (b) Anything put into environment which was not
nonbiodegradables. there in its natural state.
• Biodegradable industrial waste is generated by cotton (c) Direct or indirect changes in one or more compo-
mills, food processing units, paper mills and sugar nents of the ecosystem which are not harmful to
industry. living organisms.
(d) International release of any chemical substance
• Non-biodegradable wastes are generated by thermal
into the environment with harmful effects.
power plants which produce fly ash, slag from steel in-
dustry, mud and tailings from metallurgical industries. 2. CO in air is called as
(a) contaminant
(b) pollutant
Strategies to control
(c) contaminant and pollutant
Environmental pollution (d) none
• Domestic wastes should be collected and separated 3. Which of the following is a wrong statement?
into biodegradable and non-biodegradable materials.
(a) The value of dissolved oxygen in polluted water
• Non-biodegradable materials should be sent to is < 4 ppm.
recycling. (b) COD gives the measure of organic pollution of
• Fuel obtained from plastic waste has high octane rat- water.
ing. It does not contain lead and is known as green (c) COD value determination is based on chemical
fuel. oxidation of organic substances.
• Recycled plastic can be used in chemical and textile (d) If BOD of a river is high, it means the river is not
industries. polluted.
• Biogas mainly contains methane and can be obtained 4. Identify the false statement.
by culturing the garbage with bacterial species after
(a) Sink is a medium which removes the pollutant
removing ferrous metals, plastic, glass, paper, etc.
from the environment.
(b)  The medium which interacts with long-lived
Green Chemistry ­pollutant is receptor.
(c) The sink for dead plants and animals is microor-
• Green chemistry is the way of reducing the ­adverse ganisms.
effect on environment by utilizing the existing
(d) Sea water is a sink for CO2.
­knowledge and principles of chemistry.
• A process in the production of certain chemical 5. BOD values of four samples A, B, C and D of water
should be selected such that all the reactions should are 60, 80, 100 and 150 mg/litre, respectively. Which
be ­completely converted into environmental friendly is more polluted?
products by using environmental friendly medium. (a) A (b) B (c) C (d) D

Chapter_21.indd 5 3/26/2014 3:32:33 PM

 21.6  Objective Chemistry - Vol. I

6. Biosphere interacts with (c) SO2 pollution causes decrease in photo­ -

(a) Hydrosphere (b)  Lithosphere synthesis rate.
(c) Atmosphere (d)  All the above (d) The holes in ozone layer are formed by hydro­
carbons.
7. The correct statement among the following is
(a) Carbon monoxide in air is a pollutant. 15. The green house effect is
(b)  Methyl isocyanate in air is known as a (a) rise in pressure on earth
contaminant. (b) decrease in oxygen content on the earth’s atmos-
(c) The important sinks of most atmosphere gases phere
are both oceans and vegetation. (c) rise in temperature of earth
(d) All the above are correct. (d) decrease in CO2 content of earth atmosphere
8. Biodegradable materials are 16. Acid rain
(a) those which spoil the biological environment (a) causes loss of flora and fauna
(b) are toxic (b) retards the growth of trees
(c) those which can be broken down by bacteria. (c) effects big marble constructions
(d) used for converting waste to greenery. (d) all the above

9. The wrong statement among the following is 17. The correct statement among the following is
(a) Lithosphere does not include seas and oceans. (a) Ozone layer is harmful when present in tropo-
(b) Biosphere includes water sources. sphere and protects life when present in strato-
(c) Hydrosphere is mainly related to water. sphere.
(d) The medium which is affected by a pollutant is (b)  The industrial usage of fluorocarbons is very
called environment. high because they can be manufactured cheaply.
(c) Acid rains contain the oxoacids of sulphur and
10. The amount of oxygen utilized by the microorgan- nitrogen.
isms present in water to break down the organic (d) All are correct.
­matter is called
18. Lung diseases are four times more in urban areas than
(a) DO (b)  BOD (c) COD (d)  TLV
in rural areas. This is due to the presence of
11. The permissible level of a pollutant by a healthy (a) SO2 (b) CO2 (c) N2 (d)  Water vapour
­person exposed for eight hours is called
19. The false statement among the following is
(a) pollutant limit value
(b) toxic limit value (a) The loss or reduction of chlorophyll in the leaves
(c) threshold limit value is termed as chlorosis.
(d) contaminant limit value (b) The loss or reduction of chlorophyll in the leaves
is due to bleaching by SO2
12. The false statement among the following is (c) Growing more trees helps to increase CO2 in
(a) The heat balance on the earth surface is main- ­environment.
tained by hydrosphere. (d) SO2 is a dangerous air pollutant and harms plant
(b)  The major components in atmosphere are life by bleaching leaves.
N2 and O2. 20. The correct statement among the following is
(c) Solid crust of the earth is lithosphere.
(a)  Metal liberated into the environment through
(d) BOD test is a valuable test in the analysis of
­exhaust fumes of motor vehicles is lead.
­sewage.
(b) The main air pollutant is CO.
13. The green house gas is (c)  The gas that causes yellowing of Taj Mahal
(a) CO2 (b) Chlorofluorocarbons is SO2.
(c) O3 (d) All (d) All are correct.
14. The wrong statement among the following is 21. Which of the following is false statement about green
(a) Ozone layer protects the life on earth from UV house effect?
radiations. (a)  It is due to high concentration of CO2 in
(b) CO combines with haemoglobin forming carbox- ­atmosphere.
yhaemoglobin and interferes with functioning of (b) It is influenced by gases such as CH4, O3 and
haemoglobin leading to death. chloroflouro carbons.

Chapter_21.indd 6 3/26/2014 3:32:34 PM

 Environmental Chemistry  21.7

(c) It results in the warming up of the earth. 29. From marshy places methane gas is liberated due to
(d) It would result in lowering the level of oceans due (a) degradation of biomass
to high evaporation. (b) oxidation of biomass
(c) burning of biomass
22. Photochemical oxidants such as PAN and PBN are
(d) reduction of biomass
formed
(a) by the action of nitrogen oxides on hydrocarbons 30. Which of the following is a correct statement?
in the presence of sunlight (a) The permissible limit of fluoride ion in drinking
(b) by the action of carbon dioxide on hydrocarbons water is 1 to 2 ppm.
in the presence of sunlight (b) the disease caused by excess fluoride in water is
(c) by the action of hydrogen sulphide on hydrocar- skeletal fluorosis.
bons in the presence of sunlight (c) The disease caused by fluoride less than 1 ppm is
(d) none of the above dental caries.
(d) All the above.
23. CO seems to be removed from the atmosphere
mostly by 31. Identify the false statement.
(a) dissolving in the oceans (a) Eutrophication is due to over nutrition.
(b) reacting with O2 to from CO2 (b) Eutrophication is due to sediment formation by
(c) thermal decomposition to carbon and oxygen soil erosion.
(d) consumption by soil microorganisms (c) Eutrophication is caused by phosphate pollution
in water is due to detergents.
24. The correct statement among the following is (d) All are correct.
(a) vegetables grown by the roadside have higher 32. Generally water-borne diseases are caused by­
content of lead. polluted water due to
(b) diesel vehicles pollute the environment largely
(a) detergents
through CO, NO2 and particulates.
(b) sediments
(c) the pH of the acid rain is approximately 5.5.
(c) human and animal excreta
(d) All are correct.
(d) organic pollutants
25. Which one of the following statements is false? 33. Pesticides reach the bodies of aquatic organisms
(a) O3 layer is destroyed by fluorocarbons through
(b) O3 involved in photochemical smog (a) Eutrophication (b) Oxidation
(c) A product of photochemical smog is PAN (c) Adsorption (d) Bioamplification
(d) Temperature inversion is caused by smog
34. The excessive use of phosphates as water softeners
26. Fluorocarbons are effective scavengers for ozone leads to aquatic pollution called
due to (a) denitrification (b)  phosphorylation
(a) photolytic reaction of O2 producing Cl radicals (c) deoxygenation (d)  eutrophication
(b) photolytic decomposition of O3 producing O2
(c) photolytic decomposition of O3 by Cl into O2 35. Which of the following statements is wrong?
(d) photolytic production of oxides of nitrogen (a) Biodegradable materials can be broken for con-
verting waste to greenery.
27. Compound formed in the depletion of O3 layer by (b) DDT is a non-degradable pollutant.
chlorofluorocarbons is (c) Domestic wastes are biodegradable pollutants.
(a) O2F2 (b) OCl (c) 
OF2 (d) OCl2 (d)  Oxygen demanding wastes are not water
­pollutants.
28. Smog is a mixture of smoke and fog. Smog is mainly
caused by pollutants from automobiles and industries 36. In the minimization of pollution which is not the
when they ­correct statement?
(a) hit a dense shower of snow flakes (a)  Manures and biofertilizers should be used in
(b) heat with oxygen in the air place of chemical fertilizers.
(c)  react photochemically in the presence of UV (b) Clean and green technology must be developed.
light (c) Population growth must be controlled.
(d) form a smoke smog (d) Domestic garbage must be burnt.

Chapter_21.indd 7 3/26/2014 3:32:34 PM

 21.8  Objective Chemistry - Vol. I

37. Untreated domestic sewage has a low 45. Due to the unwanted growth of algae and other plants
(a) BOD value the ponds and lakes are filled with sediments and
(b) % dissolved oxygen ­become dry. This is known as
(c) Amounts of dissolved salts (a) bioamplification (b)  eutrophication
(d) % of suspended organic matter (c) phosphorylation (d)  soil erosion
38. In the polluted environment “receptor” is the 46. The domestic waste is decomposed in the presence of
(a) damaged part of the human system (a) aerobic bacteria
(b) damaged part of the animals (b) enzymes
(c) affected system by contaminants (c)  Bacillus acidilatic
(d) adversely affected medium by the pollutants (d) H2SO4
39. Contaminant is 47. Which of the following statement is correct?
(a) a pollutant (a) The region which is greatly affected by air pollu-
(b) a component originally not present in environ- tion is troposphere.
ment but released into environment by human (b) The region which contains water vapour is tropo-
activity sphere.
(c) pollutant released into the environment in natural (c) Ozone layer is present in stratosphere.
calamities (d) All the above.
(d) pollutant released from industries
48. Photochemical smog is formed in
40. The reagents used in the determination of COD of
water samples is (a) summer during morning time
(b) summer during day time
(a) KNO3 (b) KMnO4
(c) winter during morning time
(c) Oxalic acid (d) K2Cr2O7 + 50% H2SO4
(d) winter during day time
41. Threshold limit value is the maximum limit value of
49. Ozone hole refers to
(a) pollutants in the atmosphere
(b) toxic substances that do not cause damage to the (a) hole in ozone layer
industrial workers (b)  reduction in the thickness of ozone layer in
(c) pollutants that should be present in mines ­troposphere
(d) the chemical absorbed by a person in a polluted (c)  reduction in the thickness of ozone layer in
area strato­sphere
(d) increase in concentration of ozone
42. There is a possibility of melting of polar ice caps and
increase in the level of sea water due to 50. Addition of phosphate fertilizers into water leads to
(a) depletion of ozone layer (a) increased growth of decomposers
(b) green house effect (b) reduced algal growth
(c) acid rain (c) increased algal growth
(d) any one of these (d) nutrient enrichment (eutrophication)

43. Bioamplification means 51. Modes of controlling pollution in large cities include
(a) increase in pollutants in water (a) less use of insecticides
(b) gradual accumulation of pesticides from lower (b) proper disposal of organic wastes, sewage and
animals to higher animals industrial effluents
(c)  gradual decrease in the concentration of (c) shifting of factories out of the residential area
­pesticides in water (d) all the above
(d) increase in pollutants in air
52. Which of the following statement is false?
44. The microorganisms and enzymes that can degrade (a) The lower the concentration of DO the more pol-
many pollutants are called luted is the water sample.
(a) bioremedies (b)  bioamplifiers (b) The tolerable limit of lead in drinking water is
(c) biochemicals (d)  sinks 50 ppm.

Chapter_21.indd 8 3/26/2014 3:32:34 PM

 Environmental Chemistry  21.9

(c) Water is considered pure if it has BOD less than 58. Classical smog occurs in places of
5 ppm. (a) excess of SO2
(d) In COD determination, the pollutant resistant to (b) low temperature
microbial oxidation are not oxidized by oxidizing (c) high temperature
agents like K2Cr2O7. (d) excess NH3
53. Positive soil pollution is 59. Aquatic animals die in water polluted by sewage
(a) Reduction in soil productivity due to erosion and due to
over use. (a) pathogens
(b) Reduction in soil productivity due to addition of (b) clogging of gills by slit
pesticides and industrial wastes. (c) reduction in oxygen
(c) Converting fertile land into barren land by dump- (d) foul smell
ing ash, sludge and garbage.
60. Eutrophication causes reduction in
(d) None of these.
(a) dissolved hydrogen (b) dissolved oxygen
54. Which of the following statements about sewage (c) dissolved salts (d) all the above
treatment is false?
61. Increasing skin cancer and high mutation rate are
(a) In primary treatment, large-sized particles are
due to
filtered through screens and residual water is
­
­subjected to sedimentation. (a) Acid rain (b) Ozone depletion
(b) Secondary treatment involves aerobic digestion (c) CO pollution (d) CO2 pollution
of the organic waste. 62. Ozone layer of stratosphere requires protection from
(c) In tertiary treatment, the waste water is treated indiscriminate use of
with lime to remove phosphate followed by (a) Fungicides, insecticides, bactericide and mediums
­coagulation. (b)  Aerosols, high flying jets and chlorofluoro-
(d) Coagulation can be carried out by passing ozone carbons
through waste water. (c) Atomic explosions and industrial wastes
55. By green chemistry we mean (d) Balloons and turbo-prop aeroplanes
(a) Producing chemicals of our daily use from green 63. Which of the following is a viable particulate?
house gases. (a) algae (b)  smoke
(b) Performing chemical processes which use green (c) mist (d)  fumes
plants.
64. Non-viable particulate is
(c)  Performing only those reactions which are of
­biological origin. (a) Bacteria (b)  Mould
(d) The use of non-toxic reagents and solvents to (c) Fungi (d)  Dust
produce environmental friendly products. 65. Which of the following statement is false?
56. When rain is accompanied by thunderstorm the (a) Limestone acts as a sink for SO2.
­collected rain water will have pH value (b) SO2 can be removed from flue gases by passing
through a solution of citrate ions.
(a) Slightly higher than that when the thunderstorm
(c) Ammonia acts as a sink for SO2.
is not there.
(d) The average residence time of NO is one month.
(b) Uninfluenced by occurrence of thunderstorm.
(c) Which depends upon the amount of dust in air. 66. The brown hazy fumes of photochemical smog are
(d) Slightly lower than that of rain water without due to
thunderstorm. (a) Nitrogen dioxide (b)  PAN formation
(c) Aldehydes (d)  SO2
57. Air pollutants that produce photochemical oxidants
include 67. Which of the following is not a soil pollutant?
(a) CO2, CO and SO2 (a) polythene bags
(b) Oxygen, chlorine and nitric acid (b) pesticides
(c) Nitrous oxide, nitric oxide and nitric acid (c) detergents
(d) Ozone, chlorine and sulphur dioxide (d) nitrate and phosphate fertilizers

Chapter_21.indd 9 3/26/2014 3:32:34 PM

 21.10  Objective Chemistry - Vol. I

68. Which of the following is not a herbicide? (c) radical trops

(a) Sodium chlorate (b) Sodium arsenite (d) peroxyacetyl nitrate
(c) Polyphosphate (d) Triazines 76. Green chemistry means such reactions which
69. Proper management of disposal of household and (a) are related to the depletion of ozone layer
industrial wastes can be done by (b) produce colour during reactions
(a)  Recycling the waste material to give useful (c) study the reactions in plants
products again (d)  reduce the use and production of hazardous
(b) Burning and incineration of combustible waste chemicals
(c) Sewage treatment 77. Which of the following is a secondary pollutant?
(d) All the above
(a) CO2 (b) N2O
70. Which of the following is not an example of green (c) PAN (d)  SO2
chemistry?
78. The secondary precursors of photochemical smog are
(a) catalytic dehydrogenation of the diethanol amine
without using cyanide and formaldehyde. (a) SO2 and NO2
(b) Replacement of CFCs by CO2 as a blowing agent (b) SO2 and hydrocarbons
in the manufacture of polystyrene foam sheets. (c) NO2 and hydrocarbons
(c) Reacting methyl amine and phosgene to produce (d) O3 and PAN
methyl isocyanate. 79. Particulates are added to the atmosphere by
(d)  Replacement of organotins by sea-nine as (a) industrial process
­antifouling capound sea marines. (b) combustion of fuels
71. Which one is not a correct statement regarding the (c) agricultural burning
minimization of pollution? (d) all of these
(a)  manures and biofertilizers should be used in 80. Which of the following statement is correct?
place of chemical fertilizers. (a) Classical smog is reducing in nature.
(b) all nuclear tests must be stopped. (b) Photochemical smog is oxidizing in nature.
(c) green belts in cities should be developed. (c) Classical smog is formed in cool, humid climate
(d) domestic garbage must be burnt. while photochemical smog is formed in dry,
72. Pollution can be controlled by warm climates.
(a) sewage treatment (d) All are correct.
(b) manufacturing electrically operated vehicles
(c) adopting green chemistry
Answers
(d) all of the above
73. If there was no carbon dioxide on earth’s surface, the  (1) 3  (2) 2  (3) 4  (4) 2  (5) 4
temperature of earth’s surface would be  (6) 4  (7) 4  (8) 3  (9) 4 (10) 2
(a) same as present (11) 3 (12) 1 (13) 4 (14) 4 (15) 3
(b) less than the present (16) 4 (17) 4 (18) 1 (19) 3 (20) 4
(c) more than the present (21) 4 (22) 1 (23) 2 (24) 4 (25) 4
(d)  dependent on the amount of oxygen in the (26) 3 (27) 2 (28) 3 (29) 1 (30) 4
atmosphere (31) 4 (32) 3 (33) 4 (34) 4 (35) 4
74. Pollutant is a chemical substance or factor which (36) 4 (37) 2 (38) 4 (39) 2 (40) 4
­disturbs (41) 2 (42) 2 (43) 2 (44) 1 (45) 2
(46) 1 (47) 4 (48) 2 (49) 3 (50) 4
(a) our balanced environment
(51) 4 (52) 4 (53) 1 (54) 4 (55) 4
(b) geochemical cycles
(56) 4 (57) 3 (58) 2 (59) 3 (60) 3
(c) flora of any region
(61) 2 (62) 2 (63) 1 (64) 4 (65) 4
(d) fauna of any region
(66) 1 (67) 3 (68) 3 (69) 4 (70) 3
75. Photochemical smog can be suppressed by (71) 4 (72) 4 (73) 2 (74) 1 (75) 3
(a) nitrogen oxides (76) 4 (77) 3 (78) 4 (79) 4 (80) 4
(b) formaldehyde

Chapter_21.indd 10 3/26/2014 3:32:34 PM