Our victory is not in the last step actually it starts from our first step

11th std Chemistry Bestie

With additional question & answers

Name :
Std & Sec :
School :

Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D.

PG Assistant in chemistry
Government Higher Secondary School - Vallipattu
 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933

INDEX

Page
S. No LESSON
No

1 Basic Concepts of Chemistry and Chemical Calculation 1

2 Quantum Mechanical Model of Atom 10

3 Periodic Classification of Elements 17

4 Hydrogen 24

5 Alkali and Alkaline Earth Metals 31

6 Gaseous State 36

7 Thermodynamics 45

8 Physical and Chemical Equilibrium 52

9 Solutions 59

10 Chemical Bonding 65

11 Fundamentals of Organic Chemistry 76

12 Basic Concepts of Organic Reactions 91

13 Hydrocarbons 100

14 Haloalkanes and Haloarenes 111

15 Environmental Chemistry 123

தெய்வத்ொன் ஆகா தெனினும் முயற்சிென்

தெய்வருத்ெக் கூலி ெரும் - ெிருக்குறள்

Even if God has given up, perseverance will pay

the wages for one’s efforts.

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Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933

1. BASIC CONCEPTS OF CHEMISTRY AND CHEMICAL CALCULATION

1 Define relative atomic mass.
Average mass of the atom
Relative atomic mass =
Unified atomic mass
2 What do you understand by the term mole. (Jun-19, Jun-23)
One mole is the amount of substance of a system, which contains as many elementary
particles as there are atoms in 12 g of carbon-12 isotope. The elementary particles can be
molecules, atoms, ions, electrons or any other specified particles.
3 Define equivalent mass. (May-22, Mar-24)
Gram equivalent mass is defined as the mass of an element (compound or ion) that
combines or displaces 1.008 g hydrogen or 8 g oxygen or 35.5 g chlorine.
4 What do you understand by the term oxidation number.
It is defined as the imaginary charge left on the atom when all other atoms of the
compound have been removed in their usual oxidation states
5 Distinguish between Oxidation and Reduction. (Mar-23)
Oxidation Reduction
1 Addition of oxygen Addition of hydrogen
2 Removal of hydrogen Removal of oxygen
3 Reaction in which oxidation number of the Reaction in which oxidation number of the
element increases element decreases
4 Loss of electron Gain of electron
6 Calculate the molar mass of the following compounds.
i) Urea [CO(NH2)2] ii) Acetone [CH3COCH3]
N = 2 X 14 = 28 C = 3 X 12 = 36
H=4X1 = 4 H=6X1 = 6
C = 1 X 12 = 12 O = 1 X 16 = 16
O = 1 X 16 = 16 58
60 molar mass = 60 g mol-1. molar mass = 58 g mol-1.
iii) Boric acid [H3BO3] iv) Sulphuric acid [H2SO4]
B = 1 X 11 = 11 S = 1 X 32 = 32
H=3X1 = 3 H=2X1 = 2
O = 3 X 16 = 48 O = 4 X 16 = 64
62 98
molar mass = 62 g mol-1. molar mass = 98 g mol-1.
7 The density of carbon dioxide is equal to 1.965 kgm-3 at 273 K and 1 atm pressure.
Calculate the molar mass of CO2.
At 273 K and 1 atm pressure, 1 mole of CO2 occupies a volume of 22.4L
1.965Kg 1.965 X 103 g X 22.4 X 10−3 m3
Mass of 1 mole of CO2 = x 22.4 L = = 44.01 g mol-1.
1m3 1m3
Molar mass of CO2 = 44.01 g mol-1.
8 Which contains the greatest number of moles of oxygen atoms
i) 1 mol of ethanol ii) 1 mol of formic acid iii) 1 mol of H2O
Compound Given number of atoms Number of oxygen atoms
Ethanol – C2H5OH 1 1 X 6.022 X 1023
Formic acid - HCOOH 1 1 X 6.022 X 1023
Water – H2O 1 1 X 6.022 X 1023

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
9 Calculate the average atomic mass of naturally occurring magnesium using the
following data
Isotope Isotopic atomic mass Abundance (%)
Mg24 23.99 78.99

Mg25 24.99 10.00

Mg26 25.98 11.01

((78.99 X 23.99)+(10 X 24.99)+(11.01 X 25.98)) 2430.9
Average atomic mass = = = 24.31u
100 100
10 In a reaction x + y + z2 → xyz2 identify the Limiting reagent if any, in the following reaction
mixtures. a) 200 atoms of x + 200 atoms of y + 50 molecules of z2 b) 1 mol of x
+ 1 mol of y+3 mol of z2 c) 50 atoms of x + 25 atoms of y+50 molecules of z2
d) 2.5 mol of x +5 mol of y+5 mol of z2
Number of moles of reactants Number of moles of reactance
Limiting
allowed to react consumed during reaction
reagent
x y Z2 x y Z2
200 200 50
a) 50 molecules 50 atoms 50 molecules Z2
atoms atoms atoms
b) 1 mole 1 mole 3 mole 1 mole 1 mole 1 mole x and y
50 25 25
c) 25 atoms 50 molecules 25 molecules y
atoms atoms atoms
2.5
d) 2.5 mole 5 mole 5 mole 2.5 mole 2.5 mole x
mole
11 Mass of one atom of an element is 6.645 x 10-23 g. How many moles of element are
there in 0.320 kg.
Mass of one atom = 6.645 x 10-23 g
Mass of one mole of atom = 6.645 x 10-23 g X 6.022 X 1023 = 40 g
1 mole 1 mole
Number of moles of element in 0.320 kg = x 0.320 kg = x 320 g = 8 mole.
40 g 40 g
12 What is the difference between molecular mass and molar mass? Calculate the
molecular mass and molar mass for carbon monoxide.
Molecular mass Molar mass
It is the ratio of the mass of a molecule to The mass of one mole of a substance
1
the unified atomic mass unit.
The relative molecular mass of any The molar mass of a compound is equal to
compound can be calculated by adding the sum of the relative atomic masses of its
2
the relative atomic masses of its constituents
constituent atoms.
3 It is expressed in amu (or) u. It is expressed in g mol-1.
4 Molecular mass of CO = 12+16 = 28u. Molar mass of CO = 12+16 = 28 g mol-1.
13 What is the empirical formula of the
following? (Sep-21) Molecular Empirical
Compound
i) Fructose (C6H12O6) found in honey formula formula
ii) Caffeine (C8H10N4O2) a substance fructose C6H12O6 CH2O
found in tea and coffee. Caffein C 8H10N4O2 C4H5N2O

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
14 The reaction between aluminium and ferric oxide can generate temperatures up to 3273
K and is used in welding metals. (Atomic mass of Al = 27 u atomic mass of O = 16 u)
2Al + Fe2O3 → Al2O3 +2Fe; If, in this process, 324 g of aluminium is allowed to react with
1.12 kg of ferric oxide.
i) Calculate the mass of Al2O3 formed.
ii) How much of the excess reagent is left at the end of the reaction?
Reagents Products
Al Fe2O3 Al2O3 Fe
amount of reactant allowed to react 324 g 1.12 kg - -
1.12X103
324
number of moles allowed to react = 12mol 160 - -
27
= 7mol
stock your metric coefficient 2 1 1 2
number of moles consumed during reaction 12 mol 6 mol - -
number of moles of reactant unreacted and 12
- 1 mol 6 mol
number of moles of product formed mol
Molar mass of Al2O3 formed Al2O3 = (2 x 27) + (3 x 16) = 54 + 48 = 102
= 6 mol X 102 g mol-1
= 612 g
Excess reagent left at the end of the reaction = Fe2O3
The excess amount of reagent left at the end of the reaction
= 1 mol x 160 g mol-1 = 160 g [Fe2O3 = (2x56) + (3x16) = 112 + 48 = 160]
15 How many moles of ethane is required to produce 44 g of CO2 (g) after combustion.
7
C2H6 + 2 O2 2CO2 + 3H2O

To produce 2 moles of CO2, 1 mole of ethane is required

 To produce 1 mole (44g) of CO2, required number of moles of ethane
1 mole ethane x 1 mole CO2
=
2 mole CO2
1
= mole of ethane
2
= 0.5 mole of ethane
16 Hydrogen peroxide is an oxidising agent. It oxidises ferrous ion to ferric ion and
reduced itself to water. Write a balanced equation.
-1 -2
H2O2 + Fe+2 Fe+3 + H2O

(1e- x 2) 1e-
H2O2 + 2Fe+2 Fe+3 + 2H2O
H2O2 + 2Fe+2 + 2H+ Fe+3 + 2H2O

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
17 Calculate the empirical and molecular formula of a compound containing 76.6%
carbon, 6.38 % hydrogen and rest oxygen. (Jul-22) Its vapour density is 47. (Sep-20)
Relative number whole
Element Percentage Atomic mass simple ratio
of moles number

76.6 6.38
C 76.6 12 = 6.38 =6 6
12 1.06

6.38 6.38
H 6.38 1 = 6.38 =6 6
1 1.06

17.02 1.06
O 17.02 16 = 1.06 =1 1
16 1.06

Emperical formula = C6H6O (Mar-19)

Molar mass
n=
Calculated empirical formula mass
2 X vapour density 2 X 47
= = = 1.
94 94
Molecular formula (C6H6O) x 1 = C6H6O
18 A Compound on analysis gave Na = 14.31% S = 9.97% H= 6.22% and O= 69.5%
calculate the molecular formula of the compound, if all the hydrogen in the compound
is present in combination with oxygen as water of crystallization. (molecular mass of
the compound is 322). (Mar-23)

Relative
whole
Element Percentage Atomic mass number of simple ratio
number
moles
14.31 0.62
Na 14.31 23 = 0.62 =2 2
23 0.31
9.97 0.31
S 9.97 32 = 0.31 =1 1
32 0.31
6.22 6.22
H 6.22 1 = 6.22 = 20 20
1 0.31
69.5 4.34
O 69.5 16 = 4.34 = 14 14
16 0.31

Emperical formula = Na2SH20O14

Molar mass
n=
Calculated empirical formula mass
322
= = 1. Na2SH20O14 = (2x23) + (1x32) + (20x1) + (14x16)
322 = 46 + 32 + 20 + 224 = 322
Molecular formula= Na2SH20O14
All the hydrogen in the compound present as water, molecular formula is = Na2SO4 . 10H2O.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
19 Balance the following equations by oxidation number method
i) K2Cr2O7 + KI + H2SO4 K2SO4 + Cr2(S04)3 + I2 + H2O
+6 -1 +3 0
K2Cr2O7 + KI + H2SO4 K2SO4 + Cr2(S04)3 + I2 + H2O

2 x 3e- 1e-
K2Cr2O7 + 6KI + H2SO4 K2SO4 + Cr2(S04)3 + I2 + H2O
K2Cr2O7 + 6KI + H2SO4 K2SO4 + Cr2(S04)3 + 3I2 + H2O
K2Cr2O7 + 6KI + 7H2SO4 4K2SO4 + Cr2(S04)3 + 3I2 + 7H2O
ii) KMnO4 + Na2SO3 MnO2 + Na2SO4 + KOH (Mar-23)
+7 +4 +4 +6
KMnO4 + Na2SO3 MnO2 + Na2SO4 + KOH

3e- 2e-
2KMnO4 + 3Na2SO3 MnO2 + Na2SO4 + KOH
2KMnO4 + 3Na2SO3 2MnO2 + 3Na2SO4 + KOH
2KMnO4 + 3Na2SO3 + H2O 2MnO2 + 3Na2SO4 + 2KOH
iii) Cu + HNO3 Cu(NO3)2 + NO2 + H2O (Mar-23)
0 +5 +2 +4
Cu + HNO3 Cu(NO3)2 + NO2 + H2O

2e- 1e-
Cu + 2HNO3 Cu(NO3)2 + NO2 + H2O
Cu + 4HNO3 Cu(NO3)2 + 2NO2 + 2H2O
iv) KMnO4 + H2C2O4 + H2SO4 K2SO4 + MnSO4 + CO2 + H2O
+7 +3 +2 +4
KMnO4 + H2C2O4 + H2SO4 K2SO4 + MnSO4 + CO2 + H2O

5e- 1e- x 2
2KMnO4 + 5H2C2O4 + H2SO4 K2SO4 + MnSO4 + CO2 + H2O
2KMnO4 + 5H2C2O4 + H2SO4 K2SO4 + 2MnSO4 + 10CO2 + H2O
2KMnO4 + 5H2C2O4 + 3H2SO4 K2SO4 + 2MnSO4 + 10CO2 + 8H2O
20 Balance the following equations by ion electron method.
i) KMnO4 + SnCl2 + HCl MnCl2 + SnCl4 + H2O + KCl
Half reaction:
+7
MnO4- Mn2+ ………(1)
and Sn2+ Sn4+ …...….(2)
(1) ⇒ MnO4- + 8H+ + 5e- Mn2+ + 4H2O
(2) ⇒ Sn2+ Sn4+ + 2e-
(1) x 2 ⇒ 2MnO4- + 16H+ + 10e- 2Mn2+ + 8H2O
(2) x 5 ⇒ 5Sn2+ 5Sn4+ + 10e-
2MnO4- + 5Sn2+ + 16H+ 2Mn2+ + 5Sn4+ + 8H2O

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
ii) C2O42- + Cr2O72- Cr3+ + CO2 (in acid medium)
Half reaction:
+3 +4
C2O42- CO2 ………(1)
+6
and Cr2O72- Cr3+ …...….(2)
(1) ⇒ C2O42- 2 CO2 + 2e- ……….(3)
Cr2O72- + 14H+ 2 Cr3+ + 7H2O ……….(4)
(3) x 3 ⇒ 3C2O42- 6CO2 + 6e-
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
Cr2O72- + 3C2O42- + 14H+ 2Cr3+ + 6CO2 + 7H2O

iii) Na2S2O3 + I2 Na2S4O6 + NaI

Half reaction:
S2O32- S4O62- ………(1)
and I2 I- …...….(2)
(1) ⇒ 2S2O32- S4O62- + 2e-
(2) ⇒ I2 + 2e- 2I-
2S2O32- + I2 S4O62- + 2I-
iv) Zn + NO3- Zn2+ + NO (in acid medium)
Half reaction:
0
Zn Zn2+ ………(1)
+6
and NO3- NO …...….(2)
(1) ⇒ Zn +Zn2+ ……….(3)
2e-
(2) ⇒ NO3- -
+ 3e + 4H + NO + 2H2O ……….(4)
(3) x 3 ⇒ 3Zn 3Zn2+ + 6e-
(4) x 2 ⇒ 2NO3- + 6e- + 8H+ 2NO + 4H2O
-
3Zn + 2NO3 + 8H + 3Zn2+ + 2NO + 4H2O
21 Define unified atomic mass?
The C-12 atom is considered as standard by the IUPAC and its mass is fixed as 12 amu
(or) u. The amu (or) unified atomic mass unit is defined as one twelfth of the mass of a
Carbon-12 atom in its ground state. (1 amu (or) 1 u= 1.6605x10-27 kg)
22 Define Avogadro Number?
The total number of entities present in one mole of any substance is equal to 6.022 x
23
10 . This number is called Avogadro number
23 Define molar volume?
The volume occupied by one mole of any substance in the gaseous state at a given
temperature and pressure is called molar volume.
24 Define limiting reagent? (Jul-22)
when a reaction is carried out using non-stoichiometric quantities of the reactants, the
product yield will be determined by the reactant that is completely consumed. It limits the
further reaction from taking place and is called as the limiting reagent. The other reagents
which are in excess are called the excess reagents.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
25 Write the equations for calculating equivalent mass of acids, bases, oxidizing and
reducing agents?
Molar mass of the acid
Equivalent mass of acid =
Basicity of the acid
Molar mass of the base
Equivalent mass of base =
Acidity of the base
Molar mass of the oxidising agent
Equivalent mass of oxidising agent = No.of moles of electrons gained by
one mole of the oxidising agent
Molar mass of the reducing agent
Equal and mass of reducing agent = No.of moles of electrons lost by
one mole of the reducing agent

26 Explain the types of redox reactions?

1. Combination reactions:
Redox reactions in which two substances combine to form a single compoundare called
combination reaction.

2. Decomposition reactions:
Redox reactions in which a compound breaks down into two or more components are
called decomposition reactions. In these reactions, the oxidation number of the different
elements in the same substance is changed.

3. Displacement reactions:
Redox reactions in which an ion (or an atom) in a compound is replaced by an ion (or
atom) of another element are called displacement reactions. They are further classified into
two types.
(i) Metal displacement reactions:

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
ii) Non-metal displacement

4. Disproportionation reaction (Auto redox reactions) (Jun-19)

In some redox reactions, the same compound can undergo both oxidation and
reduction. In such reactions, the oxidation state of one and the same element is both
increased and decreased.

5. Competitive electron transfer reaction

These reactions explain the electron releasing and gaining behavior between metals.
Among the three metals, namely, zinc, copper and silver, the electron releasing tendency is in
the following order.
Zinc > Copper > Silver

27 An organic compound present in vinegar has 40 % carbon, 6.6 % hydrogen and 53.4 %
oxygen. Find the empirical formula of the compound.

The empirical formula is CH2O

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
28 Calculate the oxidation number of underlined elements

i) CO2 x +2(-2) = 0 ; x – 4 = 0 ; x = +4
12
ii) K2Cr2O7 2(+1)+2x+7(-2) = 0 ; 2+2x-14 = 0 ; 2x-12 = 0 ; 2x = 12 ; x = ;x=6
2
iii) KMnO4 1+x+4(-2) = 0 ; 1+x-8 = 0 ; x-7 = 0 ; x = +7

iv) H2SO4 2(+1)+x+4(-2) = 0 ; 2+x-8 = 0 ; x - 6 = 0 ; x = +6

12
v) S2O72- 2x + 7(-2) = -2 ; 2x – 14 = -2 ; 2x = 14-2 ; 2x = 12 ; x = ;x=6
2
H2O2 -2
vi) 2(+1)+2x =0 ; 2 + 2x = 0 ; 2x = -2 ;x= ; x = -1
(Jun-23) 2
29 Calculate the equivalent mass of
i) Acids (Eg – H2SO4) (Mar-19)
H2SO4 basicity = 2 eq mol–1
Molar mass of H2SO4 = (2 × 1) + (1 × 32) + (4 × 16) = 98 g mol-1
Molar mass of the acid 98
Equivalent mass = = = 49 g eq–1
Basicity of the acid 2
Ii) Bases (Eg – KOH)
KOH acidity = 1 eq mol–1
Molar mass of KOH = (1 × 39)+(1 × 16)+(1 ×1) = 56 g mol-1
Molar mass of the base 56
Equivalent mass = = = 56 g eq–1
Acidity of the Base 1
Iii) Oxidizing or Reducing agent (Eg – KMnO4)
KMnO4 is an oxidising agent
Molar mass of KMnO4 = (1 × 39) +(1 × 55) + (4 ×16) = 158 g mol–1
In acid medium permanganate is reduced during oxidation and is given by the following
equation,
.MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
∴n = 5 eq mol–1.
Molar mass of the oxidising (or) reducing agent 158
Equivalent mass = No.of moles of electrons gained or lost by = = 31.6 g eq–1
5
one mole of the oxidising (or) reducing agent

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
2. QUANTUM MECHANICAL MODEL OF ATOM
1 Which quantum number reveal information about the shape, energy, orientation and
size of orbitals?
1. Principal quantum number - Size and shape
2. Azimuthal Quantum number - Energy
3. Magnetic quantum number - Orientation
2 How many orbitals are possible for n =4?
4s, 4p, 4d and 4f orbitals = 1 + 3 + 5 + 7 = 16 orbitals
3 How many radial nodes for 2s, 4p, 5d and 4f orbitals exhibit? How many angular
nodes?
radial nodes angular nodes
orbitals n l
n-l-1 l
2s 2 0 1 0
4p 4 1 2 1
5d 5 2 2 2
4f 4 3 0 3
4 The stabilisation of a half-filled d - orbital is more pronounced than that of the p-orbital
why?
The half field orbitals are more stable due to symmetry and exchange energy.
when a greater number of exchanges are possible, more exchange energy is released and
more stable
half-filled d orbitals - 10 possible exchanges.
half-filled p orbitals - 3 possible exchanges.
5 Consider the following electronic arrangements for the d5 configuration.

(i) which of these represents the ground state - arrangement (c)

(ii) which configuration has the maximum exchange energy. - arrangement (c)
6 Define orbital? what are the n and l values for 3px and 4dx2-y2 electron?
Orbital is a three-dimensional space in which the probability of finding the electron is
maximum
Orbitals n l
3px 3 1
4dx2−𝑦 2 4 2
7 State and explain pauli exclusion principle.
No two electrons in an atom can have the same set of values of all four quantum numbers.
8 Explain Aufbau principle?
In the ground state of the atoms, the orbitals are filled in the order of their increasing
energies. That is the electrons first occupy the lowest energy orbital available to them.
9 Define Hund's rule?
It states that electron pairing in the degenerate orbitals does not take place until all the
available orbitals contain one electron each.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
10 Explain briefly the time independent schrodinger wave equation?
Erwin Schrödinger expressed the wave nature of electron in terms of a differential
equation. This equation determines the change of wave function in space depending on the
field of force in which the electron moves. The time independent Schrödinger equation can be
expressed as,

Where is called Hamiltonian operator,  is the wave function and is a function of

position co-ordinates of the particle and is denoted as  (x,y,z) E is the energy of the system

The above schrodinger wave equation does not contain time as a variable and is referred to
as time independent Schrödinger wave equation.
11 Determine the values of all the four quantum numbers of the 8th electron in O- atom
and 15th electron in Cl atom.
i) 8 electron of oxygen atom is present in 2px orbital
1s2 2s2 2p2X 2p1Y 2p1Z
↿⇂ ↿⇂ ↿⇂ ↿ ↿ Electron n l m s
ii) 15th electron of chlorine atom is present in 3pZ 2p4 th 2 1 +1 or -1 -1/2
orbital
1s2 2s2 2p6 3s2
3p3 th 3 1 +1 or -1 +1/2
3p2X 3p2Y 3p1Z
↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿

12 How fast must a 54g tennis ball travel in order to have a de Broglie wavelength that is
equal to that of a photon of green light 5400 A°?

λ = 5400 A° = 5400 x 10-10 m ; m = 54g = 54 x 10-3 Kg ; V=?

h h 6.626 x 10−34 Kg m2 s−1
λ= ;V= = ; V = 2.27 x 10-26 ms-1
mV mλ 54 x 10−3 Kg x 5400 x 10−10 m
13 For each of the following, give the sub level designation, the allowable m values and
the number of orbitals
i) n = 4, l = 2, ii) n = 5, l = 3 iii) n= 7, l = 0
n l sub level m values number of orbitals
i) 4 2 4d -2, -1, 0, +1, +2 5
ii) 5 3 5f -3, -2, -1, 0, +1, +2, +3 7
iii) 7 0 7s 0 1
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14 An atom of an element contains 35 electrons and 45 neutrons. Deduce
i) the number of protons
ii) the electronic configuration for the element
iii) All the four quantum numbers for the last electron
An atom of an element has 35 electrons and 45 neutrons contains,
i) the number of protons = 35
ii) the electronic configuration for the element = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5
iii) All the 4 quantum numbers for the last electron are ↿⇂ ↿⇂ ↿

4p2X 4p2Y 4p1Z

n = 4: l = 1; m = +1 (or) -1; s = -1/2
15 Calculate the energy required for the process. He+(g) → He2+ (g) + e-. The ionisation
energy for the H atom in its ground state is -13.6 ev atom-1.
He+(g) He+(g) + e- E =?
13.6 Z2
En =−
n2
13.6 x (2)2
E1 =− = -56.4 ev (ஃ Atomic number of He Z = 2)
12
13.6 x (2)2
E∞ = − = 0 ev
∞2
The energy required for the process = E∞ - E1 = 0 - (-56.4) = 56.4 eV.
16 Show that the circumference of the Bohr orbit for the hydrogen atom is an integral
multiple of the de Broglie wave length associated with the electron revolving arround
the nucleus.
According to the de Broglie concept, the electron that revolves around the nucleus
exhibits both particle and wave character.
In order for the electron wave to exist in phase, the circumference of the orbit should be
an integral multiple of the wavelength of the electron wave. Otherwise, the electron wave is
out of phase.
Circumference of the orbit = nλ
2πr = nλ
h nh
Here, λ = 2πr =
mv mv The above equation was already
nh predicted by Bohr. Hence, De
mvr =
2π Broglie and Bohr’s concepts are in
nh agreement with each other.
Angular momentum =
2π
17 Give the electronic configuration of Mn2+ and Cr3+
The electronic configuration of Mn2+ and Cr3+ were,
2+ (23 e-s) : 1s2 2s2 2p6 3s2 3p6 4s0 3d5
25Mn

3+ (21 e-s) : 1s2 2s2 2p6 3s2 3p6 4s0 3d3

24Cr

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
18 An ion with mass number 37 possesses unit negative charge. If the ion contains 11.1%
more neutrons than electrons. Find the symbol of the ion.
Given: An ion with mass number 37 is 37ZX −
If No. of electrons = x
Then No. of protons = x – 1
No. of neutrons = 11.1% more neutrons than electrons = = x + 11.1% x
11.1
=x+ x = 1.11 x
100
⇒ (x - 1) + 1.11 x = 37 ஃ Atomic number Z = No. of protons
2.11 x -1 = 37 ⇒ 2.11 x = 37 + 1 =x–1
2.11 x = 38 = 18-1 = 17
38 So, the symbol of the ion = 37 −
x= = 18 17Cl ஆகும்.
2.11
19 The Li2+ ion is a hydrogen like ion that can be described by the Bohr model. Calculate
the Bohr radius of the third orbit and calculate the energy of an electron in 4th orbit.
0.529n2 13.6 Z2
rn = A° ; En = − eV atom-1
Z n2
Atomic number of Li2+ ion = 3; No. of electrons = 1
0.529(3)2
i) Bohr radius of the third orbit r3 = = 1.587 A°
3
13.6 (3)2
ii) Energy of an electron in 4 orbit E4 = −
th = -7.65 eV atom-1
42
20 Identify the missing quantum numbers and the sub energy level
n l m Sub energy level
Ans:
? ? 0 4d n l m Sub energy level
3 1 0 ? 4 2 0 4d
? ? ? 5p 3 1 0 3p
? ? -2 3d 5 1 0 (or) +1 (or) -1 5p
3 2 -2 3d

21 Calculate the total number of angular nodes and radial nodes present in 3d and 4f
orbitals? (Sep-20)
Radial nodes Angular nodes Total nodes
Orbitals n l
(n – l – 1) l (n – 1)
3d 3 2 0 2 2
4f 4 3 0 3 3

22 Energy of an electron in ground state of hydrogen atom is -13.6ev What is the energy
of this electron in the second excited state?
13.6 Z2
En = − eV atom-1
n2
For first excited state n = 2. so, for second excited state n = 3
13.6 (1)2
ஃ E3 = − = -1.51 eV atom-1
32

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23 Write the assumptions of Bohr’s atomic model?
1. The energies of electrons in an atom are quantised.
2. The electron is revolving around the nucleus in a certain circular path of fixed energy
called stationary orbit.
3. Electron can revolve only in those orbits in which the angular momentum (mvr) of the
electron must be equal to an integral multiple of h/2π.
i.e. mvr = nh/2π where n = 1, 2, 3... etc.,
4. As long as an electron revolves in the fixed stationary orbit, it doesn’t lose its energy.
However, when an electron jumps from higher energy state (E2) to a lower energy state
(E1), the excess energy is emitted as radiation.
E2 − 𝐸1
The frequency of the emitted radiation is E2 – E1 = h and  =
ℎ

−13.6 Z2 −1312.8 Z2
Energy of an electron En = eV atom-1 (or) En = KJmol-1
n2 n2
(0.529)n2
Radius of an atom rn = A°
Z
24 Write two limitation of Bohr's atom model?
1. The Bohr's atom model is applicable only to species having one electron such as
hydrogen, Li2+ etc... and not applicable to multi electron atoms.
2. It was unable to explain the splitting of spectral lines in the presence of magnetic field
(Zeeman effect) or an electric field (Stark effect).

25 Derive de Broglie equation? (Mar-19)

Planck’s quantum hypothesis: E = h (particle nature) ……..(1)
Einstein's mass-energy relationship E = mc2 (wave nature)……(2)
From eqn (1) and (2), h = mc2
c c
ஃ = h = mc2
λ λ

h
=
mc
For a particle of matter with mass m and moving with a velocity v, the above equation can be
h
written as, =
mv
26 State Heisenberg uncertainty principle? (Sep-20, Jul-22, Mar-23)
It is impossible to accurately determine both the position and the momentum of a
microscopic particle simultaneously.
h
Δx.Δp ≥
4
where, Δx and Δp are uncertainties in determining the position and momentum, respectively.

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27 Write the main features of the quantum mechanical model of an atom?
1. The energy of electrons in atoms is quantised
2. The solutions of Schrödinger wave equation gives the allowed energy levels (orbits).
3. Orbital is a three-dimensional space in which the probability of finding the electron is
maximum.
4. The solution of SchrÖdinger wave equation for the allowed energies of an atom gives the
wave function ψ, which represents an atomic orbital. The wave nature of electron present in
an orbital can be well defined by the wave function ψ.
5. The wave function ψ itself has no physical meaning. However, the probability of finding the
electron in a small volume dxdydz around a point (x,y,z) is proportional to |ψ(x,y,z)|2 dxdydz
|ψ(x,y,z)|2 is known as probability density and is always positive.
28 Explain (n+l) rule?
• Other than hydrogen atom the relative order of energies of various orbitals is given
approximately by the (n+ l) rule.
• It states that, the lower the value of (n + l) for an orbital, the lower is its energy. If two
orbitals have the same value of (n + l), the orbital with lower value of n will have the lower
energy.
29 Define Exchange energy? (Sep-21)
If two or more electrons with the same spin are present in degenerate orbitals, there is a
possibility for exchanging their positions. During exchange process the energy is released
and the released energy is called exchange energy.
30 Explain the experiment conforms the wave nature of an electron? (Davison and Germer
experiment)
• The wave nature of electron was experimentally confirmed by Davisson and Germer.
• They allowed the accelerated beam of electrons to fall on a nickel crystal and recorded
the diffraction pattern. The resultant diffraction pattern is similar to the x-ray diffraction
pattern.
31 Define radial node? Give examples.
•The region where this probability density function reduces to zero is called nodal surface
or a radial node.
• it has been found that ns-orbital has (n–1) nodes. In other words, number of radial nodes
for 2s orbital is one, for 3s orbital it is two and so on.
32 What is effective nuclear charge?
• In a multi-electron atom, in addition to the electrostatic attractive force between the
electron and nucleus, there exists a repulsive force among the electrons. These two
forces are operating in the opposite direction.
• This results in the decrease in the nuclear force of attraction on electron. The net charge
experienced by the electron is called effective nuclear charge.
33 Write a short note on Quantum numbers?
The electron in an atom can be characterised by a set of four quantum numbers, namely
principal quantum number (n), azimuthal quantum number (l), magnetic quantum number (m)
and spin quantum number (s).
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Principal quantum number (n) (Sep-21, Mar-23):
• This quantum number represents the energy level in which electron revolves around the
nucleus and is denoted by the symbol 'n'.
• The 'n' can have the values 1, 2, 3,… n=1 represents K shell; n=2 represents L shell and
n = 3, 4, 5 represent the M, N, O shells, respectively.
• The maximum number of electrons that can be accommodated in a given shell is 2n 2.
(-1312.8)Z 2
• 'n' gives the energy of the electron, En = KJ mol-1 and the distance of the
n2
(0.529)n2
electron from the nucleus is given by rn = A°
Z
Azimuthal Quantum number (l) or subsidiary quantum number (Jun-23):
• It is represented by the letter ' l ', and can take integral values from zero to n-1, where n is
the principal quantum number
• Each l value represents a subshell (orbital). l = 0, 1, 2, 3 and 4 represents the s, p, d, f
and g orbitals respectively.
• The maximum number of electrons in a given subshell (orbital) is 2(2 l +1).
• It is used to calculate the orbital angular momentum using the expression, Angular
h
momentum = √l(l+1)
2π
Magnetic quantum number (ml) (Jul-22, Jun-23):
• It is denoted by the letter ' ml '. It takes integral values ranging from -l to +l through 0. i.e. if
l=1; m = -1, 0 and +1
• Different values of m for a given l value, represent different orientation of orbitals in space.
• The Zeeman Effect (the splitting of spectral lines in a magnetic field justifies this quantum
number.
• The magnitude of the angular momentum is determined by the quantum number l while its
direction is given by magnetic quantum number.
Spin quantum number (ms) (Mar-24):
• It represents the spin of the electron and is denoted by the letter 'ms'
• The electron in an atom revolves not only around the nucleus but also spins in its own
axis either in a clockwise direction or in anti-clockwise direction.
• Corresponding to the clockwise and anti-clockwise spinning of the electron, maximum two
values are possible for this quantum number.
• The values of 'ms' is equal to +½ and -½

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3. PERIODIC CLASSIFICATION OF ELEMENTS
1 Define modern periodic law. (Mar-23)
Modern periodic law states that, “the physical and chemical properties of the elements
are periodic functions of their atomic numbers.”
2 What are isoelectronic ions? Give examples.
Ions of different elements having the same number of electrons are called isoelectronic
ions. Eg: Na+, Mg2+, Al3+, F-, O2- (all having 10 electrons)
3 What is effective nuclear charge?
The net nuclear charge experienced by valence electrons in the outermost shell is called
the effective nuclear charge.
Zeff = Z – S Where Z is the atomic number and 'S' is the screening constant.
4 Is the definition given below for ionisation enthalpy is correct?
"Ionisation enthalpy is defined as the energy required to remove the most loosely
bound electron from the valence shell of an atom"
The above definition for ionisation enthalpy is correct. Ionisation enthalpy is defined as
“the minimum amount of energy required to remove the most loosely bound electron from the
valence shell of the isolated neutral gaseous atom in its ground state”.
5 Magnesium loses electrons successively to form Mg+, Mg2+ and Mg3+ ions. Which step
will have the highest ionisation energy and why?
Mg + IE1 Mg+ + e- step: 1
Mg+ + IE2 Mg2+ + e- step: 2
Mg2+ + IE3 Mg3+ + e- step: 3
The formation of the Mg+3 ion from Mg+2 ion requires more ionization energy because,
• Mg+2 has stable noble gas configurations of 2,8 electrons
• Since the valence orbital is completely filled it requires more energy to remove an electron.
• Mg+2 ion has more effective nuclear charge.
6 Define electronegativity. (Sep-21, Mar-24)
It is defined as the relative tendency of an element present in a covalently bonded
molecule, to attract the shared pair of electrons towards itself.
7 How would you explain the fact that the second ionisation potential is always higher
than first ionisation potential? (Jun-23)
The total number of electrons are less in the cation than the neutral atom while the
nuclear charge remains the same.
Therefore, the effective nuclear charge of the cation is higher than the corresponding
neutral atom.
Thus, the successive ionisation energies, always increase in the following order
IE1 < IE2 < IE3 …………
8 The electronic configuration of atom is one of the important factors which affects the
value of ionisation potential and electron gain enthalpy. Explain
Ionisation potential:
• Since the half-filled or completey filled electronic configuration is more stable than partially
filled orbitals.
• Due to this type of stable electronic configuration, it requires higher energy to remove an
electron from the orbital.

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Electron gain enthalpy:
• The half-filled or completey filled electronic configuration is more stable than partially filled
orbitals. Therefore, addition of electron is not possible.
• The addition of extra electron to the half-filled or completey filled orbitals will disturb their
stable electronic configuration and they have almost zero electron affinity.
9 In what period and group will an element with Z = 118 will be present?
The electronic configuration of the element having atomic number 118 (Z = 118) is [86Rn]
5f 6d10 7s2 7p6. It presents in p – block elements (due to the presence of last electron in p
14

orbital).
Period = 7 (due to n=7)
Group = 18 (due to completely filled p orbital)
10 Justify that the fifth period of the periodic table should have 18 elements on the basis of
quantum numbers.
• According to Aufbau principle, nine orbitals can be fille in the fifth period. (one 5s, five 4d
and three 5p orbitals)
• Maximum 18 electrons can be filled in the above said nine orbitals.
• So, the fifth period has 18 elements starts with Rubidium (Rb – 5s1) and ends with Xenon
(Xe – 5s2 5p6)
11 Elements a, b, c and d have the following electronic configurations:
a: 1s2, 2s2, 2p6 b: 1s2, 2s2, 2p6, 3s2, 3p1
c: 1s2, 2s2, 2p6, 3s2, 3p6 d: 1s2, 2s2, 2p1
Which elements among these will belong to the same group of periodic table?
• Elements (a) and (c) belongs to 18th group (outer electronic configuration = np6)
• Elements (b) and (d) belongs to 13th group (outer electronic configuration = np1)
12 Give the general electronic configuration of lanthanides and actinides? (Jun-19, Mar-24)
Lanthanides = [54Xe] 4f1-14 5d0-1 6s2
Actinides = [86Rn] 5f0-14 6d0-2 7s2
13 Why halogens act as oxidising agents?
Halogens have high electron affinitybecause it readily accepts an electron to get the
stable noble gas electronic configuration (ns2 np6). So, it acts as oxidising agent.
14 Explain the pauling method for the determination of ionic radius. (Jun-19, May-22)
Pauling assumed that ions present in a crystal lattice are perfect spheres, and they are in
contact with each other. Therefore, 𝑑 = 𝑟𝐶 + + 𝑟𝐴− … … … … … (1)
Where d is the distance between the centre of the nucleus of cation C+ and anion A- and 𝑟𝐶 + ,
𝑟𝐴− are the radius of the cation and anion respectively.
Pauling also assumed that the radius of the ion having noble gas electronic configuration is
inversely proportional to the effective nuclear charge felt at the periphery of the ion.
1
𝑟𝐶 + ∝ ………………….. (2)
Zeff (𝐶 + )
1
𝑟𝐴− ∝ ………………….. (3)
Zeff (𝐴− )
Where Zeff is the effective nuclear charge and Zeff = Z - S
Dividing the equation 2 by 3
rC+ Zeff (A− )
= ……………..… (4)
rA− Zeff (C+ )
On solving equation (1) and (4) the values of rC+ and rA− can be obtained.
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15 Mention any two anomalous properties of second period elements.
• Lithium and beryllium form more covalent compounds, unlike the alkali and alkaline earth
metals which predominantly form ionic compounds.
• The elements of the second period have only four orbitals (2s & 2p) in the valence shell
and have a maximum co-valence of 4, whereas the other members of the subsequent
periods have more orbitals in their valence shell and shows higher valences. For example,
boron forms BF4–and aluminium forms AlF63–
16 Explain the periodic trend of ionisation potential. (Mar-24)
Periodic Trends in Ionisation Energy:
• The ionisation energy usually increases along a period with few exceptions.
• when we move from left to right along a period, the valence electrons are added to the
same shell, at the same time protons are added to the nucleus.
• This successive increase of nuclear charge increases the electrostatic attractive force on
the valence electron
• Thus, more energy is required to remove the valence electron resulting in high ionisation
energy.
Periodic variation in group:
• The ionisation energy decreases down a group.
• As we move down a group, the valence electron occupies new shells.
• The distance between the nucleus and the valence electron increases.
• So, the nuclear forces of attraction on valence electron decreases
• Hence ionisation energy also decreases down a group.
17 Explain the diagonal relationship.
• On moving diagonally across the periodic table, the second and third period elements show
certain similarities.
• Even though the similarity is not same as we see in a group, it is quite pronounced in the
following pair of elements.
Li Be B C

Na Mg Al Si
• The similarity in properties existing between the diagonally placed elements is called
‘diagonal relationship’.
18 Why the first ionisation enthalpy of sodium is lower than that of magnesium while its
second ionisation enthalpy is higher than that of magnesium?
• Electronic configuration of sodium 2 2 6
11Na = 1s 2s 2p 3s
1

• Electronic configuration of magnesium 12Mg = 1s2 2s2 2p6 3s2

• 3s orbital of magnesium is completely filled. Hence, it is difficult to remove an electron from
it. But, 3s orbital of sodium is partially filled. Hence an electron can be easily be removed
from its orbital.
• Therefore, the first ionization potential of sodium is lower than that of magnesium.
• It is difficult to remove the second electron from sodium, due to the stability of the
completely filled 2p orbital. Therefore, the second ionization energy of sodium is higher
than that of magnesium.
19 Define valency?
The valence of an atom is the combining capacity relative to hydrogen atom. It is usually
equal to the total number of electrons in the valence shell or equal to eight minus the number
of valence electrons.
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20 Explain the following, give appropriate reasons.
(i) Ionisation potential of N is greater than that of O
• Electronic configuration of nitrogen: 2 2
7N = 1s 2s 2p
3

• Electronic configuration of oxygen: 8O = 1s2 2s2 2p4

• Nitrogen has half field 2p orbital which is more stable than partially filled valence shell
electronic configuration of oxygen.
• so, the ionization potential of nitrogen is greater than that of oxygen
(ii) First ionisation potential of C-atom is greater than that of B atom, whereas the
reverse is true is for second ionisation potential.
• Electronic configuration of boron: 2 2
5B = 1s 2s 2p
1

• Electronic configuration of carbon : 6C = 1s2 2s2 2p2

• The first ionization potential of carbon is higher because the nuclear charge of carbon is
higher than that of boron and carbon is smaller in size than boron.
• Boron loses an electron 1s2 2s2 so, its secondary ionization energy is higher than that of
carbon due to its fully-filled electron configuration
(iii) The electron affinity values of Be and Mg are almost zero and those of N (0.02 eV)
and P (0.80 eV) are very low.
• Electronic configuration of beryllium: 2
4Be = 1s 2s
2

• Electronic configuration of magnesium: 12Mg= 1s2 2s2 2p6 3s2

• Beryllium and magnesium have completely filled stable electronic configuration. Hence,
addition of further electron is unfavourable and has zero electron affinity.
• Electronic configuration of nitrogen: 2 2
7N = 1s 2s 2p
3

• Electronic configuration of phosphorus: = 1s2 2s2 2p6 3s2 3p3

15P

• Nitrogen and phosphorus have half-filled stable electronic configuration and the addition of
further electron is unfavourable and has very low electron affinity.
(iv) The formation of F-(g) from F(g) is exothermic while that of O2-(g) from O(g) is
endothermic.
• F is highly electronegative. Hence, it accepts an electron and has a stable electron
configuration and becomes ionized F-.
• The heat is released during the above process. therefore, the formation of F-(g) from F(g) is
exothermic.
• The reaction that adds an electron to oxygen is exothermic. But when a second electron is
added, an electron-electron repulsion force occurs.
• To accomplish this, an electron enters the orbital by absorbing heat from outside.
• Therefore, the formation of O2- (g) from O(g) is an endothermic reaction.
21 What is screening effect?
• In addition to the electrostatic forces of attraction between the nucleus and the electrons,
there exists repulsive forces among the electrons.
• The repulsive force between the inner shell electrons and the valence electrons leads to a
decrease in the electrostatic attractive forces acting on the valence electrons by the
nucleus.
• Thus, the inner shell electrons act as a shield between the nucleus and the valence
electrons. This effect is called shielding effect.

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22 What is the fundamental difference in approach between Mendeleev's periodic table and
modern periodic table?
Mendeleev arranged the elements in ascending order of their atomic masses, but Henry
Moseley arranged the elements in ascending order of atomic number in the modern periodic
table.
23 Briefly give the basis for pauling's scale of electronegativity.
• Pauling assigned arbitrary value of electronegativities for hydrogen and fluorine as 2.1 and
4.0 respectively.
• Based on this the electronegativity values for other elements can be calculated using the
following expression
1
(XA – XB) = 0.182 √(EAB − (EAA x EBB )2
Where EAB, EAA and EBB are the bond dissociation energies (Kcal) of AB, A2 and B2
molecules respectively.
• The electronegativity of any given element is not a constant and its value depends on the
element to which it is covalently bound.
24 State the trends in the variation of electronegativity in group and periods. (Sep-21, Jul-22)
Variation of Electronegativity in a period:
• The electronegativity generally increases across a period from left to right.
• The atomic radius decreases in a period, as the attraction between the valence electron
and the nucleus increases.
• Hence the tendency to attract shared pair of electrons increases.
• Therefore, electronegativity also increases in a period
Variation of Electronegativity in a group:
• The electronegativity generally decreases down a group.
• As we move down a group the atomic radius increases and the nuclear attractive force on
the valence electron decreases. Hence, the electronegativity decreases.
25 Define Electron Affinity? (May-22)
It is defined as the amount of energy released, when an electron is added to the valence
shell of an isolated neutral gaseous atom in its ground state to form its anion. It is expressed in
kJ mol-1.
26 Define law of octaves?
J. Newland made an attempt to classify the elements and proposed the law of octaves.
On arranging the elements in the increasing order of atomic weights, he observed that the
properties of every eighth element are similar to the properties of the first element. This law
holds good for lighter elements up to calcium.
27 Explain the anomalies of Mendeleev’s periodic table?
• Some elements with similar properties were placed in different groups and those with
dissimilar properties were placed in same group.
• Similarly, elements with higher atomic weights were placed before lower atomic weights
based on their properties in contradiction to his periodic law.
28 Why do inert gases not react chemically?
Inert gases do not gain or lose electrons because they have a completely filled electron
configuration.
29 Define covalent bond?
It is one-half of the internuclear distance between two identical atoms linked together by
a single covalent bond.
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30 Explain the nomenclature of elements with atomic number greater than 100?

1. The numerical roots corresponding to the atomic number are put together and ‘ium’ is
added as suffix
2. The final ‘n’ of ‘enn’ is omitted when it is written before ‘nil’ (enn + nil = enil) similarly the
final ‘i' of ‘bi’ and ‘tri’ is omitted when it written before ‘ium’ (bi + ium = bium; tri + ium =
trium)
3. The symbol of the new element is derived from the first letter of the numerical roots.

31 Oxygen and fluorine have lower electron affinity values than sulphur and chlorine
respectively. Why?
• They are smaller in size and have higher electron density.
• An extra electron added to oxygen and chlorine goes to 2p orbital.
• This 2p orbital has a close structure compared to the 3p orbital of sulphur and chlorine.
• Hence, oxygen and fluorine have a lower electron affinity value than sulfur and chlorine
which present next to them in their group.
32 Differentiate electronegativity and electron affinity?
Electronegativity Electron affinity
The tendency of an element present in a The amount of energy released, when an
1 covalently bonded molecule, to attract electron is added to the valence shell of an
the shared pair of electrons towards itself isolated neutral gaseous atom in its ground
state to form its anion
It is not a measurable quantity. However, It will be calculated by experiments.
2 a number of scales are available to
calculate its value.
3 No unit. Unit: ev / atom, KJ / mol or Kcal / mol

4 Not having a constant value. The electron affinity of an element does not
change.
5 varies steadily in periods and does not Does not vary smoothly in periods and
vary smoothly in groups. groups.
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33 Why the covalent radius is always shorter than the atomic radius?
The formation of covalent bond involves the overlapping of atomic orbitals and it reduces
the expected internuclear distance. Therefore, covalent radius is always shorter than the
actual atomic radius.
34 Using Slater's rule calculate the effective nuclear charge on a 3p electron in aluminium
and chlorine. Explain how these results relate to the atomic radii of the two atoms?

Atomic number of Aluminium Z = 13 Atomic number of chlorine Z = 17

Electronic configuration of Aluminium = Electronic configuration of chlorine =
1s2 2s2 2p6 3s2 3p1 1s2 2s2 2p6 3s2 3p5
others (n - 1) n others (n - 1) n
Electron Electron
Contribution contribution Contribution contribution
Electron No. of Electron No. of
of each of of each of
Group electrons Group electrons
electron particular electron particular
group group
n 2 0.35 0.70 n 6 0.35 2.10
n–1 8 0.85 6.80 n–1 8 0.85 6.80
others 2 1.00 2.00 others 2 1.00 2.00
S value 9.50 S value 10.90
Effective nuclear charge = Z - S Effective nuclear charge = Z - S
(Zeff) Al = 13 - 9.5 = 3.5 (Zeff) Cl = 17 - 10.90 = 6.10

ஃ (Zeff)Cl > (Zeff)Al so rCl < rAl

35 Calculate the effective nuclear charge on Calculate the effective nuclear charge on
4s electron in scandium. (Jun-23) 3d1 electron in scandium.
Atomic number of scandium Z = 21 Atomic number of scandium Z = 21
Electronic configuration of scandium = Electronic configuration of scandium =
1s2 2s2 2p6 3s2 3p6 3d1 4s2 1s2 2s2 2p6 3s2 3p6 3d1 4s2
(n - 3) (n - 2) (n - 1) n (n - 3) (n - 2) (n - 1) n
Electron Electron
Contribution contribution Contribution contribution
Electron No. of Electron No. of
of each of of each of
Group electrons Group electrons
electron particular electron particular
group group
n 1 0.35 0.35 n 0 0.35 0
n–1 9 0.85 7.65 (n–1) &
18 1 18
(n-2) & 10 1.00 10.00 others
others S value 18
S value 18.00 Effective nuclear charge = Z - S
Effective nuclear charge = Z - S (Zeff)Sc = 21 - 18 = 3
(Zeff) Sc = 21 - 18 = 3

36 Define atomic radius? (Sep-21)

Atomic radius of an atom is defined as the distance between the centre of its nucleus and
the outermost shell containing the valence electron.
37 Define Metallic radius?
It is defined as one-half of the distance between two adjacent metal atoms in the closely
packed metallic crystal lattice.
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4. HYDROGEN
1 Explain why hydrogen is not placed with the halogen in the periodic table.
• Like the formation of halides (X-) from halogens, hydrogen also has a tendency to gain one
electron to form hydride ion (H-)
• However, the electron affinity of hydrogen is much less than that of halogen atoms.
• So, hydrogen is not placed with the halogen in the periodic table
2 Discuss the three types of covalent hydrides.
• Electron precise hydrides (CH4, C2H6, SiH4, GeH4),
• Electron-deficient hydrides (B2H6)
• Electron-rich hydrides (NH3, H2O).
3 Predict which of the following hydrides is a gas on a solid (a) HCl (b) NaH. Give your
reason.
HCl – They are individual, small molecules. It is in the form of gas due to less force of
attraction between them.
NaH – It is a hydride. It is formed by transferring an electron from sodium metal to hydrogen as
a gas on solid.
4 Write the expected formulas for the hydrides of 4th period elements. What is the trend
in the formulas? In what way the first two members of the series different from the
others?
• The expected formulas for the hydrides of 4th period elements are MH or MH2.
• Hydrides possesses non-stoichiometric with variable composition.
• First two elements form ionic hydrides others form covalent and metallic hydrides.
5 Write chemical equation for the following reactions.
i) Reaction of hydrogen with tungsten (VI) oxide on heating.
ii) Hydrogen gas and chlorine gas.
i) WO3 + 3H2 W + 3H2O
ii) H2 + Cl2 2HCl
6 Complete the following chemical reactions and classify them in to (a) hydrolysis (b)
redox (c) hydration reactions.
i) KMnO4 + H2O2 →
ii) CrCl3 + H2O →
iii) CaO + H2O →
i) 2KMnO4 + 3H2O2 2MnO2 + 2KOH +2H2O + 3O2 – Redox reaction
ii) CrCl3 + 6H2O [Cr(H2O)6]Cl3 – Hydration reaction
iii) CaO + H2O Ca(OH)2 – Hydrolysis reaction
7 Hydrogen peroxide can function as an oxidising agent as well as reducing agent.
substantiate this statement with suitable examples.
Hydrogen peroxide can act both as an oxidizing agent and a reducing agent.
Oxidation is usually performed in acidic medium
H2O2 + 2H+ + 2e- 2H2O (E° = +1.77V)
Eg: 2FeSO4 + H2SO4 + H2O2 Fe2(SO4)3 + 2H2O
Reduction reactions are performed in basic medium
H2O2 + OH- O2 + 2H2O + 2e- (E° = +0.08V)
Eg: 2KMnO4 (aq) + 3H2O2 (aq) 2MnO2 + 2KOH +2H2O + 3O2 (g)
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8 Do you think that heavy water can be used for drinking purposes?
• There are differences in properties between water and heavy water.
• Because of the difference, the reactions of hydrogen and deuterium take place in different
ways.
• The rate of reaction involving heavy water is lower than the rate of reaction involving water.
• Hence, drinking of heavy water will affect physiological processes. Therefore, hard water is
not suitable for drinking.
9 What is water-gas shift reaction?
400℃
water gas + steam → CO2 + H2
Fe/Cu
In this method, carbon monoxide in water gas (CO + H2) mixture is converted to
carbon dioxide. This reaction is called as water-gas shift reaction.
10 Justify the position of hydrogen in the periodic table?
Similarities with alkali metals:
• The hydrogen has the electronic configuration of 1s1 which resembles with ns1 general
valence shell configuration of alkali metals and shows similarity with them as follows.
• It forms unipositive ion (H+) like alkali metals (Na+, K+, Cs+)
• It forms halides (HX), oxides (H2O), peroxides (H2O2) and sulphides (H2S) like alkali metals
• It also acts as a reducing agent.
Variation from alkali metals:
• unlike alkali metals which have ionization energy ranging from 377 to 520 kJ mol -1, the
hydrogen has 1,314 KJ mol-1 which is much higher than alkali metals.
• Like the formation of halides (X-) from halogens, hydrogen also has a tendency to gain one
electron to form hydride ion (H-) whose electronic configuration is similar to the noble gas,
helium.
• The electron affinity of hydrogen is much less than that of halogen atoms, the tendency of
hydrogen to form hydride ion is low compared to that of halogens to form the halide ions.
• However, in most of its compound’s hydrogen exists in +1 oxidation state. Therefore, it is
reasonable to place the hydrogen in group 1 along with alkali metals
11 What are isotopes? Write the names of isotopes of hydrogen.
Atoms of the same element having same atomic number and different mass numbers are
called as isotopes.
Isotopes of Hydrogen:
1. Protium (1H1 or H)
2. Deuterium (1H2 or D)
3. Tritium (1H3 or T)
12 Give the uses of heavy water.
1. Heavy water is widely used as moderator in nuclear reactors as it can lower the energies of
fast neutrons
2. It is commonly used as a tracer to study organic reaction mechanisms and mechanism of
metabolic reactions
3. It is also used as a coolant in nuclear reactors as it absorbs the heat generated.
13 Explain the exchange reactions of deuterium.
CH4 + 2D2 CD4 + 2H2
2NH3 + 3D2 2ND3 + 3H2

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14 How do you convert para hydrogen into ortho hydrogen?
The para-form can be catalytically transformed into ortho-form by,
• Adding platinum or iron catalyst.
• By passing an electric discharge.
• Heating above 800°C.
• Mixing with paramagnetic molecules such as O2, NO, NO2.
• By adding nascent/atomic hydrogen.
15 Mention the uses of deuterium.
• To prepare heavy water – used as a moderator in nuclear reactors.
• Deuterium exchange reactions - deuterium can replace reversibly hydrogen in compounds
either partially or completely depending upon the reaction conditions.
• It is commonly used as a tracer to study organic reaction mechanisms.
16 Explain preparation of hydrogen using electrolysis.
• High purity hydrogen (>99.9 %) is obtained by the electrolysis of water containing traces of
acid or alkali.
• The electrolysis of aqueous solution of sodium hydroxide or potassium hydroxide using a
nickel anode and iron cathode.
• However, this process is not economical for large-scale production.
1
• At anode: 2OH- H2O + O2 + 2e-
2
• At cathode: 2H2O + 2e- 2OH- + H2
1
• Overall reaction: H2O H2 + O2
2
17 Arrange NH3, H2O and HF in the order of increasing magnitude of hydrogen bonding
and explain the basis for your arrangement.
• The increasing order of hydrogen bonding is NH3 < H2O < HF
• The nature of hydrogen bonding depends on the shape and electronegativity of the other
atoms.
• The electronegativity order of N, O and F is F > O > N
• Therefore, HF has high hydrogen bonding properties.
18 A group-1 metal (A) which is present in common salt reacts with (B) to give compound
(C) in which hydrogen is present in –1 oxidation state. (B) on reaction with a gas (C) to
give universal solvent (D). The compound (D) on reacts with (A) to give (E), a strong
base. Identify A, B, C, D and E. Explain the reactions.
common salt – NaCl
The 1st group element (A) present in it is Na
Na + (B) (C) Name / formula
Oxidation state of hydrogen in it is -1 (A) Sodium (Na)
2Na + H2 2NaH
(B) Hydrogen (H2)
(A) (B) (C)
H2 + D E (universal solvent) (C) Sodium hydride (NaH)
H2 + O2 2H2O (D) Oxygen (O2)
(B) (D) (E)
(E) Water (H2O)
Water is an universal solvent
Na + H2O NaOH + H2 (F) Sodium hydroxide (NaOH)
(A) (E) (F)

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19 An isotope of hydrogen (A) reacts with diatomic molecule of element which occupies
group number 16 and period number 2 to give compound (B) is used as a moderator in
nuclear reaction. (A) adds on to a compound (C), which has the molecular formula C3H6
to give (D). Identify A, B, C and D.
An isotope of hydrogen (A) reacts with oxygen to Name / formula
give heavy water (B). (A) Deuterium (D2)
2D2 + O2 2D2O
(B) Heavy water (D2O)
(A) (B)
Deuterium (A) reacts with propene (C) to form (C) Propene (CH3-CH=CH3)
deutero propene (D). Deutero propene
(D)
D2 + CH3-CH=CH3 CH3-CHD-CH2D (CH3-CHD-CH2D)
(A) (C) (D)
20 NH3 has exceptionally high melting point and boiling point as compared to those of the
hydrides of the remaining element of group 15 - Explain.
• Due to the presence of intermolecular hydrogen bonding in NH3.
• The amount of energy required to break hydrogen is high therefore melting and boiling
points are high.
21 Why interstitial hydrides have a lower density than the parent metal.
• In interstitial hydrides, hydrogen occupies the interstitial sites.
• Most of the hydrides are non-stoichiometric with variable composition so, it has lower
density than the parent metal.
22 How do you expect the metallic hydrides to be useful for hydrogen storage?
• In some metal hydrides, hydrogen is absorbed as a hydrogen atom.
• The interstitial space widens due to the adsorbed hydrogen atom.
• During heating the hydrogen atoms diffuse through the metal and recombine at the surface
to form molecular hydrogen.
• Technically metal hydride formation is caused by a chemical reaction. But it works like a
natural storage system.
• It acts like a water sponge, absorbing and releasing.
• Thus, the reversible acceptance of hydrogen by metals and metal alloys is suitable for
applications in hydrogen storage and rechargeable metal hydride batteries.
23 What is responsible for the antibacterial action of chlorine water?
Chlorine forms hydrochloric acid and hypo chlorous acid. It is responsible for the
antibacterial action of chlorine water, and for its use as bleach.

Cl2 + H2O HCl + HOCl

24 Compare the structures of H2O and H2O2.
Structure of H2O Structure of H2O2
1 It has a bend structure It has open book structure. i.e.,
H2O2 has a non-planar structure
2 Bond angle of H-O-H is 104.5° Bond angle of H-O-O-H in gaseous state is
94.8° and in solid state is 101.9°
3 Structurally, H2O2 is represented by the
dihydroxyl formula in which the two OH
groups do not lie in the same plane.

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25 Define ortho and para hydrogen?
In the hydrogen atom, the nucleus has a spin. When molecular hydrogen is formed, the
spins of two hydrogen nuclei can be in the same direction or in the opposite direction as shown
in the figure. These two forms of hydrogen molecules are called ortho and para hydrogens
respectively.

Ortho hydrogen Para hydrogen

26 Differentiate ortho and para hydrogen?
Ortho hydrogen Para hydrogen
1 The spins of two hydrogen nuclei in H2 The spins of two hydrogen nuclei in H2 can
can be in the same direction be in the opposite direction
2 melting point is 13.95 K melting point is 13.83 K
3 Boiling point is 20.39 K Boiling point is 20.26 K
4 The magnetic moment of ortho Since the nuclear spins are in opposite
hydrogen is twice that of a proton directions the magnetic moment of para
hydrogen is zero
27 Explain the preparation of Tritium?
6
3Li + 10n 4
2He + 31T
28 Give the uses of hydrogen peroxide?
1. It is used in water treatment to oxidize pollutants
2. It is used as a mild antiseptic
3. It is used to bleach in textile, paper and hair-care industry
29 What is water gas?
• Mixture of carbon monoxide and hydrogen is called as water gas.
• steam is passed over a red-hot coke to produce water gas (CO+H2). This is also called
syngas (Synthetic gas) as it is used in the synthesis of organic compounds.

30 Give the uses of hydrogen?

1. Over 90 % hydrogen produced in industry is used for synthetic applications.
2. Unsaturated fatty oils can be converted into saturated fats called vanaspati by the reduction
reaction with Pt / H2.
3. In metallurgy, it can be used to reduce many metal oxides to metals at high temperatures.
4. Atomic hydrogen and oxy-hydrogen torches are used for cutting and welding.
5. Liquid hydrogen is used as a rocket fuel.
6. Hydrogen is also used in fuel cells for generating electrical energy.
31 What is hard water and soft water?
• Hard water contains high amounts of mineral ions like, magnesium & calcium, though iron,
aluminium, and manganese may also be found in certain areas. Presence of these metal
salts in the form of bicarbonate, chloride and sulphate in water makes water ‘hard’.
• On the other hand, water free from soluble salts of calcium and magnesium is called soft
water.

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32 What is temporary hardness? How it can be removed.
• Temporary hardness is due to the presence of soluble bicarbonates of magnesium and
calcium.
• This can be removed by boiling the hard water followed by filtration. Upon boiling, these
salts decompose into insoluble carbonate which leads to their precipitation.
• The magnesium carbonate thus formed further hydrolysed to give insoluble magnesium
hydroxide.
33 What is permanent hardness? How it can be removed.
Permanent hardness of water is due to the presence of soluble salts of magnesium and
calcium in the form of chlorides and sulphates in it.
It can be removed by adding washing soda, which reacts with these metal (Ca or Mg)
chlorides and sulphates in hard water to form insoluble carbonates.
34 Explain ion-exchange process?
• ion-exchange is the process used to soften the hard water.
• hardness can be removed by passing through an ion-exchange bed like zeolites or column
containing ion-exchange resin.
• Zeolites are hydrated sodium alumino-silicates with a general formula,
Na2O∙Al2O3∙xSiO2∙yH2O (x = 2 to 10, y = 2 to 6).
• Zeolites have porous structure in which the monovalent sodium ions are loosely held and
can be exchanged with hardness producing metal ions (M = Ca2+ or Mg2+) in water.
• When exhausted, the materials can be regenerated by treating with aqueous sodium
chloride.
35 What are hydrides? Explain its types.
Hydrogen forms binary hydrides with many electropositive elements including
metals and non-metals. They are 3 types,
Ionic (Saline) hydrides:
These are hydrides composed of an electropositive metal, generally, an alkali or
alkaline-earth metal, except beryllium and magnesium, formed by transfer of electrons
from metal to hydrogen atoms.
They can be prepared by the reaction of elements at about 400° C.
These are salt-like, high-melting, white crystalline solids having hydride ions (H−) and
metal cations (Mn+).
Covalent (Molecular) hydrides:
• They are compounds in which hydrogen is attached to another element by sharing of
electrons.
• The most common examples of covalent hydrides of non-metals are methane, ammonia,
water and hydrogen chloride.
• Since most of the covalent hydrides consist of discrete, small molecules that have relatively
weak intermolecular forces, they are generally gases or volatile liquids.
• Covalent hydrides are further divided into three categories, viz., electron precise (CH 4,
C2H6, SiH4, GeH4), electron-deficient (B2H6) and electron-rich hydrides (NH3, H2O).
Metallic (Interstitial) hydrides:
• Metallic hydrides are usually obtained by hydrogenation of metals and alloys.
• In metals and alloys, hydrogen occupies the interstitial sites so, they are called as
interstitial hydrides.
• The hydrides show properties similar to parent metals and hence they are also

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known as metallic hydrides.
Eg: TiH1.5-1.8 (or) PdH0.6-0.8 (or) MH (or) MH2 (M = Ti, Zr, Hf, V, Zn)
36 Define hydrogen bonding?
• When a hydrogen atom (H) is covalently bonded to a highly electronegative atom
such as fluorine (F) or oxygen (O) or nitrogen (N), the bond is polarized.
• Due to this effect, the polarized hydrogen atom is able to form a weak
electrostatic interaction with another electronegative atom present in the vicinity.
This interaction is called as a hydrogen bond
37 Explain the types of hydrogen bonding?
Intramolecular Hydrogen Bond
• Intramolecular hydrogen bonds are those which occur within a single molecule.
• Eg: Ortho-Nitrophenol, Salicilaldehyde
Intermolecular hydrogen bond
• Intermolecular hydrogen bonds occur between two separate molecules.
• They can occur between any numbers of like or unlike molecules as long as hydrogen
donors and acceptors are present in positions which enable the hydrogen bonding
interactions.
• For example, intermolecular hydrogen bonds can occur between ammonia molecule
themselves or between water molecules themselves or between ammonia and water.

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5. ALKALI AND ALKALINE EARTH METALS
1 Why sodium hydroxide is much more water soluble than sodium chloride?
• NaOH is a stronger base
• NaOH dissolve freely in water with evolution of much heat on account of intense hydration
• NaOH ionises easily due to ionic character. Whereas, NaCl is partially covalent in nature
• at 273 K temperature, 36.0g of NaCl dissolves in 100g of water.
• Rise in temperature does not increase the solubility.
2 Write the chemical equations for the reactions involved in solvay process of
preparation of sodium carbonate.
2NH3 + H2O + CO2 (NH4)2CO3
(NH4)2CO3 + H2O + CO2 2NH4HCO3
2NH4HCO3 + NaCl NH4Cl + NaHCO3
2 NaHCO3 Na2CO3 + CO2 + H2O
3 Write balanced chemical equation for each of the following chemical reactions.
(i) Lithium metal with nitrogen gas
6Li + N2 2Li3N
(ii) Heating solid sodium bicarbonate
Δ
2NaHCO3 → Na2CO3 + CO2 + H2O
(iii) Rubidum with oxygen gas
Δ
Rb + O2 → RbO2 (Rubidium superoxide)
Δ
2Rb + O2 → Rb2O2 (Rubidium peroxide)
(iv) Solid potassium hydroxide with CO2
KOH + CO2 KHCO3
(v) Heating calcium carbonate
Δ
CaCO3 ⇋ CaO + CO2
(vi) Heating calcium with oxygen
Δ
2Ca + O2 → 2CaO
4 Discuss briefly the similarities between beryllium and aluminium. (May-22, Sep-21, Jun-
23, Mar-24)
Beryllium shows a diagonal relationship with aluminium. So, their properties per unit area
is closer.
Properties
1 Beryllium chloride forms a dimeric structure like aluminium chloride with chloride
bridges. Beryllium chloride also forms polymeric chain structure in addition to dimer.
Both are soluble in organic solvents and are strong Lewis acids.
2 Beryllium hydroxide dissolves in excess of alkali and gives beryllate ion and [Be(OH) 4]2–
and hydrogen as aluminium hydroxide which gives aluminate ion, [Al(OH)4]–.
3 Beryllium and aluminium ions have strong tendency to form complexes, BeF 42–, AlF63–.
4 Both beryllium and aluminium hydroxides are amphoteric in nature.
5 Carbides of beryllium (Be2C) like aluminium carbide (Al4C3) give methane on hydrolysis.
6 Both beryllium and aluminium are rendered passive by nitric acid.

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5 An alkali metal (x) forms a hydrated sulphate, X2SO4. 10H2O. Is the metal more likely to
be sodium (or) potassium.
• The chance of hydration of alkali metal is inversely proportional to its size. Li+ < Na+ < K+
• The hydration of Na+ ion is due to its smaller size than K+ ions.
• Na2SO4.10H2O is more likely to be formed. So, X is sodium.
6 Give the systematic names for the following
(i) Milk of magnesia = Magnesium hydroxide [Mg(OH)2]
(ii) Lye = Sodium hydroxide (NaOH)
(iii) Lime = Calcium oxide (CaO)
(iv) Caustic potash = Potassium hydroxide (KOH)
(v) Washing soda = Sodium carbonate (hydrated) (NaCO3.10H2O)
(vi) Soda ash = Sodium carbonate (NaCO3)
(v) Trona = Trisodium hydrogen dicarbonate dihydrate (Na2CO3.NaHCO3.2H2O)
7 Substantiate Lithium fluoride has the lowest solubility among group one metal
fluorides.
• LiF is a covalent compound whereas other flurides are ionic compounds.
• Li+ is a small cation
• Li has high polarising power.
8 Beryllium halides are covalent whereas magnesium halides are ionic why?
• Beryllium is smaller in size and has high electronegativity
• Beryllium has high ionisation potential and high polarising power so, it is covalent.
• Whereas, magnesium has vast difference in these properties so it is ionic.
9 Alkaline earth metal (A), belongs to 3rd period reacts with oxygen and nitrogen to form
compound (B) and (C) respectively. It undergoes metal displacement reaction with
AgNO3 solution to form compound (D). Identify A,B.C and D.
Alkali earth metal belongs to 3rd period
is magnesium (A) Symbol Name / formula
Δ (A) Magnesium (Mg)
5Mg + O2 + N2 → 2MgO + Mg3N2
(A) (B) (C) (B) magnesium oxide (MgO)
Mg + 2AgNO3 Mg(NO3)2 + 2Ag (C) Magnesium nitride (Mg3N2)
(D) (D) Magnesium nitrate Mg(NO3)2

10 Write balanced chemical equation for the following processes

(a) Heating calcium in oxygen
2Ca + O2 2CaO
(b) Heating calcium carbonate
CaCO3 CaO + CO2
(c) Evaporating a solution of calcium hydrogen carbonate
Ca(HCO3)2 CaCO3 + CO2 + H2O
(d) Heating calcium oxide with carbon
Δ
CaO + 3C → CaC2 + CO
2000℃
11 Why alkaline earth metals are harder than alkali metals.
• The atomic radius of the alkaline earth metals is smaller and its density is higher than that
of the alkali metals.
• The metallic bond of alkaline earth metals is stronger than that of alkali metals.
• Therefore, alkaline earth metals are harder than alkali metals.
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12 Explain the important common features of Group 2 elements.
1. Electron configuration is ns2.
2. It is highly reactive and does not occur alone in nature.
3. Atomic and ionic radius increases in group.
4. General oxidation state is +2.
5. The ionization energy decreases in group.
6. Electronegativity decreases in group.
7. It possess higher hydration enthalpy. Hydration series Be > Mg > Ca > Sr > Ba.
8. HCl wetted alkali metal salts impart a specific color to the flame.
o Calcium - brick red
o Strontium - crimson red
o Barium - apple green
13 How is plaster of paris prepared?
• It is a hemihydrate of calcium sulphate.
• It is obtained when gypsum, CaSO4·2H2O, is heated to 393 K.
1
2CaSO4.2H2O(S) 2CaSO4. 2 H2O + 3H2O
14 Mention the uses of plaster of paris. (Mar-23)
It is used in,
• Building industries (plasters)
• Immobilising (bone fracture or sprain)
• Dentistry, in ornamental work and for making casts of statues and busts.
15 Give the uses of gypsum.
• Gypsum is used in making drywalls or plaster boards. Plaster boards are used as the finish
for walls and ceilings, and for partitions.
• Gypsum is heated to about 300°F to produce plaster of Paris, which is also known as
gypsum plaster. It is mainly used as a sculpting material.
• Gypsum is used in making surgical and orthopedic casts, such as surgical splints and
casting moulds.
• Gypsum plays an important role in agriculture as a soil additive, conditioner, and fertilizer. It
helps loosen up compact or clay soil, and provides calcium and sulphur, which are
essential for the healthy growth of a plant.
• Gypsum is used in toothpastes, shampoos, and hair products, mainly due to its binding and
thickening properties.
• Gypsum is a component of Portland cement, where it acts as a hardening retarder to
control the speed at which concrete sets.
16 Describe briefly the biological importance of Calcium and magnesium.
A typical adult human body contains about 25 g of magnesium and 1200 g of calcium.
Biological importance of magnesium:
• Magnesium plays an important role in many biochemical reactions catalysed by enzymes.
• It is the co-factor of all enzymes that utilize ATP in phosphate transfer and energy release.
• It also essential for DNA synthesis and proper functioning of DNA.
• It is also used for balancing electrolytes in our body.
• Deficiency of magnesium results into convulsion and neuromuscular irritation.
• The main pigment that is responsible for photosynthesis, chlorophyll, contains magnesium.
Biological importance of calcium:
• Calcium is a major component of bones and teeth.
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•It is also present in in blood and its concentration is maintained by hormones (calcitonin
and parathyroid hormone).
• Deficiency of calcium in blood causes it to take longer time to clot.
• It is also important for muscle contraction.
17 Which would you expect to have a higher melting point, magnesium oxide or
magnesium fluoride? Explain your reasoning.
MgO has a high melting point. because,
• Ionic character of O2-. is twice in MgO.
• Due to its strong ionic bond, more energy is required to break it.
• The melting enthalpy of MgO is very high. Hence, stability is also high.
18 Why do beryllium and nitrogen have almost zero electron affinity?
Be - 1s2 2s2
N - 1s2 2s2 2p3
When an electron is added to elements like beryllium and nitrogen, their stable electron
configuration is lost. Hence, such elements have an almost zero electron affinity value.
19 Compare the distinctive properties of lithium with other elements of the group? (Jul-22)
The distinctive behaviour of Li+ ion is due to its exceptionally small size, high polarising
power, high hydration energy and non-availability of d-orbitals.
Lithium Other elements of the family
Hard, high melting and boiling point Soft and Lower melting and boiling point
Least reactive More reactive
Reacts with nitrogen to give Li3N
No reaction
6Li + N2 --> 2Li3N
Reacts with bromine slowly React violently
Reacts directly with carbon to form ionic Do not react with carbon directly, but can
carbides. react with carbon compounds.
For example, 2Li + 2C --> Li2C2 2Na + C2H2 --> Na2C2 + H2
Lithium nitrate decomposes to give an oxide Decompose to give nitrites
20 Explain the preparation of calcium oxide and write its properties?
It is produced on a commercial scale by heating limestone in a lime kiln in the temperature
range 1070-1270K.
CaCO3 ⇌ CaO + CO2
The reaction being reversible, carbon dioxide is removed as soon as it is produced to enable
the reaction to proceed to completion.
Properties:
Calcium oxide is a white amorphous solid. It has a melting point of 2870 K.
(i)It absorbs moisture and carbon dioxide on exposure to atmosphere.
CaO + H2O Ca(OH)2
CaO + CO2 CaCO3
(ii)The addition of limited amount of water breaks the lump of lime. This process is called
slaking of lime and the product is slaked lime.
CaO + H2O Ca(OH)2
21 Write a balanced equation for the effect of heat on calcium carbonate. (May-22, Mar-24)
CaCO3 ⇌ CaO + CO2

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
22 Compare the distinctive properties of Beryllium with other elements of the group?
(May-22)
The anomalous properties of beryllium is mainly due to
• Its small size and high polarising power
• High ionisation energy and high electronegativity
Beryllium Other elements of the family
Forms covalent compounds Forms ionic compounds
High melting and boiling point Low melting and boiling point
Does not react with water even at elevated
React with water
temperature
Does not combine directly with hydrogen Combine directly with hydrogen
Does not combine directly with halogens. Combine directly with halogens
Halides are covalent. Halides are electrovalent.
Hydroxide and oxides of beryllium are
Basic in nature.
amphoteric in nature
It is not readily attacked by acids because of
Readily attacked by acids
the presence of an oxide film
Beryllium carbide evolves methane with evolve acetylene with water.
water.
Salts of Be are extensively hydrolysed Hydrolysed
23 Explain the biological importance of sodium and potassium?
Monovalent sodium and potassium ions are found in large proportions in biological fluids.
• These ions perform important biological functions such as maintenance of ion balance and
nerve impulse conduction.
• A typical 70 kg man contains about 90 g of sodium and 170 g of potassium.
• Sodium ions are found primarily on the outside of cells, being located in blood plasma and
in the interstitial fluid which surrounds the cells.
• These ions participate in the transmission of nerve signals, in regulating the flow of water
across cell membranes and in the transport of sugars and amino acids into cells.
• potassium ions are the most abundant cations within cell fluids, where they activate many
enzymes, participate in the oxidation of glucose to produce ATP.
• Sodium–potassium pump plays an important role in transmitting nerve signals.
24 Write the uses of sodium bicarbonate? (Jun-23)
• Primarily used as an ingredient in baking.
• Sodium hydrogen carbonate is a mild antiseptic for skin infections.
• It is also used in fire extinguishers.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
6. GASEOUS STATE
1 State Boyle's law?
At a given temperature the volume occupied by a fixed mass of a gas is inversely
proportional to its pressure.
1
V∝ (T and n are fixed)
P
1
(or) V=kx (or) PV = k
P
2 Name two items that can serve as a model for Gay Lusaac’ law and explain.
• The candle test proves that air contains one-fifth oxygen.
• A test in which a hard-boiled egg is placed in the lid of a vial.
3 What are ideal gases? (Mar-19) In what way real gases differ from ideal gases.
Gases that obey the gas equation PV = nRT under all conditions are called ideal gases.
Ideal gases Real gases
It obeys the gas law under all conditions of It obeys the gas law only at low pressure
temperature and pressure and high temperature
The individual gas molecules occupy The volume occupied by the individual gas
negligible volume when compared to the molecules can’t be negleted
total volume of the gas
There are no attractive forces between the There are attractive forces between the
gaseous molecules gaseous molecules
4 Give the mathematical expression that relates gas volume and moles? (Jun-19, Mar-23)
Avagadro hypothesis gives the mathematical expression which relates gas volume and
moles. Vn
5 Can a Vander Waals gas with a=0 be liquefied? explain.
When Vander Waals constant a=0 for a gas, then there will be no intermolecular forces of
attraction between the gas molecules. So, it cannot be liquefied.
6 Suppose there is a tiny sticky area on the wall of a container of gas. Molecules hitting
this area stick there permanently. Is the pressure greater or less than on the ordinary
area of walls?
The pressure on the sticky wall is greater than on the ordinary area of walls.
7 Explain the following observations
a) Aerated water bottles are kept under water during summer
As the temperature rises during the summer, the aerated water bottles containing CO 2
gas expands and the pressure increases (according to Gay-Lussac’s Law). The aerated water
bottle is likely to explode due to increase in pressure. To avoid this, soft drinks are kept in
water.
b) Liquid ammonia bottle is cooled before opening the seal
• The vapour pressure of ammonia at room temperature is very high and hence the
ammonia will evaporate unless the vapour pressure is decreased.
• On cooling, the vapour pressure decreases so that the liquid remains in the same state.
• Hence, the bottle is cooled before opening
c) The tyre of an automobile is inflated to slightly lesser pressure in summer than in
winter
In summer, due to hot weather conditions, the air inside the tyre expands to a large
volume due to heat as compared to winter, therefore inflated to lesser pressure in summer.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
d) The size of a weather balloon becomes larger and larger as it ascends up into larger
altitude
As we move to higher altitude, the atmospheric pressure degree, Decreases, therefore
the balloon can easily expand to a large volume.
8 Give suitable explanation for the following facts about gases.
a) Gases don’t settle at the bottom of a container
According to kinetic theory, gas molecules are moving continuously at random motion
due to less attractive forces between the molecules. Hence, they do not settle at the bottom of
a container.
b) Gases diffuse through all the space available to them
Due to the less attractive forces between the gaseous molecules the kinetic energy
increases and diffuses through all the space available to them.
9 Suggest why there is no hydrogen (H2) in our atmosphere. Why does the moon have no
atmosphere?
• Hydrogen has tendency to combine with oxygen to form water vapour, so there is no
hydrogen in our atmosphere.
• The gravitational force on the moon is very less so all the gases escape easily from the
moon’s surface. hence, there is no atmosphere in the moon.
10 Explain whether a gas approaches ideal behaviour or deviates from ideal behaviour if
a) It is compressed to a smaller volume at constant temperature.
• When the gas is compressed to a smaller volume at constant temperature, pressure
increased.
• At high pressure, the gas molecules are, close to each other and the interaction between
gas molecules is increased. The gas deviate from ideal behaviour.
b) The temperature is raised while keeping the volume constant
• At constant volume, the pressure of a fixed mass of a gas is directly proportional to
temperature. (Gay-Lussac’s Law)
• At high temperature keeping the volume constant, the pressure of the gas will increase. At
high pressure the gas deviates from ideal behaviour.
c) More gas is introduced into the same volume and at the same temperature
• When more gases are introduced in to the same volume the pressure increases.
• Due to more pressure, the attractive forces between the molecules increase. So, it
deviates from ideal behaviour.
11 Which of the following gases would you expect to deviate from ideal behaviour under
conditions of low temperature F2, Cl2 or Br2? Explain.
• The conditions to deviate from ideal behaviour are high pressure and low temperature. In
both these conditions the amount of attraction between molecules increases.
• The larger the size of the molecule, greater the deviation from an ideal gas clearly
bromine has the biggest size than others and deviates from the ideal gas behaviour.
12 Distinguish between diffusion and effusion. (Jul-22, Jun-23)
Diffusion Effusion (Mar-19)
This property of gas which involves the Effusion is another process in which a gas
movement of the gas molecules through escapes from a container through a very
another gases is called diffusion. small hole.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
13 Aerosol cans carry clear warning of heating of the can. Why?
This is because the pressure will build up to so much that the can will burst. So the
Aerosol cans carry clear warning of heating of the can
14 Would it be easier to drink water with a straw on the top of Mount Everest?
It is difficult to drink water with a straw on the top of mount Everest. This is because at
higher altitudes the pressure decreases and hence it is difficult to drink water through straw.
15 Write the Van der Waals equation for a real gas. (Mar-24) Explain the correction term for
pressure and volume
an2
The van der Waals equation of state for real gases (P + V2
) (V - nb) = nRT
Pressure Correction:
• The pressure of a gas is directly proportional to the force created by the bombardment of
molecules on the walls of the container.
• The speed of a molecule moving towards the wall of the container is reduced by the
attractive forces exerted by its neighbours.
• Hence, the measured gas pressure is lower than the ideal pressure of the gas. Hence, van
der Waals introduced a correction term to this effect.

Van der Waals found out the forces of attraction experienced by a molecule near the wall
are directly proportional to the square of the density of the gas.
P’  2
n Where, n is the number of moles of gas
= V is the volume of the container
V
n2
 P’ 
V2
where a is proportionality constant and
n2
 P’ = a depends on the nature of gas
V2
an2
Therefore, Pideal = P +
V2
Volume Correction
• As every individual molecule of a gas occupies a certain volume, the actual volume is less
than the volume of the container, V.
• Van der Waals introduced a correction factor V' to this effect. Let us calculate the
correction term by considering gas molecules as spheres.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
V = excluded volume
4 4
Excluded volume for two molecules = π(2r 3 ) = 8 ( πr 3 ) = 8 Vm
3 3
where Vm is a volume of a single molecule
8 Vm
Excludeed volume for single molecule = = 4 Vm
2
Excluded volume for n molecule = n (4 Vm) = nb
Where b is vander waals constant whch is equal to 4 Vm
 V’ = nb
Videal = V – nb
Replacing the corrected pressure and volume in the ideal gas equation PV=nRT we get
the van der Waals equation of state for real gases as below,
an2
(P + V2
) (V - nb) = nRT
The constants a and b are van der Waals constants and their values vary with the nature
of the gas. It is an approximate formula for the non-ideal gas.
16 Derive the values of critical constants in terms of van der Waals constants. (Mar-23)
The van der Waals equation for n moles is
an2
(P + V2
) (V - nb) = nRT ………. (1)
For 1 mole,
a
(P + V2
) (V - b) = RT ………. (2)
From the equation we can derive the values of critical constants Pc, Vc and Tc in terms of a
and b, the van der Waals constants, On expanding the above equation,
a ab
PV + – Pb – 2 – RT = 0 ………. (3)
V V
V2
Multiply equation (3) by
P
V2 a ab
(PV + – Pb – – RT ) = 0
P V V2
aV ab RTV2
V3 + – bV2 – – =0 ………. (4)
P P P
When the above equation is rearranged in powers of ‘V’
RT a ab
V3 – [ + b]V2 + [ ]V – [ ] = 0 ………. (5)
P P P
The equation (5) is a cubic equation in V. On solving this equation, we will get three
solutions.
At the critical point all these three solutions of V are equal to the critical volume V C. The
pressure and temperature become Pc and Tc respectively.
i.e, V = VC
V – VC = 0
(V – VC)3 = 0
V3 – 3VCV2 + 3VC2 V – VC3 = 0 ………. (6)
As equation (5) is identical with equation (6) we can equate the coefficients of V2, V and
constant terms in equation (5) and (6).

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
RT
-3 VC V2 = - [ c + b] V2
PC
RTC
3 VC = + b ………. (7)
PC
a
3VC2 = ………. (8)
PC
ab
VC3 = ………. (9)
PC
Divide equation (9) by equation (8),
ab
V3C PC
= a
3V2C
PC
VC
=b
3
i.e. VC = 3b ………. (10)
the value of VC is substituted in equation (8),
a
3VC2 =
PC
a a a a
PC = = = =
3 V2C 3(3b2 ) 3 x 9b2 27b2
a
PC = ………. (11)
27b2
substituting the values of Vc and Pc in equation (7)
RTC
3 VC = b +
PC
RTC
3 (3b) = b + a
( )
27 b2

RTC
9b – b = ( ) 27b2
a
TC R 27b2
8b =
a
8ab 8a
ஃ TC = =
27 R b2 27 R b
8a
TC = ………. (12)
27 R b
The critical constants can be calculated using the values of van der waals constant of a gas
and vice versa.
VC
a = 3 VC2 PC and b =
3
17 Why do astronauts have to wear protective suits when they are on the surface of moon?
• Astronauts must wear space suits whenever they leave a space craft. In a space there is
no air to breath and no air pressure.
• Space is extremely cold and filled with dangerous radiation without protection an
astronauts would quickly die in space.
• Space suits are specially designed to protect astronauts from the cold, radiation and low
pressure they also provide air to breathe.
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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
18 When ammonia combines with HCl, NH4Cl is formed as white dense fumes. Why do
more fumes appear near HCl?
• The Molecular weight of Ammonia is less than HCl.
• The rate of diffusion is inversely proportional to the molecular weight of the gas. Lower the
molecular weight, faster is the diffusion.
• Hence ammonia diffuses faster than HCl and thus appear as dense whiter fumes near HCl.
19 What happens when a balloon is moved from an ice-cold water bath to a boiling water
bath?
When a balloon is moved from an ice-cold water bath to a boiling water bath, the
temperature of the gas increases. As a result, the gas molecules inside the balloon move
faster and gas expands. Hence, the volume increases.
20 Explain the following laws.
1) Charles Law: For a fixed mass of a gas at constant pressure, the volume is directly
proportional to its temperature (K).
V
at constant P and n, V  T (or) = Constant
T
2) Gay-Lussac’s Law: At constant volume the pressure of a fixed mass of a gas is directly
proportional to temperature.
P
PT or = Constant k
T
3) Dalton’s law of partial pressures (May-22, May-24): The total pressure of a mixture of non-
reacting gases is the sum of partial pressures of the gases present in the mixture.
Ptotal = P1 + P2 + P3 + …………
4) Graham’ s Law of Diffusion: The rate of diffusion or effusion is inversely proportional to
the square root of molar mass.
1
Rate of diffusion 
√M
5) Avogadro’s Hypothesis: Avogadro hypothesised that equal volumes of all gases under the
same conditions of temperature and pressure contain equal number of molecules.
Vn
21 Explain the below:
1) Critical temperature (Tc): It is defined as the temperature above which it cannot be
liquefied at any pressure.
2) Critical pressure (Pc): It is defined as the minimum pressure required to liquefy 1 mole of a
gas at its critical temperature.
3) Critical volume (Vc): It is defined as the volume occupied by 1 mole of a gas at its critical
temperature and critical pressure.
4) Boyle temperature: The temperature at which a real gas obeys ideal gas law over an
appreciable range of pressure is called Boyle temperature or Boyle point.
22 Define the below:
1) Joule-Thomson effect (Jun-23): The phenomenon of lowering of temperature when a gas
is made to expand adiabatically from a region of high pressure into a region of low pressure is
known as Joule- Thomson effect.
2) Inversion temperature (Ti) (Jun-19): The temperature below which a gas obeys Joule-
Thomson effect is called inversion temperature (Ti). This value is given using van der waals
2a
constants a and b. Ti =
Rb

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
23 Give the significance of van der Waals constants?
• Van der waal's constant ‘a’ is a measure of the attractive force between gas molecules. As
the value of ‘a’ increases, the force of attraction between the molecules increases.
• Van der waals constant ‘b’ is the measure of volume of a gas. Its value is the exact volume
of 4 times of a molecule (b = 4 Vm). It is assigned as excluded volume of a molecule.
24 H2 And He gases are not liquefied using high pressure at room temperature. Why?
H2 and He gases have critical temperature values lower than room temperature.
Therefore, the Joule Thomson effect can be used for effective cooling.
25 Differentiate ideal and real gases?
Ideal gas Real gas
Ideal gases obey the gas law Real gases only obey at low
under all conditions of temperature and pressure and high temperature
pressure
No gas is ideal. All gases are real gases.
The volume occupied by the gas The volume occupied by the gas is
is very small compare to the not small compare to the total volume of the
total volume of the gas gas
There is no force of attraction There is a force of attraction
between the gas molecules between the gas molecules
They obey Ideal gas equation They obey the Van der waals
(PV=nRT) an2
equation. (P + 2 ) (V - nb) = nRT
V
Z=1 Z1
26 What is compressibility factor(Z) (Sep-20)? How does it relate with ideal gas volume and
real gas volume?
The deviation of real gases from ideal behaviour is measured in terms of a ratio of PV to
PV
nRT. This is termed as compressibility factor. Mathematically, Z =
nRT
PVreal
For real gases it can be rewritten as, Z = ……….(1)
nRT
nRT
For ideal gases Videal = ……….(2)
P
Comparing equations (1) and (2),
Vreal
Z=
Videal
Here, Vreal = molar volume of real gases
Videal = molar volume of ideal gases
27 Explain Pressure-Volume isotherms of Carbon dioxide using Andrew's isotherm?
• Thomas Andrew gave the first complete data on pressure-volume- temperature of a
substance in the gaseous and liquid states. He plotted isotherms of carbon dioxide at
different temperatures, from the plots we can infer the following.
• At low temperature isotherms, for example, at 13°C as the pressure increases, the volume
decreases along AB and is a gas until the point B is reached. At B, a liquid separates along
the line BC, both the liquid and gas co-exist and the pressure remains constant. At C, the
gas is completely converted into liquid. If the pressure is higher than at C, only the liquid is
compressed so, there is no significant change in the volume.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933

• The successive isotherms show similar trend with the shorter flat region. i.e. The volume
range in which the liquid and gas coexist becomes shorter. At the temperature of 31.1°C
the length of the shorter portion is reduced to zero at point P. In other words, the CO 2 gas
is liquefied completely at this point. This temperature is known as the liquefaction
temperature or critical temperature of CO2.
• At this point the pressure is 73 atm. Above this temperature CO2 remains as a gas at all
pressure values.
28 What are the methods used for liquefaction of gases? (Sep-20, Jun-23)
1) In Linde’s method, Joule-Thomson effect is used to get liquid air or any other gas.
2) In Claude’s process, the gas is allowed to perform mechanical work in addition to Joule-
Thomson effect so that more cooling is produced.
3) In Adiabatic process, cooling is produced by removing the magnetic property of magnetic
material such as gadolinium sulphate. By this method, a temperature of 10 -4 K
i.e. as low as 0 K can be achieved.
29 State and explain Dalton’s law of partial pressures?
• The total pressure of a mixture of non-reacting gases is the sum of partial pressures of the
gases present in the mixture.
• The partial pressure of a component gas is the pressure that it would exert if it were
present alone in the same volume and temperature. This is known as dalton’s law of partial
pressures.
• For a mixture containing three gases 1, 2 and 3 with partial pressures p 1, p2 and p3 in a
container with volume V, the total pressure Ptotal will be given by,
Ptotal = p1 + p2 + p3
• Assuming that the gases behave ideally,
RT RT RT
P1 = n 1 ; P2 = n 2 ; P3 = n 3 ;
V V V
RT RT RT
Ptotal = n1 + n2 + n3
V V V
RT
= ( n1 + n 2 + n3 )
V
RT
Ptotal = ntotal
V

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
30 The transition temperatures of H2O, NH3 and CO2 are 647.4K, 405.5K and 304.2K
respectively. When we perform cooling from 700K temperature, find out which turns
into liquid first and which turns into liquid last?
• The temperature above which a gas cannot be liquefied at high pressure is called transition
temperature.
• Water first liquefies when cooled from a temperature of 700K. It is followed by ammonia
and finally carbon dioxide.
31 why do all passenger aeroplane cabins have to be artificially pressurised?
• Most commercial aeroplanes fly at about 30,000 feet altitude. The pressure decreases with
the increase in altitude as there are fewer molecules per unit volume of air.
• Hence, while at air, the pressure around the aeroplane will be so low that one could pass
out for lack of oxygen.
• For this reason, aeroplanes cabins are artificially pressurized.
32 Why does a mountaineer feel a slight pain in his ears?
• The effect of drop in pressure is felt as a little pain in the ears by a person while ascending
a mountain in a plain.
• Though the external pressure drops, the internal pressure within the ear cavities remains
the same. This creates an imbalance.
• The greater internal pressure forces the eardrum to bulge outward causing pain.
• The excess air within the ear cavities escapes after some time and with the help of yawning
and thereby equalizing the internal and external pressure to relieve the pain.
33 Derive the ideal gas equation? (June 2019 & April 2022)
1
Boyle’s law: V∝
P

Charles law: VT

Avogadro law: V  n
By combining above equations,
nT
V∝
P
nRT
V=
P

PV = nRT

This is called as ideal gas equation

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
7. THERMODYNAMICS
1 State the first law of thermodynamics. (Sep-21)
The first law of thermodynamics, known as the law of conservation of energy, states that
"Energy can neither be created nor destroyed, but may be converted from one form to
another".
2 Define Hess's law of constant heat summation. (Sep-21, Mar-24)
According to Hess’s law, the enthalpy change of a reaction either at constant volume or
constant pressure is the same whether it takes place in a single or multiple steps provided the
initial and final states are same.
3 Explain intensive properties with two examples. (Sep-20, Jun-23)
The property that is independent of the mass or the size of the system is called an
intensive property. Examples: Refractive index, Surface tension, density, temperature, Boiling
point, Freezing point, molar volume, etc.,

Explain extensive properties with two examples.

The property that depends on the mass or the size of the system is called an extensive
property. Examples: Volume, Number of moles, Mass, Internal energy, etc.,
4 Define the following terms:
a. isothermal process
An isothermal process is defined as one in which the temperature of the system remains
constant, during the change from its initial to final state. The system exchanges heat with its
surrounding and the temperature of the system remains constant. dT = 0
b. adiabatic process
An adiabatic process is defined as one in which there is no exchange of heat (q) between
the system and surrounding during the process. This condition is attained by thermally
insulating the system. q = 0
c. isobaric process
An isobaric process is defined as one in which the pressure of the system remains
constant during its change from the initial to final state. dP = 0
d. isochoric process
An isochoric process is defined as the one in which the volume of system remains
constant during its change from initial to final state. dV = 0
5 What is the usual definition of entropy? What is the unit of entropy? (Jul-22)
Entropy is a measure of the molecular disorder (randomness) of a system.
dqrev
ds = ; SI unit = JK-1
T
6 Predict the feasibility of a reaction when
i) both ΔH and ΔS positive
Both ΔH and ΔS positive means reaction is spontaneous at high temperature, i.e, ΔG
becomes negative at high temperature only.
ii) both ΔH and ΔS negative
Both ΔH and ΔS negative means reaction is spontaneous at low temperature, i.e, ΔG
becomes negative at low temperature only.
iii) ΔH decreases but ΔS increases
ΔH decreases but ΔS increases means reaction is spontaneous at all temperatures, i.e,
ΔG is negative at all temperatures.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
7 Define is Gibb’s free energy. (Jul-22)
It is defined as the “available energy” to do work in a system.
G = H - TS
G = Gibb’s energy, H = Enthalpy T = Temperature S = Entropy
8 Define enthalpy of combustion.
It is defined as “The change in enthalpy of a system when one mole of the substance is
completely burnt in excess of air or oxygen”. It is denoted by ΔHC
9 Define molar heat capacity. Give its unit. (Jun-19)
It is defined as “The amount of heat absorbed by one mole of the substance to raise its
temperature by 1 kelvin”. SI unit: JK-1 mol-1
10 Define the calorific value of food. What is the unit of calorific value?
The calorific value is defined as the amount of heat produced in calories (or joules) when
one gram of the substance is completely burnt. SI unit: JKg-1, However, it is usually expressed
in Cal g-1.
11 Define enthalpy of neutralization.
It is defined as “The change in enthalpy when one gram equivalent of an acid is
completely neutralised by one gram equivalent of a base or vice versa in dilute solution”.
12 What is lattice energy?
Lattice energy is defined as the amount of energy required to completely remove the
constituent ions from its crystal lattice to an infinite distance from one mole of crystal.
13 What are state and path functions? Give two examples.
• State function (Mar-23): A thermodynamic system can be defined by using the variables P,
V, T and `n'.
• A state function is a thermodynamic property of a system
• which has a specific value for a given state and does not depend on the path (or manner)
by which the particular state is reached.
• Example: Pressure (P), Volume (V), Temperature(T), Internal energy (U), Enthalpy (H),
free energy (G) etc.

❖ Path functions (Jul-22, Mar-23):

❖ A path function is a thermodynamic property of the system.
❖ whose value depends on the path by which the system changes from its initial to final
states.
❖ Example: Work (w), Heat (q).
14 Give Kelvin statement of second law of thermodynamics.
Kelvin-Planck statement: It is impossible to construct a machine that absorbs heat from a hot
source and converts it completely into work by a cyclic process without transferring a part of
heat to a cold sink.
15 The equilibrium constant of a reaction is 10, what will be the sign of ΔG? Will this
reaction be spontaneous?
ΔG = - 2.303 RT log K
= - 2.303 RT log (10) ( log 10 = 1)
ΔG = - 2.303 RT
ΔG is negative. So the reaction will be spontaneous.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
16 Enthalpy of neutralization is always a constant when a strong acid is neutralized by a
strong base: account for the statement.
The reason for this can be explained on the basis of Arrhenius theory of acids and bases
which states that strong acids and strong bases completely ionise in aqueous solution to
produce H+ and OH- ions respectively.
H+(aq) + OH-(aq) H2O(l) ΔH = -57.32 KJ
The value does not changes depending on the nature of acid or base used.
17 State the third law of thermodynamics. (Mar-19)
• The entropy of pure crystalline substance at absolute zero is zero.
• it can also be stated as it is impossible to lower the temperature of an object to absolute
zero in a finite number of steps.
• Mathematically, lim S = 0 for a perfectly ordered crystalline state.
T→0
18 Write down the Born-Haber cycle for the formation of CaCl2?
Born-Haber cycle for the formation of CaCl2
ΔHf ΔH1 = Heat of Sublimation of Ca(S)
Ca(S) + Cl2(g) → CaCl2(s) ΔH2 = Dissociation Energy of Cl2(g)
ΔH3 = Ionisation Energy of Ca(g)
ΔH2 ΔH5
ΔH4 = Electron Affinity of Cl(g)
ΔH4
ΔH1 -
2Cl(g) + 2e → -
2Cl (g) ΔH5= Lattice Energy of CaCl2
+ ΔHf = Heat of Formation of CaCl2
Ca(g) →
ΔH3
Ca2+ + 2e- ΔHf = ΔH1 + ΔH2 + ΔH3 + ΔH4 + ΔH5

19 Identify the state and path functions out of the following:

a) Enthalpy b) Entropy c) Heat d) Temperature e) Work f) Free energy.
State functions Path functions
1. Enthalpy 1. Heat
2. Entropy 2. Work
3. Temperature
4. Free energy
20 State the various statements of second law of thermodynamics. (Mar-23)
1. Entropy statement: The entropy of an isolated system increases during a spontaneous
process.
• Entropy is a measure of the molecular disorder (randomness) of a system.
2. Kelvin-Planck statement: It is impossible to construct a machine that absorbs heat from
a hot source and converts it completely into work by a cyclic process without transferring a part
of heat to a cold sink.
3. Clausius statement: It is impossible to transfer heat from a cold reservoir to a hot
reservoir without doing some work.

4. Efficiency:
work performed TC
Efficiency = ; Efficiency = [1 − ] X 100
heat absorbed Th
21 Write Zeroth law of thermodynamics? (Sep-20)
The law states that `If two systems are separately in thermal equilibrium with a third one,
then they tend to be in thermal equilibrium with themselves'.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
22 What are spontaneous reactions? What are the conditions for the spontaneity of a
process? (May-22)
A reaction that occurs under the given set of conditions without any external driving force
is called a spontaneous reaction.
Criteria for spontaneity of a process:
If the enthalpy change of a process is negative, then the process is exothermic and may be
spontaneous. (ΔH < 0)
If the entropy change of a process is positive, then the process may occur spontaneously.
(ΔS > 0)
The Gibbs free energy should be negative. (ΔG < 0)
23 Define cyclic process?
When a system returns to its original state after completing a series of changes, then it is
said that a cycle is completed. This process is known as a cyclic process.
For a cyclic process dU = 0, dH = 0, dP=0, dV=0, dT=0
24 List the characteristics of internal energy. (May-22, Mar-24)
• The internal energy of a system is an extensive property.
• The internal energy of a system is a state function.
• The change in internal energy of a system is expressed as ΔU = Uf - Ui
• In a cyclic process, there is no internal energy change. (ΔUcyclic = 0)
• If Uf < Ui, then ΔU would be negative.
• If Uf > Ui, then ΔU would be positive.
25 Derive the relation between Cp and Cv for an ideal gas.
∂H ∂U
As we know, CP = ( ) and CV = (∂T)
∂T P V
From the definition of enthalpy, H = U + PV ………. (1)
for 1 mole of an ideal gas, PV = nRT ………. (2)
By substituting eqn. (2) in eqn. (1), H = U + nRT ………. (3)
Differentiating the above equation with respect to T,
∂H ∂U ∂T
= + nR ∂H
ஃ ( ∂T ) = CP
∂T ∂T ∂T P
∂U
CP = CV + nR(1) ஃ ( )
∂T V
= CV
CP - CV = nR
26 List the characteristics of Gibbs free energy. (Sep-21)
1. G = H - TS; where H, S are state functuons so G is also a state function.
2. Gibbs free energy (G) is an extensive property
3. G has a single value for the thermodynamic state of the function.
4. ΔG < 0 (or) ΔG = negative value - spontaneous process
ΔG > 0 (or) ΔG = positive value – non-spontaneous process
ΔG = 0 equilibrium process.
5. – ΔG = W – PΔV
Here, −PΔV represents the work done due to expansion against a constant external
pressure. Therefore, it is clear that the decrease in free energy (–ΔG) accompanying a
process taking place at constant temperature and pressure is equal to the maximum work
obtainable from the system other than the work of expansion.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
27 Explain how heat absorbed at constant volume is measured using bomb calorimeter
with a neat diagram.
• For chemical reactions, heat evolved at constant volume, is measured in a bomb
calorimeter.
• The inner vessel (the bomb) and its cover are made of strong steel. The cover is fitted
tightly to the vessel by means of metal lid and screws.
• A weighed amount of the substance is taken in a platinum cup connected with electrical
wires for striking an arc instantly to kindle combustion.
• The bomb is then tightly closed and pressurized with excess oxygen. The bomb is
immersed in water, in the inner volume of the calorimeter.
• A stirrer is placed in the space between the wall of the
calorimeter and the bomb, so that water can be stirred,
uniformly. The reaction is started by striking the
substance through electrical heating.
• A known amount of combustible substance is burnt in
oxygen in the bomb. Heat evolved during the reaction is
absorbed by the calorimeter as well as the water in
which the bomb is immersed. The change in
temperature is measured using a Beckman
thermometer.
• Since the bomb is sealed its volume does not change
and hence the heat measurements is equal to the heat
of combustion at a constant volume (ΔUC°).
• The amount of heat produced in the reaction (ΔUC°) is
equal to the sum of the heat abosrbed by the calorimeter
and water.
• Heat absorbed by the calorimeter, q1 = k.ΔT
• where k is a calorimeter constant equal to mC CC (mc is
mass of the calorimeter and Cc is heat capacity of
calorimeter)
• Heat absorbed by the water, q2 = mW CW ΔT
• where mw is molar mass of water
• Cw is molar heat capacity of water (75.29 JK-1 mol-1)
• Therefore UC = q1 + q2
= k. ΔT + mW CW ΔT
= (k + mW CW) ΔT
• Calorimeter constant can be determined by burning a known mass of standard sample
(benzoic acid) for which the heat of combustion is known (-3227 kJmol-1)
• The enthalpy of combustion at constant pressure of the substance is calculated from the
below equation
ΔHC°(pressure) = ΔUC° (Vol) + Δng RT
28 Calculate the work involved in expansion and compression process.
Let us consider a cylinder which contains 'n' moles of an ideal gas fitted with a frictionless
piston of cross-sectional area A. The total volume of the gas inside is Vi and pressure of the
gas inside is Pint.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
If the external pressure Pext is greater than Pint, the piston moves inward till the pressure
inside becomes equal to Pext. Let this change be achieved in a single step and the final volume
be Vf.
In this case, the work is done on the system (+w). It can be
calculated as follows
w = - F.Δx ………. (1)
where Δx is the distance moved by the piston during the
compression and F is the force acting on the gas.
F = Pext A ………. (2)
Substituting eqn. (2) in eqn. (1)
w = - Pext. A. Δx
A.Δx = change in volume = Vf - Vi
w = - Pext. (Vf – Vi) ………. (3)
w = - Pext ( - ΔV) ………. (4)
w = Pext .ΔV
Since work is done on the system, it is a positive quantity.
If the pressure is not constant, but changes during the process such that it is always
infinitesimally greater than the pressure of the gas, then, at each stage of compression, the
volume decreases by an infinitesimal amount, dV. In such a case we can calculate the work
V
done on the gas by the relation wrev = - ∫V f Pext dV
i
In a compression process, Pext the external pressure is always greater than the pressure
of the system. Pext = (Pint + dP)
In an expansion process, the external pressure is always less than the pressure of the system
Pext = (Pint - dP)
When pressure is not constant and changes in
infinitesimally small steps (reversible conditions) during
compression from Vi to Vf, the P-V plot looks like in figure. Work
done on the gas is represented by the shaded area.
In general case we can write, Pext = (Pint  dP). Such processes
are called reversible processes. For a compression process
work can be related to internal pressure of the system under
reversible conditions by writing equation
V
wrev = - ∫V f Pint dV
i
For a given system with an ideal gas,
Pint V = nRT
nRT
Pint = V
𝑉𝑓 nRT
Wrev = - ∫𝑉 dV
𝑖 V
Vf dV
Wrev = - nRT ∫V ( )
i V
Vf
Wrev = - nRT ln ( )
VI

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
Vf
Wrev = - 2.303 nRT log ( )
VI

If Vf >Vi (expansion), the sign of work done by the process is negative.

If Vf <Vi (compression) the sign of work done on the process is positive.
29 Derive the relation between ΔH and ΔU for an ideal gas. Explain each term involved in
the equation. (Sep-20, Jun-23)
Consider a closed system of gases which are chemically reacting to form gaseous
products at constant temperature and pressure with Vi and Vf as the total volumes of the
reactant and product gases respectively, and ni and nf as the number of moles of gaseous
reactants and products, then, For reactants (initial state),
PVi = ni RT ………. (1)
For products (final state),
PVf = nf RT ………. (2)
eqn. (2) - eqn. (1),
P (Vf – Vi) = (nf – ni) RT
PΔV = Δng RT ………. (3)
As we know, ΔH = ΔU + PΔV ………. (4)
Substituting eqn. (3) in eqn. (4),
ΔH = ΔU + Δng RT ………. (5)
30 Suggest and explain an indirect method to calculate lattice enthalpy of sodium chloride
crystal.
• Let us use the Born - Haber cycle for determining the lattice enthalpy of NaCl as follows.
• Since the reaction is carried out with reactants in elemental forms and products in their
standard states, at 1 bar, the overall enthalpy change of the reaction is also the enthalpy of
formation for NaCl.
• Also, the formation of NaCl can be considered in 5 steps.
• The sum of the enthalpy changes of these steps is equal to the enthalpy change for the
overall reaction from which the lattice enthalpy of NaCl is calculated.
• Let us calculate the lattice energy of sodium chloride using Born-Haber cycle

1 ΔHf
Na(S) + Cl2(g) → NaCl(s)
2

ΔH1 ΔH3 U
ΔH4
Cl(g) → Cl-(g)
+
ΔH2
Na(g) → Na+(g)
ΔHf = heat of formation of sodium chloride = – 411.3 kJ mol–1
ΔH1 = heat of sublimation of Na(g) = 108.7 kJ mol–1
ΔH2 = ionisation energy of Na(g) = 495.0 kJ mol–1
ΔH3 = dissociation energy of Cl2(g) = 244 kJ mol–1
ΔH4 = Electron affinity of Cl(S)= – 349.0 kJ mol–1
U = lattice energy of NaCl
1
ΔHf = ΔH1 + ΔH2 + ΔH3 + ΔH4 + U
2

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
1
U = (ΔHf) – (ΔH1 + ΔH2 + ΔH3 + ΔH4)
2
U = (- 411.3) – (108.7 + 495.0 + 122 - 349)
U = (- 411.3) – (376.7)
U = - 788 kJ mol-1
This negative sign in lattice energy indicates that the energy is released when sodium is
formed from its constituent gaseous ions Na+ and Cl-.
31 How do you measure the heat change at constant pressure using a coffee cup
calorimeter?
Instead of bomb, a Styrofoam cup is used in this calorimeter. It acts as good adiabatic
wall and doesn't allow transfer of heat produced during the reaction to its surrounding. This
entire heat energy is absorbed by the water inside the cup. This method can be used for the
reactions where there is no appreciable change in volume. The change in the temperature of
water is measured and used to calculate the amount of heat that has been absorbed or
evolved in the reaction using the following expression.
q = mW CW ΔT
where mW is the molar mass of water and CW is the molar heat capacity of water (75.29 J K-1
mol-1.)

8. PHYSICAL AND CHEMICAL EQUILIBRIUM

1 If there is no change in concentration, why is the equilibrium state considered
dynamic?
• Chemical reactions which are reversible do not cease, when equilibrium is attained.
• At equilibrium the forward and the backward reactions are proceeding at the same rate and
no macroscopic change is observed.
• So chemical equilibrium is in a state of dynamic equilibrium.
2 For a given reaction at a particular temperature, the equilibrium constant has constant
value. Is the value of Q also constant? Explain.
• As the reaction proceeds, there is a continuous change in the concentration of reactants
and products and also the Q value until the reaction reaches the equilibrium.
• At equilibrium Q is equal to Kc at a particular temperature.
• Once the equilibrium is attained, there is no change in the Q value.
3 What is the relation between KP and KC. Give one example for which KP is equal to KC.
KP = KC (RT)Δng
Δng = (nP – nr)
If nP = nr Δng = 0, so, KP = KC
Eg. H2(g) + I2(g) ⇌ 2HI(g)
Δng = 2 – 2 = 0, so, KP = KC
4 When the numerical value of the reaction quotient (Q) is greater than the equilibrium
constant (K), in which direction does the reaction proceed to reach equilibrium?

If Q > Kc, the reaction will proceed in the reverse direction i.e., formation of reactants.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
5 For a gaseous homogeneous reaction at equilibrium, number of moles of products are
greater than the number of moles of reactants. Is KC is larger or smaller than KP.
For a gaseous homogeneous reaction at equilibrium, if the number of moles of products
are greater than the number of moles of reactants, KC will be smaller than KP.
Eg. PCl5(g) ⇋ PCl3(g) + Cl2(g)
Δng = 2 – 1 = 1,
so, KP = KC (RT)1

ஃ KP > K C
6 For the reaction, A2(g) + B2(g) ⇌ 2AB(g) ; ΔH - is –ve. the following molecular scenes
represent different reaction mixture (A – green, B – blue)

i) Calculate the equilibrium constant KP and KC.

4 2
[AB]2 [V] 16
KC = = 2 2 = =4
[A2 ][B2 ] [V][V] 4

⇒ KP = KC (RT)Δng
KP = 4 (RT)0 = 4
ii) For the reaction mixture represented by scene (x), (y) the reaction proceeds in which
directions?
6 2
[AB]2 [ ] 36
V
i) At stage ‘x’: Q= = 2 1 = = 18
[A2 ][B2 ] [ ][ ] 2
V V
KC = 4, Q = 18, ஃ Q > KC So, the reaction will proceed in the reverse direction.
3 2
[AB]2 [ ] 9
V
ii) At stage ‘y’: Q= = 3 3 = =1
[A2 ][B2 ] [ ][ ] 9
V V
KC = 4, Q = 1, ஃ Q < KC So, the reaction will proceed in the forward direction.
iii) What is the effect of increase in pressure for the mixture at equilibrium.
At equilibrium nP = nr = 2; ஃ Δng = 2 – 2 = 0 So, the pressure does not affect the reaction.
7 State Le-Chatelier principle. (Mar-19, Mar-23)
It states that “If a system at equilibrium is disturbed, then the system shifts itself in a
direction that nullifies the effect of that disturbance.”
8 State law of mass action. (Mar-23)
“At any instant, the rate of a chemical reaction at a given temperature is directly
proportional to the product of the active masses of the reactants at that instant”.
Rate  [Reactant]x
where, x is the stoichiometric coefficient of the reactant and the square bracket represents the
active mass (concentration) of the reactants.
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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
9 Consider the following reactions,
a) H2(g) +I2(g) ⇋ 2 HI
b) CaCO3(s) ⇋ CaO(s) + CO2(g)
c) S(s) + 3F2(g) ⇋ SF6(g)
In each of the above reaction find out whether you have to increase (or) decrease the
volume to increase the yield of the product.
a) Δng = 2 – 2 = 0; So, there is no effect on changing the volume.
b) Δng = 2 – 1 = 1; Δng = +ve So, the increase in volume, favours the forward reaction to
increase the yield of the product.
c) Δng = 1 – 4 = -3; Δng = -ve So, the decrease in volume, favours the forward reaction to
increase the yield of the product.
10 Explain how will you predict the direction of an equilibrium reaction.
The direction of the reaction can be predicted by comparing Q with K C.
• If Q = KC, the reaction is in equilibrium state.
• If Q > KC, the reaction will proceed in the reverse direction i.e., formation of reactants.
• If Q < KC, the reaction will proceed in the forward direction i.e., formation of products.
11 Derive a general expression for the equilibrium constant KP and KC for the reaction
3H2(g) + N2(g) ⇌ 2NH3(g). (Jul-22)
N2 H2 NH3
Initial number of moles a b 0
Number of moles reacted x 3x 0
Number of moles at equilibrium a-x b - 3x 2x
Molar concentration at equilibrium a−x b − 3x 2x
v v v
Applying law of mass action,
2x 2
[NH3 ]2 (V)
KC = =
[N2 ] [H2 ]3 a−x b −3x 3
( V )( V )

4x2
( 2)
V
=
a−x b −3x 3
( V )( V )

4x2 V2
KC =
(a−x)(b−3x)3

The equilibrium constant Kp can also be calculated as follows:

KP = KC (RT) Δng
Here, Δng = nP – nr = 2 – 4 = -2
4x2 V2
KP = (RT) -2
(a−x)(b−3x)3

Total number of moles at equilibrium,

n = a – x + b – 3x + 2x = a + b – 2x
4x2 V2 PV −2
KP =
(a−x)(b−3x)3
x[ ]
n

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
4x2 V2 n 2
KP =
(a−x)(b−3x)3
x[ ]
PV

4x2 V2 a + b – 2x 2
KP =
(a−x)(b−3x)3
x[ ]
PV

4x2 V2 (a+b-2x)2
KP = x
(a−x)(b−3x)3 p2 v 2
4x2 (a+b−2x)2
KP =
P2 (a−x)(b−3x)3

12 Write a balanced chemical equation for the equilibrium reaction for which the
[𝐍𝐇𝟑 ]𝟒 [𝐎𝟐 ]𝟓
equilibrium constant is given by expression KC = .
[𝐍𝐎]𝟒 [𝐇𝟐 𝐎]𝟔
4NO + 6H2O ⇌ 4NH3 + 5O2
13 What is the effect of added inert gas on the reaction at equilibrium at constant volume.
(Jun-19)
• When an inert gas is added to an equilibrium system at constant volume, the total number
of moles of gases present in the container increases, that is, the total pressure of gases
increases.
• The partial pressure of the reactants and the products are unchanged.
• Hence at constant volume, addition of inert gas has no effect on equilibrium.
14 Derive the relation between KP and KC. (Jun-19, Sep-21)
Let us consider the general reaction in which all reactants and products are ideal gases.
xA + yB ⇋ lC + mD
The equilibrium constant, Kc is
[C]𝑙 [D]m
KC = ………. (1)
[A]x [B]y

and Kp is,
PlC x Pm
D
KP = y ………. (2)
PxA x PB

The ideal gas equation is,

n
PV = nRT (or) P= RT
V
Since, Active mass = molar concentration = n/V
P = active mass × (RT)
PAx = [A]X (RT)x
y
PB = [B]y (RT)y
PC𝑙 = [C]l (RT)l
PDm = [D]m (RT)m
On substitution in Eqn. 2,
[C]𝑙 [𝑅𝑇]𝑙 [D]m [𝑅𝑇]𝑚
KP = ………. (3)
[A]x [𝑅𝑇]𝑥 [B]y [𝑅𝑇]𝑦

[C]𝑙 [D]m (𝑅𝑇)𝑙+𝑚

KP =
[A]x [B]y (𝑅𝑇)𝑥+𝑦

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
[C]𝑙 [D]m
KP = (RT)(𝑙+m) −(x+y) ……. (4)
[A]x [B]y

By comparing equation (1) and (4), we get

KP = KC (RT)Δng
where, Δng is the difference between the sum of number of moles of products and the sum of
number of moles of reactants in the gas phase. The following relations become immediately
obvious. When Δng = 0
KP = KC (RT) 0
KP = K C
When Δng = +ve
KP = KC (RT)+ve
KP > K C
When Δng = - ve
KP = KC (RT)-ve
KP < K C
15 Deduce the Vant Hoff equation. (Mar-24)
This equation gives the quantitative temperature dependence of equilibrium constant (K).
The relation between standard free energy change (ΔG°) and equilibrium constant is
ΔG° = - RT lnK ………. (1)
ΔG° = ΔH° - TΔS° ………. (2)
Substituting (1) in equation (2)
- RT lnK = ΔH° - TΔS°
Rearranging,
−ΔH° ΔS°
ln K = + ………. (3)
RT R
Differentiating equation (3) with respect to temperature,
d(lnK) ΔH°
= ………. (4)
dT RT2
Equation (4) is known as differential form of van’t Hoff equation. On integrating the
equation 4, between T1 and T2 with their respective equilibrium constants K1 and K2.
K
2 ΔH° T2 dT
∫K d(ln K) = R
∫T T2
1 1

ΔH° 1 T2
[ln K]KK21 = [− ]
R T T1

ΔH° 1 1
ln K2 – ln K1 = [− + ]
R 𝑇2 𝑇1
K2 ΔH° T2 −T1
ln = [ ]
K1 R T2 T1
K2 ΔH° T2 −T1
log = [ ] ………. (5)
K1 2.303 R T2 T1

Equation 5 is known as integrated form of van’t Hoff equation.

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 Dr.R.Karthic M.Sc., B.Ed., M.A(Edu)., M.Phil., Ph.D. P.G Assistant, GHSS – vallipattu, 9943119933
16 Derive a general expression for the equilibrium constant KP and KC for the reaction
H2(g) + I2(g) ⇌ 2HI(g). (Mar-24)
H2 I2 HI
Initial number of moles a b 0
Number of moles reacted x x 0
Number of moles at equilibrium a-x b-x 2x
Molar concentration at equilibrium a − x b−x 2x
v v v
Applying law of mass action,
2x 2
[HI]2 (V) 4x 2 V2 4x2
KC = = a−x b−x = x KC =
[H2 ] [I2 ]
( V )( V ) v2 (a-x) (b-x) (a−x) (b−x)

The equilibrium constant Kp can also be calculated as follows:

KP = KC (RT) Δng
Here, Δng = nP – nr = 2 – 2 = 0
4x2
Hence, KP = K C KP =
(a−x) (b−x)

17 Derive a general expression for the equilibrium constant KP and KC for the reaction
PCl5(g) ⇌ PCl3(g) + Cl2(g)
PCl5 PCl3 Cl2
Initial number of moles a 0 0
Number of moles reacted x 0 0
Number of moles at equilibrium a-x x x
Molar concentration at equilibrium a−x x x
v v v
Applying law of mass action,
x x
[PCl3 ] [Cl2 ] (V )(V) x2 v
KC =
[PCl5 ]
= a−x = 2 x
( V ) v a-x
x2
KC =
(a−x) V
The equilibrium constant Kp can also be calculated as follows:
KP = KC (RT) Δng
Here, Δng = nP – nr = 2 – 1 = 1
Hence, KP = KC (RT)1
We know that, PV = nRT
PV
RT =
n
Where n is the total number of moles at equilibrium.
n = (a-x) + x + x = (a+x)
x2 PV
KP =
(a−x) V n
x2 PV
KP =
(a−x) V (a+x)

x2 P
KP =
(a−x) (a+x)

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18 What is Equilibrium constant?
At a given temperature, the ratio of the product of active masses of reaction products
raised to the respective stoichiometric coefficients in the balanced chemical equation to that of
the reactants is a constant, known as equilibrium constant.
[C]𝑙 [D]m
KC =
[A]x [B]y
19 What are the applications of equilibrium constant?
The knowledge of equilibrium constant helps us to,
1. predict the direction in which the net reaction will take place
2. predict the extent of the reaction and
3. calculate the equilibrium concentrations of the reactants and products.
20 Define reaction quotient? (Sep-20, Jul-22, Jun-23)
Under non-equilibrium conditions, reaction quotient ‘Q’ is defined as the ratio of the
product of active masses of reaction products raised to the respective stoichiometric
coefficients in the balanced chemical equation to that of the reactants.
[C]l [D]m non-equilibrium condition
Q=
[A]x [B]y non-equilibrium condition
21 What is the effect of added catalyst on the reaction at equilibrium.
• Addition of a catalyst does not affect the state of the equilibrium.
• The catalyst increases the rate of both the forward and the reverse reactions to the same
extent. Hence, it does not change the equilibrium composition of the reaction mixture.
• However, it speeds up the attainment of equilibrium by providing a new pathway having a
lower activation energy.
22 Using Le-Chatelier's Principle explain the effects of the following conditions at
equilibrium?
1) Effect of concentration: According to Le Chatelier’s principle, the effect of increase in
concentration of a substance will shift the equilibrium in a direction that consumes the added
substance. Eg: H2(g) + I2(g) ⇌ 2HI(g)
The addition of H2 or I2 to the equilibrium mixture, disturbs the equilibrium. To minimize
the stress, the system shifts the reaction in a direction where H2 and I2 are consumed.
2) Effect of pressure: The change in pressure has significant effect only on equilibrium
systems with gaseous components. When the pressure on the system is increased, the
volume decreases proportionately and the system responds by shifting the equilibrium in a
direction that has fewer moles of gaseous molecules.
Eg: 3H2(g) + N2(g) ⇌ 2NH3(g)
In this reaction, if we increase the pressure, the volume decreases. The system responds
to this effect by reducing the number of gas molecules. i.e. it favours the formation of ammonia
If we reduce the pressure, the volume increases. It favours the decomposition of ammonia
3) Effect of temperature: If the temperature of a system at equilibrium is changed, the system
will shif the equilibrium in the direction that attempts to nullify the effect of temperature.
Eg:
• In this equilibrium, the forward reaction is exothermic i.e. heat is liberated while the reverse
reaction is endothermic i.e. heat is absorbed.
• If the temperature is increased, the system responds by decomposing some of the
ammonia molecules to nitrogen and hydrogen by absorbing the supplied heat energy.
• Similarly, the system responds to a drop in the temperature by forming more ammonia
molecules from nitrogen and hydrogen, which releases heat energy.
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9. SOLUTIONS
1 Define molality? (Jun-23)
It is defined as the number of moles of the solute dissolved in 1 kilogram of the solvent.
Number of moles of the solute
Molality (m) =
Mass of the solvent (in kg)
2 Define molarity?
It is defined as the number of moles of the solute dissolved in 1 litre of the solution.
Number of moles of the solute
Molarity (M) =
Volume of solution (in L)
3 Define Normality?
It is defined as the number of gram equivalents of the solute present in 1 litre of the
solution.
Number of gram equivalents of solute
Normality (N) =
Volume of solution (in L)

4 Define mole fraction?

Number of moles of the component
Mole fraction (x) =
Total number of moles of all the components present in solution

5 Define formality?
It is defined as the number of formula mass of the solute present in 1 litre of the solution.
Number of Formula mass of solute
Normality (F) =
Volume of solution (in L)
6 What is a vapour pressure of liquid? What is relative lowering of vapour pressure? (Jun-
19)
• The pressure exerted by the vapours above the liquid surface which is in equilibrium with
the liquid at a given temperature is called vapour pressure of the liquid.
• The difference between the vapour pressure of pure solvent and the solution is called as
lowering of vapour pressure. ΔP = (P° - P)
• The relative lowering of vapour pressure is defined as the ratio of lowering of vapour
ΔP (P°-P)
pressure to the vapour pressure of pure solvent. =
P° P°
7 State and explain Henry’s law?
“The partial pressure of the gas in vapour phase (vapour pressure of the solute) is
directly proportional to the mole fraction(x) of the gaseous solute in the solution at low
concentrations”. This statement is known as henry’s law.
Psolute  Xsolute in solution
Psolute = KHXsolute in solution
Psolute = partial pressure of the gas in vapour state (vapour pressure)
KH = empirical constant with the dimensions of pressure
Xsolute in solution = mole fraction of solute in the solution
8 What are the limitations of Henry’s law?
• Henry’s law is applicable at moderate temperature and pressure only.
• Only the less soluble gases obey Henry’s law
• The gases reacting with the solvent do not obey Henry’s law. Eg: ammonia or HCl.
• The gases obeying Henry’s law should not associate or dissociate while dissolving in the
solvent.

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9 What is solubility of the solute?
Solubility of a solute is the maximum amount of solute that can be dissolved in a specific
amount of solvent at a specified temperature.
10 What is molal depression constant? Does it depend on nature of the solute?
The depression in freezing point is directly proportional to the molal concentration of the
solute particles.
Hence, ΔTf  m (or) ΔTf = Kf m
Here, ‘m’ = is the molality of the solution
Kf = molal freezing point depression constant or cryoscopic constant.
The Kf is equal to the depression in freezing point for 1 molal solution.
It depends on nature of the solute
11 State Raoult law (Mar-24) and obtain expression for lowering of vapour pressure when
non-volatile solute is dissolved in solvent.
Raoult’s law (Mar-24) = “In the case of a solution of volatile liquids, the partial vapour pressure
of each component of the solution is directly proportional to its mole fraction”.
Psolution  xA ………. (1) (Where xA is the mole fraction of the solvent)

Psolution = kxA ………. (2)

When xA = 1, K = Posolvent (Posolvent is the partial pressure of pure solvent)

Psolution = Posolvent xA ………. (3)
Psolution
= XA ………. (4)
Posolvent
subtract eqn (4) from one,
Psolution
1- = 1 - XA ………. (5) [XA + XB = 1
Posolvent
Posolvent − Psolution XB = 1 - XA]
= XB ………. (6)
Posolvent
P° - P ΔP
[ = = relative lowering of vapour pressure]
P° P°
Where xB is the mole fraction of the solute
Based on this expression, Raoult’s Law can also be stated as “the relative lowering of vapour
pressure of an ideal solution containing the non-volatile solute is equal to the mole fraction of
the solute at a given temperature”.
12 What is osmosis?
Osmosis is a spontaneous process by which the solvent molecules pass through a semi
permeable membrane from a solution of lower concentration to a solution of higher
concentration.
13 What is osmotic pressure? (Mar-23)
The pressure that must be applied to the solution to stop the influx of the solvent (to stop
osmosis) through the semipermeable membrane is called osmotic pressure.
14 Define the term ‘isotonic solution’? (Mar-19, May-22)
• Two solutions having same osmotic pressure at a given temperature are called isotonic
solutions.
• When such solutions are separated by a semipermeable membrane, solvent flow between
one to the other on either direction is same, i.e. the net solvent flow between the two
isotonic solutions is zero.
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15 Define the term ‘hypotonic solution’?
Too dilute solution of the two solutions separated by a semipermeable membrane is
called hypotonic solution.
16 Define the term ‘hypertonic solution’?
Too concentrated solution of the two solutions separated by a semipermeable membrane
is called hypertonic solution.
17 You are provided with a solid ‘A’ and three solutions of A dissolved in water - one
saturated, one unsaturated, and one super saturated. How would you determine which
solution is which?
The three solutions of the given solid ‘A’ can be determined by the following method.
Substance dissolved in
Solubility Type of solution
the given solution
Insoluble saturated
Large amount of solid ‘A’ Soluble unsaturated
Insoluble and precipitated super saturated
18 Explain the effect of pressure on the solubility.
• Generally, the change in pressure does not have any significant effect in the solubility of
solids and liquids as they are not compressible. However, the solubility of gases generally
increases with increase of pressure.
• Consider a saturated solution of a gaseous solute dissolved in a liquid solvent in a closed
container. In such a system, the following equilibrium exists.
Gas (in gaseous state) ⇆ Gas (in solution)
• According to Le-Chatelier principle, the increase in pressure will shift the equilibrium in the
direction which will reduce the pressure. Therefore, more number of gaseous molecules
dissolves in the solvent and the solubility increases.
19 What is standard solution or a stock solution? What are its advantages.
It is a solution whose concentration is accurately known.
Advantages:
• The error in weighing the solute can be minimised by using concentrated stock solution that
requires large quantity of solute.
• We can prepare working standards of different concentrations by diluting the stock solution,
which is more efficient since consistency is maintained.
• Some of the concentrated solutions are more stable and are less likely to support microbial
growth than working standards used in the experiments.
20 What is working standard?
The solution with required concentration is prepared by diluting the stock solution is
called as working standard.
21 What are colligative properties? (or) write four colligative properties? (Jun-23)
The properties that do not depend on the chemical nature of the solute but depends only
on the number of solute particles (ions/molecules) present in the solution is called as
colligative properties.
Eg: i) Relative lowering of vapour pressure
ii) Elevation of boiling point
iii) Depression in freezing point
iv) Osmotic pressure

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22 What is molal boiling point elevation?
Molal boiling point elevation is equal to the elevation in boiling point for 1 molal solution.
ΔTb = Kb m ; m=1
ஃ ΔTb = Kb
23 Define boiling point and freezing point?
• The boiling point of a liquid is the temperature at which its vapour pressure becomes equal
to the atmospheric pressure (1 atm).
• Freezing point is defined as “the temperature at which the solid and the liquid states of the
substance have the same vapour pressure”.
24 Define ideal (Sep-21, Jul-22) and non-ideal solutions?
• An ideal solution is a solution in which each component i.e. the solute as well as the
solvent obeys the Raoult’s law over the entire range of concentration.
• The solutions which do not obey Raoult’s law over the entire range of concentration, are
called non-ideal solutions.
25 Explain the factors which are responsible for the solutions get deviation from Raoult’s
law?
The deviation of solution from ideal behavior is attributed to the following factors.
i) Solute-solvent interactions: For an ideal solution, the interaction between the solvent
molecules (A-A), the solute molecules (B-B) and between the solvent & solute molecules (A-B)
are expected to be similar. If these interactions are dissimilar, then there will be a deviation
from ideal behavior.
ii) Dissociation of solute: When a solute present in a solution dissociates to give its
constituent ions, the resultant ions interact strongly with the solvent and cause deviation from
Raoult’s law.
iii) Association of solute: Association of solute molecules can also cause deviation from
ideal behaviour. For example, in solution, acetic acid exists as a dimer by forming
intermolecular hydrogen bonds, and hence deviates from Raoult’s law.
iv) Temperature: An increase in temperature of the solution increases the average kinetic
energy of the molecules present in the solution which causes decrease in the attractive force
between them. As a result, the solution deviates from ideal behaviour.
v) Pressure: At high pressure the molecules tend to stay close to each other and therefore
there will be an increase in their intermolecular attraction. Thus, a solution deviates from
Raoult’s law at high pressure.
vi) Concentration: If a solution is sufficiently dilute there is no pronounced solvent-solute
interaction because the number of solute molecules are very low compared to the solvent.
When the concentration is increased by adding solute, the solvent-solute interaction becomes
significant. This causes deviation from the Raoult’s law.
26 Prove elevation of boiling point is a colligative property? (Mar-22)
• The boiling point of a liquid is the temperature at which its vapour pressure becomes equal
to the atmospheric pressure (1 atm).
• When a non-volatile solute is added to a pure solvent at its boiling point, the vapour
pressure of the solution is lowered below 1 atm. To bring the vapour pressure again to 1
atm, the temperature of the solution has to be increased.
• As a result,the solution boils at a higher temperature (Tb) than the boiling point of the pure
solvent (Tb°).
• This increase in the boiling point is known as elevation of boiling point. ΔTb = Tb - T°b

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• The elevation of boiling point is directly proportional to the concentration of the solute
particles.
ΔTb  m ; m = molality
ΔTb = Kb m ; Kb = molal boiling point elevation constant
n2
ΔTb = Kb
W1 (𝐤𝐠)
W2
ΔTb = Kb
M2 W1 (𝐤𝐠)
• When a solute is dissolved in a pure solvent, evaporation of the solute molecules is
inhibited due to increased solvent-solute interactions and the vapor pressure of the solution
decreases. Hence its boiling point increases. So, the boiling point elevation is a colligative
property as it depends on the number of solutes.
27 Prove depression in freezing point is a colligative property? (Sep-21)
• The temperature at which the solid and the liquid states of the substance have the same
vapour pressure is called freezing point.
• At freezing point, the solid and liquid phases of the substance are in equilibrium.
• When a non-volatile solute is added to water at its freezing point, the freezing point of the
solution is lowered from 0 ˚c.
• The lowering of the freezing point of the solvent when a solute is added is called
depression in freezing point (ΔTf). ΔTf = T°f - Tf
• The depression in freezing point is directly proportional to the concentration of the solute
particles.
ΔTf  m ; m = molality
ΔTf = Kf m ; Kf = molal depression in freezing point
n2
ΔTf = Kf
W1 (𝐤𝐠)

W2
ΔTf = Kf
M2 W1 (𝐤𝐠)
•When a solute is dissolved in a pure solvent, evaporation of the solute molecules is
inhibited due to increased solvent-solute interactions and the vapor pressure of the solution
decreases. The attraction force between solvent - solute increases and freezes at lower
temperature. The freezing point of the solution decreases. Hence the freezing point is a
colligative property as it depends on the particle number of the solute.
28 Explain reverse osmosis?
• It can be defined as a process in which a solvent passes through a semipermeable
membrane in the opposite direction of osmosis, when subjected to a hydrostatic pressure
greater than the osmotic pressure is called reverse osmosis.
• Eg: The pure water moves through the semipermeable membrane to the NaCl solution due
to osmosis. This process can be reversed by applying pressure greater than the osmotic
pressure to the solution side. Now the pure water moves from the solution side to the
solvent side and this process is called reverse osmosis.
• Uses: Reverse osmosis is used in the desalination of sea water and also in the purification
of drinking water.
• There are different types of semipermeable membranes used in this process like, cellulose
acetate and polyamide membranes.
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29 Why the carbonated drinks show effervescence when opened?
• The carbonated beverages contain carbon dioxide dissolved in them. To dissolve the
carbon dioxide in these drinks, the CO2 gas is bubbled through them under high pressure.
• These containers are sealed to maintain the pressure. When we open these containers at
atmospheric pressure, the pressure of the CO2 drops to the atmospheric level and hence
bubbles of CO2 rapidly escape from the solution and show effervescence.
30 Write van’t Hoff equation and explain?
For dilute solutions, the osmotic pressure is directly proportional to the molar
concentration of the solute and the temperature of the solution.
 = CRT
Here, C = Concentration of the solution in molarity, T = Temperature and R = Gas constant
31 Define van’t Hoff factor?
It is defin;ed as the ratio of the actual molar mass to the abnormal (calculated) molar
mass of the solute.
Normal actual molar mass
i=
Observed abnormal molar mass
32 Explain how does the van’t Hoff factor value vareis for different solutes?
• For a solute that does not dissociate or associate the van’t Hoff factor is equal to 1 (i = 1)
and the molar mass will be close to the actual molar mass.
• For the solutes that associate to form higher oligomers in solution the van’t Hoff factor will be
less than one (i <1) and the observed molar mass will be greater than the actual molar mass.
• For solutes that dissociates into their constituent ions the van’t Hoff factor will be more than
one (i > 1) and the observed molar mass will be less than the normal molar mass.
33 Calculate the molality of the solution containing 90 g of glucose dissolved in 2 kg of
water?
No. of moles of solute 90/180
Molality = = = 0.25 m
Mass of the solvent (in Kg) 2

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10. CHEMICAL BONDING
1 Define the following
i) Bond order (Sep-21): The number of covalent bonds between the two combining atoms is
Nb - Na
called bond order. Bond order =
2
Where, Nb = Total number of electrons present in the bonding molecular orbitals
Na = Total number of electrons present in the antibonding molecular orbitals
ii) Hybridisation: It is the process of mixing of atomic orbitals of the same atom with
comparable energy to form equal number of new equivalent orbitals with same energy.
iii) σ- bond (Jun-23): When two atomic orbitals overlap linearly along the axis, the resultant
bond is called a sigma () bond.
2 What is a pi bond? (Jun-23, Mar-24)
When two atomic orbitals overlap sideways, the resultant covalent bond is called a pi
() bond.
3 In CH4, NH3 and H2O, the central atom undergoes sp3 hybridisation - yet their bond
angles are different. why?
Methane (CH4):
Tetrahedral
(AB4 type)

No lone pair (lp) electrons present in it. So, the bond angle is 109° 28’ (or) 109.5°.
Ammonia (NH3):
Pyramidal shape
(AB3L type)

Number of lone pair (lp) electrons = 1

lp – bp repulsive force exists. So, the bond angle is decreased to 107°
Water (H2O) :
Bent shaped - V Shaped
(AB2L2 type)

Number of lone pair (lp) electrons = 2

lp – lp and lp – bp repulsive force exists. So, the bond angle is decreased to 104.5°
4 Explain sp2 hybridisation in BF3? (Sep-20)
Electronic configuration of boron (Z = 5)
In ground state 1s2 2s2 2p1
↿⇂ ↿⇂ ↿

In excited state 1s2 2s1 2p2

↿⇂ ↿ ↿ ↿

sp2 hybridisation

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• In the ground state boron has only one unpaired electron in the valence shell.
• In order to form three covalent bonds with fluorine atoms, three unpaired electrons are
required.
• To achieve this, one of the paired electrons in the 2s orbital is promoted to the 2p orbital in
the excite state.
• In boron, the s orbital and two p orbitals in the valence shell hybridses, to generate three
equivalent sp2 orbitals
• The three sp2 hybridised orbitals of boron now overlap with the 2p orbitals of 3 fluorine
atoms along the axis to form 3 covalent bonds as shown in the figure.
5 What do you understand by Linear combination of atomic orbitals in MO theory.
• The wave functions for the molecular orbitals can be obtained by solving Schrödinger wave
equation for the molecule.
• Since solving the Schrödinger equation is too complex, approximation methods are used to
obtain the wave function for molecular orbitals. The most common method is the linear
combination of atomic orbitals (LCAO).
• The atomic orbitals are represented by the wave function .
• Let us consider two atomic orbitals represented by the wave function A and B with
comparable energy, combines to form two molecular orbitals.
•  bonding = A +  A
•  antibonding = A - A
6 Draw the M.O diagram for oxygen molecule calculate its bond order and show that O2 is
paramagnetic. (Jun-19, Jul-22)

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Electronic configuration of Oxygen atom = 1s2 2s2 2p4
Electronic configuration of O2 molecule = σ21s , σ*2 2 *2 2 2 2 *1 *1
1s , σ2s , σ2s , σ2px , π2py , π2pz , π2py , π2pz

Nb - Na 10 - 6
Bond order = = = 2.
2 2
O2 Molecule has two unpaired electrons. Hence, it is paramagnetic.
7 Draw MO diagram of CO and calculate its bond order.

Electronic configuration of Carbon atom = 1s2 2s2 2p2

Electronic configuration of Oxygen atom = 1s2 2s2 2p4
Electronic configuration of CO molecule = σ21s , σ*2 2 *2 2 2 2
1s , σ2s , σ2s , π2py , π2pz , σ2px

Nb - Na 10 - 4
Bond order = = = 3.
2 2
Molecule has no unpaired electrons. Hence, it is diamagnetic.
8 Discuss the formation of N2 molecule using MO Theory? (Jun-23, Mar-24)

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Electronic configuration of Nitrogen atom = 1s2 2s2 2p3
Electronic configuration of N2 molecule = σ21s , σ*2 2 *2 2 2 2
1s , σ2s , σ2s , π2py , π2pz , σ2px

Nb - Na 10 - 4
Bond order = = = 3.
2 2
Molecule has no unpaired electrons. Hence, it is diamagnetic.
9 What is dipolemoment?
The polarity of a covalent bond can be measured in terms of dipole moment which is
defined as  = q x 2d
Where, μ is the dipole moment,
q is the charge and
2d is the distance between the two charges.
• The dipole moment is a vector
• The direction of dipole moment vector points from the negative charge to positive charge.
• The unit for dipole moment is columb meter (Cm).
10 Linear form of carbondioxide molecule has two polar bonds. Yet the molecule has Zero
dipolement why? (Jun-19)
In CO2, the dipole moments of two polar bonds (CO) are equal in magnitude but have
opposite direction.

Hence, the net dipole moment of the CO2 = 0

In this case,

11 Draw the Lewis structures for the following species.

i) NO3- : ii) SO42- : iii) HNO3 (Mar-23) : iv) O3 :
Nitrate ion Sulphate ion Nitric acid Ozone

12 Explain the bond formation in BeCl2 and MgCl2.

Bond formation in BeCl2:
Electronic configuration of beryllium (Z = 4)
In ground state 1s2 2s2 2p0
↿⇂ ↿⇂

In excited state 1s2 2s1 2p1

↿⇂ ↿ ↿

sp hybridisation
Each sp hybridized orbital of beryllium linearly overlap with 3p orbital of the chlorine to form a
covalent bond.
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Bond formation in MgCl2:
Electronic configuration of Magnesium (Z = 4)
In ground state 3s2 3p0
↿⇂

In excited state 3s1 3p1

↿ ↿

sp hybridisation
Each sp hybridized orbital of magnesium linearly overlap with 3p orbital of the chlorine to form
a covalent bond.
13 Which bond is stronger  or ? Why?
• When two atomic orbitals overlap linearly along the axis, the resultant bond is called a
sigma () bond and when two atomic orbitals overlap sideways, the resultant covalent bond
is called a pi ()bond.
• sigma () bond is stronger between these two bonds because, head-on overlap is stronger
than side by side overlap.
14 Define bond energy. (May-22)
• The bond energy is defined as the minimum amount of energy required to break one mole
of a particular bond in molecules in their gaseous state.
• The unit of bond enthalpy is kJ mol-1.
15 Hydrogen gas is diatomic whereas inert gases are monoatomic – explain on the basis of
MO theory.
According to MO theory,
• Electronic configuration of hydrogen = 1s1
• Electronic configuration of hydrogen molecule = 2 1s
Nb - Na 2-0
• Bond order = = = 1.
2 2
• The bond order of hydrogen molecule is 1 so it can form the molecule.
• But the electronic configuration of inert gas = ns2 np6
• Bond order of inert gas is zero so, it can’t form the molecule and exist as monoatomic.
16 What is polar covalent bond? explain with example.
In the case of covalent bond formed between atoms having different electronegativities, the
atom with higher electronegativity will have greater tendency to attract the shared pair of
electrons more towards itself than the other atom.
So, the atom with high electronegativity will get partially negative charge and the other atom
gets partially positive charge. It is called as polar covalent bond.
Eg: HF molecule. H+ - F-
(The electronegativities of hydrogen and fluorine on Pauling's scale are 2.1 and 4 respectively)
17 Considering x- axis as molecular axis, which out of the following will form a sigma bond
i) 1s and 2py: 1s orbital overlaps with 2py orbital along the axis, so it forms  bond.
ii) 2Px and 2Px: 2Px orbital overlaps with 2Px orbital along the axis, so it forms  bond.
iii) 2px and 2pz: 2Px orbital overlaps with 2Pz orbital along sideways, so it forms  bond.
iv) 1s and 2pz: 1s orbital overlaps with 2pz orbital along the axis, so it forms  bond.

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18 Explain resonance with reference to carbonate ion?
• The skeletal structure of carbonate ion (The oxygen atoms are denoted as OA, OB & OC)

• Total number of valence electrons = [1 x 4(carbon)] + [3 x 6 (oxygen)] + [2 (charge)] = 24

electrons. Distribution of these valence electrons gives us the following structure.

• Complete the octet for carbon by moving a lone pair from one of the oxygens (O A) and
write the charge of the ion (2-) on the upper right side as shown in the figure.

• In this case, we can draw two additional Lewis structures by moving the lone pairs from the
other two oxygens (OB and OC) thus creating three similar structures as shown below in
which the relative position of the atoms are same.
• They only differ in the position of bonding and lone pair of electrons. Such structures are
called resonance structures (canonical structures) and this phenomenon is called
resonance.

• It is evident from the experimental results that all carbon-oxygen bonds in carbonate ion
are equivalent. The actual structure of the molecules is said to be the resonance hybrid, an
average of these three resonance forms.

• It is important to note that carbonate ion does not change from one structure to another and
vice versa. It is not possible to draw the resonance hybrid by using a single Lewis structure.
19 Explain the bond formation in ethylene and acetylene.
Bond formation in ethylene:
Molecular formula of ethylene is C2H4. Electronic configuration of carbon,
In ground state 1s2 2s2 2px1 2py1 2pz0
↿⇂ ↿⇂ ↿ ↿

In excited state 1s2 2s1 2px1 2py1 2pz1

↿⇂ ↿ ↿ ↿ ↿

sp2 hybridisation
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In hybridised state ↿ ↿ ↿ ↿
sp2 sp2 sp2 2pz1
• Each carbon atom undergoes hybridisation resulting in three equivalent sp 2 hybridised
orbitals lying in the xy plane at an angle of 120⁰ to each other. The unhybridised 2p z orbital
lies perpendicular to the xy plane.
• One of the sp2 hybridised orbitals of each carbon lying on the molecular axis (x-axis)
linearly overlaps with each other resulting in the formation a C-C sigma bond.
• Other two sp2 hybridised orbitals of both carbons linearly overlap with the four 1s orbitals of
four hydrogen atoms leading to the formation of two C-H sigma bonds on each carbon.

• The unhybridised 2pz orbital of both carbon atoms can overlap only sideways as they are
not in the molecular axis. This lateral overlap results in the formation a pi(π) bond between
the two carbon atoms.
Bond formation in acetylene:
Molecular formula of ethylene is C2H2. Electronic configuration of carbon,
In ground state 1s2 2s2 2px1 2py1 2pz0
↿⇂ ↿⇂ ↿ ↿

In excited state 1s2 2s1 2px1 2py1 2pz1

↿⇂ ↿ ↿ ↿ ↿

sp2 hybridisation
In hybridised state ↿ ↿ ↿ ↿
sp2 sp2 2py1 2pz1
• Each carbon atom undergoes hybridisation resulting in equivalent sp hybridised orbitals
lying in a straight line along the molecular axis (x-axis). The unhybridised 2py and 2pz
orbitals lie perpendicular to the molecular axis.
• One of the two sp hybridised orbitals of each carbon linearly overlaps with each other
resulting in the formation a C-C sigma bond.
• The other sp hybridised orbital of both carbons linearly overlap with the two 1s orbitals of
two hydrogen atoms leading to the formation of one C-H sigma bonds on each carbon.
• The unhybridised 2py and 2pz orbitals of each carbon overlap sideways. This lateral overlap
results in the formation of two pi bonds between the two carbon atoms

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20 What type of hybridisations are possible in the following geometries?
a) Octahedral = sp3 d2
b) Tetrahedral = sp3
c) Square planer = dsp2
21 Explain VSEPR theory. Applying this theory to predict the shapes of IF7, and SF6.
Important principles of VSEPR Theory:
The shape of the molecules depends on the number of valence shell electron pair around the
central atom.
There are two types of electron pairs namely bond pairs and lone pairs.
The bond pair of electrons are those shared between two atoms
the lone pairs are the valence electron pairs that are not involved in bonding.
Each pair of valence electrons around the central atom repels each other and hence, they are
located as far away as possible in three-dimensional space to minimize the repulsion between
them.
The repulsive interaction between the different types of electron pairs is in the following order
lp – lp > lp – bp > bp – bp
where, lp - lone pair
bp- bond pair
Shape of IF7:

• It is the type of molecule that has a central atom with no lone pair of
electrons.
• It belongs to AB7 type
• In this shape I present in the center and there are seven bonding
electron pairs around it.
• The molecule has a regular pentagonal bipyramidal shape

Shape of SF6:

• It is the type of molecule that has a central atom with no lone pair of
electrons.
• It belongs to AB6 type
• In this shape there are six bonding electron pairs around central
sulphur atom.
• The molecule has a regular octahedral shape
22 CO2 and H2O both are triatomic molecule but their dipole moment values are different.
Why?
• The linear form of carbon dioxide has zero dipole moment, even though it has two polar
bonds.
• In CO2, the dipole moments of two polar bonds (CO) are equal in magnitude but have
opposite direction. Hence, the net dipole moment of the CO2 is zero.

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• Incase of water net dipole moment is the vector sum of μ1+ μ2 as shown.

• Dipole moment in water is found to be 1.85D

23 Which one of the following has highest bond order? N2, N2+ or N2–
Nb - Na
• Bond order =
2
10 - 4
• Bond order of N2 = = 3.
2
9-4
• Bond order of N2+ = = 2.5.
2
10 - 5
• Bond order of N2- = = 2.5.
2

• So, N2 as highest bond order.

24 Explain the covalent character in ionic bond.
• Like the partial ionic character in covalent compounds, ionic compounds show partial
covalent character.
• Eg: LiCl is an ionic compound but shows partial covalent character and is soluble in organic
solvents such as ethanol.
• The positively charged cation attracts the valence electrons of anion while repelling the
nucleus.
• This causes a distortion in the electron cloud of the anion and its electron density drifts
towards the cation
• It results in some sharing of the valence electrons between these ions. Thus, a partial
covalent character is developed between them. This phenomenon is called polarisation.
• The ability of a cation to polarise an anion is called its polarising ability and the tendency of
an anion to get polarised is called its polarisability.
25 Describe fajan's rule. (Jul-22, Jun-23)
• The extent of polarisation in an ionic compound is given by the Fajans rules
• Higher the positive charge on the cation, greater will be the attraction on the electron cloud
of the anion.
• Similarly higher the magnitude of negative charge on the anion, greater is its polarisability.
• Hence, the increase in charge on cation or in anion increases the covalent character
• The smaller cation and larger anion show greater covalent character due to the greater
extent of polarisation.
• Cations having ns2 np6 nd10 configuration show greater polarising power than the cations
with ns2 np6 configuration. Hence, they show greater covalent character.
26 Define octet rule?
Octet rule states that, the atoms transfer or share electrons so that all atoms involved in
chemical bonding obtain 8 electrons in their outer shell (valence shell).
27 Define covalent bond?
The mutual sharing of one or more pairs of electrons between two combining atoms
results in the formation of a chemical bond called a covalent bond.
Eg: H2, O2

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28 How does the extent of ionic character in a covalent bond is calculated?
The extent of ionic character in a covalent bond can be related to the electro negativity
difference to the bonded atoms.
In a typical polar molecule, Aδ--Bδ+, the electronegativity difference (χA- χB) can be used
to predict the percentage of ionic character as follows.
If the electronegativity difference (χA- χB ), is
If (XA - XB) = 1 .7, then the bond A-B has 50% ionic character
if (XA - XB) > 1.7, then the bond A-B has more than 50% ionic character,
if (XA - XB) < 1.7, then the bond A-B has less than 50% ionic character.
29 Explain the exceptions to octet rule with examples?
• Molecules with electron deficient central atoms Eg: BF3.
• Molecules containing odd electrons Eg: NO2.
• Molecules with expanded valence shells Eg: PCl5.
30 Define ionic bond?
The complete transfer of electrons between the two combining atoms leads to the
formation of a cation and an anion. Both these ions are held together by the electrostatic
attractive force which is known as ionic bond. Eg: HCl, NaCl
31 How does the bond length depends on the size of the atom and the number of bonds
between the combining atoms?
• Greater the size of the atom, greater will be the bond length.
• Eg: carbon-carbon single bond length (1.54 Å) is longer than the carbon-nitrogen single
bond length (1.43 Å).
• Increase in the number of bonds between the two atoms decreases the bond ength.
• Eg: The length of carbon-carbon single bond = 1.54 A°
• The length of carbon-carbon double bond = 1.33 A°
• The length of carbon-carbon triple bond = 1.20 A°.
32 Define hybridisation? (Sep-20)
Hybridisation is the process of mixing of atomic orbitals of the same atom with
comparable energy to form equal number of new equivalent orbitals with same energy. The
resultant orbitals are called hybridised orbitals
33 Define bond length? (Mar-19, May-22)
The distance between the nuclei of the two covalently bonded atoms is called bond
length.
34 Write the salient features of Molecular orbital Theory? (Sep-20, Mar-23)
• When atoms combine to form molecules, their individual atomic orbitals lose their identity
and forms new orbitals called molecular orbitals.
• The shapes of molecular orbitals depend upon the shapes of combining atomic orbitals.
• The number of molecular orbitals formed is the same as the number of combining atomic
orbitals.
• Half the number of molecular orbitals formed will have lower energy than the corresponding
atomic orbital, while the remaining molecular orbitals will have higher energy. The
molecular orbital with lower energy is called bonding molecular orbital and the one with
higher energy is called anti-bonding molecular orbital.
• The bonding molecular orbitals are represented as  (Sigma),  (pi),  (delta) and the
corresponding antibonding orbitals are denoted as *, * and *.

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• The electrons in a molecule are accommodated in the newly formed molecular orbitals. The
filling of electrons in these orbitals follows Aufbau's principle, Pauli's exclusion principle and
Hund's rule as in the case of filling of electrons in atomic orbitals.
• Bond order gives the number of covalent bonds between the two combining atoms.
Nb - Na
Bond order =
2
Here, Nb = Total number of electrons present in the bonding molecular orbitals
Na = Total number of electrons present in the antibonding molecular orbitals.
35 Give the salient features of VB Theory? (Sep-21)
1. When half-filled orbitals of two atoms overlap, a covalent bond will be formed between
them.
2. The resultant overlapping orbital is occupied by the two electrons with opposite spins.
3. The strength of a covalent bond depends upon the extent of overlap of atomic orbitals.
4. Each atomic orbital has a specific direction (except s-orbital which is spherical) and hence
orbital overlap takes place in the direction that maximizes overlap
36 Write the hybridisation present in the following compounds? (Mar-24)
a) BF3 - SP2
b) CH4 - SP3
c) PCl5 - SP3d
d) SF6 - SP3d2

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11. FUNDAMENTALS OF ORGANIC CHEMISTRY
1 Give the general characteristics of organic compounds? (Mar-23)
• They are covalent compounds of carbon
• They are generally insoluble in water
• They are readily soluble in organic solvent such as benzene, toluene, ether, chloroform etc
• Many of the organic compounds are inflammable (except CCl4).
• They possess low boiling and melting points due to their covalent nature
• Organic compounds are characterised by functional groups.
• They exhibit isomerism which is a unique phenomenon.
2 Describe the classification of organic compounds based on their structure. (Jun-23)

3 Write a note on homologous series. (Sep-21, Mar-24)

Series of organic compounds each containing a characteric functional group and the
successive members differ from each other in molecular formula by a CH2 group is called
homologous series.
Compounds of the homologous series are represented by a general formula
Alkanes – CnH2n+2
Alkenes – CnH2n
Alkynes – CnH2n-2
4 Write the molecular formula of the first six members of homologous series of nitro
alkanes.
i) CH3NO2
ii) C2H5NO2
iii) C3H7NO2
iv) C4H9NO2
v) C5H11NO2
vi) C6H13NO2
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5 What is meant by a functional group? Identify the functional group in the following
compounds. (a) acetaldehyde (b) oxalic acid (c) di methyl ether (d) methylamine
A functional group is an atom or a specific combination of bonded atoms that react in a
characteristic way, irrespective of the organic molecule in which it is present.
Compound Compound Functional group
a Acetaldehyde CH3CHO - CHO
b Oxalic acid
- COOH
c Di methyl ether CH3 – O – CH3 -O-
d Methylamine CH3 – NH2 - NH2
6 Give the general formula for the following classes of organic compounds
(a) Aliphatic monohydric alcohol = R - OH
(b) Aliphatic ketones. = R – CO - R
(c) Aliphatic amines. = R – NH2
7 Write the molecular and possible structural formula of the first four members of
homologous series of carboxylic acids.
Molecular formula Structural formula
1 CH2O2 H – COOH
2 C2H4O2 CH3 - COOH
3 C3H6O2 CH3 – CH2 - COOH
4 C4H8O2 CH3 – CH2 - CH2 - COOH
8 Give the IUPAC names of the following compounds.

i 2,3,5-trimethylhexane

ii 2-bromo-3-methylbutane

iii Methoxymethane

iv 2-hydroxybutanal

v Buta-1,3-diene

vi 4-chloropent-2-yne

vii 1-bromobut-2-ene

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viii 5-oxohexanoic acid

ix 3-ethyl-4-ethenylheptane

x 2,4,4-trimethylpent-2-ene

xi 2-methyl-1-phenylpropan-1-amine

xii 2,2-dimethyl-4-oxopentanenitrile

xiii 2-ethoxypropane

xiv 1-fluoro-4-methyl-2-nitrobenzene

xv 3-bromo-2-methylpentanal

9 Give the structure for the following compound.

i 3- ethyl - 2 methyl -1-pentene

ii 1,3,5- Trimethyl cyclohex - 1 -ene

iii tertiary butyl iodide

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iv 3 - Chlorobutanal

v 3 - Chlorobutanol

vi 2 - Chloro - 2- methyl propane

vii 2,2-dimethyl-1-chloropropane

viii 3 - methylbut -1- ene

ix Butan - 2, 2 - diol

x Octane - 1,3- diene

xi 1,3- Dimethylcyclohexane

xii 3-Chlorobut - 1 - ene

xiii 3 - methylbutan - 2 - ol

xiv acetaldehyde

10 Describe the reactions involved in the detection of nitrogen in an organic compound by

Lassaigne method. (Mar-19)
• If nitrogen is present, it gets converted to sodium cyanide which reacts with freshly
prepared ferrous sulphate and ferric ion followed by conc. HCl and gives a Prussian blue
colour or green colour or precipitate. It confirms the presence of nitrogen.
• HCl is added to dissolve the greenish precipitate of ferrous hydroxide produced by the
excess of NaOH on FeSO4 which would otherwise mark the Prussian blue precipitate.

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• The following reaction takes part in the formation of Prussian blue.
Na + C + N NaCN
(from organic compounds)
FeSo4 + 2NaOH Fe(OH)2 + Na2SO4
(from excess of sodium)
6NaCN + [Fe(OH)2] Na4[Fe(CN)6] + 2NaOH
Sodium ferrocyanide
Na4[Fe(CN)6] + 4FeCl3 Fe4[Fe(CN)6]3 + 12NaCl
ferric ferrocyanide
Prussian blue or green ppt
Incase if both N & S are present, a blood red colour is obtained due to the following reactions.

11 Give the principle involved in the estimation of halogen in an organic compound by

carius method.
Estimation of halogens (carius method): A known mass of the organic compound is heated
with fuming HNO3 and AgNO3. C,H &S get oxidized to CO2, H2O & SO2 and halogen
combines with AgNO3 to form a precipitate of silver halide.

The ppt of AgX is filtered, washed, dried and weighed. From the mass of AgX and the mass of
the organic compound taken, percentage of halogens are calculated.
12 Give a brief description of the principles of
i) Fractional distillation (Jul-19):
• This is one method to purify and separate liquids present in the mixture having their boiling
point close to each other.
• In this method, a fractionating column is fitted with distillation flask and a condenser.
• A thermometer is fitted in the fractionating column near the mouth of the condenser. This
will enable to record the temperature of vapour passing over the condenser.
• The process of separation of the components in a liquid mixture at their respective boiling
points in the form of vapours and the subsequent condensation of those vapours is called
fractional distillation.
• If necessary, the process of fractional distillation is repeated.
• This method is very useful in distillation of petroleum, coal-tar and crude oil.
ii) Column Chromatography
• This is the simplest chromatographic method carried out in long glass column having a
stop cock near the lower end.
• This method involves separation of a mixture over a column of adsorbent (Stationery
phase) packed in a column.

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• In the column a plug of cotton or glass wool is placed at the lower end of the column to
support the adsorbent powder. The tube is uniformLy packed with suitable absorbent
constitute the stationary phase. (Activated aluminum oxides (alumina), Magnesium
oxide, starch are also used as absorbents).
• The mixture to be separated is placed on the top of the adsorbent column. Eluent
which is a liquid or a mixture of liquids is allowed to flow down the column slowly.
• Different components are eluted depending upon the degree to which the components
are adsorbed and complete separation takes place. The most readily adsorbed are
retained near the top and others come down to various distances in the column.
13 Explain paper chromatography
• It is an example of partition chromatography.
• A strip of paper acts as an adsorbent. This method involves continues differential
portioning of components of a mixture between stationary and mobile phase.
• In this method, a special quality paper known as chromatography paper is used. This
paper act as a stationary phase.
• A strip of chromatographic paper spotted at the base with the solution of the mixture is
suspended in a suitable solvent which act as the mobile phase. The solvent rises up and
flows over the spot.
• The paper selectively retains different components according to their different partition in
the two phases where a chromatogram is developed.
• The spots of the separated colored compounds are visible at different heights from the
position of initial spots on the chromatogram.
• The spots of the separated colorless compounds may be observed either under
ultraviolent light or by the use of an appropriate spray reagent.
14 Explain various types of constitutional isomerism (structural isomerism) in organic
compounds. (Jul-22)
This type of isomers has same molecular formula but differ in their bonding sequence.
(a) Chain or nuclear or skeletal isomerism: These isomers differ in the way in which the
carbon atoms are bonded to each other in a carbon chain or in other words isomers have
similar molecular formula but differ in the nature of the carbon skeleton (ie. Straight or branch)

(b) Position isomerism: If different compounds belonging to same homologous series with
the same molecular formula and carbon skeleton, but differ in the position of substituent or
functional group or an unsaturated linkage are said to exhibit position isomerism.

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(c) Functional isomerism: Different compounds having same molecular formula but different
functional groups are said to exhibit functional isomerism.

(d) Metamerism: This type of isomerism is a special kind of structural isomerism arises due
to the unequal distribution of carbon atoms on either side of the functional group or different
alkyl groups attached to the either side of the same functional group and having same
molecular formula.

(e) Tautomerism: It is a special type of functional isomerism in which a single compound

exists in two readily inter convertible structures that differ markedly in the relative position of
atleast one atomic nucleus, generally hydrogen. The two different structures are known as
tautomers. There are two important types are dyad and triad systems.
(i) Dyad system: In this system hydrogen atom oscillates between two directly linked
polyvalent atoms.
Eg:
(ii) Triad system: In this system hydrogen atom oscillates between three polyvalent atoms. It
involves 1,3 migration of hydrogen atom from one polyvalent atom to other within the mole-
cule. The most important type of triad system is keto–enol tautomerism and the two groups of
tautomers are ketoform and enol-form.
Eg:

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(f) Ring chain isomerism: The compounds having same molecular formula but differ in
terms of bonding of carbon atom to form open chain and cyclic structures.

eg:

15 Describe optical isomerism with suitable example. (May-22)

• Compounds having same physical and chemical property but differ only in the rotation of
plane of the polarized light are known as optical isomers and the phenomenon is known as
optical isomerism.
• Glucose has the ability to rotate the plane of the plane polarized light and they are said to
be optically active compounds and this property of a compound is called optical activity.
• The optical isomer, which rotates the plane of the plane polarised light to the right or in
clockwise direction is said to be dextro rotatory denoted by the sign (+),
• The compound which rotates to the left or anticlockwise is said to be leavo rotatory
denoted by sign (-).
• Dextrorotatory compounds are represented as ‘d’ or by sign (+) and leavorotatory
compounds are represented as ‘l’ or by sign (-).
16 Briefly explain geometrical isomerism in alkene by considering 2- butene as an
example. (Sep-20)
CH3 – CH = CH -CH3
• Geometrical isomers are the stereoisomers which have different arrangement of groups or
atoms around a rigid frame work of double bonds.
• This type of isomerism occurs due to restricted rotation of double bonds, or about single
bonds in cyclic compounds.
• The carbon-carbon double bond consists of a σ bond and a π bond. Rotation around C=C
bond is not possible. This restriction of rotation about C-C double bond is responsible for
geometrical isomerism in alkenes.

• The cis isomer is one in which two similar groups are on the same side of the double bond.
The trans isomer is that in which the two similar groups are on the opposite side of the
double bond, hence this type of isomerism is often called cis-trans isomerism.
• The cis-isomer can be converted to trans isomer or vice versa is only if either isomer is
heated to a high temperature or absorbs light.
• The heat supplies the energy (about 62kcal/ mole) to break the π bond so that rotation
about σ bond becomes possible.
• Upon cooling, the reformation of the π bond can take place in two ways giving a mixture
both cis and trans forms of trans-2-butene and cis-2-butene.
17 Which is more stable in cis and trans isomers.
• The trans isomer is more stable than the corresponding cis isomers.
• This is because in the cis isomer, the bulky groups are on the same side of the double
bond.
• The steric repulsion of the groups makes the cis isomers less stable than the trans
isomers in which bulky groups are on the opposite side.
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18 Explain oximes and azo compounds?
• Restricted rotation around C=N (oximes) gives rise to geometrical isomerism in oximes.
Here ‘syn’ and ‘anti’ are used instead of cis and trans respectively.
• In the syn isomer the H atom of a doubly bonded carbon and –OH group of doubly bonded
nitrogen lie on the same side of the double bond, while in the anti-isomer, they lie on the
opposite side of the double bond.

19 Define Catenation?
The tendency of an atom to form a chain of bonds with the atoms of the same element is
called catenation.
20 Define isomerism?
It represents the existence of two or more compounds with the same molecular formula
but different structure and properties is called isomerism.
21 What are enantiomers?
An optically active substance may exist in two or more isomeric forms which have same
physical and chemical properties but differ in terms of direction of rotation of plane polarized
light, such optical isomers which rotate the plane of polarized light with equal angle but in
opposite direction are known as enantiomers.
22 Give the conditions for optical isomerism?
A molecule should possess,
1) chiral carbon (carbon atom whose tetra valency is satisfied by four different atoms or
groups).
2) A molecule possessing non-super imposable to its own mirror image
23 Explain the preparation of lassaigne’s extract?
• A small piece of Na dried by pressing between the folds of a filter paper is taken in a
fusion tube and it is gently heated.
• When it melts to a shining globule, put a pinch of the organic compound on it. Heat the
tube till reaction ceases and becomes red hot. Plunge it in about 50 ml of distilled water
taken in a china dish and break the bottom of the tube by striking against the dish.
• Boil the contents of the dish for about 10 mts and filter. This filtrate is known as
lassaigne’s extract or sodium fusion extract and it used for detection of nitrogen, sulfur
and halogens present in organic compounds.

24 Define Sublimation?
• Few substances like benzoic acid, naphthalene and camphor when heated pass directly
from solid to vapor without melting (ie liquid). On cooling the vapours will give back solids.
Such phenomenon is called sublimation. It is a useful technique to separate volatile and
non-volatile solid.
• Substances to be purified is taken in a beaker. It is covered with a watch glass. The
beaker is heated for a while and the resulting vapours condense on the bottom of the
watch glass. Then the watch glass is removed and the crystals are collected.

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25 Define Crystallization? (Sep-20)
Selection of solvent: Most of the organic substances being covalent do not dissolve in polar
solvents like water, hence selection of solvent (suitable) becomes necessary. Hence the
powdered organic substance is taken in a test tube and the solvent is added little by little with
constant stirring and heating, till the amount added is just sufficient to dissolve the solute(ie)
organic compound. If the solid dissolves upon heating and throws out maximum crystals on
cooling, then the solvent is suitable. This process is repeated with other solvents like
benzene, ether, acetone and alcohol till the most suitably one is sorted out.
Preparation of solution: The organic substance is dissolved in a minimum quantity of
suitable solvent. Small amount of animal charcoal can be added to decolorize any coloured
substance. The heating may be done over a wire gauze or water bath depending upon the
nature of liquid.
Filtration of hot solution: The hot solution so obtained is filtered through a fluted filter paper
placed in a funnel.
Crystallization: The hot filtrate is then allowed to cool. Most of the impurities are removed on
the filter paper, the pure solid substance separates as crystal. When copious amount of
crystal has been obtained, then the crystallization is complete. If the rate of crystallization is
slow, it is induced either by scratching the walls of the beaker with a glass rod or by adding a
few crystals of the pure compounds to the solution.
Isolation and drying of crystals: The crystals are separated from the mother liquor by
filtration. Filtration is done under reduced pressure using a Bucher funnel. When the whole of
the mother liquor has been drained into the filtration flask, the crystals are washed with small
quantities of the pure cold solvent and then dried.
26 Explain Differential extraction?
• The process of removing a substance from its aqueous solution by shaking with a suitable
organic solvent is termed extraction.
• When an organic substance present as solution in water can be recovered from the
solution by means of a separating funnel.
• The aqueous solution is taken in a separating funnel with little quantity of ether or
chloroform (CHCl3). The organic solvent immiscible with water will form a separate layer
and the contents are shaken gently.
• The solute being more soluble in the organic solvent is transfered to it. The solvent layer is
then separated by opening the tap of the separating funnel, and the substance is
recovered.
27 Explain Thin layer chromatography?
• This method is possible to separate even minute quantities of mixtures.
• A sheet of a glass is coated with a thin layer of adsorbent (cellulose, silica gel or
alumina). This sheet of glass is called chromoplate or thin layer chromatography plate.
• After drying the plate, a drop of the mixture is placed just above one edge and the plate
is then placed in a closed jar containing eluent (solvent). The eluent is drawn up the
adsorbent layer by capillary action.
• The components of the mixture move up along with the eluent to different distances
depending upon their degree of adsorption of each component of the mixture.
• It is expressed in terms of its retention factor (i.e.) Rf value
Distance moved by the substance from base line (x)
Rf =
Distance moved by the solvent from base line (y)
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28 Explain briefly about simple distillation?
The process of distillation involves the impure liquid when boiled gives out vapour and
the vapour so formed is collected and condensed to give back the pure liquid in the receiver.
This method is called simple distillation.
Liquids with large difference in boiling point (about 40k) and do not decompose under
ordinary pressure can be purified by simply distillation
Eg. The mixture of C6H5NO2 (b.p 484k) & C6H6(354k) and mixture of diethyl ether (b.p
308k) and ethyl alcohol (b.p 351k)
29 Explain Steam distillation?
• This method is applicable for solids and liquids. If the compound to be steam distilled the it
should not decompose at the steam temperature, should have a fairly high vapour
pressure at 373k, it should be insoluble in water and the impurities present should be non-
volatile.
• The impure liquid along with little water is taken in a round-bottom flask which is
connected to a boiler on one side and water condenser on the other side, the flask is kept
in a slanting position so that no droplets of the mixture will enter into the condenser on the
brisk boiling and bubbling of steam.
• The mixture in the flask is heated and then a current of steam passed in to it. The vapours
of the compound mix up with steam and escape into the condenser. The condensate
obtained is a mixture of water and organic compound which can be separated.
• This method is used to recover essential oils from plants and flowers, also in the
manufacture of aniline and turpentine oil.
30 Explain Azeotropic Distillation?
• These are the mixture of liquids that cannot be separated by fractional distillation. The
mixtures that can be purified only by azeotropic distillation are called as azeotropes.
• These azeotropes are constant boiling mixtures, which distil as a single component at a
fixed temperature. For example, ethanol and water in the ratio of 95.87 : 4.13.
• In this method the presence of a third component like C6H6, CCl4, ether, glycerol, glycol
which act as a dehydrating agent depress the partial pressure of one component of
azeotropic mixture and raises the boiling point of that component and thus other
component will distil over.
• Substances like C6H6, CCl4 have low boiling points and reduce the partial vapour pressure
of alcohol more than that of water while substances like glycerol & glycol etc. have high
boiling point and reduce the partial vapour pressure of water more than that of alcohol.
31 Describe the method to estimate carbon and hydrogen present in organic compound?
Both carbon and hydrogen are estimated by the same method. A known weight of the
organic substance is burnt in excess of oxygen and the carbon and hydrogen present in it are
oxidized to carbon dioxide and water, respectively. The weight of carbon dioxide and water
thus formed are determined and the amount of carbon and hydrogen in the organic substance
is calculated.
Procedure: The combustion tube is heated strongly to dry its content. It is then cooled slightly
and connected to the absorption apparatus. The other end of the combustion tube is open for
a while and the boat containing weighed organic substance is introduced. The tube is again
heated strongly till the substance in the boat is burnt away. This takes about 2 hours.
Finally, a strong current of oxygen is passed through the combustion tube to sweap
away any traces of carbon dioxide or moisture which may be left in it. The U-tube and the
potash bulbs are then detached and the increase in weight of each of them is determined.
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Calculation:
Weight of the organic substance taken = w g
Increase in weight of H2O = x g
Increase in weight of CO2 = y g
18 g of H2O contains 2g of hydrogen
2x
∴ x g of H2O contains ( ) g of hydrogen
18
2x x
Percentage of hydrogen = ( X X 100) %
18 w
44g of CO2 contains 12g of carbon
12y
∴ y g of CO2 contains ( ) g of carbon
44
12y y
Percentage of Carbon = ( X X 100) %
44 w

32 Describe the method to estimate sulphur present in organic compound?

Carius method: A known mass of the organic substance is heated strongly with fuming
HNO3. C & H get oxidized to CO2& H2O while sulphur is oxidized to sulphuric acid as per the
following reaction.

The resulting solution is treated with excess of BaCl2 solution H2SO4 present in the solution in
quantitatively converted into BaSO4, from the mass of BaSO4, the mass of sulphur and hence
the percentage of sulphur in the compound can be calculated.
Procedure: A known mass of the organic compound is taken in clean carius tube and added
a few mL of fuming HNO3. The tube is the sealed. It is then placed in an iron tube and heated
for about 5 hours. The tube is allowed to cool to room temperature and a small hole is made
to allow gases produced inside to escape.
The carius tube is broken and the content collected in a beaker. Excess of BaCl 2 is
added to the beaker contains H2SO4 acid as a result of the reaction is converted to BaSO4.
The precipitate of BaSO4 is filtered, washed, dried and weighed. From the mass of BaSO 4,
percentage of S is found.
Mass of the organic compound = w g
Mass of the BaSO4 formed = x g
233g of BaSO4 contains 32 g of Sulphur
32
∴ x g of BaSO4 contains ( x) g of S
233
32 x
Percentage of Sulphur = ( X X 100) %
233 w

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33 Describe the method to estimate halogens present in organic compound?
• A known mass of the substance is taken along with fuming HNO3 and AgNO3 is taken in a
clean carius tube.
• The open end of the Carius tube is sealed and placed in a iron tube for 5 hours in the
range at 530- 540 K Then the tube is allowed to cool and a small hole is made in the tube
to allow gases produced to escape. The tube is broken and the ppt is filtered, washed,
dried and weighed.
• From the mass of AgX obtained, percentage of halogen in the organic compound is
calculated.
Weight of the organic compound = w g
➢ Weight of AgCl precipitate = a g
➢ 143.5 g of AgCl contains 35.5 g of Cl
35.5
➢ ∴ a g of AgCl contains = xa
143.5
➢ w g Organic compound gives a g AgCl
35.5 a
➢ Percentage of Cl in w g = ( X X 100) % organic compound
143.5 w
o Let Weight of silver Bromide be 'b'g
o 188g of AgBr contains 80 g of Br
80b
o ∴ b g of AgBr contains ( ) g of Br
188
o w g Organic compound gives b g AgBr
80 b
o Percentage of Br in w g = ( X X 100) % organic compound
188 w
• Let Weight of silver Iodide be 'c'g
• 235g of AgI contains 127 g of I
127c
• ∴ C g of AgI contains ( ) g of I
235

• w g Organic compound gives c g AgI

127 c
• Percentage of I in w g = ( X X 100) % organic compound
235 w
34 Describe carius method to estimate phosphorus present in organic compound?
• A known mass of the organic compound (w) containing phosphorous is heated with fuming
HNO3 in a sealed tube where C is converted into CO2 and H to H2O. phosphorous present
in organic compound is oxidized to phosphoric acid which is precipitated, as ammonium
phosphomolybdate by heating with Conc. HNO3 and then adding ammonium molybdate.
• The precipitate of ammonium phosphomolybdate thus formed is filtered washed, dried and
weighed.
Mass of organic compound is wg
Weight of ammonium phosphomolybdate = x g
Mole mass of (NH4)3.PO4.12MoO3 is =1877g

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1877g of (NH4)3.PO4.12MoO3 contains 31g of P

31 x
xg of (NH4)3.PO4.12MoO3 in w g of organic compound contains ( X ) of phosphorous
1877 w
31 x
Percentage of Phosphorous = ( X X 100) %
1877 w
35 Describe the method to estimate phosphorus using phosphoric acid or magnesia
mixture?
• The phosphoric acid is precipitated as magnesium-ammonium phosphate by adding
magnesia mixture (a mixture containing mgcl2, NH4Cl and ammonia) This ppt is washed,
dried and ignited to get magnesium pyrophosphate which is washed, dried a weighed.
• By knowing the mass of the organic compound and the mass of magnesium
pyrophosphate formed, the percentage of P is calculated.
Mass of organic compound is wg
Weight of magnesium pyrophosphate = y g
Molar mass of Mg2P2O7 is 222 g
222 of Mg2P2O7 contains 62 g of P
62 y
Y g of of Mg2P2O7 in w g of Organic compound contains ( X ) of P.
222 w
62 y
Percentage Phosphorous = ( X X 100) %
222 w
36 Describe Dumas method to estimate nitrogen present in organic compound?
• Procedure: To start with the tap of nitro meter is left open. CO2 is passed through the
combustion tube to expel the air in it.
• When the gas bubbles rising through, the potash solution fails to reach the top of it and is
completely absorbed it shows that only CO2 is coming and that all air has been expelled
from the combustion tube. The nitrometer is then filled with KOH solution by lowering the
reservoir and the tap is closed.
• The combustion tube is now heated in the furnace and the temperature rises gradually.
• The nitrogen set free form the compound collects in the nitro meter. When the combustion
is complete a strong current of CO2 is sent through, the apparatus in order to sweep the
last trace of nitrogen from it.
• The volume of the gas gets collected is noted after adjusting the reservoir so that the
solution in it and the graduated tube is the same. The atmospheric pressure and the
temperature are also recorded.
Calculations:
Weight of the substance taken = wg
Volume of nitrogen = V1 L
Room Temperature = T1 K
Atmospheric Pressure = P mm of Hg
Aqueous tension at
room temperature = P1 mm of Hg
Pressure of dry nitrogen = (P-P1) = P1 mm of Hg.

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Let p0 V0 and T0 be the pressure, Volume and temperature respectively of dry nitrogen at
STP,
P0 V0 P1 V1
=
T0 T1
P1 V1 T0
ஃ V0 = X
T1 P0
P1 V1 273 K
V0 = ( X ) mm of Hg
T1 760

Calculation of percentage of nitrogen. 22.4 L of N2 at STP weigh 28g of N2

28
∴ V0 L of N2 at S.T.P weigh ( X V0 )
22.4
28 V0
Wg of Organic compound contain ( X ) g of nitrogen
22.4 w
28 V0
∴Percentage of nitrogen = ( X ) X 100
22.4 w

37 Describe the Kjeldahls method to estimate nitrogen present in organic compound?

Procedure: A weighed quantity of the substance (0.3 to 0.5 g) is placed in a special long –
necked Kjeldahl flask made of pyrex glass. About 25 mL of Conc. H 2SO4 together with a little
K2SO4 and CuSO4 (catalyst) are added to it the flask is loosely stoppered by a glass bulb and
heated gently in an inclined position.
The heating is continued till the brown color of the liquid first produced, disappears leaving the
contents clear as before.
At this point all the nitrogen in the substance is converted to (NH 4)2SO4. The Kjeldahl flask is
then cooled and its contents are diluted with distilled water and then carefully transferred into a
1 lit round bottom flask. An excess NaOH solution is poured down the side of the flask and it is
fitted with a Kjeldahl trap and a water condenser.
N
The lower end of the condenser dips in a measured volume of excess the H2SO4 solution.
20
The liquid in the round bottom flask is then heated and the liberated ammonia is distilled into
sulphuric acid. The Kjeldahl trap serves to retain any alkali splashed up on vigorous boiling.
When no more ammonia passes over (test the distillate with red litmus) the receiver is
removed. The excess of acid is then determined by titration with alkali, using phenolphthalein
as the indicator.
Calculation:
Weight of the substance = Wg.
Volume of H2SO4 required for the complete neutralisation of evolved NH3 = V mL.
Strength of H2SO4 used to neutralise NH3 = N
Let the Volume and the strength of NH3 formed are V1 and N1 respectively
we know that V1N1 = VN
14 X NV
The amount of nitrogen present in the w g of Organic Compound =
1 X 1000 X W
14 X NV
Percentage of Nitrogen = ( ) X 100 %
1000 X W

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12. BASIC CONCEPTS OF ORGANIC REACTIONS
1 Write short notes on
(a) Resonance (Sep-21):
• The resonance is a chemical phenomenon which is observed in certain organic
compounds possessing double bonds at a suitable position.
• Certain organic compounds can be represented by more than one structure and they differ
only in the position of bonding and lone pair of electrons.
• Such structures are called resonance structures and this phenomenon is called
resonance. This phenomenon is also called mesomerism or mesomeric effect.
(b) Hyperconjucation:
• The delocalisation of electrons of σ bond is called as hyper conjugation.
• It is a special stabilising effect that results due to the interaction of electrons of a σ-bond
(usually C-H or C-C) with the adjacent, empty non-bonding p-orbital or an anti-bonding σ*
or π*-orbitals resulting in an extended molecular orbital.
• Unlike electromeric effect, hyper conjugation is a permanent effect.
2 What are electrophiles and nucleophiles? (Mar-19, May-22) Give suitable examples for
each. (or) Differentiate electrophiles and nucleophiles? (Mar-24)
Nucleophiles: Electrophiles:

• They are reagents that has high affinity • They are reagents that are attracted
for electro positive centers. towards negative charge or electron
• They possess an atom has an rich center.
unshared pair of electrons • They are either positively charged
• They are usually negatively charged ions or electron deficient neutral
ions or electron rich neutral molecules molecules.
• All Lewis bases act as nucleophiles • All Lewis acids act as electrophiles
• They are electrons donors. • They are electron acceptors
• Eg: NH3, H2S, Cl-, CN- • Eg: CO2, +NO2, H+

3 Show the heterolysis of covalent bond by using curved arrow notation and complete
the following equations. Identify the nucleophile is each case.
i) CH3 – Br + KOH CH3 – OH + KBr
-
Here OH is the nucleophile.
Step-1: CH3 – Br +
CH3 + Br –

Step-2: +
CH3 + K+ - OH- CH3 – OH + KBr
ii) CH3 – OCH3 + HI CH3OH + CH3 – I
Here I- is the nucleophile.

Step-1; CH3 – OCH3 +

CH3 + -OCH3

Step-2; +
CH3 + I- CH3 – I
4 Explain inductive effect with suitable example. (Mar-23)
• Inductive effect is defined as the change in the polarisation of a covalent bond due to the
presence of adjacent bonds, atoms or groups in the molecule. This is a permanent
phenomenon.
• Let us explain the inductive effect by considering ethane and ethylchloride as examples.
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• The C-C bond in ethane is non polar while the C-C bond in ethyl chloride is polar.
• We know that chlorine is more electronegative than carbon, hence it attracts the shared
pair of electrons between C-Cl in ethyl chloride towards itself. This develops a slight
negative charge on chlorine and a slight positive charge on carbon to which chlorine is
attached.
• To compensate it, the C1 draws the shared pair of electrons between itself and C2.
• This polarisation effect is called inductive effect. This effect is greatest for the adjacent
bonds, but they also be felt farther away.
• However, the magnitude of the charge separation decreases rapidly, as we move away
from C1 and is observed maximum for 2 carbons and almost insignificant after 4 bonds
from the active group.

5 Explain electromeric effect.

• Electromeric is a temporary effect which operates in unsaturated compounds (containing
>C=C<, >C=O, etc...) in the presence of an attacking reagent.
• Let us consider two different compounds (i) compounds containing carbonyl group (>C=O)
and (ii) unsaturated compounds such as alkenes (>C=C<).
• When a nucleophile approaches the carbonyl compound, the π electrons between C and
O is instantaneously shifted to the more electronegative oxygen.
• This makes the carbon electron deficient and thus facilitating the formation of a new bond
between the incoming nucleophile and the carbonyl carbon atom.

• On the other hand, when an electrophile such as H+ approaches an alkene molecule, the
π electrons are instantaneously shifted to the electrophile and a new bond is formed
between carbon and hydrogen.
• This makes the other carbon electron deficient and hence it acquires a positive charge.

6 Give examples for the following types of organic reactions

(i) β - elimination (Mar-24)
n-Propyl bromide on reaction with alcoholic KOH gives propene. In this reaction
hydrogen and Br are eliminated.

(ii) Electrophilic substitution.

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Nitration of Benzene is an example for electrophilic substitution.

Here, NO2+ acts as an electrophile.

7 Why does a cutted apple turns brown when kept in air?
• Apples contain an enzyme called polyphenol oxidase (PPO), also known as tyrosinase.
• Cutting an apple exposes its cells to the atmospheric oxygen and oxidizes the phenolic
compounds present in apples.
• This is called the enzymatic browning that turns a cutted apple brown.
8 Write a short note on hybridisation of carbon in carbocation?
In a carbocation, the carbon bearing positive charge is sp2 hybridised and hence it has a
planar structure. In the reaction involving such a carbocation, the attack of a negatively
charged species (nucleophiles) take place on either side of the carbocation as shown below.

Relative stability carbocations: +C(CH3)3 > +CH(CH3)2 > +CH2CH3 > +CH3
9 Write a short note on hybridisation of carbon in carbanion?
The carbanions are generally pyramidal in shape and the lone pair occupies one of the
3
sp hybridised orbitals. An alkyl free radical may be either pyramidal or planar.

Relative stability of carbanions: -C(CH3)3 > -CH(CH3)2 > -CH2CH3 > -CH3
10 Explain +I effect and -I effect with example? (Jun-19)
+I effect:
• Highly electropositive atoms and atoms are groups which carry a negative charge are
electron donating or +I group.
• Eg: Alkali metals, alkyl groups such as methyl, ethyl, negatively charged groups such as
CH3O–, C2H5O–, COO– etc.
• Lesser the electronegativity of the elements, greater is the +I effect.
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-I effect:
• Highly electronegative atoms and groups with an atom carrying a positive charge are
electron withdrawing groups or –I groups.
• Eg: -F, -Cl, -COOH, -NO2, -NH2
• Higher the electronegativity of the substituent, greater is the -I effect.
11 Explain the change in reactivity of organic compound and acidity of carboxylic acids
due to induction effect?
• When a highly electronegative atom such as halogen is attached to a carbon then it makes
the C-X bond polar.
• In such cases the -I effect of halogen facilitates the attack of an incoming nucleophile at
the polarised carbon, and hence increases the reactivity.

• If a -I group is attached nearer to a carbonyl carbon, it decreases the availability of

electron density on the carbonyl carbon, and hence increases the rate of the nucelophilic
addition reaction.
Acidity of carboxylic acids:
• When a halogen atom is attached to the carbon which is nearer to the carboxylic acid
group, its -I effect withdraws the bonded electrons towards itself and makes the ionisation
of H+ easy.
• The acidity of various chloro acetic acid is in the following order.
CCl3 COOH > CHCl2 COOH > CH2Cl COOH > CH3COOH
• The strength of the acid increases with increase in the -I effect of the group attached to the
carboxyl group.
12 Explain +E effect and -E effect with suitable example?
+E effect:
When the π electron is transferred towards the attacking reagent, it is called + E
(positive electromeric) effect.

The addition of H+ to alkene as shown above is an example of +E effect.

- E effect:
When the π electron is transfered away from the attacking reagent, it is called, -E
(negative electromeric) effect.

The attack of CN- on a carbonyl carbon, as shown above, is an example of -E effect.

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13 Explain the acidity of phenol using resonance effect?
The phenoxide ion is more stabilised than phenol by resonance effect (+M effect) and
hence resonance favours ionisation of phenol to form H+ and shows acidity.

The above structures shows that there is a charge separation in the resonance structure
of phenol which needs energy, where as there is no such hybrid structures in the case of
phenoxide ion. This increased stability accounts for the acidic character of phenol.
14 Define Positive Mesomeric Effect and Negative Mesomeric Effect?
Positive Mesomeric Effect:
• Positive resonance effect occurs, when the electrons move away from substituent
attached to the conjugated system.
• It occurs, if the electron releasing substituents are attached to the conjugated system.
• In such cases, the attached group has a tendency to release electrons through resonance.
These electron releasing groups are usually denoted as +R or +M groups.
• Eg: -OH, -SH, -OR, -SR, -NH2, -O- etc.
Negative Mesomeric Effect:
• Negative resonance effect occurs, when the electrons move towards the substituent
attached to the conjugated system.
• It occurs if the electron withdrawing substituents are attached to the conjugated system.
• In such cases, the attached group has a tendency to withdraw electrons through
resonance. These electron withdrawing groups are usually denoted as -R or -M groups.
• Eg: NO2, >C=O, -COOH, - C≡N etc
15 Explain the following substitution reactions with example?
i) Nucelophilic substituion:
This reaction can be represented as,

Here Y– is the incoming nucleophile or and attacking species and X – is the leaving group.

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Example: Hydrolysis of alkyl halides.

Aliphatic nucleophilic substitution reactions take places either by S N1 or SN2 mechanism.

ii) Free radical substitution:

Aliphatic electrophilic substitution

A general aliphatic electrophilic substitution is represented as,

16 Explain the following substitution reactions with example?

i) Electrophilic Addition reaction
ii) Nucleophilic addition reaction
iii) Free radical addition Reaction
• It is a characteristic reaction of an unsaturated compound (compounds containing C-C
localised double or triple bond).
• In this reaction two molecules combine to give a single product.
• Like substitution this reaction also can be classified as nucleophilic, electrophilic and free
radical addition reactions depending the type of reagent which initiates the reaction.
• During the addition reaction the hydridisation of the substrate changes (from sp2 → sp3 in
the addition reaction of alkenes or sp → sp2 in the addition reaction of alkynes) as only
one bond breaks and two new bonds are formed.

i) Electrophilic Addition reaction:

A general electrophilic addition reaction can be represented as below.

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Example: Brominatin of alkene to give bromo alkane.

ii) Nucleophilic addition reaction:

Example: Addition of HCN to acetaldehyde

iii) Free radical addition Reaction:

A General free radical addition reaction can be represented as below.

Example:

In the above reaction, Benzoyl peroxide acts as a radical initiator. The mechanism
involves free radicals.
17 Briefly explain about free radicals?
• Homolytic cleavage of covalent bonds results into free radicals.
• They are short lived and are highly reactive.
• The type of reagents that promote homolytic cleavage in substrate are called as free
radical initiators.
• For example, Azobisisobutyronitrile (AIBN) and peroxides such as benzoyl peroxide are
used as free radical initiators in polymerisation reactions.
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• As a free radical with an unpaired electron is neutral and unstable, it has a tendency to
gain an electron to attain stability.
• Organic reactions involve homolytic fission of C-C bonds to form alkyl free radicals.
• The stability of alkyl free radicals is in the following order
C(CH3)3 > CH(CH3)2 > CH2CH3 > CH3
18 Explain Homolytic Cleavage and Heterolytic Cleavage?
Homolytic Cleavage:
• Homolytic cleavage is the process in which a covalent bond breaks symmetrically in such
way that each of the bonded atoms retains one electron.
• It is denoted by a half-headed arrow (fish hook arrow).
• This type of cleavage occurs under high temperature or in the presence of UV light in a
compound containing non polar covalent bond formed between atoms of similar
electronegativity.
• In such molecules, the cleavage of bonds results into free radicals.
high temperature
• Eg: CH3 – CH3 → 2CH3
UV light

Heterolytic Cleavage:
• In this process a covalent bond breaks unsymmetrically such that one of the bonded
atoms retains the bond pair of electrons.
• It results in the formation of a cation and an anion.
• Of the two bonded atoms, the most electronegative atom becomes the anion and the other
atom becomes the cation.
• The cleavage is denoted by a curved arrow pointing towards the more electronegative
atom.

19 Explain the structure of 1,3-butadiene using resonance effect? (Jun-19)

• In 1,3-butadiene, it is expected that the bond between C1-C2 and C3 –C4 should be shorter
than that of C2-C3, but the observed bond lengths are of same.
• This property cannot be explained by a simple structure in which two π bonds localised
between C1-C2 and C3 –C4. Actually, the π electrons are delocalised as shown below.

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• These resonating structures are called canonical forms and the actual structure lies
between these three resonating structures, and is called a resonance hybrid.
• The resonance hybrid is represented as below.

20 Explain Hyper conjugation effect (or) Baker-Nathan effect? (S-20,J-22)

• It requires an α-CH group or a lone pair on atom like N, O adjacent to a π bond (sp 2 hybrid
carbon).
• It occurs by the overlapping of the σ-bonding orbital or the orbital containing a lone pair
with the adjacent π-orbital or p-orbital.

• In propene, the σ-electrons of C-H bond of methyl group can be delocalised into the π-
orbital of doubly bonded carbon as represented above.
• In the above structure the sigma bond is involved in resonance and breaks in to supply
electrons for delocalisation giving rise to 3 new canonical forms.
• In the contributing canonical structures: (II), (III) & (IV) of propene, there is no bond
between an α-carbon and one of the hydrogen atoms.
• Hence the hyperconjugation is also known as “no bond resonance” or “Baker-Nathan
effect”.
• The structures (II), (III) & (IV) are polar in nature.
21 What are the effects of free radicals in human body and give the methods to reduce its
effect?
• Human body produces free radicals when it is exposed to x-rays, cigarette smoke,
industrial chemicals and air pollutants.
• Free radicals can disrupt cell membranes, increase the risk of many forms of cancer,
damage the interior lining of blood vessels and lead to a high risk of heart disease and
stroke.
Methods to decrease the effect of free radicals:
• Body uses vitamins and minerals to counter the effects of free radicals.
• Fruits contains antioxidants which decrease the effects of free radicals.

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13. HYDROCARBONS
1 Give IUPAC names for the following compounds
1) CH3 – CH = CH – CH = CH – C ≡ C – CH3 : octa – 2, 4 – diene – 6 – yne
2)

: 5 – ethyl – 4, 5 – dimethyl – 2 – hexyne

3) (CH3)3 C – C ≡ C – CH (CH3)3 : 2, 2, 5 – trimethyl – 3 – hexyne

4) ethyl isopropyl acetylene : 2 – methyl – 3 – hexyne
(CH3)2 – CH – C ≡ C – CH2 CH3
5) CH ≡ C – C ≡ C – C ≡ CH : hexa – 1, 3, 5 – triyne
2 Identify the compound A, B, C and D in the following series of reactions

Ans:
alc. KOH Cl2 / CCl4
CH3-CH2-Br → CH2 = CH2 → CH2 – CH2
-HBr
Ethylene Cl Cl
(A) Ethylene dichloride (B)
i) O3 ii) Zn / H2O NaNH2
2 HCHO + H2O2 CH ≡ CH
Formaldehyde (C) Acetylene (D)
3 Write short notes on ortho, para directors in aromatic electrophilic substitution
reactions.
• When mono substituted benzene undergoes an electrophilic substitution reaction, the rate
of the reaction and the site of attack of the incoming electrophile depends on the functional
group already attached to it.
• Some groups increase the reactivity of benzene ring and are known as activating groups.
• Some groups which decrease the reactivity are known as deactivating groups.
• We further divide these groups into two categories depending on the way they influence
the orientation of attack by the incoming groups.
• Those which increases electron density at ‘ortho’ and ‘para’ position are known as ortho-
para directors
• while those which increase electron density at ‘meta’ position is known as meta-directors.
Ortho and para directing groups:
• All the activating groups are ‘ortho-para’ directors.
• Eg: –OH, –NH2, –NHR, –NHCOCH3, –OCH3, –CH3, –C2H5 etc.
• Let us consider the directive influences of phenolic (-OH) group. Phenol is the resonance
hybrid of following structures.

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• In these resonance structures, the (-) charge residue is present on ortho and para position
of ring structure.
• Therefore, phenolic group activates the benzene ring for electrophilic attack at ‘ortho’ and
‘para positions and hence –OH group is an ortho-para director and activator.
Meta directing groups:
• Generally, all deactivating groups are meta-directors.
• Eg: –NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H etc.
• Let us consider the directive influence of aldehyde (-CHO) group. Benzaldehyde is the
resonance hybrid of following structures.

• Here overall density of benzene ring decreases due to –I effect of –CHO group there by
deactivating the benzene for electrophilic attack.
• However resonating structure shows that electron density is more in meta position,
compared to o & p-position. Hence –CHO group is a meta-director and deactivator.
4 How is propyne prepared from an alkylene dihalide?
alcoholic KOH
CH3-CH-CH2 → CH3-C≡CH + 2 KBr + 2 H2O
Δ
Br Br propyne
1, 2 – dibromo propane
5 An alkylhalide with molecular formula C6H13Br on dehydro halogenation gave two
isomeric alkenes X and Y with molecular formula C6H12. On reductive ozonolysis, X and
Y gave four compounds CH3COCH3, CH3CHO, CH3CH2CHO and (CH3)2CHCHO. Find the
alkylhalide.
An alkylhalide with molecular formula C6H13Br
CH3 – CH – CH – CH2CH3
CH3 Br
Δ alcoholic KOH

CH3 – C = CH – CH2 – CH3 CH3 – CH – CH = CH – CH3

CH3 CH3
2 – methyl pent – 2 – ene 2 – methyl pent – 3 – ene

1) O3 1) O3
2) Zn / H2O 2) Zn / H2O

CH3COCH3 + CH3CH2CHO (CH3)2 – CH – CHO + CH3CHO

So, the alkyl halide is 3 – bromo – 2 – methyl propane.

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6 Describe the mechanism of nitration of benzene.

Reagents: Conc.HNO3 / Conc. H2SO4 ; Electrophile: NO2+ (Nitronium ion)

Mechanism:
Step – 1:

Step – 2:

Step – 3:

7 How does Huckel rule help to decide the aromatic character of a compound. (Sep-21,
Jun-23)
A compound may be aromatic, if it obeys the following rules
(i) The molecule must be co-planar
(ii) Complete delocalization of π electron in the ring
(iii) Presence of (4n+2) π electrons in the ring where n is an integer (n=0,1,2….)
This is known as Huckel’s rule.
8 Suggest the route for the preparation of the following from benzene.
1) 3 – chloro nitrobenzene

2) 4 – chlorotoluene

3) Bromo benzene

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4) m - dinitro benzene

9 Suggest a simple chemical test to distinguish propane and propene.

• Propene decolourises reddish brown colour of bromine water, but propane does not
decolourise bromine water.
• Propene decolourises pink coloured acidified KMnO4 solution but propane does not
decolourise it.
10 Describe the conformers of n - butane. (Jun-19)
n-Butane may be considered as a derivative of ethane, as one hydrogen on each carbon
is replaced by a methyl group
Eclipsed conformation:
In this conformation, the distance between the two-methyl group is minimum. So, there
is maximum repulsion between them and it is the least stable conformer.
Anti or staggered form
In this conformation, the distance between the two methyl groups is maximum and so
there is minimum repulsion between them. And it is the most stable conformer.
The following potential energy diagram shows the relative stabilities of various
conformers of n-butane.

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11 What happens when isobutylene is treated with acidified potassium permanganate?

12 How will you convert ethyl chloride in to

i) ethane
Zn / HCl
CH3CH2Cl → CH3 – CH3 + HCl
2[H]
Ethane
ii) n – butane
dry ether
CH3CH2Cl + ClCH2CH3 + 2Na → CH3CH2CH2CH3
n – butane
13 Explain Markownikoff's rule with suitable example.
“When an unsymmetrical alkene reacts with hydrogen halide, the hydrogen adds to the
carbon that has more number of hydrogen and halogen add to the carbon having fewer
hydrogen”. Eg:

14 Write the chemical equations for combustion of propane.

CH3-CH2-CH3 + 5O2 3CO2 + 4H2O + Energy

15 What happens when ethylene is passed through cold dilute alkaline potassium
permanganate.
Cold dilute alkaline KMnO4
CH2=CH2 + H2O → CH2 – CH2 + MnO2
H2 O+[O]
OH OH
Ethylene glycol
16 Write the structures of folowing alkanes.
1) 2, 3 – Dimethyl – 6 – (2 – methyl propyl) decane

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2) 5 – (2 – Ethyl butyl) – 3, 3 – dimethyldecane

3) 5 – (1, 2 – Dimethyl propyl) – 2 – methylnonane

17 How will you prepare propane from a sodium salt of fatty acid?
NaOH / CaO
CH3CH2CH2COONa → CH3CH2CH3 + Na2CO3
Δ
Sodium butyrate Propane
18 H + / Heat HBr
CH3 – CH(CH3) – CH(OH) – CH3 → (A) major product → (B) major product.
Identify A and B.

19 Complete the following:

Lindlar Catalyst
i) 2 – butyne →
Lindlar Catalyst
CH3 – C ≡ C – CH3 + H2 →
I2
ii) CH2 = CH2 → ?

Zn / C2 H5 OH
iii) CH2 – CH2 → ?
Br Br
Zn / C2 H5 OH
→

H2 O
iv) CaC2 → ? (Jun-23)

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20 How will you distinguish 1 – butyne and 2 – butyne?
• 1 – butyne and 2 – butyne can be distinguished by treating it with ammonical silver nitrate.
• 1 – butyne gives white precipitate with ammoniated silver nitrate and gives red precipitate
with ammoniated cuprous chloride, but 2 – butyne does not reacts with ammonical AgNO3
solution.

21 Write a short note on corey – House mechanism?

An alkyl halide and lithium di alkyl copper are reacted to give higher alkane.
CH3CH2Br + (CH3)2 LiCu CH3CH2CH3 + CH3Cu + LiBr
22 What are hydrocarbons present in LPG? Give its uses.
A mixture of propane and butane present in LPG. It is used as fuel for household
cooking purpose.
23 Define polymerisation? (Jun-19)
A polymer is a large molecule formed by the combination of larger number of small
molecules. The process in known as polymerisation.
Red hot iron tube
Eg: nCH2 = CH2 → ( CH2 – CH2 )n
873K
24 How does polystyrene prepared from styrene? Give its uses.
free radical polymerisation
nCH2 = CH → ( CH2 – CH2 )n
Uses: it is used to prepare disposable plates, mugs, insulators in refrigerators, freezers, etc
25 What is BHC? How is it prepared (May-22)? Give its uses. (or) how benzene is converted
into BHC? (May-24)
Benzene reacts with three molecules of Cl2 in the presence of sun light or UV light to
yield Benzene Hexa Chloride (BHC) C6H6Cl6. This is known as gammaxane or Lindane.

Uses: it is a powerful insecticide.

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26 How does acetylene react with ozone? (Jul-19)

27 Give the uses of acetylene?

• Acetylene is used in oxy acetylene torch used for welding and cutting metals.
• It is used for manufacture of PVC, polyvinyl acetate, polyvinyl ether, orlon and neoprene
rubbers.
28 What happens when acetylene is passed through red hot iron tube? (Mar-19, Sep-21) (or)
How does benzene prepared from the following? (Mar-24)
a) Acetylene: (Mar-19, Mar-24)
Ethyne undergoes cyclic polymerization on passing through red hot iron tube. Three
molecules of ethyne polymerises to benzene.

b) Phenol: (Mar-19, Mar-24)

C6H5OH + Zn C6H6 + ZnO
Phenol
29 Define Friedel Craft’s Alkylation? (or) How does toluene prepared from benzene? (Mar-
19, Mar-23)

30 Define Friedel Craft’s Acylation (Acetylation)? (Mar-23)

31 Define Birch reduction? (Jul-22)

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32 Explain Anti-Markovnikoff ’s Rule (or) Peroxide Effect (or) Kharasch Addition?
The addition of HBr to an alkene in the presence of organic peroxide, gives the anti
Markovnikoff’s product. This effect is called peroxide effect.
peroxide
CH3 – CH = CH2 + HBr → CH3 – CH2 – CH2 – Br
(C6 H5 CO)2 O2
Mechanism:
The reaction proceeds via free radical mechanism.
Step:1

Step:2

Step:3
The Bromine radical adds to the double bond in the way to form more stable alkyl free
radical.

Step:4

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33 Explain the structure of benzene?
1. Elemental Analysis and molecular weight determination have proved that the molecular
formula of benzene is C6H6. This indicates that benzene is a highly unsaturated
compound.
2. Benzene could be constructed as a straight chain or ring compound but it not feasible
since it does not show the properties of alkenes or alkynes.
3. Benzene reacts with bromine in the presence of AlCl3 to form mono bromo benzene. It
indicates that all the six hydrogen atoms in benzene were identical. This is possible only if
it has a cyclic structure of six carbons each containing one hydrogen.
4. Benzene can add on to three moles of hydrogen in the presence of nickel catalyst to give
cyclohexane. This confirms cyclic structure of benzene and the presence of three carbon-
carbon double bond.
5. In 1865, August Kekule suggested that benzene consists of a cyclic planar structure of six
carbon with alternate single and double bonds. There were two objections:
(i) Benzene forms only one ortho disubstituted products whereas the Kekule’s structure
predicts two o-di substituted products as shown below.

(ii) Kekule’s structure failed to explain why benzene with three double bonds did not give
addition reactions like other alkenes.
6. The phenomenon in which two or more structures can be written for a substance which
has identical position of atoms is called resonance. The actual structure of the molecule is
said to be resonance hybrid of various possible alternative structures. In benzene,
Kekule’s structures I & II represented the resonance structure, and structure III is the
resonance hybrid of structure I &II

7. Spectroscopic measurements show that benzene is planar and all of its carbon-carbon
bonds are of equal length 1.40A°. This value lies between carbon-carbon single bond
length 1.54A° and carbon-carbon double bond length 1.34A°.
8. All the six carbon atoms of benzene are sp2 hybridized. six sp2 hybrid orbitals of carbon
linearly overlap with six 1s orbitals of hydrogen atoms to form six C - H sigma bonds.
Overlap between the remaining sp2 hybrid orbitals of carbon forms six C-C sigma bonds.
9. All the σ bonds in benzene lie in one plane with bond angle 120°. Each carbon atom in
benzene possesses an unhybridized p-orbital containing one electron. The lateral overlap
of their p-orbital produces 3 π- bond The six electrons of the p-orbitals cover all the six
carbon atoms and are said to be delocalised. Due to delocalization, strong π-bond is
formed which makes the molecule stable.

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10. Hence unlike alkenes and alkynes benzene undergoes substitution reactions rather
addition reactions under normal conditions.

11. Hence, there are three ways in which benzene can be represented.

34 Explain the conformations of ethane?

The two tetrahedral methyl groups can rotate about the carbon – carbon bond axis
yielding several arrangements called conformers. The extreme conformations are staggered
and eclipsed conformation. There can be number of other arrangements between staggered
and eclipsed forms and their arrangements are known as skew forms.
Eclipsed conformation:
• In this conformation, the hydrogen’s of one carbon are directly
behind those of the other.
• The repulsion between the atoms is maximum and it is the least
stable conformer.
Staggered conformation:
• In this conformation, the hydrogens of both the carbon atoms are
far apart from each other.
• The repulsion between the atoms is minimum and it is the most
stable conformer.
Skew Conformation:
The infinite numbers of possible intermediate conformations
between the two extreme conformations are referred as skew conformations.
35 Write Sabatier- Sendersens reaction?
Ni
CH2 = CH2 + H2 → CH3 - CH3
298 K
36 Write wurtz reaction?
dry ether
CH3 – Br + 2Na + Br – CH3 → CH3 - CH3 + 2NaBr
37 Write Wurtz – Fittig Reaction?
ether
C6H5Br + 2Na +CH3I → C6H5CH3 + NaBr + NaI
38 Write Friedel Craft’s Reaction?
anhydrous AlCl3
C6H6 + CH3Cl → C6H5CH3 + HCl

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14. HALOALKANES AND HALOARENES
1 Differentiate the following compounds into alkyl, allylic, vinyl and benzylic halide?
i) CH3 – CH = CH – Cl : vinyl halide
ii) C6H5CH2I : benzylic halide
iii) CH3 – CH – CH3 : alkyl halide
Br
iv) CH2 = CH – Cl : vinyl halide
2 Why chlorination of methane is not possible in dark?
This reaction is a free radical substitution reaction. The energy required to form free
radical by homolytic cleavage can’t be received from dark. So, this reaction is not possible in
dark.
3 How will you prepare n-propyl iodide from n-propyl bromide?
It can be prepared by Finkelstein reaction.
Acetone
CH3CH2CH2Br + NaI → CH3CH2CH2I + NaBr
Δ
n-propyl bromide n-propyl iodide
4 Which alkyl halide from the following pair is i) chiral ii) undergoes faster S N2 reaction?

i) chiral molecule:

(Secondary butyl bromide)

ii) undergoes faster SN2 reaction:

(n-butyl chloride)
5 How does chlorobenzene react with sodium in the presence of ether? What is the name
of the reaction?
Haloarenes react with sodium metal in dry ether, two aryl groups combine to give biaryl
products. This reaction is called Fittig reaction.
Ether
C6H5Cl + 2Na + Cl - C6H5 → C6H5 - C6H5 + 2NaCl
Δ
6 Give reasons for polarity of C-X bond in halo alkane.
Carbon halogen bond is a polar bond as halogens are more electro negative than
carbon. The carbon atom exhibits a partial positive charge (+) and halogen atom a partial
negative charge (-).

7 Why is it necessary to avoid even traces of moisture during the use of Grignard
reagent?
Grignard reagents react with water to form alkanes. Even traces of water is enough to
form alkanes. So, all the reagents used should be dry.
RMgX + H2O RH + MgX (OH)

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8 What happens when acetyl chloride is treated with excess of CH3MgI?
Acetyl chloride reacts with Grignard reagent to form ketones. However, with excess of
Grignard reagent it forms tertiary alcohol.
O OMgI O OH
H2 O / H+ CH3 MgI
CH3 – C – Cl + CH3MgI CH3–C–Cl → CH3 – C – CH3 + MgI(Cl) → CH3 –C – CH3
CH3 CH3
9 Arrange the following alkyl halide in increasing order of bond enthalpy of RX.
CH3Br, CH3F, CH3Cl, CH3I
increasing order of bond enthalpy: CH3I < CH3Br < CH3Cl < CH3F
10 What happens when chloroform reacts with oxygen in the presence of sunlight?
1 Air
CHCl3 + 2 O2 → COCl2 + HCl
Sunlight
Phosgene
11 Write down the possible isomers of C5H11Br and give their IUPAC and common names.
possible isomers IUPAC Name Common Name
1 CH3CH2CH2CH2CH2Br 1 – Bromo pentane n – pentyl bromide
2 CH3CH2CH2CH – CH3
2 - Bromo pentane 2 – pentyl bromide
Br
3 CH3CH2CH – CH2CH3
3 - Bromo pentane 3 – pentyl bromide
Br
4 CH3CH – CH2CH2Br 1 - Bromo – 3 – methyl
isopentyl bromide
CH3 butane
5 CH3 – CH – CH – CH3 2 - Bromo – 3 – methyl
2 - Bromo – 3 – methyl butane
CH3 Br butane
6 CH3 –CH2 –CH– CH2Br 1 - Bromo – 2 – methyl
2 – methyl butyl bromide
CH3 butane
7 CH3
2 - Bromo – 2 – methyl
CH3 – C – CH2 – CH3 Tertiary pentyl bromide
butane
Br
8 CH3
1 - Bromo – 2, 2 – dimethyl
CH3 – C – CH2 – Br Neo-pentyl bromide
propane
CH3
13 Reagents and the conditions used in the reactions are given below. Complete the table
by writing down the product and the name of the reaction.
Name of the
Reaction Product
reaction
pyridine CH3CH2Cl
CH3CH2OH + SOCl2 → CH3CH2Cl +SO2+ HCl Darzen's reaction
Ethyl chloride
CH3CH2Br + AgF CH3CH2F + AgBr CH3CH2F
Swarts reaction
Ethyl fluoride
ether C6H5 – C6H5
2C6H5Cl + 2Na → C6H5 – C6H5 + 2NaCl Fittig reaction
Biphenyl
12 Mention any three methods of preparation of haloalkanes from alcohols.
1) Reaction with hydrogen halide:
anhydrous ZnCl2
CH3CH2OH + HCl → CH3CH2Cl + H2O
Δ

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2) Reaction with phosphorus halide:
CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl
3) Reaction with thionyl chloride:
pyridine
CH3CH2OH + SOCl2 → CH3CH2Cl + SO2 + HCl

14 Compare SN1 and SN2 reaction mechanisms.

SN1 reaction SN2 reaction
1 The rate of the following SN1 reaction The rate of SN2 reaction depends upon the
depends upon the concentration of alkyl concentration of both alkyl halide and the
halide (RX) and is independent of the nucleophile.
concentration of the nucleophile (OH−).
2 Rate of the reaction = k [alkyl halide] Rate of reaction = k2 [alkylhalide]
[nucleophile]
3 It follows first order kinetics It follows second order kinetics
4 It occurs in two steps. It occurs in one step.
5 Nucleophile attacks alkyl halide from both The attack of nucleophile occurs from the
the sides back side
6 Carbocation is formed No carbocation formation
7 Tertiary alkyl halide undergoes this Primary alkyl halide undergoes this
reaction reaction
8 If halo alkane substrate is optically active SN2 reaction of an optically active
then, the product obtained will be optically haloalkane is always accompanied by
inactive racemic mixture. inversion of configuration at the
asymmetric centre.
15 Discuss the aromatic nucleophilic substitution reaction of chlorobenzene.
Halo arenes do not undergo nucleophilic substitution reaction readily. This is due to C–X
bond in aryl halide is short and strong and also the aromatic ring is a centre of high electron
density.
The halogen of haloarenes can be substituted by OH–, NH2–, or CN– with appropriate
nucleophilic reagents at high temperature and pressure.
Eg: Dow’s Process

16 Account for the following

(i) t-butyl chloride reacts with aqueous KOH by SN1 mechanism while n-butyl chloride
reacts with SN2 mechanism.
tertiary butyl chloride readily loses Cl- to form stable tertiary butyl carbocation and reacts
with aqueous KOH by SN1 mechanism but n-butyl chloride does not undergoes ionisation to
form n-butyl carbocation because it is not stable. So it prefers to undergo reaction by SN2
mechanism.
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(ii) p-dichloro benzene has higher melting point than those of o-and m-dichloro
benzene.
The higher melting point of p-isomer is due to its,
➢ Symmetry
➢ Close packing of its molecules in the crystal lattice
➢ Strong intermolecular attractive force.
17 In an experiment ethyl iodide in ether is allowed to stand over magnesium pieces.
Magnesium dissolves and product is formed
a) Name the product and write the equation for the reaction.
Ether
Methyl magnesium iodide is formed. CH3I + Mg → CH3MgI
b) Why all the reagents used in the reaction should be dry? Explain.
All the reagents used in the reaction should be dry because the moisture present in the
reagents will decompose ethyl iodide to form alkane.
c) How is acetone prepared from the product obtained in the experiment.

18 Write a chemical reaction useful to prepare the following:

i) Freon-12 from Carbon tetrachloride

ii) Carbon tetrachloride from carbon disulphide

19 What are Freons? Discuss their uses and environmental effects

The chloro fluoro derivatives of methane and ethane are called freons.
Uses:
(i) Freons are a used as refrigerants in refrigerators and air conditioners.
(ii) It is used as a propellant for aerosols and foams
(iii) It is used as propellant for foams to spray out deodorants, shaving creams, and
insecticides.
(iv) chlorine free radicals were formed from chloro fluoro derivatives. It forms hole in ozone
layer.
20 Predict the products when bromoethane is treated with the following
i) KNO2
C2H5Br + KNO2 C2H5ONO + KBr
ii) AgNO2
C2H5Br + AgNO2 C2H5NO2 + AgBr
21 Chloroform is kept with a little ethyl alcohol in a dark coloured bottle why?
Chloroform undergoes oxidation in the presence of light and air to form phosgene
(carbonyl chloride) which is very poisonous. To avoid chloroform to undergo oxidation
reaction it is kept with a little ethyl alcohol in a dark coloured bottle.

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22 Explain the mechanism of SN1 reaction by highlighting the stereochemistry behind it?
SN1 Mechanism:
• SN1 stands for unimolecular nucleophilic substitution
• ‘S’ stands for substitution
• ‘N’ stands for nucleophilic
• ‘1’ stands for unimolecular (one molecule is involved in the rate determining step)
• The rate of the following SN1 reaction depends upon the concentration of alkyl halide (RX)
and is independent of the concentration of the nucleophile (OH−).
• Hence, Rate of the reaction = k [alkyl halide]
• This SN1 reaction follows first order kinetics and occurs in two steps.
• We understand SN1 reaction mechanism by taking a reaction between tertiary butyl
bromide with aqueous KOH.

Mechanism:
Step – 1:
• This step is slow and hence it is the rate determining step.

Step – 2:
• This step is fast and hence does not affect the rate of the reactions. The nucleophilic
reagent OH- can attack carbocation from both the sides, to form equal proportion of dextro
and levorotatory optically active isomers which results in optically inactive racemic mixture.

23 Write short notes on the the following

i) Raschig process

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ii) Dows Process
350 ℃
C6H5Cl + NaOH → C6H5OH + HCl
300 atm

iii) Darzens process

pyridine
C6H5OH + SOCl2 → C6H5Cl + SO2 + HCl
23 Starting from CH3MgI, how will you prepare the following?
i) Preparation of primary alcohol: (Mar-23)

ii) Preparation of secondary alcohol:

iii) Preparation of Tertiary alcohol:

iv) Preparation of aldehyde: (Jul-22, Mar-23)

v) Preparation of ketone: (Jul-22)

vi) Preparation of carboxylic acids:

vii) Preparation of esters: (Mar-23)

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viii) Preparation of higher ethers:

ix) Preparation of alkyl cyanide:

x) Preparation of Alkanes: (Mar-19, Jul-22)

24 Complete the following reactions

peroxide
i) CH3 – CH = CH2 + HBr → CH3CH2CH2Br (n – propyl bromide)
𝐚𝐥𝐜𝐨𝐡𝐨𝐥
ii) CH3 – CH2 – Br + NaSH → CH3CH2SH + NaBr (Ethanethiol)
𝐇𝟐 𝐎
THF
iii) C6H5Cl + Mg → C6H5MgCl (phenyl magnesium chloride)
Δ
iv) CHCl3 + HNO3 → CCl3NO2 + H2O (Chloropicrin)
Δ
v) CCl4 + H2O → COCl2 + 2H2O (phosgene)
25 Explain the preparation of the following compounds
i) DDT: (Sep-20, Jun-23)

ii) Chloroform:
It is prepared in the laboratory by the reaction between ethyl alcohol with bleaching
powder followed by the distillation of the product chloroform.

Step – 1: Oxidation:

Step – 2: Chlorination:

Step – 3: Hydrolysis:

iii) Biphenyl:

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iv) Chloropicrin:

v) Freon-12

27 An organic compound (A) with molecular formula C2H5Cl reacts with KOH gives
compounds (B) and with alcoholic KOH gives compound (C). Identify (A), (B) and (C).

aqueous KOH Compound Formula Name

CH3CH2Cl → CH3CH2OH + KCl
A CH3CH2Cl Ethyl chloride
(A) (B)
alcoholic KOH
B CH3CH2OH Ethyl alcohol
CH3CH2Cl → CH2 = CH2 + KCl + H2O C CH2 = CH2 Ethylene
(A) (C)
28 Simplest alkene (A) reacts with HCl to form compound (B). Compound (B) reacts with
ammonia to form compound (C) of molecular formula C2H7N. Compound (C) undergoes
carbylamine test. Identify (A), (B) and (C).
HCl Compound Formula Name
CH2 = CH2 → CH3CH2Cl A CH2 = CH2 Ethylene
(A) (B)
B CH3CH2Cl Ethyl chloride
CH3CH2Cl + NH3 CH3CH2NH2 + HCl C CH3CH2NH2 Ethyl amine
(B) (C)
29 A hydrocarbon C3H6 (A) reacts with HBr to form compound (B). Compound (B) reacts
with aqueous potassium hydroxide to give (C) of molecular formula C3H8O. What are
(A), (B) and (C). Explain the reactions.
Compound Formula Name
HBr
CH3 – CH = CH2 → CH3 – CH – CH3 A CH3 – CH = CH2 Propene
(A) Br CH3 – CH – CH3 Isopropyl
B
Br bromide
(B)
CH3 – CH – CH3 Isopropyl
aqueous KOH C
CH3 – CH – CH3 → CH3 – CH – CH3 + KBr OH alcohol
Br OH
30 What is the IUPAC name of the insecticide DDT? Why is their use banned in most of
the countries?
• IUPAC name of the DDT is 2, 2 – bis (4 – chloro phenyl) – 1, 1, 1 – trichloro ethane
• DDT is more stable and non-biodegradable.
• DDT is banned because of its long-term toxic effect through food chain.
31 Two isomers (A) and (B) have the same molecular formula C2H4Cl2. Compound (A)
reacts with aqueous KOH gives compound (C) of molecular formula C2H4O. Compound
(B) reacts with aqueous KOH gives compound (D) of molecular formula C2H6O2. Identify
(A), (B), (C) and (D).
Cl
CH3CH மற்றும் CH2 – CH2
Cl Cl Cl
(A) (B)

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Compound Formula Name

A CH3 CH Cl2 Ethylene chloride
(A) B Ethylene dichloride

C CH3 CHO Acetaldehyde

(C)
D Ethylene glycol

(B) (D)
32 Write a note on Williamson’s synthesis? (Mar-19)
Δ
CH3CH2Br + NaOCH2CH3 → CH3CH2OCH2CH3 + NaBr
33 Give any two uses of the following Poly halogen compounds.
1) Chloroform:
• it is used as an anaesthetic.
• it is used as solvent
2) Carbon tetrachloride:
• it is used in dry cleaning process
• Carbon tetrachloride is used in fire extinguishers.
3) DDT (Sep-19, Mar-24)
• It is used to control certain insects which carries diseases like malaria and yellow fever
• It is used in farms to control some agricultural pests
• It is used in building construction as pest control.
4) Iodoform:
• It is used as an antiseptic
• It is used in pharmaceutical industry.
34 Explain the mechanism of SN2 reaction? (Mar-24)
• SN2 stands for bimolecular nucleophilic substitution
• ‘S’ stands for substitution
• ‘N’ stands for nucleophilic
• ‘2’ stands for bimolecular
• The rate of SN2 reaction depends upon the concentration of both alkyl halide and the
nucleophile.
• Rate of reaction = k2 [alkylhalide][nucleophile]
• It follows second order kinetics and occurs in one step.
• This reaction involves the formation of a transition state in which both the reactant
molecules are partially bonded to each other. The attack of nucleophile occurs from the
back side.
• The carbon at which substitution occurs has inverted configuration during the course of
reaction just as an umbrella has tendency to invert in a wind storm. This inversion of
configuration is called Walden inversion.

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(-) 2 – Bromo octane Transition State (+) 2 – Octanol

35 Explain the mechanism of Elimination reaction?
E2 reaction mechanism:

• The rate of E2 reaction depends on the concentration of alkyl halide and base
• Rate = k [alkyl halide] [base]
• It is therefore, a second order reaction. Generally primary alkyl halide undergoes this
reaction in the presence of alcoholic KOH.
• It is a one step process in which the abstraction of the proton from the  carbon and
expulsion of halide from the  carbon occur simultaneously.

E1 reaction mechanism:

• Generally, tertiary alkyl halide which undergoes elimination reaction by this mechanism in
the presence of alcoholic KOH.
• Rate = k [alkyl halide]
• It follows first order kinetics.

Step – 1:

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Step – 2:

36 Write short notes on Swarts reaction? (Sep-21)

Δ
CH3CH2Br + AgF → CH3CH2F + AgBr
Bromo ethane Fluoro ethane
37 Write Hunsdiccker reaction?
CCl4
CH3CH2COOAg + Br2 → CH3CH2Br + CO2 + AgBr
Silver propionate Bromo ethane
38 Explain Electrophilic substitution reaction of chloro benzene? (or) Write the following
reactions of chlorobenzene. Halogenation, Nitration, Sulphonation and Friedel - Crafts
alklation.

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39 Write Sandmeyer reaction (or) Gattermann reaction?

40 alcoholic KOH 𝑵𝒂𝑵𝑯𝟐

CH2 = CH2 + Br2 A→ B→ C. Identify A, B and C. (Mar-24)

Compound Name
A 1,2 – dibromo ethane
B Vinyl bromide (or) Bromo ethene
C Acetylene (or) Ethyne

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15. ENVIRONMENTAL CHEMISTRY

1 Dissolved oxygen in water is responsible for aquatic life. What processes are
responsible for the reduction in dissolved oxygen in water?
• Human activities
• Organic matters
• Eutrophication
• Growth of algae
Due to these above activities, microorganisms present in water decompose organic
matter and consume dissolved oxygen in water causes reduction in dissolved oxygen in water.
2 What would happen, if the greenhouse gases were totally missing in the earth’s
atmosphere?
If the greenhouse gases were totally missing in the earth’s atmosphere, then earth’s
average surface temperature would be only about −18 °C (0 °F).
3 Define smog.
• Smog = smoke + fog
• It forms droplets that remain suspended in the air.
4 Which is considered to be earth’s protective umbrella? Why? (Jun-23)
• Ozone layer is considered to be the earth’s protective umbrella
• It acts as an umbrella or shield for harmful UV radiations.
• It protects us from harmful effect such as skin cancer.
5 What are degradable and non-degradable pollutants?
i. Bio-degradable pollutants:
• The pollutants which can be easily decomposed by the natural biological processes
• Eg: plant wastes, animal wastes etc.
ii. Non bio-degradable pollutants:
• The pollutants which cannot be decomposed by the natural biological processes
• Eg: metal wastes, plastics, nuclear wastes etc.,
6 From where does ozone come in the photo chemical smog?
Ozone in the photo chemical smog is formed through sequence of following reactions.
N2 + O2 2NO
2NO + O2 2NO2
Sunlight
NO2 → NO+ (O)
(O)+O2 O3
O3+NO NO2 + O2
Sunlight
NO2 → NO+ (O)
7 A person was using water supplied by corporation. Due to shortage of water he started
using underground water. He felt laxative effect. What could be the cause?

Excessive concentration (>500ppm) of sulphates in drinking water causes laxative effect.

8 What is green chemistry? (Jun-19, Jun-23)
Green chemistry is a chemical philosophy encouraging the design of products and
processes that reduce or eliminate the use and generation of hazardous substances.

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9 Explain how does greenhouse effect cause global warming? (Sep-20)
• The trapping of heat in the atmosphere by certain gases is called as greenhouse effect.
• The earth’s atmosphere allows most of the visible light from the Sun to pass through and
reach Earth’s surface. As Earth’s surface is heated by sunlight, it radiates part of this
energy back toward space as longer wavelengths (IR).
• Some of the heat is trapped by CH4, CO2, CFCs and water vapour present in the
atmosphere. They absorb IR radiation and effectively block a large portion of earth’s
emitted radiation. The radiation thus absorbed is partly reemitted to earth’s surface.
Therefore, the earth’s surface gets heated up by a phenomenon called greenhouse effect.
• Thus, Greenhouse effect may be defined as the heating up of the earth surface due to
trapping of infrared radiations reflected by earth’s surface by CO2 layer in the atmosphere”.
• The heating up of earth through the greenhouse effect is called global warming.
10 Mention the standards prescribed by BIS for quality of drinking water

11 How does classical smog differ from photochemical smog?

Smog is a combination of smoke and fog which forms droplets that remain suspended in
the air.
Classical smog Photochemical smog
It occurs in cool humid climate. It occurs in warm, dry and sunny climate.
It generally occurs in the morning and It forms when the sun shines and becomes
becomes worse when the sun rises. worse in the afternoon.
This is mainly due to the induced It is is formed by the combination of smoke, dust
oxidation of SO2 to SO3, which reacts and fog with air pollutants like oxides of nitrogen
with water yielding sulphuric acid aerosol. and hydrocarbons in the presence of sunlight.
12 What are particulate pollutants? Explain any three. (Mar-23)
Particulate pollutants are small solid particles and liquid droplets suspended in air.
(i) Smoke: Smoke particulate consists of solid particles (or) mixture of solid and liquid particles
formed by combustion of organic matter.
(ii) Dust: Dust composed of fine solid particles produced during crushing and grinding of solid
materials.
(iii) Mists: They are formed by particles of spray liquids and condensation of vapours in air.

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13 Even though the use of pesticides increases the crop production, they adversely affect
the living organisms. Explain the function and the adverse effects of the pesticides.
Pesticides are the chemicals that are used to kill or stop the growth of unwanted
organisms. But these pesticides can affect the health of human beings. These are further
classified as
a. Insecticides: Insecticides like DDT, BHC, aldrin etc. can stay in soil for long period of time
and are absorbed by soil. They contaminate root crops like carrot, raddish, etc.
b. Fungicide: Organo mercury compounds are used as most common fungicide. They
dissociate in soil to produce mercury which is highly toxic.
c. Herbicides: Herbicides are the chemical compounds used to control unwanted plants. They
are otherwise known as weed killers. Example sodium chlorate (NaClO3) and sodium arsenite
(Na3AsO3). Most of the herbicides are toxic to mammals.
14 Ethane burns completely in air to give CO2, while in a limited supply of air gives CO.
The same gases are found in automobile exhaust. Both CO and CO2 are atmospheric
pollutants
i) What is the danger associated with these gases
• CO is a poisonous gas
• CO2 is responsible for global warming.
ii) How do the pollutants affect the human body?
1. CO:
• It binds with haemoglobin and forms carboxy haemoglobin
• It impairs normal oxygen transport by blood and hence the oxygen carrying capacity of
blood is reduced.
• This oxygen deficiency results in headache, dizziness, tension, Loss of consciousness,
blurring of eye sight and cardiac arrest.
2. CO2:
• It s responsible for global warming.
• It causes headache and nausea.
15 On the basis of chemical reactions involved, explain how do CFC’s cause depletion of
ozone layer in stratosphere?
• The chloro fluoro derivatives of methane and ethane are referred by trade name Freons.
• These Chloro Fluoro Carbon compounds are stable, non-toxic, noncorrosive and non-
inflammable, easily liquefiable
• They are used in refrigerators, air- conditioners and in the production of plastic foams.
• CFC’s are the exhaust of supersonic air craft’s and jumbo jets flying in the upper
atmosphere.
• They slowly pass from troposphere to stratosphere.
• They stay for very longer period of 50 - 100 years.
• In the presence of uv radiation, CFC’s break up into chlorine free radical

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• Chlorine radical is regenerated in the course of reaction. Due to this continuous attack of
Cl˚ thinning of ozone layer takes place which leads to formation of ozone hole.
• It is estimated that for every reactive chlorine atom generated in the stratosphere 1,00,000
molecules of ozone are depleted.
16 How is acid rain formed? Explain its effect. (Mar-19, Mar-24)
• Rain water normally has a pH of 5.6 due to dissolution of atmospheric CO 2 into it.
• Oxides of sulphur and nitrogen in the atmosphere may be absorbed by droplets of water
that make up clouds and get chemically converted into sulphuric acid and nitric acid
respectively.
• As a result, pH of rain water drops below the level 5.6, hence it is called acid rain.
Harmful effects of acid rain:
• Acid rain causes extensive damage to buildings and structural materials of marbles. This
attack on marble is termed as Stone leprosy.
CaCO3 + H2SO4 CaSO4 + H2O + CO2
• Acid rain affects plants and animal life in aquatic ecosystem.
• It is harmful for agriculture, trees and plants as it dissolves and removes the nutrients
needed for their growth.
• It corrodes water pipes resulting in the leaching of heavy metals such as iron, lead and
copper into drinking water which have toxic effects.
• It causes respiratory ailment in humans and animals.
17 Differentiate the following
(i) BOD and COD (Jun-23)
BOD COD
The total amount of oxygen in milligrams It is defined as the amount of
consumed by microorganisms in decomposing oxygen required by the organic
1 the waste in one litre of water at 20oC for a period matter in a sample of water for its
of 5 days is called biochemical oxygen demand oxidation by a strong oxidising agent
(BOD) and its value is expressed in ppm. like K2Cr2O7 in acid medium for a
BOD is used as a measure of degree of water period of 2 hrs.
pollution. Clean water would have BOD value less
2
than 5 ppm whereas highly polluted water has
BOD value of 17 ppm or more.
(ii) Viable and non-viable particulate pollutants
Viable particulate Non-viable particulate
The viable particulates are the small size The non- viable particulates are small
1 living organisms such as bacteria, fungi, solid particles and liquid droplets
moulds, algae, etc. which are dispersed in air. suspended in air.
Some of the fungi cause allergy in human There are four types of non-viable
2 beings and diseases in plants. particulates in the atmosphere.
Eg: Smoke, Dust, Mists and Fumes
18 Explain how oxygen deficiency is caused by carbon monoxide in our blood? Give its
effect.
• Carbon monoxide is a poisonous gas produced as a result of incomplete combustion of
coal or firewood. It is released into the air mainly by automobile exhaust.
• It binds with haemoglobin and forms carboxy haemoglobin which impairs normal oxygen
transport by blood. Hence the oxygen carrying capacity of blood is reduced.

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Effects:
• This oxygen deficiency results in headache, dizziness, tension, Loss of consciousness,
blurring of eye sight and cardiac arrest.
19 What are the various methods you suggest to protect our environment from pollution?
(Sep-20)
• Waste management: Environmental pollution can be controlled by proper disposal of
wastes.
• Recycling: A large amount of disposed waste material can be reused by recycling the
waste, thus it reduces the land fill and converts waste into useful forms.
• Green Chemistry: Substitution of less toxic solvents for highly toxic ones used in certain
industrial processes.
• Use of fuels with lower sulphur content.
• Growing more trees.
• Control measures in vehicle emissions are adequate.
20 What causes methemoglobinemia or blue baby syndrome?
Use of drinking water having concentration of nitrate higher than 45 ppm may causes
methemoglobinemia (blue baby syndrome) disease in children.
21 Explain Eutrophication? (Mar-23)
• Eutrophication is a process by which water bodies receive excess nutrients that stimulates
excessive plant growth (algae, other plant weeds). This enhanced plant growth in water
bodies is called as algae bloom.
• The growth of algae in extreme abundance covers the water surface and reduces the
oxygen concentration in water. Thus, bloom-infested water inhibits the growth of other
living organisms in the water body.
• This process in which the nutrient rich water bodies support a dense plant population, kills
animal life by depriving it of oxygen and results in loss of biodiversity is known as
eutrophication.
22 What are the effects of classical smog?
• Smog is primarily responsible for acid rain.
• Smog results in poor visibility and it affects air and road transport.
• It also causes bronchial irritation.
23 What is the Impact of ozone depletion on environment?
The formation and destruction of ozone is a regular natural process, which never disturbs
the equilibrium level of ozone in the stratosphere. Any change in the equilibrium level of the
ozone in the atmosphere will adversely affect life in the biosphere in the following ways.
i) Depletion of ozone layer will allow more UV rays to reach the earth surface and layer would
cause skin cancer and also decrease the immunity level in human beings.
ii) UV radiation affects plant proteins which leads to harmful mutation of cells.
iii) UV radiation affects the growth of phytoplankton, as a result ocean food chain is disturbed
and even damages the fish productivity.
24 What includes in Total dissolved solids (TDS)? Give its effects.
• It includes cations like calcium, magnesium, sodium, potassium, iron and anions like
carbonate, bicarbonate, chloride, sulphate, phosphate and nitrate.
• Use of drinking water having total dissolved solids concentration higher than 500 ppm
causes possibilities of irritation in stomach and intestine.

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25 How does oxides of sulphur forms? What are its effects on humans and other living
things?
Sulphur dioxide and sulphur trioxide are produced by burning sulphur containing fossil
fuels and roasting sulphide ores.
Effects:
• Sulphur dioxide is a poisonous gas to both animals and plants.
• Sulphur dioxide causes eye irritation, coughing and respiratory diseases like asthma,
bronchitis,etc.
• Sulphur dioxide is oxidised into more harmful sulphur trioxide in the presence of particulate
matter present in polluted air.
Particulate matter
2SO2 + O2 → 2SO3
• SO3 combines with atmospheric water vapour to form H2SO4 , which comes down in the
form of acid rain. SO3 + H2O H2SO4
26 Write a note on oxides of nitrogen?
• Oxides of nitrogen are produced during high temperature combustion processes, oxidation
of nitrogen in air and from the combustion of fuels.

Effects:
• The oxides of nitrogen are converted into HNO3 which comes down in the form of acid rain.
• They also form reddish brown haze in heavy traffic.
• Nitrogen dioxide potentially damages plant leaves and retards photosynthesis.
• NO2 is a respiratory irritant and it can cause asthma and lung injury.
• NO2 is also harmful to various textile fibres and metals.
27 List out few contributions of green chemistry in our day to day life?
(1) Dry cleaning of clothes:
• Solvents like tetrachloroethylene used in dry cleaning of clothes, pollute the ground water
and are carcinogenic.
• In the place of tetrachloroethylene, liquefied CO2 with suitable detergent, is an alternate
solvent used. Liquified CO2 is not harmful to the ground water.
• Now a days H2O2 used for bleaching clothes in laundry, gives better results and utilises
less water.
(2) Bleaching of paper
• Conventional method of bleaching was done with chlorine.
• Now a days H2O2 can be used for bleaching paper in presence of catalyst.
(3) Synthesis of chemicals
• Acetaldehyde is now commercially prepared by one step oxidation of ethene in the
presence of ionic catalyst in aqueous medium with 90% yield.
• Instead of petrol, methanol is used as a fuel in automobiles.
• Neem based pesticides have been synthesised, which are safer than the chlorinated
hydrocarbons.
Don’t wait for the opportunity, create one – Dr. A.P.J. Abdul Kalam
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