

  

 


  

I. Multiple Choice Questions (Type-I)
1. Two students performed the same experiment separately and each one of
them recorded two readings of mass which are given below. Correct reading
of mass is 3.0 g. On the basis of given data, mark the correct option out of the
following statements.
Student Readings
(i) (ii)
A 3.01 2.99
B 3.05 2.95
(i) Results of both the students are neither accurate nor precise.
(ii) Results of student A are both precise and accurate.
(iii) Results of student B are neither precise nor accurate.
(iv) Results of student B are both precise and accurate.

2. A measured temperature on Fahrenheit scale is 200 °F. What will this reading
be on Celsius scale?
(i) 40 °C
(ii) 94 °C
(iii) 93.3 °C
(iv) 30 °C

3. What will be the molarity of a solution, which contains 5.85 g of NaCl(s) per
500 mL?
–1
(i) 4 mol L
–1
(ii) 20 mol L

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 –1
(iii) 0.2 mol L
–1
(iv) 2 mol L

4. If 500 mL of a 5M solution is diluted to 1500 mL, what will be the molarity of

the solution obtained?
(i) 1.5 M
(ii) 1.66 M
(iii) 0.017 M
(iv) 1.59 M

5. The number of atoms present in one mole of an element is equal to Avogadro

number. Which of the following element contains the greatest number of
atoms?
(i) 4g He
(ii) 46g Na
(iii) 0.40g Ca
(iv) 12g He

–1
6. If the concentration of glucose (C6H12O6) in blood is 0.9 g L , what will be the
molarity of glucose in blood?
(i) 5M
(ii) 50 M
(iii) 0.005 M
(iv) 0.5 M

7. What will be the molality of the solution containing 18.25 g of HCl gas in
500 g of water?
(i) 0.1 m
(ii) 1M
(iii) 0.5 m
(iv) 1m

8. One mole of any substance contains 6.022 × 1023 atoms/molecules. Number

of molecules of H2SO4 present in 100 mL of 0.02M H2SO4 solution is ______.
20
(i) 12.044 × 10 molecules
23
(ii) 6.022 × 10 molecules
23
(iii) 1 × 10 molecules
23
(iv) 12.044 × 10 molecules

9. What is the mass percent of carbon in carbon dioxide?

(i) 0.034%
(ii) 27.27%
Exemplar Problems, Chemistry 2

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 (iii) 3.4%
(iv) 28.7%

10. The empirical formula and molecular mass of a compound are CH2O and
180 g respectively. What will be the molecular formula of the compound?
(i) C9H18O9
(ii) CH2O
(iii) C6H12O6
(iv) C2H4O2

–1
11. If the density of a solution is 3.12 g mL , the mass of 1.5 mL solution in
significant figures is _______.
(i) 4.7g
(ii) 4680 × 10 –3 g
(iii) 4.680g
(iv) 46.80g

12. Which of the following statements about a compound is incorrect?

(i) A molecule of a compound has atoms of different elements.
(ii) A compound cannot be separated into its constituent elements by
physical methods of separation.
(iii) A compound retains the physical properties of its constituent elements.
(iv) The ratio of atoms of different elements in a compound is fixed.

13. Which of the following statements is correct about the reaction given below:
4Fe(s) + 3O2(g) → 2Fe2O3(g)
(i) Total mass of iron and oxygen in reactants = total mass of iron and
oxygen in product therefore it follows law of conservation of mass.
(ii) Total mass of reactants = total mass of product; therefore, law of multiple
proportions is followed.
(iii) Amount of Fe2O3 can be increased by taking any one of the reactants
(iron or oxygen) in excess.
(iv) Amount of Fe2O3 produced will decrease if the amount of any one of the
reactants (iron or oxygen) is taken in excess.

14. Which of the following reactions is not correct according to the law of
conservation of mass.
(i) 2Mg(s) + O2(g) → 2MgO(s)
(ii) C3H8(g) + O2(g) → CO2(g) + H2O(g)
(iii) P4(s) + 5O2(g) → P4O10(s)
(iv) CH4(g) + 2O2(g) → CO2(g) + 2H2O (g)

3 Some Basic Concepts of Chemistry

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 15. Which of the following statements indicates that law of multiple proportion is
being followed.
(i) Sample of carbon dioxide taken from any source will always have carbon
and oxygen in the ratio 1:2.
(ii) Carbon forms two oxides namely CO2 and CO, where masses of oxygen
which combine with fixed mass of carbon are in the simple ratio 2:1.
(iii) When magnesium burns in oxygen, the amount of magnesium taken
for the reaction is equal to the amount of magnesium in magnesium
oxide formed.
(iv) At constant temperature and pressure 200 mL of hydrogen will combine
with 100 mL oxygen to produce 200 mL of water vapour.

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

16. One mole of oxygen gas at STP is equal to _______.

(i) 6.022 × 1023 molecules of oxygen
(ii) 6.022 × 1023 atoms of oxygen
(iii) 16 g of oxygen
(iv) 32 g of oxygen

17. Sulphuric acid reacts with sodium hydroxide as follows :

H2SO4 + 2NaOH → Na2SO4 + 2H2O

When 1L of 0.1M sulphuric acid solution is allowed to react with 1L of 0.1M
sodium hydroxide solution, the amount of sodium sulphate formed and its
molarity in the solution obtained is
–1
(i) 0.1 mol L
(ii) 7.10 g
–1
(iii) 0.025 mol L
(iv) 3.55 g

18. Which of the following pairs have the same number of atoms?
(i) 16 g of O2(g) and 4 g of H2(g)
(ii) 16 g of O2 and 44 g of CO2
(iii) 28 g of N2 and 32 g of O2
(iv) 12 g of C(s) and 23 g of Na(s)

19. Which of the following solutions have the same concentration?

(i) 20 g of NaOH in 200 mL of solution
(ii) 0.5 mol of KCl in 200 mL of solution

Exemplar Problems, Chemistry 4

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 (iii) 40 g of NaOH in 100 mL of solution
(iv) 20 g of KOH in 200 mL of solution
20. 16 g of oxygen has same number of molecules as in
(i) 16 g of CO
(ii) 28 g of N2
(iii) 14 g of N2
(iv) 1.0 g of H2
21. Which of the following terms are unitless?
(i) Molality
(ii) Molarity
(iii) Mole fraction
(iv) Mass percent
22. One of the statements of Dalton’s atomic theory is given below:
“Compounds are formed when atoms of different elements combine in a fixed
ratio”
Which of the following laws is not related to this statement?
(i) Law of conservation of mass
(ii) Law of definite proportions
(iii) Law of multiple proportions
(iv) Avogadro law

III. Short Answer Type

23. What will be the mass of one atom of C-12 in grams?

24. How many significant figures should be present in the answer of the following
calculations?

2.5 × 1.25 × 3.5

2.01

25. What is the symbol for SI unit of mole? How is the mole defined?

26. What is the difference between molality and molarity?

27. Calculate the mass percent of calcium, phosphorus and oxygen in calcium
phosphate Ca3(PO4)2.

28. 45.4 L of dinitrogen reacted with 22.7 L of dioxygen and 45.4 L of nitrous
oxide was formed. The reaction is given below:
2N2(g) + O2(g) → 2N2O(g)
Which law is being obeyed in this experiment? Write the statement of the law?
5 Some Basic Concepts of Chemistry

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 29. If two elements can combine to form more than one compound, the masses of
one element that combine with a fixed mass of the other element, are in whole
number ratio.
(a) Is this statement true?
(b) If yes, according to which law?
(c) Give one example related to this law.

30. Calculate the average atomic mass of hydrogen using the following data :
Isotope % Natural abundance Molar mass
1
H 99.985 1
2
H 0.015 2

31. Hydrogen gas is prepared in the laboratory by reacting dilute HCl with
granulated zinc. Following reaction takes place.
Zn + 2HCl → ZnCl2 + H2
Calculate the volume of hydrogen gas liberated at STP when 32.65 g of zinc
reacts with HCl. 1 mol of a gas occupies 22.7 L volume at STP; atomic mass of
Zn = 65.3 u.
–1
32. The density of 3 molal solution of NaOH is 1.110 g mL . Calculate the molarity
of the solution.

33. Volume of a solution changes with change in temperature, then, will the molality
of the solution be affected by temperature? Give reason for your answer.

34. If 4 g of NaOH dissolves in 36 g of H2O, calculate the mole fraction of each

component in the solution. Also, determine the molarity of solution (specific
–1
gravity of solution is 1g mL ).

35. The reactant which is entirely consumed in reaction is known as limiting reagent.
In the reaction 2A + 4B → 3C + 4D, when 5 moles of A react with 6 moles of B,
then
(i) which is the limiting reagent?
(ii) calculate the amount of C formed?

IV. Matching Type

36. Match the following:
(i) 88 g of CO2 (a) 0.25 mol
23
(ii) 6.022 ×10 molecules of H2O (b) 2 mol
(iii) 5.6 litres of O2 at STP (c) 1 mol
(iv) 96 g of O2 (d) 6.022 × 1023 molecules
(v) 1 mol of any gas (e) 3 mol

Exemplar Problems, Chemistry 6

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37. Match the following physical quantities with units

Physical quantity Unit

–1
(i) Molarity (a) g mL
(ii) Mole fraction (b) mol
(iii) Mole (c) Pascal
(iv) Molality (d) Unitless
–1
(v) Pressure (e) mol L
(vi) Luminous intensity (f) Candela
(vii) Density (g) mol kg–1
(viii) Mass (h) Nm–1
(i) kg

V. Assertion and Reason Type

In the following questions a statement of Assertion (A) followed by a
statement of Reason (R) is given. Choose the correct option out of the
choices given below each question.

38. Assertion (A) : The empirical mass of ethene is half of its molecular mass.
Reason (R) : The empirical formula represents the simplest whole number
ratio of various atoms present in a compound.
(i) Both A and R are true and R is the correct explanation of A.
(ii) A is true but R is false.
(iii) A is false but R is true.
(iv) Both A and R are false.

39. Assertion (A) : One atomic mass unit is defined as one twelfth of the mass of
one carbon-12 atom.
Reason (R) : Carbon-12 isotope is the most abundunt isotope of carbon
and has been chosen as standard.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

40. Assertion (A) : Significant figures for 0.200 is 3 where as for 200 it is 1.
Reason (R) : Zero at the end or right of a number are significant provided
they are not on the right side of the decimal point.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not a correct explanation of A.
7 Some Basic Concepts of Chemistry

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 (iii) A is true but R is false.
(iv) Both A and R are false.

41. Assertion (A) : Combustion of 16 g of methane gives 18 g of water.

Reason (R) : In the combustion of methane, water is one of the products.
(i) Both A and R are true but R is not the correct explanation of A.
(ii) A is true but R is false.
(iii) A is false but R is true.
(iv) Both A and R are false.

VI. Long Answer Type

42. A vessel contains 1.6 g of dioxygen at STP (273.15K, 1 atm pressure). The
gas is now transferred to another vessel at constant temperature, where
pressure becomes half of the original pressure. Calculate
(i) volume of the new vessel.
(ii) number of molecules of dioxygen.

43. Calcium carbonate reacts with aqueous HCl to give CaCl2 and CO2 according
to the reaction given below:
CaCO3 (s) + 2HCl (aq) → CaCl2(aq) + CO2(g) + H2O(l)
What mass of CaCl2 will be formed when 250 mL of 0.76 M HCl reacts with
1000 g of CaCO3? Name the limiting reagent. Calculate the number of moles
of CaCl2 formed in the reaction.

44. Define the law of multiple proportions. Explain it with two examples. How
does this law point to the existance of atoms?

45. A box contains some identical red coloured balls, labelled as A, each weighing
2 grams. Another box contains identical blue coloured balls, labelled as B,
each weighing 5 grams. Consider the combinations AB, AB2, A2B and A2B3
and show that law of multiple proportions is applicable.

Exemplar Problems, Chemistry 8

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ANSWERS
I. Multiple Choice Questions (Type-I)

1. (ii) 2. (iii) 3. (iii) 4. (ii) 5. (iv) 6. (iii)

7. (iv) 8. (i) 9. (ii) 10. (iii) 11. (i) 12. (iii)

13. (i) 14. (ii) 15. (ii)

II. Multiple Choice Questions (Type-II)

16. (i), (iv) 17. (ii), (iii) 18. (iii), (iv)

19. (i), (ii) 20. (iii), (iv) 21. (iii), (iv)

22. (i), (iv)

III. Short Answer Type

23. 1.992648 × 10–23 g ≈ 1.99 × 10–23 g

24. 2

25. Symbol for SI Unit of mole is mol.

One mole is defined as the amount of a substance that contains as many
particles or entities as there are atoms in exactly 12 g (0.012 kg) of the 12C
isotope.

26. Molality is the number of moles of solute present in one kilogram of solvent
but molarity is the number of moles of solute dissolved in one litre of
solution.
Molality is independent of temperature whereas molarity depends on
temperature.

3 × (atomic mass of calcium)

27. Mass percent of calcium = × 100
molecular mass of Ca 3 (PO 4 )2

120 u
= ×100 = 38.71%
310 u

2 × (atomic mass of phosphorus)

Mass percent of phosphorus = × 100
molecular mass of Ca 3 (PO4 )2

2 × 31 u
= ×100 = 20%
310 u

9 Some Basic Concepts of Chemistry

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 8 × ( Atomic mass of oxygen)
Mass percent of oxygen = molecular mass of Ca (PO ) × 100
3 4 2

8 × 16 u
= ×100 = 41.29%
310 u

28. According to Gay Lussac’s law of gaseous volumes, gases combine or are
produced in a chemical reaction in a simple ratio by volume, provided
that all gases are at the same temperature and pressure.

29. (a) Yes

(b) According to the law of multiple proportions
(c) H2 + O2 → H2O
2g 16 g 18 g
(c) H2 + O2 → H2O2
2g 32 g 34 g
Here masses of oxygen, (i.e., 16 g in H2O and 32 g in H2O2) which combine
with fixed mass of hydrogen (2 g) are in the simple ratio i.e., 16 : 32 or 1 : 2

1
{(Natural abundance of H × molar mass) +
2 2
(Natural abundance of H × molar mass of H)}
30. Average Atomic Mass =
100

99.985 × 1 + 0.015 × 2
=
100
99.985 + 0.030 1 0 0 .0 1 5
= = = 1.00015 u
100 100

31. From the equation, 63.5 g of zinc liberates 22.7 litre of hydrogen. So
32.65 g of zinc will liberate

22.7 L H2 22.7
32.65 g Zn × = L = 11.35 L
65.3 g Zn 2

32. 3 molal solution of NaOH means that 3 mols of NaOH are dissolved in
1000 g of solvent.
∴ Mass of Solution = Mass of Solvent + Mass of Solute
= 1000 g + (3 × 40 g) = 1120 g

1120
Volume of Solution = mL = 1009.00 mL
1.110

Exemplar Problems, Chemistry 10

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 –1
(Since density of solution = 1.110g mL )
Since 1009 mL solution contains 3 mols of NaOH

Number of moles of solute

∴ Molarity =
Volume of solution in litre

3 mol
= × 1000 = 2.97 M
1009.00

33. No, Molality of solution does not change with temperature since mass
remains unaffected with temperature.

34. Mass of NaOH = 4 g

4g
Number of moles of NaOH = = 0.1 mol
40 g
Mass of H2O = 36 g

36 g
Number of moles of H2 O = = 2 mol
18 g

Number of moles of H2O

Mole fraction of water =
No. of moles of water + No. of moles of NaOH

2 2
= = = 0.95
2 + 0.1 2.1

Number of moles of NaOH

Mole fraction of NaOH =
No. of moles of NaOH + No. of moles of water

0.1 0.1
= = = 0.047
2 + 0.1 2.1

Mass of solution = mass of water + mass of NaOH = 36 g + 4 g = 40 g

Volume of solution = 40 × 1 = 40 mL
–1
(Since specific gravity of solution is = 1 g mL )

Number of moles of solute

Molarity of solution =
Volume of solution in litre

0.1 mol NaOH

= = 2.5 M
0.04 L

35. 2A + 4B → 3C + 4D
According to the above equation, 2 mols of ‘A’ require 4 mols of ‘B’ for the
reaction.

11 Some Basic Concepts of Chemistry

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 4 mol of B
Hence, for 5 mols of ‘A’, the moles of ‘B’ required = 5 mol of A ×
2 mol of A
= 10 mol B
But we have only 6 mols of ‘B’, hence, ‘B’ is the limiting reagent. So amount
of ‘C’ formed is determined by amount of ‘B’.
Since 4 mols of ‘B’ give 3 mols of ‘C’. Hence 6 mols of ‘B’ will give

3 mol of C
6 mol of B × = 4.5 mol of C
4 mol of B

IV. Matching Type

36. (i) → (b) (ii) → (c) (iii) → (a) (iv) → (e)

(v) → (d)

37. (i) → (e) (ii) → (d) (iii) → (b) (iv) → (g)

(v) → (c), (h) (vi) → (f) (vii) → (a) (viii) → (i)

V. Assertion and Reason Type

38. (i) 39. (ii) 40. (iii) 41. (iii)

VI. Long Answer Type

42. (i) p1=1 atm, T1=273 K, V1=?

32 g of oxygen occupies 22.4 L of volume at STP*

22.4 L
Hence,1.6 g of oxygen will occupy, 1.6 g oxygen × = 1.12 L
32 g oxygen
V1=1.12 L

p11
p2 = = = 0.5 atm.
2 2
V2=?
According to Boyle’s law :
p1V1 = p2V2

p1 ×V1 1 atm. × 1.12 L

V2 = = = 2.24 L
p2 0.5 atm.

* Old STP conditions 273.15 K, 1 atm, volume occupied by 1 mol of gas = 22.4 L.
New STP conditions 273.15 K, 1 bar, volume occupied by a gas = 22.7 L.

Exemplar Problems, Chemistry 12

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 23
6.022 × 10 × 1.6
(ii) Number of molecules of oxygen in the vessel =
32
= 3.011 × 1022

0.76 M
43. Number of moles of HCl = 250 mL × = 0.19 mol
1000
Mass of CaCO3 = 1000 g

1000 g
Number of moles of CaCO3 = = 10 mol
100 g
According to given equation 1 mol of CaCO3 (s) requires 2 mol of HCl (aq).
Hence, for the reaction of 10 mol of CaCO3 (s) number of moles of HCl
required would be:

2 mol HCl (aq)

10 mol CaCO3 ×
1 mol CaCO3 (s) = 20 mol HCl (aq)

But we have only 0.19 mol HCl (aq), hence, HCl (aq) is limiting reagent.
So amount of CaCl2 formed will depend on the amount of HCl available.
Since, 2 mol HCl (aq) forms 1 mol of CaCl2, therefore, 0.19 mol of HCl (aq)
would give:
1 mol CaCl 2 (aq)
0.19 mol HCl (aq) × = 0.095 mol
2 mol HCl (aq)
or 0.095 × molar mass of CaCl2 = 0.095 × 111 = 10.54 g

45. (Hint : Show that the masses of B which combine with the fixed mass of
A in different combinations are related to each other by simple whole
numbers).

13 Some Basic Concepts of Chemistry

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 

  
 


I. Multiple Choice Questions (Type-I)
1. Which of the following conclusions could not be derived from Rutherford’s
α -particle scattering experiement?
(i) Most of the space in the atom is empty.
(ii) The radius of the atom is about 10–10 m while that of nucleus is 10–15 m.
(iii) Electrons move in a circular path of fixed energy called orbits.
(iv) Electrons and the nucleus are held together by electrostatic forces of
attraction.

2. Which of the following options does not represent ground state electronic
configuration of an atom?
(i) 1s2 2s2 2p6 3s2 3p6 3d8 4s2
(ii) 1s2 2s2 2p6 3s2 3p6 3d9 4s2
(iii) 1s2 2s2 2p6 3s2 3p6 3d10 4s1
(iv) 1s2 2s2 2p6 3s2 3p6 3d5 4s1

3. The probability density plots of 1s and 2s orbitals are given in Fig. 2.1:

1s 2s

Fig. 2.1
The density of dots in a region represents the probability density of finding
electrons in the region.

16-04-2018
 On the basis of above diagram which of the following statements is incorrect?
(i) 1s and 2s orbitals are spherical in shape.
(ii) The probability of finding the electron is maximum near the nucleus.
(iii) The probability of finding the electron at a given distance is equal in all
directions.
(iv) The probability density of electrons for 2s orbital decreases uniformly
as distance from the nucleus increases.

4. Which of the following statement is not correct about the characteristics of

cathode rays?
(i) They start from the cathode and move towards the anode.
(ii) They travel in straight line in the absence of an external electrical or
magnetic field.
(iii) Characteristics of cathode rays do not depend upon the material of
electrodes in cathode ray tube.
(iv) Characteristics of cathode rays depend upon the nature of gas present
in the cathode ray tube.

5. Which of the following statements about the electron is incorrect?

(i) It is a negatively charged particle.
(ii) The mass of electron is equal to the mass of neutron.
(iii) It is a basic constituent of all atoms.
(iv) It is a constituent of cathode rays.

6. Which of the following properties of atom could be explained correctly by

Thomson Model of atom?
(i) Overall neutrality of atom.
(ii) Spectra of hydrogen atom.
(iii) Position of electrons, protons and neutrons in atom.
(iv) Stability of atom.

7. Two atoms are said to be isobars if.

(i) they have same atomic number but different mass number.
(ii) they have same number of electrons but different number of neutrons.
(iii) they have same number of neutrons but different number of electrons.
(iv) sum of the number of protons and neutrons is same but the number of
protons is different.

8. The number of radial nodes for 3p orbital is __________.

(i) 3
(ii) 4
(iii) 2
(iv) 1
15 Structure of Atom

16-04-2018
 9. Number of angular nodes for 4d orbital is __________.
(i) 4
(ii) 3
(iii) 2
(iv) 1

10. Which of the following is responsible to rule out the existence of definite paths
or trajectories of electrons?
(i) Pauli’s exclusion principle.
(ii) Heisenberg’s uncertainty principle.
(iii) Hund’s rule of maximum multiplicity.
(iv) Aufbau principle.

11. Total number of orbitals associated with third shell will be __________.
(i) 2
(ii) 4
(iii) 9
(iv) 3

12. Orbital angular momentum depends on __________.

(i) l
(ii) n and l
(iii) n and m
(iv) m and s

13. Chlorine exists in two isotopic forms, Cl-37 and Cl-35 but its atomic mass is
35.5. This indicates the ratio of Cl-37 and Cl-35 is approximately
(i) 1:2
(ii) 1:1
(iii) 1:3
(iv) 3:1

14. The pair of ions having same electronic configuration is __________.

(i) Cr3+, Fe3+
(ii) Fe3+, Mn2+
(iii) Fe3+, Co3+
(iv) Sc3+, Cr3+

15. For the electrons of oxygen atom, which of the following statements is correct?
(i) Zeff for an electron in a 2s orbital is the same as Zeff for an electron in a 2p
orbital.
(ii) An electron in the 2s orbital has the same energy as an electron in the
2p orbital.

Exemplar Problems, Chemistry 16

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 (iii) Zeff for an electron in 1s orbital is the same as Zeff for an electron in a 2s
orbital.
(iv) The two electrons present in the 2s orbital have spin quantum numbers
ms but of opposite sign.

16. If travelling at same speeds, which of the following matter waves have the
shortest wavelength?
(i) Electron
(ii) Alpha particle (He2+)
(iii) Neutron
(iv) Proton

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

17. Identify the pairs which are not of isotopes?

12 13
(i) 6
X, 6
Y

35 37
(ii) 17
X, 17
Y

14 14
(iii) 6
X, 7
Y

8 8
(iv) 4
X, 5
Y

18. Out of the following pairs of electrons, identify the pairs of electrons present
in degenerate orbitals :

1
(i) (a) n = 3, l = 2, ml = –2, ms = −
2

1
(b) n = 3, l = 2, ml = –1, ms = −
2

1
(ii) (a) n = 3, l = 1, ml = 1, ms = +
2

1
(b) n = 3, l = 2, ml = 1, ms = +
2

1
(iii) (a) n = 4, l = 1, ml = 1, ms = +
2

1
(b) n = 3, l = 2, ml = 1, ms = +
2

17 Structure of Atom

16-04-2018
 1
(iv) (a) n = 3, l = 2, ml = +2, ms = −
2

1
(b) n = 3, l = 2, ml = +2, ms = +
2

19. Which of the following sets of quantum numbers are correct?

n l ml
(i) 1 1 +2
(ii) 2 1 +1
(iii) 3 2 –2
(iv) 3 4 –2

20. In which of the following pairs, the ions are iso-electronic?

(i) Na+, Mg2+
(ii) Al3+, O–
(iii) Na+, O2–
–
(iv) N3–, Cl

21. Which of the following statements concerning the quantum numbers are
correct?
(i) Angular quantum number determines the three dimensional shape of
the orbital.
(ii) The principal quantum number determines the orientation and energy
of the orbital.
(iii) Magnetic quantum number determines the size of the orbital.
(iv) Spin quantum number of an electron determines the orientation of the
spin of electron relative to the chosen axis.

III. Short Answer Type

22. Arrange s, p and d sub-shells of a shell in the increasing order of effective
nuclear charge (Zeff) experienced by the electron present in them.

23. Show the distribution of electrons in oxygen atom (atomic number 8) using
orbital diagram.

24. Nickel atom can lose two electrons to form Ni2+ ion. The atomic number of
nickel is 28. From which orbital will nickel lose two electrons.

25. Which of the following orbitals are degenerate?

3d xy ,4d xy 3d 2 ,3d yz ,4d yz ,4d 2
z z

Exemplar Problems, Chemistry 18

16-04-2018
26. Calculate the total number of angular nodes and radial nodes present in 3p
orbital.

27. The arrangement of orbitals on the basis of energy is based upon their (n+l )
value. Lower the value of (n+l ), lower is the energy. For orbitals having same
values of (n+l ), the orbital with lower value of n will have lower energy.
I. Based upon the above information, arrange the following orbitals in the
increasing order of energy.
(a) 1s, 2s, 3s, 2p
(b) 4s, 3s, 3p, 4d
(c) 5p, 4d, 5d, 4f, 6s
(d) 5f, 6d, 7s, 7p
II. Based upon the above information, solve the questions given below :
(a) Which of the following orbitals has the lowest energy?
4d, 4f, 5s, 5p
(b) Which of the following orbitals has the highest energy?
5p, 5d, 5f, 6s, 6p

28. Which of the following will not show deflection from the path on passing
through an electric field?
Proton, cathode rays, electron, neutron.

29. An atom having atomic mass number 13 has 7 neutrons. What is the atomic
number of the atom?

30. Wavelengths of different radiations are given below :

0
λ( A) = 300 nm λ(B) = 300 µ m λ (C) = 3 nm λ(D) = 30 A
Arrange these radiations in the increasing order of their energies.

31. The electronic configuration of valence shell of Cu is 3d104s1 and not 3d 94s2.
How is this configuration explained?

32. The Balmer series in the hydrogen spectrum corresponds to the transition
from n 1 = 2 to n 2 = 3,4,......... . This series lies in the visible region. Calculate
the wave number of line associated with the transition in Balmer series when
the electron moves to n = 4 orbit.
(RH = 109677 cm–1)

33. According to de Broglie, matter should exhibit dual behaviour, that is both
particle and wave like properties. However, a cricket ball of mass 100 g does
not move like a wave when it is thrown by a bowler at a speed of 100 km/h.
Calculate the wavelength of the ball and explain why it does not show wave
nature.

19 Structure of Atom

16-04-2018
 34. What is the experimental evidence in support of the idea that electronic energies
in an atom are quantized?
35. Out of electron and proton which one will have, a higher velocity to produce
matter waves of the same wavelength? Explain it.
36. A hypothetical electromagnetic wave is shown in Fig. 2.2. Find out the
wavelength of the radiation.

Fig. 2.2

37. Chlorophyll present in green leaves of plants absorbs light at 4.620 × 1014 Hz.
Calculate the wavelength of radiation in nanometer. Which part of the
electromagnetic spectrum does it belong to?
38. What is the difference between the terms orbit and orbital?
39. Table-tennis ball has a mass 10 g and a speed of 90 m/s. If speed can be
measured within an accuracy of 4% what will be the uncertainty in speed
and position?
40. The effect of uncertainty principle is significant only for motion of microscopic
particles and is negligible for the macroscopic particles. Justify the statement
with the help of a suitable example.
41. Hydrogen atom has only one electron, so mutual repulsion between electrons
is absent. However, in multielectron atoms mutual repulsion between the
electrons is significant. How does this affect the energy of an electron in the
orbitals of the same principal quantum number in multielectron atoms?

IV. Matching Type

In some of the following questions, one option of left column may be
correlated to more than one option in the right column.

42. Match the following species with their corresponding ground state electronic
configuration.

Atom / Ion Electronic configuration

(i) Cu (a) 1s2 2s2 2p6 3s2 3p6 3d10

(ii) Cu2+ (b) 1s2 2s2 2p6 3s2 3p6 3d10 4s2

Exemplar Problems, Chemistry 20

16-04-2018
 (iii) Zn2+ (c) 1s2 2s2 2p6 3s2 3p6 3d10 4s1

(iv) Cr3+ (d) 1s2 2s2 2p6 3s2 3p6 3d 9

(e) 1s2 2s2 2p6 3s2 3p6 3d 3

43. Match the quantum numbers with the information provided by these.

Quantum number Information provided

(i) Principal quantum number (a) orientation of the orbital
(ii) Azimuthal quantum number (b) energy and size of orbital
(iii) Magnetic quantum number (c) spin of electron
(iv) Spin quantum number (d) shape of the orbital

44. Match the following rules with their statements :

Rules Statements
(i) Hund’s Rule (a) No two electrons in an atom
can have the same set of four
quantum numbers.
(b) Half-filled and completely filled
orbitals have extra stablity.
(ii) Aufbau Principle
(c) Pairing of electrons in the
orbitals belonging to the same
subshell does not take place
until each orbital is singly
(iii) Pauli Exclusion Principle occupied.
(d) It is impossible to determine
the exact position and exact
momentum of a subatomic
particle simultaneously.
(iv) Heisenberg’s Uncertainty
Principle (e) In the ground state of atoms,
orbitals are filled in the order
of their increasing energies.

45. Match the following

(i) X-rays (a) ν = 100 – 104 Hz

(ii) UV (b) ν = 1010 Hz

(iii) Long radio waves (c) ν = 1016 Hz

(iv) Microwave (d) ν = 1018 Hz

21 Structure of Atom

16-04-2018
 46. Match the following
(i) Photon (a) Value is 4 for N shell
(ii) Electron (b) Probability density
2
(iii) ψ (c) Always positive value
(iv) Principal quantum number n (d) Exhibits both momentum and
wavelength

47. Match species given in Column I with the electronic configuration given in Column II.

Column I Column II
(i) Cr (a) [Ar]3d84s0
(ii) Fe2+ (b) [Ar]3d104s1
(iii) Ni2+ (c) [Ar]3d64s0
(iv) Cu (d) [Ar] 3d54s1
(e) [Ar]3d64s2

V. Assertion and Reason Type

In the following questions a statement of Assertion (A) followed by a statement
of Reason (R) is given. Choose the correct option out of the choices given
below each question.

48. Assertion (A) : All isotopes of a given element show the same type of chemical
behaviour.
Reason (R) : The chemical properties of an atom are controlled by the
number of electrons in the atom.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

49. Assertion (A) : Black body is an ideal body that emits and absorbs radiations
of all frequencies.
Reason (R) : The frequency of radiation emitted by a body goes from a lower
frequency to higher frequency with an increase in
temperature.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the explanation of A.
(iii) A is true and R is false.
(iv) Both A and R are false.

Exemplar Problems, Chemistry 22

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50. Assertion (A) : It is impossible to determine the exact position and exact
momentum of an electron simultaneously.
Reason (R) : The path of an electron in an atom is clearly defined.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true and R is not the correct explanation of A.
(iii) A is true and R is false.
(iv) Both A and R are false.

VI. Long Answer Type

51. What is photoelectric effect? State the result of photoelectric effect experiment
that could not be explained on the basis of laws of classical physics. Explain
this effect on the basis of quantum theory of electromagnetic radiations.

52. Threshold frequency, ν0 is the minimum frequency which a photon must

possess to eject an electron from a metal. It is different for different metals.
When a photon of frequency 1.0×1015 s–1 was allowed to hit a metal surface,
an electron having 1.988 × 10–19 J of kinetic energy was emitted. Calculate
the threshold frequency of this metal. Show that an electron will not be emitted
if a photon with a wavelength equal to 600 nm hits the metal surface.

53. When an electric discharge is passed through hydrogen gas, the hydrogen
molecules dissociate to produce excited hydrogen atoms. These excited atoms
emit electromagnetic radiation of discrete frequencies which can be given by
the general formula

1 1
ν = 109677 2
− 2
ni nf

What points of Bohr’s model of an atom can be used to arrive at this formula?
Based on these points derive the above formula giving description of each
step and each term.

54. Calculate the energy and frequency of the radiation emitted when an electron
jumps from n = 3 to n = 2 in a hydrogen atom.

55. Why was a change in the Bohr Model of atom required? Due to which important
development (s), concept of movement of an electron in an orbit was replaced
by, the concept of probability of finding electron in an orbital? What is the
name given to the changed model of atom?

23 Structure of Atom

16-04-2018
 ANSWERS
I. Multiple Choice Questions (Type-I)

1. (iii) 2. (ii) 3. (iv) 4. (iv) 5. (ii) 6. (i)

7. (iv) 8. (iv) 9. (iii) 10. (ii) 11. (iii) 12. (i)

13. (iii) 14. (ii) 15. (iv) 16. (ii)

II. Multiple Choice Questions (Type-II)

17. (iii), (iv) 18. (i), (iv) 19. (ii), (iii)

20. (i), (iii) 21. (i), (iv)

III. Short Answer Type

22. d < p < s

23.

24. 4s

25. 3dxy, 3d 2 , 3dyz and 4dxy , 4dyz, 4d 2

z z

26. For 3p orbital n = 3, l = 1

Number of angular nodes = l = 1
Number of radial nodes = n – l – 1 = 3–1–1=1

27. I. (a) Is < 2s < 2p < 3s II. (a) 5s (b) 5f

(b) 3s < 3p < 4s < 4d
(c) 4d < 5p < 6s < 4f < 5d
(d) 7s < 5f < 6d < 7p

28. neutron

29. A = 13, A – Z = 7 ∴ Z = 6
atomic number = 6

30. B<A<C=D
1
Hint : E α
λ

Exemplar Problems, Chemistry 24

16-04-2018
31. Completely filled and half filled orbitals have extra stability. In 3d104s1, d
orbital is completely filled and s is half filled. So it is more stable
configuration.

1 1
32. ν = 109677 2
− 2 cm −1
ni nf
For ni = 2 to nf = 4 transition in Balmer series.

∴ ν = 109677 12 − 12 cm −1
2 4
1 1 −1
= 109677 − cm = 20564.44 cm–1
4 16

h
33. λ=
mv
m = 100 g = 0.1 kg.
100 × 1000 m 1000 −1
v = 100 km/hr = = ms
60 × 60 s 36
h = 6.626 × 10–34 Js
−34
6.626 × 10 Js −36 −1
λ= = 6.626 × 10 × 36 m = 238.5 × 10–36m–1
1000 −1
0.1 kg × ms
36

Since the wavelength is very small, the wave nature cannot be detected.

35. Being lighter particles, electrons will have higher velocity.

h
Hint : λ =
mv

36. Wavelength is the distance between two successive peaks or two successive
troughs of a wave. So λ = 4 × 2.16 pm = 8.64 pm

8 –1
c 3.0 × 10 ms –6
37. λ= = 14
= 0.6494 × 10 m = 649.4 nm; Visible light.
ν 4.620 × 10 Hz

90 × 4 360 –1
39. Uncertainty in the speed of ball = = = 3.6 ms
100 100

h
Uncertainty in position =
4π m∆v

25 Structure of Atom

16-04-2018
 –34
6.626 × 10 Js
= –3 –1 –1
4 × 3.14 × 10 × 10 kg g × 3.6 ms

= 1.46 × 10–33 m

41. The energy of electron is determined by the value of n in hydrogen atom

and by n + l in multielectron atom. So for a given principal quantum
number electrons of s, p, d and f orbitals have different energy.

IV. Matching Type

42. (i) → (c) (ii) → (d) (iii) → (a) (iv) → (e)

43. (i) → (b) (ii) → (d) (iii) → (a) (iv) → (c)
44. (i) → (c) (ii) → (e) (iii) → (a) (iv) → (d)
45. (i) → (d) (ii) → (c) (iii) → (a) (iv) → (b)
46. (i) → (d) (ii) → (d) (iii) → (b), (c) (iv) → (a), (c)
47. (i) → (d) (ii) → (c) (iii) → (a) (iv) → (b)

V. Assertion and Reason Type

48. (i) 49. (ii) 50. (iii)

VI. Long Answer Type

1
52. Hint : h ν = hν 0 + mv 2
2

54. ∆E = –3.052 × 10–19 J, ν = 4.606 × 1016 Hz

Exemplar Problems, Chemistry 26

16-04-2018
 

 

 

 
   
 


I. Multiple Choice Questions (Type-I)

2+ – 2–
1. Consider the isoelectronic species, Na+, Mg , F and O . The correct order of
increasing length of their radii is _________.
2– 2+ +
(i) F- < O < Mg < Na
2+ + – 2–
(ii) Mg < Na < F < O
2– – + 2+
(iii) O < F < Na < Mg
2– – 2+ +
(iv) O < F < Mg < Na

2. Which of the following is not an actinoid?

(i) Curium (Z = 96)
(ii) Californium (Z = 98)
(iii) Uranium (Z = 92)
(iv) Terbium (Z = 65)

3. The order of screening effect of electrons of s, p, d and f orbitals of a given

shell of an atom on its outer shell electrons is:
(i) s>p>d>f
(ii) f>d >p>s
(iii) p<d < s >f
(iv) f>p >s>d

4. The first ionisation enthalpies of Na, Mg, Al and Si are in the order:
(i) Na < Mg > Al < Si
(ii) Na > Mg > Al > Si

16-04-2018
 (iii) Na < Mg < Al < Si
(iv) Na > Mg > Al < Si

5. The electronic configuration of gadolinium (Atomic number 64) is

3 5 2
(i) [Xe] 4f 5d 6s
7 2 1
(ii) [Xe] 4f 5d 6s
7 1 2
(iii) [Xe] 4f 5d 6s
8 6 2
(iv) [Xe] 4f 5d 6s

6. The statement that is not correct for periodic classification of elements is:
(i) The properties of elements are periodic function of their atomic numbers.
(ii) Non metallic elements are less in number than metallic elements.
(iii) For transition elements, the 3d-orbitals are filled with electrons after
3p-orbitals and before 4s-orbitals.
(iv) The first ionisation enthalpies of elements generally increase with
increase in atomic number as we go along a period.

7. Among halogens, the correct order of amount of energy released in electron

gain (electron gain enthalpy) is:
(i) F > Cl > Br > I
(ii) F < Cl < Br < I
(iii) F < Cl > Br > I
(iv) F < Cl < Br < I

8. The period number in the long form of the periodic table is equal to
(i) magnetic quantum number of any element of the period.
(ii) atomic number of any element of the period.
(iii) maximum Principal quantum number of any element of the period.
(iv) maximum Azimuthal quantum number of any element of the period.

9. The elements in which electrons are progressively filled in 4f-orbital are called
(i) actinoids
(ii) transition elements
(iii) lanthanoids
(iv) halogens

10. Which of the following is the correct order of size of the given species:
– +
(i) I>I >I
+ –
(ii) I >I >I
+ –
(iii) I>I >I
– +
(iv) I >I>I

Exemplar Problems, Chemistry 28

16-04-2018
11. The formation of the oxide ion, O2– (g), from oxygen atom requires first an
exothermic and then an endothermic step as shown below:
 –1
O (g) + e– → O– (g) ; ∆ H = – 141 kJ mol
 –1
O – (g) + e– → O2– (g); ∆ H = + 780 kJ mol
2–
Thus process of formation of O in gas phase is unfavourable even though
2–
O is isoelectronic with neon. It is due to the fact that,
(i) oxygen is more electronegative.
(ii) addition of electron in oxygen results in larger size of the ion.
(iii) electron repulsion outweighs the stability gained by achieving noble
gas configuration.
–
(iv) O ion has comparatively smaller size than oxygen atom.

12. Comprehension given below is followed by some multiple choice questions.

Each question has one correct option. Choose the correct option.
In the modern periodic table, elements are arranged in order of increasing
atomic numbers which is related to the electronic configuration. Depending
upon the type of orbitals receiving the last electron, the elements in the periodic
table have been divided into four blocks, viz, s, p, d and f. The modern periodic
table consists of 7 periods and 18 groups. Each period begins with the filling
of a new energy shell. In accordance with the Arfbau principle, the seven
periods (1 to 7) have 2, 8, 8, 18, 18, 32 and 32 elements respectively. The
seventh period is still incomplete. To avoid the periodic table being too long,
the two series of f-block elements, called lanthanoids and actinoids are placed
at the bottom of the main body of the periodic table.
(a) The element with atomic number 57 belongs to
(i) s-block
(ii) p-block
(iii) d-block
(iv) f-block

(b) The last element of the p-block in 6th period is represented by the
outermost electronic configuration.
(i) 7s 2 7p 6
(ii) 5f 14 6d 10 7s 2 7p 0
(iii) 4f 14 5d 10 6s 2 6p 6
(iv) 4f 14 5d 10 6s 2 6p 4

(c) Which of the elements whose atomic numbers are given below, cannot
be accommodated in the present set up of the long form of the periodic
table?
(i) 107
(ii) 118

29 Classification of Elements and Periodicity in Properties

16-04-2018
 (iii) 126
(iv) 102

(d) The electronic configuration of the element which is just above the
element with atomic number 43 in the same group is ________.
(i) 1s2 2s2 2p6 3s 2 3p6 3d 5 4s2
(ii) 1s2 2s2 2p6 3s2 3p6 3d 5 4s3 4p6
(iii) 1s2 2s2 2p6 3s2 3p6 3d 6 4s2
(iv) 1s2 2s2 2p6 3s2 3p6 3d 7 4s2

(e) The elements with atomic numbers 35, 53 and 85 are all ________.
(i) noble gases
(ii) halogens
(iii) heavy metals
(iv) light metals
13. Electronic configurations of four elements A, B, C and D are given below :
(A) 1s2 2s2 2p6 (B) 1s2 2s 2 2p 4
(C) 1s2 2s2 2p6 3s1 (D) 1s2 2s 2 2p 5
Which of the following is the correct order of increasing tendency to gain
electron :
(i) A<C<B<D
(ii) A<B<C<D
(iii) D<B<C<A
(iv) D<A<B<C

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

14. Which of the following elements can show covalency greater than 4?
(i) Be
(ii) P
(iii) S
(iv) B

15. Those elements impart colour to the flame on heating in it, the atoms of which
require low energy for the ionisation (i.e., absorb energy in the visible region
of spectrum). The elements of which of the following groups will impart colour
to the flame?
(i) 2
(ii) 13
Exemplar Problems, Chemistry 30

16-04-2018
 (iii) 1
(iv) 17
16. Which of the following sequences contain atomic numbers of only
representative elements?
(i) 3, 33, 53, 87
(ii) 2, 10, 22, 36
(iii) 7, 17, 25, 37, 48
(iv) 9, 35, 51, 88
17. Which of the following elements will gain one electron more readily in
comparison to other elements of their group?
(i) S (g)
(ii) Na (g)
(iii) O (g)
(iv) Cl (g)
18. Which of the following statements are correct?
(i) Helium has the highest first ionisation enthalpy in the periodic table.
(ii) Chlorine has less negative electron gain enthalpy than fluorine.
(iii) Mercury and bromine are liquids at room temperature.
(iv) In any period, atomic radius of alkali metal is the highest.
19. Which of the following sets contain only isoelectronic ions?
2+ 2+ 3+ 3+
(i) Zn , Ca , Ga , Al
+ 2+ 3+ –
(ii) K , Ca , Sc , Cl
3– 2– – +
(iii) P , S , Cl , K
4+ 3+ 5+
(iv) Ti , Ar, Cr , V
20. In which of the following options order of arrangement does not agree with
the variation of property indicated against it?
3+ 2+ + –
(i) Al < Mg < Na < F (increasing ionic size)
(ii) B < C < N < O (increasing first ionisation enthalpy)
(iii) I < Br < Cl < F (increasing electron gain enthalpy)
(iv) Li < Na < K < Rb (increasing metallic radius)
21. Which of the following have no unit?
(i) Electronegativity
(ii) Electron gain enthalpy
(iii) Ionisation enthalpy
(iv) Metallic character

31 Classification of Elements and Periodicity in Properties

16-04-2018
 22. Ionic radii vary in
(i) inverse proportion to the effective nuclear charge.
(ii) inverse proportion to the square of effective nuclear charge.
(iii) direct proportion to the screening effect.
(iv) direct proportion to the square of screening effect.
23. An element belongs to 3rd period and group-13 of the periodic table. Which of
the following properties will be shown by the element?
(i) Good conductor of electricity
(ii) Liquid, metallic
(iii) Solid, metallic
(iv) Solid, non metallic

III. Short Answer Type

24. Explain why the electron gain enthalpy of fluorine is less negative than that
of chlorine.
25. All transition elements are d-block elements, but all d-block elements are not
transition elements. Explain.
26. Identify the group and valency of the element having atomic number 119. Also
predict the outermost electronic configuration and write the general formula
of its oxide.
27. Ionisation enthalpies of elements of second period are given below :
Ionisation enthalpy/ k cal mol–1 : 520, 899, 801, 1086, 1402, 1314,
1681, 2080.

Match the correct enthalpy

with the elements and
complete the graph given in
Fig. 3.1. Also write symbols
of elements with their
atomic number.

28. Among the elements B, Al,

C and Si,
(i) which element has
the highest first
ionisation enthalpy?
(ii) which element has
the most metallic
character?
Justify your answer
in each case. Fig. 3.1

Exemplar Problems, Chemistry 32

16-04-2018
29. Write four characteristic properties of p-block elements.

30. Choose the correct order of atomic radii of fluorine and neon (in pm) out of
the options given below and justify your answer.
(i) 72, 160
(ii) 160, 160
(iii) 72, 72
(iv) 160, 72

31. Illustrate by taking examples of transition elements and non-transition

elements that oxidation states of elements are largely based on electronic
configuration.

32. Nitrogen has positive electron gain enthalpy whereas oxygen has negative.
However, oxygen has lower ionisation enthalpy than nitrogen. Explain.

33. First member of each group of representative elements (i.e., s and p-block
elements) shows anomalous behaviour. Illustrate with two examples.

34. p-Block elements form acidic, basic and amphoteric oxides. Explain each
property by giving two examples and also write the reactions of these oxides
with water.

35. How would you explain the fact that first ionisation enthalpy of sodium is
lower than that of magnesium but its second ionisation enthalpy is higher
than that of magnesium?

36. What do you understand by exothermic reaction and endothermic reaction?

Give one example of each type.

37. Arrange the elements N, P,

O and S in the order of-
(i) increasing first
ionisation enthalpy.

(ii)increasing non
metallic character.
Give reason for the
arrangement assigned.

38. Explain the deviation in

ionisation enthalpy of
some elements from the
general trend by using
Fig. 3.2.
Fig. 3.2

33 Classification of Elements and Periodicity in Properties

16-04-2018
 39. Explain the following:
(a) Electronegativity of elements increase on moving from left to right in the
periodic table.
(b) Ionisation enthalpy decrease in a group from top to bottom?

40. How does the metallic and non metallic character vary on moving from left to
right in a period?
41. The radius of Na+ cation is less than that of Na atom. Give reason.
42. Among alkali metals which element do you expect to be least electronegative
and why?

IV. Matching Type

43. Match the correct atomic radius with the element.
Element Atomic radius (pm)
Be 74
C 88
O 111
B 77
N 66
44. Match the correct ionisation enthalpies and electron gain enthalpies of the
following elements.
Elements ∆ H1 ∆ H2 ∆ eg H
(i) Most reactive non metal A. 419 3051 – 48
(ii) Most reactive metal B. 1681 3374 – 328
(iii) Least reactive element C. 738 1451 – 40
(iv) Metal forming binary halide D. 2372 5251 + 48

45. Electronic configuration of some elements is given in Column I and their

electron gain enthalpies are given in Column II. Match the electronic
configuration with electron gain enthalpy.

Column (I) Column (II)

Electronic configuration Electron gain enthalpy/kJ mol–1
(i) 1s2 2s2 sp6 (A) – 53

(ii) 1s2 2s2 2p6 3s1 (B) – 328

(iii) 1s2 2s2 2p5 (C) – 141

(iv) 1s2 2s2 2p4 (D) + 48

Exemplar Problems, Chemistry 34

16-04-2018
V. Assertion and Reason Type
In the following questions a statement of Assertion (A) followed by a statement
of reason (R) is given. Choose the correct option out of the choices given
below each question.

46. Assertion (A) : Generally, ionisation enthalpy increases from left to right in a
period.
Reason (R) : When successive electrons are added to the orbitals in the
same principal quantum level, the shielding effect of inner
core of electrons does not increase very much to compensate
for the increased attraction of the electron to the nucleus.
(i) Assertion is correct statement and reason is wrong statement.
(ii) Assertion and reason both are correct statements and reason is correct
explanation of assertion.
(iii) Assertion and reason both are wrong statements.
(iv) Assertion is wrong statement and reason is correct statement.

47. Assertion (A) : Boron has a smaller first ionisation enthalpy than beryllium.
Reason (R) : The penetration of a 2s electron to the nucleus is more than
the 2p electron hence 2p electron is more shielded by the
inner core of electrons than the 2s electrons.
(i) Assertion and reason both are correct statements but reason is not
correct explanation for assertion.
(ii) Assertion is correct statement but reason is wrong statement.
(iii) Assertion and reason both are correct statements and reason is correct
explanation for assertion.
(iv) Assertion and reason both are wrong statements.

48. Assertion (A) : Electron gain enthalpy becomes less negative as we go down
a group.
Reason (R) : Size of the atom increases on going down the group and the
added electron would be farther from the nucleus.
(i) Assertion and reason both are correct statements but reason is not
correct explanation for assertion.
(ii) Assertion and reason both are correct statements and reason is correct
explanation for assertion.
(iii) Assertion and reason both are wrong statements.
(iv) Assertion is wrong statement but reason is correct statement.

VI. Long Answer Type

49. Discuss the factors affecting electron gain enthalpy and the trend in its
variation in the periodic table.
35 Classification of Elements and Periodicity in Properties

16-04-2018
 50. Define ionisation enthalpy. Discuss the factors affecting ionisation enthalpy
of the elements and its trends in the periodic table.
51. Justify the given statement with suitable examples— “the Properties of the
elements are a periodic function of their atomic numbers”.
52. Write down the outermost electronic configuration of alkali metals. How will
you justify their placement in group 1 of the periodic table?
53. Write the drawbacks in Mendeleev’s periodic table that led to its modification.
54. In what manner is the long form of periodic table better than Mendeleev’s
periodic table? Explain with examples.
55. Discuss and compare the trend in ionisation enthalpy of the elements of
group1 with those of group17 elements.

Exemplar Problems, Chemistry 36

16-04-2018
ANSWERS
I. Multiple Choice Questions (Type-I)

1. (ii) 2. (iv) 3. (i) 4. (i) 5. (iii) 6. (iii)

7. (iii) 8. (iii) 9. (iii) 10. (iv) 11. (iii)

12.(a) (iii), (b) (iii), (c) (iii), (d) (i), (e) (ii) 13. (i)

II. Multiple Choice Questions (Type-II)

14. (ii), (iii) 15. (i), (iii) 16. (i), (iv)

17. (i), (iv) 18. (i), (iii), (iv) 19. (ii), (iii)

20. (ii), (iii) 21. (i), (iv) 22. (i), (iii)

23. (i), (iii)

III. Short Answer Type

24. The added electron in fluorine goes to second quantum level. Due to small
size of fluorine it experiences repulsion from other electrons much more
in comparison to that in chlorine because in chlorine, the electron is added
to 3rd quantum level in which larger space is available for movement.

26. Group : 1, Valency : 1

Outermost electronic configuration = 8s1
Formula of Oxide = M2O

27. Compare your plot with the plot given in the textbook.

28. (i) Carbon

(ii) Aluminium

30. (i)

32. The outermost electronic configuraton of nitrogen (2s2 2px1 2py1 2p1z ) is very
stable because p-orbital is half filled. Addition of extra electron to any of
the 2p orbital requires energy.
Oxygen has 4 electrons in 2p orbitals and acquires stable configuration
i.e., 2p3 configuration after removing one electron.

35. After removing 1 electron from the sodium atom the ion formed acquires
the configuration of inert gas, neon. The second electron is removed from
one of the 2p-orbitals which are completely filled i.e., have a total of 6
electrons and are closer to the nucleus.
37 Classification of Elements and Periodicity in Properties

16-04-2018
 37. (i) S < P < N < O
(ii) P < S < N < O

39. (a) Decrease in size of atom and increase in nuclear charge.

(b) Increase in atomic size.

40. Metallic character decreases and non metallic character increases in moving
from left to right in a period. It is due to increase in ionisation enthalpy
and electron gain enthalpy.

41. Decrease of one shell.

42. Electronegativity decreases in a group from top to bottom. Thus, caesium

is the least electronegative element.

IV. Matching Type

43. Be = 111, O = 66, C = 77, B = 88, N = 74.

44. Most reactive non metal = B, Most reactive metal = A, Least reactive
element = D, Metal forming binary halide = C
45. (i) → (D); (ii) → (A) (iii) → (B) (iv) → (C)

V. Assertion and Reason Type

46. (ii)

47. (iii)
48. (iv)

Exemplar Problems, Chemistry 38

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 

  



 
 

I. Multiple Choice Questions (Type-I)
1. Isostructural species are those which have the same shape and hybridisation.
Among the given species identify the isostructural pairs.
(i) [NF3 and BF3]
– +
(ii) [BF4 and NH4 ]
(iii) [BCl3 and BrCl3]
–
(iv) [NH3 and NO3 ]
2. Polarity in a molecule and hence the dipole moment depends primarily on
electronegativity of the constituent atoms and shape of a molecule. Which of
the following has the highest dipole moment?
(i) CO2
(ii) HI
(iii) H2O
(iv) SO2
+ – +
3. The types of hybrid orbitals of nitrogen in NO 2 , NO3 and NH4 respectively are
expected to be
(i) sp, sp3 and sp2
(ii) sp, sp2 and sp3
(iii) sp2, sp and sp3
(iv) sp2, sp3 and sp
4. Hydrogen bonds are formed in many compounds e.g., H2O, HF, NH3 . The
boiling point of such compounds depends to a large extent on the strength
of hydrogen bond and the number of hydrogen bonds. The correct decreasing
order of the boiling points of above compounds is :
(i) HF > H2O > NH3

16-04-2018
 (ii) H2O > HF > NH3
(iii) NH3 > HF > H2O
(iv) NH3 > H2O > HF
3–
5. In PO4 ion the formal charge on the oxygen atom of P–O bond is
(i) +1
(ii) –1
(iii) – 0.75
(iv) + 0.75
–
6. In NO3 ion, the number of bond pairs and lone pairs of electrons on nitrogen
atom are
(i) 2, 2
(ii) 3, 1
(iii) 1, 3
(iv) 4, 0

7. Which of the following species has tetrahedral geometry?

–
(i) BH4
–
(ii) NH2
2–
(iii) CO3
+
(iv) H3O

8. Number of π bonds and σ bonds in the following structure is–

(i) 6, 19
(ii) 4, 20
(iii) 5, 19
(iv) 5, 20

9. Which molecule/ion out of the following does not contain unpaired electrons?
+
(i) N2
(ii) O2
2–
(iii) O2
(iv) B2

Exemplar Problems, Chemistry 40

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10. In which of the following molecule/ion all the bonds are not equal?
(i) XeF4
–
(ii) BF4
(iii) C2H4
(iv) SiF4

11. In which of the following substances will hydrogen bond be strongest?

(i) HCl
(ii) H2O
(iii) HI
(iv) H2S

12. If the electronic configuration of an element is 1s2 2s2 2p6 3s2 3p6 3d2 4s2, the
four electrons involved in chemical bond formation will be_____.
(i) 3p6
(ii) 3p6, 4s2
(iii) 3p6, 3d2
(iv) 3d2, 4s2

13. Which of the following angle corresponds to sp2 hybridisation?

(i) 90°
(ii) 120°
(iii) 180°
(iv) 109°

The electronic configurations of three elements, A, B and C are given below.

Answer the questions 14 to 17 on the basis of these configurations.

A 1s 2 2s 2 2p6
B 1s 2 2s 2 2p6 3s 2 3p3
C 1s 2 2s 2 2p6 3s 2 3p5

14. Stable form of A may be represented by the formula :

(i) A
(ii) A2
(iii) A3
(iv) A4

15. Stable form of C may be represented by the formula :

(i) C
(ii) C2

41 Chemical Bonding and Molecular Structure

16-04-2018
 (iii) C3
(iv) C4

16. The molecular formula of the compound formed from B and C will be
(i) BC
(ii) B2C
(iii) BC2
(iv) BC3

17. The bond between B and C will be

(i) Ionic
(ii) Covalent
(iii) Hydrogen
(iv) Coordinate

18. Which of the following order of energies of molecular orbitals of N2 is correct?

(i) (π2py ) < (σ2pz) < (π*2px) ≈ (π*2py )
(ii) (π2py ) > (σ2pz) > (π*2px) ≈ (π*2py )
(iii) (π2py ) < (σ2pz) > (π*2px) ≈ (π*2py )
(iv) (π2py ) > (σ2pz) < (π*2px) ≈ (π*2py )

19. Which of the following statement is not correct from the view point of molecular
orbital theory?
(i) Be2 is not a stable molecule.
+
(ii) He2 is not stable but He2 is expected to exist.
(iii) Bond strength of N2 is maximum amongst the homonuclear diatomic
molecules belonging to the second period.
(iv) The order of energies of molecular orbitals in N2 molecule is
σ2s < σ* 2s < σ2pz < (π2px = π2py ) < (π* 2px = π* 2py) < σ*2pz

20. Which of the following options represents the correct bond order :
– +
(i) O2 > O2 > O2
– +
(ii) O2 < O2 < O2
– +
(iii) O2 > O2 < O2
– +
(iv) O2 < O2 > O2

21. The electronic configuration of the outer most shell of the most electronegative
element is
(i) 2s22p5
(ii) 3s23p5
(iii) 4s24p5
(iv) 5s25p5
Exemplar Problems, Chemistry 42

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22. Amongst the following elements whose electronic configurations are given
below, the one having the highest ionisation enthalpy is
(i) [Ne]3s23p1
(ii) [Ne]3s23p3
(iii) [Ne]3s23p2
(iv) [Ar]3d104s24p3

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

23. Which of the following have identical bond order?

–
(i) CN
+
(ii) NO
–
(iii) O2
2–
(iv) O2

24. Which of the following attain the linear structure:

(i) BeCl2
(ii) NCO+
(iii) NO2
(iv) CS2

25. CO is isoelectronic with

+
(i) NO
(ii) N2
(iii) SnCl2
–
(iv) NO2

26. Which of the following species have the same shape?

(i) CO2
(ii) CCl4
(iii) O3
–
(iv) NO2
2–
27. Which of the following statements are correct about CO3 ?
(i) The hybridisation of central atom is sp3.
(ii) Its resonance structure has one C–O single bond and two C=O double
bonds.
(iii) The average formal charge on each oxygen atom is 0.67 units.
(iv) All C–O bond lengths are equal.
43 Chemical Bonding and Molecular Structure

16-04-2018
 28. Dimagnetic species are those which contain no unpaired electrons. Which
among the following are dimagnetic?
(i) N2
2–
(ii) N2
(iii) O2
2–
(iv) O2

29. Species having same bond order are :

(i) N2
–
(ii) N2
+
(iii) F2
–
(iv) O2

30. Which of the following statements are not correct?

(i) NaCl being an ionic compound is a good conductor of electricity in the
solid state.
(ii) In canonical structures there is a difference in the arrangement of atoms.
(iii) Hybrid orbitals form stronger bonds than pure orbitals.
(iv) VSEPR Theory can explain the square planar geometry of XeF4.

III. Short Answer Type

31. Explain the non linear shape of H2S and non planar shape of PCl3 using valence
shell electron pair repulsion theory.

32. Using molecular orbital theory, compare the bond energy and magnetic
+ –
character of O2 and O2 species.

33. Explain the shape of BrF5.

34. Structures of molecules of two compounds are given below :

Exemplar Problems, Chemistry 44

16-04-2018
 (a) Which of the two compounds will have intermolecular hydrogen bonding
and which compound is expected to show intramolecular hydrogen
bonding.

(b) The melting point of a compound depends on, among other things, the
extent of hydrogen bonding. On this basis explain which of the above
two compounds will show higher melting point.

(c) Solubility of compounds in water depends on power to form hydrogen

bonds with water. Which of the above compounds will form hydrogen
bond with water easily and be more soluble in it.

35. Why does type of overlap given in the following figure not result in bond
formation?

36. Explain why PCl5 is trigonal bipyramidal whereas IF 5 is square pyramidal.

37. In both water and dimethyl ether ( CH3 — Ο — CH3 ), oxygen atom is central
atom, and has the same hybridisation, yet they have different bond angles.
Which one has greater bond angle? Give reason.

38. Write Lewis structure of the following compounds and show formal charge
on each atom.
HNO3, NO2, H2SO4

39. The energy of σ2pz molecular orbital is greater than π2px and π2py molecular
orbitals in nitrogen molecule. Write the complete sequence of energy levels in
the increasing order of energy in the molecule. Compare the relative stability
and the magnetic behaviour of the following species :
+ – 2+
N2, N2 , N2 , N2

40. What is the effect of the following processes on the bond order in N2 and O2?
+ +
(i) N2 → N2 + e– (ii) O2 → O2 + e–

41. Give reasons for the following :

(i) Covalent bonds are directional bonds while ionic bonds are non-
directional.
(ii) Water molecule has bent structure whereas carbon dioxide molecule is
linear.
(iii) Ethyne molecule is linear.
45 Chemical Bonding and Molecular Structure

16-04-2018
 42. What is an ionic bond? With two suitable examples explain the difference
between an ionic and a covalent bond?

43. Arrange the following bonds in order of increasing ionic character giving
reason.
N—H, F—H, C—H and O—H
2–
44. Explain why CO3 ion cannot be represented by a single Lewis structure. How
can it be best represented?

45. Predict the hybridisation of each carbon in the molecule of organic compound
given below. Also indicate the total number of sigma and pi bonds in this
molecule.

46. Group the following as linear and non-linear molecules :

H2O, HOCl, BeCl2, Cl2O
47. Elements X, Y and Z have 4, 5 and 7 valence electrons respectively. (i) Write
the molecular formula of the compounds formed by these elements individually
with hydrogen. (ii) Which of these compounds will have the highest dipole
moment?

48. Draw the resonating structure of

(i) Ozone molecule
(ii) Nitrate ion

49. Predict the shapes of the following molecules on the basis of hybridisation.
BCl3, CH4, CO2, NH3
2–
50. All the C—O bonds in carbonate ion (CO3 ) are equal in length. Explain.

51. What is meant by the term average bond enthalpy? Why is there difference in
bond enthalpy of O—H bond in ethanol (C2H5OH) and water?

IV. Matching Type

52. Match the species in Column I with the type of hybrid orbitals in Column II.

Column I Column II
(i) SF4 (a) sp3d2
(ii) IF5 (b) d2sp3
+
(iii) NO2 (c) sp3d
+
(iv) NH 4
(d) sp3
(e) sp
Exemplar Problems, Chemistry 46

16-04-2018
53. Match the species in Column I with the geometry/shape in Column II.

Column I Column II
+
(i) H3O (a) Linear
(ii) HC ≡ CH (b) Angular
–
(iii) ClO 2
(c) Tetrahedral
+
(iv) NH 4
(d) Trigonal bipyramidal
(e) Pyramidal

54. Match the species in Column I with the bond order in Column II.

Column I Column II
(i) NO (a) 1.5
(ii) CO (b) 2.0
–
(iii) O2
(c) 2.5
(iv) O2 (d) 3.0

55. Match the items given in Column I with examples given in Column II.

Column I Column II
(i) Hydrogen bond (a) C
(ii) Resonance (b) LiF
(iii) Ionic solid (c) H2
(iv) Covalent solid (d) HF
(e) O3

56. Match the shape of molecules in Column I with the type of hybridisation in
Column II.

Column I Column II
(i) Tetrahedral (a) sp2
(ii) Trigonal (b) sp
(iii) Linear (c) sp3

V. Assertion and Reason Type

In the following questions a statement of Assertion (A) followed by a statement of
Reason (R) is given. Choose the correct option out of the choices given below each
question.

57. Assertion (A) : Sodium chloride formed by the action of chlorine gas on
sodium metal is a stable compound.
Reason (R) : This is because sodium and chloride ions acquire octet in
sodium chloride formation.

47 Chemical Bonding and Molecular Structure

16-04-2018
 (i) A and R both are correct, and R is the correct explanation of A.
(ii) A and R both are correct, but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A and R both are false.

58. Assertion (A) : Though the central atom of both NH3 and H2O molecules are
sp3 hybridised, yet H–N–H bond angle is greater than that of
H–O–H.
Reason (R) : This is because nitrogen atom has one lone pair and oxygen
atom has two lone pairs.
(i) A and R both are correct, and R is the correct explanation of A.
(ii) A and R both are correct, but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A and R both are false.

59. Assertion (A): Among the two O–H bonds in H2O molecule, the energy
required to break the first O–H bond and the other O–H bond
is the same.
Reason (R) : This is because the electronic environment around oxygen is
the same even after breakage of one O–H bond.
(i) A and R both are correct, and R is correct explanation of A.
(ii) A and R both are correct, but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A and R both are false.

VI. Long Answer Type

60. (i) Discuss the significance/ applications of dipole moment.
(ii) Represent diagrammatically the bond moments and the resultant dipole
moment in CO2 , NF3 and CHCl3.

61. Use the molecular orbital energy level diagram to show that N2 would be
expected to have a triple bond, F 2, a single bond and Ne2, no bond.

62. Briefly describe the valence bond theory of covalent bond formation by taking
an example of hydrogen. How can you interpret energy changes taking place
in the formation of dihydrogen?

63. Describe hybridisation in the case of PCl5 and SF6. The axial bonds are longer
as compared to equatorial bonds in PCl5 whereas in SF6 both axial bonds and
equatorial bonds have the same bond length. Explain.

64. (i) Discuss the concept of hybridisation. What are its different types in a
carbon atom.

Exemplar Problems, Chemistry 48

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 (ii) What is the type of hybridisation of carbon atoms marked with star.

(a)

(b)

(c)

(d)

(e)

Comprehension given below is followed by some multiple choice questions.

Each question has one correct option. Choose the correct option.

Molecular orbitals are formed by the overlap of atomic orbitals. Two atomic orbitals
combine to form two molecular orbitals called bonding molecular orbital (BMO)
and anti bonding molecular orbital (ABMO). Energy of anti bonding orbital is raised
above the parent atomic orbitals that have combined and the energy of the bonding
orbital is lowered than the parent atomic orbitals. Energies of various molecular
orbitals for elements hydrogen to nitrogen increase in the order :
σ1s < σ * 1s < σ 2s < σ * 2s < ( π 2 p x ≈ π 2 py ) < σ 2 pz < ( π * 2 px ≈ π * 2 py ) < σ * 2 pz and
for oxygen and fluorine order of energy of molecular orbitals is given below :
σ1s < σ * 1s < σ 2s < σ * 2s < σ 2 p z < ( π 2 p x  π 2 p y ) < ( π * 2 p x  π * 2 p y ) < σ * 2 p z
Different atomic orbitals of one atom combine with those atomic orbitals of the
second atom which have comparable energies and proper orientation. Further, if
the overlapping is head on, the molecular orbital is called ‘Sigma’, (σ) and if the
overlap is lateral, the molecular orbital is called ‘pi’, (π). The molecular orbitals
are filled with electrons according to the same rules as followed for filling of atomic
orbitals. However, the order for filling is not the same for all molecules or their
ions. Bond order is one of the most important parameters to compare the strength
of bonds.

65. Which of the following statements is correct?

(i) In the formation of dioxygen from oxygen atoms 10 molecular orbitals
will be formed.
(ii) All the molecular orbitals in the dioxygen will be completely filled.
(iii) Total number of bonding molecular orbitals will not be same as total
number of anti bonding orbitals in dioxygen.
(iv) Number of filled bonding orbitals will be same as number of filled anti
bonding orbitals.

49 Chemical Bonding and Molecular Structure

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 66. Which of the following molecular orbitals has maximum number of nodal
planes?
(i) σ*1s
(ii) σ*2pz
(iii) π2px
(iv) π*2py

67. Which of the following pair is expected to have the same bond order?
(i) O2 , N2
+ –
(ii) O2 , N2
– +
(iii) O2 , N2
– –
(iv) O2 , N2

68. In which of the following molecules, σ2pz molecular orbital is filled after π2px
and π2py molecular orbitals?
(i) O2
(ii) Ne2
(iii) N2
(iv) F2

Exemplar Problems, Chemistry 50

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ANSWERS
I. Multiple Choice Questions (Type-I)
1. (ii) 2. (iii) 3. (ii) 4. (ii) 5. (ii) 6. (iv)
7. (i) 8. (iii) 9. (iii) 10. (iii) 11. (ii) 12. (iv)
13. (ii) 14. (i) 15. (ii) 16. (iv) 17. (ii) 18. (i)
19. (iv) 20. (ii) 21. (i) 22. (ii)

II. Multiple Choice Questions (Type-II)

23. (i), (ii) 24. (i), (iv) 25. (i), (ii)
26. (iii), (iv) 27. (iii), (iv) 28. (i), (iv)
29. (iii), (iv) 30. (i), (ii)

III. Short Answer Type

32. (i) According to molecular orbital theory electronic configurations of
+ –
O2 and O2 species are as follows :
+ 2 2 2 2 2
O2 : (σ1s) (σ* 1s ) (σ2s) (σ* 2s ) (σ2pz) (π2px2 , π2p2y ) (π* 2px1 )
– 2 2 2 2 2
O2 : (σ1s) (σ* 1s ) (σ2s) (σ* 2s ) (σ2pz) (π2p2x , π2p2y ) (π* 2px2 , π* 2py1)

+ 10 − 5 5
Bond order of O2 = = = 2.5
2 2

10 − 7 3
–
Bond order of O2 = = = 1.5
2 2
+ –
Higher bond order of O2 shows that it is more stable than O2 . Both the
species have unpaired electrons. So both are paramagnetic in nature.

34. (a) Compound (I) will form intramolecular hydrogen bond because
NO2 and OH group are close together in comparison to that in
compound (II).

51 Chemical Bonding and Molecular Structure

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 (b) Compound (II) will have higher melting point because it forms
intermolecular hydrogen bonds. Thus, more and more molecules
are joined together through hydrogen bond formation.
(c) Due to intramolecular hydrogen bonding compound (I) will not be
able to form hydrogen bonds with water thus will be less soluble in
it while compound (II) can form hydrogen bond with water more
easily and will be soluble in water.

37. [Hint : Dimethyl ether will have larger bond angle. There will be more
repulsion between bond pairs of CH3 groups attached in ether than
between bond pairs of hydrogen atoms attached to oxygen in water. The
carbon of CH3 in ether is attached to three hydrogen atoms through σ
bonds and electron pairs of these bonds add to the electronic charge density
on carbon atom. Hence, repulsion between two —CH3 groups will be more
than that between two hydrogen atoms.]

IV. Matching Type

52. (i) → (c) (ii) → (a) (iii) → (e) (iv) → (d)

53. (i) → (e) (ii) → (a) (iii) → (b) (iv) → (c)

54. (i) → (c) (ii) → (d) (iii) → (a) (iv) → (b)

55. (i) → (d) (ii) → (e) (iii) → (b) (iv) → (a)

56. (i) → (c) (ii) → (a) (iii) → (b)

V. Assertion and Reason Type

57. (i) 58. (i) 59. (iv)

65. (i) 66. (ii) 67. (ii) 68. (iii)

Exemplar Problems, Chemistry 52

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 



I. Multiple Choice Questions (Type-I)
1. Thermodynamics is not concerned about______.
(i) energy changes involved in a chemical reaction.
(ii) the extent to which a chemical reaction proceeds.
(iii) the rate at which a reaction proceeds.
(iv) the feasibility of a chemical reaction.

2. Which of the following statements is correct?

(i) The presence of reacting species in a covered beaker is an example of
open system.
(ii) There is an exchange of energy as well as matter between the system
and the surroundings in a closed system.
(iii) The presence of reactants in a closed vessel made up of copper is an
example of a closed system.
(iv) The presence of reactants in a thermos flask or any other closed insulated
vessel is an example of a closed system.

3. The state of a gas can be described by quoting the relationship between___.

(i) pressure, volume, temperature
(ii) temperature, amount, pressure
(iii) amount, volume, temperature
(iv) pressure, volume, temperature, amount

4. The volume of gas is reduced to half from its original volume. The specific
heat will be ______.
(i) reduce to half
(ii) be doubled

16-04-2018
 (iii) remain constant
(iv) increase four times

5. During complete combustion of one mole of butane, 2658 kJ of heat is released.

The thermochemical reaction for above change is
–1
(i) 2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O( l ) ∆cH = –2658.0 kJ mol

13 –1
(ii) C4H10(g) + O (g) → 4CO2 (g) + 5H2O (g) ∆cH = –1329.0 kJ mol
2 2

13 –1
(iii) C4H10(g) + O (g) → 4CO2 (g) + 5H2O ( l ) ∆cH = –2658.0 kJ mol
2 2

13 –1
(iv) C4H10 (g) + O (g) → 4CO2 (g) + 5H2O ( l ) ∆cH = +2658.0 kJ mol
2 2


6. ∆f U of formation of CH4 (g) at certain temperature is –393 kJ mol–1. The

value of ∆f H is
(i) zero

(ii) < ∆f U

(iii) > ∆f U

(iv) equal to ∆f U

7. In an adiabatic process, no transfer of heat takes place between system and

surroundings. Choose the correct option for free expansion of an ideal gas
under adiabatic condition from the following.
(i) q = 0, ∆T ≠ 0, w = 0
(ii) q ≠ 0, ∆T = 0, w = 0
(iii) q = 0, ∆T = 0, w = 0
(iv) q = 0, ∆T < 0, w ≠ 0

8. The pressure-volume work for an ideal gas can be calculated by using the
Vf

expression w = − ∫ pex dV . The work can also be calculated from the pV– plot
Vi

by using the area under the curve within the specified limits. When an ideal
gas is compressed (a) reversibly or (b) irreversibly from volume Vi to Vf . choose
the correct option.
(i) w (reversible) = w (irreversible)
(ii) w (reversible) < w (irreversible)
(iii) w (reversible) > w (irreversible)
(iv) w (reversible) = w (irreversible) + pex.∆V

69 Thermodynamics

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 qrev
9. The entropy change can be calculated by using the expression ∆S = .
T
When water freezes in a glass beaker, choose the correct statement amongst
the following :
(i) ∆S (system) decreases but ∆S (surroundings) remains the same.
(ii) ∆S (system) increases but ∆S (surroundings) decreases.
(iii) ∆S (system) decreases but ∆S (surroundings) increases.
(iv) ∆S (system) decreases and ∆S (surroundings) also decreases.

10. On the basis of thermochemical equations (a), (b) and (c), find out which of the
algebric relationships given in options (i) to (iv) is correct.
–1
(a) C (graphite) + O2 (g) → CO2 (g) ; ∆rH = x kJ mol

1 –1
(b) C (graphite) + O (g) → CO (g) ; ∆rH = y kJ mol
2 2

1 –1
(c) CO (g) + O (g) → CO2 (g) ; ∆rH = z kJ mol
2 2
(i) z=x+y
(ii) x=y–z
(iii) x=y+z
(iv) y = 2z – x

11. Consider the reactions given below. On the basis of these reactions find out
which of the algebric relations given in options (i) to (iv) is correct?
–1
(a) C (g) + 4 H (g) → CH4 (g); ∆rH = x kJ mol
–1
(b) C (graphite,s) + 2H2 (g) → CH4 (g); ∆rH = y kJ mol
(i) x=y
(ii) x = 2y
(iii) x>y
(iv) x<y

12. The enthalpies of elements in their standard states are taken as zero. The
enthalpy of formation of a compound
(i) is always negative
(ii) is always positive
(iii) may be positive or negative
(iv) is never negative

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13. Enthalpy of sublimation of a substance is equal to
(i) enthalpy of fusion + enthalpy of vapourisation
(ii) enthalpy of fusion
(iii) enthalpy of vapourisation
(iv) twice the enthalpy of vapourisation
14. Which of the following is not correct?
(i) ∆G is zero for a reversible reaction
(ii) ∆G is positive for a spontaneous reaction
(iii) ∆G is negative for a spontaneous reaction
(iv) ∆G is positive for a non-spontaneous reaction

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

15. Thermodynamics mainly deals with

(i) interrelation of various forms of energy and their transformation from
one form to another.
(ii) energy changes in the processes which depend only on initial and final
states of the microscopic systems containing a few molecules.
(iii) how and at what rate these energy transformations are carried out.
(iv) the system in equilibrium state or moving from one equilibrium state to
another equilibrium state.
16. In an exothermic reaction, heat is evolved, and system loses heat to the
surrounding. For such system
(i) qp will be negative
(ii) ∆rH will be negative
(iii) qp will be positive
(iv) ∆rH will be positive
17. The spontaneity means, having the potential to proceed without the assistance
of external agency. The processes which occur spontaneously are
(i) flow of heat from colder to warmer body.
(ii) gas in a container contracting into one corner.
(iii) gas expanding to fill the available volume.
(iv) burning carbon in oxygen to give carbon dioxide.
18. For an ideal gas, the work of reversible expansion under isothermal condition
Vf
can be calculated by using the expression w = – nRT ln
Vi
71 Thermodynamics

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 A sample containing 1.0 mol of an ideal gas is expanded isothermally and
reversibly to ten times of its original volume, in two separate experiments.
The expansion is carried out at 300 K and at 600 K respectively. Choose the
correct option.
(i) Work done at 600 K is 20 times the work done at 300 K.
(ii) Work done at 300 K is twice the work done at 600 K.
(iii) Work done at 600 K is twice the work done at 300 K.
(iv) ∆U = 0 in both cases.
19. Consider the following reaction between zinc and oxygen and choose the correct
options out of the options given below :
–1
2 Zn (s) + O2 (g) → 2 ZnO (s) ; ∆H = – 693.8 kJ mol
(i) The enthalpy of two moles of ZnO is less than the total enthalpy of two
moles of Zn and one mole of oxygen by 693.8 kJ.
(ii) The enthalpy of two moles of ZnO is more than the total enthalpy of two
moles of Zn and one mole of oxygen by 693.8 kJ.
–1
(iii) 693.8 kJ mol energy is evolved in the reaction.
–1
(iv) 693.8 kJ mol energy is absorbed in the reaction.

III. Short Answer Type

20. 18.0 g of water completely vapourises at 100°C and 1 bar pressure and the
–1
enthalpy change in the process is 40.79 kJ mol . What will be the enthalpy
change for vapourising two moles of water under the same conditions? What
is the standard enthalphy of vapourisation for water?

21. One mole of acetone requires less heat to vapourise than 1 mol of water. Which
of the two liquids has higher enthalpy of vapourisation?

22. Standard molar enthalpy of formation, ∆f H is just a special case of enthalpy
  
of reaction, ∆r H . Is the ∆r H for the following reaction same as ∆f H ? Give
reason for your answer.
 –1
CaO(s) + CO2(g) → CaCO3(s); ∆f H = –178.3 kJ mol
 –1
23. The value of ∆f H for NH3 is – 91.8 kJ mol . Calculate enthalpy change for the
following reaction :
2NH3(g) → N2(g) + 3H2(g)

24. Enthalpy is an extensive property. In general, if enthalpy of an overall reaction

A→B along one route is ∆r H and ∆r H1, ∆rH2, ∆r H3 ..... represent enthalpies of
intermediate reactions leading to product B. What will be the relation between
∆r H for overall reaction and ∆r H1 , ∆r H2 ..... etc. for intermediate reactions.
25. The enthalpy of atomisation for the reaction CH4(g)→ C(g) + 4H (g) is
1665 kJ mol–1. What is the bond energy of C–H bond?

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 
26. Use the following data to calculate ∆lattice H  for NaBr.
 –1
∆sub H  for sodium metal = 108.4 kJ mol
–1
Ionization enthalpy of sodium = 496 kJ mol
–1
Electron gain enthalpy of bromine = – 325 kJ mol
Bond dissociation enthalpy of bromine = 192 kJ mol–1
 –1
∆f H for NaBr (s) = – 360.1 kJ mol
27. Given that ∆H= 0 for mixing of two gases. Explain whether the diffusion of these
gases into each other in a closed container is a spontaneous process or not?
28. Heat has randomising influence on a system and temperature is the measure
of average chaotic motion of particles in the system. Write the mathematical
relation which relates these three parameters.
29. Increase in enthalpy of the surroundings is equal to decrease in enthalpy of
the system. Will the temperature of system and surroundings be the same
when they are in thermal equilibrium?

30. At 298 K. Kp for the reaction N2O4 (g)  2NO2 (g) is 0.98. Predict whether the
reaction is spontaneous or not.
31. A sample of 1.0 mol of a monoatomic ideal gas is taken through a cyclic
process of expansion and compression as shown in Fig. 6.1. What will be the
value of ∆H for the cycle as a whole?

Fig. : 6.1

32. The standard molar entropy of H2O (l ) is 70 J K–1 mol–1. Will the standard
molar entropy of H2O(s) be more, or less than 70 J K–1 mol–1?
33. Identify the state functions and path functions out of the following :
enthalpy, entropy, heat, temperature, work, free energy.
34. The molar enthalpy of vapourisation of acetone is less than that of water. Why?
35. Which quantity out of ∆rG and ∆rG will be zero at equilibrium?
36. Predict the change in internal energy for an isolated system at constant volume.

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 37. Although heat is a path function but heat absorbed by the system under
certain specific conditions is independent of path. What are those conditions?
Explain.
38. Expansion of a gas in vacuum is called free expansion. Calculate the work
done and the change in internal energy when 1 litre of ideal gas expands
isothermally into vacuum until its total volume is 5 litre?
39. Heat capacity (Cp ) is an extensive property but specific heat (c) is an intensive
property. What will be the relation between Cp and c for 1 mol of water?
40. The difference between CP and CV can be derived using the empirical relation
H = U + pV. Calculate the difference between CP and CV for 10 moles of an ideal gas.
41. If the combustion of 1g of graphite produces 20.7 kJ of heat, what will be
molar enthalpy change? Give the significance of sign also.
42. The net enthalpy change of a reaction is the amount of energy required to
break all the bonds in reactant molecules minus amount of energy required
to form all the bonds in the product molecules. What will be the enthalpy
change for the following reaction.
H2(g) + Br2(g) → 2HBr(g)
–1 –1
Given that Bond energy of H2, Br2 and HBr is 435 kJ mol , 192 kJ mol and
–1
368 kJ mol respectively.
–1
43. The enthalpy of vapourisation of CCl4 is 30.5 kJ mol . Calculate the heat
required for the vapourisation of 284 g of CCl4 at constant pressure. (Molar
–1
mass of CCl4 = 154 g mol ).
44. The enthalpy of reaction for the reaction :
–1
2H2(g) + O2(g) → 2H2O(l) is ∆rH= – 572 kJ mol .
What will be standard enthalpy of formation of
H2O (l ) ?

45. What will be the work done on an ideal gas enclosed

in a cylinder, when it is compressed by a constant
external pressure, pext in a single step as shown in
Fig. 6.2. Explain graphically.

46. How will you calculate work done on an ideal gas

in a compression, when change in pressure is
carried out in infinite steps?
Fig. : 6.2
47. Represent the potential energy/enthalpy change in
the following processes graphically.
(a) Throwing a stone from the ground to roof.
1 1 
(b) H2(g) + Cl2(g)  HCl(g) ∆rH = –92.32 kJ mol–1
2 2
In which of the processes potential energy/enthalpy change is contributing
factor to the spontaneity?
Exemplar Problems, Chemistry 74

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48. Enthalpy diagram for a particular reaction is
given in Fig. 6.3. Is it possible to decide
spontaneity of a reaction from given diagram.
Explain.

49. 1 . 0 m o l o f a m o noa t o m i c i d e a l g a s i s
expanded from state (1) to state (2) as shown in
Fig. 6.4. Calculate the work done for the expansion
of gas from state (1) to state (2) at 298 K.

50. An ideal gas is allowed to expand against a Fig. : 6.3

constant pressure of 2 bar from 10 L to 50 L in
one step. Calculate the amount of work done by
the gas. If the same expansion were carried out
reversibly, will the work done be higher or lower
than the earlier case?
(Given that 1 L bar = 100 J)

IV. Matching Type Fig. : 6.4

In the following questions more than one correlation is possible between

options of both columns.

51. Match the following :

A B
(i) Adiabatic process (a) Heat
(ii) Isolated system (b) At constant volume
(iii) Isothermal change (c) First law of thermodynamics
(iv) Path function (d) No exchange of energy and matter
(v) State function (e) No transfer of heat
(vi) ∆U = q (f) Constant temperature
(vii) Law of conservation of energy (g) Internal energy
(viii) Reversible process (h) pext = 0
(ix) Free expansion (i) At constant pressure
(x) ∆H = q (j) Infinitely slow process which
proceeds through a series of
equilibrium states.
(xi) Intensive property (k) Entropy
(xii) Extensive property (l) Pressure
(m) Specific heat

75 Thermodynamics

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 52. Match the following processes with entropy change:
Reaction Entropy change
(i) A liquid vapourises (a) ∆S = 0
(ii) Reaction is non-spontaneous (b) ∆S = positive
at all temperatures and ∆H
is positive
(iii) Reversible expansion of an (c) ∆S = negative
ideal gas

53. Match the following parameters with description for spontaneity :

∆ (Parameters) Description
  
∆ rH ∆ rS ∆ rG

(i) + – + (a) Non-spontaneous at high

temperature.
(ii) – – + at high T (b) Spontaneous at all temperatures
(iii) – + – (c) Non-spontaneous at all
temperatures
54. Match the following :
(i) Entropy of vapourisation (a) decreases
(ii) K for spontaneous process (b) is always positive
(iii) Crystalline solid state (c) lowest entropy

∆H vap
(iv) ∆U in adiabatic expansion (d) Tb
of ideal gas

V. Assertion and Reason Type

In the following questions a statement of Assertion (A) followed by a statement
of Reason (R) is given. Choose the correct option out of the choices given
below each question.

55. Assertion (A): Combustion of all organic compounds is an exothermic

reaction.
Reason (R) : The enthalpies of all elements in their standard state are zero.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A is false but R is true.

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56. Assertion (A) : Spontaneous process is an irreversible process and may be
reversed by some external agency.
Reason (R) : Decrease in enthalpy is a contributory factor for spontaneity.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A is false but R is true.

57. Assertion (A) : A liquid crystallises into a solid and is accompanied by

decrease in entropy.
Reason (R) : In crystals, molecules organise in an ordered manner.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A is false but R is true.

VI. Long Answer Type

58. Derive the relationship between ∆H and ∆U for an ideal gas. Explain each
term involved in the equation.
59. Extensive properties depend on the quantity of matter but intensive properties
do not. Explain whether the following properties are extensive or intensive.
Mass, internal energy, pressure, heat capacity, molar heat capacity, density,
mole fraction, specific heat, temperature and molarity.
60. The lattice enthalpy of an ionic compound is the enthalpy when one mole of
an ionic compound present in its gaseous state, dissociates into its ions. It is
impossible to determine it directly by experiment. Suggest and explain an
indirect method to measure lattice enthalpy of NaCl(s).
61. ∆G is net energy available to do useful work and is thus a measure of “free
energy”. Show mathematically that ∆G is a measure of free energy. Find the
unit of ∆G. If a reaction has positive enthalpy change and positive entropy
change, under what condition will the reaction be spontaneous?
62. Graphically show the total work done in an expansion when the state of an
ideal gas is changed reversibly and isothermally from (pi , Vi ) to (pf , Vf ). With
the help of a pV plot compare the work done in the above case with that
carried out against a constant external pressure pf .

77 Thermodynamics

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 ANSWERS
I. Multiple Choice Questions (Type-I)

1. (iii) 2. (iii) 3. (iv) 4. (iii) 5. (iii) 6. (ii)

7. (iii)
Justification : free expansion w=0
adiabatic process q = 0
∆U = q + w = 0, this means that internal energy remains
constant. Therefore, ∆T = 0.

In ideal gas there is no intermolecular attraction. Hence when such a gas

expands under adiabatic conditions into a vaccum no heat is absorbed or
evolved since no external work is done to separate the molecules.

8. (ii) w (reversible) < w (irreversible)

Justification : Area under the curve is always more in irreversible
compression as can be seen from Fig. 6.5 (a) and (b).

(a) Reversible compression (b) Irreversible compression

Fig. : 6.5

9. (iii)
Justification : Freezing is exothermic process. The heat released increases
the entropy of surrounding.

10. (iii)
11. (iii)
Justification : Same bonds are formed in reaction (a) and (b) but bonds
between reactant molecules are broken only in reaction (b).

12. (iii) 13. (i) 14. (ii)

Exemplar Problems, Chemistry 78

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II. Multiple Choice Questions (Type-II)

15. (i), (iv) 16. (i), (ii) 17. (iii), (iv)

18. (iii), (iv)

10
w 600K 1 × R × 600 K ln
= 1 = 600 = 2
Justification : w 10 300
300K 1 × R × 300 K ln
1
For isothermal expansion of ideal gases, ∆U = 0

since temperature is constant this means there is no change in internal energy.

Therefore, ∆U = 0

19. (i), (iii)

III. Short Answer Type


+ 81.58 kJ, ∆vapH = + 40.79 kJ mol
–1
20.
21. Water
22. No, since CaCO3 has been formed from other compounds and not from its
constituent elements.
 –1
23. ∆r H = +91.8 kJ mol

24. ∆r H = ∆r H1+ ∆r H2 + ∆r H3 .....

1665 –1 –1
25. kJ mol = 416.2 kJ mol
4
–1
26. +735.5 kJ mol
27. It is spontaneous process. Although enthalpy change is zero but
randomness or disorder (i.e., ∆ S ) increases. Therefore, in equation
∆G = ∆H – T∆S, the term T∆S will be negative. Hence, ∆G will be negative.

qrev
28. ∆S =
T
29. Yes
30. The reaction is spontaneous

∆r G = – RT ln Kp

31. ∆H (cycle) = 0
32. Less, because ice is more ordered than H2O (l ).
33. State Functions : Enthalpy, Entropy, Temperature, Free energy
Path Functions : Heat, Work
79 Thermodynamics

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 34. Because of strong hydrogen bonding in water, its enthalpy of
vapourisation is more.
35. ∆rG will always be zero.
  
∆rG is zero for K = 1 because ∆G = – RT lnK, ∆G will be non zero for
other values of K.

36. For isolated system, there is no transfer of energy as heat or as work i.e.,
w=0 and q=0. According to the first law of thermodynamics.
∆U = q + w
= 0+0=0
∴ ∆U = 0
37. At constant volume
By first law of thermodynamics:
q = ∆U + (–w)
(–w) = p∆V
∴ q = ∆U + p∆V
∆V = 0, since volume is constant.
∴ qV = ∆U + 0
⇒ qV = ∆U = change in internal energy
At constant pressure
qp = ∆U + p∆V
But, ∆U + p∆V = ∆H
∴ qp = ∆H = change in enthalpy.
So, at a constant volume and at constant pressure heat change is a state
function because it is equal to change in internal energy and change in
enthalpy respectively which are state functions.

38. (–w) = pext (V2–V1) = 0 × (5 – 1) = 0

For isothermal expansion q = 0
By first law of thermodynamics
q = ∆U + (–w)
⇒ 0 = ∆U + 0 so ∆U = 0

39. For water, heat capacity = 18 × specific heat

or Cp = 18 × c
–1 –1
Specific heat = c = 4.18 Jg K
–1 –1
Heat capacity = Cp = 18 × 4.18 JK = 75.3 J K

40. CP – CV = nR
= 10 × 4.184 J

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41. Molar enthalpy = enthalpy change for 1 g carbon × molar mass of carbon
change of graphite
–1 –1
= – 20.7 kJ g × 12g mol
∴ ∆H = – 2.48 × 102 kJ mol–1

Negative value of ∆H ⇒ exothermic reaction.


42. ∆rH = Bond energy of H2 + Bond energy of Br2 – 2 × Bond energy of HBr
–1
= 435 + 192 – (2 × 368) kJ mol

⇒ ∆rH = –109 kJ mol–1

43. qp = ∆H = 30.5 kJ mol–1

284g
∴ Heat required for vapourisation of 284 g of CCl4 = –1
× 30.5 kJ mol–1
154g mol
= 56.2 kJ

44. According to the definition of standard enthalpy of formation, the enthalpy

change for the following reaction will be standard enthalpy of formation
of H2O (l)
1
H2(g) + O (g) → H2O(l ).
2 2
or the standard enthalpy of formation of H2O(l ) will be half of the enthalpy

of the given equation i.e., ∆rH is also halved.
–1
1 − 572 kJ mol
∆f H H O(l ) =
 
×∆r H = = – 286 kJ/mol.
2 2 2

45. Work done on an ideal gas can be calculated from p-V graph shown in
Fig. 6.6. Work done is equal to the shaded area ABVIVII .

Fig. : 6.6

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 46. The work done can be calculated with the help of p–V plot. A p–V plot of
the work of compression which is carried out by change in pressure in
infinite steps, is given in Fig. 6.7. Shaded area represents the work done
on the gas.

Fig. : 6.7

47.

Fig. : 6.8 Enthalpy change in processes (a) and (b)

48. No.
Enthalpy is one of the contributory factors in deciding spontaneity but it
is not the only factor. One must look for contribution of another factor
i.e., entropy also, for getting the correct result.

49. It is clear from the figure that the process has been carried out in infinite
steps, hence it is isothermal reversible expansion.

V2
w = – 2.303nRT log V
1

V2 p1 2
But, p1V1 = p2V2 ⇒ V = p = =2
1 2 1

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 p1
∴ w = – 2.303 nRT log p
2

–1
= – 2.303 × 1 mol × 8.314 J mol K–1 × 298 K–1 × log 2

= – 2.303 × 8.314 × 298 × 0.3010 J = –1717.46 J

50. w = – pex (Vf –Vi ) = –2 × 40 = – 80 L bar = – 8 kJ

The negative sign shows that work is done by the system on the
surrounding. Work done will be more in the reversible expansion because
internal pressure and exernal pressure are almost same at every step.

IV. Matching Type

51. (i) → (e) (ii) → (d) (iii) → (f) (iv) → (a)

(v) → (g), (k), (l) (vi) → (b) (vii) → (c) (viii) → (j)

(ix) → (h) (x) → (i) (xi) → (a), (l), (m) (xii) → (g), (k)

52. (i) →(b) (ii) → (c) (iii) → (a)

53. (i) → (c) (ii) → (a) (iii) → (b)

54. (i) → (b), (d) (ii) → (b) (iii) → (c) (iv) → (a)

V. Assertion and Reason Type

55. (ii) 56. (ii) 57. (i)

VI. Long Answer Type

59. Hint : Ratio of two extensive properties is always intensive

Extensive
= Intensive .
Extensive

Moles (Extensive)
e.g., Mole fraction = =
Total number of moles (Extensive)

1  – 
60. • Na (s) + Cl (g) → Na+(g) + Cl (g) ; ∆latticeH
2 2

83 Thermodynamics

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 • Bonn - Haber Cycle
• Steps to measure lattice enthalpy from Bonn - Haber cycle
• Sublimation of sodium metal

(1) Na(s) → Na (g) ; ∆sub H
(2) Ionisation of sodium atoms

Na(g) → Na+(g) + e–(g) ; ∆tH i.e., ionisation enthalpy
(3) Dissociation of chlorine molecule

1 1 
Cl (g) → Cl(g) ; ∆ H i.e., One-half of bond dissociation
2 2 2 bond
enthalpy.


(4) Cl(g) + e–(g) → Cl–(g) ; ∆egH i.e., electron gain enthalpy.

+
Na (g) + Cl (g)
1  
∆ H ∆egH
2 bond
+ 1
Na (g) + Cl2(g) –
Na+(g) + Cl (g)
2

∆iH

1
Na(g) + Cl (g)
2 2

 ∆latticeH
∆subH

1
Na(s) + Cl (g)
2 2

∆f H

NaCl(s)

61. ∆STotal = ∆Ssys + ∆Ssurr

- ∆H sys
∆STotal = ∆Ssys + T

T ∆STotal = T ∆Ssys – ∆Hsys

For spontaneous change, ∆Stotal > 0

∴ T ∆ Ssys – ∆Hsys > 0

⇒ – (∆Hsys – T ∆ Ssys ) > 0

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 But, ∆Hsys – T ∆ Ssys = ∆Gsys

∴ – ∆Gsys > 0

⇒ ∆Gsys = ∆Hsys – T ∆Ssys < 0

∆Hsys= Enthalpy change of a reaction.

T ∆Ssys = Energy which is not available to do useful work.
∆Gsys = Energy available for doing useful work.
• Unit of ∆G is Joule
• The reaction will be spontaneous at high temperature.
62.

Fig. : 6.9

(i) Reversible Work is represented by the combined areas and .

(ii) Work against constant pressure, pf is represented by the area
Work (i) > Work (ii)

85 Thermodynamics

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 



I. Multiple Choice Questions (Type-I)

1. We know that the relationship between Kc and Kp is

∆n
Kp = Kc (RT)
What would be the value of ∆n for the reaction
NH4Cl (s)  NH3 (g) + HCl (g)
(i) 1
(ii) 0.5
(iii) 1.5
(iv) 2

2. For the reaction H2(g) + I2(g)  2HI (g), the standard free energy is ∆G > 0.
The equilibrium constant (K ) would be __________.
(i) K=0
(ii) K>1
(iii) K=1
(iv) K<1

3. Which of the following is not a general characteristic of equilibria involving

physical processes?
(i) Equilibrium is possible only in a closed system at a given temperature.
(ii) All measurable properties of the system remain constant.
(iii) All the physical processes stop at equilibrium.
(iv) The opposing processes occur at the same rate and there is dynamic
but stable condition.

16-04-2018
4. PCl5, PCl3 and Cl2 are at equilibrium at 500K in a closed container and their
concentrations are 0.8 × 10–3 mol L–1, 1.2 × 10–3 mol L–1 and 1.2 × 10–3 mol L–1
respectively. The value of K c for the reaction PCl5 (g)  PCl3 (g) + Cl2 (g)
will be
3 –1
(i) 1.8 × 10 mol L
–3
(ii) 1.8 × 10
–3 –1
(iii) 1.8 × 10 L mol
4
(iv) 0.55 × 10

5. Which of the following statements is incorrect?

(i) In equilibrium mixture of ice and water kept in perfectly insulated flask
mass of ice and water does not change with time.
(ii) The intensity of red colour increases when oxalic acid is added to a
solution containing iron (III) nitrate and potassium thiocyanate.
(iii) On addition of catalyst the equilibrium constant value is not affected.
(iv) Equilibrium constant for a reaction with negative ∆H value decreases
as the temperature increases.

6. When hydrochloric acid is added to cobalt nitrate solution at room

temperature, the following reaction takes place and the reaction mixture
becomes blue. On cooling the mixture it becomes pink. On the basis of this
information mark the correct answer.
3+ – 2–
[Co (H2O)6] (aq) + 4Cl (aq)  [CoCl4] (aq) + 6H2O (l )
(pink) (blue)
(i) ∆H > 0 for the reaction
(ii) ∆H < 0 for the reaction
(iii) ∆H = 0 for the reaction
(iv) The sign of ∆H cannot be predicted on the basis of this information.

7. The pH of neutral water at 25°C is 7.0. As the temperature increases, ionisation

+ –
of water increases, however, the concentration of H ions and OH ions are
equal. What will be the pH of pure water at 60°C?
(i) Equal to 7.0
(ii) Greater than 7.0
(iii) Less than 7.0
(iv) Equal to zero

8. The ionisation constant of an acid, Ka, is the measure of strength of an acid.

The Ka values of acetic acid, hypochlorous acid and formic acid are
–5 –8 –4
1.74 × 10 , 3.0 × 10 and 1.8 × 10 respectively. Which of the following
orders of pH of 0.1 mol dm–3 solutions of these acids is correct?
(i) acetic acid > hypochlorous acid > formic acid
(ii) hypochlorous acid > acetic acid > formic acid

87 Equilibrium

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 (iii) formic acid > hypochlorous acid > acetic acid
(iv) formic acid > acetic acid > hypochlorous acid

9. K a , K a and K a are the respective ionisation constants for the following

1 2 3

reactions.
+ –
H2S  H + HS
– + 2–
HS  H + S
+ 2–
H2S  2H + S

The correct relationship between K a1 , K a 2 and K a 3 is

(i) Ka = K a1 × K a 2
3

(ii) K a = Ka + K a
3 1 2

(iii) K a = Ka – K a
3 1 2

(iv) K a = Ka / K a
3 1 2

10. Acidity of BF3 can be explained on the basis of which of the following concepts?
(i) Arrhenius concept
(ii) Bronsted Lowry concept
(iii) Lewis concept
(iv) Bronsted Lowry as well as Lewis concept.

11. Which of the following will produce a buffer solution when mixed in equal
volumes?
(i) 0.1 mol dm–3 NH4OH and 0.1 mol dm–3 HCl
(ii) 0.05 mol dm–3 NH4OH and 0.1 mol dm–3 HCl
(iii) 0.1 mol dm–3 NH4OH and 0.05 mol dm–3 HCl
(iv) 0.1 mol dm–3 CH4COONa and 0.1 mol dm–3 NaOH

12. In which of the following solvents is silver chloride most soluble?

(i) 0.1 mol dm–3 AgNO3 solution
(ii) 0.1 mol dm–3 HCl solution
(iii) H2O
(iv) Aqueous ammonia

–5
13. What will be the value of pH of 0.01 mol dm–3 CH3COOH (Ka = 1.74 × 10 )?
(i) 3.4
(ii) 3.6

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 (iii) 3.9
(iv) 3.0
–5 –5
14. Ka for CH3COOH is 1.8 × 10 and K b for NH4OH is 1.8 × 10 . The pH of
ammonium acetate will be
(i) 7.005
(ii) 4.75
(iii) 7.0
(iv) Between 6 and 7

15. Which of the following options will be correct for the stage of half completion
of the reaction A  B.

(i) ∆G = 0

(ii) ∆G > 0

(iii) ∆G < 0

(iv) ∆G = –RT ln2

16. On increasing the pressure, in which direction will the gas phase reaction
proceed to re-establish equilibrium, is predicted by applying the Le Chatelier’s
principle. Consider the reaction.

N2 (g) + 3H2 (g)  2NH3 (g)

Which of the following is correct, if the total pressure at which the equilibrium
is established, is increased without changing the temperature?
(i) K will remain same
(ii) K will decrease
(iii) K will increase
(iv) K will increase initially and decrease when pressure is very high

17. What will be the correct order of vapour pressure of water, acetone and ether
at 30°C. Given that among these compounds, water has maximum boiling
point and ether has minimum boiling point?
(i) Water < ether < acetone
(ii) Water < acetone < ether
(iii) Ether < acetone < water
(iv) Acetone < ether < water

18. At 500 K, equilibrium constant, Kc , for the following reaction is 5.

1 1
H2 (g) + I2 (g)  HI (g)
2 2
What would be the equilibrium constant Kc for the reaction

2HI (g)  H2 (g) + I2 (g)

89 Equilibrium

16-04-2018
 (i) 0.04
(ii) 0.4
(iii) 25
(iv) 2.5

19. In which of the following reactions, the equilibrium remains unaffected on

addition of small amount of argon at constant volume?
(i) H2 (g) + I2 (g)  2HI (g)
(ii) PCl5 (g)  PCl3 (g) + Cl2 (g)
(iii) N2 (g) + 3H2 (g)  2NH3 (g)
(iv) The equilibrium will remain unaffected in all the three cases.

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

20. For the reaction N2O4 (g)  2NO2 (g), the value of K is 50 at 400 K and 1700
at 500 K. Which of the following options is correct?
(i) The reaction is endothermic
(ii) The reaction is exothermic
(iii) If NO2 (g) and N2O4 (g) are mixed at 400 K at partial pressures 20 bar
and 2 bar respectively, more N2O4 (g) will be formed.
(iv) The entropy of the system increases.

21. At a particular temperature and atmospheric pressure, the solid and liquid
phases of a pure substance can exist in equilibrium. Which of the following
term defines this temperature?
(i) Normal melting point
(ii) Equilibrium temperature
(iii) Boiling point
(iv) Freezing point

III. Short Answer Type

22. The ionisation of hydrochloric in water is given below:
+ –
HCl(aq) + H2O (l )  H3O (aq) + Cl (aq)
Label two conjugate acid-base pairs in this ionisation.
23. The aqueous solution of sugar does not conduct electricity. However, when
sodium chloride is added to water, it conducts electricity. How will you explain
this statement on the basis of ionisation and how is it affected by concentration
of sodium chloride?
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24. BF3 does not have proton but still acts as an acid and reacts with NH3. Why is
it so? What type of bond is formed between the two?

25. Ionisation constant of a weak base MOH, is given by the expression

+ –
[M ][OH ]
Kb =
[MOH]

Values of ionisation constant of some weak bases at a particular temperature

are given below:
Base Dimethylamine Urea Pyridine Ammonia
–4 –14 –9 –5
Kb 5.4 × 10 1.3 × 10 1.77 × 10 1.77 × 10

Arrange the bases in decreasing order of the extent of their ionisation at

equilibrium. Which of the above base is the strongest?

26. Conjugate acid of a weak base is always stronger. What will be the decreasing
order of basic strength of the following conjugate bases?
– – – –
OH , RO , CH3COO , Cl

27. Arrange the following in increasing order of pH.

KNO3 (aq), CH3COONa (aq), NH4Cl (aq), C6H5COONH4 (aq)
–4
28. The value of Kc for the reaction 2HI (g)  H2 (g) + I2 (g) is 1 × 10
At a given time, the composition of reaction mixture is
–5 –5 –5
[HI] = 2 × 10 mol, [H2] = 1 × 10 mol and [I2] = 1 × 10 mol
In which direction will the reaction proceed?
+ –8
29. On the basis of the equation pH = – log [H ], the pH of 10 mol dm–3 solution
of HCl should be 8. However, it is observed to be less than 7.0. Explain the
reason.
30. pH of a solution of a strong acid is 5.0. What will be the pH of the solution
obtained after diluting the given solution a 100 times?

31. A sparingly soluble salt gets precipitated only when the product of
concentration of its ions in the solution (Qsp) becomes greater than its solubility
–4
product. If the solubility of BaSO4 in water is 8 × 10 mol dm–3. Calculate its
–3
solubility in 0.01 mol dm of H2SO4.

32. pH of 0.08 mol dm–3 HOCl solution is 2.85. Calculate its ionisation constant.

33. Calculate the pH of a solution formed by mixing equal volumes of two solutions
A and B of a strong acid having pH = 6 and pH = 4 respectively.
–11
34. The solubility product of Al (OH)3 is 2.7 × 10 . Calculate its solubility in gL–1
and also find out pH of this solution. (Atomic mass of Al = 27 u).

91 Equilibrium

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 35. Calculate the volume of water required to dissolve 0.1 g lead (II) chloride to
–8
get a saturated solution. (Ksp of PbCl2 = 3.2 × 10 , atomic mass of Pb = 207 u).
36. A reaction between ammonia and boron trifluoride is given below:
: NH3 + BF3 → H3N : BF3
Identify the acid and base in this reaction. Which theory explains it? What is
the hybridisation of B and N in the reactants?
37. Following data is given for the reaction: CaCO3 (s) → CaO (s) + CO2 (g)
 –1
∆f H [CaO(s)] = – 635.1 kJ mol
 –1
∆f H [CO2(g)] = – 393.5 kJ mol
 –1
∆f H [CaCO3(s)] = – 1206.9 kJ mol

Predict the effect of temperature on the equilibrium constant of the above

reaction.

IV. Matching Type

38. Match the following equilibria with the corresponding condition
(i) Liquid  Vapour (a) Saturated solution
(ii) Solid  Liquid (b) Boiling point
(iii) Solid  Vapour (c) Sublimation point
(iv) Solute (s)  Solute (solution) (d) Melting point
(e) Unsaturated solution

39. For the reaction : N2 (g) + 3H2(g)  2NH3(g)

2
[NH3 ]
Equilibrium constant Kc = 3
[N 2 ][H2 ]

Some reactions are written below in Column I and their equilibrium constants
in terms of Kc are written in Column II. Match the following reactions with the
corresponding equilibrium constant
Column I (Reaction) Column II (Equilibrium constant)
(i) 2N2(g) + 6H2(g)  4NH3(g) (a) 2Kc

1
(ii) 2NH3(g)  N2(g) + 3H2(g) (b) Kc2

1 3 1
(iii) N2(g) + H2(g)  NH3(g) (c) Kc
2 2
2
(d) Kc

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40. Match standard free energy of the reaction with the corresponding equilibrium
constant

(i) ∆G >0 (a) K>1

(ii) ∆G <0 (b) K=1

(iii) ∆G =0 (c) K=0
(d) K<1

41. Match the following species with the corresponding conjugate acid
Species Conjugate acid
2–
(i) NH3 (a) CO3
– +
(ii) HCO3 (b) NH4
+
(iii) H2O (c) H3 O
–
(iv) HSO4 (d) H2SO4

(e) H2CO3

42. Match the following graphical variation with their description

A B

(i) (a) Variation in product concentration

with time

(ii) (b) Reaction at equilibrium

(iii) (c) Variation in reactant concentration

with time

93 Equilibrium

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 43. Match Column (I) with Column (II).
Column I Column II
(i) Equilibrium (a) ∆G > 0, K < 1

(ii) Spontaneous reaction (b) ∆G = 0


(iii) Non spontaneous reaction (c) ∆G = 0

(d) ∆G < 0, K > 1

V. Assertion and Reason Type

In the following questions a statement of Assertion (A) followed by a statement
of Reason (R) is given. Choose the correct option out of the choices given
below each question.

44. Assertion (A) : Increasing order of acidity of hydrogen halides is

HF < HCl < HBr < HI
Reason (R) : While comparing acids formed by the elements belonging to
the same group of periodic table, H–A bond strength is a more
important factor in determining acidity of an acid than the
polar nature of the bond.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

45. Assertion (A) : A solution containing a mixture of acetic acid and sodium
acetate maintains a constant value of pH on addition of small
amounts of acid or alkali.
Reason (R) : A solution containing a mixture of acetic acid and sodium
acetate acts as a buffer solution around pH 4.75.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

46. Assertion (A): The ionisation of hydrogen sulphide in water is low in the
presence of hydrochloric acid.
Reason (R) : Hydrogen sulphide is a weak acid.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not correct explanation of A.

Exemplar Problems, Chemistry 94

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 (iii) A is true but R is false
(iv) Both A and R are false

47. Assertion (A): For any chemical reaction at a particular temperature, the
equilibrium constant is fixed and is a characteristic property.
Reason (R) : Equilibrium constant is independent of temperature.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

48. Assertion (A) : Aqueous solution of ammonium carbonate is basic.

Reason (R) : Acidic/basic nature of a salt solution of a salt of weak acid
and weak base depends on Ka and Kb value of the acid and
the base forming it.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

49. Assertion (A): An aqueous solution of ammonium acetate can act as a

buffer.
Reason (R) : Acetic acid is a weak acid and NH 4OH is a weak base.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not correct explanation of A.
(iii) A is false but R is true.
(iv) Both A and R are false.

50. Assertion (A): In the dissociation of PCl 5 at constant pressure and

temperature addition of helium at equilibrium increases the
dissociation of PCl5 .
Reason (R) : Helium removes Cl2 from the field of action.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

VI. Long Answer Type

51. How can you predict the following stages of a reaction by comparing the value
of Kc and Qc?
(i) Net reaction proceeds in the forward direction.
95 Equilibrium

16-04-2018
 (ii) Net reaction proceeds in the backward direction.
(iii) No net reaction occurs.

52. On the basis of Le Chatelier principle explain how temperature and pressure
can be adjusted to increase the yield of ammonia in the following reaction.
N2(g) + 3H2(g)  2NH3(g) ∆ H = – 92.38 kJ mol–1
What will be the effect of addition of argon to the above reaction mixture at constant
volume?
p+ q−
53. A sparingly soluble salt having general formula A x B y and molar solubility
S is in equilibrium with its saturated solution. Derive a relationship between
the solubility and solubility product for such salt.

54. Write a relation between ∆G and Q and define the meaning of each term and
answer the following :
(a) Why a reaction proceeds forward when Q < K and no net reaction occurs
when Q = K.
(b) Explain the effect of increase in pressure in terms of reaction quotient Q.
for the reaction : CO (g) + 3H2 (g)  CH4 (g) + H2O (g)

Exemplar Problems, Chemistry 96

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ANSWERS
I. Multiple Choice Questions (Type-I)

1. (iv) 2. (iv) 3. (iii) 4. (ii) 5. (ii) 6. (i)

7. (iii) 8. (iv) 9. (i) 10. (iii) 11. (iii) 12. (iv)

13. (i) 14. (iii)


15. (i) ∆G = 0

Justification : ∆G = – RT lnK
At the stage of half completion of reaction [A] = [B], Therefore, K = 1.

Thus, ∆G = 0

16. (i), Justification: According to Le-Chatelier’s principle, at constant

temperature, the equilibrium composition will change
but K will remain same.
17. (ii)

18. (i)

19. (iv)

II. Multiple Choice Questions (Type-II)

20. (i), (iii) and (iv)

Justification : (i) K increases with increase in temperature.
(iii) Q > K, Therefore, reaction proceeds in the backward
direction.
(iv) ∆ n > 0, Therefore, ∆ S > 0.

21. (i) and (iv)

III. Short Answer Type

–
22. HCl Cl
acid conjugate base
+
H2O H3O
base conjugate acid

23. • Sugar does not ionise in water but NaCl ionises completely in water
+ –
and produces Na and Cl ions.
• Conductance increases with increase in concentration of salt due to
release of more ions.
97 Equilibrium

16-04-2018
 24. BF3 acts as a Lewis acid as it is electron deficient compound and coordinate
bond is formed as given below :
H3N : → BF3

25. • Order of extent of ionisation at equilibrium is as follows :

Dimethylamine > Ammonia > Pyridine > Urea
• Since dimethylamine will ionise to the maximum extent it is the
strongest base out of the four given bases.
– – – –
26. RO > OH > CH3COO > Cl

27. NH4Cl < C6H5COONH4 < KNO3 < CH3COONa

28. At a given time the reaction quotient Q for the reaction will be given by the
expression.

[H 2 ][ I 2 ]
Q= 2
[HI ]

–5 –5
1 × 10 × 1 × 10 1
= –5 2
=
(2 × 10 ) 4
–1
= 0.25 = 2.5 × 10
–4
As the value of reaction quotient is greater than the value of Kc i.e. 1× 10
the reaction will proceed in the reverse direction.
–8 –3
29. Concentration of 10 mol dm indicates that the solution is very dilute.
Hence, the contribution of H3O+ concentration from water is significant
and should also be included for the calculation of pH.

30. (i) pH = 5
+ –5 –1
[H ] = 10 mol L
On 100 times dilution
+ –7 –1
[H ] = 10 mol L
+
On calculating the pH using the equation pH = – log [H ], value of pH
comes out to be 7. It is not possible. This indicates that solution is very
dilute. Hence,
Total hydrogen = [H+]
ion concentration

Contribution of Contribution of
+ +
H3 O ion H3 O ion
= +
concentration concentration
of acid of water
–7 –7
= 10 + 10 .
pH = 2 × 10–7 = 7 – log 2 = 7 – 0.3010 = 6.6990

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 2–
31. BaSO4 (s)  Ba2+ (aq) + SO 4 (aq)
At t = 0 1 0 0
At equilibrium in water 1–S S S
At equilibrium in the presence 1–S S (S+0.01)
of sulphuric acid
2– 2
K sp for BaSO4 in water = [Ba2+] [ SO 4 ] = (S) (S) = S

But S = 8 × 10–4 mol dm–3

–4 2 –8
∴ K sp = (8×10 ) = 64 × 10 ... (1)
The expression for Ksp in the presence of sulphuric acid will be as follows :
Ksp = (S) (S + 0.01) ... (2)
Since value of Ksp will not change in the presence of sulphuric acid,
therefore from (1) and (2)
–8
(S) (S + 0.01) = 64 × 10
2 –8
S + 0.01 S = 64 × 10
2 –8
S + 0.01 S – 64 × 10 = 0

2 –8
– 0.01 ± (0.01) + (4 × 64 × 10 )
S=
2

–4 –8
– 0.01 ± 10 + (256 × 10 )
=
2

–4 –2
– 0.01 ± 10 (1 + 256 × 10 )
=
2

–2
– 0.01 ± 10 1 + 0.256
=
2

–2
– 0.01 ± 10 1.256
=
2

–2 –2
– 10 + (1.12 × 10 )
=
2

–2
(–1+1.12) × 10 0.12 –2
= = × 10
2 2
–4
= 6 × 10 mol dm–3
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 32. pH of HOCl = 2.85
+
But, – pH = log [H ]
+
∴ – 2.85 = log [H ]
+
3 .15 = log [H ]
+
[H ] = 1.413 × 10–3

+
For weak mono basic acid [H ] = Ka × C

+ 2 –3 2
[H ] (1.413 × 10 )
Ka = =
C 0.08
–6 –5
= 24.957 × 10 = 2.4957 × 10

33. pH of Solution A = 6
+ –6 –1
Therefore, concentration of [H ] ion in solution A = 10 mol L
pH of Solution B = 4
+ –4 –1
Therefore, Concentration of [H ] ion concentration of solution B = 10 mol L
On mixing one litre of each solution, total volume = 1L + 1L = 2L
+
Amount of H ions in 1L of Solution A= Concentration × volume V
–6
= 10 mol × 1L
+ –4
Amount of H ions in 1L of solution B = 10 mol × 1L
+
∴ Total amount of H ions in the solution formed by mixing solutions A
–6 –4
and B is (10 mol + 10 mol)
This amount is present in 2L solution.

−4 –4 –4
10 (1 + 0.01) 1.01 × 10 –1 1.01 × 10 –1
∴ Total [H+] = = mol L = mol L
2 2 2
–4 –1
= 0.5 × 10 mol L
–5 –1
= 5 × 10 mol L
+
pH = – log [H ] = – log (5 × 10–5)
= – [log 5 + (– 5 log 10)]
= – log 5 + 5
= 5 – log 5
= 5 – 0.6990
= 4.3010 = 4.3

Exemplar Problems, Chemistry 100

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34. Let S be the solubility of Al(OH)3.
3+ –
Al (OH)3  Al (aq) + 3OH (aq)
Concentration of
species at t = 0 1 0 0
Concentration of various
species at equilibrium 1–S S 3S
3+ – 3 3 4
Ksp = [Al ] [OH ] = (S) (3S) = 27 S

–11
4
K sp 27 × 10 –12
S = = = 1 × 10
27 27 × 10
–3 –1
S = 1× 10 mol L
(i) Solubility of Al(OH)3
Molar mass of Al (OH)3 is 78 g. Therefore,
–1 –3 –3 –1
Solubility of Al (OH)3 in g L = 1 × 10 × 78 g L–1 = 78 × 10 gL
–2 –1
= 7.8 × 10 g L
(ii) pH of the solution
–3 –1
S = 1×10 mol L
– –3 –3
[OH ] = 3S = 3×1×10 = 3 × 10
pOH = 3 – log 3
pH = 14 – pOH = 11 + log 3 = 11.4771
–8
35. Ksp of PbCl2 = 3.2 × 10
Let S be the solubility of PbCl2.
2+ –
PbCl2 (s)  Pb (aq) + 2Cl (aq)
Concentration of
species at t = 0 1 0 0
Concentration of various
species at equilibrium 1–S S 2S

2+ – 2 2 3
Ksp = [Pb ] [Cl ] = (S) (2S) = 4S
3
Ksp = 4S

–8
3
K sp 3.2 × 10 –1 –9 –1
S = = mol L = 8 × 10 mol L
4 4

–1 –3 –1
S= 3
8 × 10
–9
= 2 × 10
–3 mol L ∴ S = 2 × 10 mol L

101 Equilibrium

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 Molar mass of PbCl2 = 278
–3 –1
∴ Solubility of PbCl2 in g L–1 = 2 × 10 × 278 g L
–3 –1
= 556 × 10 gL
–1
= 0.556 g L
To get saturated solution, 0.556 g of PbCl2 is dissolved in 1 L water.

0.1
0.1 g PbCl2 is dissolved in L = 0.1798 L water.
0.556

To make a saturated solution, dissolution of 0.1 g PbCl2 in 0.1798 L ≈ 0.2 L of

water will be required.

   
37. ∆rH = ∆f H [CaO(s)] + ∆f H [CO2(g)] – ∆f H [CaCO3(s)]
  –1
∴ ∆rH = 178.3 kJ mol
The reaction is endothermic. Hence, according to Le-Chatelier’s principle,
reaction will proceed in forward direction on increasing temperature.

IV. Matching Type

38. (i) → (b) (ii) → (d) (iii) → (c) (iv) → (a)

39. (i) → (d) (ii) → (c) (iii) → (b)
40. (i) → (d) (ii) → (a) (iii) → (b)
41. (i) → (b) (ii) → (e) (iii) → (c) (iv) → (d)
42. (i) → (c) (ii) → (a) (iii) → (b)
43. (i) → (b) and (c) (ii) → (d) (iii) → (a)

V. Assertion and Reason Type

44. (i) 45. (i) 46. (ii) 47.(iii) 48. (i) 49. (iii)

50. (iv)

VI. Long Answer Type

51. (i) Qc < Kc

(ii) Qc > Kc
(iii) Qc = Kc
where, Qc is reaction quotient in terms of concentration and Kc is
equilibrium constant.

Exemplar Problems, Chemistry 102

16-04-2018
 p+ q− p+ q–
53. [Hint : A x B y  xA (aq) + y B (aq)
p+ q–
S moles of AxBy dissolve to give x S moles of A and y S moles of B .]


54. ∆G = ∆G + RT lnQ

∆G = Change in free energy as the reaction proceeds
∆G = Standard free energy change
Q = Reaction quotient
R = Gas constant
T = Absolute temperature

Since ∆G = – RT lnK

Q
∴ ∆G = – RT lnK + RT lnQ = RT ln K

If Q < K, ∆G will be negative. Reaction proceeds in the forward direction.

If Q = K, ∆G = 0, no net reaction.
[Hint: Next relate Q with concentration of CO, H2, CH4 and H2O in view of
reduced volume (increased pressure). Show that Q < K and hence the
reaction proceeds in forward direction.]

103 Equilibrium

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 Unit

REDOX REAC
8
TIONS
REACTIONS

I. Multiple Choice Questions (Type-I)

1. Which of the following is not an example of redox reaction?
(i) CuO + H2 → Cu + H2O
(ii) Fe2O3 + 3CO → 2Fe + 3CO2
(iii) 2K + F2 → 2KF
(iv) BaCl2 + H2SO4 → BaSO4 + 2HCl
V
2. The more positive the value of E , the greater is the tendency of the species to
get reduced. Using the standard electrode potential of redox couples given
below find out which of the following is the strongest oxidising agent.
V –
E values: Fe3+/Fe2+ = + 0.77; I2(s)/I = + 0.54;
Cu2+/Cu = + 0.34; Ag+/Ag = + 0.80V
(i) Fe3+
(ii) I2(s)
(iii) Cu2+
(iv) Ag+
V
3. E values of some redox couples are given below. On the basis of these values
choose the correct option.
V –
E values : Br2/Br = + 1.90; Ag+ /Ag(s) = + 0.80
–
Cu2+/Cu(s) = + 0.34; I2(s)/I = + 0.54
–
(i) Cu will reduce Br
(ii) Cu will reduce Ag
–
(iii) Cu will reduce I
(iv) Cu will reduce Br2

16-04-2018
4. Using the standard electrode potential, find out the pair between which redox
reaction is not feasible.
V 3+ 2+ –
E values : Fe /Fe = + 0.77; I2/I = + 0.54;
2+ +
Cu /Cu = + 0.34; Ag /Ag = + 0.80 V
3+ –
(i) Fe and I
+
(ii) Ag and Cu
3+
(iii) Fe and Cu
3+
(iv) Ag and Fe

5. Thiosulphate reacts differently with iodine and bromine in the reactions given
below:
2– 2– –
2S2O3 + I2 → S4O6 + 2I
2– 2– – +
S2O3 + 2Br2 + 5H2O → 2SO4 + 2Br + 10 H

Which of the following statements justifies the above dual behaviour of

thiosulphate?
(i) Bromine is a stronger oxidant than iodine.
(ii) Bromine is a weaker oxidant than iodine.
(iii) Thiosulphate undergoes oxidation by bromine and reduction by iodine
in these reactions.
(iv) Bromine undergoes oxidation and iodine undergoes reduction in these
reactions.

6. The oxidation number of an element in a compound is evaluated on the basis

of certain rules. Which of the following rules is not correct in this respect?
(i) The oxidation number of hydrogen is always +1.
(ii) The algebraic sum of all the oxidation numbers in a compound is zero.
(iii) An element in the free or the uncombined state bears oxidation
number zero.
(iv) In all its compounds, the oxidation number of fluorine is – 1.

7. In which of the following compounds, an element exhibits two different

oxidation states.
(i) NH2OH
(ii) NH4NO3
(iii) N2H4
(iv) N3H

8. Which of the following arrangements represent increasing oxidation number

of the central atom?
– – 2– –
(i) CrO2 , ClO3 , CrO4 , MnO4
– 2– – –
(ii) ClO3 , CrO4 , MnO4 , CrO2

105 Redox Reactions

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 – – – 2–
(iii) CrO2 , ClO3 , MnO4 , CrO4
2– – – –
(iv) CrO4 , MnO4 , CrO2 , ClO3
9. The largest oxidation number exhibited by an element depends on its outer
electronic configuration. With which of the following outer electronic
configurations the element will exhibit largest oxidation number?
1 2
(i) 3d 4s
3 2
(ii) 3d 4s
5 1
(iii) 3d 4s
5 2
(iv) 3d 4s

10. Identify disproportionation reaction

(i) CH4 + 2O2 → CO2 + 2H2O
(ii) CH4 + 4Cl2 → CCl4 + 4HCl
– –
(iii) 2F2 + 2OH → 2F + OF2 + H2O
– – –
(iv) 2NO2 + 2OH → NO2 + NO3 + H2O
11. Which of the following elements does not show disproportionation tendency?
(i) Cl
(ii) Br
(iii) F
(iv) I

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

12. Which of the following statement(s) is/are not true about the following
decomposition reaction.

2KClO3 → 2KCl + 3O2

(i) Potassium is undergoing oxidation
(ii) Chlorine is undergoing oxidation
(iii) Oxygen is reduced
(iv) None of the species are undergoing oxidation or reduction

13. Identify the correct statement (s) in relation to the following reaction:

Zn + 2HCl → ZnCl2 + H2
(i) Zinc is acting as an oxidant
(ii) Chlorine is acting as a reductant
(iii) Hydrogen ion is acting as an oxidant
(iv) Zinc is acting as a reductant

Exemplar Problems, Chemistry 106

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14. The exhibition of various oxidation states by an element is also related to the
outer orbital electronic configuration of its atom. Atom(s) having which of the
following outermost electronic configurations will exhibit more than one oxidation
state in its compounds.
1
(i) 3s
1 2
(ii) 3d 4s
2 2
(iii) 3d 4s
2 3
(iv) 3s 3p

15. Identify the correct statements with reference to the given reaction
– –
P4 + 3OH + 3H2O → PH3 + 3H2PO2
(i) Phosphorus is undergoing reduction only.
(ii) Phosphorus is undergoing oxidation only.
(iii) Phosphorus is undergoing oxidation as well as reduction.
(iv) Hydrogen is undergoing neither oxidation nor reduction.

16. Which of the following electrodes will act as anodes, when connected to
Standard Hydrogen Electrode?
3+ V
(i) Al/Al E = –1.66
2+ V
(ii) Fe/Fe E = – 0.44
2+ V
(iii) Cu/Cu E = + 0.34
– V
(iv) F2 (g)/2F (aq) E = + 2.87

III. Short Answer Type

17. The reaction
– – –
Cl2 (g) + 2OH (aq) → ClO (aq) + Cl (aq) + H2O (l )
represents the process of bleaching. Identify and name the species that
bleaches the substances due to its oxidising action.

–
18. MnO 24 – undergoes disproportionation reaction in acidic medium but MnO4
does not. Give reason.

19. PbO and PbO2 react with HCl according to following chemical equations :
2PbO + 4HCl → 2PbCl2 + 2H2O

PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O

Why do these compounds differ in their reactivity?

20. Nitric acid is an oxidising agent and reacts with PbO but it does not react
with PbO2. Explain why?

107 Redox Reactions

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 21. Write balanced chemical equation for the following reactions:
–
(i) Permanganate ion (MnO4 ) reacts with sulphur dioxide gas in acidic
medium to produce Mn2+ and hydrogensulphate ion.
(Balance by ion electron method)
–
(ii) Reaction of liquid hydrazine (N2H4) with chlorate ion (ClO3 ) in basic
medium produces nitric oxide gas and chloride ion in gaseous state.
(Balance by oxidation number method)
(iii) Dichlorine heptaoxide (Cl2O7) in gaseous state combines with an aqueous
solution of hydrogen peroxide in acidic medium to give chlorite ion
–
(ClO2 ) and oxygen gas.
(Balance by ion electron method)
22. Calculate the oxidation number of phosphorus in the following species.
2– 3–
(a) HPO 3 and (b) PO 4

23. Calculate the oxidation number of each sulphur atom in the following
compounds:

(a) Na2S2O3 (b) Na2S4O6 (c) Na2SO3 (d) Na2SO4

24. Balance the following equations by the oxidation number method.

2– 3+ 3+
(i) Fe2+ + H+ + Cr2 O7 → Cr + Fe + H2O
– –
(ii) I2 + N O3 → NO2 + I O 3
2– – 2–
(iii) I2 + S2 O3 → I + S4 O6
2– 2+
(iv) MnO2 + C2 O 4 → Mn + CO2

25. Identify the redox reactions out of the following reactions and identify the
oxidising and reducing agents in them.
(i) 3HCl(aq) + HNO3 (aq) → Cl2 (g) + NOCl (g) + 2H2O (l )
(ii) HgCl2 (aq) + 2KI (aq) → HgI2 (s) + 2KCl (aq)

(iii) ∆ → 2Fe (s) + 3CO (g)

Fe2O3 (s) + 3CO (g)  2

(iv) PCl3 (l) + 3H2O (l) → 3HCl (aq) + H3 PO3 (aq)

(v) 4NH3 + 3O2 (g) → 2N2 (g) + 6H2O (g)

26. Balance the following ionic equations

2– + – 3+
(i) Cr2 O7 + H + I → Cr + I2 + H2O
2– 2+ + 3+ 3+
(ii) Cr2 O7 + Fe + H → Cr + Fe + H2O
– 2– + 2+ 2–
(iii) Mn O 4 + S O 3 + H → Mn + S O 4 + H2O
– + – 2+
(iv) Mn O 4 + H + Br → Mn + Br2 + H2O

Exemplar Problems, Chemistry 108

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IV. Matching Type
27. Match Column I with Column II for the oxidation states of the central atoms.
Column I Column II
2–
(i) Cr2O 7
(a) +3
–
(ii) MnO 4
(b) +4
–
(iii) VO3 (c) +5
3–
(iv) FeF6 (d) +6
(e) +7
28. Match the items in Column I with relevant items in Column II.
Column I Column II
(i) Ions having positive charge (a) +7
(ii) The sum of oxidation number (b) –1
of all atoms in a neutral molecule (c) +1
+
(iii) Oxidation number of hydrogen ion (H ) (d) 0
(iv) Oxidation number of fluorine in NaF (e) Cation
(v) Ions having negative charge (f) Anion

V. Assertion and Reason Type

In the following questions a statement of assertion (A) followed by a statement
of reason (R) is given. Choose the correct option out of the choices given
below each question.

29. Assertion (A) : Among halogens fluorine is the best oxidant.

Reason (R) : Fluorine is the most electronegative atom.

(i) Both A and R are true and R is the correct explanation of A.

(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

30. Assertion (A): In the reaction between potassium permanganate and

potassium iodide, permanganate ions act as oxidising agent.
Reason (R) : Oxidation state of manganese changes from +2 to +7 during
the reaction.

(i) Both A and R are true and R is the correct explanation of A.

(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

109 Redox Reactions

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 31. Assertion (A) : The decomposition of hydrogen peroxide to form water and
oxygen is an example of disproportionation reaction.
Reason (R) : The oxygen of peroxide is in –1 oxidation state and it is
converted to zero oxidation state in O2 and –2 oxidation state
in H2O.

(i) Both A and R are true and R is the correct explanation of A.

(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

32. Assertion (A) : Redox couple is the combination of oxidised and reduced
form of a substance involved in an oxidation or reduction
half cell.
V V
Reason (R) : In the representation E Fe3+ /Fe2+ and ECu2+ /Cu , Fe3+/ Fe2+
and Cu2+ / Cu are redox couples.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.

VI. Long Answer Type

33. Explain redox reactions on the basis of electron transfer. Give suitable examples.
34. On the basis of standard electrode potential values, suggest which of the
V
following reactions would take place? (Consult the book for E value).
2+ 2+
(i) Cu + Zn → Cu + Zn
2+ 2+
(ii) Mg + Fe → Mg + Fe
– –
(iii) Br2 + 2Cl → Cl2 + 2Br
2+ 2+
(iv) Fe + Cd → Cd + Fe
35. Why does fluorine not show disporportionation reaction?
36. Write redox couples involved in the reactions (i) to (iv) given in question 34.
37. Find out the oxidation number of chlorine in the following compounds and
arrange them in increasing order of oxidation number of chlorine.
NaClO4, NaClO3, NaClO, KClO2, Cl2O7, ClO3, Cl2O, NaCl, Cl2, ClO2.
Which oxidation state is not present in any of the above compounds?

38. Which method can be used to find out strength of reductant/oxidant in a

solution? Explain with an example.

Exemplar Problems, Chemistry 110

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ANSWERS
I. Multiple Choice Questions (Type-I)

1. (iv) 2. (iv) 3. (iv) 4. (iv) 5. (i) 6. (i)

7. (ii) 8. (i) 9. (iv) 10. (iv) 11. (iii)

II. Multiple Choice Questions (Type-II)

12. (i), (iv) 13. (iii), (iv) 14. (iii), (iv)

15. (iii), (iv) 16. (i), (ii)

III. Short Answer Type

17. Hypochlorite ion

18. In MnO 4– , Mn is in the highest oxidation state i.e. +7. Therefore, it does
2–
not undergo disproportionation. MnO4 undergoes disproportionation
as follows :
2– + –
3MnO4 + 4H → 2MnO4 + MnO2 + 2H2O

19. 2PbO + 4HCl → 2PbCl2 + 2H2O (Acid base reaction)

PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O (Redox reaction)
(Hint : Note the oxidation number of lead in the oxides)
20. PbO is a basic oxide and simple acid base reaction takes place between
PbO and HNO3. On the other hand in PbO2 lead is in + 4 oxidation state
and cannot be oxidised further. Therefore no reaction takes place. Thus,
PbO2 is passive, only PbO reacts with HNO3.

2PbO + 4HNO3 → 2Pb (NO3)2 + 2H2O (Acid base reaction)

22. (a) +3, (b) +5

23. (a) +2 (b) +5, 0, 0, +5 (c) +4 (d) +6

Justification :
Write Lewis structure of each ion then assign electron pair shared between
atoms of different electronegativity to more electronegative atom and distribute
the electron pair shared between atoms of same element equally. Now count
the number of electrons possessed by each atom. Find out the difference in
number of electrons possessed by neutral atom and that possessed by atom in
the compound. This difference is the oxidation number. If atom present in the
compound possesses more electrons than the neutral atom, the oxidation

111 Redox Reactions

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 number is negative. If it possesses less electrons then oxidation number is
positive.
2–
(i) Lewis structure of S2O4 can be written as follows :

Electron pair shared between sulphur and oxygen atom is assigned to

oxygen atom because of more electronegativity of oxygen. Thus each
sulphur atom is deficient of two electrons with respect to neutral sulphur
atom. Hence, each sulphur atom is in +2 oxidation state. Each oxygen
atom gets two excess electrons hence it is in –2 oxidation state. Lewis
2–
structure of S4O6 can be written as follows :

To find out oxidation state of each atom we distribute electrons of electron

pair shared between two sulphur atoms equally (i.e. one electron is assigned
to each sulphur atom). Both electrons of electron pair shared between
sulphur and oxygen atom are assigned to oxygen as oxygen is more
electronegative. Thus we find that each of the central sulphur atoms obtains
six electrons. This number is same as that in the outer shell of neutral
sulphur atom. Hence, oxidation state of each central sulphur atom is zero.
Each of the sulphur atoms attached to oxygen atoms finally obtains only
one electron as its share. This number is less by five electrons in comparison
to the neutral sulphur atom. So, outer sulphur atoms are in +5 oxidation
state. Therefore average oxidation state of sulphur atoms is :

5 + 0 + 0 + 5 10
= = 2.5
4 4
By using the formula we obtain average oxidation state of the particular
type of atoms. Real oxidation state can be obtained only by writing the
complete structural formula. Similarly we can see that each oxygen atom
is in – 2 oxidation state.
2–
In the same way one can find out the oxidation state of each atom in SO3
2–
and SO4 ions. Oxidation state of metal atoms will be +1 as these will lose
one electron in each case.

IV. Matching Type

27. (i)→ (d) (ii)→ (e) (iii) → (c) (iv)→(a)

28. (i)→ (e) (ii) → (d) (iii) → (c) (iv) → (b) (v) → (f)

V. Assertion and Reason Type

29. (ii) 30. (iii) 31. (i) 32. (ii)

Exemplar Problems, Chemistry 112

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 












 







I. Multiple Choice Questions (Type-I)

1. Which of the following is the correct IUPAC name?
(i) 3-Ethyl-4, 4-dimethylheptane
(ii) 4,4-Dimethyl-3-ethylheptane
(iii) 5-Ethyl-4, 4-dimethylheptane
(iv) 4,4-Bis(methyl)-3-ethylheptane

2. The IUPAC name for is ________.

(i) 1-hydroxypentane-1,4-dione
(ii) 1,4-dioxopentanol
(iii) 1-carboxybutan-3-one
(iv) 4-oxopentanoic acid

3. The IUPAC name for

16-04-2018
 (i) 1-Chloro-2-nitro-4-methylbenzene
(ii) 1-Chloro-4-methyl-2-nitrobenzene
(iii) 2-Chloro-1-nitro-5-methylbenzene
(iv) m-Nitro-p-chlorotoluene

4. Electronegativity of carbon atoms depends upon their state of hybridisation.

In which of the following compounds, the carbon marked with asterisk is
most electronegative?
(i) CH3 – CH2 – *CH2 –CH3
(ii) CH3 – *CH = CH – CH3
(iii) CH3 – CH2 – C ≡ *CH
(iv) CH3 – CH2 – CH = *CH2

5. In which of the following, functional group isomerism is not possible?

(i) Alcohols
(ii) Aldehydes
(iii) Alkyl halides
(iv) Cyanides

6. The fragrance of flowers is due to the presence of some steam volatile organic
compounds called essential oils. These are generally insoluble in water at
room temperature but are miscible with water vapour in vapour phase. A
suitable method for the extraction of these oils from the flowers is:
(i) Distillation
(ii) Crystallisation
(iii) Distillation under reduced pressure
(iv) Steam distillation

7. During hearing of a court case, the judge suspected that some changes in the
documents had been carried out. He asked the forensic department to check
the ink used at two different places. According to you which technique can
give the best results?
(i) Column chromatography
(ii) Solvent extraction
(iii) Distillation
(iv) Thin layer chromatography

8. The principle involved in paper chromatography is

(i) Adsorption
(ii) Partition
(iii) Solubility
(iv) Volatility

145 Organic Chemistry – Some Basic Principles and Techniques

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 9. What is the correct order of decreasing stability of the following cations.

I. II. III.

(i) II > I > III

(ii) II > III > I
(iii) III > I > II
(iv) I > II > III

10. Correct IUPAC name for is ___________.

(i) 2- ethyl-3-methylpentane
(ii) 3,4- dimethylhexane
(iii) 2-sec-butylbutane
(iv) 2, 3-dimethylbutane

11. In which of the following compounds the carbon marked with asterisk is
expected to have greatest positive charge?
(i) *CH3—CH2—Cl
+ –
(ii) *CH3—CH2—Mg Cl
(iii) *CH3—CH2—Br
(iv) *CH3—CH2—CH3

12. Ionic species are stabilised by the dispersal of charge. Which of the
following carboxylate ion is the most stable?

(i)

(ii)

(iii)

(iv)

13. Electrophilic addition reactions proceed in two steps. The first step
involves the addition of an electrophile. Name the type of intermediate
formed in the first step of the following addition reaction.
H3C—HC = CH2 + H+ →?

Exemplar Problems, Chemistry 146

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 (i) 2° Carbanion
(ii) 1° Carbocation
(iii) 2° Carbocation
(iv) 1° Carbanion
14. Covalent bond can undergo fission in two different ways. The correct
representation involving a heterolytic fission of CH3—Br is

(i)

(ii)

(iii)

(iv)

15. The addition of HCl to an alkene proceeds in two steps. The first step is the
attack of H+ ion to portion which can be shown as

(i)

(ii)

(iii)

(iv) All of these are possible

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

16. Which of the following compounds contain all the carbon atoms in the same
hybridisation state?
(i) H—C ≡ C—C ≡ C—H
(ii) CH3—C ≡ C—CH3
(iii) CH2 = C = CH2
(iv) CH2 = CH—CH = CH2

17. In which of the following representations given below spatial arrangement of

group/ atom different from that given in structure ‘A’?

(A)
147 Organic Chemistry – Some Basic Principles and Techniques

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 (i)

(ii)

(iii)

(iv)

18. Electrophiles are electron seeking species. Which of the following groups
contain only electrophiles?
(i) BF3 , NH3 , H2O

(ii) AlCl3, SO3 , NO+2

+ +
(iii) NO2 , CH3 , CH 3 – =O

– +
(iv) C2 H5 , , C 2 H5

Note : Consider the following four compounds for answering questions 19

and 20.

I.

II.

III.

IV.

19. Which of the following pairs are position isomers?

(i) I and II

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 (ii) II and III
(iii) II and IV
(iv) III and IV
20. Which of the following pairs are not functional group isomers?
(i) II and III
(ii) II and IV
(iii) I and IV
(iv) I and II
21. Nucleophile is a species that should have
(i) a pair of electrons to donate
(ii) positive charge
(iii) negative charge
(iv) electron deficient species
22. Hyperconjugation involves delocalisation of ___________.
(i) electrons of carbon-hydrogen σ bond of an alkyl group directly attached
to an atom of unsaturated system.
(ii) electrons of carbon-hydrogen σ bond of alkyl group directly attached to
the positively charged carbon atom.
(iii) π-electrons of carbon-carbon bond
(iv) lone pair of electrons

III. Short Answer Type

Note : Consider structures I to VII and answer the questions 23–26.

I. CH3—CH2—CH2—CH2—OH

II.

III.

IV.

149 Organic Chemistry – Some Basic Principles and Techniques

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 V. CH3—CH2—O—CH2—CH3

VI. CH3—O—CH2—CH2—CH3

VII.

23. Which of the above compounds form pairs of metamers?

24. Identify the pairs of compounds which are functional group isomers.
25. Identify the pairs of compounds that represents position isomerism.
26. Identify the pairs of compounds that represents chain isomerism.

27. For testing halogens in an organic compound with AgNO3 solution, sodium
extract (Lassaigne’s test) is acidified with dilute HNO3. What will happen if a
student acidifies the extract with dilute H2SO4 in place of dilute HNO3?
28. What is the hybridisation of each carbon in H2C = C = CH2.
29. Explain, how is the electronegativity of carbon atoms related to their state of
hybridisation in an organic compound?
30. Show the polarisation of carbon-magnesium bond in the following structure.
CH3—CH2—CH2—CH2—Mg—X

31. Compounds with same molecular formula but differing in their structures are
said to be structural isomers. What type of structural isomerism is shown by

CH3—S—CH2—CH2—CH3 and

32. Which of the following selected chains is correct to name the given compound
according to IUPAC system.

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33. In DNA and RNA, nitrogen atom is present in the ring system. Can Kjeldahl
method be used for the estimation of nitrogen present in these? Give reasons.
34. If a liquid compound decomposes at its boiling point, which method (s) can
you choose for its purification. It is known that the compound is stable at low
pressure, steam volatile and insoluble in water.

Note : Answer the questions 35 to 38 on the basis of information given below:

“Stability of carbocations depends upon the electron releasing inductive effect

of groups adjacent to positively charged carbon atom involvement of
neighbouring groups in hyperconjugation and resonance.”

35. Draw the possible resonance structures for and predict which
of the structures is more stable. Give reason for your answer.
36. Which of the following ions is more stable? Use resonance to explain your
answer.

37. The structure of triphenylmethyl cation is given below. This is very stable and
some of its salts can be stored for months. Explain the cause of high stability
of this cation.

38. Write structures of various carbocations that can be obtained from

2-methylbutane. Arrange these carbocations in order of increasing stability.

39. Three students, Manish, Ramesh and Rajni were determining the extra
elements present in an organic compound given by their teacher. They
prepared the Lassaigne’s extract (L.E.) independently by the fusion of the
compound with sodium metal. Then they added solid FeSO4 and dilute
sulphuric acid to a part of Lassaigne’s extract. Manish and Rajni obtained
prussian blue colour but Ramesh got red colour. Ramesh repeated the test
with the same Lassaigne’s extract, but again got red colour only. They were
surprised and went to their teacher and told him about their observation.
Teacher asked them to think over the reason for this. Can you help them by
giving the reason for this observation. Also, write the chemical equations to
explain the formation of compounds of different colours.

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 40. Name the compounds whose line formulae are given below :

(i) (ii)

41. Write structural formulae for compounds named as-

(a) 1-Bromoheptane (b) 5-Bromoheptanoic acid

42. Draw the resonance structures of the following compounds;

(i)

(ii) CH2 = CH—CH = CH2

(iii)

43. Identify the most stable species in the following set of ions giving reasons :

(i)

(ii)

44. Give three points of differences between inductive effect and resonance effect.
45. Which of the following compounds will not exist as resonance hybrid. Give
reason for your answer :

(i) CH3OH (ii) R—CONH2 (iii) CH3CH = CHCH2NH2

46. Why does SO3 act as an electrophile?

47. Resonance structures of propenal are given below. Which of these resonating
structures is more stable? Give reason for your answer.

48. By mistake, an alcohol (boiling point 97°C) was mixed with a hydrocarbon
(boiling point 68°C). Suggest a suitable method to separate the two
compounds. Explain the reason for your choice.
49. Which of the two structures (A) and (B) given below is more stabilised by
resonance? Explain.

CH3COOH and
(A) (B)
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IV. Matching Type
In the following questions more than one correlation is possible between
options of Column I and Column II. Make as many correlations as you can.

50. Match the type of mixture of compounds in Column I with the technique of
separation/purification given in Column II.

Column I Column II
(i) Two solids which have different (a) Steam distillation
solubilities in a solvent and which
do not undergo reaction when
dissolved in it.
(ii) Liquid that decomposes at its (b) Fractional distillation
boiling point
(iii) Steam volatile liquid (c) Simple distillation
(iv) Two liquids which have boiling (d) Distillation under reduced
points close to each other pressure
(v) Two liquids with large difference in (e) Crystallisation
boiling points.

51. Match the terms mentioned in Column I with the terms in Column II.

Column I Column II
(i) Carbocation (a) Cyclohexane and 1- hexene
(ii) Nucleophile (b) Conjugation of electrons of C–H
σ bond with empty p-orbital present
at adjacent positively charged
carbon.
(iii) Hyperconjugation (c) sp2 hybridised carbon with empty
p-orbital
(iv) Isomers (d) Ethyne
(v) sp hybridisation (e) Species that can receive a pair of
electrons

(vi) Electrophile (f) Species that can supply a pair of

electrons

52. Match Column I with Column II.

Column I Column II
(i) Dumas method (a) AgNO3

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 (ii) Kjeldahl’s method (b) Silica gel
(iii) Carius method (c) Nitrogen gas
(iv) Chromatography (d) Free radicals
(v) Homolysis (e) Ammonium sulphate

53. Match the intermediates given in Column I with their probable structure in
Column II.

Column I Column II
(i) Free radical (a) Trigonal planar

(ii) Carbocation (b) Pyramidal

(iii) Carbanion (c) Linear

54. Match the ions given in Column I with their nature given in Column II.

Column I Column II

(i) (a) Stable due to resonance

(ii) (b) Destabilised due to inductive effect

(iii) (c) Stabilised by hyperconjugation

(iv) (d) A secondary carbocation

V. Assertion and Reason Type

In the following questions a statement of Assertion (A) followed by a statement
of Reason (R) is given. Choose the correct option out of the choices given
below each question.

55. Assertion (A) : Simple distillation can help in separating a mixture of

propan-1-ol (boiling point 97°C) and propanone (boiling point
56°C).
Reason (R) : Liquids with a difference of more than 20°C in their boiling
points can be separated by simple distillation.

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 (i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

56. Assertion (A) : Energy of resonance hybrid is equal to the average of energies
of all canonical forms.
Reason (R) : Resonance hybrid cannot be presented by a single structure.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

57. Assertion (A) : Pent- 1- ene and pent- 2- ene are position isomers.
Reason (R) : Position isomers differ in the position of functional group or
a substituent.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

58. Assertion (A) : All the carbon atoms in H2C = C = CH2 are sp2 hybridised
Reason (R) : In this molecule all the carbon atoms are attached to each other
by double bonds.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

59. Assertion (A) : Sulphur present in an organic compound can be estimated

quantitatively by Carius method.
Reason (R) : Sulphur is separated easily from other atoms in the molecule
and gets precipitated as light yellow solid.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

60. Assertion (A): Components of a mixture of red and blue inks can be
separated by distributing the components between stationary
and mobile phases in paper chromatography.
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 Reason (R) : The coloured components of inks migrate at different rates
because paper selectively retains different components
according to the difference in their partition between the two
phases.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

VI. Long Answer Type

61. What is meant by hybridisation? Compound CH2 = C = CH2 contains sp or sp2
hybridised carbon atoms. Will it be a planar molecule?

62. Benzoic acid is a organic compound. Its crude sample can be purified by
crystallisation from hot water. What characteristic differences in the properties
of benzoic acid and the impurity make this process of purification suitable?

63. Two liquids (A) and (B) can be separated by the method of fractional distillation.
The boiling point of liquid (A) is less than boiling point of liquid (B). Which of
the liquids do you expect to come out first in the distillate? Explain.

64. You have a mixture of three liquids A, B and C. There is a large difference in
the boiling points of A and rest of the two liquids i.e., B and C. Boiling point of
liquids B and C are quite close. Liquid A boils at a higher temperature than B
and C and boiling point of B is lower than C. How will you separate the
components of the mixture. Draw a diagram showing set up of the apparatus
for the process.

65. Draw a diagram of bubble plate type fractionating column. When do we require
such type of a column for separating two liquids. Explain the principle involved
in the separation of components of a mixture of liquids by using fractionating
column. What industrial applications does this process have?

66. A liquid with high boiling point decomposes on simple distillation but it can
be steam distilled for its purification. Explain how is it possible?

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ANSWERS
I. Multiple Choice Questions (Type-I)

1. (ii) 2. (iv) 3. (ii) 4. (iii) 5. (iii) 6. (iv)

7. (iv) 8. (ii) 9. (i) 10. (ii) 11. (i) 12. (iv)
13. (iii) 14. (ii) 15. (ii)

II. Multiple Choice Questions (Type-II)

16. (i), (iv) 17. (i), (iii), (iv) 18. (ii), (iii)

19. (ii) 20. (i), (iii) 21. (i), (iii)

22. (i), (ii)

III. Short Answer Type

27. White ppt. of Ag2SO4 will be formed.

29. Electronegativity increases with increasing ‘s’ character.

sp3 < sp2 < sp

30. . Since electronegativity of carbon is more

than magnesium it will behave as .

31. Metamerism.

32. The four carbon chain. Selected chain should have maximum number of
functional groups.

33. DNA and RNA have nitrogen in the heterocyclic rings. Nitrogen present in
rings, azo groups and nitro groups cannot be removed as ammonia.

35.
I. II.
Structure II is more stable because every atom has complete octet.

36. Structure I is more stable due to resonance. (See resonance structure ‘A’
and ‘B’). No resonance is possible in structure II.

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 37. Stabilised due to nine possible canonical structures.

38. Four possible carbocations are

Order of increasing stability I < IV < II < III

–
39. In Lassaigne’s test SCN ions are formed due to the presence of sulphur
and nitrogen both. These give red colour with Fe3+ ions. This happens
when fusion is not carried out in the excess of sodium. With excess of
sodium the thiocyanate ion, if formed, is decomposed as follows:
NaSCN + 2Na → NaCN + Na2S

40. (i) 3-Ethyl-4-methylheptan-5-en-2-one

(ii) 3-Nitrocyclohex-1-ene.

41. (a) CH3—CH2—CH2—CH2—CH2—CH2—CH2Br

(b)

42. (i)

(ii)

(iii)

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43. (i) , The replacement of hydrogen by bromine increases positive
charge on carbon atom and destabilises the species.
(ii) is most stable because electronegativity of chlorine is more
than hydrogen. On replacing hydrogen by chlorine, negative charge
on carbon is reduced and species is stabilised.

44. Inductive effect Resonance effect

(i) Use σ-electrons (a) Use π- electrons or lone pair of
electrons

(ii) Move up to 3-carbon atoms (b) All along the length of

conjugated system

(iii) Slightly displaced electrons (c) Complete transfer of electrons

45. CH3OH; Any possible contributing structure will have charge separation
and incomplete octet of electrons on atoms. So the structure will be unstable
due to high energy. e.g., .

46.

Three highly electronegative oxygen atoms are attached to sulphur atom.

It makes sulphur atom electron deficient. Due to resonance also, sulphur
acquires positive charge. Both these factors make SO3 an electrophile.

47. I > II

48. Simple distillation can be used because the two compounds have a
difference of more than 20° in their boiling points and both the liquids
can be distilled without any decomposition.

49. Resonating structures are as follows:

(A)

(B)

Structure ‘B’ is more stabilised as it does not involve charge separation.

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 IV. Matching Type

50. (i) → (e) (ii) → (d) (iii) → (a) (iv) → (b) (v) → (c)
51. (i) → (c) (ii) → (f ) (iii) → (b) (iv) → (a) (v) → (d)
(vi) → (e)
52. (i) → (c) (ii) → (e) (iii) → (a) (iv) → (b) (v) → (d)
53. (i) → (a), (ii) → (a) (iii) → (b)
54. (i) → (a), (b), (d) (ii) → (b) (iii) → (b) (iv) → (c), (d)

V. Assertion and Reason Type

55. (i) 56. (iv) 57. (i) 58. (iv) 59. (iii) 60. (i)

VI. Long Answer Type

61. No. It is not a planar molecule.

Central carbon atom is sp hybridised and its two unhybridised p-orbitals

are perpendicular to each other. The p-orbitals in one plane overlap with
one of the p-orbital of left terminal carbon atom and the p-orbital in other
plane overlaps with p-orbital of right side terminal carbon atom. This
fixes the position of two terminal carbon atoms and the hydrogen atoms
attached to them in planes perpendicular to each other. Due to this the
pair of hydrogen atoms attached to terminal carbon atoms are present in
different planes.

Exemplar Problems, Chemistry 160

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 







I. Multiple Choice Questions (Type-I)

1. Arrange the following in decreasing order of their boiling points.
(A) n–butane (B) 2–methylbutane
(C) n-pentane (D) 2,2–dimethylpropane
(i) A>B>C>D
(ii) B>C>D>A
(iii) D>C>B>A
(iv) C>B>D>A

2. Arrange the halogens F2 , Cl2 , Br2 , I2 , in order of their increasing reactivity

with alkanes.
(i) I2 < Br2 < Cl2 < F2
(ii) Br2 < Cl2 < F2 < I2
(iii) F2 < Cl2 < Br2 < I2
(iv) Br2 < I2 < Cl2 < F2

3. The increasing order of reduction of alkyl halides with zinc and dilute HCl is
(i) R–Cl < R–I < R–Br
ii) R–Cl < R–Br < R–I
(iii) R–I < R–Br < R–Cl
(iv) R–Br < R–I < R–Cl

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 4. The correct IUPAC name of the following alkane is

(i) 3,6 – Diethyl – 2 – methyloctane

(ii) 5 – Isopropyl – 3 – ethyloctane
(iii) 3 – Ethyl – 5 – isopropyloctane
(iv) 3 – Isopropyl – 6 – ethyloctane

5. The addition of HBr to 1-butene gives a mixture of products A, B and C

(A) (B) (C)

The mixture consists of

(i) A and B as major and C as minor products
(ii) B as major, A and C as minor products
(iii) B as minor, A and C as major products
(iv) A and B as minor and C as major products

6. Which of the following will not show geometrical isomerism?

(i)

(ii)

(iii)

(iv)

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 7. Arrange the following hydrogen halides in order of their decreasing reactivity
with propene.
(i) HCl > HBr > HI
(ii) HBr > HI > HCl
(iii) HI > HBr > HCl
(iv) HCl > HI > HBr

8. Arrange the following carbanions in order of their decreasing stability.

– –
(A) H3C – C ≡ C (B) H – C ≡ C (C)
(i) A>B>C
(ii) B>A>C
(iii) C>B>A
(iv) C>A>B

9. Arrange the following alkyl halides in decreasing order of the rate of

β– elimination reaction with alcoholic KOH.

(A) (B) CH3—CH2—Br (C) CH3—CH2—CH2—Br

(i) A>B>C
(ii) C>B>A
(iii) B>C>A
(iv) A>C>B

10. Which of the following reactions of methane is incomplete combustion:

(i) Cu/523 K/100 atm

2CH4 + O2  → 2CH3OH
(ii) Mo2O3
CH4 + O2  → HCHO + H2O
(iii) CH4 + O2 → C(s) + 2H2O (l)
(iv) CH4 + 2O2 → CO2 (g) + 2H2O (l)

II. Multiple Choice Questions (Type-II)

In the following questions two or more options may be correct.

11. Some oxidation reactions of methane are given below. Which of them is/are
controlled oxidation reactions?
(i) CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l)
(ii) CH4 (g) + O2 (g) → C (s) + 2H2O (l)

(iii) Mo2O3
CH4 (g) + O2 (g)  → HCHO + H2O
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 (iv) Cu/523 /100 atm
2CH4 (g) + O2 (g)  → 2CH3OH

12. Which of the following alkenes on ozonolysis give a mixture of ketones only?
(i) CH3—CH CH—CH3

(ii)

(iii)

(iv)

13. Which are the correct IUPAC names of the following compound?

(i) 5– Butyl – 4– isopropyldecane

(ii) 5– Ethyl – 4– propyldecane
(iii) 5– sec-Butyl – 4– iso-propyldecane
(iv) 4–(1-methylethyl)– 5 – (1-methylpropyl)-decane

14. Which are the correct IUPAC names of the following compound?

(i) 5 – (2′, 2′–Dimethylpropyl)-decane

(ii) 4 – Butyl – 2,2– dimethylnonane
(iii) 2,2– Dimethyl – 4– pentyloctane
(iv) 5 – neo-Pentyldecane

15. For an electrophilic substitution reaction, the presence of a halogen atom in

the benzene ring _______.
(i) deactivates the ring by inductive effect
(ii) deactivates the ring by resonance

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 (iii) increases the charge density at ortho and para position relative to meta
position by resonance
(iv) directs the incoming electrophile to meta position by increasing the
charge density relative to ortho and para position.
16. In an electrophilic substitution reaction of nitrobenzene, the presence of nitro
group ________.
(i) deactivates the ring by inductive effect.
(ii) activates the ring by inductive effect.
(iii) decreases the charge density at ortho and para position of the ring
relative to meta position by resonance.
(iv) increases the charge density at meta position relative to the ortho and
para positions of the ring by resonance.
17. Which of the following are correct?

(i) CH3—O— CH⊕

2
is more stable than CH3— CH⊕
2

(ii) (CH3)2 CH⊕ is less stable than CH3—CH2— CH⊕

2

(iii) CH2 CH— CH⊕

2
is more stable than CH3—CH2— CH⊕
2

(iv) CH2 CH⊕ is more stable than CH3— CH⊕2

18. Four structures are given in options (i) to (iv). Examine them and select the
aromatic structures.

(i) (ii)

(iii) (iv)

19. The molecules having dipole moment are __________.

(i) 2,2-Dimethylpropane
(ii) trans-Pent-2-ene
(iii) cis-Hex-3-ene
(iv) 2, 2, 3, 3 - Tetramethylbutane.

III. Short Answer Type

20. Why do alkenes prefer to undergo electrophilic addition reaction while arenes
prefer electrophilic substitution reactions? Explain.
21. Alkynes on reduction with sodium in liquid ammonia form trans alkenes.
Will the butene thus formed on reduction of 2-butyne show the geometrical
isomerism?

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 22. Rotation around carbon-carbon single bond of ethane is not completely free.
Justify the statement.
23. Draw Newman and Sawhorse projections for the eclipsed and staggered
conformations of ethane. Which of these conformations is more stable and why?
24. The intermediate carbocation formed in the reactions of HI, HBr and HCl with
–1
propene is the same and the bond energy of HCl, HBr and HI is 430.5 kJ mol ,
–1 –1
363.7 kJ mol and 296.8 kJ mol respectively. What will be the order of
reactivity of these halogen acids?
25. What will be the product obtained as a result of the following reaction and why?

26. How will you convert benzene into (i) p – nitrobromobenzene

(ii) m – nitrobromobenzene
27. Arrange the following set of compounds in the order of their decreasing relative
reactivity with an electrophile.Give reason.

28. Despite their - I effect, halogens are o- and p-directing in haloarenes. Explain.
29. Why does presence of a nitro group make the benzene ring less reactive in
comparison to the unsubstituted benzene ring. Explain.
30. Suggest a route for the preparation of nitrobenzene starting from acetylene?
31. Predict the major product (s) of the following reactions and explain their formation.
(Ph-CO-O)
H3C—CH CH2 
HBr
2
→

HBr
H3C—CH CH2  →
32. Nucleophiles and electrophiles are reaction intermediates having electron rich
and electron deficient centres respectively. Hence, they tend to attack electron
deficient and electron rich centres respectively. Classify the following species
as electrophiles and nucleophiles.

–
(i) H3CO (ii) (iii) (iv)
+ –
(v) (H3C)3C (vi) Br (vii) H3COH (viii) R–NH–R
33. The relative reactivity of 1°, 2°, 3° hydrogen’s towards chlorination is 1 : 3.8 : 5.
Calculate the percentages of all monochlorinated products obtained from
2-methylbutane.

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34. Write the structures and names of products obtained in the reactions of sodium
with a mixture of 1-iodo-2-methylpropane and 2-iodopropane.
35. Write hydrocarbon radicals that can be formed as intermediates during
monochlorination of 2-methylpropane? Which of them is more stable? Give
reasons.
36. An alkane C8H18 is obtained as the only product on subjecting a primary alkyl
halide to Wurtz reaction. On monobromination this alkane yields a single isomer
of a tertiary bromide. Write the structure of alkane and the tertiary bromide.
37. The ring systems having following characteristics are aromatic.
(i) Planar ring containing conjugated π bonds.
(ii) Complete delocalisation of the π−electrons in ring system i.e. each
atom in the ring has unhybridised p-orbital, and
(iii) Presence of (4n+2) π−electrons in the ring where n is an integer
(n = 0, 1, 2,...........) [Huckel rule].

Using this information classify the following compounds as aromatic/nonaromatic.

38. Which of the following compounds are aromatic according to Huckel’s rule?

(A) (B) (C)

(D) (E) (F)

39. Suggest a route to prepare ethyl hydrogensulphate (CH3–CH2–OSO2—OH)

starting from ethanol (C2H5OH).
167 Hydrocarbons

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 IV. Matching Type
40. Match the reagent from Column I which on reaction with CH3—CH=CH2 gives
some product given in Column II as per the codes given below :

Column I Column II
(i) O3/Zn + H2O (a) Acetic acid and CO2
(ii) KMnO4/H+ (b) Propan-1-ol
–
(iii) KMnO4/OH (c) Propan-2-ol
(iv) H2O/H+ (d) Acetaldehyde and formaldehyde
(v) B2H6/NaOH and H2O2 (e) Propane-1,2-diol

41. Match the hydrocarbons in Column I with the boiling points given in Column II.

Column I Column II
(i) n–Pentane (a) 282.5 K
(ii) iso-Pentane (b) 309 K
(iii) neo-Pentane (c) 301 K

42. Match the following reactants in Column I with the corresponding reaction
products in Column II.

Column I Column II

(i) AlCl3
Benzene + Cl2  (a) Benzoic acid
→

(ii) AlCl3
Benzene + CH3Cl  (b) Methyl phenyl ketone
→

(iii) AlCl3
Benzene + CH3COCl  (c) Toluene
→
KMnO /NaOH
(iv) Toluene 
4
→ (d) Chlorobenzene
(e) Benzene hexachloride

43. Match the reactions given in Column I with the reaction types in Column II.

Column I Column II
+
(i) CH2 H
CH2 + H2O → CH3CH2OH (a) Hydrogenation

(ii) CH2 Pd
CH2 + H2  → CH3—CH3 (b) Halogenation

(iii) CH2 CH2 + Cl2 → Cl—CH2—CH2—Cl (c) Polymerisation

Cu tube
(iv) 3 CH CH 
Heat → C6H6 (d) Hydration
(e) Condensation

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V. Assertion and Reason Type
In the following questions a statement of assertion (A) followed by a statement
of reason (R) is given. Choose the correct option out of the choices given
below each question.
44. Assertion (A) : The compound cyclooctane has the following structural
formula :

It is cyclic and has conjugated 8π-electron system but it is not

an aromatic compound.
Reason (R) : (4n + 2) π electrons rule does not hold good and ring is not
planar.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

45. Assertion (A) : Toluene on Friedal Crafts methylation gives o– and p–xylene.
Reason (R) : CH3-group bonded to benzene ring increases electron density
at o– and p– position.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.

46. Assertion (A) : Nitration of benzene with nitric acid requires the use of
concentrated sulphuric acid.
Reason (R) : The mixture of concentrated sulphuric acid and concentrated
+
nitric acid produces the electrophile, NO2 .
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.
47. Assertion (A) : Among isomeric pentanes, 2, 2-dimethylpentane has highest
boiling point.
Reason (R) : Branching does not affect the boiling point.
(i) Both A and R are correct and R is the correct explanation of A.
(ii) Both A and R are correct but R is not the correct explanation of A.
(iii) Both A and R are not correct.
(iv) A is not correct but R is correct.
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 VI. Long Answer Type
48. An alkyl halide C5H11Br (A) reacts with ethanolic KOH to give an alkene ‘B’,
which reacts with Br2 to give a compound ‘C’, which on dehydrobromination
gives an alkyne ‘D’. On treatment with sodium metal in liquid ammonia one
mole of ‘D’ gives one mole of the sodium salt of ‘D’ and half a mole of hydrogen
gas. Complete hydrogenation of ‘D’ yields a straight chain alkane. Identify
A,B, C and D. Give the reactions invovled.

49. 896 mL vapour of a hydrocarbon ‘A’ having carbon 87.80% and hydrogen
12.19% weighs 3.28g at STP. Hydrogenation of ‘A’ gives 2-methylpentane.
Also ‘A’ on hydration in the presence of H2SO4 and HgSO4 gives a ketone ‘B’
having molecular formula C6H12O. The ketone ‘B’ gives a positive iodoform
test. Find the structure of ‘A’ and give the reactions involved.

50. An unsaturated hydrocarbon ‘A’ adds two molecules of H2 and on reductive

ozonolysis gives butane-1,4-dial, ethanal and propanone. Give the structure
of ‘A’, write its IUPAC name and explain the reactions involved.
51. In the presence of peroxide addition of HBr to propene takes place according
to anti Markovnikov’s rule but peroxide effect is not seen in the case of HCl
and HI. Explain.

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ANSWERS
I. Multiple Choice Questions (Type-I)

1. (iv) 2. (i) 3. (ii) 4. (i) 5. (i) 6. (iv)

7. (iii) 8. (ii) 9. (iv) 10. (iii)

II. Multiple Choice Questions (Type-II)

11. (iii), (iv) 12. (iii), (iv) 13. (iii), (iv)

14. (i), (iv) 15. (i), (iii) 16. (i), (iii)
17. (i), (iii) 18. (i), (iii) 19. (ii), (iii)

III. Short Answer Type

20. Both alkenes and arenes are electron-rich. Therefore undergo electrophilic
reactions. Olefins undergo addition reactions because addition of a reagent
to an olefin gives a more stable product as sp2 hybridisation changes to
sp3 hybridisation. Addition to the double bond of an arene would give a
product with less or no resonance stability hence addition is difficult
arenes. On the other hand in substitution reaction resonance stabilisation
is retained therefore, arenes undergo substitution reaction.
21. 2-Butene is capable of showing geometrical isomerism.
22. The rotation about C—C bond is restricted because of repulsion between
electron cloud of C—H bonds on either carbon atoms.
24. Bond dissociation energy is least for HI and maximum for HCl therefore,
order of reactivity will be HI > HBr > HCl.
⊕
25. Propyl chloride forms less stable CH3—CH2—CH2 carbocation with
anhydrous AlCl3 which rearranges to a more stable
carbocation and gives isopropylbenzene as the product of the reaction.

27. The +R effect of —OCH3 > —Cl and —NO2 has a – R effect. Relative reactivity
of the substituted benzene rings is as follows :

C6H5—OCH3 > C6H5—Cl > C6H5–NO2

28. Halogens attached to benzene rings exert – I and +R effect. +R effect

dominates – I effect and increases the electron density at ortho and
para positions of the benzene ring with respect to halogens.

33. 2-Methyl butane is . Possible compounds are A, B

and C given below :

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 Nine possibilities for compound ‘A’
because nine methyl hydrogens
are present in 2-methylbutane.

Two possibilities for ‘B’ compound

because two CH hydrogens are
present in 2-methylbutane.

Only one possibility for ‘C’

compound because one CH
hydrogen is present in 2-
methylbutane.

Relative amounts of A, B
= number of hydrogen × relative reactivity
and C compounds

A (1°) B (2°) C (3°)

Relative amount 9×1= 9 2×3.8 = 7.6 1×5=5

Total Amount of monohaloginated compounds = 9 + 7.6 + 5 = 21.6

9
Percentage of A = × 100 = 41.7%
21.6

7.6
Percentage of B = × 100 = 35.2%
21.6

5
Percentage of C = × 100 = 23.1%
21.6

35.

Radical I is tertiary where as radical II is primary. Radical I is more stable

due to hyperconjugation.

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 36.

37. A = Planar ring, all atoms of the ring sp2 hybridised, has six delocalised
π electrons, follows Huckel rule. It is aromatic.
B = Has six π electrons, but the delocalisation stops at sp3 hybridised
CH2- carbon. Hence, not aromatic.
C = Six delocalised π-electrons (4 π electrons + 2 unshared electrons on
negatively charged carbon) in a planar ring, follows Huckel’s rule.
It is aromatic.
D = Has only four delocalised π-electrons. It is non aromatic.
E = Six delocalised π-electrons follows Huckel’s rule. π electrons are in
sp2 hybridised orbitals, conjugation all over the ring because of
positively charged carbon. The ring is planar hence is aromatic.
F = Follows Huckel’s rule, has 2 π electrons i.e. (4n+2) π-electrons where
(n=0), delocalised π-electrons. It is aromatic.
G = 8π electrons, does not follow Huckel’s rule i.e., (4n+2) π-electrons
rule. It is not aromatic.

38. A = Has 8π electrons, does not follow Huckel rule. Orbitals of one carbon
atom are not in conjugation. It is not aromatic.
B = Has 6π delocalised electrons. Hence, is aromatic.
C = Has 6π electrons in conjugation but not in the ring. Non aromatic.
D = 10π electrons in planar rings, aromatic.
E = Out of 8π electrons it has delocalised 6π electrons in one six
membered planar ring, which follows Huckel’s rule due to which it
will be aromatic.
F = 14 π electrons are in conjugation and are present in a ring. Huckel’s
rule is being followed. Compound will be aromatic if ring is planar.

IV. Matching Type

40. (i) → (d) (ii) → (a) (iii) → (e) (iv) → (c)

(v) → (b)
41. (i) → (b) (ii) → (c) (iii) → (a)
42. (i) → (d) (ii) → (c) (iii) → (b) (iv) → (a)

43. (i) → (d) (ii) → (a) (iii) → (b) (iv) → (c)

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 V. Assertion and Reason Type

44. (i) 45. (i) 46. (i) 47. (iii)

VI. Long Answer Type

Br in CS
48. alc.KOH
C5H11Br  → Alkene (C5H10) 
2 2
→ C5H10Br2
(A) (B) (C)

Alc.KOH Na–liq.NH 1
–2HBr → C5H8  → C5H7–Na + H
3

2 2
D (Alkyne) Sodium alkylide
The reactions suggest that (D) is a terminal alkyne. This means triple
bond is at the end of the chain. It could be either (I) or (II).
CH3— CH2—CH2—CH2 ≡ CH

I II
Since alkyne ‘D’ on hydrogenation yields straight chain alkane, therefore
structure I is the structure of alkyne (D).
Hence, the structures of A, B and C are as follows :
(A) CH3—CH2—CH2—CH2—CH2Br
(B) CH3—CH2—CH2—CH CH2
(C) CH3—CH2—CH2—CH (Br)—CH2Br
49. Step I
896 mL vapour of CxHy (A) weighs 3.28 g

3.28×22700 –1
22700 mL vapour of CxHy (A) weighs g mol = 83.1 g mol–1
896

Step II
Element (%) Atomic Relative ratio Relative no. Simplest
mass of atoms ratio
C 87.8 12 7.31 1 3
H 12.19 1 12.19 1.66 4.98≈5

Empirical formula of ‘A’ C3H5

Empirical formula mass = 35 + 5 = 41 u

Molecular mass 83.1

n= = = 2.02 ≈ 2
Empirical formula mass 41

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 ⇒ Molecular mass is double of the empirical formula mass.
∴ Molecular Formula is C6H10
Step III

Structure of 2-methylpentane is

Hence, the molecule has a five carbon chain with a methyl group at the
second carbon atom.
‘A’ adds a molecule of H2O in the presence of Hg2+ and H+, it should be an
alkyne. Two possible structures for ‘A’ are :

or

I II
Since the ketone (B) gives a positive iodoform test, it should contain a
—COCH3 group. Hence the structure of ketone is as follows :

Therefore structure of alkyne is II.

50. Two molecules of hydrogen add on ‘A’ this shows that ‘A’ is either an
alkadiene or an alkyne.
On reductive ozonolysis ‘A’ gives three fragments, one of which is
dialdehyde. Hence, the molecule has broken down at two sites. Therefore,
‘A’ has two double bonds. It gives the following three fragments :
OHC—CH2—CH2—CHO, CH3CHO and CH3—CO—CH3

Hence, its structure as deduced from the three fragments must be

(A)
Reactions

Ozone
(A)  →

Zn /H2O
 → CH3—CHO + OHC—CH2—CH2—CHO +

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