Exercise - 01 - Chemical Equilibrium

(Physical Chemistry) CHEMICAL EQUILIBRIUM
EXERCISE # O-I
Characteristics of Equilibrium State

1. A chemical reaction is at equilibrium when
(A) Reactants are completely transformed into products
(B) The rates of forward and backward reactions are equal
(C) Formation of products is minimised
(D) Equal amounts of reactants and products are present
2. Which of the following statement is incorrect :

(A) At equilibrium, vapour pressure of solution and refractive index of equilibrium mixture
becomes constant.
(B) Equilibrium can be attained in both homogenous and heterogeneous reaction.
(C) At equilibrium concentration of reactants and products becomes constant and equal.
(D) Equilibrium is dynamic in nature
3. Concentrations of reactants and products at equilibrium can be like :
(A) (B) (C) (D) All of these
4. Rate of reaction curve for equilibrium can be like :

[rf = rate of forward, rb = rate of backward]
(A) (B)
(C) (D)
APNI KAKSHA 66
5. Initially the reactions in the container a & b are at equilibrium when the products & reactants
are put together in a container c then at the equilibrium the total number of different chemical
compounds are –
(A) 5 (B) 7 (C) 6 (D) 8
Characteristics of Equilibrium Constant
6. In a chemical equilibrium, the rate constant for the backward reaction is 2 × 10–4 and the
equilibrium constant is 1.5. The rate constant for the forward reaction is:-
(A) 2 × 10–3 (B) 5 × 10–4 (C) 3 × 10–4 (D) 9.0 × 10–4
7. The equilibrium concentration of B[(B)e]for the reversible reaction A B can be evaluated by

the expression :–
kf
(A) KC  A e
−1
(B) [A]e−1 (C) k f k b−1 [A]e (D) kfkb [A]–1
kb
8. For any reversible reaction if concentration of reactants increases then the equilibrium
constant:-
(A) will change depending on amount of concentration (B) remains same
(C) will decrease (D) will increase
9. If some He gas is introduced into the equilibrium PCl5(g) ⇌ PCl3(g) + Cl2(g) at constant pressure
and temperature then equilibrium constant of reaction:
(A) Increase (B) Decrease (C) remains same (D) Nothing can be said
10. The equilibrium constant for the reaction : N2(g) + O2(g) ⇇ 2NO(g) at 2000 K is 4  104. In
presence of a catalyst the equilibrium is established ten times faster at the same temperature.
What is the value of equilibrium constant in presence of catalyst :
(A) 40  104 (B) 4  10–4 (C) 4  104 (D) 2.5 10–5
APNI KAKSHA 67
11. The equilibrium constant (Kc)for the reaction 2X(g) + 2Y(g) ⎯⎯→ 2Z(g) is given as :
[Z]2 [Z]2
(A) [2 X][2Y] (B) [X][Y] (C) (D)
[2 Z] [Z] [X]2 [Y]2 [X][Y]
12. For the reaction

CuSO4.5H2O(s) ⇌ CuSO4.3H2O(s)+ 2H2O(g)
Which one is correct representation :–
(A) KP = P(H O)2 (B) Kc = [H2O]2 (C) Kp = Kc (RT)2 (D) All
2
13. For hypothetical equilibrium, 4A(g) + 5B(g) ⇇ 4X(g) + 6Y(g)

The unit of KC will be :
(A) litre mole–1 (B) mole litre–1 (C) litre mole–2 (D) mole2 litre–2
14. What is the unit of KP for the reaction ?

CS2 (g) + 4H2 (g) ⇌ CH4 (g) + 2H2S (g)
(A) atm (B) atm–2 (C) atm2 (D) atm–1
15. The equilibrium constant for the given reaction :

1
SO3(g) ⇌ SO2(g) + O2(g) ; Kc = 5 × 10–2
2
The value of Kc for the reaction
2SO2(g) + O2(g) ⇌ 2SO3(g), will be
(A) 400 (B) 2.40 × 10–3 (C) 9.8 × 10–2 (D) 4.9 × 10–2
16. The equilibrium constant for the reaction ;

N2(g) + O2(g) ⇌ 2NO(g) at temperature T is 4 × 10–4. The value of equilibrium constant for the
1 1
reaction NO (g) ⇌ 2 N2(g) + O2(g) at the same temperature is : –
2
(A) 0.02 (B) 50 (C) 4 × 10–4 (D) 2.5 × 10–2
17. For the following three reactions 1, 2 and 3, equilibrium constants are given :
(1) CO(g) + H2O(g) ⇌ CO2(g) + H2(g) ; K1
(2) CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g) ; K2
(3) CH4(g) + 2H2O(g) ⇌ CO2(g) + 4H2(g) ; K3
APNI KAKSHA 68
Which of the following relations is correct ?
(A) K1 K 2 = K3 (B) K2K3 = K1 (C) K3 = K1K2 (D) K3·K23K12
18. Equilibrium constant for following reactions respectively K1, K2 and K3

N2 + 3H2 ⇌ 2NH3 K1
N2 + O2 ⇌ 2NO K2
1
H2 + O2 ⇌ H2O K3
2
5
2NH3 + O2 ⇌ 2NO + 3H2O K4
2
Which of the following relation is incorrect.
K 2 ×(K3 )3 K ×K K 2 ×(K3 )3
(A) K1 = (B) K4 = K1 × K2/(K3)3 (C) K2 = 4 3 1 (D) K4 =
K4 (K 3 ) K1
19. Sulfide ion in alkaline solution reacts with solid sulfur to form polysulfide ions having formulas
S22–, S32–, S42– and so on. The equilibrium constant for the formation of S22– is 12 ( K1) & for the
formation of S32– is 132 (K2), both from S and S2–.What is the equilibrium constant for the
formation of S32– from S22– and S?
(A) 11 (B) 12 (C) 132 (D) None of these
20. For which reaction is Kp = Kc :–

(A) 2NOCl ⇌ 2NO(g) + Cl2(g) (B) N2(g) + 3H2(g) ⇌ 2NH3(g)
(C) H2(g) + I2(g) ⇌ 2HI (g) (D) 2SO2(g) + O2(g) ⇌ 2SO3(g)
KP
21. log + log RT = 0 is true relationship for the following reaction :
KC
(A) PCl5 ⇌ PCl3 + Cl2 (B) 2SO2 + O2 ⇌ 2SO3
(C) N2 + 3H2 ⇌ 2NH3 (D) (B) and (C) both
Kp
22. For which reaction at 298 K, the value of will be maximum and minimum respectively :
Kc
(a) N2O4(g) ⇇ 2NO2(g) (b) 2SO2(g) + O2(g) ⇇ 2SO3(g)
(c) X(g) + Y(g) ⇇ 4Z(g) (d) A(g) + 3B(g) ⇇ 7C(g)

(A) d,c (B) d,b (C) c,b (D) d,a
APNI KAKSHA 69
23. For the following gases equilibrium. N2O4 (g) ⇌ 2NO2 (g)
Kp is found to be equal to Kc. This is attained when temperature is
(A) 0°C (B) 273 K (C) 1 K (D) 12.19 K
Application of Equilibrium Constant
24. When Kc >> 1 for a chemical reaction,

(A) the equilibrium would be achieved rapidly
(B) the equilibrium would be achieved slowly
(C) product concentrations would be much greater than reactant concentrations at equilibrium
(D) reactant concentrations would be much greater then product concentrations at
equilibrium.
25. Equilibrium constant of some reaction are given as under ;
(a) x ⇇ y K = 10–1
(b) y ⇇ z K = 2 × 10–2
(c) P ⇇ Q K = 3 × 10–4
(d) R ⇇ S K = 2 × 10–3
Initial concentration of the reactants for each reaction was taken be equal :
Review the above reaction and indicate the reactions in which the reactants and products
respectively were of highest concentration :
(A) d, c (B) c, a (C) a, d (D) b, c
[NH3 ]2
26. The reaction quotient Q for N2(g) + 3H2(g) ⇌ 2NH3(g) is given by Q = . The
[N2 ][H2 ]3
reaction will proceed in backward direction, when
(A) Q = KC (B) Q < KC (C) Q > KC (D) Q = 10
27. A reaction mixture containing H2, N2 and NH3 has partial pressure 2 atm, 1 atm and 3 atm
respectively at 725 K. If the value of KP for the reaction, N2 + 3H2 2NH3 is 4.28  10–5 atm–2 at
725 K, in which direction the net reaction will go :
(A) Forward (B) Backward
(C) No net reaction (D) Direction of reaction cannot be predicted
APNI KAKSHA 70
Problems on Kc
28. What should be the value of Kc for the reaction 2SO2(g) + O2(g) ⇌ 2SO3(g), if the amount are SO3 =
48 g, SO2= 12.8 g and O2 = 9.6 g at equilibrium and the volume of the container is one litre?
(A) 64 (B) 30 (C) 42 (D) 8.5
29. A certain quantity of PCl5 was heated in a 10 litre vessel at 250ºC. At equilibrium the vessel
contains 0.1 mole of PCl5 0.20mole of PCl3 and 0.2 mole of Cl2; The equilibrium constant of the
reaction PCl5(g) ⇇ PCl3(g) + Cl2(g) is :

(A) 0.02 (B) 0.05 (C) 0.04 (D) 0.025
30. The figure show the change in concentration of species A and B as a function of time . The
equilibrium constant KC for the reaction A(g) ⇌ 2B (g) is :
(A) Kc > 1 (B) K < 1 (C) K = 1 (D) data insufficient
31. For the reaction A + 2B ⇌ 2C + D, initial concentration of A is ‘a’ and that of B is 1.5 times that of
A. Concentration of A and D are same at equilibrium. What should be the concentration of B at
equilibrium?
a a 3a
(A) (B) (C) (D) a
4 2 4
32. What is the minimum mass of CaCO3 (s) which is required to establish equilibrium in a 6.50
litre container for the reaction : CaCO3(s) ⇌ CaO(s) + CO2(g); Kc = 0.05 mole/litre
(A) 32.5 g (B) 24.6 g (C) 40.9 g (D) 8.0 g
33. Kc = 9 for the reaction, A + B ⇌ C + D, If one mole of each A and B are taken, then amount of C in
equilibrium is :
(A) 1 (B) 0.25 (C) 0.75 (d) None of these
APNI KAKSHA 71
34. For the reaction 3 A (g) + B (g) ⇌ 2 C (g) at a given temperature, Kc = 9.0 . What must be the
volume of the flask, if a mixture of 2.0 mol each of A , B and C exist in equilibrium ?
(A) 6L (B) 9L (C) 36 L (D) None of these
35. In the reaction A(g) + 2B(g) ⇇ 2C(g) , if 2 mole of A, 3.0 moles of B and 2.0 moles of C are
placed in a 2L flask. If equilibrium concentration of C is 0.5 mole/L. The value of equilibrium
constant (KC) will be:
(A) 0.073 (B) 0.147 (C) 0.05 (D) 0.026
36. The equilibrium constant for the reaction

A(g) + 2B(g) ⇌ C(g)
is 0.25 dm6mol–2. In a volume of 5 dm3, what amount of A must be mixed with 4 mol of B to
yield 1 mol of C at equilibrium.
(A) 3 moles (B) 24 moles (C) 26 moles (D) None of these
37. Equimolar concentrations of H2 and I2 are heated to equilibrium in a 2 litre flask. The forward
and the backward rate constants are found to be equal, what percentage of initial concentration
of H2 has reacted at equilibrium for the reaction H2 + I2 ⇇ 2HI

(A) 33 % (B) 66 % (C) 50 % (D) 40 % (E) 20 %
38. When alcohol (C2H5OH (l)) and acetic acid (CH3COOH (l)) are mixed together in equimolar ratio
at 27ºC, 33% of each is converted into ester. Then the KC for the equilibrium
C2H5OH(l) + CH3COOH (l)⇌ CH3COOC2H5 (l) + H2O(l) is :
(A) 4 (B) 1/4 (C) 9 (D) 1/9
Problems on Kp
39. PCl5 ⇌ PCl3 + Cl2 in the reversible reaction the moles of PCl5, PCl3 and Cl2 are a, b and c
respectively and total pressure is P then value of Kp is :
bc b bc.P c
(A) .RT (B) .P (C) (D) .P
a (a + b + c) a (a + b + c) (a + b + c)
40. In the reaction, PCl5 ⇌ PCl3 + Cl2, the amount of each PCl5, PCl3 and Cl2 is 2 mole at equilibrium
and total pressure is 3 atmosphere. The value of Kp will be
(A) 1.0 atm. (B) 3.0 atm. (C) 2.9 atm. (D) 6.0 atm.
APNI KAKSHA 72
41. The equilibrium constant, Kp for the reaction 2SO2(g) + O2(g) ⇌ 2SO3(g) is 4.0 atm–1 at 1000
K. What would be the partial pressure of O2 if at equilibrium the amount of SO2 and SO3 is the
same ?
(A) 16.0atm (B) 0.25 atm (C) 1 atm (D) 0.75 atm
42. For the reaction

A2(g) + 2B2 ⇌ 2C2(g)
the partial pressure of A2, B2 at equilibrium are 0.80 atm and 0.40 atm respectively. The
pressure of the system is 2.80 atm. The equilibrium constant Kp will be
(A) 20 (B) 5.0 (C) 0.02 (D) 0.2
43. A sample of pure NO2 gas heated to 1000 K decomposes : 2NO2(g) ⇌ 2NO(g) + O2(g). The
equilibrium constant KP is 100 atm. Analysis shows that the partial pressure of O2 is 0.25 atm.
at equilibrium. The partial pressure of NO2 at equilibrium is:
(A) 0.03 (B) 0.25 (C) 0.025 (D) 0.04
44. On decomposition of NH4HS, the following equilibrium is established :

NH4HS(s) ⇌NH3(g) + H2S (g)
If the total pressure is P atm, then the equilibrium constant KP is equal to
(A) P atm (B) P2 atm2 (C) P2 / 4 atm2 (D) 2P atm
45. In the reaction C(s) + CO2(g) ⇌ 2CO(g), the equilibrium pressure is 12 atm. If 50% of CO2 reacts
then Kp will be :
(A) 12 atm (B) 16 atm (C) 20 atm (D) 24 atm
46. For NH4HS(s) ⇌ NH3(g) + H2S(g) reaction started only with NH4HS(s), the observed pressure
for reaction mixture in equilibrium is 1.2 atm at 100°C. What is the value of Kp for the reaction ?
(A) 1.44 atm2 (B) 0.36 atm2 (C) 0.16 atm2 (D) 3.6 atm2
47. Consider the decomposition of solid NH4HS in a flask containing NH3(g) at a pressure of 2 atm.
What will be the partial pressure of NH3(g) and H2S(g) after the equilibrium has been attained?
KP for the reaction is 3 atm2.
(A) p NH3 = 4 atm, pH2S = 2 atm (B) p NH3 = 1.732 atm, pH2S = 1.732 atm
(C) p NH3 = 3 atm, pH2S = 1 atm (D) p NH3 = 1 atm, pH2S = 1 atm
APNI KAKSHA 73
Relation Between Kp and Kc
48. For which reaction is Kp = Kc :-
(A) 2NOCl(g) ⇇ 2NO(g) + Cl2(g) (B) N2(g) + 3H2(g) ⇇ 2NH3(g)
(C) H2(g) + I2(g) ⇇ 2HI(g) (D) 2SO2(g) + O2(g) ⇇ 2SO3(g)
49. For the following equilibrium N2O4(g) ⇇ 2NO2(g) KP is found to be equal to KC. This is attained
when
(A) T = 1K (B) T = 12.18 K (C) T = 27.3 (D) T = 273 K
1 KP
50. Reaction CO(g) + O2(g) ⇇ CO2(g). The value of is -
2 KC
1 1
(A) (B) RT (C) (D) RT
RT RT
51. At 527°C the reaction :

1 3
NH3(g) ⇇ N2(g) + H2(g) has Kc = 4
2 2
What is Kp for the reaction
N2(g) + 3H2(g) ⇇ 2NH3(g) :

−2 2
(B) 
800R 
(C) 
527R 
(A) 16 × (800 R)2   (D) None of these
 4   4 
Problems involving degree of dissociation, Average Molar Mass.

Degree of dissociation ()
52. For the reaction : P ⇌ Q + R. Initially 2 moles of P are taken. Up to equilibrium 0.5 moles of P
was dissociated. What would be the degree of dissociation :-
(A) 0.5 (B) 1 (C) 0.25 (D) 4.2
53. Two sample of HI, each of 5 gm. were taken separately into different vessels of volume 5 and 10
litres respectively at 27ºC . The extent of dissociation of HI will be :
(A) More in 5 litre vessel (B) More in 10 litre vessel
(C) Equal in both vessel (D) None of these
APNI KAKSHA 74
54. The degree of dissociation of SO3 is  at equilibrium pressure p0.
Kp for 2SO3(g) ⇌ 2SO2(g) + O2(g)
(A) p03 (B) p 0 3 (C) p0 2 (D) None of these

2 (1 −  ) ( 2 +  )(1 −  ) 2 (1 −  )
3 2 2
55. For the reaction : 2Hl (g) ⇌ H2(g) + I2(g), the degree of dissociated () of Hl(g) is related to
equilibrium constant KP by the expression
2 + 2 Kp 1 + 2K p 2K p 2 Kp
(A) (B) (C) (D)
2 2 1 + 2K p 1+ 2 Kp
56. The degree of dissociation of PCl5 () obeying the equilibrium, PCl5 PCl3 + Cl2 , is approximately
related to the pressure at equilibrium by (given  << 1) :
1 1 1
(A)   P (B)   (C)   (D)  
P P2 P4
57. For the reaction N2O4(g) ⇌ 2NO2(g), if percentage dissociation of N2O4 are 20%, 45%, 65% &
80%, then the sequence of observed vapour densities will be :
(A) d20 > d45 > d65 > d80 (B) d80 > d65 > d45 > d20
(C) d20 = d45 = d65 = d80 (D) (d20 = d45) > ( d65 = d80)
58. The vapour density of N2O4 at a certain temperature is 30. What is the % dissociation of N2O4 at
this temperature?
(A) 53.3% (B) 106.6% (C) 26.7% (D) None
59. The equilibrium constant KP (in atm) for the reaction is 9 at 7 atm and 300 K.
A2 (g) ⇌ B2(g) + C2 (g)
Calculate the average molar mass (in gm/mol) of an equilibrium mixture.
Given : Molar mass of A2, B2 and C2 are 70, 49 & 21 gm/mol respectively.
(A) 50 (B) 45 (C) 40 (D) 37.5
60. The degree of dissociation is 0.5 at 800 K and 2 atm for the gaseous reaction
PCl5 ⇌ PCl3 + Cl2
Assuming ideal behaviour of all the gases.
Calculate the density of equilibrium mixture at 800 K and 2 atm.
(A) 4.232 g/L (B) 6.4 g/L (C) 8.4 g/L (D) 2.2 g/L
APNI KAKSHA 75
61. At 727°C and 1.23 atm of total equilibrium pressure, SO3 is partially dissociated into SO2 and O2
according to SO3(g) ⇌ SO2(g) + 1/2O2(g). The density of equilibrium mixture is 0.9 g/litre. The
degree of dissociation is:
(A) 1/3 (B)2/3 (C) l/4 (D) 1/5.
62. Attainment of the equilibrium

A(g) ⇌ 2C(g) + B(g)
gave the following graph.
Find the correct option.
(% dissociation = fraction dissociated × 100)
(A) At t = 5sec equilibrium has been reached and K e = 128( mol/litre)2
(B) At t = 5sec equilibrium has been reached and % dissociation of A is 60%
(C) Att = 5sec equilibrium has been reached and % dissociation of A is 40%
(D) None of these
63. Solid ammonium carbamate dissociates to give ammonia and carbon dioxide as follows
NH2COONH4(s) ⇌ 2NH3(g) + CO2(g)
which of the following graph correctly represents the equilibrium.
NH2COONH4(s)
8M
8M
7M 7M
6M
Conc.(mol/Lt.)
Conc.(mol/Lt.)
6M
NH3(g)
5M 5M
NH2COONH4(s) NH3(g)
4M 4M
CO2(g)
3M 3M
2M 2M
CO2(g)
(A) 1M (B) 1M
1 2 3 4 5 1 2 3 4 5
Time (sec.) Time(sec.)
NH2COONH4(s) NH2COONH4(s)
8M 8M
7M 7M
6M
Conc.(mol/Lt.)
Conc.(mol/Lt.)
6M
NH3(g)
5M 5M
4M 4M
CO2(g) NH3(g)
3M 3M
2M 2M
CO2(g)
(C) 1M (D) 1M
1 2 3 4 5 1 2 3 4 5
Time (sec.) Time(sec.)
APNI KAKSHA 76
Le-Chatelier’s mix problems
64. The following reaction is at equilibrium in a closed vessel NH4HS(s) ⇌ NH3(g) + H2S(g) what is
the effect of adding H2S at constant volume :
(A) Reaction moves forward (B) Reaction moves backward
(C) No change occurs (D) Change cannot be predicted
65. In an equilibrium system involving solids and gases, an increase in the amount of the solid
reactant will
(A) Increase the concentration of the gas product
(B) Decrease the concentration of the gas product
(C) Increase the concentration of all the product
(D) Not effect the concentration of the gas products
66. In which of the following reactions, increase in the pressure at constant temperature does not
affect the moles at equilibrium :
1
(A) 2NH3(g) ⇌ N2(g) + 3H2(g) (B) C(g) + O2(g) ⇌ CO(g)
2
1
(C) H2(g) + O2(g) ⇌ H2O(g) (D) H2(g) + I2(g) ⇌ 2HI(g)
2
67. Au(s) ⇌ Au()
Above equilibrium is favoured at :

(A) High pressure low temperature (B) High pressure high temperature
(C) Low pressure, high temperature (D) Low pressure, low temperature
68. For the reaction PCl5 ⇌ PCl3 + Cl2, at constant temperature If the volume is increased 16 times
the initial volume, the degree of dissociation for this reaction will becomes :–
1 1
(A) 4 time (B) times (C) 2 time (D) times
4 2
69. What is the effect of the reduction of the volume of the system for the equilibrium
2C(s) + O2(g) ⇌ 2CO (g) ?
(A) The equilibrium will be shifted to the left by the increased pressure caused by the
reduction in volume.
(B) The equilibrium will be shifted to the right by the decreased pressure caused by the
(C) The equilibrium will be shifted to the left by the increased pressure caused by the increase
in volume.
APNI KAKSHA 77
(D) The equilibrium will be shifted to the right by the increased pressure caused by the
70. For an equilibrium H2O(s) ⇌ H2O() which of the following statements is true.
(A) The pressure changes do not affect the equilibrium

(B) More of ice melts if pressure on the system is increased
(C) More of liquid freezes if pressure on the system is increased
(D) The degree of advancement of the reaction do not depend on pressure
71. A gas 'X' when dissolved in water heat is evolved. Then solubility of 'X' will increase :
(A) Low pressure, high temperature (B) Low pressure, low temperature
(C) high pressure, high temperature (D) high pressure, low temperature
72. Consider the reactions

(i) PCl5(g) ⇌ PCl3(g) + Cl2(g)
(ii) N2O4(g) ⇌2NO2(g)
The addition of an inert gas at constant volume
(A) will increase the dissociation of PCl5 as well as N2O4
(B) will reduce the dissociation of PCl5 as well as N2O4
(C) will increase the dissociation of PCl5 and step up the formation of NO2
(D) will not disturb the equilibrium of the reactions
73. The equilibrium SO2Cl2(g) ⇌ SO2(g) + Cl2(g) is attained at 25°C in a closed rigid container and
an inert gas, helium is introduced. Which of the following statements is/are correct.
(A) concentrations of SO2, Cl2 and SO2Cl2 do not change
(B) more chlorine is formed
(C) concentration of SO2 is reduced
(D) more SO2Cl2 is formed
74. Some quantity of water is contained in a container as shown in figure. As neon is added
to this system at constant pressure, the amount of liquid water in the vessel
(A) increases (B) decreases

APNI KAKSHA 78
(C) remains same (D) changes unpredictably
75. Which of the following reaction will shift in backward direction. When the respective change is
made at equilibrium:
(A) N2(g) + 3H2(g) ⇌ 2NH3(g) increase in pressure at eq.
(B) H2O(s) ⇌ H2O() addition of inert gas at constant volume
(C) PCl5(g) ⇌ PCl3(g) + Cl2(g) addition of inert gas at constant pressure

(D) CO2(g) + CaO(s) ⇌ CaCO3 increase in temperature
76. The equilibrium 2SO2(g) + O2(g) ⇌ 2SO3(g) shifts forward if :–

(A) A catalyst is used.
(B) An adsorbent is used to remove SO3 as soon as it is formed.
(C) Small amounts of reactants are removed.
(D) temperature is increased
77. Densities of diamond and graphite are 3.5 and 2.3 gm/mL.
C (diamond) C (graphite) rH = –1.9 kJ/mole
favourable conditions for formation of diamond are
(A) high pressure and low temperature (B) low pressure and high temperature
(C) high pressure and high temperature (D) low pressure and low temperature
78. For a system at equilibrium some changes are made which is reported by a graph (shown
below). Changes has been made at constant temperature.
Choose the correct options :
(A) (B)
(C) (D)
APNI KAKSHA 79
79. Sulfuryl chloride is in equilibrium with sulfur dioxide and chlorine gas:
SO2 Cl2 ( g) ⇌ SO2 ( g) + Cl2 ( g)
A system with a volume of 1.00 L is in equilibrium at a certain temperature with p(SO2 Cl2 ) = 1.00
bar and p(SO2 ) = p(Cl2 ) = 0.10 bar. By how much will the number of moles of SO2 Cl2 at equilibrium
change if the volume is reduced to 0.50 L ?
(A) Increase 1-10% (B) Increase 11 − 50%
(C) Decrease 1-10% (D) Decrease 11-50%
APNI KAKSHA 80
EXERCISE # S-I
Characteristics of Equilibrium Constant

1. Consider the gas-phase hydration of hexafluoroacetone, (CF3)2CO:
kf kr
(CF3)2 CO (g) + H2O (g) ⇇ (CF3)2 C(OH)2 (g)
At 76°C, the forward and reverse rate constants are kf = 0.15 M–1 s–1 and kr = 6 × 10–4 s–1. What
is the value of the equilibrium constant Kc?
2. Consider the reaction of chloromethane with OH– in aqueous solution

kf kr
CH3Cl (aq) + OH– (aq) ⇇ CH3OH (aq) + Cl– (aq)
At 25°C, the rate constant for the forward reaction is 6 × 10–6 M–1 s–1, and the equilibrium
constant Kc is 1 × 1016. Calculate the rate constant for the reverse reaction at 25°C.
3. If Kc = 0.5 × 10–9 at 1000 K for the reaction N2 (g) + O2 (g) ⇌ 2NO (g), what is Kc at 1000 K for
the reaction 2NO (g) ⇌ N2 (g) + O2 (g)?
Application of Equilibrium constant
4. The initial concentrations or pressure of reactants and products are given for each of the
following systems. Calculate the reaction quotient and determine the directions in which each
system will shift to reach equilibrium.
(a) 2NH3(g) ⇌ N2(g) + 3H2(g) K = 17
[NH3] = 0.20 M ; [N2] = 1.00 M ; [H2] = 1.00 M
(b) 2NH3 (g) ⇌ N2 (g) + 3H2 (g) Kp = 6.8 × 104 atm2
Initial pressure : NH3 = 3.0 atm ; N2 = 2.0 atm ; H2 = 1.0 atm
(c) 2SO3(g) ⇌ 2SO2 (g) + O2 (g) Kp = 16.5 atm
Initial pressure : SO3 = 1.0 atm ; SO2 = 1.0 atm ; O2 = 1.0 atm
(d) 2NO(g) + Cl2 (g) ⇌ 2NOCl (g) Kc = 4.6 × 104 M-1
[NO] = 1.00 M ; [Cl2] = 1.00 M ; [NOCl] = 0 M
5. At 1400 K, Kc = 2.5 × 10–3 for the reaction CH4 (g) + 2H2S ⇌ CS2(g) + 4H2(g). A 10.0 L reaction
vessel at 1400 K contains 2.0 mol of CH4, 3.0 mol of CS2,
3.0 mol of H2 and 4.0 mol of H2S. Is the reaction mixture at equilibrium?
If not, in which direction does the reaction proceed to reach equilibrium?
APNI KAKSHA 81
6. The first step in the industrial synthesis of hydrogen is the reaction of steam and methane to
give water gas, a mixture of carbon monoxide and hydrogen.
H2O (g) + CH4(g) ⇌ CO (g) + 3H2 (g) Kc = 4.7 at 1400 K
A mixture of reactants and product at 1400 K contains 0.03 M H2O, 0.050M CH4, 0.15 M CO, and
0.20 M H2. In which direction does the reaction proceed to reach equilibrium?
7. Which of the following reactions goes almost all the way to completion, and which proceeds
hardly at all?
(a) N2(g) + O2(g) ⇌ 2NO (g); Kc = 2.7 × 10–18
(b) 2NO(g) + O2(g) ⇌ 2NO2 (g); Kc = 6.0 × 1013
Problems on Kc
8. An equilibrium mixture of PCl5, PCl3 and Cl2 at a certain temperature contains
0.5 × 10–3 M PCl5, 1.5 × 10–2 M PCl3, and 3 × 10–2 M Cl2.
Calculate the equilibrium constant Kc for the reaction PCl5(g) ⇌ PCl3(g) +Cl2(g).
9. An equilibrium mixture of N2, H2, and NH3 at 700 K contains 0.036 M N2 and 0.15 M H2.
At this temperature, Kc for the reaction N2(g) + 3H2(g) 2NH3(g) is 0.29. What is the
concentration of NH3?
10. The value of Kc for the reaction 3O2 (g) ⇌ 2O3 (g) is 8 × 10–55 at 25°C. Do you expect pure air at
25°C to contain much O3 (ozone) when O2 and O3 are in equilibrium? If the equilibrium
concentration of O2 in air at 25°C is 8 × 10–3 M, what is the equilibrium concentration of O3 ?
11. The progress of the reaction

A ⇌ nB with time, is presented in figure. Determine
0.5
0.3
0.1
1 3 5 7
(i) the value of n. 2

(ii) the equilibrium constant K.
APNI KAKSHA 82
12. 2 moles of A & 3 moles of B are mixed in 1 litre vessel and the reaction is carried at 400°C
according to the equation; A + B ⇌ 2C. The equilibrium constant of the reaction is 4. Find the
number of moles of C at equilibrium.
13. The air pollutant NO is produced in automobile engines from the high temperature reaction
N2(g) + O2(g) ⇌ 2NO (g) ; Kc = 16 at 2300 K. If the initial concentrations of N2 and O2 at 2300 K
are both 1.5 M, what are the concentrations of NO, N2, and O2 when the reaction mixture
reaches equilibrium?
14. At a certain temperature, the reaction PCl5(g) ⇌ PCl3(g) + Cl2(g) has an equilibrium constant Kc
= 10–2. Calculate the equilibrium concentrations of PCl5, PCl3 and Cl2 if only PCl5 is present
initially, at a concentration of 0.1 M.
15. A sample of HI (9.6 × 10–3 mol) was placed in an empty 2.00 L container at 1000 K. After
equilibrium was reached, the concentration of I2 was 4 × 10–4 M. Calculate the value of Kc at
1000 K for the reaction H2 (g) + I2 (g) . 2HI (g).
16. Following equilibrium is established at temperature T.

A(g) ⇌ B(g) + C (g)
at eq. 1M 2M 2M.
If volume of the vessel is doubled then find the equilibrium concentration of each species.
(Given that : 40 = 6.324)
Problems on Kp
17. At 90°C, the following equilibrium is established :
H2(g) + S(s) ⇌ H2S(g) Kp = 6.8 × 10–2
If 0.2 mol of hydrogen and 1.0 mol of sulphur are heated to 90°C in a 1.0 litre vessel, what will
be the partial pressure of H2S at equilibrium?
18. The equilibrium constant for the reaction is 9 at 900°C S2(g) + C(s) ⇌ CS2(g). Calculate the
pressure of two gases at equilibrium, when initial 2 atm of S2 and excess of C(s) allowed to
come to equilibrium.
APNI KAKSHA 83
19. At 700 K, Kp = 0.2 for the reaction ClF3 (g) ⇌ ClF (g) + F2(g). Calculate the equilibrium partial
pressure of ClF3, ClF, and F2 if only ClF3 is present initially, at a partial pressure of 0.150 atm.
20. A sample of CaCO3(s) is introduced into a sealed container of volume 0.821 litre & heated to
1000K until equilibrium is reached. The equilibrium constant for the reaction
CaCO3(s) ⇌ CaO(s) + CO2(g) is 4 × 10–2 atm at this temperature. Calculate the mass of CaO
present at equilibrium.
21. 20.0 grams of CaCO3(s) were placed in a closed vessel, heated & maintained at 727º C under
equilibrium CaCO3(s) ⇌ CaO(s) + CO2(g) and it is found that 75% of CaCO3 was decomposed.
What is the value of Kp? The volume of the container was 15 litres.
22. Equilibrium constant for the following equilibrium is given at 0ºC.

Na2HPO4. 12H2O (s) ⇌ Na2HPO4. 7H2O (s) + 5H2O(g) KP = 31.25 × 10–13
At equilibrium what will be partial pressure of water vapour :
23. Anhydrous calcium chloride is often used as a desiccant. In the presence of excess of CaCl2,, the
amount of the water taken up is governed by Kp = 6.4 × 1085 for the following reaction at room
temperature, CaCl2(s) + 6H2O(g) ⇌ CaCl2 . 6H2O(s). What is the equilibrium vapour pressure of
water in a closed vessel that contains CaCl2(s) ?
Relationship between Kp and Kc
24. The vapour pressure of water at 27°C is 0.2463 atm. Calculate the values of
Kp and Kc at 27°C for the equilibrium H2O (l) H2O (g).
25. When 36.8g N2O4 (g) is introduced into a 1.0-litre flask at 27°C . The following equilibrium
reaction occurs :
N2O4 (g) ⇌ 2NO2 (g) ; Kp = 0.1642 atm.
(a) Calculate Kc of the equilibrium reaction.
(b) What are the number of moles of N2O4 and NO2 at equilibrium?
(c) What is the total gas pressure in the flask at equilibrium?
(d) What is the percent dissociation of N2O4?
APNI KAKSHA 84
Problems involving degree of dissociation, Average Molecular Mass.
26. The degree of dissociation of N2O4 into NO2 at 1.5 atmosphere and 40°C is 0.25. Calculate its Kp
at 40°C. Also report degree of dissociation at 10 atmospheric pressures at same temperature.
27. At 46°C, Kp for the reaction N2O4(g) ⇌ 2NO2(g) is 0.667 atm. Compute the percent dissociation
of N2O4 at 46° C at a total pressure of 380 Torr .
28. 2 NOBr (g) ⇌ 2 NO (g) + Br2 (g). If nitrosyl bromide (NOBr) is 33.33% dissociated at 25° C & a
total pressure of 0.28 atm. Calculate Kp for the dissociation at this temperature.
29. At some temperature and under a pressure of 4 atm, PCl5 is 10% dissociated . Calculate the
pressure at which PCl5 will be 20% dissociated, temperature remaining same.
30. The system N2O4 ⇌ 2 NO2 maintained in a closed vessel at 60º C & a pressure of 5 atm has an
average (i.e. observed) molecular weight of 69, calculate Kp. At what pressure at the same
temperature would the observed molecular weight be (230/3) ?
31. PCl5 dissociates according to the reaction PCl5 ⇌ PCl3(g) + Cl2(g). At 523 K, Kp = 1.78 atm. Find
the density of the equilibrium mixture at a total pressure of 1 atm.
Effect of Temperature
1
32. Variation of log10 ⁡ K with T
is shown by the following graph in which straight line is at 45∘ ,
hence ΔH ∘ is :
(A) +4.606cal (B) −4.606cal (C) 2cal (D) −2cal
33. Listed in the table are forward and reverse rate constants for the reaction
2NO(g) ⇌ N2(g) + O2(g)
Temperature (K) kf (M–1s–1) kb (M–1s–1)
1400 0.29 1.1 × 10–6
1500 1.3 1.4 × 10–5
Is the reaction endothermic or exothermic?
APNI KAKSHA 85
34. From the following data :
(i) H2(g) + CO2(g) H2O(g) + CO(g) ; K2000K = 4.4
(ii) 2H2O(g) 2H2(g) + O2(g) ; K2000K = 5.31 x 10–10
(iii) 2CO(g) + O2(g) 2CO2(g) ; K1000K = 2.24 x 1022
State whether the reaction (iii) is exothermic or endothermic?
Le-Chatelier’s mix problem
35. Using Le Chatelier's principle, predict the effect of

(i) decreasing the temperature and
(ii) increasing the pressure on each of the following equilibria :
(A) N2(g) + 3H2(g) ⇌ 2NH3(g) + Heat
(B) N2(g) + O2(g) ⇌ 2NO(g) + Heat
(C) H2O(g) + Heat ⇌ H2 (g) + O2 (g)
(D) 2CO (g) + O2 (g) ⇌ 2CO2 (g) + Heat
36. Suggest four ways in which the concentration of hydrazine, N2H4, could be increased in an
equilibrium described by the equation
N2 (g) + 2H2 (g) ⇌ N2H4 (g) H = 95 kJ
37. Ammonia is a weak base that reacts with water according to the equation
NH3 (aq) + H2O (l) ⇌ NH4+ + OH– (aq)
Will any of the following increase the percent of ammonia that is converted to the ammonium
ion in water?
(a) Addition of NaOH. (b) Addition of HCl. (c) Addition of NH4Cl.
38. Consider the reaction, 2Cl2(g) + 2H2O(g) ⇌ 4HCl(g) + O2(g) ; Hº = + 113 kJ
The four gases, Cl2, H2O, HCl and O2, are mixed and the reaction is allowed to come to
equilibrium. Each operation is to be considered separately. Temperature and volume are
constant unless stated otherwise. Report the number of operations in the left column which
lead to increase in the equilibrium value of the quantity in the right column.
(a) Increasing the volume of the container Number of moles of H2O
(b) Adding O2 Number of moles of H2O
(c) Adding O2 Number of moles of HCl
(d) Decreasing the volume of the container Number of moles of Cl2
(e) Decreasing the volume of the container Partial pressure of Cl2
APNI KAKSHA 86
(f) Decreasing the volume of the container KC
(g) Raising the temperature KC
(h) Raising the temperature Concentration of HCl
(i) Adding He Number of moles of HCl
(j) Adding catalyst Number of moles of HCl
39. The decomposition of solid ammonium carbamate, (NH4)(NH2CO2), to gaseous ammonia and
carbon dioxide is an endothermic reaction.
(NH4)(NH2CO2) (s) ⇌ 2NH3 (g) + CO2(g)
(a) When solid (NH4) (NH2CO2) is introduced into an evacuated flask at 25°C, the total pressure
of gas at equilibrium is 0.3 atm. What is the value of Kp at 25°C ?
(b) Given that the decomposition reaction is at equilibrium, how would the following changes
affect the total quantity of NH3 in the flask once equilibrium is re-established ?
(i) Adding CO2 (ii) Adding (NH4) (NH2CO2)
(iii) Removing CO2 (iv) Increasing the total volume
(v) Adding neon (at constant volume) (vi) Increasing the temperature.
40. (a) Water gas, a mixture of H2 and CO, is an important industrial fuel produced by the
reaction of steam with red-hot coke, essentially pure carbon. Write the expression for
the equilibrium constant for the reversible reaction.
C(s) + H2O (g) ⇌ CO (g) + H2 (g) H = 131.30 kJ
(b) Assume that equilibrium has been established and predict how the concentration of
each reactant and product will differ at a new equilibrium if (1) more C is added.
(2) H2O is removed. (3) CO is added. (4) the pressure on the system is increased.
(5) the temperature of the system is increased.
41. (a) Methanol, a liquid fuel that could possibly replace gasoline, can be prepared from water
gas and additional hydrogen at high temperature and pressure in the presence of a
suitable catalyst. Write the expression for the equilibrium constant for the reversible
reaction.
2H2 (g) + CO (g) ⇌ CH3OH (g) H = – 90.2 kJ
(b) Assume that equilibrium has been established and predict how the concentration of
H2, CO and CH3OH will differ at a new equilibrium if (1) more H2 is added.
(2) CO is removed. (3) CH3OH is added. (4) the pressure on the system is increased.
(5) the temperature of the system is increased. (6) more catalyst is added.
APNI KAKSHA 87
Simultaneous Equilibrium
42. For given simultaneous reaction :

X(s) ⇌ A(g) + B(s) + C(g) K P1 = 500 atm
Y(s) ⇌ D(g) + A(g) + E(s) K P2 = 2000 atm
Find total pressure at equilibrium containing both X(s) and Y(s)
43. NH4HS(s) ⇌ NH3(g) + H2S(g) 𝐾𝑐1

NH3(g) ⇌ (½)N2(g) +(3/2) H2(g) 𝐾𝑐2
2 mol NH4HS(s)is taken & 50% of this is dissociated till at equilibrium in 1 litre container. Find
𝐾𝑐22
, if 0.25 moles of N2 are found finally.
𝐾𝑐61
Should be Kc instead of Kp
44. When NO & NO2 are mixed, the following equilibria readily obtained;
2NO2 ⇌ N2O4 Kp = 6.8 atm–1
NO + NO2 ⇌ N2O3 Kp = ?
In an experiment when NO & NO2 are mixed in the ratio of 1 : 2, the total final pressure was
5.05 atm & the partial pressure of N2O4 was 1.7 atm. Calculate
(a) the equilibrium partial pressure of NO.
(b) Kp for NO + NO2 N2O3
APNI KAKSHA 88
EXERCISE # O-II
More than one may be correct
1. For a reaction N2 + 3H2 ⇌ 2NH3, the value of KC does not depends upon :-
(a) Initial concentration of the reactants (b) Pressure
(c) Temperature (d) Catalyst
2. N2O4(g) ⇌ 2NO2(g), Kc = 4. This reversible reaction is studied graphically as shown in figure.

Select the correct statement.
(A) Reaction quotient has maximum value at point A

(B) Reaction proceeds left to right at a point when [N2O4] = [NO2] = 0.1 M
(C) Kc = Q when point F is reached :
(D) Point C represents state of equilibrium
3. 2 mole each of SO3, CO, SO2 and CO2 is taken in a one lit. vessel. If KC for
SO3(g) + CO(g) ⇌ SO2(g) + CO2(g) is 1/9 then
(A) total no. of moles at equilibrium are less than 8
(B) n(SO3) + n(CO2) = 4
(C) [n(SO2)/n(CO)] < 1
(D) n(SO3) + n(SO2) = 2
4. For the reaction PCl5(g) ⇌ PCl3(g) + Cl2(g), the forward reaction at constant temperature is
favoured by
(A) introducing an inert gas at constant volume
(B) introducing chlorine gas at constant volume
(C) introducing an inert gas at constant pressure
(D) introducing PCl5 at constant volume.
5. When NaNO3 is heated in a closed vessel, oxygen is liberated and NaNO2 is left.
At equilibrium
(A) addition of NaNO2 favours reverse reaction
(B) addition of NaNO3 favours forward reaction
(C) increasing temperature favours forward reaction
(D) increasing pressure favours reverse reaction
APNI KAKSHA 89
6. For the gas phase reaction, C2H4 + H2 ⇌ C2H6 (H = –32.7 kcal), carried out in a closed vessel,
the equilibrium moles of C2H4 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) removing some H2 (D) adding some C2H6
7. Decrease in the pressure for the following equilibria : H2O (s) H2O() result in the :
(A) formation of more H2O (s) (B) formation of more H2O()
(C) increase in melting point of H2O(s) (D) decrease in melting point of H2O(s)
8. 2CaSO4(s) ⇌ 2CaO(s) + 2SO2(g) + O2(g), H > 0
Above equilibrium is established by taking some amount of CaSO4(s) in a closed container at

1600 K. Then which of the following may be incorrect option.
(A) moles of CaO(s) will increase with the increase in temperature
(B) If the volume of the container is doubled at equilibrium, then partial pressure of SO2(g) will
change at new equilibrium.
(C) If the volume of the container is halved partial pressure of O2(g) at new equilibrium will
remain same
(D) If two moles of the He gas is added at constant pressure then the moles of CaO(s) will
increase.
9. Following two equilibrium is simultaneously established in a container

PCl5(g) ⇌ PCl3(g) + Cl2(g)
CO(g) + Cl2(g) ⇌ COCl2(g)
If some Ni(s) is introduced in the container forming Ni (CO)4 (g) then at new equilibrium
(A) PCl3 concentration will increase (B) PCl3 concentration will decrease
(C) Cl2 concentration will remain same (D) CO concentration will remain same
10. The equilibrium between, gaseous isomers A, B and C can be represented as

Reaction Equilibrium constant
A (g) ⇌ B (g) : K1 = ?
B (g) ⇌ C (g) : K2 = 0.4
C (g) ⇌ A (g) : K3 = 0.6
If one mole of A is taken in a closed vessel of volume 1 litre, then
APNI KAKSHA 90
(A) [A] + [B] + [C] = 1 M at any time of the reactions
(B) Concentration of C is 1/4.1 M at the attainment equilibrium in all the reactions
1
(C) The value of K is
0.24
(D) Isomer [A] is least stable
11. Consider the equilibrium HgO(s) + 4I– (aq) + H2O () → HgI42– (aq) + 2OH– (aq), which changes
will decrease the equilibrium concentration of HgI42–

(A) Addition of HI (s) (B) Addition of HgO (s)
(C) Addition of H2O (l) (D) Addition of KOH (aq)
12. Phase diagram of CO2 is shown as following

73
Solid Liquid
67
P(atm) 5
1 Gas
195 217 298 304

T(K)
Based on above find the correct statement(s)

(A) 298K is the normal boiling point of liquid CO2
(B) At 1 atm & 190 K CO2 will exist as gas.
(C) CO2(s) will sublime above 195K under normal atmospheric pressure
(D) Melting point & boiling point of CO2 will increase on increasing pressure
Assertion Reason
13. Statement–1 : Total number of moles in a closed system at new equilibrium is less than
the old equilibrium if some amount of a substance is removed from a system
(consider a reaction A(g) ⇌ B(g) ) at equilibrium.
Statement–2 : The number of moles of the substance which is removed, is partially
compensated as the system reached to new equilibrium.
(A) Statement–1 is true, statement–2 is true and statement–2 is correct explanation for
statement–1.
(B) Statement–1 is true, statement–2 is true and statement–2 is NOT the correct explanation
for statement–1.
APNI KAKSHA 91
(C) Statement–1 is false, statement–2 is true.
(D) Statement–1 is true, statement–2 is false.
14. Statement–1 : Ammonia at a pressure of 10 atm and CO2 at a pressure of 20 atm are
introduced into an evacuated chamber. If Kp for the reaction
NH2COONH4 (s) ⇌ 2NH3(g) + CO2 (g) is 2020 atm3, the total pressure after a
long time is less than 30 atm.
Statement–2 : Equilibrium can be attained from both directions.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Comprehension
Paragraph for Question Nos. 15 to 18
In a 7.0 L evacuated chamber, 0.50 mol H2 and 0.50 mol I2 react at 427°C .
H2(g) + I2(g) ⇌ 2HI(g). At the given temperature, KC = 49 for the reaction.
15. What is the value of Kp ?

(A) 7 (B) 49 (C) 24.5 (D) None
16 . What is the total pressure (atm) in the chamber?

(A) 83.14 (B) 831.4 (C) 8.21 (D) None
17. How many moles of the iodine remain unreacted at equilibrium?

(A) 0.388 (B) 0.112 (C) 0.25 (D) 0.125
18. What is the partial pressure (atm) of HI in the equilibrium mixture?

(A) 6.385 (B) 12.77 (C) 40.768 (D) 646.58

Influence of pressure, temperature, concentration and addition of inert gas on a reversible
chemical reaction in equilibrium can be explained by formulating the expression for
equilibrium constant Kc or Kp for the equilibrium. On the other hand Le Chatelier principle can
APNI KAKSHA 92
be theoretically used to explain the effect of P, T or concentration on the physical or chemical
equilibrium both.
19. For the reaction : PCl5 ⇌ PCl3 + Cl2 increase of pressure shows :
(A) An increase in degree of dissociation and a decrease in Kc
(B) A decrease in degree of dissociation and a decrease in Kc
(C) An increase in degree of dissociation but Kc remains constant
(D) A decrease in degree of dissociation but Kc remains constant
20. For the reaction : 2SO2 + O2 ⇌ 2SO3; H = –ve, An increase in temperature shows :
(A) More dissociation of SO3 and a decrease in Kc
(B) Less dissociation of SO3 and an increase in Kc
(C) More dissociation of SO3 and an increase in Kc
(D) Less dissociation of SO3 and an decrease in Kc

The two equilibria, AB(aq) ⇌ A+(aq) + B−(aq) and AB(aq) + B−(aq) ⇌ AB2−(aq) are
simultaneously maintained in a solution with equilibrium constants, K1 and K2 respectively.
21. The ratio of concentration of A+ to AB2− in the solution is :

(A) directly proportional to the concentration of B– (aq.).
(B) inversely proportional to the concentration of B– (aq.).
(C) directly proportional to the square of the concentration of B– (aq.).
(D) inversely proportional to the square of the concentration of B– (aq.).
22. If [A+] and [AB2−] are y and x respectively, under equilibrium produced by adding the substance
AB to the solvents, then K1/K2 is equal to
y y 2 (x + y) y 2 (x + y) y
(A) (y – x) 2 (B) (C) (D) (x – y)
x x x x
Match the column
23. Column I Column II
(A) KP < KC (P) N2 + 3H2 ⇌ 2NH3
(B) Introduction of inert gas at constant pressure (Q) PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
will decrease the concentration of reactants
(C) K°P is dimensionless (R) 2NO2 (g) ⇌ N2O4 (g)
APNI KAKSHA 93
(D) increase in temperature will shift equilibrium
to forward direction (S) NH3 (g) + HI (g) ⇌ NH4I (s)
24. Column-I Column-II
(Reactions) (Favourable conditions)
(A) Oxidation of nitrogen (P) Addition of inert gas at
constant pressure
N2(g) + O2(g) + 180.5 kJ⇌2NO(g)
(B) Dissociation of N2O4(g) (Q) Decrease in pressure
N2O4(g) + 57.2 kJ ⇌ 2NO2(g)
(C) Oxidation of NH3(g) (R) Decrease in temperature
4NH3(g) + 5O2(g) ⇌ 4NO(g) + 6H2O(g)
+ 905.6 kJ
(D) Formation of NO2(g) (S) Increase in temperature
NO(g) + O3(g) ......NO2(g) + O2(g) + 200 kJ
Matching list type

25. Column-I Column-II
(Reaction) (If a is negligible w.r.t. 1, V = 1 litre)
(P) 2X(g) ⇌ Y(g) + Z(g) (1) =2× Kc
(Q) X(g) ⇌ Y(g) + Z(g) (2) =3× Kc
(R) 3X(g) ⇌ Y(g) + Z(g) (3)  = (2Kc)1/3
(S) 2X(g) ⇌ Y(g) + 2Z(g) (4) = Kc
Code:
P Q R S
(A) 4 1 3 2
(B) 2 4 1 3
(C) 1 4 2 3
(D) 2 3 1 4
APNI KAKSHA 94
EXERCISE # S-II
1. A mixture of hydrogen & iodine in the mole ratio 1.5 : 1 is maintained at 450º C. After the
attainment of equilibrium H2(g) + I2(g) ⇌ 2 HI(g), it is found on analysis that the mole ratio of I2
to HI is 1 : 18. Calculate the equilibrium constant and the number of moles of each species
present under equilibrium, if initially, 127 grams of iodine were taken.
2. Solid Ammonium carbamate dissociates as: NH2 COONH4 (s) ⇌ 2NH3(g) + CO2(g).
In a closed vessel solid ammonium carbamate is in equilibrium with its dissociation products.
At equilibrium, ammonia is added such that the partial pressure of NH3 at new equilibrium now
equals the original total pressure. Calculate the ratio of total pressure at new equilibrium to
that of original total pressure.
3. For the reaction A(g) + 2B(g) ⇌ C(g) + D(g) ; Kc = 1012 .

If the initial moles of A,B,C and D are 0.5, 1, 0.5 and 3.5 moles respectively in a one litter vessel.
What is the equilibrium concentration of B?
4. Consider the equilibrium

Ni(s) + 4CO(g) ⇌ Ni(CO)4(g) ; Kp = 0.125 atm–3.
If equal number of moles of CO and Ni(CO)4 (ideal gases) are mixed in a small container fitted
with a piston, find the maximum total pressure (in atm) to which this mixture must be brought
in order to just precipitate out metallic Ni ?
5. For the equilibrium CuSO4.5H2O(s) ⇌ CuSO4.3H2O(s) + 2H2O(g)

Kp = 2.25 × 10–4 atm2 and vapour pressure of water is 22.8 Torr at 298 K.
CuSO4.5H2O(s) is efflorescent (i.e., loses water) when relative humidity is :
6. Equilibrium constants are given (in atm) for the following reactions at 0° C:
SrCl2 × 6H2O(s) ⇌ SrCl2 × 2H2O (s) + 4H2O(g) Kp = 5 × 10–12
Na2HPO4 . 12 H2O(s) ⇌ Na2HPO4 . 7 H2O (s) + 5H2O(g) Kp = 2.43 × 10–13
Na2SO4 . 10 H2O(s) ⇌ Na2SO4 (s) + 10 H2O (g) Kp = 1.024 × 10–27
The vapor pressure of water at 0°C is 4.56 torr.
Out of SrCl2 × 2H2O (s), Na2HPO4 . 7 H2O (s) and Na2SO4 (s),
Which is the most effective drying agent at 0°C?
APNI KAKSHA 95
7. Two solids X and Y dissociate into gaseous products at a certain temperature as follows:
X(s) ⇌ A(g) + C(g), and Y(s) ⇌ B(g) + C(g). At a given temperature, pressure over excess solid X
is 40 mm and total pressure over solid Y is 60 mm. When they are preset in separate
containers. Calculate
(a) the values of Kp for two reactions (in mm)
(b) the ratio of moles of A and B in the vapour state over a mixture of X and Y.
(c) the total pressure of gases over a mixture of X and Y.
8. When 1 mole of A(g) is introduced in a closed rigid 1 litre vessel maintained at constant
temperature the following equilibria are established.
A (g) ⇌ B(g) + C(g) : K C1
C(g) ⇌ D(g) + B(g) : K C2
K C2  Ceq 1
The pressure at equilibrium is twice the initial pressure. Calculate the value of if =
K C1  Beq 5
9. At certain temperature (T) for the gas phase reaction
2H2O(g) + 2Cl2 (g) ⇌ 4HCl(g) + O2(g) Kp = 12 × 108 atm
If Cl2, HCl & O2 are mixed in such a manner that the partial pressure of each is 2 atm and the
mixture is brough into contact with excess of liquid water. What would be approximate partial
pressure of Cl2 when equilibrium is attained at temperature (T)?
[Given : Vapour pressure of water is 380 mm Hg at temperature (T)]
10. The value of Kp for the reaction at 270C

Br2(l) + Cl2(g) ⇌ 2BrCl(g)
is ‘1 atm’. At equilibrium in a closed container partial pressure of BrCl gas is 0.1 atm and at this
temperature the vapour pressure of Br2(l) is also 0.1 atm. Then what will be minimum moles of
Br2(l) to be added to 1 mole of Cl2 , initially, to get above equilibrium situation ?
APNI KAKSHA 96
EXERCISE # (JEE-MAIN)
1. One of the following equilibrium is not affected by change in volume of the flask
[AIEEE-2002]
(1) PCl5(g) ⇌ PCl3(g) + Cl2(g) (2) N2(g) + 3H2(g) ⇌ 2NH3(g)
(3) N2(g) + O2 ⇌ 2NO(g) (4) SO2Cl2(g) ⇌ SO2(g) + Cl2(g)
1 Kp
2. Reaction CO(g) + O2(g) ⇌ CO2(g). The value of is – [AIEEE-2002]
2 Kc
1 1
(1) (B) RT (3) (4) RT
RT RT
3. Consider the reaction equilibrium [AIEEE–2003]

2SO2(g) + O2(g) ⇌ 2 SO3(g) ; H° = – 198 kJ
On the basis of Le–Chatelier's principle, the condition favourable for the forward reaction is -
(1) Lowering the temperature and increasing the pressure
(2) Any value of temperature as well as pressure
(3) Lowering of temperature as well as pressure
(4) Increasing temperature as well as pressure
4. For the reaction equilibrium,

N2O4 (g) ⇌ 2NO2(g) the concentration of N2O4 and NO2 at equilibrium are 4.8 × 10–2 and
1.2 × 10–2 mol L–1 respectively. The value of KC for the reaction is– [AIEEE-2003]
(1) 3 × 10–3 mol L–1 (2) 3 × 103 mol L–1
(3) 3.3 × 102 mol L–1 (4) 3 × 10–1 mol L–1
5. The equilibrium constant for the reaction

N2(g) + O2(g) ⇌ 2NO(g) at temperature T is 4 × 10– 4. The value of KC for the reaction
1 1 1 1
NO(g) ⇌ 2 N2(g) + O2(g) ⇌ 2 N2(g) + O2(g) [AIEEE-2003]
2 2
(1) 2.5 × 102 (2) 50 (3) 4 × 10– 4 (4) 0.02
6. What is the equilibrium expression for the reaction P4(s) + 5O2(g) ⇌ P4O10(s)?[AIEEE-2004]
(1) KC = [P4O10] / [P4] [O2]5 (2) KC = [P4O10] / 5 [P4] [O2]
(3) KC = [O2]5 (4) KC = 1 / [O2]5
APNI KAKSHA 97
Kp
7. For the reaction CO(g) + Cl2(g) ⇌ COCl2(g) the is equal to – [AIEEE-2004]
KC
1
(1) (2) RT (3) RT (4) 1.0
RT
8. For the reaction 2NO2(g) ⇌ 2NO(g) + O2(g), (Kc = 1.8 × 10– 6 at 184° C) (R = 0.831 kJ(mol.K))
When Kp and kc are compared at 184°C it is found that [AIEEE-2005]
(1) KP is less than Kc
(2) Kp is greater than Kc
(3) Whether Kp is greater than, less than or equal to Kc depends upon the total gas pressure
(4) Kp = Kc
9. The exothermic formation of ClF3 is represented by the equation [AIEEE-2005]

Cl2(g) + 3F2(g) ⇌ 2ClF3(g) ; Hr = – 329 kJ
Which of the following will increase the quantity of ClF3 in an equilibrium mixture of Cl2, F2 and
ClF3?
(1) Removing Cl2 (2) Increasing the temperature
(3) Adding F2 (4) Increasing the volume of the container
10. A schematic plot of ln Keq verus inverse of temperature for a reaction is shown below.
The reaction must be [AIEEE-2005]
(1) endothermic
(2) exothermic
(3) highly spontaneous at ordinary temperature
(4) one with negligible enthalpy change
11. Phosphorus pentachloride dissociates as follows, in a closed reaction vessel,
PCl5(g) ⇌ PCl3(g) + Cl2(g) [AIEEE-2006]
If total pressure at equilibrium of the reaction mixture is P and degree of dissociation of PCl5 is
x, the partial pressure of PCl3 will be–
 2x   x   x   x 
(1)  P (2)  P (3)  P (4)  P
 1− x   x −1   1− x   x +1 
APNI KAKSHA 98
1
12. The equilibrium constant for the reaction SO3(g) ⇌ SO2(g) + O2(g) is Kc = 4.9 × 10–2.
2
The value of Kc for the reaction [AIEEE-2006]
2SO2(g) + O2(g) ⇌ 2SO3(g) will be
(1) 2.40 × 10–3 (2) 9.8 × 10– 2 (3) 4.9 × 10– 2 (4) 416
13. The equilibrium constants Kp1 and Kp2 for the reaction X ⇌ 2Y and Z ⇌ P + Q, respectively are in
the ratio of 1 : 9. If the degree of dissociation of X and Z be equal then the ratio of total pressure
at these equilibria is [AIEEE-2008]
(1) 1 : 36 (2) 1 : 1 (3) 1 : 3 (4) 1 : 9
14. A vessel at 1000 K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted into
CO on the addition of graphite. If the total pressure at equilibrium is 0.8 atm, the value of K is:
[AIEEE-2011]
(1) 0.3 atm (2) 0.18 atm (3) 1.8 atm (4) 3 atm
15. The equilibrium constant (KC) for the reaction N2(g) + O2(g) ⎯→ 2NO(g) at temperature T is
4×10–4. The value of KC for the reaction. NO(g) ⎯→ ½N2(g) + ½O2(g) at the same temperature
is : [AIEEE-2012]
(1) 50.0 (2) 0.02 (3) 2.5 × 102 (4) 4 × 10–4
16. The value of Kp for the equilibrium reaction N2O4(g) ⇌ 2NO2(g) is 2. The percentage
dissociation of N2O4(g) at a pressure of 0.5 atm is [JEE-MAINS(online)-12]
(1) 71 (2) 50 (3) 88 (4) 25
17. 8 mol of AB3(g) are introduced into a 1.0 dm3 vessel. If it dissociates as 2AB3(g) ⇌ A2(g) +
3B2(g) At equilibrium, 2mol of A2 are found to be present. The equilibrium constant of this
reaction is :- [JEE-MAINS(online)-12]
(1) 36 (2) 3 (3) 27 (4) 2
18. One mole of O2(g) and two moles of SO2(g) were heated in a closed vessel of one litre capacity
at 1098 K. At equilibrium 1.6 moles of SO3(g) were found. The equilibrium constant KC of the
reaction would be [JEE-MAINS(online)-12]
(1) 60 (2) 80 (3) 30 (4) 40
APNI KAKSHA 99
19. K1, K2 and K3 are the equilibrium constants of the following reactions (I), (II) and (III),
respectively [JEE-MAINS(online)-12]
(I) N2 + 2O2 ⇌ 2NO2
(II) 2NO2 ⇌ N2 + 2O2
1
(III) NO2 ⇌ 2 N2 + O2
The correct relation from the following is :

1 1 1 1 1
(1) K1 = K 2 = K3 (2) K1 = = (3) K1 = = K3 (4) K1 = =
( K3 )
2
K 2 K3 K2 K2
20. In reaction A + 2B ⇌ 2C + D, initial concentration of B was 1.5 times of |A|, but at equilibrium
the concentrations of A and B became equal. The equilibrium constant for the reaction is :
[JEE-MAINS(online)-13]
(1) 4 (2) 6 (3) 12 (4) 8
21. N2(g) + 3H2(g) ⇌ 2NH3(g), K1 (1) [JEE-MAINS(online)-13]

N2(g) + O2(g) ⇌ 2NO(g), K2 (2)
1
H2(g) + O2(g) ⇌ H2O(g), K3 (3)
2
The equation for the equilibrium constant of the reaction
5
2 NH3(g) + O2(g) ⇌ 2NO (g) + 3H2O(g), (K4)
2
in terms of K1, K2 and K3 is :
K 1K 32 K 2 K 33 K 1K 2
(1) (2) (C) (D) K1 K2 K3
K2 K1 K3
1
22. For the reaction SO2(g) + O2(g) ⇌ SO3(g) , if KP = Kc (RT)x where the symbols have usual
2
meaning then the value of x is : (assuming ideality) [JEE-MAINS-14]
1 1
(1) (2) 1 (3) –1 (4) –
2 2
23. For the decomposition of the compound, represented as [JEE-MAINS(online)-14]

NH2COONH4(s) ⇌ 2NH3(g) + CO2(g)
the KP=2.9 × l0–5 atm3.
If the reaction is started with 1 mol of the compound, the total pressure at equilibrium would
be
(1) 38.8 × 10–2 atm (2) 1.94 × 10–2 atm (3) 5.82 × 10–2 atm (4) 7.66 × 10–2 atm
APNI KAKSHA 100

24. The equilibrium constants at 298 K for a reaction A + B C + D is 100. If the initial
concentration of all the four species were 1 M each, then equilibrium concentration of D
(in mol L–1) will be : [JEE-MAINS-16]
(1) 1.182 (2) 0.182 (3) 0.818 (4) 1.818
25. Which of the following lines correctly show the temperature dependence of equilibrium
constant, K, for an exothermic reaction ? [JEE-MAINS-18]
(1) A and D (2) A and B (3) B and C (4) C and D
26. Consider the following reversible chemical reactions : [JEE-MAINS(Jan)-19]

A2(g) + B2(g) 2AB(g) .....(1)
6AB(g) 3A2(g) + 3B2(g) .....(2)

1
(1) K1K2 = 3 (2) K2 = K1–3 (3) K2 = K13 (4) K1K2 =
2
27. The value of Kp/KC for the following reactions at 300 K are, respectively :
(At 300 K, RT = 24.62 dm3 atm mol–1) [JEE-MAINS(Jan)-19]
N2(g) + O2(g) ⇌ 2NO(g)
N2O4(g) ⇌ 2NO2(g)
N2(g) + 3H2(g) ⇌2NH3(g)
(1) 24.62 dm3 atm mol–1
606.0 dm6 atm2 mol–2
1.65 × 10–3 dm–6 atm–2 mol–2
(2) 1, 4.1 × 10–2 dm–3 atm–1 mol,
606.0 dm6 atm2 mol–2
(3) 1, 24.62 dm3 atm mol–1,
606.0 dm6 atm2 mol–2,
(4) 1, 24.62 dm3 atm mol–1,
1.65 × 10–3 dm–6 atm–2 mol2.
APNI KAKSHA 101

28. 5.1g NH4SH is introduced in 3.0 L evacuated flask at 327°C. 30% of the solid NH4SH
decomposed to NH3 and H2S as gases. The Kp of the reaction at 327°C is (R = 0.082 L atm
mol–1K–1, Molar mass of S = 32 g mol/–1, molar mass of N = 14 g mol–1)
[JEE-MAINS(Jan)-19]
(1) 0.242 × 10–4 atm2 (2) 0.242 atm2 (3) 1 × 10–4 atm2 (4) 4.9 × 10–3 atm2
29. Consider the reaction, [JEE-MAINS(Jan)-19]
N2 (g) + 3 H2 ( g) ⇇ 2NH3 (g)

The equilibrium constant of the above reaction is KP. If pure ammonia is left to dissociate, the
partial pressure of ammonia at equilibrium is given by (Assume that PNH3  Ptotal at
equilibrium)
3 1 1 1 3 1
3 2 K P2 P 2 K P2 P 2 K P2 P 2 3 2 K P2 P 2
(1) (2) (3) (4)
4 16 4 16
30. Two solids dissociate as follows [JEE-MAINS(Jan)-19]
The total pressure when both the solids dissociate simultaneously is :-
(1) x2 + y2 (2) 2 ( )
x + y atm (3) (x + y) atm (4) x + y atm
31. In a chemical reaction, A + 2B 2C + D, the initial concentration of B was 1.5 times of the
concentration of A, but the equilibrium concentrations of A and B were found to be equal. The
equilibrium constant(K) for the aforesaid chemical reaction is : [JEE-MAINS(Jan)-19]
1
(1) (2) 4 (3) 16 (4) 1
4
32. For the following reactions, equilibrium constants are given : [JEE-MAINS(Apr.)-19]
S(s) + O2(g) ⇌ SO2(g); K1 = 1052
2S(s) + 3O2(g) ⇌ 2SO3(g); K2 = 10129
The equilibrium constant for the reaction,
2SO2(g) + O2(g) ⇌ 2SO3(g) is :
(1) 1025 (2) 10154 (3) 10181 (4) 1077
APNI KAKSHA 102

33. For the reaction, 2SO2(g) + O2(g) ⇌ 2SO3(g), H = –57.2 kJ mol–1 and KC = 1.7×1016.Which of the
following statement is INCORRECT ? [JEE-MAINS(Apr.)-19]
(1) The equilibrium constant is large suggestive of reaction going to completion and so no
catalyst is required.
(2) The addition of inert gas at constant volume will not affect the equilibrium constant.
(3) The equilibrium constant decreases as the temperature increases.
(4) The equilibrium will shift in forward direction as the pressure increases.
34. In which one of the following equilibria, Kp ≠ Kc ? [JEE-MAINS(Apr.)-19]

(1) 2HI(g) ⇌H2(g) + I2(g) (2) NO2(g) + SO2(g) ⇌NO(g) + SO3(g)
(3) 2C(s) + O2(g) ⇌2CO(g) (4) 2NO(g) ⇌N2(g) + O2(g)
35. In the figure shown below reactant A (represented by square) is in equilibrium with product B
represented by circle). The equilibrium constant is : [Jee Main, 2020]
(1) 4 (2) 8 (3) 1 (4) 2
36. For the reaction [Jee Main, 2020]


Fe2N(s) + H2(g) ⇇ 2Fe(s) + NH3(g)
2
(1) Kc = Kp(RT) (2) Kc = Kp(RT)3/2 (3) Kc = Kp(RT)1/2 (4) Kc = Kp(RT)–1/2
37. Consider the following reaction: [Jee Main, 2020]
N2O4(g) ⇇ 2NO2(g) ; H° = +58K

For each of the following cases (a, b), the direction in which the equilibrium shifts is:
(a) Temperature is decreased
(b) Pressure is increased by adding N2 at constant T.
(1) (a) towards product, (b) no change
(2) (a) towards reactant, (b) no change
(3) (a) towards product, (b) towards reactant
(4) (a) towards reactant, (b) towards product
APNI KAKSHA 103

38. For the reaction; A + B 2C
the value of equilibrium constant is 100 at 298 K. If the initial concentration of all the three
species is 1 M each, then the equilibrium concentration of C is x × 10–1 M. The value of x
is__________. (Nearest integer) [JEE Main, July 2021]
39. At 1990 K and 1 atm pressure, there are equal number of Cl2 molecules and Cl atoms in the
reaction mixture. The value KP for the reaction Cl2 2Cl(g) under the above conditions is x
× 10–1. The value of x is (Rounded of to the nearest integer) [JEE Main, Feb 2021]
40. When 5.1 g of solid NH4HS is introduced into a two litre evacuated flask at 27°C, 20% of the
solid decomposes into gaseous ammonia and hydrogen sulphide. The Kp for the reaction at
27°C is x × 10–2. The value of x is _______. (Integer answer)
[Given R = 0.082 L atm K–1 mol–1] [JEE Main, August 2021]
41. At 298 K, the equilibrium constant is 2 × 1015 for the reaction:

Cu(s) + 2Ag + (aq) ⇇ Cu2+ (aq) + 2Ag(s)
The equilibrium constant for the reaction

1 1
Cu2+ (aq) + Ag(s) ⇇ Cu(s) + Ag + (aq) is x × 10–8. The value of x is ________.
2 2
(Nearest Integer) [JEE Main, July 2022]
42. PCl5 dissociates as

PCl5 (g)  PCl3 (g) + Cl2 (g)
5 moles of PCl5 are placed in a 200 litre vessel which contains 2 moles of N2 and is maintained
at 600 K. The equilibrium pressure is 2.46 atm. The equilibrium constant Kp for the
dissociation of PCl5 is_____ × 10–3. (nearest integer)
(Given: R = 0.082 L atm K–1 mol–1 : Assume ideal gas behaviour) [JEE Main, June 2022]
APNI KAKSHA 104

EXERCISE # (JEE-ADVANCED)
1. The degree of dissociation is 0.4 at 400K & 1.0 atm for the gasoeus reaction
PCl5 ⇌ PCl3 + Cl2(g). Assuming ideal behaviour of all gases. Calculate the density of equilibrium
mixture at 400K & 1.0 atm pressure. [JEE 1999]
2. For the reversible reaction : [JEE 2000]

N2(g) + 3H2(g) ⇌ 2NH3(g) at 500°C. The value of Kp is 1.44 × 10–5, when partial pressure is
measured in atmospheres. The corresponding value of Kc with concentration in mol L–1 is :
(A) 1.44 × 10–5 /(0.082 × 500)2 (B) 1.44 × 10–5 /(8.314 × 773)2
(C) 1.44 × 10–5 /(0.082 × 500)2 (D) 1.44 × 10–5 /(0.082 × 773)–2
3. When two reactants A and B are mixed to give products C and D, the reaction quotient Q, at the
initial stages of the reaction : [JEE 2000]
(A) is zero (B) decrease with time
(C) independent of time (D) increases with time
4. When 3.06g of solid NH4HS is introduced into a two litre evacuated flask at 27°C, 30% of the
solid decomposes into gaseous ammonia and hydrogen sulphide. [JEE 2000]
(i) Calculate KC & KP for the reaction at 27°C.
(ii) What would happen to the equilibrium when more solid NH4HS is introduced into the flask?
5. At constant temperature, the equilibrium constant (KP) for the decomposition reaction.
N2O4⇌2NO2 is expressed by KP = 4x2P/(1 – x2) where P is pressure, x is extent of
decomposition.
Which of the following statement is true ? [JEE 2001]
(A) KP increases with increase of P (B) KP increases with increase of x
(C) KP increases with decrease of x (D) KP remains constant with change in P or x
6. Consider the following equilibrium in a closed container : N2O4(g) 2NO2(g).

At a fixed temperature, the volume of the reaction container is halved. For this change, which of
the following statements holds true regarding the equilibrium constant (KP) and degree of
dissociation () : [JEE 2002]
(A) Neither KP nor  changes (B) Both KP and  change
(C) KP changes, but  does not change (D) KP does not change, but  changes
APNI KAKSHA 105

7. If Ag+ + NH3 ⇌ [Ag(NH3)]+ ; K1 = 1.6 × 103 and [JEE 2006]
[Ag(NH3)]+ + NH3 ⇌ [Ag(NH3)2]+ ; K2 = 6.8 × 103.
The formation constant of [Ag(NH3)2]+ is :
(A) 6.08 × 10–6 (B) 6.8 × 10–6 (C) 1.6 × 103 (D) 1.088 × 107
8. The thermal dissociation equilibrium of CaCO3(s) is studied under different conditions.

CaCO3(s) ⇌ CaO(s) + CO2(g) [JEE 2013]
For this equilibrium, the correct statement(s) is(are)
(A) H is dependent on T
(B) K is independent of the initial amount of CaCO3
(C) K is dependent on the pressure of CO2 at a given T
(D) H is independent of the catalyst, if any
1
9. For the reaction SO2( s) + 2 O2 ( g) ⇌ SO3( g), if K p = K C (RT)x where the symbols have usual
meaning then the value of 𝑥 is: (assuming ideality) ? [JEE Adv. 2014]
(A) 1/2 (B) 1 (C) −1 (D) −1/2
10. For the following reaction, the equilibrium constant KC at 298 K is 1.6 × 1017.
Fe2+ (aq) +S2–(aq) ⇇ FeS (s) [JEE Advanced-2019]

When equal volumes of 0.06 M Fe2+ (aq) and 0.2 M S2– (aq) solutions are mixed, the equilibrium
concentration of Fe2+(aq) is found to be Y × 10–17 M. The value of Y is________
APNI KAKSHA 106

ANSWER KEY
EXERCISE O-I
1. (B) 2. (C) 3. (D) 4. (A) 5. (A) 6. (C) 7. (C)
8. (B) 9. (C) 10. (C) 11. (C) 12. (D) 13. (B) 14. (B)
15. (A) 16. (B) 17. (C) 18. (B) 19. (A) 20. (C) 21. (B)
22. (B) 23. (D) 24. (C) 25. (B) 26. (C) 27. (B) 28. (B)
29. (C) 30. (A) 31. (D) 32. (A) 33. (C) 34. (A) 35. (D)
36. (C) 37. (A) 38. (B) 39. (C) 40. (A) 41. (B) 42. (A)
43. (C) 44. (C) 45. (B) 46. (B) 47. (C) 48. (C) 49. (B)
50. (C) 51. (D) 52. (C) 53. (C) 54. (B) 55. (D) 56. (B)
57. (A) 58. (A) 59. (C) 60. (A) 61. (B) 62. (D) 63. (C)
64. (B) 65. (D) 66. (D) 67. (C) 68. (A) 69. (A) 70. (B)
71. (D) 72. (D) 73. (A) 74. (B) 75. (D) 76. (B) 77. (C)
78. (B) 79. (A)
EXERCISE S-I
1. (250) 2. (6 × 10–22) 3. 2 × 109
4. (a) backward, (b) forward, (c) forward, (d) forward
5. The reaction is not an equilibrium because Qc > Kc. The reaction will proceed from right to left
to reach equilibrium
6. Forward reaction.
7. (a) very small extent (b) almost complete
8. (0.9) 9. 5.9 × 10–3 M 10. No, 64 × 10–32
11. (i) 2; (ii) 1.2 mol/L 12. 2.4 mole
13. [NO] = 2M, [N2] = [O2] = 0.5M 14. [PCl3] = [Cl2] = 0.027 M, [PCl5] = 0.073
15. KC = 100 16. [A] = 0.34 M, [B] = 1.16 M, [C] = 1.16 M
17. 0.379 atm 18. PCS2 = 1.8 atm, PS2 = 0.2 atm
19. PCIF = PF2 = 0.1 atm, PClF3 = 05 atm 20. 22.4 g
21. 0.821 atm 22. 5 × 10–3 atm
23. P = 5 × 10–15 atm 24. Kp = 0.2463
25. (a) 6.667 × 10–3 mol L–1; (b) n (N2O4)=0.374 mol; n (NO2)=0.052 mol ; (c) 10.49 atm (d)
6.44 %
26. KP = 0.4, a ~ 0.1 27. 50 % 28. Kp = 0.01 atm
29. 0.97 atm 30. Kp= 2.5 atm, P = 15 atm
31. 2.7 g/lit 32. (B)
APNI KAKSHA 107
33. kr increase more than kf, this means that Ea (reverse) is greater than Ea (forward). Hence
exothermic reaction.
34. Exothermic
35. (i) When decreasing temperature
(a) Forward (b) Forward (c) Backward (d) Forward
(ii) Increasing the pressure
(a) Forward (b) No change (c) Backward (d) Forward
36. Decreasing volume of container
Increasing temperature
Addition of N2
Addition of H2
37. (2)
38. (a) decrease (b) increase (c) decrease (d) increase (e) increase (f)no change
(g) increase (h) increase (i) no change (j) no change
39. (a) 4 × 10–3
(b) (i) decrease
(ii) no change
(iii) increase
(iv) increase
(v) no change
(vi) increase
40. (a) K = [CO][H2]/[H2O] ;
(b) in each of the following cases the mass of carbon will change, but its concentration
(activity) will not change.
1. [H2O] no change, [CO] no change, [H2] no change ;
2. [H2O] decrease, [CO] decrease, [H2] decrease ;
3. [H2O] increase, [CO] increase, [H2] decrease;
4. [H2O] increase, [CO] increase, [H2] increase ;
5. [H2O] decrease , [CO] increase , [H2] increase
41. (a) K = [CH3OH]/[H2]2[CO] ,
(b)
1. [H2] increase, [CO] decrease, [CH3OH] increase ;
2. [H2] increase, [CO] decrease, [CH3OH] decrease ;
3. [H2] increase, [CO] increase, [CH3OH] increase ;
APNI KAKSHA 108

4. [H2] increase, [CO] increase,[CH3OH] increase ;
5. [H2] increase, [CO] increase, [CH3OH] decrease ;
6. no change
42. 100 43. (27) 44. (a) 1.05 atm, (b) 3.43 atm–1
APNI KAKSHA 109

EXERCISE O-II
1. (ABD) 2. (BC) 3. (BCD) 4. (C, D) 5. (C, D)
6. (A, B, C, D) 7. (A, C) 8. (ACD) 9. (B) 10. (A, B, C, D)
11. (C, D) 12. (C, D) 13. (B) 14. (D) 15. (B)
16. (C) 17. (B) 18. (A) 19. (D) 20. (A)
21. (D) 22. (A) 23. (A)-P,R,S; (B)-P,Q,R,S; (C)-P,Q,R,S; (D)-Q;
24. (A)-S; (B)-P,Q,S; (C)-P,Q,R; (D)-R 25. (C)
EXERCISE S-II
1. Kc=54, nHI=0.9 mol, nI2= 0.05 mol, nH2 = 0.3 mol 2. 31/27 3. 2 × 10–4
4. (4) 5. Less than 50 % 6. SrCl2 × 2H2O
7. (a) 400mm2, 900mm2 (b) 4: 9, (c) 72.15 mm Hg
15
8. 4 9. 3.6 × 10–3 atm 10.
6
JEE MAIN
1. (3) 2. (3) 3. (1) 4. (1) 5. (2) 6. (4) 7. (1)
8. (2) 9. (3) 10. (2) 11. (4) 12. (4) 13. (1) 14. (3)
15. (1) 16. (1) 17. (3) 18. (2) 19. (4) 20. (1) 21. (2)
22. (4) 23. (3) 24. (4) 25. (2) 26. (2) 27. (4) 28. (2)
29. (4) 30. (2) 31. (2) 32. (1) 33. (1) 34. (3) 35. (4)
36. (3) 37. (2) 38. (25) 39. (5) 40. (6) 41. (2) 42. (1107)
JEE ADVANCED
1. 4.54 g dm–3 2. (D) 3. (D)
4. (i) Kc= 8.1 × 10–5 mol2 L2 ; Kp = 4.91 × 10–2 atm2 (ii) No effect;
5. (D)
6. (D)
7. (D)
8. (A, B, D)
9. (D)
10. 8.92 or 8.93
APNI KAKSHA 110

SOLUTION
EXERCISE O-I
3. At equilibrium conc. Becomes constant.
4. rf = rb
5. NH3, ND3, NH2D, NHD2, N2, H2, H-D, D2
Kf
6. Keq =
Kb
7. Keq = [B]
[A]
[B]e Kf
KC = =  [A]e = Kf Kb–1 [B]e
[A]e K b
ng
 mol 
13. KC =  
 L 
1
 mol 
=  = mol L
–1
 L 
14. KP = (a/m)ng
1
15. K2 =
K 12
1
16. K2 =
1
(K1 )
2
17. K 3 = K1 × K 2
(iii) = (i) + (ii)
19. S + S2– ⎯→ S22– K1 – 12
2S + S2– ⎯→ S32– K2 = 132
S + S22– ⎯→ S32– K3
(iii) = (ii) – (i)
K2
K3 =
K1
20. KP = KC(RT)ng
KP
21. log + log RT = 0
KC
APNI KAKSHA 111

KP
= (RT)–1  ng = – 1
KC
KP
22. = (RT)ng
KC
23. KP = KC(RT)1
RT = 1 T= 1 K
R
2
 48 
 
 80  0.6  0.6
28. KC = 2 = = 30
 12.8  9.6 0.2  0.2  0.3
  
 64  32
29. PCl5 (g) ⇇ PCl3(g) + Cl2(g)
neq 0.1 0.2 0.2

0.2 0.2

KC = 10 10 = 0.04
0.1
10
31. A(g) + 2B(g) ⇇ 2C(g) + D(g)
Ci 2a 3a 0 0
Ceq 2a-x 3a-2x 2x x
2a – x = x
x=a
34. 3A (g) + B(g) ⇇ 2C (g)

neq 2 2 2
–2
22 1
9= 3  
2 2  V 
V2 = 9 × 22 V=6L
36. A(g) + 2B(g) ⇇ C(g)

ni a 4 0
neq a-1 2 1
APNI KAKSHA 112

1
0.25 = 5
a −1  2 
2
 
5 5
0.25 = 1
 25
(a − 1)  4
a = 26
37. H2(g) + I2(g) ⇇ 2HI(g)

Ci a a 0
Ceq a–x a–x 2x
(2 x) 2
Kf = Kb Kc = 1 =1
(a − x)(a − x)
2x = a – x
a
x=
3
38. C2H5OH (l) + CH3COOH(l) ⇇ CH3COOC2H5(l) + H2O(l)

ni a a 0 0
2a 2a a a
neq
3 3 3 3
aa
·
1
KC = 3 3 =
2a 2a 4
·
3 3
41. 2SO2(g) + O2(g) ⇇ 2SO3(g)

n SO2 = n SO3  PSO2 = PSO3
2
PSO
4=
3
2
PSO 2
 PO2
PO2 = 1
4
P
44. PNH3 = PH2S =
2
P P P2
KP = . =
2 2 4
45. C(s) + CO2(g) ⇇ 2CO(g)

Pi P 0
APNI KAKSHA 113

P
Peq P
2
PCO 2 = 4 atm PCO = 8 atm
(8) 2
KP = = 16
4
46. NH4HS(s) ⇇ NH3(g) + H2S(g)

0.6atm 0.6atm
KP = 0.6×0.6
= 0.36 atm2
51. For reaction, N2(g) + 3H2(g) ⇇ 2NH3(g)

2
Kc =  
1
4
1
Kp = (R × 800)–2
16
54. 2SO3(g) ⇇ 2SO2(g) + O2(g)

ni 1 0 0
neq 1–  
2
1
 1 
 .
2
KP = 2 . 
(1 − ) 2  1 +  
 2
3  2
2
= .P
(1 − )2 (2 + )
Kp = 3 .P
(1 − )2 (2 + )
55. 2HI(g) ⇇ H2 (g) + I2 (g)

neq 1–  
2 2
 . 0
KP = 2 2 . P 
 
(1 − )2  1 
KP = 2
4(1 − ) 2
2
56. KP = .P
1 − 2
APNI KAKSHA 114

2 1
  << 1
1−  2
P
 1
P
46
58. 30 =
1+ 
46
= – 1 = 0.533
30
2
59. KP = .P
1 − 2
2
9= .7
1 − 2
7 2 = 9 – 9 2
3
16 2 = 9 = = 0.75
4
70 70
Mmix = = = 40
1 + 0.75 1.75
208.5
60. Mmix = = 139
1.5
PM mix 2 139
dmix = =
RT 0.0821 800
= 4.23 g/L
62. A(s) ⇌ 2C(s) + B(g) at t = 0, [ A] = 10M from graph, [A]eq. = 10(1 − 𝛼) = 8, [C] = 10(2𝛼) =
[C]2 [ B]1 4×4×2
4, [𝐵] = 10𝛼 = 2k c = = = 4( mol/L)2
[ A]1 8
67. Au(s) ⇇ Au() H = +ve
d d
68.  1
P
1 P
= 2
2 P1
P
1 16 1 1
=  =
2 P 2 4
70. H2O(s) ⇇ H2O() H = +ve
APNI KAKSHA 115

d d
high temperature and high pressure
77. C(diamond) ⇇ C(graphite) H = –ve

d d
High T and high pressure
79. The decrease in volume will lead to an increase in pressure. According to Le Chatelier's principle,
the equilibrium is going to shift to the left side with less moles of gases as pressure increases. This is
because the shift to fever gas moles will reduce the pressure increase. First, let's find 𝐾𝑝 𝑢 ing the
equilibrium data.
(PSO2 )(PCl2 ) (0.10)(0.10)
Kp = = = 0.010
(PSO2 Cl2 ) (1.00)
Now let's find 𝑄𝑃 . Since the volume was halved, all pressures are now doubled.
(PSO2 )(PCl2 ) (0.20)(0.20)
QP = = = 0.020
(PSO2 Cl2 ) (2.00)
This confirms that the reaction must shift left. As the reaction reaches equilibrium, the pressure of
SO2 Cl2 will increase by some amount 𝑥. We see from the reaction that SO2 and Cl2 will decrease by
(0.20−x)(0.20−x)
the same amount. Thus, K p = (2.00+x)
We could solve this equation for 𝑥 to find the final pressure of SO2 Cl2 , but it would take time.
Instead, notice that 𝑥 > 0 because by Le Chatelier's principle, SO2 Cl2 must increase. Also notice that
𝑥 < 0.20 because otherwise the partial pressures of SO2 and Cl2 would be negative. Therefore, the
final SO2 Cl2 is between 2.00 bar and 2.20 bar, which fits the range of an increase 1 − 10%. Thus, the
answer is A. If we were to actually solve for 𝑥, we would get 0.06, meaning an increase of 3%.
APNI KAKSHA 116

EXERCISE S-I
1. KC = K f
Kb
2. KC = K f
Kb
3. N2(g) + O2(g) ⇇ 2NO(g) KC = 0.5×10–9

1
2NO ⇇ N2(g) + O2(g) KC = = 2×109
0.5  10−9
(a) QC = 112 =
1
4. = 25
(0.2) 0.04
QC > KC , backward shift
(b) QP = 2  (1)
2 2
2
=
(3) 9
QP < KP , forward shift

1 1
(c) QP = =
1
QP < KP , forward shift
(d) Since initially only reactants are present, so reaction will shift to forward
5. CH4(g) + 2H2S(g) ⇇ CS2(g) + 4H2(g)

3 4 3 3
QC = 0.3  (0.3)4
0.3  (0.4)2
81 104 81
= −2
= ×10–2
16  10 16
6. H2O(g) + CH4(g) ⇇ CO(g) + 3H2(g)

0.03 M 0.05 M 0.15 M 0.2 M
0.15  (0.2)3
QC = = 0.8
0.03  0.05
QC < KC , forward shift
7. (a) very small extent (b) almost complete
8. PCl5 (g) ⇇ PCl3 (g) + Cl2 (g)

Ceq 0.5×10–3 1.5×10–2 3×10–2
1.5  10−2  3  10−2
KC = = 0.9
0.5  10−3
9. N2(g) + 3H2(g) ⇇ 2NH3(g)

0.036 M 0.15 M x
APNI KAKSHA 117
0.29 = x2
0.036  (0.15)3
x = 5.9×10–3
10. 3O2 (g) ⇇ 2O3 (g) KC = 8×10–55

Ceq 8×10–3 x
8×10–55 = x2
(8  10−3 )3
x2 = 8×10–55 × (8)3 × 10–9

x2 = (8)4 × 10–64
x = 64 × 10–32
11. (i) Amount if  formed = 2 × amount of A reacted
n=2
(ii) A ⇇ 2B
2
K = [B] = (0.6) = 1.2
2
[A] 0.3
12. A + B ⇇ 2C
ni 2 3 0
neq 2–x 3–x 2x
4= 4x 2
(2 − x)(3 − x)
x = 1.2
13. N2(g) + O2(g) ⇇ 2NO(g)

Ci 1.5 1.5 0
Ceq 1.5–x 1.5–x 2x
KC = (2x) 2 = 16
(1.5 − x)(1.5 − x)
2x =4
(1.5 − x)
x=1
14. PCl5 (g) ⇇ PCl3(g) + Cl2(g)

Ci 0.1 0 0
Ceq 0.1–x x x
x2
= 10–2
0.1 − x
x = 0.027
APNI KAKSHA 118
15. H2(g) + I2(g) ⇇ 2HI(g)

Ci 0 0 4.8×10–3
Ceq 0.4×10–3 0.4×10–3 4×10–3
(4 10−3 ) 2
KC = = 100
0.4  10−3  0.4 10−3
2 2
16. KC = =4
1
A(g) ⇇ B(g) + C(g)

Ceq 0.5–x 1+x 1+x
(1 + x) 2
=4
0.5 − x
x = 0.16
17. K P = KC
H2(g) + S(s) ⇇ H2S(g)

ni 0.2 1 0
neq 0.2–x 1–x x
x
6.8×10–2 =
0.2 − x
x = 0.0127
18. S2(g) + C(s) ⇇ CS2(g)

Pi 2 0
Peq 2–x x
x
=9
2−x
11x = 18
18
x=
11
19. ClF3(g) ⇇ ClF(g) + F2(g)

Pi 0.15 0 0
Peq 0.15 – x x x
x2
0.2 =
0.15 − x
x = 0.01
20. CaCO3(s) ⇇ CaO(s) + CO2(g)
APNI KAKSHA 119

KP + PCO 2 = 4×10–2
4  10−2  0.521
n CO 2 =
0.0821 1000
= 4×10–4
nCaO = n CO 2 = 4×10–4
WCaO = 4×10–4× 56 g
= 0.4×56 g
= 22.4 mg
21. CaCO3(s) ⇇ CaO(s) + CO2(g)

neq 0.2×0.75
0.2  0.75  0.08211000
KP = PCO 2 =
15
KP = 0.821
2
22. KP = (PH 2O ) = 2.25×10–4
PH 2O = 15×10–3 = 1.5×10–2
1.5  10−2
R.H. = ×760×100
22.8
= 50 %
If RH < 50% reaction will shift forward
24. KP = PH 2O = 0.2463
KP = KC(RT)2
0.2463
KC = = 0.01
0.0821 300
(0.1) 2 4
25. KP = ×4=
1 − (0.1) 2 99
1
25 × P = 4
1− 1 99
25
96
P= = 0.97 atm
99
4 2
26. KP = .P
1 − 2
APNI KAKSHA 120

( 4)
2
4 1 4 2
× 1.5 = × 10
1− ( 1 ) 1 − 2
2
4
4  0.01
= ×10 = 0.4
1 − 0.01
27. N2O4 (g) ⇇ 2NO2(g)

2 4 2 1
= ×
3 1−  2
2
2 1
=
1−  2
3
42 = 1
1
2 =
2
28. 2NOBr(g) ⇇ 2NO(g) + Br2(g)

ni a 0 0
2a a a
neq
3 3 6
Peq 0.16 0.8 0.4
KP = (0.8) 2  0.4 = 0.1

(0.16) 2
(0.1) 2 4
29. KP = ×4=
1 − (0.1) 2 99
1
25 × P = 4
1− 1 99
25
96
P= = 0.97 atm
99
92
30. 69 =
1+ 
1
=
3
4 1
4
KP = 9 ×5 = 9 ×5
1− 1 8
9 9
APNI KAKSHA 121

20
= = 2.5
8
230 92
=
3 1+ 
 = 0.2
1 4
20
= 25 .P
8 1− 1
25
P = 15 atm
31. PCl5 (g) ⇇ PCl3(g) + Cl2(g)

2
KP = ×P
1 − 2
2
0.178 = ×1
1 − 2
 = 0.8
208.5
Mmix = = 115.83
1.8
1115.83
d= = 2.7 g/L
0.0821 523
−ΔH∘
32. Slope of plot = 2.303R = 1
⇒ ΔH ∘ = −2.303 × 2 = −4.606cal
0.29
33. Keq at 1400 K =
1.1  10−6
2.9
= × 105
1.1
= 2.6×105
1.3
Keq at 1500 K =
1.4  10−5
1.3
= × 105
1.4
= 0.92×105
T, Keq e×0
34. Keq at 2000 K
APNI KAKSHA 122

(iii) = –[2(i) + (ii) ]
K= 1
(4.4)  5.3110−10
2
= 1010
(4.4) 2  5.31
Keq at 1000 K
K = 2.24 × 22
T, K e×0
35. On increasing temperature reaction will shift towards endothermic direction and on increasing
pressure reaction will more towards lesser number of gaseous moles.
38. (a) Forward shift

No of moles of H2O will decrease
(b) For ward shift  moles of H2O will decrease
(c) Forward shift  moles of HCl will increase
(d) Backward shift  moles of Cl2 will increase
(e) Backward shift  partical pressure of each goes will increase
(f) No change
(g) H > 0, T, KC
(h) T, forward shift [HCl]
(i) At constant volume – no change
41. (i) 2H2(g) + CO(g) ⇇ CH3OH (g)

conc.   
(ii) conc.   
(iii) conc.  
(iv) conc.  
(v) conc.   
42. X(s) ⇇ A(g) B(s) + C(g)
P1 + P2 P1
Y(s) ⇇ D(g) + A(s) + E(s)
P2 P2 + P 1
APNI KAKSHA 123
P1 (P1 + P2) = 500
P2 (P1 + P2) = 2000
P1 + P2 = 50
P1 = 2×50 = 100 atm
43. NH4HS(s) ⇇ NH3(g) + H2S (g)
1–x 1
 3
NH3(g) ⇇ N2(g) + H2(g)
2 2
x 3x
1–x
2 2
x
= 0.25  x = 0.5
2
APNI KAKSHA 124

EXERCISE O-II
1. KC depends only only on temp
15. KP = KC (RT)ng
ng = 0
KP = 49
16 . H2(g) + I2(g)  2HI(g)
neq 0.5–x 0.5–x 2x

(2x) 2
= 49
(0.5 – x)(0.5 − x)
2x
=7
0.5 – x
x = 0.38
1 0.0821  700
P=
7
= 8.21 atm
17. mole of I2, eq. = 0.5 – 0.38

= .012
2  0.38  0.0821 700

18. PHI =
7
= 6.385 atm
APNI KAKSHA 125

JEE MAINS
1. In this reaction the ratio of number of moles of reactants to products in same i.e., 2 : 2, hence
change in volume will not alter the number of moles .
3. The conversion of SO2 to SO3 is an exothermic reaction, hence there is no need to increase the
temperature. There is also a decrease in volume or moles in product side. Thus the reaction is
favoured by low temperature and high pressure. (Le-Chatelier’s principle).
4. C[ N 2O4 ] = 4.8 × 10–2 mol L–1, C[ NO2 ] = 1.2 × 10–2 mol L–1
[ NO2 ]2 1.2 10−2 1.2 10−3

Kc = = = 0.3 × 10–2 = 3 × 10–3 mol L–1
[ N 2O4 ] 4.8 10−2
[NO]2
5. N2(g) + O2(g) ⇇ 2NO(g) ; Kc = = 4  10−4
[N 2 ][O 2 ]
1 1 [N ]1/2 [O2 ]1/2 1 1 1 100

NO(g) ⇇ N2(g) + O2(g) ; K c = 2 = = = −2
= = 50
2 2 [NO] Kc 4 10 −4 2 10 2
7. CO(g) + CI2(g) ⇇ COCI2(g)

Kp 1
n = 1 – 2 = – 1; Kp = Kc (RT)n  = ( RT ) −1 =
Kc RT
8. Kp = Kc (RT)n n = 3 – 2 = 1.
Kp = Kc (0.0821 × 457)1 . Kp > Kc.
9. Cl2(g) + 3F2(g) ⇇ 2CIF3(g) ; H = – 329 kJ. Favourable conditions:

(i) Decrease in temperature, (ii) Addition of reactants, (iii) Increase in pressure i.e., decrease in
volume.
11. Given : PCI5(g) ⇇ PCI3(g) + CI2(g)

t=0 1 0 0
teq 1–x x x
Total number of moles = 1 – x + x + x = 1 + x
 x 
Thus partial pressure of PCl3 =   P.
 1+ x 
APNI KAKSHA 126

12. SO3(g) ⇇ SO2(g) + O2(g)

[ SO2 ][O2 ]1/2
= KC = 4.9 × 10–2 ...........(i)
[ SO3 ]
SO3(g) + 1/25 O2(g) ⇇ SO3(g) ...........(ii)

[ SO3 ] 1
1/2 = K'C = For 2SO2(g) + O2(g) ⇇ 2SO3(g)
[ SO2 ][O2 ] 4.9  10 –2
[ SO3 ]2 1 10000
= KC 2 = −4
= = 416.49
2
[ SO2 ] [O2 ] 4.9  4.9  10 24.01
13. X ⇇ 2Y Z ⇇ P + Q
1– 2 1–  
 α  α 
2
 2α 
 PT1   PT2   PT2 
Kp =  1+ α  Kp =  1+ α  1+ α 
1
 1- α  2
 1- α 
 PT1   PT 
 1+ α   1+ α 2 
 1- α 
2
 2α 
 PT1   PT2 
K P1
=  1+ α  ×  1+ α 
K P2  1- α   α  α 
 PT2   PT2   PT2 
 1+ α   1+ α   1+ α 
1 4P PT1 1
= T1 ; =
9 PT2 PT2 36
14. CO2(g) + C(s) ⇇ 2CO (g)

0.5 atm
0.5–p 2p
Total pressure = 0.5 – P + 2P = 0.8
P = 0.3
2 2
2
PCO (2P) (0.6)
Kp = = =
PCO2 (0.5 - P) (0.5 − 0.3)
Kp = 1.8
Kp = Kc ( RT )
n g
22.
1
ng = –
2
APNI KAKSHA 127

24. A + B ⇇ C + D
t=0 1 1 1 1
teq 1–x 1–x 1+x 1+x
(1 + x) 2 1+ x
 = 100  = 10
(1 − x) 2 1− x
 1 + x = 10 – 10x  11x = 9
9
 x=
11
9
 [D] = 1 +
11
 [D] = 1.818
H 1
25. ln K = ln A – ·
R T
Reaction is exothermic (i.e. H = –ve) so slope

1
of the curve between lnK and will be positive .
T
[AB]2
26. K1 = ... (1)
[A 2 ][B2 ]
[A 2 ]3 [B2 ]3
K2 = ... (2)
[AB]6
 K2 = K1–3
27. 1. N2 + O2 ⇌2NO
ng = 0
Kp = Kc(RT)ng
Kp
=1
Kp
2. N2O4 ⇌ 2NO2
Kp
=(RT)1 = 24.62
Kc
Kp 1
3. = (RT)–2 = = 1.62 × 10–3
Kc (24.62) 2
APNI KAKSHA 128

28. NH4 HS(s) ⇇ NH3(g) + H2 S(g)

5.1
Number of mole of given NH4HS = = 0.1 mole
51
0.1  30
moles of NH3 formed = = moles of H2S
100
0.03  0.0821 600
pressure of NH3 = = pressure of H2S = 0.492
3
 Kp = PNH3  PH 2S = 0.492 ×0.492 = 0.242 atm2
29. N2 + 3H2 ⇌ 2NH3

t=0   P
teq P 3p x
x2
Kp =
p  (3p)3
x = (Kp × 27 p4)1/2
x = (27)1/2 Kp1/2 P2
PT = 4P
PT
P=
4
33/2 K1/2
p PT
2
X=
16
30. A (s) ⎯→ B(g) + C(g) K P1 = x atm2
P1 P1 + P2
D(s) ⎯→ C(g) + E(g) K P2 = y atm2
P2+P1 P2
P1 (P1 + P2) = x
P2 (P1 + P2) = y
P1 + P2 = x+y
Total pressure = 2 (P1 + P2)
= 2 x + y atm
31. A + 2B ⎯→ 2C + D
Ci a 1.5a 0 0
APNI KAKSHA 129

Ceq a–x 1.5a – 2x 2x x
[A]eq = [B]eq
a–x = 1.5a – 2x
x = 0.5a
[C]2 [D] a 2  0.5a

KC = = =4
[A] [B]2 0.5a  (0.5a) 2
1
32. Equation 1: S(s) + O2 (g) ⇌ SO2 (g) : K1 = 1052
2
Equation 2 : 2S(s) + 3O2(g) 2SO3(g) : K2 = 10129
Equation 2 – 2 × Equation 1 gives,
2SO2(g) + O2(g) 2SO3(g) : K
K 2 10129
 K= = = 1025
(K1 ) 2 10104
33. On addition of catalyst value of equilibrium constant does not change.
34. As, Kp = Kc (RT)ng  Kp  Kc if ng  o

1. 2 HI(g) ⇌ H2 (s) + I2(g), ng = 0  kp = kc
2. NO2(g) + SO2(g) ⇌ NO(g) + SO3(g) , ng = 0  kp = kc
3. 2C(s) + O2 (g) ⇌2CO(g) , ng = 1  kp  kc
4. 2NO(g) ⇌ N2(g) + O2(g), ng = 0  kp = kc
35. A→B
[B] 11
K= = =2
[A] 6
1
36. Kp = Kc(RT)ng & ng = −
2
37. N2O4(g) ⇇ 2NO2(g) ; H = +58K

(a) on decreasing temperature reaction equilibrium shift in the direction in which it is
exothermic. Therefore in backward direction.
(b) Here pressure increases due to addition of N2 gas, so there will be no effect.
APNI KAKSHA 130

39. Cl2 2Cl
Let mol of both of Cl2 and Cl is x
x 1
PCl = ×1 =
2x 2
x 1
PCl = ×1 =
2
2x 2
2
1
2
K p =   = = 0.5  5 × 10 –1
1
1 2
2
5.1g
40. moles of NH4HS initially taken =
51g / mol
1 1
41. K 'eq = = = x 10−8
K eq 2 1015
1 1
  7 = x 10−8
20 10
1
 10−7 = x 10−8
20
10
=x
20
10
x= = 5 = 2.236
2
=2.24
42. Given : 2 mole of N2 gas was present as inert gas.

Equilibrium pressure = 2.46 atm
PCl5 (g)  PCl3 (g) + Cl2 (g)
t=0 5 0 0
t = Eqn 5–x x x
from ideal gas equation
PV = nRT
2.46 × 200 = (5 – x + x + x + 2) × 0.082 × 600
APNI KAKSHA 131

x=3
n PCl3  n Cl2 P 
KP =   total 
n PCl5  n total 
3  3 2.46
 = 1.107 = 1107 10−3
2 10
Volume of vessel = 2
NH 4 HS(s) NH3(g) + H 2S(g)

t=0 0.1 mol
t =  0.1(1–0.2) 0.1×0.2 0.1×0.2
 partial pressure of each component
nRT 0.1 0.2  0.082  300
P= =
V 2
= 0.246 atm
 kP = PNH3  PH2S = (0.246)2 = 0.060516

= 6.05 × 10–2
6
APNI KAKSHA 132

EXERCISE - JEE ADVANCED
5. With change of pressure, x will change in such a way that Kp remains a constant.
6. N2O4 (g) 2NO2.

moles t=0, 1 0
moles at eq. 1– 2
2
 2 
 (1 + )  P  4 2
KP =   = × P.
1– 
P
1 – 2
1+ 
Let total pressure at eq. = P.
4 2
or KP = × P.
1 – 2
When volume is halved, P is double.
 a will change as KP is independent of pressure change.
8. (A) H2 – H1 = CP (rxn) (T2 – T1)

and Cp depends on temperature. Hence enthalpy also depends on temperature.
(B) CaCO3(s) CaO(s) + CO2(g) Kp = ( PCO2 )at equlibrium
For a given reaction.

Keq. depends only on temperature.
(C) Keq depends only on temperature.
(D) Enthalpy of reaction is independent of the catalyst. Catalyst generally changes activation
energy.
9. Equal volumes of both the reactant are taken so, initial concentrations will be halved.
Fe2+ (aq) +S2–(aq) ⇇ FeS (s)

t=0 0.03M 0.1M
teq. x 0.07M since KC is very high
1 1
KC = = = 1.6 × 1017
2+ 2–
[Fe ][S ] x  0.07
x = 8.928 × 10–17
So, Y = 8.92 (after truncate) or 8.93 (after round off).
APNI KAKSHA 133

Exercise - 01 - Chemical Equilibrium

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Exercise - 01 - Chemical Equilibrium

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(Physical Chemistry) CHEMICAL EQUILIBRIUM

Characteristics of Equilibrium State

2. Which of the following statement is incorrect :

3. Concentrations of reactants and products at equilibrium can be like :

(A) (B) (C) (D) All of these

4. Rate of reaction curve for equilibrium can be like :

(A) 5 (B) 7 (C) 6 (D) 8

Characteristics of Equilibrium Constant

7. The equilibrium concentration of B[(B)e]for the reversible reaction A B can be evaluated by

12. For the reaction

13. For hypothetical equilibrium, 4A(g) + 5B(g) ⇇ 4X(g) + 6Y(g)

14. What is the unit of KP for the reaction ?

15. The equilibrium constant for the given reaction :

16. The equilibrium constant for the reaction ;

(A) K1 K 2 = K3 (B) K2K3 = K1 (C) K3 = K1K2 (D) K3·K23K12

18. Equilibrium constant for following reactions respectively K1, K2 and K3

20. For which reaction is Kp = Kc :–

(a) N2O4(g) ⇇ 2NO2(g) (b) 2SO2(g) + O2(g) ⇇ 2SO3(g)

(c) X(g) + Y(g) ⇇ 4Z(g) (d) A(g) + 3B(g) ⇇ 7C(g)

Application of Equilibrium Constant

24. When Kc >> 1 for a chemical reaction,

25. Equilibrium constant of some reaction are given as under ;

reaction PCl5(g) ⇇ PCl3(g) + Cl2(g) is :

(A) Kc > 1 (B) K < 1 (C) K = 1 (D) data insufficient

36. The equilibrium constant for the reaction

of H2 has reacted at equilibrium for the reaction H2 + I2 ⇇ 2HI

42. For the reaction

44. On decomposition of NH4HS, the following equilibrium is established :

(A) 2NOCl(g) ⇇ 2NO(g) + Cl2(g) (B) N2(g) + 3H2(g) ⇇ 2NH3(g)

(C) H2(g) + I2(g) ⇇ 2HI(g) (D) 2SO2(g) + O2(g) ⇇ 2SO3(g)

51. At 527°C the reaction :

N2(g) + 3H2(g) ⇇ 2NH3(g) :

Problems involving degree of dissociation, Average Molar Mass.

(A) p03 (B) p 0 3 (C) p0 2 (D) None of these

62. Attainment of the equilibrium

67. Au(s) ⇌ Au()

Above equilibrium is favoured at :

(A) The pressure changes do not affect the equilibrium

72. Consider the reactions

(A) increases (B) decreases

(C) PCl5(g) ⇌ PCl3(g) + Cl2(g) addition of inert gas at constant pressure

76. The equilibrium 2SO2(g) + O2(g) ⇌ 2SO3(g) shifts forward if :–

Choose the correct options :

Characteristics of Equilibrium Constant

2. Consider the reaction of chloromethane with OH– in aqueous solution

Application of Equilibrium constant

11. The progress of the reaction

(i) the value of n. 2

16. Following equilibrium is established at temperature T.

22. Equilibrium constant for the following equilibrium is given at 0ºC.

Relationship between Kp and Kc

(A) +4.606cal (B) −4.606cal (C) 2cal (D) −2cal

Le-Chatelier’s mix problem

35. Using Le Chatelier's principle, predict the effect of

42. For given simultaneous reaction :

Y(s) ⇌ D(g) + A(g) + E(s) K P2 = 2000 atm

Find total pressure at equilibrium containing both X(s) and Y(s)

43. NH4HS(s) ⇌ NH3(g) + H2S(g) 𝐾𝑐1

2. N2O4(g) ⇌ 2NO2(g), Kc = 4. This reversible reaction is studied graphically as shown in figure.

(A) Reaction quotient has maximum value at point A

(A) formation of more H2O (s) (B) formation of more H2O()

8. 2CaSO4(s) ⇌ 2CaO(s) + 2SO2(g) + O2(g), H > 0

Above equilibrium is established by taking some amount of CaSO4(s) in a closed container at