Page # 14 CHEMICAL EQUILIBRIUM

Exercise - I (Only one option is correct)

1. For the reaction equilibrium : 7. A definite amount of solid NH4HS is placed in a flask
N2O4 (g) 2NO2(g) ; the concentration of N2O4 already containing ammonia gas at a certain tem-
perature and 0.50 atm pressure. NH4HS decomposes
and NO2 at equilibrium are 4.8 × 10–2 and 1.2 × 10–2
to give NH3 and H2S and at equilibrium total pressure
mol/L respectively. The value of Kc for the reaction is :
in flask is 0.84 atm. The equilibrium constant for the
(A) 3 × 10–3 M (B) 3 × 103 M
reaction is :
(C) 3.3 × 102 M (D) 3 × 10–1 M
(A) 0.30 (B) 0.18
2. What is the equilibrium constant for the reaction (C) 0.17 (D) 0.11
P4(s) + 5O2(g) P4O10(s) :
1 [P4 O10 ] 8. For the reaction 3A(g) + B(g) 2C(g) at a
(A) K c  (B) K c 
[O 2 ] 5 5[P4 ] [O 2 ]5 given temperature, Kc = 9.0. What must be the vol-
[P4 O10 ] ume of the flask, if a mixture of 2.0 mol each of A, B
(C) Kc = [O2]5 (D) K c  and C exist in equilibrium ?
[P4 ] [O 2 ] 5
(A) 6 L (B) 9 L
3. The equilibrium constant for the reaction : (C) 36 L (D) None of these
N2(g) + O2(g) 2NO(g) at temperature
T is 4 × 10–4. The value of Kc for the reaction. 9. Sulfide ion in alkaline solution reacts with solid sulfur
1 1 to form polysulfide ions having formulas S22–, S32–,
NO(g) N (g) + O2(g) at the same tem- S42– and so on. The equilibrium constant for the for-
2 2 2
perature is : mation of S22– is 12 (K1) & for the formation of S32– is
(A) 0.02 (B) 50 132 (K2), both from S and S2–. What is the equilib-
(C) 4 × 10–4 (D) 2.5 × 10–2 rium constant for the formation of S32– from S22– and S
(A) 11 (B) 12
4. The equilibrium constant for the given reaction : (C) 132 (D) None of these
1
SO3(g) SO2(g) + O2(g); Kc = 4.9 × 10–2 10. 1 mole N2 and 3 mol H2 are placed in a closed con-
2
The value of Kc for the reaction : tainer at a pressure of 4 atm. The pressure falls to 3
atm at the same temperature when the following
2SO2(g) + O2(g) 2SO3(g), will be equilibrim is attained.
(A) 416 (B) 2.40 × 10–3
(C) 9.8 × 10–2 (D) 4.9 × 10–2 N2(g) + 3H2(g) 2NH3(g). The equilibrium
constant Kp for dissociation of NH3 is :
5. For the following three reactions 1, 2 and 3, equilib- 1
rium constants are given : (A)  (1.5 )3 atm–2 (B) 0.5 × (1.5)3 atm2
0. 5
(1) CO(g) + H2O(g) CO2(g) + H2(g) ; K1
(2) CH4(g) + H2O(g) CO(g) + 3H2(g) ; K2 0.5  (1.5)3 33
atm – 2
(C) atm 2 (D)
33 0.5  (1.5)3
(3) CH4(g) + 2H2O(g) CO2(g) + 4H2(g) ; K3
11. One mole of N2O4(g) at 300 K is left in a closed con-
Which of the following relations is correct ?
tainer under one atm. It is heated to 600 K when 20%
(A) K 1 K 2  K 3 (B) K2K3 = K1 by mass of N2O4 (g) decomposes to NO2(g). The re-
sultant pressure is :
(C) K3 = K1K2 (D) K3. K23K12
6. Consider following reactions in equilbrium with equi- (A) 1.2 atm (B) 2.4 atm
librium concentration 0.01M of every species (C) 2.0 atm (D) 1.0 atm
(I) PCl5(g) PCl3(g) + Cl2(g) (II) 2HI(g)
H2(g) + I2(g) 12. For the following gases equilibrium. N2O4(g)
(III) N2(g) + 3H2 (g) 2NH3(g) 2NO2(g)
Extent of the reactions taking place is : Kp is found to be equal to Kc. This is attained when
(A) I > II > III (B) I < II < III temperature is
(C) II < III < I (D) III < I < II (A) 0°C (B) 273 K
(C) 1 K (D) 12.19 K

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1
13. For the reaction : CO(g) + O (g) CO2(g), 19. The equilibrium constant Kc for the reaction,
2 2
Kp/Kc is : A(g) + 2B(g) 3C(g) is 2 × 10–3
(A) RT (B) (RT)–1
(C) (RT)–1/2 (D) (RT)1/2 What would be the equilibrium partial pressure of gas
C if initial pressure of gas A & B are 1 & 2 atm re-
spectively.
14. For the reaction : 2NO2(g) 2NO(g) + O2(g)
(A) 0.0625 atm (B) 0.1875 atm
Kc = 1.8 × 10–6 at 184° C and R = 0.083 JK–1 mol–1. (C) 0.21 atm (D) None of these
When Kp and Kc are compared at 184°C, it is found
that :
20. A 20.0 litre vessel initially contains 0.50 mole each of
(A) Kp > Kc (B) Kp < Kc (C) Kp = Kc
H2 and I2 gases. These substances react and finally
(D) Kp  Kc depends upon pressure of gases
reach an equilibrium condition. Calculate the equilib-
rium concentration of HI if Keq = 49 for the reaction
15. PCl5 dissociation a closed container as :
H2 + I2 2HI.
PCl5(g) PCl3(g) + Cl2(g)
(A) 0.78 M (B) 0.039 M
If total pressure at equilibrium of the reaction mixture
(C) 0.033 M (D) 0.021 M
is P and degree of dissociation of PCl5 is , the par-
tial pressure of PCl3 will be :
21. A vessel of 250 litre was filled with 0.01 mole of Sb2S3
    2       
(A) P.  (B) P. 1 –   (C) P.  – 1 (D) P. 1 –   and 0.01 mole of H2 to attain the equilibrium at 440°c
   1      
as Sb2S3(s) + 3H2(g) 2Sb(s) + 3H2S(g).
After equilibrium the H2S formed was analysed by
16. For the reaction : 2HI (g) H2(g) + I2(g), the dissolving it in water and treating with excess of Pb2+
degree of dissociated () of HI(g) is related to equilib- to give. 1.195 g of PbS (Molecular weight = 239) pre-
rium constant Kp by the expression : cipitate.
1 2 Kp 1  2K p What is value of Kc of the reaction at 440°C ?
(A) (B)
2 2 (A) 1 (B) 2
(C) 4 (D) None of these
2K p 2 Kp
(C) 1  2K p (D)
1 2 Kp 22. The equilibrium constant for the reaction CO(g) +
H2O(g) CO2(g) + H2(g) is 3 at 500 K. In a 2
17. The equilibrium constant for the reaction litre vessel 60 gm of water gas [equimolar mixture of
CO(g) and H2(g)] and 90 gm of steam is initially taken.
A(g) + 2B(g) C(g)
What is the equilibrium concentration of H2(g) at equi-
is 0.25 dm mol . In a volume of 5 dm3, what amount
6 –2
librium (mole/L) ?
of A must be mixed with 4 mol of B to yield 1 mol of C
at equilibrium. (A) 1.75 (B) 3.5
(A) 3 moles (B) 24 moles (C) 1.5 (D) 0.75
(C) 26 moles (D) None of these
23. At 87°C, the following equilibrium is established
18. For the reaction A(g) + 2B(g) C(g) + D(g); H2(g) + S(s) H2S(g) Kp = 7 × 10–2
Kc = 1012
If 0.50 mole of hydrogen and 1.0 mole of sulfur are
If the initial moles of A, B, C and D are 0.5, 1, 0.5 and
heated to 87°C in 1.0 L vessel, what will be the par-
3.5 moles respectively in a one litre vessel. What is
tial pressure of H2S at equilibrium ?
the equilibrium concentration of B ?
(A) 10–4 (B) 2 × 10–4 (A) 0.966 atm (B) 1.38 atm
(C) 4 × 10–4 (D) 8 × 10–4 (C) 0.0327 (D) 9.66 atm

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24. At certain temperature (T) for the gas phase reaction 29. The exothermic formation of ClF3 is represented by
the equation :
2H2O(g) + 2Cl2(g) 4HCl(g) + O2(g)
Kp = 12 × 108 atm Cl2(g) + 3F2(g) 2ClF3(g) H = – 329 kJ
If Cl2, HCl & O2 are mixed in such a manner that the Which of the following will increase the quantity of
partial pressure of each is 2 atm and the mixture is ClF3 in an equilibrium mixture of Cl2, F2 and ClF3 :
brough into contact with excess of liquid water. What (A) Increasing the temperature
would be approximate partial pressure of Cl2 when
(B) Removing Cl2
equilibrium is attained at tmeperature (T) ?
(C) Increasing the volume of container
[Given : Vapour pressure of water is 380 mm Hg
at temperature (T)] (D) Adding F2
(A) 3.6 × 10–5 atm (B) 10–4 atm
(C) 3.6 × 10–3 atm (D) 0.01 atm 30. Densities of diamond and graphite are 3.5 and 2.3
gm/mL.

25. At 675 K, H2(g) and CO2(g) react to form CO(g) and C(diamond) C (graphite) rH = – 1.9 kJ/
H2O(g), Kp for the reaction is 0.16. mole favourable conditions for formation of dia-
If a mixture of 0.25 mole of H2(g) and 0.25 mol of CO2 mond are
is heated at 675 K, mole% of CO(g) in equilibrium (A) high pressure and low temperature
mixture is : (B) low pressure and high temperature
(A) 7.14 (B) 14.28 (C) high pressure and high temperature
(C) 28.57 (D) 33.33 (D) low pressure and low temperature

31. The equilibrium SO2Cl2(g) SO2(g) + Cl2(g) is

26. In which of the following reactions, increase in the
pressure at constant temperature does not affect the attained at 25°C in a closed rigid container and an
moles at equilibrium. inert gas, helium in introduced. Which of the follow-
ing statements is/are correct.
(A) 2NH3(g) N2(g) + 3H2(g) (A) concentrations of SO2, Cl2 and SO2Cl2 do not
1 change
(B) C(g) + O (g) CO(g) (B) more chlorine is formed
2 2
(C) concentration of SO2 is reduced
1
(C) H2(g) + O (g) H2O(g) (D) more SO2Cl2 is formed
2 2
(D) H2(g) + I2(g) 2 HI(g)
32. Following two equilibrium is simultaneously estab-
lished in a container
27. Change in volume of the system does not alter the PCl5(g) PCl3(g) + Cl2(g)
number of moles in which of the following equilibrium
CO(g) + Cl2(g) COCl2(g)
(A) N2(g) + O2(g) 2NO(g)
If some Ni(s) is introduced in the container forming Ni
(B) PCl5(g) PCl3(g) + Cl2(g) (CO)4(g) then at new equilibrium
(C) N2(g) + 3H2(g) 2NH3(g) (A) PCl3 concentration will increase
(B) PCl3 concentration will decrease
(D) SO2Cl2(g) SO2(g) + Cl2(g)
(C) Cl2 concentration will remain same
(D) CO concentration will remain same
28. The conditions favourable for the reaction :
33. The yield of product in the reaction
2SO2(g) + O2(g) 2SO3(g) ; H° = – 198 kJ
2A(g) + B(g) 2C(g) + Q kJ
are :
would be lower at :
(A) low temperature, high pressure
(A) low temperature and low pressure
(B) any value of T and P
(B) high temperature & high pressure
(C) low temperature and low pressure
(C) low temperature and high pressure
(D) high temperature and high pressure (D) high temperature & low pressure

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34. What is the effect of the reduction of the volume of

9. The equilibrium constants K P1 and K P2 for the reac-
the system for the equilibrium 2C(s) + O2(g)
2CO(g) ? tions X 2Y and Z P + Q, respec-
(A) The equilibrium will be shifted to the left by the tively are in the ratio of 1 : 9. If the degree of dissocia-
increased pressure caused by the reduction in volume tion of X and Z be equal then the ratio of total pres-
(B) The equilibrium will be shifted to the right by the sures at these equilibria is :
decreased pressure caused by the reduction in volume. (A) 1 : 36 (B) 1 : 1
(C) The equilibrium will be shifted to the left by the (C) 1 : 3 (D) 1 : 9
increased pressure caused by the increase in volume.
(D) The equilibrium will be shifted to the right by the
increased pressure caused by the reduction in volume. 40. When N2O5 is heated at temp. T, it dissociates as
35. The vapour density of N2O4 at a certain temperature N2O5 N2O3 + O2 , Kc = 2.5. At the same time
is 30. What is the % dissociation of N2O4 at this tem-
perature ? N2O3 also decomposes as : N2O3 N2O + O2.
(A) 53.3 % (B) 106.6 % If initially 4.0 moles of N2O5 are taken in 1.0 litre flask
(C) 26.7 % (D) None and allowed to attain equilibrium, concentration of O2
was formed to be 2.5 M. Equilibrium concentration of
36. The equilibrium constant Kp (in atm) for the reaction N2O is
is 9 at 7 atm and 300 K. (A) 1.0 (B) 1.5
A2(g) B2(g) + C2(g) (C) 2.166 (D) 0.334

Calculate the average molar mass (in gm/mol) of an

equilibrium mixture. 41. An exothermic reaction is represented by the graph :
Given : Molar mass of A2, B2 and C2 are 70, 49 & 21
gm/mol respectively.
(A) 50 (B) 45
(C) 40 (D) 37.5 lnK p lnK p

(A) (B)
37. Vapour density of the equilibrium mixture of the reac-
tion
1/T 1/T
2NH3(g) N2(g) + 3H2 (g) is 6.0
Percent dissociation of ammonia gas is :
(A) 13.88 (B) 58.82
(C) 41.66 (D) None of these lnK p lnK p
38. Equimolar mixture of two gases A2 and B2 is taken in (C) (D)
a rigid vessel at temperature 300 K. The gases re-
acts according to given equations : 1/T 1/T
A2(g) 2 A (g) K P1  ?
42. The correct relationship between free energy change
B2(g) 2 B (g) K P2  ? in a reaction and the corresponding equilibrium con-
K P3  2 stant K is
A2(g) + B2(g) 2 AB (g)
(A) – G° = R T ln K (B) G = RT ln
If the initial pressure in the container was 2 atm and
K
final pressure developed at equilibrium is 2.75 atm.
in which equilibrium partial pressure of gas AB was (C) – G = RT ln K (D) G° = RT ln K
K p2
0.5 atm, calculate the ratio of K . 43. The value of G°f of gaseous mercury is 31 K J/mole.
p1 At what total external pressure mercury start boiling
[Given : Degree of dissociation of B2 is greater at 25°C. [R = 8.3 J/K mole]
than A2].
(A) 10–5.44 (B) 10–12.5
(A) 8 (B) 9
(C) 1/8 (D) None of these (C) 10–6.52 (D) 10–3.12

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44. What is rG (KJ/mole) for synthesis of ammonia at 49. Statement-1 : An exothermic reaction, non-sponta-
298 K at following sets of partial pressure : neous at high temperature, may become spontane-
N2(g) + 3H2(g) 2NH3(g) ; rG° = – 33 KJ/ ous at low temperature.
mole. [Take R = 8.3 J/K mole, log 2 = 0.3 ; log 3 = 0.48] Statement-2 : Entropy of an exothermic reaction al-
ways decrease with decrease in temperature.
Gas N2 H2
NH3 Pressure (atm) 1 (A) Statement-1 is true, statement-2 is true and state-
3 0.02 ment-2 is correct explanation for statement-1
(A) + 6.5 (B) – 6.5 (B) Statement-1 is true, statement-2 is true and state-
(C) + 60.5 (D) – 60.5 ment-2 is NOT the correct explanation for statement-1
45. G° for the dissociation of the dimer (A2 (C) Statement-I is true, statement-2 is false.
2A) in benzene solution at 27°C is 6.909 kcal/mol. If (D) Statement-1 is false, statement-2 is true.
8 moles of A is dissolved in 10 dm3 of benzene at
50. Statement-1 : Ammonia at a pressure of 10 atm and
27°C. What is the ratio of equilibrium concentration
CO2 at a pressure of 20 atm are intoduced into an
of monomer to dimer ([A] /[A2]) ? Given : R = 2 cal/
evacuated chamber. If Kp for the reaction.
mol. K
(A) 1 : 200 (B) 1 : 100 NH2COONH4(s) 2NH3(g) + CO2(g) is 2020
(C) 200 : 1 (D) 800 : 1 atm3, the total pressure after a long time is less than
46. For the reaction takes place at certain temperature 30 atm.
NH4HS(s) NH3(g) + H2S(g) Statement-2 : Equilibrium can be attained from both
directions.
if equilibrium pressure is X bar, then rG°
would be (A) Statement-1 is true, statement-2 is true and state-
(A) – 2RTln X (B) – RT ln (X – ln 2) ment-2 is correct explanation for statement-1
(C) – 2RT (ln X – ln 2) (D) None of these (B) Statement-1 is true, statement-2 is true and state-
ment-2 is NOT the correct explanation for statement-1
47. Calculate log10 {[C]eq/ [A]eq} where [C] and [A] are (C) Statement-I is true, statement-2 is false.
equilibrium molar concentration of respective species, (D) Statement-1 is false, statement-2 is true.
when 2 mole each of A and B were allowed to come
to equilibrium at 900 K.
COMPREHENSION
900 K
A+B C + D ; G° = 460.6 Calorie
Paragraph for Questions No. 51 to 54
lnX = 2.303 log X In a 7.0 L evacuated chamber, 0.50 mol H2 and 0.50
Take : R = 2 Cal/K mole mol I2 react at 427°C

(A) – 5.56 × 10–02 (B) – 5.57 × 10–03 H2(g) + I2 (g) 2HI(g). At the given tempera-
(C) – 1.1 × 10–2 (D) – 1.1 × 10–3 ture, Kc = 49 for the reaction.
51. What is the value of Kp ?
ASSERTION - REASON
(A) 7 (B) 49
48. Statement-1 : Total number of moles in a closed
system at new equilibrium is less than the old equi- (C) 24.5 (D) None
librium is some amount of a substance is removed 52. What is the total pressure (atm) in the chamber ?
from a system. (A) 83.14 (B) 831.4
(Consider a reaction A(g) B(g) at equilib- (C) 8.21 (D) None
rium.
Statement-2 : The number of moles of the substance 53. How many moles of the iodine remain unreacted at
which is removed, is partially compensated as the equilibrium ?
system reached to new equilibrium.
(A) 0.388 (B) 0.112
(A) Statement-1 is true, statement-2 is true and state-
(C) 0.25 (D) 0.125
ment-2 is correct explanation for statement-1
(B) Statement-1 is true, statement-2 is true and state-
54. What is the partial pressure (atm) of HI in the equilib-
ment-2 is NOT the correct explanation for statement-1
rium mixture ?
(C) Statement-I is false, statement-2 is true.
(A) 6.385 (B) 12.77
(D) Statement-1 is true, statement-2 is false.
(C) 40.768 (D) 646.58

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Pragraph for Question Nos. 55 to 57 58. In a study of equilibrium

Equilibrium constants are given (in atm) for the H2(g) + I2(g) 2HI (g)
following reactions at 0°C :
1 mole of H2 and 3 mole of I2 gave rise at equilibrium
SrCl2. 6H2O(s) SrCl2 . 2H2O(s) + 4H2O(g) to x mol of HI.

Kp = 5 × 10–12 Addition of a further 2 mol of H2 gave an additional x

mol of HI. What is x ?
Na2HPO4.12H2O(s) Na2HPO4. 7H2O (s) + (A) 0.5 (B) 1
5H2O(g) Kp = 2.43 × 10 –13
(C) 1.5 (D) None of these

Na2SO4.10H2O(s) Na2SO4(s) + 10 H2O(g) 59. In above prolem, what is Kp at the temperature of the
Kp = 1.024 × 10–27 experiment.
The vapour pressure of water at 0° C is 4.56 torr. (A) 1 (B) 2
(C) 4 (D) None of these
55. Which is the most effective drying agent at 0°C ?
(A) SrCl2.2H2O (B) Na2HPO4. 7H2O 60. In a study of equilibrium
(C) Na2SO4 (D) all equally 2SO2(g) + O2(g) 2SO3(g)
Starting with 2 mole SO2 and 1.5 mole O2 in 5 litre
56. At what relative humidities will Na2SO4. 10 H2O be
flask. Equilibrium mixture required 0.4 mole KMnO4
efflorescent (release moisture) when exposed to air at in acidic medium. Hence Kc is :
0°C ?
(A) 0.2 (B) 5.0
(A) above 33.33 % (B) below 33.33 % (C) 675.0 (D) None of these
(C) above 66.66% (D) below 66.66%
Match the column :
57. At what relative humidities will Na 2 SO 4 be
61. Column I
deliquescent (i.e. absorb moisture) when exposed to
Column II
the air at 0°C?
(A) above 33.33 % (B) below 33.33 % (A) Kp < Kc (P) N2 + 3 H2 2NH3

(C) above 66.66% (D) below 66.66% (B) Introduction (Q) PCl5(g) PCl3(g) + Cl2(g)
of inert gas at pressure will decrease the
Paragraph for Question Nos. 58 to 60 constant concentration of reactants.
If we know the equilibrium constant for a particular (C) K P0 is dimensionless (R) 2NO2(g) N2O4(g)
reaction, we can calculate the concentrations in the
equilibrium mixture from the initial ocncentrations. (D) Temperature increase (S) NH3(g) + HI (g)
Commonly only the initial concentration of reactants will shift the reaction NH4I (s) on product side.
are given.

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