CHEMICAL EQUILIBRIUM

SECTION - I : STRAIGHT OBJECTIVE TYPE

1 The unit of equilibrium constant KC of a reaction is mol–2l2. For this reaction, the product concentration
increases by -
(A) Increasing the pressure (B) Lowering the temperature
(C) Lowering the pressure (D) Both B and C
Ans (A)
KC = (mole/litre)n
where n = no of moles on product side – no. of moles on reactant side
Hence n = – 2
so moles on reactant side > moles on product side
so on increasing pressure reaction will get shifted in forward direction.

2 At 1400 K, Kc = 2.5×10–3 for the reaction CH4(g) + 2H2S(g) CS2(g) + 4H2(g) . A 10.0L reaction
vessel at 1400 K contains 2.00 mole of CH4, 3.0 mol of CS2, 3.0 mole of H2 and 4.0 mole of H2S. Then
(A) This reaction is at equilibrium with above concentrations.
(B) The reaction will proceed in forward direction to reach equilibrium
(C) The reaction will proceed in backward direction to reach equilibrium
(D) The information is insufficient to decide the direction of progress of reaction
Ans (C)
4
 3   3 
 10   10 
    243
QC = 2
=  10–2 = 7.59 × 10–2> Kc
 2  4  32
 10   10 
  
So, reaction will proceed in backward direction.

3 In a basic aqueous solution chloromethane undergoes a substitution reaction in which Cl¯ is replaced
by OH¯ as.
CH3Cl (aq) + OH¯ CH3OH(aq) + Cl¯ (aq)
The equilibrium constant of above reaction Kc = 1 × 1016. If a solution is prepared by mixing equal
volumes of 0.1 M CH3Cl and 0.2 M NaOH (100% dissociated) then [OH¯] concentration at equilibrium
in mixture will be:
(A) 0.1 M (B) 0.5 M (C) 0.2 M (D) 0.05 M
Ans (D)
CH3Cl (aq) + OH¯ CH3OH (aq) + Cl¯ (aq)
t=0 0.05 0.1 0 0
teq. 0 0.1 – 0.05 = 0.05 0.05 0.05
As equilibrium constant is very large so reaction will be almost 100% complete.
4 Equilibrium constant for the given reaction is K = 1020 at temperature 300 K
A(s) + 2B (aq.) 2C (s) + D (aq.) K = 1020
The equilibrium conc. of B starting with mixture of 1 mole of A and 1/3 mole/litre of B at 300 K is
(A) ~ 4 × 10– 11 (B) ~ 2 × 10– 10 (C) ~ 2 × 10– 11 (D) ~ 10– 10
Ans (A)
A(s) + 2B(aq) 2C(s) + D(aq)
1
Initial 1 0 0
3
1
At eq. 1–x –x 2x x
3
a
×  1/3
1 1
3 3 1 10 20 1010
1020 = 2
1020 = 2 a2 = = a =  4 × 10–11 M
B  a 3  1020 3 3

5 10 t. box contain O3 and O2 at equilibrium at 2000 K. The G° = –534.52 kJ at 8 atm equilibrium
pressure. The following equilibrium is present in the container
2O3(g) 3O2(g). The partial pressure of O3 will be ( ln 10 = 2.3, R = 8.3 Jmole–1K–1):
(A) 8 x 10–6 (B) 22.62 x 10–7 (C) 9.71 x 10–6 (D) 9.71 x 10–2
Ans (B)
G° = – RT ln K = – 2.3 x 2000 x 8.3 log K
534.52 x 103
= log K
2.3 x 8.3 x 2000
K = 1014
2O3(g) 3O2(g); K = 1014
So PO3  PO2
So PO2  PO3  8
PO2  8 atm
(PO2 )3 (8)3
K = 1014 = =
(PO3 )2 PO3
PO3 = 22.62 x 10–7 atm.

6 What is the minimum mass of CaCO3 (s), below which it decomposes completely, required to establish
equilibrium in a 6.50 litre container for the reaction : [Kc = 0.05 mole/litre]
CaCO3 (s) CaO(s) + CO2(g)
(A) 32.5 g (B) 24.6 g (C) 40.9 g (D) 8.0 gm
Ans (A)
KC = [CO2] = 0.05 mole/litre
so moles of CO2 = 6.50 × 0.05 moles = 0.3250 moles
CaCO3 CaO + CO2
1 mole of CO2 = 1 mole of CaCO3
0.3250 moles of CO2 = 0.3250 moles of CaCO3 = 0.3250 × 100 gm of CaCO3 = 32.5 gm of CaCO3
7 The value of kp for the reaction at 270C
Br2() + 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() is also 0.1 atm. Then what will be minimum moles of Br 2()
to be added to 1 mole of Cl2 , initially, to get above equilibrium situation :
10 5 15
(A) moles (B) moles (C) moles (D) 2 moles
6 6 6
Ans (C)
Br2() + Cl2(g) 2Br Cl(g)
t=0 1 0
(1 – x) 2x
2
(P )
kp = BrCl = 1 so, PCl2 = (PBrCl )2 = 0.01 atm
PCl2
nBrCl 0.1 2x
then at equilibrium, = = 10 =
nCl2 0.01 1 x
10 5
So, 10 – 10x = 2x or x= = moles
12 6
Moles of Br2() required for maintaining vapour pressure of 0.1 atm
5 10
=2× moles = moles = moles of BrCl(g).
6 6
5
Moles required for taking part in reaction = moles of Cl 2 used up = moles.
6
10 5 15
Therefore required total mole = + = mole.
6 6 6

8 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 pressure changes may increase or decrease the degree of advancement of the reaction
depending upon the temperature of the system
Ans (B)
Volume of solid is more than volume of liquid water. Hence increase in pressure moves the
equilibrium forward.

SECTION - II : MULTIPLE CORRECT ANSWER TYPE

9 An arbitrary combound P2Q decomposes according to reaction :
2P2Q (g) 2P2 (g) + Q2 (g)
If one starts the decomposition reaction with 4 moles of P2Q and value of equilibrium constant Kp is
numerically equal to total pressure at equilibrium. Then which option is/are correct at equilibrium :
(A) moles of nP Q = nQ
2 2

(B) moles of nP2 = (8/3)

(C) degree of dissociation is  = (2/3)
(D) total number of moles of products (P2 & Q2) at equilibrium is 4
 Ans (A, B, C, D)
2P2Q 2P2 + Q2
t=0 4 0 0
t= eq 4 (1–) 4 2
2
 4   2 
 4  2  P   4  2  P 
    23
Kp =  4(1   ) 
2 = (1  )2 (4  2)  P
 4  2  P 
 
But Kp = P (given)  23 = (1–)2 (4 + 2)  – 6  = (2/3)
Total moles at eq = 4 + 2 = (16/3)
nP 2Q = nQ2 = (4/3), nP2 = (8/3)
8 4 12
 Total number of moles of products = 3  3  3  4 .
10 Consider the following statements :
(I) An increase in pressure (caused by decrease in volume) at equilibrium results in increase in molar
concentration of each gaseous substance involved.
(II) An increase in pressure (caused by decrease in volume) at equilibrium results in increase in no. of
moles of each gaseous substance involved.
(III) For the reaction A(s) B(g) + C(g) at constant temperature, total pressure at equilibrium (of
B(g) & C(g)) is not affected by changing the volume of container.
(IV) H2O() H2O(g)
on temperature increase, K of this reaction is increased.
p

Tick the correct statement(s)

(A) (I) (B) (II) (C) (III) (D) (IV)
Ans (A)
(I) : P  n on P
n

V V
(II) : P  on , equation shifts in a direction in which no. of moles of gases
(III) : KP = (PB) (PC) (constant at constant temp)
(IV) : H2O() H2O(g) H = + ve
on T  forward reaction.

11 CuSO4 . 5H2O(s) CuSO4(s) + 5H2O(g) Kp = 10–10 (atm). 10–2 moles of CuSO4 . 5H2O(s) is taken in
1
a 2.5L container at 27°C then at equilibrium [Take : R = litre atm mol–1 K–1]
12
(A) Moles of CuSO4 . 5H2O left in the container is 9 × 10–3
(B) Moles of CuSO4 . 5H2O left in the container is 9.8 × 10–3
(C) Moles of CuSO4 left in the container is 10–3
(D) Moles of CuSO4 left in the container is 2 × 10–4
Ans (B, D)
5 PV 102  2.5
10–10 atm5 = PH2O  PH2O = 10–2 atm. n= = = 10–3
RT 1
 300
12
12 Solid ammonium carbamate, NH4CO2NH2 (s), dissociates into ammonia and carbon dioxide when it
evaporates as shown by
NH4CO2NH2(s) 2NH3(g) + CO2(g)
At 25ºC, the total pressure of the gases in equilibrium with the solid is 0.116 atm. If 0.1 atm of CO 2 is
introduced after equilibrium is reached then :
(A) Final pressure of CO2 will be less than 0.1 atm
(B) Final pressure of CO2 will be more than 0.1 atm
(C) Pressure of NH3 will decrease due to addition of CO2
(D) Pressure of NH3 will increase due to addition of CO2
Ans (B, C)
The pressure of NH3 will decrease due to addition of CO2 (backward, shifting Le-chatelies’s principle).
The pressure of CO2 will be more than 0.1 atm.

13 1 mole each of N2(g) and 2(g) are introduced in a 1L evacuated vessel at 523K and equilibrium
N2(g) + 2(g) 2NO (g) is established. The concentration of NO(g) at equilibrium :
(A) Changes on changing volume of the vessel.
(B) Changes on changing temperature.
(C) Changes on changing pressure.
(D) Remains same even when a platinum gauze is introduced to catalyse the reaction.
Ans (A, B, C, D)
N2(g) + 2(g) 2NO (g)
(A) For changing pressure volume has to be changed, though number of moles of NO(g) do not get
changed but its concentration will get changed.
(B) Temperature change will change KP and hence concentration.
(C) Volume change will change concentration, not the number of moles.
(D) Catalyst does not change equilibrium concentrations.

14 138 gm of N2O4 (g) is placed in 8.2L container at 300 K. The equilibrium vapour density of mixture was
found to be 30.67. Then (R = 0.082 L atm mol–1 K–1)
(A)  = degree of dissociation of N2O4 = 0.25
(B) Kp of N2O4 2NO2(g) will be 9 atm.
(C) Total pressure at equilibrium = 6.75 atm
(D) The density of equilibrium mixture will be 16.83 gm/litre.
Ans (B, C, D)
N2 O 4 2NO2
t=0 a 0
t a(1 –) 2a
46
vapour density = = 30.67
1 
so 1 +  = 1.5 = 0.5 = 50 %
1.5  1.5  0.082  300
Total pressure = = 6.75 atm
8.2
42 138
so Kp = P = 9 atm and for density of mixture = gm/L = 16.83 gm/L
1  2 8.2
15 Consider two equilibrium 2Cl2(g) + 2H2O(g) 4HCl(g) + O2(g) and N2(g) + O2(g) 2NO(g)
simultaneously established in a closed vessel. When some amount of HCl is added at equilibrium,
which of the following statements is/are correct :
(A) Amount of N2 gas will increase.
(B) Amount of O2 gas will increase.
(C) Amount of O2 gas will decrease.
(D) Nothing can be said with certainty about amount of O 2 gas.
Ans (A, C)
When some amount of HCl is added to equilibrium, the first eq will shift in backward direction leading
to decrease in amount of O2. Then, the second eq. will shift in backward direction to increase the
amount of O2. Thus, amount of N2 gas will increase.

16 In a closed jar having water vapours in equilibrium with liquid suddenly all the vapours of the jar is
transferred to another identical jar and is subjected to compression. Assume initial temperature to be
the same and negligible volume occupied by the liquid water. Select the observation in the record jar.
(A) Liquid water will start forming in the jar
(B) Vapour will undergo gradual compression without any condensation.
(C) Temperature of the vapour will increases.
(D) Final pressure will be the same as initial pressure.
Ans (A, D)
liquid water will start forming in the jar by compression since temperature remain same so pressure
also remain same (P  T) .

17 If two gases AB2 and B2C are mixed the following equilibria are readily established
AB2(g) + B2C(g)  AB3(g) + BC (g)
BC(g) + B2C(g)  B3C2 (g)
It the reaction is started only with AB2 with B2C, then which of the following is necessarily true at
equilibrium:
(A) [AB3]eq = [BC]eq (B) [AB2]eq = [B2C]eq
(C) [AB3]eq > [B3C2]eq (D) [AB3]eq> [BC]eq
Ans (C, D)
Let reactions is started with a mole of AB2 and b mole of B2C
 AB2 (g) + B2C(g)  AB3(g) + BC(g)
a b 0 0
a–x b–x–y x x–y
BC(g) + B2C(g)  B3C2 (g)
x–y b–x–y y As y>x (why ??)
Clearly [AB3]eq> [B3C2]eq and [AB3]eq> [BC]eq

18 The following reaction attains equilibrium at high temperature.

N2(g) + 2H2O(g) + heat 2NO(g) + 2H2(g)
The yield of NO is affected by
(A) Increasing the nitrogen concentration (B) Decreasing the hydrogen concentration
(C) Compressing the reaction mixture (D) None of these
Ans (A, B, C)
 As concentration of reaction (gaseous) are increased at equilibrium reaction will go in the forward
direction. Also above reaction is endothermic therefore increase in temperature will favour it.
Kp
19 For which reaction at 298 K, the value of is maximum and minimum respectively :
Kc

(A) N2O4 2NO2 (B) 2SO2 + O2 2SO3

(C) X + Y 4Z (D) A + 3B 7C
Ans (B, D)

20 For the equilibrium 2SO2(g) + O2(g) 2SO3(g), H = –198 kJ, the equilibrium concentration of SO 3
will be affected by
(A) doubling the volume of the reaction vessel
(B) increasing the temperature at constant volume
(C) adding more oxygen to the reaction vessel
(D) adding helium to the reaction vessel at constant volume
Ans (A, B, C)

21 AB(s) A(g) + B(g) Kp = 4, H = +ve

In a container, A (g) and B (g) are filled to partial pressure of 1 atm each. Now AB (s) is added (in
excess quantity). Which of the following is CORRECT ? (No other gas is present in container) :
(A) At equilibrium, the total pressure in the container is 4 atm.
(B) Equilibrium pressure decreases uniformly on increasing the volume by container.
(C) At equilibrium, the total pressure in the container is more than 4 atm, if temperature is increased.
(D) None of these
Ans (A, C, D)

22 Following two equilibria are established seperately in 2 different containers of unequal volume.
PCl5(g) PCl3(g) + Cl2(g)
COCl2(g) CO(g) + Cl2(g)
Now the containers are connected together by a thin tube of negligible volume.
Select incorrect statements. (Assume T constant)
(A) Degree of dissociation of both PCl5(g) & COCl2(g) will decrease
(B) Degree of dissociation of both PCl5(g) & COCl2(g) will increase
(C) Degree of dissociation of PCl5(g)may increase ; decrease or remain the same irrespective of
effect on degree of dissociation of COCl2(g).
(D) Degree of dissociation of PCl5(g) may increase, decrease or remain the same, but the effect
would be same as that on degree of dissociation of COCl2.
Ans (A, B, D)

SECTION - III : COMPREHENSION TYPE

Comprehension # 1
Le chatelier's principle
If a system at equilibrium is subjected to a change of any one of the factors such as concentration,
pressure or temperature, the system adjusts itself in such a way so as to minimise the effect of that
change.
 

Change of pressure : If a system in equilibrium consists of gases, then the concentrations of all the
components can be altered by changing the pressure. When the pressure on the system is increased,
the volume decreases proportionately. The total number of moles per unit volume will now be more
and the equilibirum will shift in the direction in which there is decrease in number of moles i.e.,
towards the direction in which there is decrease in volume.
Effect of pressure on melting point : There are two types of solids :
(a) Solids whose volume decreases on melting, e.g., ice, diamond, carborundum, magnesium nitride
and quartz.
Solid (higher volume) Liquid (lower volume)
The process of melting is facilitated at high pressure, thus melting point is lowered.
(b) Solids whose volume increase on melting, e.g., Fe, Cu, Ag, Au, etc.
Solid (lower volume) Liquid (higher volume)
In this case the process of melting becomes difficult at high pressure; thus melting point becomes
high.
(c) Solubility of substances : When solid substance are dissolved in water, either heat is evolved
(exothermic) or heat is absorbed (endothermic).
KCl + aq KCl(aq) – heat
In such cases, solubility increase with increase in temperature.
Consider the case of KOH; when this is dissolved, heat is evolved.
KOH + aq KOH(aq) + heat
In such cases, solubility decrease with increase in temperature.
(d) Solubility of gases in liquids : When a gas dissolves in liquid, there is decrease in volume.
Thus, increase of pressure will favour the dissolution of gas in liquid.
Effect of temperature : Le-Chatelier's principle predicts a system at equilibrium will tend to shift
in the endothermic direction when temperature is raised, for then energy is absorbed as heat and
the rise in temperature is opposed. Conversely, an equilibrium will shift in the exothermic direction
if the temperature is lowered, for then that energy is released and the reduction in temperature is
opposed.
Van't Hoff equation shows the dependence of equilibrium constant K on temperature as:
d H H 1
nK  or n K = constant – .
dT RT2 R T

23 A gas 'X' when dissolved in water heat is evolved. Then solublity of 'X' will increase
(A) Low pressure, high temperature (B) Low pressure, low temperature
(C) High pressure, high temperature (D) High pressure, low temperature
Ans (D)
Solublity of gas is favourable at high pressure and this process is exothermic hence solubility will be
more at low temperature.
24 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
Ans (C)
 Since density of gold decreases after melting therefore it is favourable at low pressure and high
temperature.
1 1
25 For the reaction N (g) + O2(g) NO(g)
2 2 2
If pressure is increased by reducing the volume of the container then
(A) Total pressure at equilibrium will change
(B) Concentration of all the component at equilibrium will not change
(C) Concentration of all the component at equilibrium will remain same
(D) Equilibrium will shift in the forward direction
Ans (A)
1
26 The plot of log K against is a straight line with positive slope (K being the equilibrium constant of a
T
reaction), which of the following is then correct ?
(A) The reaction is endothermic in nature
(B) The reaction will be exothermic in nature
(C) The reaction goes to farther extent on raising the temperature
(D) None of these
Ans (B)
1
Since the slope of the straight line graph between logK and is positive, Hreaction would be negative,
T
i.e., the forward reaction would be exothermic.

Comprehension # 2
For certain substances such as ammonium chloride, nitrogen peroxide, phosphorus pentachloride,
etc. the measured densities are found to be less than those calculated from their molecular formula.
The observed densities decrease towards a limit as the temperature is raised. This is due to the
splitting of the molecules into simpler ones. The process is reversible and is called thermal
dissociation.
Examples : NH4Cl NH3 + HCl 2 2
N2 O 4 2NO2 PCl5 PCl3 + Cl2
With increase in the number of molecules, the volume increases (pressure remaining constant) and,
in consequence, the density decreases. As the temperature rises, more and more dissociation takes
place, and when practically complete dissociation occurs the density reaches its lowest limit.
The extent of dissociation, i.e., the fraction of the total number of molecules which suffers dissociation
is called the degree of dissociation. Gas density measurements can be used to determine the degree
of dissociation. Let us take by general case where one molecule of a substance A splits up into n
molecule of A on heating; i.e.,
An (g) n A (g)
t=0 a 0
x
t = teq a–x n.x  =  x = a.
a
a–a na
Total no. of moles = a – a  + n a 
= [1 + (n – 1)] a
 * Observed molecular weight or molar mass of the mixture
MAn
Mmixture = , MAn = Molar mass of gas An
[1  (n  1)]

27 A sample of mixture of A(g), B(g) and C(g) under equilibrium has a mean molecular weight (observed)
is 80.
The equilibrium is A(g) B(g) + C(g)
(mol. wt. = 100) (mol. wt. = 60) (mo. wt. = 40)
Find the degree of dissociation  for A(g).
(A) 0.25 (B) 0.5 (C) 0.75 (D) 0.8
Ans (A)
A(g) B(g) + C(g)
Mth
MOb =
M  (n  1) 
100
80 =
1 
1
= = 0.25
4

28 If the total mass of the mixture in the above case is 300 gm, the moles of C(g) present are.
1 4 3
(A) mole (B) mole (C) mole (D) None
4 3 4
Ans (C)
mols of C = a
300 3
where a = moles of ‘A’ = moles of C = 3 × 0.25 = .
100 4

29 The Kp for the reaction N2O4 2NO2 is 640 mm at 775 K. The percentage dissociation of N 2O4 at
equilibrium pressure of 160 mm is :
(A) 80 % (B) 30 % (C) 50 % (D) 70%
Ans (D)
N2O4 2NO2
Mole before equilibrium 1
Mole at equilibrium (1 – x) 2x
n
4x 2
 P 
Kp = ×
1  x    n 
4x 2 160
640 =
1  x  (1  x)
4x2
4= or 1 – x2 = x2 or 2x2 = 1
(1  x)
x2 = 1/2 or x = 0.707 = 70.7%
D
30 x (degree of dissociation) varies with in the above reaction according to :
d

(A) (B) (C) (D)

 Ans (B)
D D
= 1 + (n – 1) x  = 1 + x [n = 2]
d d
which is a line with positive slope and X intercept = 1.
Dd
31 The equation  = is correctly matched for :
(n  1)d
(A) A nB/2 + nC/3 (B) A nB/3 + (2n/3)C
(C) A  (n/2)B + (n/4)C (D) A (n/2)B + C
Ans (B)
Dd D D
=  (n – 1)  = – 1 = 1 + (n – 1) 
(n  1)d d d
Hence one mole of reactant should produce total n moles of product.

SECTION - IV : MATRIX -MATCH LIST TYPE

32 Match the following :

List-I (Assume only reactant were present initially) List-II

(P) For the equilibrium NH4(s) NH3(g) + H(g), (1) Forward shift
if pressure is increased at equilibrium

(Q) For the equilibrium N2(g)+ 3H2(g) 2NH3(g) (2) No shift in equilibrium
volume is increased at equilibrium

(R) For the equilibrium H2O(g) + CO(g) H2(g) + CO2 (g) (3) Backward shift
inert gas is added at constant pressure at equilibrium

(S) For the equilibrium PCl5 PCl3 + Cl2 (4) Final pressure is more than
Cl2 is removed at equilibrium. initial pressure
Code
(P) (Q) (R) (S)
(A) 3 3 2 1
(B) 2 3 4 1
(C) 4 2 1 3
(D) 1 2 3 4
Ans (A)
(P) ng is +ve so as P is increased, backward shifting will take place. Total pressure even after shifting
will remain same.
(Q) ng is –ve so as V is increased, backward shifting will take place. But Pfinal< Pinitial.
(R) No change but Pfinal< Pinitial as volume has increased.
(S) Forward shifting will take place and Pfinal< Pinitial.
33 Match the following.
List-I List-II
Reaction Degree of dissociation in terms
(Homogeneous gaseous phase) of equilibrium constant
(P) A(g) + B(g) 2 C(g) (1)  k  1  k 
(Q) 2 A (g) B(g) + C(g) (2)  k  2  k 
(R) A(g) + B(g) C(g) + D(g) (3) 2 k 1  2k 
A B 2 k
(S) AB(g) (g) + (g) (4)
2 2 1 2 k
Code
(P) (Q) (R) (S)
(A) 1 3 2 4
(B) 2 4 1 3
(C) 1 2 3 4
(D) 4 3 2 1
Ans (B)
34 List-   List-
(P) N2 + 3H2(g) 2NH3(g) (t = 300ºC) (1) n > O
(Q) PCl5(g) PCl3(g) + Cl2(g) (t = 50ºC) (2) Kp< Kc
(R) C(s) + H2O CO(g) + H2(g) (3) Kp not defined
(S) CH3COOH() + C2H3OH ()
CH3COOC2H5() + H2O() (4) Pinitial> Peq.
Code
(P) (Q) (R) (S)
(A) 2 4 1 3
(B) 2,4 1 1 3
(C) 2 1 3 4
(D) 4 2 1 3
Ans (B)

SECTION - V : INTEGER TYPE

35 NH3 is heated initially at 15 atm from 27ºC to 127ºC at constant volume. At 127ºC equilibrium is
established. The new pressue at equilibrium at 127ºC becomes 30 atm for the reaction 2NH 3(g)
N2(g) + 3H2(g) . Then find the % of moles of NH3 actually decomposed.
Ans (50)
2NH3 N2 + 3H2
a 0 0
a - 2x x 3x
P1 P2 15 P a  2x 30
  = 2  P2 = 20 atm. Now 
T1 T2 300 400 a 20
1 2x
2a + 4x = 3a x = a. % of NH3 decomposed = × 100 = 50%
4 a
36 The equilibrium constant for the reaction Br2() + C2(g) 2Br C(g) at 27°C is kp = 1 atm. In a
closed container of volume 164 L initially 10 moles of C2 are present at 27ºC.
What minimum mole of Br2() must be introduced into this container so that above equilibrium is
maintained at total pressure of 2.25 atm. Vapour pressure of Br 2() at 27ºC is 0.25 atm. Assume that
volume occupied by liquid is negligible. [R = 0.082 L atm mole–1 K–1, Atomic mass of bromine = 80].
Ans (5)
To maintain the mentioned equilibrium there must be some (negligible) mass of Br 2() at equilibrium
so there will be an equilibrium
Br2 () Br2 (g) Kp = 0.25 atm
So some Br2 () will be required for this conversion (into vapour)
moles of Br2 () required for above equilibrium
PV (0.25 atm) (164 L) 5
n= = 1 1 
= moles
RT (0.082 Latm mole K )(300K) 3
Now for equilibrium
Br2 () + Cl2 (g) 2BrCl (g)
t=0 x 10 0
at eq. ~0 10 – x 2x Total gaseous moles = (10 + x)
{Let x be moles of Br2 () required just to maintain above equilibrium}
we have PCl2 + PBrCl = 2 atm
10  x  2x 
so PCl2 = . (2atm) ; PBrCl =   (2 atm)
10  x  10  x 
2
PBrCl 4x2 (10  x)
so Kp = = . (2 atm)
PCl2 (10  x)2 (10  x)
8x2 10
 = 18x2 = 100 – x29x2 = 100 sox =
100  x 2 3
Hence total moles of Br2() required to maintain both of above equilibria
5 10 15
= + = = 5 moles
3 3 3

37 Following two equilibria are established on mixing two gases A2 and C.

(i) 3A2 (g) A6 (g) KP = 1.6 atm–2
(ii) A2 (g) + C(g) A2C (g)
If A2 and C are mixed in 2 : 1 molar ratio, calculate the equilibrium partial pressure of A 2, C, A2C and
KP for the reaction (ii). Given that the total pressure to be 1.4 atm and partial pressure of A 6 to be 0.2
atm at equilibrium.
Give your answer multiply by 10.
Ans (15)
3A2 (g) A6 (g); KP = 1.6 atm–2
PA 2
KP = 1.6 =
(PA 2 )3

3 0.2
PA2 = = 0.5 atm
1.6
Also pressure of A2 used for the formation of A6 = 0.6 atm
 For A2 (g) + C(g) A2C (g)
t=0 2P P 0
At eq. 2P – P – 0.6
1
P–P 1
P1
Also for 3A2 (g) A6 (g)
t=0 2P 0
At eq. 2P – P – 0.6
1
0.2
2P – P – 0.6 = 0.5
1

(since PA2 at eq. is 0.5 for similataneous equilibria)

Also pressure of A2 + C + A2C + A6
= (2P – P1 – 0.6) + (P – P1) + P1 + 0.2 = 1.4
0.5 + P + 0.2 = 1.4
P = 0.7 atm
 2P – P1 – 0.6 = 0.5
 P1 = 2 × 0.7 – 0.6 – 0.5
P1 = 0.3 atm
 PA2 = 0.5 atm, PC = 0.7 – 0.3 = 0.4 atm, PA2C = 0.3 atm Ans.
Also KP for A2 (g) + C(g) A2C (g)
PA 2C 0.3
KP = = = 1.5 atm–1
PA 2  PC 0.5  0.4

38 Two solids AB and CB2 are simultaneously heated in a closed vessel to attain equilibrium.
AB(s) A(g) + B(g) ... (1)
CB2(s) C(s) + 2B(g) ... (2)
KP for (1) and (2) reaction are 4.8 × 10–6 and 5.76 × 10–6. If partial pressure of A at equilibrium is 2 ×
10–x, find x.
Ans (3)

39 For given simultaneous reaction :

X(s) A(g) + B(s) + C(g) KP1 = 500 atm
Y(s) D(g) + A(g) + E(s) KP2 = 2000 atm

If total pressure = x, then write your answer after dividing by 25.

Ans (4)
X(s) A(g) + B(s) + C(g)
p1 + p2
Y(s) D(g) + A(g) + E(s)
p2 p2 + p1
(p1 + p2)p1 = 500 ...(i)
(p1 + p2)p2 = 2000 ...(ii)
(i)
eq.
(ii)
p1 1
=  p2 = 4p1
p2 4
pT = (p1 + p2) + p1 + p2 = 10 + 40 + 10 + 40 = 100 atm
pT 100
= = 4 atm
25 25
40 If a mixture 0.4 mole H2 and 0.2 mole Br2 is heated at 700 K at equilibrium, the value of equilibrium
constant is 0.25 × 1010 then find out the ratio of concentrations of (Br 2) and (HBr) (Report your answer
Br2
as × 1011)
HBr
Ans (80)
H2 + Br2 2HBr
t=0 0.4 0.2 –
t = teq. 0.2 y 0.4
= negligible = y
1 0.4  0.4
 × 1010 =  y = 3.2 × 10–10
4 0.2  y
Br2 3.2
× 1011 = × 10–10 × 1011 = 80
HBr 0.2

41 If 1 mole of CH3COOH and 1 mole of C2H5OH are taken in 1 litre flask, 50% of CH3COOH is
converted into ester as ;
CH3COOH() + C2H5OH() CH3COOC2H5() + H2O()
There is 33% conversion of CH3COOH into ester, if CH3COOH and C2H5OH have been taken initially
in molar ratio x : 1, find x.
Ans (2)
CH3COOH() + C2H5OH() CH3COOC2H5() + H2O()
1 – 0.5 1 – 0.5 0.5 0.5
0.5  0.5
So, KC = =1
0.5  0.5
Now let a moles of CH3COOH and b moles of C2H5OH are taken :
a a a a
a– b–
3 3 3 3
(a / 3)  (a / 3)  a a a 2
So, KC = or 2  b   = or 2b = a or =
 a  3  3 b 1
2a / 3   b  
 3

42 Solid ammonium carbamate (NH2COONH4) was taken in excess in closed container of volume 5 Litre
according to the following reaction NH 2COONH4(s) 2NH3(g) + CO2(g). If equilibrium partial
3
pressure of ammonia is 4 atm, it’s equilibrium constant Kp is x atm . If the above equilibrium mixture is
transferred to another vessel of volume 10 Litre, total equilibrium pressure is y atm. Calculate the
value of (x + y). Assuming temperature is constant during the whole experiment.
Ans (38)
NH2COONH4(s) 2NH3(g) + CO2(g).
At eq. PNH3 = 4 atm
PCO2 = 2 atm
2 3
Kp = PNH3 × PCO2 = 32 atm .

Therefore x = 32 & y = 6  x + y = 38.

43 Find the percentage dissociation of ammonia into N 2 and H2 if the dissociation is carried out at
constant pressure and the volume at equilibrium is 20% greater than initial volume. (Initially, equal
moles of NH3 and N2 are present with no hydrogen)
Ans (40)
 2NH3 N2 + 3H2
t =0 a a 0
a 3a
teq a(1 – ) 2  a 2
3a
nT = 2a + a = a(2 + ) = 2a + 2 × 2a

2 +  = 2.4
 = 0.4  40%

44 A2B(g) is introduced in a vessel at 1000 K. If partial pressure of A2B(g) is 1 atm initially and KP for
–6
reaction A2B(g) 2A(g) + B(g) is 81 × 10 then calculate percentage of dissociation of A2B.
Ans (3)
A2B(g) 2A(g) + B(g)
at t = 0 1 0 0
at eq. (1–x) 2 
 (partial pressure)
Hence, (1 – )  1
(2x)2  () –6
= 81 × 10
(1)
–2
= 3 × 10
–2
percentage of dissociation = 3 ×10 × 100 = 3%

45 Consider the following two equilibrium established together in a closed container

A(s) 2B(g) + 3C(g) ; KP1
A(s) 3D(g) ; K P2

Starting with only A(s), molar ratio of B(g) & D(g) at equilibrium is found to be in a ratio 1 : 6 determine
K P2
.
8K P1

Ans (8)
PB : PD = 1 : 6 Let the partial pressure of Beq. be
3
2  3P 
KP1 = (P0)  0 
 2 
3
K P2 = (6P0)
KP2 63
= 3
= 64
KP1 3
2
 
K P2 64
= =8
8K P1 8

46 0.1 mol each of ethyl alcohol and acetic acid are allowed to react and at equilibrium the acid was
exactly neutralised by 100 ml of 0.75 N NaOH. If no hydrolysis of ester is supposed to have undergo
–1
find KC in terms (x)10 .
Ans (1)
CH3COOH + C2H5OH CH3COC2H5 + H2O
At t = 0 0.1 0.1 0 0
 At equilibrium 0.1–x 0.1–x x x
Meq of acetic acid left = Meq. of NaOH used = 100 × 0.75 = 75
Milimoles of acetic acid left = 75 ( monobasic)
Moles of acetic acid left = 0.075  0.1 – x = 0.075  x = 0.025
x2 (0.025)2 –2
KC = 2
= 2
= 0.111 = 1.11 × 10
(0.1– x) (0.075)

SECTION - VI : (3 COLUMN) MATCHING TYPE

Answer 47, 48 and 49 by appropriately matching the information given in the three columns of
thefollowing table.
If a change is applied to the system at equilibrium, then equilibrium will be shifted in that direction in which
it can minimise the effect of change applied and the equilibrium is established again under new conditions.
This is known as Le Chatelier's Principle.In column-1 some reactions are given at equilibrium, assuming
that initially only reactants were present.

Column-1 Column-2 Column-3

If pressure is increased at
N2(g) + 3H2(g)  2NH3(g)
(I) (i) ng> 0 (P) equilibrium then it shifts in
(T = 300°C)
forward direction.
If volume is increased at
PCl5(g)  PCl3(g) + Cl2(g)
(II) (ii) Kp< KC (Q) equilibrium then no shift in
(T = 50°C)
equilibrium
If inert gas is added at
(III) constant pressure at
C(s) + H2O(g)  CO(g) + H2(g) (iii) KP not defined (R)
) equilibrium then it shifts in
backward direction.

CH3COOH() + C2H5OH() If inert gas is added at

(IV) (iv) Pinitial >Peq (S) constant volume then no
 CH3COOC2H5() + H2O()
shift in equilibrium.

47 The only incorrect combination is :

(A) (I) (ii) (P) (B) (I) (iv) (R) (C) (III) (i) (S) (D) (IV) (ii) (Q)
Ans (D)

48 The only correct combination is :

(A) (I) (iii) (R) (B) (II) (ii) (P) (C) (IV) (ii) (S) (D) (III) (iv) (R)
Ans (C)

49 The only correct combination is :

(A) (II) (i) (S) (B) (IV) (i) (Q) (C) (III) (iv) (P) (D) (I) (ii) (Q)
Ans (A)