EQUILIBRIUM

MULTIPLE CHOICE QUESTIONS

1. 15 moles of H2 and 5.2 moles of I2 are mixed and allowed

to attain equilibrium at 500°C.
At equilibrium, the concentration of HI is found to be 10
moles. The equilibrium constant for the formation of HI is:
(a) 50 (b) 15
(c) 100 (d) 25
Sol. (a)
H2 + I2 2HI
Initially 15 5.2 0
At equilib. 15–x 5.2–x 2x
given2x = 10
[HI]2 102
Hence Kc    50 .
[H 2 ][ I 2 ] 10  0.2

2. At temperature T, a compound AB2(g) dissociates

according to the reaction
2AB2(g) 2AB(g) + B2(g)
With degree of dissociation , which is small compared
with unity. The expression of Kp, in terms of  and total
pressure PT is
3 2
(a) PT
2
(b) PT
3

1
 3 2
(c) PT
3
(d) PT
2

Sol. (a)
2AB2(g) 2AB(g) + B2(g)
(1–)  2 (At equilibrium)
2
 2  PT    PT 
   
 2     (2  )  3
Kp = 2
= PT
 2(1  )PT  2
 
 2 

3. 40% of a mixture of 0.2 mole of N2 and 0.6 mole of H2

react to give NH3 according to the equation N2(g) + 3H2(g)
2NH3(g) at given temperature and pressure. Then the
ratio of the final volume to the initial volumes of gases are
as
(a) 4:5 (b) 5:4
(c) 7:10 (d) 8:5
Sol. (a)
N2(g) + 3H2(g) 2NH3(g)
(0.2 – x) (0.6 – 3x) 2x
4x
Hence,  0 .4
0.8

x = 0.08
Total number of moles at equilibrium
= 0.2 – x + 0.6 – 3x + 2x
= 0.8 – 2x = 0.8 – 2  0.08= 0.8 – 0.16 = 0.64

2
 Vf n f 0.64 8 4
   
Vi ni 0.8 10 5

4. pH of a 0.1 M monobasic acid solution is found to be 2. Its

osmotic pressure of this solution at a temperature of ‘T(K)’
is
(a) 0.1 RT (b) 0.11 RT
(c) 1.1 RT (d) 0.01 RT
Sol. (b)
pH = 2  [H+] = 0.01 M = C = 0.1
  = 0.1
 i = 1 +  = 1.1
 = i Vn RT = 1.1  0.1 RT = 0.11 RT.

5. What is the approximate OH  ion concentration of a 0.150

M NH3 solution?
(Kb = 1.75  10–5)
(a) 2.62  10–6 (b) 4.6  10–6
(c) 1.62  10–3 (d) 3.6  10–3
Sol. (c)

NH 3  H 2 O NH 4  OH 
0.15 (1 ) 0.15 0.15

0.15 0.15
1.75  10 5   0.15 2 ;   0.011
0.15 (1  )

[OH–] = 0.15 = 1.6  10–3

3
6. Carbonic acid, H2CO3, is a diprotic acid for which K1 = 10–
7
and K2 = 10–11. Which solution will produce a pH closest
to 9?
(a) 0.1 M H2CO3
(b) 0.1 M Na2CO3
(c) 0.1 M NaHCO3
(d) 0.1 M NaHCO3 and 0.1 M Na2CO3
Sol. (c)
pH 
1
2
 1

pK a1  pK a 2  [7  11]  9 .
2

7. When pure water is saturated with CaCO3 and CaC2O4, the

concentration of calcium ion in the solution under
equilibrium is 8.426 × 10–5 M. If the ratio of the solubility
product of CaCO3 to that of CaC2O4 is 2.087, what is the
solubility product of CaCO3 in pure water?
(a) 4.80 × 10–8 (b) 9.60 × 10–9
(c) 9.60 × 10–8 (d) 4.80 × 10–9
Sol. (d)
K sp1 [CaCO 3 ] x
 2.087 
K sp 2 [CaC 2O 4 ] y

CaCO3 Ca 2  CO 32
xy x

CaC2O4 Ca 2  C 2O 4 2
y x y

K sp1 = (x + y) x
K sp 2 = (x + y) y

4
 (x + y) = 8.426 × 10–5 so Ksp1 = 4.8 × 10–9.

8. The selfionisation constant of NH3 at 50°C is given by

K NH3  [ NH 4 ] [ NH 2 ]  1030.

How many NH 2 ions are present per cm3 of pure liquid

NH3? (Assume Avogadro’s number = 6  1023)
(a) 6  106 (b) 6  105
(c) 6  105 (d) 6  106
Sol. (b)
2NH3(l) NH4+ + NH 2
K NH3 = [ NH 4 ] [ NH 2 ] = [ NH 2 ]2 = 1030 M2
[ NH 2 ] = 1015 M
10 15
NH 2 ions per cm3 of liquid NH3 = 1000
 6  10 23 = 6  10 5 ions/cm 3 .

9. A buffer solution is prepared by mixing 10 ml of 1.0 M

acetic acid and 20 ml of 0.5 M sodium acetate and then
diluted to 100 ml with distilled water. If the pKa of
CH3COOH is 4.76, what is the pH of the buffer solution
prepared?
(a) 5.21 (b) 4.76
(c) 4.34 (d) 5.21
Sol. (b)
[Salt ]  20  0.5 
pH  pK a  log  4.76  log   4.76
[Acid]  10 

5
10. The pKb value of ammonium hydroxide is 4.75. An
aqueous solution of ammonium hydroxide is titrated with
HCl. The pH of the solution at the point where half of
ammonium hydroxide has been neutralised will be
(a) 9.25 (b) 8.25
(c) 7.50 (d) 4.75
Sol. (a)
When half of the ammonium hydroxide is neutralised a
base buffer is formed.
[Salt ]
pOH  pK b  log = 4.75 + log(1)
[Base]

pH = 9.25

11. The pKb of cyanide ion is 4.7. The pH of a solution

prepared by mixing 2.5 moles of KCN and 2.5 moles of
HCN in water and making total volume upto 500 ml is
(a) 9.30 (b) 7.30
(c) 10.30 (d) 8.30
Sol. (a)
Above solution is an acidic buffer solution and [Salt]
= [Acid]
[Salt ]
Therefore, pH = pKa + log
[Acid]

or pH = pKa
pKa of HCN = 14  pKb = 14  4.7 = 9.3.

6
12. A buffer solution is to be made by using conjugate acid
base pair. Which of the following pair will be most suitable
for preparing a buffer solution having pH = 7.1? (Given:
log 2 = 0.3)
Acid Conjugate base Ka
(a)H2CO3 HCO 3 8 × 107
(b) NH 4 NH3 8 × 1010
(c)C5H5NH+ C5H5N 8 × 106
(d)NaH2PO4 Na2HPO4 8 × 108
Sol. (d)
For preparing a buffers solution of given pH, we prefer to
choose an acid/base having pKa/pKb value as close as the
pH value.
These are all acidic buffers, so pH is given by pH = pKa +
[Salt ]
log
[Acid]

In (d), pKa = log Ka = log(8 × 108)= 8  3 log 2

= 8  0.9 = 7.1.

13. A reaction, A(g) + 2B(g) 2C(g) + D(g) was studied

using an initial concentration of B which was 1.5 times that
of A. But the equilibrium concentrations of A and B were
found to be equal. The value of Kp for the equilibrium is
(a) 4 (b) 6
(c) 8 (d)12

7
Sol. (a)
A(g) + 2B(g) 2C(g) + D(g)
Initial conc. x 1.5x 0 0
At equilibrium x y 1.5x 2y 2y y
Given: x y = 1.5x2y ; y = 0.5x. Thus, at equilibrium
[A] = 0.5x [B] = 0.5x [C]
= x [D] = 0.5x
 Kc = Kp = ( x 2 ) (0.5 x)
(0.5 x) (0.5 x) 2
= 4.

14. In a system,
A(s) 2B(g) + 3C(g)
if the concentration of C at equilibrium is increased by a
factor of 2, it will cause the equilibrium concentration of B
to change to
(a) two times the original value
(b) one half of its original value
(c) 2 2 times its original value
1
(d) times the original value
2 2

Sol. (d)
A(s) 2B(g) + 3C(g)
Kp = p 2B . p 3C …(i)
Kp = p'B2 . (2p C ) 3 …(ii)
 ppB = p 3C
= 1
.
B 8p 3C 2 2

8
15. At 298 K, the equilibrium between N2O4 and NO2 is
represented as: N2O4(g) 2NO2(g). If the total pressure
of the equilibrium mixture is P and the degree of
dissociation of N2O4(g) at 298 K is x, the partial pressure of
NO2(g) under these conditions is
 2x 
(a)  P (b) 2x P
1 x 
 2x  2
(c)  P (d) xP
1 x  3

Sol. (a)
N2O4(g) 2NO2(g)
1 x2x
Total moles nt = 1 x + 2x = 1 + x
 Mole fraction of NO2 gas, X NO2 =
2x
1 x
 2x 
 Partial pressure of NO2 =   P.
1 x 

16. If for the heterogeneous equilibrium CaCO3(s) CaO(s)

+ CO2(g), the equilibrium constant Kc = 1 M, at 1 atm what
would be the temperature of the reaction?
S o H o
(a) T = (b) T =
H o S o
H o G o
(c) T = (d) T =
G o H o
Sol. (b)
G° = H°  TS°
O = H°  TS°

9
 ΔH o
T = .
ΔS o

17. 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 given statements,
holds true regarding the equilibrium constant (Kp) and
degree of dissociation ()?
(a) neither Kp nor  changes
(b) both Kp and change
(c) Kp changes, but does not changes
(d) Kp does not change, but changes
Sol. (d)
For the reaction,
N2O4(g) 2NO2(g)
4a 2  2
Kc 
(a  a).V
…(i)
where ‘a’ is initial mole of N2O4
its degree of dissociation.
n
Also, K  K (RT)
p c

V
On reducing the volume of container to 2
L, initial
2a
concentration of N2O4 becomes V
. An increase in
concentration leads to more dissociation of N2O4 in order to

10
 have Kc constant, a characteristic constant for a given
reaction at a temperature.

18. The heat of reaction at constant volume for an endothermic

reaction in equilibrium is 1200 cal more than heat of
reaction at constant pressure at 300K. The ratio of Kp and
Kc
(a) 1.648  10–3 (b) 1.648  10–4
(c) 2.648  10–3 (d) 1.648  10–2
Sol. (a)
Heat of reaction at constant volume = E
Heat of reaction at constant pressure = H
Given E – H = 1200 cal.
We KnowH = E + PV
or H= E + ngRT
H  E
or ng= RT
 1200
  2
2  300

Now KP = KC (RT)n
KP
KC
 (0.0821 300) 2 = 1.648  10–3.

11
19. 5 mol PCl5 (g) and one mole N2 gas is placed in a closed
vessel. At equilibrium 20% of PCl5(g) decomposes and
total pressure in the container is found to be 1 atm. The KP
for the reaction PCl5(g) PCl3(g) + Cl2(g) is
1 1
(a) 24
atm (b) 4
atm

1 1
(c) 16
atm (d) 28
atm

Sol. (d)
n PCl  n Cl 2  P 1
PCl5 (g) PCl3 (g) + Cl2(g), KP  3
 N 
n PCl 5  
11 1 1
n Cl 2  1 , n PCl3  1 , n PCl5  4 , K P  ·  .
4 7 28

20. Consider the equilibrium A(g) + 2B(g) C(g) when the

reaction was carried out at 120°C the equilibrium
concentration of ‘A’ and ‘B’ were 3M and 4 M
respectively. When the volume of the vessel was doubled
and system allowed to reach equilibrium the concentration
of ‘B’ was found to be 3 M. The original concentration of
‘C’ is
(a) 4 (b) 16
(c) 9 (d) 8
Sol. (a)
A(g) + 2B(g) C(g)
[A]eq = 3 M ; [B]eq = 4 M.
Let [C]eq = xM

12

[C]eq x x
Kc = = = .
2
[ A ]eq [ B]eq 3  ( 4) 2 48

When the volume of vessel is doubled, reaction moves in

the backward direction.
Let the decrease in concentration of C be yM. At new
equilibrium
A(g) + 2B(g) C(g)
x
1.5 + y2 + 2y y
2

Given that 2 + 2y = 3  y = 1
2
= 0.5
 x -1
 
 2  x
Kc = =
(1.5  0.5) (3) 2 48

On solving, x = 4 M.

21. The vapour density of N2O4 at a certain temperature is 30.

What is the percentage dissociation of N2O4 at this
temperature?
(a) 53.3 % (b) 106.6%
(c) 26.7% (d) 48.6%
Sol. (a)
N2O4 2NO2
t = 0n
t = equilibrium n(1– ) 2n
Let vapour density at t = 0 is VD1 and at t = equilibrium is
VD2
M 28  64
VD 1    46
2 2

13
 (1  )92  (46)2
VD 2   30
2(1  )

2(1  ) 
92
= 3.0667  = 0.533
30
% dissociation = 53.3 %.

22. For the equilibrium NH4HS(s) NH3(g) + H2S(g), the

expression of Kp in terms of equilibrium pressure ‘p’ is
(a) Kp = 1 p (b) Kp = 1 p
2 4
1 2 1 2
(c) Kp = p (d) Kp = p
4 2

Sol. (c)
It is given that equilibrium pressure is ‘p’.
 PNH + 3
PH 2S = p
 PNH = 3
p
2
 PH S =
2
p
2
for the given reaction
Kp = p × p
2 2
p2
Kp = .
4

14
INTEGER TYPE QUESTIONS
23. A solution of HCOOH is titrated with KOH solution. When
half of the acid is neutralised, AgCN is added to make a
saturated solution. Calculate the solubility of AgCN in
milligram per 100 litres of solution. Ka (HCN) = 10–10, Ksp
(AgCN) = 10–16, Ka (HCOOH) = 10–4.
[Salt ] 1
Sol. pH of buffer = pKa + log  4  log  4
[Acid] 1
AgCN Ag+ + CN– x is solubility of AgCN
x
H+ + CN– HCN
10–4 x
10 4 [CN – ]
Hence,  10 –10
x

 [CN ] = 10 x = 10
– –6 –16

Ksp = x 10–6x
 x2 = 10–10  x = 10–5 M
Hence, the solubility of AgCN is 10–5 M = 134 mg / 100 L.

24. What volume in ml of 0.10 M sodium formate solution

should be added to 50 ml of 0.05 M formic acid to produce
a buffer solution of pH 4.1 pKa for formic acid is 3.80.
Sol. Let x ml of 0.10 M sodium formate be added.
 Moles of HCOONa added = 0.1 x × 103
Moles of HCOOH = 0.05 × 50 × 103 = 2.5 × 103
[HCOONa ] 0.1x  10 3
= = 0.04x.
[HCOOH ] 2.5  10 3

15
 For acidic buffer, pH = pKa + log [salt]
[acid]

4.1 = 3.8 + log 0.04x.

On solving, x = 50 ml.

25. 500 ml of 0.150 M AgNO3 solution is mixed with 500 ml

of 1.09 M Fe2+ solution and the reaction is allowed to reach
equilibrium at 25°C.
Ag+(aq) + Fe2+(aq) Fe3+(aq) + Ag(s)
For 25 ml of the equilibrium solution, 30 ml of 0.0833 M
KMnO4 were required for oxidation. Calculate the
approximate equilibrium constant for the reaction at 25°C.
Sol.
Ag+(aq) + Fe2+(aq) Ag(s) + Fe3+(aq)
No. of m moles initially 500 × 0.15 500 × 1.09 0 0
= 75 =545
M moles at equilib. 75 x 545 x x x
On titration of reaction mixture with KMnO4, only Fe2+
reacts with it.
2+
 Equivalents of Fe in 25 ml = Equivalents of KMnO4
(545  x) 3
 25  103  1 = 30 × 10 × 0.0833 × 5
1000
(545  x)  25
 12.5;
1000
545 x = 500;
x = 45

16
 45
[Fe 3 ] 45  1000
 Kc =  2
= 1000
(75  45) (545  45)
= = 3.0.
[Ag ] [Fe ] 30  500

1000 1000

26. An unknown volume and unknown concentration of weak

acid HX is titrated with NaOH of unknown concentration.
After addition of 10.0 cm3 of NaOH solution, pH of
solution is 5.7 and after the addition of 20.0 cm3 of NaOH
solution, the pH is 6.3. Calculate the pKa for the weak acid,
HX. (Given: antilog of 0.6  4)
Sol. Let the molarity and volume of HX be M1 and V1 ml
respectively while the molarity of NaOH be M2.
HX + NaOH  NaX + H2O
Initial millimoles M1V1 10M2  
After the addition M1V1 10M2 0 10 M2

of 10 c.c of NaOH
Since, weak acid HX and NaX are left after the reaction
they will constitute an acidic buffer.
 pH = pKa + log [Salt ]
[Acid]
10 M 2
5.7 = pKa + log …(1)
(M1V1  10M 2 )

Let V2 ml be the volume of NaOH required to neutralize

given HX completely.
 At equivalence point, M1V1 = M2V2
17
 M 1V1
V2 =
M2

Dividing the numerator and denominator of log term by

M2, we get
10M 2

 5.7 = pKa + M2
M1V1  10M 2
= pKa + log 10
…(2)
V2  10
M2

Similarly, after the addition of 20 c.c of NaOH, we have

6.3 = pKa + log 20
…(3)
V2  20

Subtracting equation (2) from equation (3)

6.3  5.7 = log 20
 log 10
V2  20 V2  10

0.6 = log  20 V  10 

 2 
 V2  20 10 
2(V2  10)
Taking antilog, 4 =
(V2  20)

 V2 = 30 ml.
Putting V2 in equation (2),
5.7 = pKa + log 10 = pKa + log 1
30  10 2
pKa = 5.7 + log 2 = 5.7 + 0.3 = 6.0.

27. Calculate the weight in mg of HCl added to 100 ml of 0.1

N BOH to have its pH = 6.6 and Kb = 6.25 × 108 ; Antilog
(7.4) = 3.98 × 108. (Assume there is no change in volume
on addition of HCl)

18
Sol. Let the mass of HCl added be x mg
BOH + HCl  BCl + H2O
x
Millimoles 10
36.5
10  x 0 x x
36.5 36.5 36.5

This constitutes basic buffer. For basic buffer, the [OH] is

given by
[OH] = Kb [BOH]
[BCl]
 365  x   36.5 
3.98 × 108 = 6.25 × 108 ×   
 36.5   x 
On solving, n = 223
 Weight of HCl required = 223 mg.

28. For gaseous reaction A + B C, the equilibrium

concentration of A and B at a certain temperature is 15 mol
litre–1 each. When volume is doubled the reaction has
equilibrium concentration of A as 10 mol litre–1. Calculate
concentration of C in original equilibrium.
Sol.
A + B C
Concentration at I equilibrium 15 15 a (volume
is V litre)
Concentration when V is doubled 15 15 a
2 2 2
(volume is 2V litre)
Since on increasing volume, pressure decreases and the
reaction proceeds in the direction where it shows an
increase in mole, i.e., backward reaction.

19
  15   15 
Concentration at II equilibrium   x   x
 2   2 
a 
  x
2 

15
 x  10 , x  5 ,
2 2
a 5
[ C]  2  2 
Now, K C   ..... (i) for equation (II)
[A][ B] 15 5  15 5 
 2  2   2  2 
[C] a
KC   ..... (ii) for equation (I) 
[A][ B] 15 15
KC are same
(a  5) / 2
 
a
,  a = 45 M
10 10 15 15

 Concentration of C at original equilibrium = 45 M.

29. N2O4 dissociates as, N2O4(g) 2NO2(g),

At 55°C and one atmosphere pressure % decomposition of
N2O4 is 50.3%. At what pressure and same temperature, the
equilibrium mixture has the ratio of N2O4 : NO2 as 1 : 8?
Express your answer in mm of Hg.
Sol. Case I. N2O4(g) 2NO2(g)
At equilibrium (1 x) 2x
(1  x) 2x
pN O =  P ; p NO = P
2 4
(1  x) 2
(1  x)
2
 2x 
  P
1 x  4x 2P
Kp = =
1 x  (1  x 2 )
  P
1 x 
Given, x = 0.503 and P = 1
Kp = 1.3548 atm
20
 Case II. N2O4 2NO2
(1 x) 2x
(1  x ) 1
Given, =
2x 8

x = 0.8
Let the new pressure be P atm.
4x 2P 4  0 .8  0 .8  P
Kp = = = 1.3548.
(1  x )
2 (1  0.8) (1  0.8)

P = 0.1905 = 0.1905 × 760 mm ~ 145 mm.

30. At 700 K, CO2 and H2 reacts to form CO and H2O. For this
equilibrium reaction, Kc is 0.11. A mixture of 0.45 mole of
CO2 and 0.45 mole of H2 is heated to 700 K. When
equilibrium has been reached, another 0.34 mole of CO2
and 0.34 mole of H2 are added to the reaction mixture. Find
the millimoles of CO2 at the new equilibrium.
Sol. CO2(g) + H2(g) CO(g) + Kc = 0.11

H2O(g)
t=0 0.45 0.45 0 0
At equilibrium 0.45 x 0.45 
x x x
x2
= 0.11
(0.45 - x) 2
x
= 0.11 = 0.33
0.45 - x
 x = 0.11
 At equilibrium:
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Moles of CO2 = moles of H2 = 0.45 x = 0.34
Moles of CO = moles of H2O = x = 0.11
After adding CO2 and H2,
CO2(g) + H2(g) CO(g) +
H2O(g)
t=0 0.34 + 0.34 0.34 +
0.34 0.11 0.11
At new equilib. 0.68  y 0.68 
y 0.11 + y 0.11 + y
2
 0.11  y 
  = 0.11
 0.68  y 

 y = 0.086.
At new equilibrium:
Moles of CO2 = moles of H2 = 0.68  y = 0.593
 Millimoles of CO2 at the new equilibrium = 593.

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