CHEMICAL EQUILIBRIUM 1

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I [Only One Correct Option] dx
At equi.  0 ,since no change in conc. of any reactant
dt
1. A vessel at 1000 K contains CO2 with a pressure of or product w.r.t. time
0.5 atm. Some of the CO2 is converted to CO on addition dx
of graphite. If the total pressure at equilibrium is 0.8 atm,  (2  103 )[A][B]  [1 10 2 ][C]  0
the value of K is : dt
(a) 0.18 atm (b) 1.8 atm [C]
(c) 3 atm (d) 0.3 atm  
at equi. conc. K eq 
[A][B]
Ans: (b)
Sol: CO g   C(s)  2CO(g) 2  103
=  20
0.5 atm 0 1 102
At equi. 0.5 - P 2P
Total pressure  0.5  P + 2P  0.8 4. Equilibrium constant Kc for the following reaction at 800K
is, 4.
Thus P  0.3
1 3
P2  0.6
2
NH3  N2  H2 ;
KP  CO   1.8atm 2 2
PCO2 0.2 The value of KP for the following reaction will be :
N 2  3H 2  2NH 3
2. The equilibrium reaction : 2AB(aq)  2A(aq) + B2 (g) 2
has an equilibrium constant equal to 1.28. If the  800R 
(a)   (b) 16 × (800R)2
concentrations of AB and A are 5 mol/L and 4 mol/L  4 
respectively, what is [B2] ? 2
(a) 0.50 M (b) 1.60 M  1 
(c) 2.00 M (d) 2.84 M (c)   (d) (800R)1/2 4
 4  800R 
Ans: (c)
Ans: (c)
Sol: 2AB  2A  B2
1 3
5 4 x Sol: For NH3  N2  H2 ;
2 2
(4) 2  x 1 3
K
(5) 2
 1.28
Kc 
 N 2 2  H 2 2 4
 NH 3 
16 For N 2  3H 2  2NH 3 ;
x  1.28
25 2 2
25  1.28  1  1
x 2 K 
1
c   
16  KC  4
2  1 3
K p  K c (RT)
1
 K 1c (RT) 2
3. For a reversible reaction : A + B C 2 2
1  1   1 
    
 dx  4 2  RT  4  80 0 R
  = 2.0 × 103 L mol–1 s–1 [A] [B] – 1.0 × 102 s–1 [C]  
 dt 
where x is the amount of ‘A’ dissociated. The value of 5. N2O4 2NO2, Kc = 4. This reversible reaction is studied
equilibrium constant (Keq) is : graphically as shown in the given figure. Select the correct
(a) 10 (b) 0.05 statement out of I, II and III.
(c) 20 (d) Can’t be calculated I : Reaction quotient has maximum value at point A
Ans: (c) II : Reaction proceeds left to right at a point when [N2O4]
Sol: = [NO2] = 0.1 M
ABC III : Kc = Q when point D or F is reached.
dx
 (2 103 )[A][B]  (1102 )[C]
dt
where x is amount of A dissociated.
 CHEMICAL EQUILIBRIUM 2
of complex depends upon charge density thus B is more
A stable than A.
D E
NO2
8. Consider the reaction
Concentration

NaBr(aq)+H 2SO 4 (aq)  NaHSO 4 (aq)+HBr(aq) .

C –2
The equilibrium constant is 8.3 × 10 . If the equilibrium
N2O4 concentrations of NaBr, H2SO4 and NaHSO4 are 6.0 M, 9.0
F G M and 3.0 M respectively, what is the molarity of HBr ?
–2 –1
(a) 1.8 × 10 M (b) 6.7 × 10 M
0 1
(c) 1.5 × 10 M (d) 3.6 × 10 M
B Time Ans: (c)
(a) I, II (b) II, III
Sol: NaBr(aq)  H 2 SO 4 (aq)  NaHSO 4 (aq)  HBr(aq)
(c) II (d) I, II, III
Ans: (b) At Eq 6.0M 9.0M 3.0M xM
Sol: I is incorrect as Q is maximum at the point where product 3 x
is maximum. K  8.3  10 2 
69
(0.1)2 102 8.3  54
II Q   1  101  K c So yes left to right x  102  1.5  100 M
0.1 10 3
motion
III KC = Q at D or F because D and F represent equilibrium 9. For the all gas reaction at 1000 K : 2HI  H2 + I2,
reaction K = 0.0344. If you were to begin with 8.0 M of HI in a fixed
II and III are correct. volume container, what would be the equilibrium
concentration of H2 ?
6. I2 + I – I3 (a) 1.10 M (b) 0.48 M
This reaction is set-up in aqueous medium. We start with (c) 5.8 M (d) 2.92 M
1 mol of I2 and 0.5 mol of I– in 1L flask. After equilibrium is Ans: (a)
reached, excess of AgNO3 gave 0.25 mol of yellow ppt.
Equilibrium constant is : [Given : AgNO3 gives yellow ppt Sol:
with I–] 2HI  H2  I2 ; K  0.0344
(a) 1.33 (b) 2.66 [H ][I ]
(c) 2.00 (d) 3.00 ini 8 0 0; K  2 22
Ans: (a) [HI]
Sol: eq 8  2x x x
I2  I  I 3 x2
K
In itial co n c. 1 0 .5 (8  2 x ) 2
Conc.at equi. 1  0.25 0.5  0.25 0.25
x
 0.75  0.25 0.25  0.0344  0.1854
8  2x
 I 3- 
Kc   1.33 x  (8  2 x)(0.1854)
 I 2   I -  On solving we get x  1.10M

7. Equilibrium constant for two complexes are : 10. If for the heterogeneous equilibrium
37
A : K4 [Fe(CN)6] K=2.6 × 10 (for dissociation)
17
CaCO3(s)  CaO(s) + CO2 (g) ; K = 1 at 1 atm,
B : K3 [Fe(CN)6] K=1.9 × 10 (for dissociation) the temperature is given by :
(a) A and B are equally stable
(b) A is more stable than B Sº Hº
(a) T  (b) T 
(c) B is more stable than A Hº Sº
(d) the predictable stability
Gº Gº
Ans: (c) (c) T  (d) T 
R Hº
Sol: A  K 4  Fe(CN)6  ; K  2.6 1037 Ans: (b)
B  K 3  Fe(CN)6  ; K  1.9  10 17
Sol: CaCO3 (s)  CaO(s)  CO 2 (g)
It is clear from values of K, that K 3 [Fe(CN)]6 is less K 1
We know ΔG o  2.303RT log K
dissociated as compared to K 4  Fe(CN)6 also stability
 CHEMICAL EQUILIBRIUM 3

K  1;log K  0 Sol:
N 2 O 4  2NO 2
ΔG o  2.303RT(0)  0
Initial 1 0
Now ΔG o  ΔH o  TΔSo  0
At equilibrium 1   2
ΔHo  TΔSo
Relation of Observed Vapour Density and Theoretical
ΔH o Vapour Density with no. of moles is given by
 T
ΔSo Theoretical V.D no. of moles at equilibrium

11. The free energy of formation of NO is 78 kJ mol at the
–1 Observed V.D no. of moles taken initially
temperature of an automobile engine (1000 K). What is
the equilibrium constant for this reaction at this reaction 46
  1 
at 1000 K ? 26
1 1    0.77  77%
N 2  g   O 2  g   NO  g 
2 2
(a) 8.4 × 10
–5
(b) 7.1 × 10
–9
14. For the reaction N2O4 (g)  2NO2 (g), the value of Kp is
–10 –19
(c) 4.2 × 10 (d) 1.7 × 10 1.7 × 103 at 500 K and 1.78 × 104 at 600 K. Which of the
Ans: (a) following is correct ?
I. The proportion of NO2 in the equilibrium mixture is
1 1 increased by decreasing the pressure
Sol: N 2  g   O 2  g   NO  g 
2 2 II. The standard enthalpy change for the forward reaction
ΔG 0  2.303RT log K c is negative
III. units of Kp are atm
78000J / mol  2.303  8.314  1000 log K c IV. At 500 K, the degree of dissociation N2O4 decreases
 K c  anti log ( 4.0737) by 50% by increasing the pressure by 100%.
The correct choice is :
 K c  8.4  10 5 (a) I, III (b) I
(c) II, IV (d) III
12. Volume of the flask in which the following equilibria are Ans: (a)
separately established are transferred to a flask that is
double the size of the earlier flask. In which of the following Sol: N 2 O 4 (g)  2NO2 (g)
cases, equilibrium constants are affected ? K P at 500K is1.7  103
(a) N 2(g)  H 2 g   2NH3 g  , exothermic K P at 600K is1.74  10 4
(b) N 2 g   O 2 g   2NO g  , endothermic
P 
2
NO 2
(c) PCl5 g   PCl3 g   Cl 2 g  , endothermic KP   Units will be atm : also by decreasing
PN 2 O4
(d) none of these
pressure equilibrium will shift to that side containing more
Ans: (d)
no. of moles i.e., towards NO2.
Sol: According to Le-chatelier’s principle, if we subject equi-
librium with any concentration, volume or pressure
15. Consider the equilibrium
change, then equilibrium will shift itself in such a direc-
tion so as to undo the effect of change but, equilibrium 1
CO 2  CO  O2
constant will not change for any of the following reac- 2
tion. The equilibrium constant K is given by (when  <<< 1) :

13. During thermal dissociation, the observed vapour density 3/ 2 3

of N2O4 (g) is 26.0. The extent of dissociation of N2O4 (g) (a) K  (b) K 
2 2
is :
(a) 50% (b) 87%  3/ 2 3/ 2
(c) 77% (d) 23% (c) K  (d) K 
2 3
Ans: (c)
Ans: (a)
 CHEMICAL EQUILIBRIUM 4
Sol:
KP  PCO2  1
1
CO 2  CO  O2 8500
2 logKP  7.282 
C 0 0 T
8500
1 log1  7.282 
C  C C C T
2
8500
for 1mole / L, C  1 0  7.282 
T
1 8500
1 2 T   1167 Kelvin
C .  C   7.282
K 2  Incelsius  1167  273  894 C
C - C
1
 1 2 18. To the system H2 (g) + I2 (g)  2HI (g)
  3
 
 2  2 in equilibrium, some N2 gas was added at constant
  (1    1) volume. Then,
1 2
(a) Kp will remain constant and Kc will change
(b) Kc will remain constant and Kp will change
16. For the reaction, N2O4(g)  2NO2(g) ; if percentage (c) Both Kp and Kc will remain constant
dissociation of N2O4 are 25%, 50%, 75% and 100%, then (d) Both Kp and Kc will change
the sequence of observed vapour densities will be : Ans: (c)
(a) d1 > d2 > d3 > d4 (b) d4 > d3 > d2 > d1 Sol: H 2 (g)  I2 (g)  2HI(g)
(c) d1 = d2 = d3 = d4 (d) (d1 = d2) > (d3 = d4)
No. of moles of both reactant and product are same. So
Ans: (a)
by introducing inert gas equilibrium will not shift to any
Vapour density at equilibrium
Sol: = direction. Hence K p and K C both will remain same.
Initial vapour density
19. Some quantity of water is contained in a container as
Initial moles of gaseous reaction shown in figure below. As neon is added to this system at
constant pressure, the amount of liquid water in the vessel:
Total moles of gas at equilibrium

So greater dissociation means more no. of moles at

equilibrium and so V.D. will be less at equilibrium. so
d1  d 2 > d 3 > d 4 .
Vapour
17. In the preparation of CaO from CaCO3 using the equilibrium,
CaCO3 (s)  CaO(s)  CO2 (g), (At 1 atm) Water
8500
Kp is expressed as log Kp = 7.282  . (a) increases (b) decrease
T
For complete decomposition of CaCO3 the temperature in (c) remains same (d) change unpredictably
celsius to be used is : Ans: (b)
(a) 1167 (b) 894 Sol: As volume will increase by addition of inert gas so more
(c) 8500 (d) 850 space will be available for H 2 O vapours. So
Ans: (b) equilibrium will shift towards right
Sol: CaCO3 (s)  CaO(s)  CO 2 (g) H 2 O(l )  H 2 O(g)
As the reaction will proceed only if container will be open, Hence liquid water decreases.
so as more and more CO 2 goes to atmosphere that means
pressure of CO 2  1atm 20. Solubility of a substance which dissolves with a decrease
in volume and absorption of heat will be favoured by
(a) high p and high T (b) low p and low T
(c) high p and Low T (d) low p and high T
Ans: (a)
 CHEMICAL EQUILIBRIUM 5

Sol: Solubility increases with increase in pressure. Also process Sol:

is endothermic so increase in temperature also favours A + B  2C + D
forward process. Initial 1 1 0 0
At eq. 1  x 1  x 2x x
21. When a liquid in equilibrium with its vapour is heated
(a) the rate of the reaction, vapour  liquid, is increased Since K c  10 8 (is very high), we can assume
(b) the same equilibrium mixture is re-established whole amount of A and B completely change
(c) a new equilibrium mixture with a higher vapour to C and D
pressure is established Thus,
(d) a new equilibrium mixture is established in which the A+B  2C + D
rate of evaporation is greater than the rate of
condensation 2M 1M
Ans: (c) C and D decomposes.
Sol: With increase in temperature more vapours will form until 2C  D  A  B
a new equilibrium reaches with liquid.
2x 2x 2x
2  2x 1
22. Given the following reactions and associated equilibrium 2 2 2
constants, select the correct expression for the third 2  2x 1 x x x
equilibrium constant in terms of the first two.
x2
(A) 2CO(g)  O 2 (g)  2CO 2 (g); K c Thus, K1c 
1 (2  2 x) 2 (1  x)
1
(B) H 2 (g)  O 2 (g)  H 2 O(g); K c x 2  K c is very small , 2  2 x  2 
1
2 2
 10 8   
(C) CO(g)  H 2 O(g)  CO 2 (g)  H 2 (g); K c 4  1  x  1
3
 x  2 104 M
K 
1/ 2

(a) K c3 
K c1
(b) K c3 
c1  A   2  104 M
K c2 K c2
For the reaction, [Ag(CN) 2 ]  Ag + 2CN , the
– + –
24.
 
1/ 2 –19 +
(c) K c  K c  K c equilibrium constant Kc at 25ºC is 4 × 10 ; then Ag
3 1 2
concentration in a solution which has 0.1 M KCN and
   
1/ 2 1/ 2
(d) K c3  K c1  K c2 0.03M AgNO3 is :
18 –18
(a) 7.5 × 10 (b) 7.5 × 10
19 –19
Ans: (b) (c) 7.5 × 10 (d) 7.5 × 10
Sol: Ans: (b)
Sol: KCN  AgNO3  AgCN  KNO3
CO2 
2

K c1 =
[CO]2  O 2  0.1M 0.03M
0.07M 0 0.03M 0.03M
K c2 
H2O AgCN can further React with CN 
1
 H 2 O2  2
AgCN  KCN  K  Ag(CN) 2 
0.03M 0.07M
K c3 
CO2  H 2 
Final 0 0.04M 0.03M
CO H2 O
Thus,  Ag(CN) 2   0.03M


1
To find  Ag 

K 2
c1
Kc = Correct option is (b).
K c2
 Ag(CN)2 
3 
 Ag   2CN 
23. In the reaction : A + B  2C + D. The initial concentration initial 0.03M 0.04M
8
of A and B are 1M each. The value of Kc is 10 . What is the
at equilibrium 0.03  0.03  0.03 0.04  0.03
equilibrium concentration of A ?
–4 4
(a) 2 × 10 M (b) 2 × 10 M  Ag    CN  
2

(c) 0.005 M (d) 0.0025 M Kc  

 Ag(CN) 2 

Ans: (a)
 CHEMICAL EQUILIBRIUM 6

As, Kc  410  Kc  1

19
P
x
2
Ag  [0.04]2
Thus, 4 1019  P2 1
0.03 Hence K 2  x.x  
4 4
4 1019  0.03 NH2 COONH4 (s)  2NH3 (g)  CO2 (g)
 Ag    7.5 1018 M
0.04  0.04 0 0 0
at equi. 0 2x x
25. In reversible reaction A  B , the initial concentration
of A and B are a and b in moles per litre and the equilib- Total pressure 3x  P
rium concentration are (a – x) and (b – x) respectively ; P
express x in terms of k1, k2, a and b. x
3
k1a  k 2 b k1a  k 2 b 2
(a) (b)  2P  P
Hence K 3  (2 x) x    
2
k1  k 2 k1  k 2
 3  3
k1a  k 2 b k1a  k 2 b 4P3 4
(c)
k 1k 2 (d)
k1  k 2  
27 27
Ans: (b) Hence K1  K 2  K 3 correct answer (c)
[B]eq k
Sol: K eq  and K eq  1
[A]eq k2 27. The equilibrium constant for the decomposition of water,
AB  1 
 H 2 O  g   H 2  g   2 O 2  g 
Initial a b  
At equi. a-x b-x is given by :
k1 b  x  3 p1/ 2  3/ 2 p1/ 2
 
k2 a  x (a) K  (b) K 
(1   )(2   )1/ 2 (1   )(2   )1/ 2
 k1 a  k 1 x  k 2 b  k 2 x
3 p1/ 2  3 p 3/ 2
 k1 a  k 2 b  x  k1  k 2  (c) K  (d) K 
2 (1   )(2   )1/ 2
k a  k2b
x  1 Ans: (b)
k1  k 2
26. In each of the following, total pressure set-up at equilibrium Sol:
is assumed to be equal and is one atm with equilibrium 1
constants KP given : H 2 O(g)  H 2 (g)  O2 (g)
2
I : CaCO3 (s)  CaO (s) + CO2 (g), K1 Initial 1 0 0
II : NH4HS (s)  NH3 (g) + H2S (g), K2 
III : NH2COONH4 (s)  2NH3 (g) + CO2 (g), K3 at equation 1  
2
In the increasing order : 1
(a) K1 = K2 = K3 (b) K1 < K2 < K3 PH 2  PO22
(c) K3 < K2 < K1 (d) None of these Kp 
PH 2 O
Ans: (c)
Sol: Total pressure  P  1atm  
PH 2   PTotal 
P
CaCO 3 (s)  CaO(s)  CO 2  
1     1
Intially 0 atm 0 0 2 2
at equi. 0 0 x  
K1  x  P (Total pressure) PO2  2 P  2 P
 Total 
 1atm 1     1
2 2
NH 4 HS(s)  NH 3 (g)  H 2S(g) 1  1 
0 0 0 PH 2 O   PTotal  P
 
at eq n 0 x atm x atm 1     1
2 2
Total pressure  x  x  2 x  P
 CHEMICAL EQUILIBRIUM 7
1
  2
6
P  2 
 P 4
   
1 1 (b) Concentration 3 PCl3 PCl5
Thus, K p  2  2  Mol/litre
2
1  Cl2
P

1
2 Total
3 1
   P 2
2 6 PCl5
 1
(2   ) 2 4 PCl3
2 (1   ) (c) Concentration
2 Mol/litre 2 Cl2
3 1
 P
2 2
0
KP  1 Total
(1  )(2  ) 2
6 PCl5
28. In a 1.0 L aqueous solution when the reaction
4 Cl2
2 Ag (aq )  Cu (s )  Cu (2aq

)  2 Ag ( s )
(d) Concentration
Mol/litre 2 PCl3
reaches equilibrium, [Cu ] = x M and [Ag+] = y M.
2+

If the volume of solution is doubled by adding water, 0

then at equilibrium : Total
Ans: (c)
2 x  y
(a) [Cu ]  M, [Ag ]  M Sol: In option (1) , reaction in going backward and initial conc.
2 2
2 x  y of PCl3  Cl2 . So, at any stage it would remain equal.
(b) [Cu ]  M, [Ag ]  M
2 2 In option (2) , conc. of Cl2 or PCl3 can either decrease or
2 x  y
(c) [Cu ]  M, [Ag ]  M increase. Cl2  and PCl3  is not possible.
2 2
2 x  y In option (3) , initial conc. PCl3 = Cl2 as reaction move
(d) [Cu ]  M, [Ag ]  M backward, it would remain equal and that PCl5will increase.
2 2
Ans: (c) In option (4) , increase in PCl5 is not in proportion to
Sol: 2Ag  (aq)  Cu(s)  Cu 2  (aq)  2Ag(s) decrease in PCl3 or Cl2
At eq. yM xM
Now, if the volume of solution becomes double by adding 30. For the following reaction through stages I, II and III
 2+ I II III
H2O, then conc. of Ag and Cu will decrease in given A  B  C  D
volume and increase in volume will shift equilibrium quantity of the product formed (x) varies with temperature
towards more number of aqueous moles i.e, backward. (T) as given. Select correct statement :
So, concentration will become
yM x B
 Ag    and Cu 2    M . A I II
2 2 D
III
29. For the reaction PCl5 (g)  PCl3 (g) + Cl2 (g) X C
Which of the following sketch may represent above
equilibrium ? Assume equilibrium can be achieved from
either side and by taking any one or more components T
initially. (Given KC for the reaction < 2) ?
(a) Stages I and III are endothermic but II is exothermic
(b) Stages I and III are exothermic but II is endothermic
6 Cl2
(c) Stages II and III are exothermic but I is endothermic
4 PCl3 (d) Stage I is exothermic but stages II and III are
(a) Concentration endothermic
Mol/litre 2 PCl5 Ans: (a)
0
Total
 CHEMICAL EQUILIBRIUM 8

Sol: [One or more than one correct option]

B 34. Which of the following statements about the reaction

A I II quotient, Q are correct ?
D (a) the reaction quotient, Q and the equilibrium constant
III
always have the same numerical value
X C (b) Q may be lesser than, equal to or greater than Keq
(c) Q (numerical value) varies as reaction proceeds
(d) Q = 1 at equilibrium
T Ans: (b, c)
In I and III, x increases with increase in temperature. So it Sol: For general reaction
is endothermic, where as II is exothermic. A+B  C+D

31. Densities of diamond and graphite are 3.5 and 2.3 g/mL [C][D] [C][D]
Q and K C  (at equilibrium)
respectively. Increase of pressure on the equilibrium [A][B] [A][B]
C (diamond)  C (graphite) Now as conc. of reactant and product varies before
(a) favours backward reaction attaining equilibrium, the numerical values of Q also
(b) favours forward reaction changes.
(c) has no effect
(d) increase the reaction rate 35. Variation of equilibrium constant K for the reaction
Ans: (a) 2A  s   B  g   C  g   2D  g 
Sol: C (diamond)  C (graphite) is plotted against absolute temperature T in figure as : ln
With increase in pressure equilibrium can be shifted to K vs (1/T)
that side whose density is more, so it will shift towards
backward side.

32. A solution is transferred to a 1 L flask, some pure ice is

added and a stopper is inserted to close the flask. After ln K
the system has reached constant temperature, there are
still a few cubes of ice left in the flask, but no other solid.
Which of the following statements is false relative to this
system at equilibrium ?
(a) The system is a heterogeneous one. 1/T
(b) There are four phases present in the system, not (a) the forward reaction is exothermic
including the container and stopper. (b) the forward reaction is endothermic
(c) The vapour pressure is constant. (c) the slope of line is proportional to H
(d) The temperature of the system is below 0ºC. (d) adding ‘A’ favours forward reaction
Ans: (b) Ans: (a, c)
Sol: The statement (b) is incorrect. It has no relevance here. -ΔH
Sol: Slope 
2.303R
33. On heating a mixture of SO2Cl2 and CO, two equilibria are
simultaneously established : If ΔH 0  0, slope increases;
SO 2 Cl 2 (g)  SO 2 (g)  Cl 2 (g) reaction is exothermic

CO(g)  Cl2 (g)  COCl2 (g) Slope  ΔH 0 , from eq n

Also according to Le-chatelier’s principle, addition of solid
On adding more SO2 at equilibrium what will happen ?
does not affect equilibrium
(a) Amount of CO will decrease
(b) Amount of SO2Cl2 and COCl2 will increase
36. Which is/are correct ?
(c) Amount of CO will remain unaffected
(d) Amount of SO2Cl2 and CO will increase Hº Sº
Ans: (d) (a) 2.303 log K   
RT R
Sol: On adding SO2 , first reaction will shift backward and (b) Gº = – 2.303 RT log K
more Cl 2 will be consumed. Hence due to decrease in
Hº Sº
conc. of Cl 2 in second reaction, 2 nd reaction will also (c) –2.303 log K   
RT 2 R
follow backward path.
1
(d) 2.303 log K  (Hº Sº )
Objective Questions II RT
 CHEMICAL EQUILIBRIUM 9
Ans: (a, b)
ΔH0 ΔS0 39. Yield of NH3 in Haber’s process
Sol: a) 2.303log K   N 2(g )  3H 2(g )  2NH3(g), H = – 22 kcal;
RT R
can be increased by
ΔH° ΔS0 (a) compressing the reaction system
 log K  
2.303RT 2.303R (b) raising the temperature
(c) decreasing the temperature
b) ΔG 0  2.303RT log K
(d) using the catalyst to lower down the activation energy
When ΔG  0 at equilibrium. Ans: (a,c)
Sol: N 2 (g)  3H 2 (g)  2NH 3 (g)
37. The variation of equilibrium constant K with temperature
is represented by : ΔH  22kcal,
Yield of NH3 can be increased by increasing pressure,
H T2  1 
R T1  T 
(a) loge K 2  log e K1     dT which can be achieved by compressing the reaction
mixture and by decreasing the temperature as reaction is
exothermic.
 d log e K  H
(b)    40. The volume of the reaction flask is reduced to half of its
 dT P RT
initial value, temperature being constant. In which of
RT the following cases the position of the equilibrium would
(c) loge K = Constant  shift ?
H
(a) NH4HS(s)  NH3(g) + H2S(s)
H
(d) loge K = Constant  (b) 2NOCl(g)  2NO(g) + Cl2(g)
RT (c) CO(g) + H2O(g)  CO2(g) + H2(g)
Ans: (a, d)
Sol: The variation of K with temp is given as (d) I2(g)  2I(g)
Ans: (a,b,d)
ΔS0 ΔH 0 Sol: As the volume is reduced to half, so the equilibrium will
log K   ;
2.303R 2.303RT shift in that case where the no. of moles of reactant and
ΔH T2  1  product are different.
loge K2  loge K1      dT
R T1  T 
41. KNO3(s) dissociates on heating as :
ΔS0 ΔH 0 1
 2.303log K  
R RT KNO3(s)  KNO2(s) + O 2 (g )
0 0
2
ΔS ΔH At equilibrium in a closed container
loge KC  
R RT (a) addition of NaNO3(s) favours forward reaction
ΔS 0 (b) addition of KNO2(s) favours reverse reaction
 constant (c) increasing temperature favours forward reaction
R (d) decreasing pressure favours forward reaction
ΔH 0 Ans: (c,d)
 log K c  constant  1
RT Sol: KNO3 (s)  KNO 2 (s)  O 2 (g)
2
38. An industrial fuel, ‘water gas’ which consists of a mixture As dissociation is done by heating. So increase. in
of H2 and CO can be made by passing steam over red-hot temperature favours forward direction as no. of moles of
carbon. The reaction is product are more in number so decreasing pressure will
C(s)  H2O(g)  CO(g)  H2 (g);ΔH  131kJ favour forward reaction.
The yield of CO and H2 at equilibrium would be shifted to
the product side by 42. The dissociation of phosgene, which occurs according
(a) raising the relative pressure of steam to the reaction :
(b) adding hot carbon COCl2(g)  CO(g) + Cl2(g)
(c) raising the temperature is an endothermic process. Which of the following factors
(d) reducing the volume of the system will increase the degree of dissociation of COCl2 ?
Ans: (a, c) (a) Adding Cl2 to the system
Sol: C(s)  H2 O(g)  CO(g)  H2 (g);ΔH  131kJ (b) Adding helium to the system at constant pressure
(c) Decreasing the temperature of the system
As it is endothermic reaction so we can increase the yield
(d) Reducing the total pressure
of product by increasing temperature and it is also altered
Ans: (b,d)
by introducing steam.
 CHEMICAL EQUILIBRIUM 10

Sol: COCl 2 (g)  CO(g)  Cl 2 (g) (d) Increasing the volume of the container
As it is endothermic reaction and no. of moles of product Ans: (a, c, d)
are more, so increase in temperature, reduction in pressure Sol: Cl2 (g)  3F2 (g)  2ClF3 (g);
and addition of inert gas at constant pressure can increase ΔH   ve
yield of product or can say support dissociation reaction. Reaction is exothermic, so can be made backward by
increasing temperature. No. of moles of reactant are more,
43. For the following endothermic equilibrium established by so equilibrium can be made to backward by increasing
dissociation of NH4HS to its components, volume and by adding inert gas at constant pressure.
NH4HS(s)  NH3(g) + H2S(g)
partial pressure of NH3 will increase 47. For the reaction : PCl5 (g)  PCl3 (g) + Cl2 (g) , The
(a) if NH3 is added after equilibrium is established forward reaction at constant temperature is favoured by
(b) if H2S is added after equilibrium is established (a) introducing an inert gas at constant volume
(c) temperature is increased (b) introducing chlorine gas at constant volume
(d) volume of the flask is decreased (c) introducing an inert gas at constant pressure
Ans: (a,c) (d) increasing the volume of the container
Sol: NH 4 HS(g)  NH 3 (g)  H 2S(g) Ans: (c, d)
As the reaction is endothermic so more product will be Sol: PCl5 (g)  PCl3 (g)  Cl2 (g)
formed by increasing temperature and it will increase No. of moles of product are more than that of reactant. So
partial pressure of NH3 . Also, once equilibrium is decrease in pressure can move the equilibrium toward
forward direction and it can be done by adding inert gas
achieved then by introducing more NH3 , we can increase at constant pressure and by increasing the volume of
its partial pressure. container.

44. Volume of the flask in which the following equilibria are 48. The dissociation of ammonium carbamate may be
separately established are transferred to a flask that is represented by the equation
double the size of the earlier flask. In which of the following NH4CO2NH2(s)  2NH3(g) + CO2(g)
cases, equilibrium concentrations are affected ? H° for the forward reaction is negative. The equilibrium
(a) N 2 (g)  3H 2 (g)  2NH 3 (g) will shift from right to left if there is
(a) a decrease in pressure
(b) N 2 (g)  O 2 (g)  2NO(g)
(b) an increase in temperature
(c) PCl5 (g)  PCl3 (g)  Cl2 (g) (c) an increase in the concentration of ammonia
(d) an increase in the concentration of carbon dioxide
(d) 2NO(g)  N 2 (g)  O 2 (g)
Ans: (b,c,d)
Ans. (a, c) Sol: NH 4 CO 2 NH 2 (s)  2NH3 (g)  CO 2 (g)
Sol: By changing volume, only conc. of those reactions will
be affecting those having different no. of moles of reactant ΔH   ve
and product. Also according to Le Chatelier’s principle, if conc. of any
one of the product is increased then equilibrium will shift
45. For the reaction : PCl5(g)  PCl3(g) + Cl2(g), in reactant side. It is an exothermic reaction. An increase
The forward reaction at constant temperature is favoured in temperature will result in shifting equilibrium from right
by to left.
(a) introducing an inert gas at constant volume
(b) introducing chlorine gas at constant volume 49. Which of the following factors will increase solubility of
(c) introducing an inert gas at constant pressure a well known weak base, NH3(g), in H2O ?
(d) increasing the volume of the container NH3(g) + H2O(aq)  NH4OH(aq)
Ans: (c, d)
Sol: If inert gas is introduced at constant pressure, volume of (a) increase in pressure (b) addition of water
container will have to be increased and this will favour (c) addition of an acid to water
(d) addition of a base to water
the forward reaction, Also adding PCl5 (g) at constant Ans: (a,b,c)
volume will favour forward reaction because PCl5 (g) is a Sol: NH 3 (g)  H 2 O (aq)  NH 4 OH (aq)
reactant. Solubility of ammonia can be increased by increasing
pressure and by adding water. Also if we add some acid,
46. Which of the following factors will favour the backward it will react with NH 4 OH and will decrease conc. of
reaction ?
Cl2(g) + 3F2(g)  2ClF3 (g) ; H = –ve NH 4 OH , so to maintain equilibrium more NH3 will
(a) Addition of inert gas at constant pressure dissolve in H2O.
(b) Addition of Cl2 gas
(c) Increase in the temperature of reaction
 CHEMICAL EQUILIBRIUM 11
50. For the gas phase reaction,
PA ×PB
C2H4(g) + H2(g)  C2H6(g) ; Hº = –136.8 kJ mol
–1
KP   1/ 6
carried out in a vessel, the equilibrium concentration of PAB
C2H4 can be increased by : 4
(a) increase in temperature (b) decrease in pressure P
(c) removing some H2 (d) adding some C2H6  3  4 2  8
kP 1
Ans: (a, b, c, d)
6
Sol: C 2 H 4 (g)  H 2 (g)  C 2 H 6 (g);
ΔH o  136.8kJmol 53. SO2Cl2 and Cl2 are introduced into a 3L vessel. Partial
Conc. of C2 H 4 can be increased by adding product conc. pressure of SO2Cl2 and Cl2 at equilibrium are 1 atm and 2
or by removing some reactant. As no. of moles of reactant atm respectively. The value of Kp for the following reaction
are more in no. than product so decrease in pressure also SO2Cl2(g)  SO2(g) + Cl2(g) is 10.
favours reactant. Also reaction is exothermic so increase
The total pressure in atm at equilibrium would be ____.
in temperature favours backward reaction.
Ans: (8.00)
Sol: SO 2 Cl 2  SO 2  Cl2
Numerical Value Type Questions
1atm x 2atm
51. Given the hypothetical reaction : x 2
2A(s) + nB(g)  3C(g) Kp = 0.0105 KP   2x = 10
1
and Kc = 0.45 at 250ºC. What is the value of coefficient
‘n’ ? 10
x 5
Ans: (4.00) 2
Sol: 2A(s)  nB(g)  3C(g) Total pressure  1  x  2  8

K p = K c (RT)3-n 54. What weight of solid ammonium carbamate (NH2COONH4)

0.0105  0.45(523  0.082) 3 n when vaporised at 200ºC will have a volume of 8.96 litre at
1 atm ? Assume that solid completely decomposes into
 R  0.082 atm L / K mol  CO2 and NH3 at 200ºC and 1 atm.
 
 T  250  273  Ans: (6.00)
  523K  Sol: NH 2 COONH 4  2NH 3  CO 2
 
First 3 moles are formed in total after complete
log 0.0105  log 0.45  (3  n)[log 523  log 0.082]
dissociation of NH 2 COONH 4 , so let’s calculate total
n 4
52. For the equilibrium AB(g)  A(g) + B(g), at a given volume of product at 200 C(473K)
P  1atm, n  3, R  0.0821atmL / Kmol, T  473K
1 P
temperature rd of AB is dissociated, then will be  PV  nRT
3 Kp
numerically equal to _____. V  116.4 L
For 116.4L volume, mass of NH 2 COONH 4  78
Ans: (8.00)
Sol: 8.96L volume will require NH 2 COONH 4  6.04
AB(g)  A(g)  B(g) 6
1atm 0 0 55. Two equilibria are simultaneously existing in a vessel
1 1 1 at 25ºC
1
3 3 3 NO(g) + NO2(g)  N2O3(g); K p (say)
1
2 1 1 4 2NO2(g)  N2O4(g); K p = 8 atm–1
Total pressure =    2
3 3 3 3
If initially only NO and NO2 are present in a 3 : 5 mole ratio
and the total pressure at equilibrium is 5.5 atm with the
pressure of NO2 is 0.5 atm, calculate K p (in 10–1)
1
Ans: (4.00)
 CHEMICAL EQUILIBRIUM 12
Sol: Given 3 : 5 mole ratio PE 900 9
So,  
PB 400 4
NO(g) + NO2(g)  N2O3(g); K p (say)
1
20  PB 9
at t = 0 3P 5P 0  
at eqm. 3P-x 5P–x–2y x PB 4
2NO2(g)  N2O4(g); K p = 8 atm–1 80
2 PB 
5P–x–2y 5
PN2 O4 PN2O4 PB  16
K P2  ,8 
(PNO2 ) 2
(0.5) 2
PD 4016 24

PN2O4  2atm PE  60  24  36
PT  PB + PD + PE  16  24  36  76 atm
 y  2atm
Ptotal = PNO  PNO2  PN2 O4  PN2O4 Assertion Reason
5.5 = 3P – x + 0.5 + x + 2
3P = 3, P = 1 (A) If both Assertion and Reason are correct and Reason is the
correct explanation of Assertion.
PNO2  5 × 1 – x – 2 × 2 = 0.5atm (B) If both Assertion and Reason are true but Reason is not the
x = 0.5atm correct explanation of Assertion.
PN2 O3 (C) If Assertion is true but Reason is false.
K P1  (D) If Assertion is false but Reason is true.
(PNO )(PNO2 )
57. (A)Assertion : Chemical equilibrium represents a state of
0.5 a reversible reaction in which measurable properties of
  0.4atm
2.5  0.5 the system (pressure, concentration, colour etc.) become
PNO = 2.5 atm constant under the given set of conditions.
PNO2  0.5atm Reason : The chemical equilibrium is an apparent state of
rest in which two opposing reactions are proceeding at
PN2O3  0.5atm the same rate.
(a) A (b) B
PN2O4  2atm (c) C (d) D
Ans: (a)
56. Two solids A and C dissociate into gas products as Sol: At equilibrium all measurable properties of system (P,
follows. conc., volume, colour etc.) becomes constant because
the rate of forward and backward reaction becomes equal
A(s)  B(g) + D(g); K p = 400 at equilibrium and the value of pressure, conc. volume
1

C(s)  E(g) + D(g); K p = 900 will not change with time.

2
At 25ºC, the pressure over excess solid A only is 40 58. Assertion : The reaction quotient, Q has the same form
atm, and that over solid C only is 60 atm. Find the as the equilibrium constant Keq and is evaluated using
pressure over the solid mixture. any given concentrations of the species involved in the
Ans: (72.00) reaction, and not necessarily equilibrium concentrations.
Sol: A(s)  B(g)  D(g), K p  400 Reason : If the numerical value of Q is not the same as the
1
C(s)  E(g)  D(g), K p  900 value of equilibrium constant, a reaction will proceed.
2 (a) A (b) B
K P1  PB  PD  400 (c) C (d) D
Ans: (b)
K P2  PE  PD  900 Sol: Yes both Q and Keq have same form, forms are same but
reaction can only proceed when Q and K are not equal.
Also PB + PD = 40 atm Assertion and reason both are correct but reason is not a
PE + PD = 60atm correct explanation of the assertion.
PE - PB = 20 atm
59. Assertion : The active mass of pure solids and pure liquids
 PE  20  PB is taken unity.
Reason : The active mass of pure solids and liquids
depends on density and molecular mass. The density and
molecular mass of pure liquids and solids are constant.
 CHEMICAL EQUILIBRIUM 13
(a) A (b) B (a) A (b) B
(c) C (d) D (c) C (d) D
Ans: (a) Ans: (b)
Sol: The active mass of pure solid and pure liquid depends on Sol: Both assertion and reason are correct but reason is not
density and molecular mass and because they are correct explanation of assertion as if pressure will remain
constant. Active mass is taken as unity for them. same, then according to Le-chatelier’s principle, then there
is no change in conc. of any of the reactant and product.
60. Assertion : For a reaction at equilibrium, the free energy
for the reaction is minimum. 64. Assertion : For the reaction
Reason : The free energy for both reactants and products A(g)  B(g)  2AB(g)
decreases and become equal.
at the given temperature, there will be no effect by addition
(a) A (b) B
of inert gas either at constant pressure or at constant
(c) C (d) D
volume.
Ans: (c)
Reason : For the reaction where n = 0, there is no effect
Sol: For a reaction at equilibrium, Gibb’s free energy of the
of inert gas either at constant volume or at constant
reaction is minimum at constant temperature and
pressure because Kp becomes purely a number.
pressure.
(a) A (b) B
G  G   RTlnK . At equilibrium G  0 (c) C (d) D
Hence, G  is minimum at equilibrium. Ans: (a)
The Gibb’s free energy of both reactants and products Sol: Correct option will be A. Because equilibrium will not shift
become equal at equilibrium. They may increase or if Δn  0 by increase or decrease in volume or pressure,
decrease. both reason and assertion are correct.
61. Assertion : If some PCl 5 (g) containing labelled 65. Assertion : Addition of an inert gas at constant pressure
phosphorus 31P is added to a system with following equilibrium will support the dissociation of PCl5 at the
equilibrium, after sometime the system was found to same temperature.
contain radioactive PCl3. Reason : The addition of an inert gas will tend to increase
PCl5(g) PCl3(g) + Cl2(g) the total pressure.
Reason : Chemical equilibrium is dynamic in nature. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D Ans: (a)
Ans: (a)
Sol: PCl5  PCl3  Cl2
Sol: Radioactive P can only be seen on product side if still
there is reaction going on and it can be possible because Because increase in inert gas will increase the pressure
equilibrium is dynamic and hence volume will decrease and tends the equilibrium
towards more no. of moles. Both assertion and reason is
62. Assertion : As a reversible system approaches correct.
equilibrium, entropy of the system increases.
Reason : The state of equilibrium is the most disordered 66. Assertion : The addition of an inert gas under constant
state of a reversible system. volume condition cause the total pressure of the system
(a) A (b) B to increase. This would thus lower the degree of
(c) C (d) D dissociation of PCl5.
Ans: (c) Reason : Addition of inert gas at equilibrium increase the
Sol: Before approaching equilibrium entropy will increase, but kinetic energy of molecules.
at equilibrium if going from reactant to product entropy (a) A (b) B
increases, then from product to reactant side entropy will (c) C (d) D
decrease. So assertion is correct, but the reason is Ans: (d)
incorrect. Sol: Addition of inert gas at constant volume will increase the
pressure, but the partial pressure of both reactant and
63. Assertion : The dissociation of CaCO3 can be represented product will remain same. But with increase in pressure
as, CaCO3(s)  CaO(s) + CO2(g). Some solid CaCO3 is K.E. will increase so assertion is wrong , reason is true.
placed in an evacuated vessel enclosed by a piston and
heated so that a portion of it is decomposed. If the piston
is moved so that the volume of the vessel is doubled,
while the temperature is held constant, the number of
moles of CO2 in the vessel increases.
Reason : The pressure of CO2 in the vessel will remain the
same.
 CHEMICAL EQUILIBRIUM 14

Match the Following 69. Match the conditions on the left column with states on
Each question has two columns. Four options are given the right column.
representing matching of elements from Column-I and Column- Column–I Column–II
II. Only one of these four options corresponds to a correct Equilibrium types Kp/Kc
matching. For each question, choose the option corresponding relationship
to the correct matching (A) A2(g)  2A(g); Kc = 1. (p) System is at
Mixture of 1.0 mole of each equilibrium
67. Match the Column-I with Column-II : is prepared in a 1.0 L flask.
Column-I Column-II (B) A(g) + 2B(g)  AB2(g) (q) Goes to right
(Equations) (Type of process) Kc= 2. A mixture of 2.0 moles
(A) Kp > Q (p) Non spontaneous of each A, B and AB2
is prepared in a 1.0 L flask.
(B) Gº < RT loge Q (q) Equilibrium
(C) A2(g)  2A(g) ; Kp = 2. At (r) n(A) > n(A2) at
(C) Kp = Q (r) Spontaneous and equilibrium the total pressure equilibrium
endothermic is 2.0 atm.
H (D) 2A(g)  A2(g)Kp = 2. A (s) n(A) < n(A2) at
(D) T  (s) Spontaneous mixture, initially containing equilibrium
S both A and A2 at 1.0 atm
(a) A -s, B - p, C - q, D - r (b) A -p, B - q, C - s, D - r partial pressure is prepared.
(c) A -r, B - q, C - p, D - r (d) A -q, B - r, C - s, D - p (a) A-p, r,; B-p,q; C-p,q,r; D-p,q,b
(b) A-p, s,; B-p,q; C-p,q,s; D-p,q,b
Ans: (a)
(c) A-p, r,; B-p,q; C-p,q,r; D-p,r,b
Sol: A) K p  Q  (s) Spontaneous (d) A-p, r,; B-p,q; C-p,s,r; D-p,r,b
Ans: (a)
B) ΔG o  RT log e Q  (p) Non-Spontaneous
Sol: A ) A2 (g)  2A(g),K c  1 , system is equilibrium. ; p
C)K p  Q  (q) Equilibrium and r; n(A)>(A2)
ΔH B) A(g)+2B(g)  AB2 (g)
D) T   (r) Spontaneous & endothermic
ΔS K c  2 goes to right and system is at equilibrium p
68. Match the Column-I with Column-II : and q
Column-I Column-II C) A 2 (g)  2(A)(g),K P  2;p,q,r
(Reaction) (Effect on equilibrium)
D) 2A(g)  A 2 (g), K P  2; p, q, r
(A) N2(g) +3H2(g)  2NH3 (p) Forward shift by
H = –ve lowering of
temperature 70. Match the Column–I with Column–II
(B) N2(g) + O2(g)  2NO(g) (q)Forward shift by rise in Column–I Column–II
H = +ve temperature (A) N2(g) + 3H2(g)  2NH3(g) (p) No effect of inert

(C) PCl5(g)  PCl3(g)+Cl2(g) (r)No effect of pressure gas addition at

H = +ve change constant volume
(D) 2SO2(g)+O2(g)  2SO3(g) (s) Forward shift by rise in
(B) N2(g) + O2(g)  2NO(g) (q) Homogenous
H = –ve pressure
(a) A- p,s B- q,r C- q D- p,s equilibria
(b) A- p,r B- q,r C- s D- p,s
(c) A- p,s B- q,r C- r D- p,s (C) CaCO3(s)  CaO(s)+CO2(g) (r) Kp > Kc
(d) A- p,r B- q,r C- r D- p,s
Ans: (a) (D) NH2COONH4(s)  2NH3(g) (s) Kp depends on
Sol: (a) A- p,s B- q,r C- q D- p,s + CO2(g) partial pressures
For exothermic reaction, H   ve, increase in T leads to of products only.
backward reaction whereas for endothermic, increase  in (a) A - q; B - q, p; C - r, s; D - s, r
T leads to forward reaction. Reaction for which
(b) A - r; B - q, s; C - s; D - s, r
n g  0, pressure has no effect. When n g  0, forward
shift by rise in pressure. (c) A - q; B - q, p; C - r; D - s, r
(d) A - q; B - r, p; C - s; D - s, r
Ans: (a)
 CHEMICAL EQUILIBRIUM 15

Sol: Addition of inert gas at constant volume do not effect (a) +50 (b) –50
equilibria in any case. (c) 10 (d) None of these
K p = K c (RT)Δng Ans: (b)
Homogeneous equilibria involves all reacting speices in -Δ H o
Sol: Slope 
ine phase. 2.303R
In option (3) and (4) , reactions are solid so wont produce 230
any pressure.   2  49.9  50 approx
2.303  2

Paragraph type questions 72. For exothermic reaction if Sº < 0, then the sketch of log K
Use the following passage, solve Q.71 to Q.73 vs 1/T may be
Passage

Effect of temperature on the equilibrium process is

analyzed by using the thermodynamics. From the
thermodynamics relation. (a) (b)
Gº = – 2.303 RT logK ...(i)
Gº : Standard free energy change
Gº = Hº – TSº ...(ii)
Hº : Standard heat of the reaction
From (i) and (ii)
–2.303 RT log K = Hº – Sº
(c) (d)
Sº : Standard entropy change
Hº Sº
 log K    ...(iii) Ans: (a)
2.303RT 2.303R
H o So
Sol: log K  
If a plot of log K vs 1/T is made then it is a straight line 2.303RT 2.303R

 Hº  Sº Given So  0
having slope  and Y intercept  for exothermic reaction H o  0,
2.303R 2.303R
If at temperature T1, equilibrium constant be K1 and at H o So
temperature T2, equilibrium constant be K2 then the above So, log K  
2.303RT 2.303R
equation reduces to :
1
Hº Sº The plot between log K and will have a positive slope
 log K1    T
2.303RT1 2.303R and negative intercept. The plot is of form y = mx + C.
Hº Sº 73. If for a particular reversible reaction : Kc = 57 at 355ºC and
 log K 2   
2.303RT2 2.303R
K 'c = 69 at 450º, then
Substracting (iv) from (v) we get.
(a) H < 0
K2 Hº  1 1  (b) H > 0
 log     (c) H = 0
K1 2.303R  T1 T2 
(d) Sign of H can’t be determined
From the above relation we can conclude that the value
Ans: (b)
of equilibrium constant increases with increase in
temperature for an endothermic reaction and the same
decreases with the increase in temperature for an
exothermic reaction. Answer the following three questions
based on the above information.

71. If standard heat of dissociation of PCl5 is 230 cal, then

1
slope of the graph of log K vs is
T
 CHEMICAL EQUILIBRIUM 16
Sol: Kc / K 'c   ΔH / 2.303(1 / T1  1 / T2 )
Use the following passage, solve Q.77 & Q.78
57 / 69  ΔH / 2.303(1/ 723  1/ 628) Passage
ΔH  1.902  95 / 628  723   ve value
These 3 questions refer to the following experiment. Some
Fe(NO3)3 solution is added to KSCN solution and a dark
Use the following passage, solve Q.74 to Q.76 red colour appears. This colour is caused by [Fe(SCN)]2+,
Passage which is formed by the reaction :
Fe3+ (aq) + SCN– (aq)  [Fe(SCN)]2+
These 3 questions deal with the following chemical Experiments show this colour becomes deeper upon
reaction: addition of more Fe(NO 3) 3 or KSCN. The colour
2 disappears when Na2HPO4 is added. Use one or more of
Ni 2   aq   6NH 3  aq    Ni  NH 3 6   aq 
the interpretations below.
 green solution   BlueSolution 
(a) Unreacted Fe 3+ (aq) is present in the original
When H+(aq) is added, the colour green is favoured. Use equilibrium mixture.
one or more of the following interpretations to answer the (b) Unreacted SCN – (aq) is present in the original
questions. equilibrium mixture.
I. Some unreacted Ni2+ (aq) is present in the solution at (c) Colour change indicates a new equilibrium ;
equilibrium. [Fe(SCN)2+ (aq)] has been reduced.
II. Some unreacted NH3 (aq) is present in the solution at (d) Colour change indicates a new equilibrium ;
equilibrium. [Fe(SCN)2+ (aq)] has been increased.
III. The colour change indicates new equilibrium
conditions with reduced [Ni(NH3)6]2+(aq). 77. The deepening of colour on addition of more Fe(NO3)3
IV. The colour change indicates new equilibrium supports
conditions with increased [Ni(NH3)6]2+(aq). (a) A only (b) A and D only
(c) A and B only (d) B and D only
74. The deepening colour on dissolving more Ni(NO3)2 Ans: (d)
supports interpretation(s)
(a) I only (b) I and IV only Sol: Solution: Unreacted SCN   aq  is present in the original
(c) II and IV only (d) I and II only equilibrium mixture. Colour change indicates a new
Ans: (c) 2
 Fe  SCN  equilibrium has been increased.
Sol: Some unreacted NH 3 (aq) is present in the solution at
equilibrium. On adding Ni(NO3)2 in solution, it will react
with NH3 and form blue colored complex. The colour 78. The disappearance of colour on addition of Na2HPO4
change indicates new equilibrium conditions with supports
(a) A only (b) A and D only
increased  Ni  NH 3 6  (aq) .
2+
(c) A and B only (d) C only
Ans: (d)
75. The deepening colour on addition of more NH3(aq) Sol: Disappearance of colour indicates a new equilibrium in
supports intepretation(s) which [Fe(SCN)]2+ has been reduced.
(a) I only (b) I and IV only Use the following passage, to solve Q. 79 to Q. 80
(c) I and II only (d) II and IV only
Ans: (b) Passage
Sol: Some unreacted Ni 2+ (aq) is present in the solution at
Le-Chatelier’s principle : If a system at equilbrium is
equilibrium. On adding NH3 in solution, it will react with
unreacted Ni2+ and form blue colored complex. The colour subjected to a change of any one of the factors such as
change indicates new equilibrium conditions with concentration, pressure or temperature, the system adjusts
increased  Ni  NH 3 6  (aq) .
2+
itself in such a way as to “Nullify” the effect of that change.
If a system in equilibrium consists of gases, then the
76. The disappearance of colour on addition of H+ (aq). concentrations of all components can be altered by changing
supports interpretation(s)
(a) I only (b) II and IV only the pressure. When the pressure on the system is increased,
(c) I and II only (d) III only the volume decreases proportionly. The total number of
Ans: (d)
moles per unit volume will now be more and the equilibrium
Sol: The colour change indicates new equilibrium conditions
will shift in that direction in which there is decrease in number
with reduced  Ni  NH 3 6  (aq)
2+

of moles i.e, towards the direction in which there is decrease

 CHEMICAL EQUILIBRIUM 17

in volume. Sol: Solid (higher volume) converts into liquid (lower volume)
so the Pressure is inversely proportional to the volume.
Solids whose volume decreases on melting e.g., ice, Low pressure favours the reaction. Endothermic reaction
diamond, carborundum, magnesium nitride and quartz. is directly proportional to the temperature.

Solid (higher volume)  liquid (lower volume)

1 1
80. For the reaction : N 2 (g)  O 2 (g)  NO(g)
The process of melting is facilitated at higher pressure, 2 2
thus the melting point is lowered. If pressure is increased by reducing the volume of the
container, then
Solids whose volume increase on melting e.g. Fe, Cu,
(a) total pressure at equilibrium will remain same
Ag, Au, etc. (b) concentration of all the components at equilibrium
Solid (lower volume)  liquid (higher volume) will change
(c) concentration of all the components at equilibrium will
In this case, the process of melting becomes difficult at remain same
high pressure ; thus melting point becomes high. (d) equilibrium will shift in the forward direction
Answer the following two questions based on the Ans: (b)
Sol: Pressure is inversely proportional to the volume so the
above information. concentration of all the components at equilibrium will
79. Au(s)  Au(l) change.
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)