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CHEMISTRY CHAPTER WISE_QUESTIONS

CHEMICAL EQUILIBRIUM (E)

29. PCl5 g
PCl3 g Cl2 g ; COCl2 g
CO g Cl2 g Simultaneous equilibrium is

established for above reactions in a vessel. Removing some amount of PCl3 from

reaction mixture, at constant volume results in (after reestablishment)

1) Decrease in concentration of PCl5 than initial equilibrium

2) Decrease in concentration of CO than initial equilibrium

3) Increase in concentration of COCl2 than initial equilibrium

4) All of these

ANS:4
SOL:
42. If 20% of N 2O4 molecules have dissociated in a sample of gas at 27 0C and 760 mm Hg,
the density of equilibrium mixture is
1) 1.48 g/L 2) 1.84 g/L 3) 2.21 g/L 4) 3.11 g/L
ANS:4
SOL: NaCN HCl

NaCl HCN
P H 8.5 P Ka 9.39
NaCN
P H P Ka log
HCN

8.5 9.39 log


NaCN
HCN
0.9 log
HCN
NaCN
x
8
0.1 x
x 0.8 8 x
0.8
9 x 0.8 x 0.089moles
9
8.8 102

22. Ammonia gas at a pressure of 20 atm and 270 C is heated in a constant volume in a
container to a temperature of 3270 C at which new pressure becomes 50 atm and the

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following equilibrium 2 NH 3( g )
N 2( g ) 3H 2( g ) is established. Percentage dissociation
of ammonia at this temperature is X 2 . The value of X is
ANS:5
SOL: 2 NH
3( g ) N 2( g ) 3 H 2( g )

3
1
2 2
Totalmoles 1
PV nRT
20V 1 R 300

50V n R 600
n 1.25
0.25
% 25 i.e. x 5

50. The equilibrium constant K p for the reaction 2SO 2 O2


2SO3 is 900 atm 1 at
800 K . A mixture containing SO3 and O2 having initial pressure of 1 atm and 2 atm
respectively is heated at constant volume to equilibriate. The partial pressure (atm) of
O2 gas at 800 K is
1) 0.9764 2) 2.01 3) 0.0236 4) 0.0118
ANS:2

SOL: 2 SO3 2SO2 O2
Int.Pressure 1 0 2
x
Pressure at eq. 1 x x 2
2
x
x2 2
p 2
pO2

2
kp SO2

1 x
2 2
p SO
3

1
kp small x 1
900
1 2 x2
kp
900 1 x 2
1 2x
, x 0.0236
30 1 x
p 'SO3 1 x 1 0.0236 0.9764 atm
p 'SO2 x 0.0236 atm
x
pO2 2 2.0118 atm
2

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2. 2 moles of N 2O4 is heated to form NO and O2 .As soon as NO and O2 are formed, they
react to form N 2O5 . Two equilibria are simultaneously established
3
N 2O4 2 NO O2 2 NO O2 N 2O5
2
at equilibrium degree of dissociation of N 2O4 was found to be 50% which of the
following is correct at equilibrium
1 1
A) [ NO ] +[ O2 ] = [ N 2O4 ] +[ N 2O5 ] B) [ O 2 ] + [ N 2O5 ] = [ NO]
2 2
1 3 3
C) [ NO] = [ O2 ] D) 2[ N 2 O4 ] = [ NO ] = [ O2 ] +[ N 2O5 ]
2 2 2
ANS:B
SOL:
66. At temperature T, a compound AB2(g) dissociates according to the reaction
2 AB2 g 2 AB g B2 g With a degree of dissociation, x, which is small
compared with unity. Deduce the expression for x in terms of the equilibrium constant,
Kp and total pressure P.
1 1 1
Kp
2) x
2 K p
3) x
K p
4) x
3 3 K p 2
1) x
4P P 4 P 8P
ANS:2

SOL:
2AB2
2AB + B2
1- x x x
2
1. The value of k p for the reaction CO2 g C gra
2CO g is 3 bar at 1000 k. If initially
PCO is 0.48 bar , PCO is zero and pure graphite is present. The partial pressure of CO2 at
2

equilibrium is
A) 0.33 bar B) 0.15 bar C) 0.30 bar D) 0.2 bar
ANS:B
SOL: NCERT Page No. 197
CO2 g C s
2CO g
0.48 x 2x
2
4x
3 4 x 2 1.44 3 x
0.48 x
4 x 2 3 x 1.44 0
3 9 23 3 32
x 0.33
8 8
PCO2 0.48 0.33 0.15 bar

In the equilibrium CaF2 s


2
23. Ca aq 2 F aq , if the concentration of F at new

equilibrium is double the concentration of F at old equilibrium, then concentration of

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Ca 2 at the new equilibrium will be how many times less than the concentration of Ca 2

at the old equilibrium.

ANS:4
SOL:
10. H 2 (g) I2 (g) 2HI(g) . When 46.0 g of I 2 and 1.00g of H 2 are heated to equilibrium
at 470o C , the equilibrium mixture contains 1.9g I 2 . Which of the following options are
correct regarding moles of a species at equilibrium and the value of equilibrium
constant.(I=127 g/mole)
a) moles of I 2 0.0075 b) moles of H 2 0.326 c) moles of HI 0.348 d) Keq = 500
ANS:ABC
SOL: Since the same number of moles of gas appears on both sides of the equation, the equilibrium constant
expression can be stated as a ratio of moles instead of concentrations.
1mol I 2
(46.0gI 2 ) 0.181 mol I 2 initially present
254g I 2
1mol H 2
(1.00g H 2 ) 0.500 mol H 2
2.00g H 2

1mol I 2
(1.9g I 2 ) 0.0075 mol I 2 at equilibrium
254g I 2

Initial Produced Used up Equilibrium


0.181 0.174 0.0075
[I 2 ]
0.500 0.174 0.326
[H 2 ]
[HI] 0 2(0.174) 0.348

[HI]2 (0.348) 2
K 50
[I2 ][H 2 ] (0.326)(0.0075)

1. At constant temperature, the equilibrium constant ( K p ) for the decomposition


reaction. N 2O4 2 NO2 is expressed by K p 4 x P / (1 x ) where P is pressure, x is
2 2

extent of decomposition. Which of the following statement is true?


1) K p increases with increase of P 2) K p increases with increase of x
3) K p increases with decrease of x 4) K p remains constant with change in P or x
ANS:4
SOL: N 2O 2 NO2 g
4 g

t=0 1 0
tequi 1-x 2x
Total moles = 1 x 2 x 1 x
1 x 2 x
PN 2O4 P PNO2 P
1 x 1 x
Q N 2O4 is 25% dissociated

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x 0.25 and P 1atm
1 0.25
PN 2O4 1 0.6 atm
1 0.25
2 0.25
PNO2 1 0.4 atm
1 0.25
2
PNO 0.4 0.4
Kp 2
0.267 atm
PN 2 04 0.6
1

Suppose the degree of dissociation of N 2O4 at 0.1 atm is


1 2
PN 2O4 0.1 PNO2 0.1
1 1
4 2 0.1
Kp 0.267
1 2
63.2%
2. At a certain temperature equilibrium constant K c is 16 for the reaction.
SO2 g NO2 g SO3 g NO g . If we take one mole of each of all the four gases in one

litre container. The % of moles of NO2 at equilibrium is?

2g
SO N
O 3
SON
O
1) 30 2) 20 3) 10 4) 40
ANS:3 2gg
1 1 1 1
t=0
1-x 1+x 1+x
SOL: tequi 1-x

Kc
SO3 NO
16
1 x
2

SO2 NO2 1 x
2

3
x moles 0.6mole
5
At equi nSO2 0.4 nNO2 0.4 nSO3 1.6 nNO 1.6
0.4
% of nNO2 100 10%
4
1
6. The preparation of SO3 g by reaction SO2 g O2 g SO3 g is an exothermic reaction. If
2

the preparation follows the following temperature - pressure relationship for its %yield,

then the temperature T1 , T2 and T3 . The correct option is

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1) T3 T2 T1 2) T1 T2 T3 3) T1 T2 T3

T
4) nothing could be predicated about temperature through given information

132
50

% yield
40
30
20
10

1 2 3 4
press (atm)

ANS:2
SOL:
7. Pure ammonia is placed in a vessel at a temperature where its dissociation constant
is appreciable. At equilibrium N 2 3H 2 NH 3
1) K p does not change significantly with pressure
2) does not change with pressure
3) concentration of NH 3 does not change with pressure
4) concentration of hydrogen is less than that nitrogen
ANS:1
SOL: N 2O5 N 2O3 O2
4 x x y x y
N 2O3 N 2O O2
x y y yx
Q O2 x y 2.5

Kc
x y x y
4 x
x 2.166
N 2O5 4 x 1.846
8. At a certain temp, K p for dissociation of solid CaCO3 is 4 102 atm and for the reaction
C s CO2( g ) 2CO( g ) is 2.0 atm respectively. The partial pressure of CO at this

temperature when solid C , CaO, CaCO3 are mixed and allowed to attain equilibrium is?
1) 0.58 atm 2) 0.78 atm 3) 0.18 atm 4) 0.28 atm

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ANS:4
SOL: For dissociation of CaCO3
CaCO3 s CaO s CO2 g
2
Given that K p 4 10 PCO2
For the formation of CO,
C s CO2 s 2CO2 g
P
2

Kp CO 2.0
PCO2
2
Now both are at equi and thus PCO2 4 10 which should remains constant
P
2

2.0 CO PCO 0.28


4 152
9. The equilibrium constants for the reactions are: m
K
H 3 PO4 1 H H 2 PO4 ; K1
K
H 2 PO4 2
H HPO42 ; K2
K
HPO42 3 H PO43 ; K3
The equilibrium constant for
H 3 PO4 3H PO43 will be:
1) K1 / K 2 K 3 2) K1 K 2 K 3 3) K 2 / K1 K3 4) K1 K 2 K 3
ANS:2

1I

2
H/22I

H 2/2
SOL: HI disscociates as

at t = 0 1 0 0

at equi
2
Kc 4
41
2

Now for the association equilibrium


H 2 I 2 2 HI
Initial 2 x 2 x 2x
1 4 x2 1 2
K c1 x
Kc 2 x 2
4 5
2 8 8
Thus I 2 left = 2 mole 2 equivalent
5 5 2
mcq of Na2 S 2O3 mcq of I 2 left
8
2 v 2 1000
5
V=1.6 lt

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10. The equilibrium constants K p1 and K P2 for the reactions x 2 y and z PQ

respectively are in the ratio of ratio of 1:9. If the degree of dissociation of x and z be equal
then the total pressure at these equilibrium is_____
1) 1:36 2) 1:1 3) 1:3 4) 1:9
ANS:1
SOL: x 2y
1 0
1-x 2x
'
2x
2
P1
K p1 .
1 x 1 x
z PQ
1 0 0
1-x x x
'
x 2 P2
K p2 .
1 x 1 x
4 P1 1 P 1
1
P2 9 P2 36
11. The equilibrium constant K c for the reaction N 2 g O2 g 2 NO g at temp T is 4 104 .
1 1
The value of K c for the reaction NO g N 2 g O2 g at the same temp is
2 2
1) 2.5 102 2) 4 104 3) 50 4) 0.02
ANS:3
SOL: N O 2 NO; K 4 104
2 2 c

1 1
N 2 O2 NO K c1 K c 2 102
2 2
1 1 1
NO N 2 O2 K c'' ' 50.0
2 2 Kc
12. The thermal dissociation of CaCO3 g is studied under different conditions
CaCO3 s CaO s CO2 g . For this equilibrium the incorrect statements is
1) H is dependent on T
2) Equilibrium constant (K) is independent of the initial amount of CaCO3
3) Equilibrium constant (K) is independent on the pressure of CO2 at a given T
4) H is independent of the catalyst, if any
ANS:3
SOL: k depends upon the temperature. But at constant temperature it depends upon products and
reactants concentration and pressures

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13. For the chemical equilibrium CaCO3 s CaO s CO2 g H o r can be determined from
which one of the following plots
logeP
C
O
2

1) 2)
P
C
O
2
T

logeP
C
O
2

1/T
3) log T 4)
ANS:1
SOL: CaCO3 CaO CO2
g

K PCO2
0
K Ae H r / RT
H r0
Log K P LogA
2.303RT
H r0
Log PCO2 LogA
2.303RT
1 3
18. G0for 2
N2(g) + 2
H2(g) NH3(g) is 16.5 kJ/mol. Then the G0 for

N2 + 3H2 2NH3 at 25C. is (nearly)


1) -33 kJ/mole 2) -53 kJ/mole 3) -73 kJ/mole 4)-93 kJmole
ANS:1
SOL: G 0 2.303 RT logK
p

1.6 103 2.303 8.314 298log K p


K P 779.4atm 1
Also K p for N 2 3H 2
'
2 NH 3
k 1p k p 779.4
2 2

6.06 105 atm 2


Also G 2.303RTLogK p
0 1

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2.303 8.314 298log 6.07 105 32.989 KJ / mole
19. For the reaction : N 2( g ) 3H 2( g )
2 NH 3( g ) ;
H ve , the correct statement is:
1) Addition of catalyst does not change K p but changes H
2) At equilibrium, 2GNH GN 3GH (G is Gibbs energy)
3 2 2

3) At higher temperature, the rate of forward and backward reaction increases by a


factor 2
4) At 400K, addition of catalyst increases rate of forward reaction by 2 times and
backward by 1.7 times.
ANS:2
SOL: NH 2COONH 4 2 NH CO2 g
3 g

Dd

n 1 d
X no. of moles of product formed by dissociation of 1 mole of rectant
M .Wt 78
Initial vapour density D 39
2 2
39 13
1
3 1 13
21. An acid-type indicator, HIn, differs in colour from its conjugate base . The human eye is

sensitive to colour differences only when the ratio In / HIn is greater than 10 or

smaller than 0.1. What should be the minimum change in the pH of the solution
to observe a complete colour change ?
K a 1.0 105

1)4 2)3 3)2 4)1


ANS:3
SOL: HIn H In
H In
ka
HIn
In
When 10; H 1 105 / 10 10 6
HIn
pH = 6
In 1

When ; H 1 105 10 104


HIn 10
pH = 4
minimum change in pH = 6 4 =2
Page 10 of 32
30. An equilibrium mixture at 300K contains N 2O4 and NO 2 at 0.28 and 1.1 atmosphere
respectively. If the volume of container is doubled. Calculate the new equilibrium
pressure of two gases (in atm)
N 2O4 NO 2
(a) 0.095 0.64
(b) 0.64 0.095
(c) 0.17 0.32
(d) 0.32 0.17
ANS:A
SOL:
26. The equilibrium, 2CO + O2 2CO2 heat , is subjected to the following combination
of stresses. In which one of the following cases, it is not possible to predict the effect of
stress on the direction of reaction?
(a) Addition of CO and removal of CO2
(b) Increase in temperature and decrease in volume
(c) Addition of O2 and decrease in volume
(d) Addition of a catalyst and decrease in temperature.
ANS:B
SOL: As both the stresses drive the reaction in opposite directions in (B), it is not possible
to determine its effect on the direction of the reaction
38. 0.2 mol of each A2(g) and B2(g) are introduced in a sealed flask and heated to 2000 K
where following reaction is established:
A2(g) + B2(g) 2 AB(g)
At equilibrium, moles of AB is 0.3. At this stage, 0.1 mol of C 2(g) is added and the
following equilibrium is also established:
A2(g) + C2(g) 2 AC(g)
At the new equilibrium, the moles of AB become 0.24. If the equilibrium constant for
the second reaction is 3x, the value of x is
ANS:6
SOL:
24. Observe the following reaction.
A(g) + 2B(g) AB2(g); H = -230 kJ mol-1
Incorrect statement(s) regarding this reaction is/are
(A) As temperature increases the rate of forward reaction decreases while rate of
backward reaction increases.
(B) Energy of activation for backward reaction is more than energy of activation of
forward reaction.
(C) As temperature increases that rate of forward reaction increases while the rate of
backward reaction decreases.
(D) Addition of an appropriate catalyst at the same temperature speeds up the reaction
by making the reaction more exothermic.
ANS:ACD
SOL:

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25. Ethyl acetate is synthesized from ethanol and acetic acid in a nonreacting solvent by
the following reaction:
CH3COOH(l )+C2H5OH(l ) CH3COOC2H5 (l ) H2O(l );K=2.2
If the reaction is set up taking [CH3CO2C2H5] = 0.22 M, [H2O] = 0.10 M,
[CH3CO2H] = 0.010 M, [C2H5OH] = 0.010 M, the changes which take place as the
system attains equilibrium is/are
(A) Concentrations of both ethyl acetate and water decrease.
(B) Concentration of ethyl acetate decreases while that of water remains
constant.
(C) Concentrations of both ethanol and acetic acid increase.
(D) No change in concentrations of reactants as well as product as the
given concentrations correspond to their equilibrium values.
ANS:AC
SOL:
39. Match the reactions in List I with appropriate effects in List II.
List I List II

(P) Fe3 (aq ) SCN (aq ) [Fe(SCN)]2 (aq ) (1) High pressures favour
forward reaction.

(Q) H2 (g) + I2(g) 2HI (g) (2) Change in pressure has no


effect on the equilibrium

(R) 2NaNO3(s) 2NaNO2(s) + O2(g) (3) Lower pressures favour


forward reaction

(S) H2O (s) H2O (l) (4) Addition of oxalate ion


drives the reaction in
backward direction

P Q R S
(A) 4 2 3 1
(B) 1 2 4 3
(C) 3 2 1 4
(D) 4 3 2 1
ANS:A
SOL:
11. Consider the following equilibria:
(1) N2 (g) + 3H2 (g) 2NH3 (g) (2) N2(g) + O2(g) 2NO (g)
(3) PCl5(g) PCl3 (g) + Cl2 (g)
Choose the correct statement/s:

Page 12 of 32
A) Addition of an inert gas at constant volume has no effect on all the three equilibria.
B) Addition of an inert gas at constant pressure favours the forward reaction in (3),
backward reaction in (1) and has no effect on (2).
C) Addition of an inert gas at constant pressure has no effect on equilibrium (2), but
favours the forward reaction in (1) and backward reaction in (3).
D) Addition of inert gas has no effect on all the three equilibria at constant temperature
and also at constant pressure.
ANS:AB
SOL:
82. For the reaction A g B g C g
K P p
1) K p p 2) K p K P p 1 3) K p K P p 4) K p
3 2 2 2

p

ANS:3
2p
SOL: K p ; K p 1 2 ; 2 p; K p 2 K p p
1
2

1
N2O5 ( g ) , if the equilibrium constant is K p
55. For the reaction 2NO2 ( g ) + O2 ( g )
2
, then the equilibrium constant for the reaction
2N2O5 ( g )
4NO2 ( g ) + O2 ( g ) would be

2 1 1
1) K p
2
2) 3) 4)
Kp K 2p Kp

ANS:3
SOL:
PCl5 PCl3 Cl2
64. For a reversible reaction . The position of equilibrium at constant
g g g
temperature can be shifted towards right side by
1) Addition of inert gas at constant volume 2)Addition of catalyst
3) Addition of inert gas at constant pressure 4) increasing pressure
ANS:3
SOL: On addition of inert gas at constant pressure, volume of vessel increases. So position of
equillibrium shifted towards more number of moles
19. A vessel of 250 litre was filled with 0.01 mole of Sb2 S3 and 0.01 mole of H 2 to attain the

equilibrium at 4400C as Sb2 S3 s 3H 2 g 2Sb s 3H 2 S g after the

equilibrium, the H 2 S formed was analyzed by dissolving it in water and treating

Page 13 of 32
with excess of Pb 2 to give 1.195g of PbS(m.wt=239) precipitate. The value of Kc of

the reaction at 4400C is______

ANS:1
SOL:

1. The equation for the reaction in the figure below is:


H 2 g I 2 g Heat 2 HI g

0.8
conc.(mmol/L)

0.6 HI

0.4

0.2 H2
I2
0 1 2 3
Time (min)
At the instant 3 min , what change was imposed into the equilibrium ?

A) pressure was increased

B) Temperature was increased

C) Iodine was added to the system

D) Hydrogen was added to the system

ANS:B
SOL: Given equilibrium reaction is endothermic

10. 2Y and Z
The equilibrium constants K 1 and K 2 for the reactions X P Q ,
respectively are in the ratio of 1:9. If the degree of dissociation of X and Z be equal then
the ratio of total pressure at these equilibria is
1) 1 : 3 2) 1 : 9 3) 1 : 36 4) 1 : 1

ANS:3
SOL: The initial moles of X and Z taken are a and b respectively
Moles at equilibrium X 2Y a 1 2 a

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2a PT
2

K p1 1

a 1 a 1
Moles at equilibrium Z P Q
b (1 ) b b

b PT
2

K p2 2

b 1 b 1
K P1 4 PT1 1 PT 1
; 1
K P2 PT2 9 PT2 36

33. If 6.25 gram of a sample of NH 4Cl (solid) is placed in an evacuated four litre container
at 270 C and after equilibrium the inside pressure becomes 0.821 atmosphere then the
amount of solid NH 4Cl left in the vessel is - NH 4C l s NH 3 g HC l vap
A) 2.69 gram B) 3.125gram C) 1.765 gram D) 2.856 gram
ANS: A
0.821 4
SOL: ngas mix 0.133mole
0.0821 300

0.133
nNH 3 nHCl 0.0666moles
2

n NH 4C l decomposed 0.0666

6.25
n initial moles of NHC l 0.1168moles
53.5
n NHC l left 0.1168 0.0666 0.05

W NH 4C l left 0.05 53.5 2.65 grm

500mL of 0.2M of HCl and 500mL of 0.2M of CH 3COOH Ka 2 10 are mixed


5
34.
together and to it six gram of NaOH is added then the pH of resulting solution
(approximately) is____
A) 5.3 B) 7 C) 6.7 D) 4.7
ANS: D
NaOH CH 3COOH CH 3COONa H 2O
SOL: 150 100 100 in mole 0
0 50 50

PH pKa log
WA
salt
Page 15 of 32
50
5 log 2 log 4.7
50

1. Which of the following statement is/are correct


A) If K1 be the equilibrium constant for A B and K 2 be the equilibrium constant for
C D then equilibrium constant for the reaction

K1
A +D B +C is
K2

B) If K1 be the equilibrium constant for P Q and K 2 be the equilibrium constant for


R S then equilibrium constant for the reaction

K1
PR Q S is
K2

C) If K1 be the equilibrium constant for A B C D the equilibrium constant for

nC nD is K1
1/ n
nA nB , n can be fraction also

D) The equilibrium constant for the gaseous reaction C2 H 4 H 2 C2 H 6 is mol2dm 3


ANS: A
K1
SOL: i.e. A D B C is
K2
2. Calculate the percentage dissociation of H 2 S g If 0.1 mole of H 2 S is kept in 0.5 L vessel
at 1000K. The value of K c for the reaction
2 H 2 S g 2 H 2 g S 2 g is 1.0 107

A) 0.1 B) 0.01 C) 1 D) 10
ANS: C
SOL: 2 H 2 S 2 H 2 g S 2 g
2
0.1x 0.1 x

v 2 v
107
Let x be the degree of dissociation K c 2
0.1 0.1x

v
x3
106 x = 0.01
2v
Degree of dissociation
0.1x
x
0.1
1% dissociation of H 2 S

Page 16 of 32
3. For the reaction CO2 g H 2 g CO g H 2O g , K eq is 0.63 at 7270 C and 1.26 at 9270 C .
Then calculate the value of K eq at 12270 C ( use log10 2 0.3 )
A) 8.32 B) 2.52 C) 7.78 D)5.04
ANS: B
SOL: Using the vant Hoff equation
H 8.32kcal / mol
Now, K 2 be the equilibrium const at T2 1500 K
T1 1000 K and then K1 0.63
K2 8.32 103 1500 1000
log10
0.63 2.303 2 1500 1000
K
log10 2 0.6 log10 4
0.63
K 2 0.63 4 2.52
CH3
CH 3 CH 2 CH 2 CH 3 g H3C C CH3(g)

4. For the equilibrium H equilibrium constant is found


to be 1.732 at 298 K. Now if in a vessel at 298 K, a mixture of these two gases be taken as
represented by the point P in the fig. predict what will happen

P
is o - b u t a n e
conc. of

0
75
-
conc. of n butane

A) Immediately, above equilibrium will be setup


B) Above reaction will go in the forward direction till it attains equilibrium
C) Above reaction will go in the backward direction till it attains equilibrium
D) Nothing can be said
ANS: C
SOL: From given information
conc.of isobu tan e
Q tan 750 KC 3
conc.of n bu tan e
So backward reaction.
5. For the chemical equilibrium , CaCO3 s CaO s CO2 g Hf 0 can be determined
from which one of the following plots?

Page 17 of 32
logePCO2 logeP CO2

A) 1/T B) 1/T

logePCO2 log2P CO2

C) log T D) log T

ANS: A
SOL: K p PCO2
HF 0
log K p log A
2.303RT
Hf 0 1
log PCO2 log A . (i)
2.0303R T
So, graph (a) respresents (i) and its slope will be used to determine the heat of the
reaction
11. N 2 O2 2 NO; K1
1 1
N 2 O2 NO; K 2
2 2
2 NO N 2 O2 ; K 3

1 1
NO N 2 O2 K 4
2 2

K1 K3 x, K1 K 4 Y , K 3 K 2 Z

What will be the value of XYZ


ANS: 1
SOL:
2. If 20% of N 2O4 molecules have dissociated in a sample of gas at 270C and 760 mm Hg,
the density of equilibrium mixture is
A ) 1.48 g/L B) 1.84 g/L C) 2.21 g/L D) 3.11 g/L
ANS:D
SOL: The reaction is N 2O4 g
2 NO2 g
20
n 2 and 0.2
100
D =46, initial vapoue density, d = Vapoue density at equilibrium
Dd 46 d
0.2 d 38.3
n 1 d 2 1 d
Mole mass equilibrium 2 38.3 766
Page 18 of 32
PM dRT
p
d M
RT
PM 1 76.6
d (mix) 3.12 g / l
RT 0.0821 300
Paragraph-II:(31-32)
Complex-ion equilibria

Agaq NH 3 aq Ag NH 3 Kf1
aq

Ag NH 3 NH 3 aq Ag NH 3 2 Kf 2
aq
Kf Kf1.Kf 2

Overall formation of the complex Ag NH 3 2

Agaq 2 NH 3 aq Ag NH 3 2
aq

Kf Ag NH 3 2 / Ag NH
2
3 1.7 107
1
3 / Ag NH 3 2
2
Kd Ag NH
Kf
31. What is the concentration of Ag aq ion in 0.01M AgNO3 that is also 1.00M NH 3 ?

A) 1.7 107 B) 1.6 1010 C) 6.1105 D) 6.11010


ANS:D
SOL: Kf of Ag NO3 2

is very high we assume Ag aq reacts completely to form Ag NH 3 2 ;

leaving 1.00 2 0.01 mol.



0.01M Agaq 1 lt. reacts completely giving 0.01M Ag NH 3
2

NH 3

Ag NH 3 2 Ag aq 2 NH 3 aq
aq
0.01 0 0.98
(0.01-x) x 0.98+2x
x 0.98 2 x
2
1 1
Kd
Kf 0.01 x 1.7 107
x. 0.98
2
10
5.9 108 x 6.1 10
0.01
The Molar solubility of AgCl in 1 M NH 3 at 250C is K sp of AgCl 1.8 10
10
32.
A) 0.01 B) 0.05 C) 0.08 D) 0.001
ANS:B

Ag NH 3 2
K C K f .K sp Ag Cl

NH 3
2
Ag
SOL:

10 3
Ag NH 3 2 Cl
1.7 10 1.8 10
7
3.1 10 K C K f .K sp
NH 3
2

Page 19 of 32
AgCl 2 NH 3 aq Ag NH 3 2 Claq
aq
1.0 0 0
(1.0-2x) x x
2
x
3.1 103 x 0.05
1.0 2 x
2

32) For the reaction, SnO2 s 2 H 2 g


2 H 2O g Sn l at 900 K, the equilibrium steam
hydrogen mixture was found to be 40% H 2 by volume. The K p is
1)1.15 2)2.25 3)7.75 4)10
ANS:2
SOL: PH O / PH 60 / 40 3 / 2 1.5
2 2

2
PH22O PH22O
2 1.5 2.25
2
KP
PH22 PH
2

1. The degree of dissociation of the reaction : N 2O4 g 2 NO2 g can be related to


K p as:
Kp
1/2 1/2
Kp Kp / P Kp
(A) PK (B) 4 K (C) (D)
4 p p 4 K p / P 4 K p
P
ANS:C
SOL:
N 2O4 g 2 NO2 g
t0 1 0 n 1 2 1
teq 1 2 ng 2 1 1
2
2 1
P
Kp
1 1

4 2
Kp P
1 2
1/2
Kp / P

4 K p / P
2.

When A2 and B2 are allowed to react, the equilibrium constant of the reaction at 27C is
found K c 4 .
A2 g B2 g 2 AB g
What will be the equilibrium concentration of AB?
(A) 1.33 M (B) 2.66 M (C) 0.66 M (D) 0.33 M
Page 20 of 32
ANS:C
SOL:
A2 g B2 g 2 AB g
t0 2 4 0
2 x 4 x 2x
teq
4 4 4
AB
2

Kc
A2 B2
2 x / 4
2

4
2 x 4 x

4 4
4x2
4 2
x 6x 8
x 6x 8 x2
2

8 4
x
6 3
2x 2 4
AB 0.66
4 4 3
3. Consider the following reactions in which all the reactants and products are in gaseous
state.
2 PQ P2 Q2 ; K1 2.5 105
1
PQ R2 PQR; K 2 5 103
2
1 1 1
The value of K3 for the equilibrium : P2 Q2 R2 PQR is :
2 2 2
(A) 2.5 103 (B) 2.5 103 (C) 1.0 105 (D) 5 103
ANS:C
SOL:
1 1 1
P2 Q2 R2 PQR K ?
2 2 2
1 1 1 1
P2 Q2 PQ K'
2 2 K1 2.5 105
1
PQ R2 PQR K 2 5 103
2
1 1
K K2 5 103
K1 2.5 10 5

1105
7. Decomposition of N 2O4 g takes place as follows : N 2O4 g 2 NO2 g . D = Initial
vapour density, d = Vapour density of mixture at any instant. We get following graph
D
when the degree of dissociation is plotted against
d

Page 21 of 32
D
What is the value of at A?
d
(A) 0 (B) 0.5 (C) 1 (D) 1.5
ANS:C
Dd
SOL:
n 1 d
At A, 0
Dd
0
2 1 d
D
1
d
8. Degree of dissociation for a reversible reaction at equilibrium is calculated as
Dd

n 1 d
D = Initial vapour density, d = Vapour density at equilibrium. The above relation is
correctly matched for which of the following reactions :
5n n n 2n
(A) X g Y g Z g (B) A g B g C g
6 6 3 3
4n n n n
(C) X g Y g Z g (D) X g Y g Y g
5 5 2 2
ANS:ABCD
Dd
SOL: In the reaction :
n 1 d
n Number of gaseous moles of products formed by 1 mol of reactant
In all the given reactions, n moles of products are formed by 1 mol of reactant.
9. Which is/are correct?
H S
(A) 2.303log K (B) G 2.303RT log K
RT R
H S 1
(C) 2.303log K 2 (D) 2.303log K H S
RT R RT
ANS:AB
SOL: We know G G 2.303RT log10 Q
At equilibrium G 0 and Q K

Page 22 of 32
0 G 2.303RT log10 K
G 2.303RT log10 K 1
H T S 2.303RT log10 K
H S
2.303RT log10 K 2
RT R
Passage-2: (15 to 16)
Mass action ration or reaction quotient Q for a reaction can be calculated using the law
of mass action,
C D
A g B g C g D g Q
A B
The value Q decides whether the reaction is at equilibrium or not.
At equilibrium Q K ; For non-equilibrium process, Q K
When Q K , reaction will favour backward direction and when Q K , it will favour
forward direction.
Thus, the relative value of Q with respect to equilibrium constant decided the direction
to which the reversible reaction will proceed.
15. In a reaction mixture containing H 2 , N 2 and NH 3 at partial pressure of 2 atm, 1 atm and
3 atm respectively, the value of K p at 725 K is 4.28 105 atm 2 . In which direction the net
reaction will go?
N 2 g 3H 2 g 2 NH 3 g
(A) Forward (B) Backward
(C) No net reaction (D) Direction cannot be predicted
ANS:B
SOL: The reaction is :
N 2 g 3H 2 g 2 NH 3 g K p 4.28 105
p 2 NH 3 32
Qp = 4.5
PN 2 pH3 2 13
Q p K p ; hence this reaction will proceed in backward direction to attain equilibrium i.e., reaction will be fast
in backward direction
16. Consider the following equilibrium in a closed container
N 2O4 g 2 NO2 g
At a fixed temperature, the volume of the reaction container is halved. For this change,
which of the following statements hold true regarding the equilibrium constant K p
and degree of dissociation ?
A) Neither K p nor changes
B) Both K p and change
C) K p changes but does not change
D) K p does not change but changes
ANS:D
SOL:

Page 23 of 32
1
17. For the equilibrium AB g A g B g , at a given temperature rd of AB is
3
P
dissociated, then K will be numerically equal to _______.
p

ANS:8
SOL: AB g A g B g
t0 1 0 0
1 1 1
teq. 1
3 3 3
2 1 1 4
n 3 3 3 3
18. SO2Cl2 and Cl2 are introduced into a 3L vessel. Partial pressure of SO2Cl2 and Cl2 at
equilibrium are 1atm and 2 atm respectively. The value of K p for the following reaction
SO2Cl2 g SO2 g Cl2 g is 10. The total pressure in atm at equilibrium would be
___.
ANS:8
SOL: SO2Cl2 g SO2 g Cl2 g
1 atm x atm 2 atm
x2
Kp 10
1
x 5atm
19. Given the hypothetical reaction :
2 A s nB g 3C g K p 0.0105 atm x and K c 0.45(mol L1 ) x at 250C . What is the value
of coefficient n? (log2.33=0.3674,log4.289=0.6322)
ANS:4
SOL: K p K c RT g
n

0.0105 0.45 0.082 523


ng

0.0233 0.082 523


ng

0.0233 42.886
ng

log 0.0233 ng log 42.886


1.632 ng 1.6323
ng 1
3 2 n 1
2n 4
n2
21. For the reaction CaCO3 s
CaO s CO2 g Kp = 1.16 atm at 1073K. If 15.0 gm of
CaCO3 was put into 10lit. flask heated to 1073K what % age of CaCO3 would remain
unreacted at equilibrium?
A) 88% B) 12% C) 10% D) 90%
ANS:B

Page 24 of 32
SOL: KP PCO2 g
22. H 2 g 0.3mol was injected into one litre vessel having the following composition at
equilibrium
CO g H 2O g
CO2 g H 2 g
0.1 mol 0.1 mol 0.1 mol 0.40 mol
Calculate the new concentration of CO2 when the equilibrium establishes again
A) 0.2 mol/L B) 3.33 mol/L C) 0.33 mol/L D) 0.022 mol/L
ANS:C
SOL:
23. 0.96 gm of HI was heated till the equilibrium 2HI g
H 2 g I 2 g is reached, The
reaction mixture was suddenly cooled and the amount of iodine produced required
N
15.7 ml hypo solution. The Kp of the reaction is
10
A) 7.85 104 B) 7.5 103 C) 5.93 103 D) 17.52 103
ANS:D
SOL:
24. For the reversible reaction N2 g 3H2 g 2NH3 g at 5000 C , the value of
K p is 1.44 10 5 when partial pressure is measured in atmosphere. The corresponding
value of K c with concentration in mol/L is
1.44 105 1.44 105
A) B)
0.082 500 8.314 773
2 2

1.44 10 5 1.44 10 5
C) D)
0.082 773 0.082 773
2 2

ANS:D
SOL:
Passage-1: (29to30)
Consider the decomposition of a pare solid of CaCO3 in a closed vessel. Let be the
extent of the reaction
CaO s CO2 g
CaCO3
d dnCaCO3 dnCaO dnCO2
G

dG CaO CO 2 CaCO3 d
T , P
G

29. At equilibrium
G G G
A) G T , P 0 B) 0 C) 0 D) 0
T ,P T ,P T ,P
ANS:B
G
SOL: At equilibrium H 0
T , P
30. Pure ice can be made to melt slightly below 0C
A) By decreasing the pressure
Page 25 of 32
B) By increasing the pressure
C) By adding more ice
D) By increasing volume of the vessel
ANS:B
SOL:
35. KNO3(s) dissociates on heating as: KNO3(s) KNO2 (s) + O2 (g). At equilibrium
in a closed vessel:
a) Addition of KNO3(s) favours forward reaction.
b) Addition of KNO2 (s) favours reverse reaction
c) Increasing temperature favours forward reaction
d) Decreasing pressure favours forward reaction
ANS:CD
SOL:
Kc 1
39. If log Kp log RT 0 then above is true for the following equilibrium reaction
1 3 CaCO3
Cao CO2
A) NH 3 g
N2 g H 2 g B)
2 2 s s g
C) 2NO2 g
N 2O4 g D) H 2 g I 2 g
2 HI g
ANS:AB
SOL:
40. If two gases AB2 and B2C are mixed the following equilibrium are readily established.
AB2 g B2C g AB3 g BC g
BC g B2C g B3C2 g
If the reaction is started only with equal moles of AB2 and B2C , then which of the
following is necessarily true at equilibrium
A) AB3 eq BC eq B) AB3 eq B2C eq
C) AB3 eq B3C2 eq D) AB3 eq BC eq
ANS:CD
SOL:
Kf
34. The rate of formation of C6 H 6 3H 2 K
C6 H12 for the forward reaction is first order
b

with respect to C6 H 6 and third order with respect to H 2 . Which one of the following
is/are correct
Kf C6 H12
a) K eq b) K eq
C6 H 6 H 2
3
Kb
d) rb K b C6 H12 H 2
1
c) rf =K f [ C6 H 8 ] [ H 2 ]
3

ANS:ABC
SOL: rf K f C6 H 6 H 2
rb K b unknown
At equilibrium rf rb

Page 26 of 32
39. A chemical reaction occurs in three paths having rate constants k1 , k2 & k3 respectively. If
k1k3
Ea1 , Ea2 and Ea3 are 4,5 & 8kJ respectively and overall rate constant k . Assuming
k2
A1 A3
Aav , the overall energy of activation in kJ is___.
A2
ANS:7
SOL: k AV AAV .e E1 E3 E2 / RT Eav 4 8 5 7 kJ
26. A vessel of volume of V lit contains an equilibrium gaseous mixture that consist of 2 mole
each of PCl5 , PCl3 and Cl2 . The equilibrium pressure is 3 atm and the temperature is T k . A
certain amount of chlorine is now introduced keeping the pressure and temperature constant ,
until the equilibrium volume is 2 V lit. Calculate the number of moles of Cl2 added . The given
equilibrium is PCl5 PCl3 Cl2
a) 3.33 b) 5.00 c)6.67 d) 2.30
ANS:C
SOL:
23. For the preparation of ammonia , N 2 and H 2 are taken initially in 1:3 mole ratio. At
equilibrium 25% of each reactant reacted and showing total equilibrium pressure as 28 atm.
Then what is the equilibrium pressure of NH 3 at the same temperature ?
ANS:4
SOL:
24. For the reaction : N 2O
4 2NO 2 (g)
This equilibrium is studied by measuring the vapour density of the equilibrium mixture.
Which of the following statement is correct at moderately high pressure?
1 1
1 K 1 K
B) 1 . K P D) 1 . K P
2 2
A) P C) P
2 P 2 P 4 P 4 P
ANS. . B
Kp

K p 4p

At moderately high pressure, KP << 4P

1 1
And so, K P / P 2
2

39. When NaNO3 is heated in a closed vessel, oxygen is liberated and NaNO2 is left behind.
At equilibrium
A) addition of NaNO2 favours reverse reaction
B) addition of NaNO3 favours forward reaction
C) increasing temperature favours forward reaction
D) increasing pressure favours reverse reaction.
Page 27 of 32
ANS. C, D

1
0
a
qm
.Ula
reo
fs
0
.ln
2
Mig21
1F 0
a
qm
lo
.Cfs
0
.ln
1
M
22. The adjoining Fig. contains two beakers (1 and 2) which are placed in a sealed
container
2

The volume of the solution in 1 and 2 beakers left respectively at equilibrium are:
A) 100ml, 100ml B) 120ml, 80m C) 80ml, 120ml D) 60ml, 140ml
ANS C
2 3
SOL. =
100 - x 100 +x
22. The equilibrium, 2CO + O2 2CO2 heat , is subjected to the following combination
of stresses. In which one of the following cases, it is not possible to predict the effect of
stress on the direction of reaction?
A) Addition of CO and removal of CO2
B) Increase in temperature and decrease in volume
C) Addition of O2 and decrease in volume
D) Addition of a catalyst and decrease in temperature.
ANS B
Conceptual
36. Which of the following represents hydrolysis process?

(a) NH 4+ + H 2O NH 3 + H 3O + (b) NH 4+ + 2 H 2O NH 4OH + H 3O +

(c) HCO3- + H 2O H 2CO3 +OH - (d) HCO3- + H 2O CO32- + H 3O +

ANS. BC

37. The dibasic acid(s) is/are ____

a) chromic acid b) permanganic acid

c) phosphorous acid d) Peroxy di sulphuric acid


ANS ACD

Page 28 of 32
1. When NaNO3 is heated in a closed vessel. Oxygen is liberated and NaNO2 is left behind.
At equilibrium
A) Addition of NaNO2 favour reverse reaction
B) Addition of NaNO3 favour forward reaction
C) Increasing temperature favour forward reaction
D) Increasing pressure favour forward reaction
ANS C
1
NaNo3 ( s)
NaNo2 ( s ) O2 ( g )
2
NaNo3 and NaNo2 are in solid state, changing their amount has no effect on equilibrium.
Increases temperature will favour forward reaction due to endothermic nature of
reaction. Also, increase pressure will favour backward reaction in which some O2 ( g )
will combine with.
NaNo2 ( s ) forming NaNo3 ( s) .
2. At 1100K, water vapour decomposes into H 2 and O2 only to the extent of 105 % when
pressure is maintained at 1 atm. The value of Kp for the decomposition of one mole of
H 2O is
A) 5 1022 B) 5 1011 C) 5 1015 D) 3.3 1011
ANS. B
1
H 2O( s )
H 2 ( g ) O2 ( g )
2
7 7 107
At equilibrium : 1 10 10
2
Total moles = 1, Total pressure = 1 atm
P
H 2 pO2
Kp P
H 2O
107
107
Kp 2 107 5 104 5 1011
1
7. 0.5 mole of H 2 g and 1.0 mole of HI g ( but no I 2 ) are added to a 1.0 litre vessel
and allowed to reach equilibrium according to the following reaction
H 2 g I 2 g 2 HI g If x is the equilibrium concentration of I 2 g . Then correct
expression for equilibrium constant is
1 2x
2
1 2x
2
x 0.5 x 0.5 x x
A) B) C) D)
0.5 x x 0.5 x x 1 2x 1 2x
2

ANS. A
H 2 g I 2 g 2 HI g
Initial con 0.5 mol/lit 0 mol/lit 1.0mol/lit
Equilibrium conc 0.5 x mol/lit x mol/lit 1 2x mol/lit
1 2x
2

Kc
0.5 x x

Page 29 of 32

8 For the reaction Ag CN 2
Ag 2CN , the equilibrium constant at 250 C is
4 1019 . If a solution is 0.1M in KCN and 0.03M in AgNO3 originally, at equilibrium,
the conc. of Ag is
A) 7.5 1016 M B) 7.5 1018 M C) 1.25 1019 M D) 1.25 1017 M
ANS. B
1
Ag CN 2 k 10

Ag 2CN 19

4
I conc 0.3 0.1 -----
F conc X 0.04 0.03
1 0.03
1019
0.04 X
2
4
X 7.5 1018 M
9. Ammonia under a pressure of 20 atm. at 1270 C is heated to 3270 C in a closed vessel.
Under these conditions, ammonia is partially decomposed to N 2 and H 2 according to the
reaction 2 NH 3
N 2 3H 2
After decomposition at constant volume in the vessel, the pressure increases to 50 atm.
which of the following statements are correct?
A) The degree of dissociation of NH 3 in 2/3
B) The Kp of the reaction at 3270 C is 2.7 103 atm 2 .
C) The pressure of N 2 and NH 3 gas at equilibrium is 10 atm. each
D) The pressure of N 2 at equilibrium is half that of NH 3 .
ANS. A,B,C
2 NH 3
N 2 3H 2
At 400k 20 atm 0 0
At 600k 30 atm 0 0
At constant value let 2x atm. NH 3 disappear
30 2 x x 3 x
P
Total 30 2 x 50 2 x 20 x 10 atm
2 x 20 2

30 30 3
10 303 27 10 4
Kp 2
2
2.7 103
10 10

10. Which of the following statements is/are wrong


A) At equilibrium, concentration of reactants and products becomes constant, because
the reaction comes to an halt
B) Addition of inert gas at equilibrium for n 0 at constant volume will favour
forward reaction.
C) Addition of catalyst speeds up the forward reaction more than the backward reaction
D) Equilibrium constant of an exothermic reaction increases with increase in
temperature.
Page 30 of 32
ANS. A,B,C,D
12. 2CaSO4 s 2CaO s 2SO2 g O2 g , H 0
Above equilibrium is established by taking sufficient amount of CaSO4 s in a closed
container at 1600K. Then which of the following may be correct option ( Assume that
solid CaSO4 is present in the container in each case)
A) Mole of CaO s will increase with the increase in temperature
B) If the volume of the container is doubled at equilibrium then partial pressure of
SO2 g will change at new equilibrium
C) If the volume of the container is halved partial pressure of O2 g at new equilibrium
will remain same
D) If two moles of the He gas is added at constant pressure then the moles of CaO s
will increase
ANS. A,C,D
22. For the reaction, A g B g C g D g the initial concentrations of A and B are
equal. The equilibrium concentration of C is two times the equilibrium concentration of

agx
agx
0xgD
0xg
A. The value of the equilibrium constant is _____.

t0eqA B C
ANS 4

x 2 a x
3 x 2a
2
x a
3
2 1
A B a a a
3 3
2
C D a
3
2 2
Kc
C D 3 a 3 a 4
.
A B 1 a 1 a
3 3
23. Equilibria, X 2Y and Z P Q are established with 1 mole of X and Z taken
initially in separate vessels with equilibrium pressures of 1 atm and 36 atm respectively.
If the degree of dissociations are same. Then K P nK P . What is the value of n?
2 1

ANS 9
19. For a reaction N 2 +3H 2
2 NH 3 , the value of K C would depend upon

Page 31 of 32
1) initial concentration of the reactants 2) pressure
3) temperature 4) all of these
ANS:3
SOL:

20. For the dissociation reaction N 2O4 ( g )


2 NO2 ( g ) , the degree of dissociation (a) in

terms of K p and total equilibrium pressure P is :


4 P +K p Kp Kp 4P
1) a = 2) a = 3) a = 4) a = K
Kp 4 P +K p 4P p

ANS:2
N O 2 NO2
SOL: 2 4
1- a 2a
2
4a
Kp = p
1 - a2
a2 K
2
= p
1- a 4p
21. Consider the partial decomposition of A as 2 A ( g )
2 B ( g ) +C ( g ) At equilibrium
700mL gaseous mixture contains 100mL of gas C at 10 atm and 300K. What is the value
of K p for the reaction ?
40 1 10 28
1) 2) 3) 4)
7 28 28 10
ANS:3
2 A
2 B +C
SOL:
400 200 100
2
2 .110
Kp = 2
4 7
2+
CoCl4 2- ( aq ) is blue in colour while ( aq ) is pink. The colour of reaction
1. Co ( H 2 O) 6

Co ( H 2O ) 2+ + 4Cl - CoCl4 2- + 6 H 2O
mixture
6
( aq) ( aq) ( aq) ( i) is blue at room temperature while it is

pink when cooled hence


A) Reaction is exothermic in forward direction
B) Reaction is endothermic in forward direction
C) Equilibrium will shift in forward direction on adding water to reaction mixture
D) Equilibrium will not shift on adding water to equilibrium mixture
ANS:B
SOL: On cooling equilibrium shift in back ward direction hence reaction is endothermic

Page 32 of 32