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CHEMICAL EQUILIBRIUM

Solution to Subjective Problems


LEVEL – I

1. N2 + O2 2NO
79 21 0 at equilibrium
(79 – x) (21 – x) 2x at equilibrium
Given that
2x 1.8

100 100
x = 0.9
(2  0.9) 2
KC = = 2.1  10–3 = KP
78.1  20.1

2. Kp = KC(RT)n
kp 1.4  10 2
KC = Δn
 = 1.7  10–4
(RT ) (0.0821  1000 ) 1

F2 2F
1 0 at initial
(1 – x) 2x at equilibrium
4x 2
1.7  10–4 = x  1
(1  x )
x2 = 0.425  10–4
x = 0.65  10–2 = 0.65

3. C2H5COOH(l) + C2H5OH(l) C2H5COOC2H5(l) + H2O(l)


0.5 0.5 0 0 at initial
(0.5 – x) (0.5 – x) x x at equilibrium
x
= 7.36  x = 0.36
( 0. 5  x ) 2
Moles of ethyl propionate = 0.36
Weight of ethyl propionate = 0.36  102 = 36.72g

4. C2H5OH9l) + C3H7COOH(l) C3H7COOC2H5(l) + H2O(l)


at initial 0.1 0.1 0 0
0.1 – x 0.1 – x x x
Given that
0.1 – x = 0.85  100  10–3

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RSM79Ph-IICECH(H&S)-2

0.1 – x = 0.085  x = 0.75


0.75  0.75
K= =9
0.25  0.25

0.150
5. Initial conc. of AgNO3 = = 0.075
2
1.09
Initial conc. of Fe2+ solution = = 0.545
2
30  0.0832  5
Final conc. of Fe2+ solution = = 0.499
25
Ag+(g) + Fe2+(aq) Fe3+(aq) + Ag(s)
0.029 0.499 0.046

Fe 3   0.046
KC =
 
Ag Fe 2
=

0.029  0.499
= 3.178

6. In the given reaction 87% of the acid is consumed at equilibrium


C6H5COOH(l) + C2H5OH (l) C6H5COOC2H5(l) + H2O(l)
Initially 1 3 0 0
At equilibrium 1–0.87 3–0.87 0.87 0.87

 KC =
C6H5COOC 2H5  H2O = 0.87  0.87 = 2.73
C6H5COOH  C2H5OH 0.13  2.13
Let n be the number of moles of acid consumed when 1 mole of the acid is mixed
with 4 moles of ethanol.
C6H5COOH (l) + C2H5OH (l) C6H5COOC2H5(l) + H2O(l)
At equilibrium 1–n 4–n n n
nn
KC = = 2.73
1  n 4  n
n2
= 2.73
4  5n  n2
On solving, we get n = 0.90 or 6.99
6.99 is not possible as we started with 1 mole of the acid
% of acid consumed = 90%

7. N2O4 2NO2
Initial (mole) 100 0
At eq. (mole) (100–25) 50 = 75
75 3 50 2
At eq. (p.p.) 1 = 1 =
125 5 125 5
2
2
 
 KP =   
5 4 4
 = 0.267 atm.
3 5  3 15
5

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RSM79Ph-IICECH(H&S)-3

(ii) Suppose x % N2O4 dissociates at 0.1 atm pressure


N2O4 2NO2
Initial (mole ) 100 0
At eq. (mole) 100–x 2x total moles at equilibrium = 100 + x
 100  x   2x 
At eq. (p.p.) 0.1  0.1 
 100  x   100  x 
2
 0.2 x 
 
 100  x  4
KP = 
 100  x  15
0.1 
 100  x 
On solving, we get x = 63.25 %

8. Let 1 mole of PCl5 be taken initially. If ‘x’ moles of PCl5 dissociate at equilibrium, its
degree of dissociation = x
Moles PCl5 PCl3 Cl2
Initially 1 0 0
At equilibrium 1-x x X
Total moles 1–x+x+x=1+x
P = 5 atm Kp = 0.82
 1 x  xP xP
PPCl5 =   P, PPCl3  , PCl 2 
 1 x  1 x 1 x
P P 
PCl5 Cl 2
Kp =
P  PCl5

2
x
Kp = P  0.82
1  x2
x 2 (5 ) 0.82
 0.82  x 2 
1  x2 5.82
x = 0.375 (0r 37.5%)
Now the new pressure P = 10 atm
Let y be the new degree of dissociation. As the temperature is same (250C), the
value of Kp will remain same. i.e. the same manner. Proceeding in the same manner.
( y )P ( y )210
Kp =  0.82 
1  ( y )2 1  ( y )2
0.82
y= or y = 0.275 (or 27.5%)
10.82
Note 1: by increasing pressure, degree of dissociation has decreased, i.e., the
system shifts to reverse direction. Compare the result by applying Le
Chatelier’s principle.

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9. a) We know that
k2 ΔH  1 1
log    
k 1 2.303R  T1 T2 
k 350 57200  1 1 
log    k350= 4.3
0.14 2.303  8.314  298 350 

b) Equilibrium constants at different temperature and heat of the reaction are


related by the equation
KP Ho  1 1
ln 2 =   
K P1 R  T1 T2 
KP Ho  T2  T1   25140  773  673 
2.303 log 2 =   =
K P1 R  T1T2  2.303  2  773  673 

log KP2  4.835 KP2  1.462  105 atm.

10. a) First determine the equilibrium constant


KC for H2 + I2 2HI
[HI]2 (0.49)2
KC =   50
[H2 ][I2 ] (0.08)(0.06)
When 0.3 mol of HI are added, equilibrium is disturbed. At the instant,
[HI] = 0.49 + 0.3 = 0.79 M
(0.79)2
Q  KC, since KC =  130
(0.08)(0.06)
 backward reaction dominate and the equilibrium shifts to the left.
Let 2x = concentration of HI consumed (while going left) then concentration of
each of H2 and I2 formed = x
[HI] = 0.79 – 2x, [H2] = 0.08 + x, [I2] = 0.06 +x and KC = 50
(0.79  2x )2
 KC =  50
(0.08  x )(0.06  x )
 46x2 + 10.2x – 0.35 = 0
x = 0.033 or – 0.25 (neglecting the –ve value)
Finally, the equilibrium concentrations are:
[HI] = 0.79 – 2x =0.79 – 0.033  2 = 0.724 M
[H2] = 0.08 + x = 0.08 + 0.033 = 0.113 M
[I2] = 0.06 + x = 0.06 + 0.033 = 0.093
b) i) Total no. of moles at equilibrium = 7.6  10–3 + 6.6  10–3 = 1.42  10–2 moles
If 1.42  10–2 moles of argon have been added and the volume has been
doubled there will not be any change in no. of moles/litre at equilibrium.
Hence no effect
ii) At constant pressure the equilibrium will shift in the direction where no. of
moles are decreasing hence to the left.
iii) No effect at constant volume

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RSM79Ph-IICECH(H&S)-5

LEVEL – II

1. At equilibrium number of mole of Cl2 in 3 litres is 0.15  3 i.e. 0.45.


PCl5 PCl3 + Cl2
Thus x(say) 0 0 Initial mole
(x – 0.45) 0.45 0.45 Mole at equilibrium
x  0.45
0.15 0.15 Equilibrium concentration
3
Now,
0.15  0.15
KC = = 0.04 (given)
 x  0.45 
 
 3 
X = 2.1 mole

2. Suppose x mole of N2O4 changes to NO2 at equilibrium


N2O4 2NO2
0.8 – x 2x mole/1 at equilibrium
2
(2x )
 KC = = 0.00466, x = 0.03 M
(0.8  x )
 at equilibrium [N2O4] = 0.8 – x = 0.8 – 0.03 = 0.77 M
[NO2] = 2x = 2  0.03 = 0.06 M
Now when the volume of halved, pressure will increase. From the Le-Chatlier’s
Principle we know that the equilibrium will shift to left hand side with the increase in
pressure (or decrease in volume). Further when volume is halved, concentration will
be doubled.
Concentration of N2O4 = 0.77  2 = 1.54 M
And concentration of NO2 = 0.06  2 = 0.12 M
The equilibrium concentration now will be
N2O4 2NO2
(1.54 – y) (0.12 – 2y)
(0.12  2y )2
KC = = 0.00466, y = 0.104 and 0.017
(1.54  y )
y = 0.104 is unacceptable as in this case 2y  0.12, y = 0.017
 At new equilibrium
[N2O4] = 1.54 + 0.017 = 1.557 M
[NO2] = 0.12 – 2  0.017 = 0.086 M

3. a) We know, at equilibrium
[SO 3 ] 2
KC = = 100
[SO 2 ][O 2 ]
As mole of SO2 is equal to that of SO3
[SO2] = [SO3]
1
[O2] =
100

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RSM79Ph-IICECH(H&S)-6

Mole of O 2 1
 (volume = 10 litre)
10 100
 mole of O2 = 0.1

b) Further, if mole of SO3 is twice that of SO2


mole of SO 3
=2 …(1)
mole of SO 2
We again have,
[SO 3 ] 2
KC  = 100
[SO 2 ] 2 [O 2 ]
2
 mole of SO 3 
 
or  10  = 100
2
 mole of SO 3   mole of O2 
   
 10   10 
2
 mole of SO 3   10 
or     = 100 …(2)
 mole of SO 2   mole of O 2 
from (1) and (2), we get,
10
= = 100
mole of O 2
Mole of O2 = 0.4

4. Suppose x mole of O2 is added by which equilibrium shifts to right hand side and y
mole of O2 changes to SO3. The new equilibrium concentration may be represented
as
2SO2 + O2 2SO3
First equilibrium 0.5 mole 0.12 mole 5 mole
Second equilibrium (0.5 – 2y) (0.12 + x – y) (5 + 2y)
But 5 + 2y = 5.2 given  y = 0.1
[SO 3 ]2 (5  2y )2
Now, KC =  = 833 (volume = 1 lit)
[SO 2 ]2 [O2 ] (0.5  2y )2 (0.12  x  y )
Substituting y = 0.1, we get
x = 0.34 mole

5. 2AB2(g) 2AB (g) + B2(g)


Initial (mole) 1 0 0
At eq. (mole) 1–  /2 Total moles at equilibrium = (1+/2)
 1   P . 2
At eq. (p.p) P  
1  2  1   2
2
 P.   P.  2 
   
1  2  1  2 
KP = 2
21  
P  
1  2 

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P3
KP =
21    1   2
2

But 1>> 
P 3
 KP =
2
1/3
 2K P 
 =  
 P 

6. 2H2S(g) 2H2(g) + S2(g)


2(1–) 2 
Where  is the degree of dissociation
Total number of moles at equilibrium = 2–2 + 2+ = 2+
21   P 2P P
p H2 S = , p H2 = , p S2 =
2 2 2
2
 2p   P 
   
2 2  3P
KP = 
 21   P  2   1   
2 2

 
 2 
If  = 0.055 and P = 1 atm

KP =
0.055 3  1 = 9.114  10–5
2  0.055 1  0.055 
KP = KC (RT)n, [Here n =1]
KP 9.114  10 5
KC =  = 3.71  10–6
RT 0.0821  298

7. i) If there is no dissociation the pressure can be calculate as PV = nRT


PV = nRT
6.745
P1=  0.0821  375 = 1.53 atm
135
ii)  n = 1
Kp Kp
 KC= Δn
 2.4 =
(RT ) (0.821  375 )1
 Kp = 73.8
SO2Cl2(g) SO2(g) + Cl2(g)
1.53 0 0 at initial
1.53 – x x x at equilibrium
x2
Kp = = 73.8  x = 1.5
(1.53  x )
 Partial pressure of SO2Cl2 = 1.53 – x
= 1.53 – 1.5 = 0.03 atm

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RSM79Ph-IICECH(H&S)-8

c) Total pressure at equilibrium = 1.53 – x + x + x


= 1.53 + x = 1.53 + 0.3 = 1.53 atm

8. NH4HS(s) NH3(g) + H2S(g)


0.018 0.018
KC = (0.18)2 = 3.24  10–4
KP = KC(RT)n n = 2
= 3.20  10–4  (0.821  300)2
= 0.19 atm
ii) No effect

9. a) 2NO(g) + Br2(g) 2NOBr(g)


Initial pressure 98.4 41.3 0
x
At eqlbm. 98.4-x 41.3 - x
2
The total pressure at equilibrium is 110.5 torr.
x
 98.4-x + 41.3- + x = 110.5
2
x = 58.4 torr
Now, 1 atm = 760.4 torr,  x = 7.68  10-2 atm.
pNOBr = 7.68  10-2 atm ; pNO = 98.4-x = 40 torr = 5.26  10-2 atm.
x
pBr = 41.3 - = 12.1 torr = 1.59  10-2 atm.
2 2

Kp 

pNOBr  2  
7.68  10 2 2 
 134
 
pNO  2 pBr2 
=
  
5.26  10  2 2 1.59  10  2 
G = -2.303 RT log K = -2.303 (1.99) (300) (log 134) = -2.92 k cal = 12.2 k J.
o

[If R is used as 1.99 cal/mol K, then Go will be in cal. If R is used as 8.314 J/mol
K, then Go will be in Joules. But KP must always be in (atm) n.]
b) B = A, G10 = {( 2.303 8.314448)log(1.395.2)}=15.998 kJ
B = C, G20 = {( 2.303 8.314448)log(3.595.2)}=12.305 kJ .
Stability order B  C > A

10. a) PCl5(g) PCl3(g) + Cl2(g)


We are given the vapour densities at equibilibrium at 200oC and 250oC.
The initial vapour density will be the same at both the temperatures as it would
MPCl5
be .
2
 Initial vapour density =
31  5  35.5  104.25
2
Vapour density at equilibrium at 200oC = 70.2

Total moles at equilibriu m Vapour density initial


  1  
Total moles initial Vapour density at equilibriu m
104.25
=  1.485
70.2

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  = 0.485
104.25
At 250oC, 1 +  =  1.8 ,   = 0.8
57.9
b) Let us assume that we start with C moles of N2O4(g) initially.
N2O4(g) 2NO2(g)
Initially C 0
At equilibrium C(1) 2C
where  is the degree of dissociation of N2O4(g)
Total moles at equilibriu m Vapour density initial
Since, 
Total moles initially Vapour density at equilibriu m
92
Initial vapour density =  46
2
C(1   ) 46

C d
Since vapour density and actual density are related by the equation,
RT 1.84  0.082  348
V.D. = = = 26.25
2P 2
46
1+=  1.752
26.25
  = 0.752
2
 2C 
2
  2  0.75 
 PT    1
 C(1   )   1.752 
 Kp = 
C(1   ) 0.248
 PT 1
C(1   ) 1.752
KP= 5.2 atm.

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RSM79Ph-IICECH(H&S)-10

Solution to Objective Problems


LEVEL – I

1. An increase in temperature favours endothermic reaction i.e. backward reaction if


KOH (s) + aqueous KOH(aq) H = – x
 (B)

2. gas liquid H = (–)ve


 (A)

3. According to Lechatlier principle.


 (C)

4. k for overall reaction = k1  k2 = 102  102 = 1


 (C)

5. Kp = KC(RT)n
n = –1 here  Kp = 25  (0.0821  523)–1 = 0.6 atm–1
 (A)

6. Solid liquid; H = positive


Increase in temperature favours forward reaction
 (A)

[H  ][HS  ]
7. K =
[H 2 S]
An increase in [H+] will show a decrease in [HS–] to maintain constant K.
 (D)

8. Since H is positive the reaction is endothermic . As per LeChatlier principle, when


the temperature is raised, it should proceed towards that direction where heat is
absorbed i.e. towards the product side.
(A)

9. For the reaction H2 + I2 2HI (g) since n = 0. Equilibrium constant KC will be


uneffected by change in pressure.
 (A)

10. C2H5OH CH3COOH + CH3COOCH3 + H2O


Initially 1 1 0 0
1 1 1 1
At equilibrium 1 - 1-
4 4 4 4
1 1
 
CH 3 COOCH 3 H2 O 4 4 1
K= =
C 2H5 OHCH 3 COOH  3

3 9
4 4
 (A)

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RSM79Ph-IICECH(H&S)-11

11. Since decomposition of PCl5 is carried out in a closed container. When helium gas is
introduced the volume remains constant and there is no change in the partial
pressures of PCl5, PCl5 and Cl2. Therefore, nothing happens on introduction of
helium gas and constant volume.
(D)

12. KP = KC(RT)n
KP <KC if n<0
For reaction (C) the value of n is –2 and for reaction (D) the value of
n is–1
 (C) & (D)

13. 2AB4(g) A2(g) + 4B2(g) H = –ve


It is an Exothermic reaction and hence favoured at low temperature. n for the
reaction is +3. Therefore low pressure will favour the forward reaction
(C)

1
14. KC = = 7.5  102
6
1.8  10
(B)

15. For the backward reaction H = + 40Kcal mol1 for endothermic reactions K increase
with increase of temperature
 (C)

16. Volume of ice  volume of water and thus increase in pressure favours forward
reaction showing decrease in volume.
 (B)

17. Cdiamond Cgraphite


For a given mass Vdiamond Vgraphite
 Thus increase in pressure will favour backward reaction.
 (A)

18. N2 + 3H2 2NH3


a a 0 at initial
(a – x) (a – 3x) 2x at equilibrium
 (a – x)  (a – 3x)
 (B)

19. N2O4(g) 2NO2(g)


1  92g 0 at initial
92 – 92  0.2 = 73.6g
= 0.8 mole 0.4 mole at equilibrium
Total moles = 0.8 + 0.4 = 1.2

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RSM79Ph-IICECH(H&S)-12

P1 P
At constant volume =  2
n1T1 n 2 T2
1 P2
  P2 = 2.4 atm
1  300 1.2  600
 (B)

20. SO2Cl2 SO2 + Cl2


1 0 0 at initial
1–   at equilibrium
1   
PSO2Cl2  , PSO2  , PCl2 
1  1  1 
2
  
 
1   2
Kp   = 2
 1    1  2
 
 1   
= K p  2.9  10 2 = 0.17
 = 17%
 (C)

21. CO2(g) + C(s) 2CO(g)


0.5 0 at initial
(0.5 – x) 2x at equilibrium
 0.5 – x + 2x = 0.8  x = 0.3 atm
p CO2 = 0.5 – 0.3 = 0.2 atm
p CO = 2x = 0.6 atm
2
PCO (0.8) 2
kp = = = 1.8 atm
p CO 2 1.2
 (A)

22. PCl5 PCl3 + Cl2


1 0 0 at initial
1–   at equilibrium
1   104.16
   = 0.68  68%
1 62
 (B)

1
23. For the reaction SO2(g) + O2(g) SO3(g)
2
Given KP = 1.7  1012 at 20°C and 1 atm pressure
 1
KP = Kc (RT)n; n = 1– 1  
 2

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RSM79Ph-IICECH(H&S)-13

1.7  1012 = Kc (0.0821  293)–1/2


1.7  1012
Kc =
(0.0821  293 )1 / 2
Kc = 7  1012  (0.0821  293)+1/2 = 8.338  1012
(C)

24. For 2A(g) 2B(g) + C(g)


KP = 1.8 at 700°C
 For 2B(g) + C(g) 2A(g) at 700°C
1
KP = n = 2 – (2+1) = –1
1 .8
KP = Kc(RT)n
Kp
Kc =
(0.0821  973 )1
1
Kc = KP  (0.0821  973)1 =  0.0821  973
1 .8
Kc = 44.3796
 (C)

25. N2O4(g) 2NO2(g)


t=0 1 0
t = equilibrium 1– 2
n = 1 + 
2
 2 
P  1   
Kp =  
 1  
P  1   
 
P  4 2
Kp =
1  2
(C)

26. For H2(g) + O2(g) 2SO3(g)


t=0 2 moles 1 moles 0
t = equilibrium 2(1 – 0.5) 1(1– 0.5) 1 mole
2–1 + 0.5 +1 = 2.5
P = P  mF
P  0 .5 5
P2 = =1 = 0.20 atm
2 .5 25
 (D)

27. Enthalpy changed of a reaction is given by

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RSM79Ph-IICECH(H&S)-14

H = (Ea)f – (Ea)b
Where (Ea)f and (Ea)b are energies of activation for the forward and backward
reactions.
H = 12–20 = –8 kJ / mol
KP for the reaction at 25C = 10 atm. Since KP is expressed in
atmosphere, n = +1
10
KP = KC (RT)n, KC = = 0.4 M
0.0821  298
KC at 40C is given by
K C 40 H 1 1  8  1000 15
log     =  = –0.06719
K C 25 2.303R  T1 T2  2.303  8.314 298  313
(KC)40/(KC)25 = 0.85
(KC)40 = 0.85 0.4 = 0.34 M
(C)

28. 2HI(g) H2(g) + I2(g)


 
1– Where  is the degree of dissociations
2 2
1 1
K diss  
K synthesis 50
 

1
 2 22
50 1   
 1

21  2 5 2
5 2  = 2–2
2+5 2=2
2
= = 0.22
25 2
(D)

29. N2O4(g) 2NO2(g)


Equilibrium 1– 2
Where  is the degree of dissociation
P2  Pressure of N2O4 at 600 K = 600 (  V is constant )
P1 Pressure of N2O4 at 300 K 300
 P2 = 2 atm
After dissociation of N2O4 at 600K,
PN2O4 = 2 (1–) = 2–2
PN2O4 = 2  2 = 4 

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RSM79Ph-IICECH(H&S)-15

Total pressure = 2–2+4 = 2+2


2+2 = 2.4 (Given)
 = 0.2
 Percentage dissociation = 20%
(B)

30. N2 + 3H2 2NH3


t=0 0.2 0.6 0
at = t 0.2–n 0.6–3x 2x
40% of N2 = 0.2 0.4 = 0.08
40% of H2= 0.6 0.4 = 0.24
 number of moles of N2 remaining = 0.2 – 0.08 = 0.12
number of moles of H2 remaining = 0.6–0.24 = 0.36
number of moles of NH3 formed = 0.16
Total number of moles = 0.12 + 0.36 + 0.16 = 0.64
Final volume Final moles 0.64 4
  = 
Initial volume Initial moles 0.80 5
(A)

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