Chapter 6

Equilibrium
1. Answer (D)
At equivalence point

N1V1  N2 V2
(base) (acid)

2 2
2.5 × = ×V
5 15
V = 7.5 ml
 Milli equivalents of salt = 1

Ch2 K w 10 –14
Kh =    10 –2
1– h K b 10 –12

0.1h2
10 –2 
1– h
h = 0.27
[H+] = Ch = 0.1 × 0.27
Hence [H+] = 2.7 × 10–2 M
2. Answer (D)
(MX) S2 = 4.0 × 10–8
S = 2.0 × 10–4
(MX2) 4S3 = 3.2 × 10–14
S3 = 0.8 × 10–14
S3 = 8 × 10–15
S = 2 × 10–5
(M3X) 27S4 = 2.7 × 10–15
S = 1 × 10–4
 Order is MX > M3X > MX2
3. Answer (C, D)
Solution of weak acid and its salt with strong base behave like buffer.
4. Answer (A)
Rate with respect to weak acid
R1 = K[H+]WA[ester]
and rate with respect to strong acid
R2 = K[H+]SA[ester]

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R1 [H+ ] WA 1
 = + =
R2 [H ]SA 100

[H ]SA 1
 H     0.01M  C
WA 100 100
 = 0.01
Ka for weak acid = C2
= 1(0.01)2 = 1 × 10–4
5. Answer (A, B, D)
CaCO3 (s)  CaO(s)  CO2 (g)
K  PCO2
K is only dependent on temperature and it is independent of the amount of reactant or product.
H is dependent on temperature according to Kirchoff's equation but independent of addition of catalyst.
6. Answer (B)

The solubility of Ag2CrO4 = CrO–2 

 4 

K sp 1.1  10 –12
  –2 
 1.1  10 –10 mol L1
CrO4    2

(0.1)2
 Ag
 

7. Answer (B)
On increasing temperature forward as well as backward reaction rate increases due to which initially %yield of
NH3 is higher at T2 K but equilibrium attain at lower time at T2 K hence its yield at equilibrium is low at T2 K.
8. Answer (A, D)
With increase in temperature, the value of rate constant for exothermic reaction decreases because favourable
change in entropy of surroundings decreases.
9. Answer (A, C)
ln K1 T2

ln K 2 T 1
 On increasing temperature, K decreases.
 H° < 0
From graph K > 1  G° < 0

– H S

ln K1 TR R T
 1  2
ln K 2 H S T1

T2R R

( H  T1S) T2 T2

( H  T2 S) T1 T1

–H° + T1S° > –H° + T2S°

 S° < 0

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10. Answer (A)

Exp-1
Energy released = 5.7 kJ
Heat absorber by temperature rise = 200 × 4.2 × 5.7 = 2 × 42 × 57 = 4.788 kJ
Calorimetric constant = 5.7 – 4.788 = 0.912 J
Exp-2
Q = 200 × 4.2 × 5.6 = 4.704 kJ
Net energy = 4.704 + 0.912 = 5.616 kJ
Per mole of neutralization energy released = 56.16 kJ
Dissociation energy = 57 – 56.16 = 0.84 kJ  1 kJ
11. Answer (B)
Buffer is formed.

CH3COO  
pH  pK a  log  
CH3COOH

As per given question concentration of CH3COO– and CH3COOH is equal.

pH = pKa = –log2 + 5 = 4.7
12. Answer (B)
X2(g) 


 2X(g)
Initial mole: 1 0

  eqbm 
Moles at equilibrium : 1   eqbm
2 

eqbm
1 eqbm
2 P P
Partial pressure :
 eqbm   eqbm 
1   1  
2  2 

(Px )2 2eqbmP
 Kp = 
Px2   2eqbm 
1  
4 

42eqbm × P
 Kp =
4   2
eqbm 
Since P = 2 bar

82eqbm
So, K p 
4   2
eqbm 

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13. Answer (C)

Since, G°, is positive
It means Kp < 1.
Kp = –2.303 RT log Kp
So,  eqbm = 0.7

8  (0.7)2
Kp = 1
4  (0.7)2
Hence, eqbm  0.7
14. Answer (D)

20  0.1– 10  0.1 1
(P) CH3COOHold  30

30

CH COO –  = 1
 3  old 30

Buffer with [Salt] = [Acid]

pH does not change on dilution (P)  (1)

20 × 0.1 2
(Q) [ CH 3COO– ] old = =
40 40

2
[ CH 3COO– ] new = 80

–
 CH3 COOH+ OH–
CH3COO + H2O 
c x x

– 2 – 2
x 2 [OH ]old [OH ]new
Kh = = =
c 2 / 40 2 / 80

– 2
 [OH ] new = [OH ]old
– 2

[OH– ]old
 [OH– ]new =
2

 [H+ ]new = 2[H+ ]old

(Q)  (5)

20 × 0.1 2
(R) [NH+4 ]old = =
40 40

2
[NH +4 ]new =
80

 NH4 OH + H+
NH+4 + H2 O 
c y y

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y 2 [H+ ]old
2
[H+ ]2
Kh = = = new
c  2 / 40   2 / 80 

+ [H+old ]2
 [Hnew ]2 =
2
+ [H+ ]old
[Hnew ]=
2
(R)  (4)

–
(S) For a saturated solution, [OH ] = 3 2K sp

irrespective of volume of solution. [H+] remains constant.

(S)  (1)
15. Answer (8)

pK a 4 2
pH = 7   log C = 7   8
2 2 2
16. Answer (3)
In basic medium, red litmus paper turn blue



(1) CN  H2O 
 HCN  OH




(2) CO32  H2 O  
 HCO 3  OH




(3) CN  H2O 
 HCN  OH


17. Answer (6)

H2SO4, H3PO3, H2CO3, H2CrO4 and H2SO3 and H2S2O7 will behave as dibasic acid.
18. Answer (7)

 Ag  Cl
AgCl 
x xy

K sp1 = 1.6 × 10–10 = x(x + y) ...(i)

 Cu  Cl
CuCl 
y yx

K sp2  1 10 –6  y(x  y) ...(ii)

From equation (i) and (ii),

K sp1 x
 1.6  10 –4  ...(iii)
K sp2 y

 x = 1.6 × 10–4 y

 K sp1  1.6  10 –10  1.6  10 –4 y(1.6  10 –4 y  y)

 10–6 = y2(1.6 × 10–4 + 1)

 y = 10–3  x = 1.6 × 10–7
 [Ag+] = x = 1.6 × 10–7

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19. Answer (4.30 – 4.60)

AB(s)  A  (aq)  B  (aq)

s s x

B   H3  HB
s x 10

Ka of HB = 1 × 10–8

H  B   s  x   103

Ka      
HB x

sx
 105 s  x  x  10 5
x

Ksp = [A+] [B–] = s(s–x) = 2 × 10–10

Sx = 2 × 10–5 s2–sx = 2 × 10–10
s2 = 2 × 10–10 + 2 × 10–5
s2 = 2 × 10–5

s  20  103  4.47  103

20. Answer [(–14.7) – (–14.5)]

1
(i) 2Cu(s)  O2 (g)  Cu2O(s), G  –78 kJ / mole
2

1
(ii) H2 (g)  O2 (g)  H2O(g), G  –178 kJ / mole
2

(i) – (ii)

2Cu(s)  H2 O(g)  Cu2O(s)  H2 (g), G  100 kJ

G  G  RT ln K  0

 pH 
 105  8  1250 ln  2 0
 pH O 
 2 
 pH 
10 4 ln  2   105  0
 pH O 
 2 

ln pH2 – ln pH2O  –10

–2
Now, pH2O  XH2O  PTotal  0.01 1  10

 ln pH2  2 ln10  –10

ln pH2  4.6  –10

ln pH2  –14.60

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21. Answer (8.70 – 9.10)

2+ 2– 17
Fe (aq) + S (aq) FeS(s), K = 1.6 × 10
t0 0.03 0.1 –
t eq x 0.1 – 0.03 –
 0.07

1
 x(0.07)   10 17
1.6

 x  8.93  10 17 M

 Y = 8.93
22. Answer (0.25)

A B
pA = 1 bar (maintained throughout the experiment)
From diagram:
PB
K  eq 1000 K 
PA
 10

 (rG°)1000 K = –RTlnKeq = – 1000Rln10

PB'
(Keq)2000 =  100
PA

(rG°)2000 K = –2000 Rln100

( r G)1000 K 1000 Rln10

 
( r G)2000 K 2000Rln100

1
  0.25
4
23. Answer (2.80 to 3.20)
B + HA  BH+ + A–
Volume of HA used till equivalence point = 6 mL (from given diagram)
At half of equivalence point, solution will be basic buffer with B and BH+.
[BH ]
 pOH  pK b  log
[B]
At half equivalence point : [BH+] = [B]
 pOH = pKb = 14 – 11 = 3

 pK b  3
24. Answer (0.2)

ZnS(s) Zn2  (aq)  S 2  (aq)

[Zn2+] = 0.05 M
K sp (ZnS)
 [S2–]max (to prevent precipitation) =
[Zn2  ]

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1.25  1022
=  2.5  1021 M
0.05
H2S 2H+ + S2–
[H ]2 [S2  ]
K1  K 2 
[H2 S]
[H ]2  2.5  1021
 1 1021 
0.1
1
 [H ]2 
25
1
 [H ]   0.2 M
5
Ans  0.20

25. Answer (166.28)



X(s) 
 Y(s)  Z(g)

pz
Given K 
po

Hº
lnK  lnA –
RT

pz H
 ln  ln A –
po RT

 p 
d ln  oz 
pz 1  p   – Hº
Slope of ln vs is  
po T  1 R
d 
T

– Hº
From the graph, we have  –2  104
R
4
  Hº  2  10  8.314 J
Hº = 166.28 kJ mol–1
26. Answer (141.34)
–RTln K = Gº = Hº – TSº

Hº Sº
lnk  – 
RT R

Sº
 17
R
Sº = 17R
= 141.338 J K–1
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27. Answer (10.02)

First acid base reaction between H2CO3 and NaOH takes place.

H2 CO3  NaOH  NaHCO3  H2O

0.01 mole 0.01 mole – –
– – 0.01 mole

In the final solution, we have 0.01 mole Na2CO3 and 0.02 moles of NaHCO3.
Here, we have a buffer of NaHCO3 and Na2CO3.

[Salt]
 pH  pK a2  log
[Acid]

 0.01 
 
0.1 
 10.32  log 
 0.02 
 0.1 
 

1
 10.32  log
2

= 10.32 – log2
= 10.32 – 0.3
= 10.02
 pH = 10.02
28. Answer (6)

H2 SO4  H  HSO24 (K a1 is very large)

1M 1M



HSO 4   2
 H  SO4 K a2  1.2  102

[SO24 ] coming from Na2SO4 = 1.8 × 10–2

[SO24 ][H ] 1.8  102  1

  K a2
[HSO 4 ] 1

 Rather than dissociation of HSO4 into H+ and SO24 ions, association between already present H+ and

SO24 will take place.

Assuming ‘x’ mol/L of SO24 and H+ combines to form HSO4

 [SO24 ]  1.8  102  x

[H ]  1  x  1 

 (assuming x  1)
[HSO4 ]  1  x  1

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(1.8  10 2  x)1
 1.2  102
1

 x = 0.6 × 10–2

[SO24 ]  1.2  102 M



PbSO4 (s)  2 2
 Pb (aq)  SO4 (aq)
If solubility of PbSO4 = s M

 [Pb2 ]  s

[SO24 ]  s  1.2  102  1.2  102 (assuming s << 1.2 × 10–2)

 s  1.2  102  1.6  10 8

1.6
s  106  1.33  106
1.2

On comparing with X × 10–Y

Y=6



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