Chapter 4

Electrochemistry

Hints and Solutions

5. Answer (1)
SECTION - A
Ka = Cα2
1. Answer (1)
Ka 36 × 10−4
Equivalent of Cu deposited = Mole of electric α = = = 6 × 10−3
C 100
charge used
Λceq 20.4
= 0.01 Λoeq = = −3
= 3.4 × 103
α 6 × 10
∴ Weight of Cu deposited = 0.01 × 31.75
6. Answer (2)
= 0.3175 g
ΔG = − nFEocell
Equivalent of oxygen discharged = 0.01
= – (2)(96500)(1.23)
∴ Weight of oxygen discharged = 0.01 × 8
= – 237390 J/mol
= 0.08 g
ΔG − 237.39 kJ/mol
η= × 100 = × 100 = 83%
Total loss in weight due to electrolysis ΔH − 285.8 kJ/mol
= 0.3175 + 0.08 7. Answer (1)
8. Answer (4)
= 0.3975 g
9. Answer (1)
∴ The weight of the resulting solution
Cr | Cr2(SO4)3 || Ag⊕ | Ag
= 10 – 0.3975
(0.1 M) (0.1 M)
= 9.625 g
2Cr + 6Ag⊕ ⎯⎯→ 2Cr 3⊕ + 6Ag
2. Answer (2) 0.2 M
Co2+ will form complex with NH4OH due to which 0.059 [Cr 3 + ]2
conc. of Co2+ decreases. Ecell = Eocell − log
6 [Ag+ ]6
3. Answer (3)
0.059 (0.2)2
1 = 0.8 − ( −0.74) − log
( ) (0.1)6
2
6
0.0591 pH2
Ecell = 0 − log 0.059
1 [H+ ] = 1.54 − log (2 × 102 )
3
1 0.059
Ecell ∝ and Ecell ∝ [H+ ] = 1.54 − [2.3]
pH2 3
= 1.54 – 0.045
4. Answer (4) = 1.495 V

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Hints & Solutions Electrochemistry 39
10. Answer (2) 21. Answer (1)
11. Answer (3) I⋅ t W
= [According to Faraday’s law of
+ 1 −
96500 E
H + e → H2 electrolysis]
2
1
VH2
0.059 PH22 =
E = E° − log + 11200 ml at STP
1 [H ]
11200 × 4 × 1930
1 ⇒ VH2 at STP = ml
0.059 (100) 2 96500
= 0− log = −0.059 V
1 1 = 896 ml or 0.896 L

12. Answer (2) 22. Answer (2)

13. Answer (2) 23. Answer (2)

Lower the value of E0red more is the reactivity
9
Al3+ + 3e– ⎯⎯→ Al ⇒ = 1 equivalent 24. Answer (2)
27/3
∴ Volume of Cl2 = 11.2 × 1 = 11.2 L 1 mole Al2(SO4)3 gives 2 mole Al3+
14. Answer (3) ∴ Charge required = 6 F
Cu2+ + 2e– → Cu, ΔG1° = –2Fx ... (1) 1 mole Bi2(SO4)3 gives 2 mole Bi3+
Cu+ → Cu2+ + e, ΔG2° = +Fy ... (2) ∴ Charge required = 6 F

Aim : Cu+ + e → Cu, ΔGo3 = ΔG1o +ΔGo2 1 mole CuSO4 gives 1 mole Cu2+

–FE° = –2Fx + Fy ∴ Charge required = 2 F

E° = 2x – y 1 mole of Ag2SO4 gives 2 mole Ag+

15. Answer (3) ∴ Charge required is 2 F

25. Answer (3)
Λm
o
Ba(OH)2 = p + 2q − 2r
26. Answer (4)
p + 2q − 2r 27. Answer (3)
Λ eq Ba(OH)2 =
2 28. Answer (1)
16. Answer (4) Specific conductance (K 1 ) of solution A =
17. Answer (3) 1 ⎛ l ⎞
⎜ ⎟
100 ⎝ A ⎠
Ag+ + e– ⎯⎯→ Ag; nAg = 3 moles from 3 F

3 1 ⎛ l ⎞
Cu2+ + 2e– ⎯⎯→ Cu; nCu = moles K2 of solution B = ⎜ ⎟
2 200 ⎝ A ⎠

18. Answer (1) When equal volume of solution A and B are

mixed then volume is doubled and net specific
19. Answer (2) conductance will become half.
20. Answer (4)
1 1 ⎛ l ⎞
∴K = (K 1 + K 2 ) = ⎜ ⎟
4OH– ⎯⎯→ 2H2O + O2 + 4e– 2 Rmix ⎝ A ⎠
2H2O ⎯⎯→ 2H2 + O2
1⎛ 1 1 ⎞ l 1 ⎛ l ⎞
∴ ⎜ + ⎟ = ⎜ ⎟
44.8 L 22.4 L 2 ⎝ 100 200 ⎠ A Rmix ⎝ A ⎠
Total volume = 44.8 + 22.4 = 67.2 L
∴ Rmix = 133.33 Ω

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40 Electrochemistry Hints & Solutions

29. Answer (2) 41. Answer (1)

30. Answer (3) 42. Answer (1)
31. Answer (1) 43. Answer (3)
32. Answer (1) 44. Answer (3)
Fe 2+
+ 2e → Fe–
...(i) (E1 ) 0

[H+ ]cathode
Fe 3+
+ e → Fe
– 2+
...(ii) (E2 ) 0 E cell = 0.059 log
[H+ ]anode
Fe 3+
+ 3e → Fe–
...(iii) (E3 )0

3rd reaction is obtained by adding (i) and (ii) 1

0.295 = 0.059 log +
ΔG1 = – 2FE1 , ΔG2 = – FE2
0 0 0 0 [H ]anode

∴ ΔG30 = – 2FE10 – FE20 = – 3FE30 [H+]anode = 1 × 10–5 M

2E10 + E02 [H+ ] = k a C ⇒ 1× 10 −5 = k a × 0.01

∴ E03 =
3
ka = 1 × 10–8
33. Answer (3)
45. Answer (2)
0.0591 [1 × 10 −3 ] For concentration cell E0Cell is zero because two
Ecell = log
1 [1 × 10 − 5 ]
electrodes of same material having different
concentration of electrolyte solution is used.
= 0.0591 × 2 = 0.118 V
46. Answer (3)
34. Answer (4)
W = – nFE0 = – 2 × 96500 × 1.10 = 212300 J
35. Answer (2)
= 212.3 kJ
It is a concentration cell
47. Answer (3)
C2
∴ Ecell = 0.059log In CaSO4 (aq.), reaction is
C1
2H+ + 2e– → H2 (g)
C2
0.118 = 0.59 log 5
10−4 5 F will liberate mole
2
⎛ C2 ⎞ In CuSO4 (aq.),
2 = log ⎜ −4 ⎟
⎝ 10 ⎠
Cu2+ + 2e– → Cu (s)
On solving pH = 2
5
36. Answer (4) 5 F will liberate mole
2
37. Answer (3)
In Al2(SO4)3 (molten)
38. Answer (3)
Al3+ + 3e– → Al (s)
0.059 log [H+ ]2
E = Eº −
2 5
∴ 5 F will deposit mole
0.059 log [10 −2 ]2 3
= 1.30 −
2
In Na2SO4 (molten)
0.236 = 1.418 V
= 1.30 + Na+ + e– → Na (s)
2
5F will deposit 5 mole
39. Answer (1)
∴ Ratio of moles obtained is 3 : 3 : 2 : 6
40. Answer (1)

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Hints & Solutions Electrochemistry 41
48. Answer (3) 61. Answer (4)
At Cathode Fact.
2H+ + 2e– → H2 62. Answer (4)
4 F will give 2 mole of H2 Fact.
∴ Volume = 2 × 22.4 = 44.8 litre 63. Answer (4)

At Anode On dilution equivalent conductance increases for

both.
4OH– → O2 + 2H2O + 4e–
64. Answer (1)
∴ 4 F gives 1 mole of O2
2H+ + 2e– → H2
∴ Volume = 22.4 litre
22400 cc H2 gas at NTP requires 2 × 96500 C
∴ Total volume = 67.2 litre.
∴ 1 cc of H2 gas at NTP requires
49. Answer (2)
2 × 96500
×1 C
EH+ /H = EH0 + /H + 0.0591log[H+ ] 22400
2 2

As Q = I × t = 8.616 C
50. Answer (2)
1 equivalent of H2 = 11.2 L at STP Q 8.616C
I= = = 8.616 A
1 equivalent of O2 = 5.6 L at STP t 1s

51. Answer (3) 65. Answer (3)

Fact. 66. Answer (3)
52. Answer (3) 3 F for Al+++, 2 F for Cu++, 1 F for Na+ are required.
Zn is most reactive metal. 67. Answer (1)
53. Answer (4)
0.059 [R]
E = Eo + log
Fact. 1 [OX]
54. Answer (1)
0.059
Slope is = –A = 0+ log100 = 0.118 V
1
CaCl2 = 2 – 1, CaSO4 2 – 2 electrolyte
68. Answer (2)
55. Answer (4)
5.4
IF of electricity liberate – 1 g equivalent of Number of equivalents of Ag = = 0.05
any substance. 108

56. Answer (2) Number of farday = 0.05

Fact. So,

57. Answer (3) Number of equivalents of Cu should be

deposited = 0.05
pH = 10, pOH = 4, (OH–) = 10–4 M
Actual number of equivalent deposited
58. Answer (3)
pH1 > pH2 0.8
=
59. Answer (1) ⎛ 63.5 ⎞
⎜ ⎟
⎝ 2 ⎠
60. Answer (3)
= 0.0125 × 2
FeO → Fe2O3 → 2F
= 0.025

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42 Electrochemistry Hints & Solutions

80. Answer (1)

0.025
% current efficiency = × 100
0.05 8H+ + MnO4– → Mn++ + 4H2O + 5 e ; 5F can
= 50% deposit 1 mole, so for 0.01 mole →

69. Answer (4) 5

× 96500 C = 4825 C
100
70. Answer (2)
71. Answer (3) 81. Answer (3)

Cell reaction 2H2 O + 2e – ⎯⎯→ 2H2 + 2OH

+ +
Ag(s) + Ag(0.01) ⎯⎯→ Ag(0.001 M) + Ag(s) 2H2 O ⎯⎯→ O2 + 4H+ + 4e –

0.0591 0.001 82. Answer (3)

Ecell = – log
1 0.01 Oxidation takes place at ANODE, in which loss
= 0.0591 of electron takes place. Cl– oxidises in the place
of OH– due to higher oxidation potential of Cl–.
72. Answer (1) (due to over voltage)

E × 1× 965 83. Answer (4)

1.08 =
96500
24125 1
24125 C = F= F
E = 108 96500 4
73. Answer (4) Let charge be n
If εext < εcell, current flows from cathode to anode.
7.42
74. Answer (3)
118 = 1
The gram equivalent of Sn+n =
S2O82–. n 4
75. Answer (4) n=4
εocell = 0, concentration cell. 84. Answer (4)

76. Answer (1) Fact.

85. Answer (4)
From eq. (i), E >E
Y2 /Y − X2 / X−
ΔG = for spontaneous process.
eq. (ii), E >E 86. Answer (3)
W2 /W − Y2 /Y−
Fact.
eq. (iii), E >E
X2 / X − Z2 /Z− 87. Answer (1)

77. Answer (4) Zn ⎯⎯→ Zn2+ + 2e − = –(–0.76) = +0.76

78. Answer (1)
2e− + Cu2+ ⎯⎯→ Cu = +0.34
Λm
c
7.40
α= ∞
= = 0.019 EMF (emf) = Eoxi + Ered = 0.76 + 0.34 = 1.10 V
Λm 390.0
88. Answer (2)
∴ Ka = Cα2 = 0.05 × (0.019)2
∵ Eocell =+ve
= 1.8 × 10–5
89. Answer (4)
79. Answer (3)
90. Answer (2)
Fact.

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Hints & Solutions Electrochemistry 43
91. Answer (1) 103. Answer (3)

Reduction Λ ∞BaSO4 = BaCl2 + H2 SO 4 − 2HCl = x + y – 2z

1 1
I– + Br2 ⎯→ Br– + I2 104. Answer (1)
2 2
Oxidation
105. Answer (1)
Fact
E° = E°c − Ea°
106. Answer (4)
= 1.09° – (0.54)
Fact
= 0.55 V
107. Answer (2)
92. Answer (4)
EMF = EC – EA
93. Answer (2)
= – 0.41 – (– 0.76) = + 0 .35 V
Ecell = ERHS – ELHS
108. Answer (1)
+
(Ag )RHS W = ZIt
= 0.0591log
(Ag+ )LHS W=Z
∴ It = 1
K sp AgBr
1
= 0.0591log (Br − ) I= = 4A
.25
K sp AgCl
(Cl− ) 109. Answer (2)
Fact
−13
3.3 × 10 0.2 110. Answer (2)
= 0.0591 log × −10
0.001 2.8 × 10
2+ +
Cu + e ⎯→ Cu ; ΔG1 = – 1 F × 0.30
= –0.0371 volt +
Cu + e ⎯→ Cu ; ΔG2 = – 1 F × 0.15
94. Answer (1) 2+
Cu + 2e ⎯→ Cu ; ΔG3 = ΔG1 + ΔG2
95. Answer (3)
96. Answer (4) – 2FE° = – 0.3 F – 0.15 F
97. Answer (1)
0.45
⇒ E° = = 0.225 V
98. Answer (2) 2
99. Answer (4) 111. Answer (4)
100. Answer (1)
∧mc 20 1
On the basis of reduction potential (Z > Y > X) α= = = = 0.02
∧m0 100 5
higher is the reduction potential, higher will be
oxidizing power.
cα 2 0.1× 0.2 × 0.2 0.004
101. Answer (1) K= = = = 5 × 10−3
(1 − α ) 1 − 0.2 0.8
102. Answer (1)
112. Answer (3)
500 × 4
Number of mole of NaCl = = 2 moles Molar conductivity increases with dilution.
1000
113. Answer (2)
= 2 moles of Cl– ions
Lower the red. potential, stronger will be reducing
= 1 mole Cl2 agent.

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44 Electrochemistry Hints & Solutions

114. Answer (1) 125. Answer (4)

27 g Al ⎯→ 3 F
Al3( + ) + 3e − ⎯⎯→ Al
3 3F 1mole
40 g Al ⎯→ × 40 = 4.4 F
27 30 F 10 mole
115. Answer (3) 126. Answer (1)
Fact ΔG° = –nFE°
116. Answer (4)
−2 × 1.67 × 96500
Fact = kJ
1000
117. Answer (2)
= –322.31 kJ
Fact
127. Answer (4)
118. Answer (1)
128. Answer (1)
0.059 C E°cell = 0.44 + 1.23 = 1.67V
Ecell = Ecell
º
+ log 2
n C1
ΔG° = –nE°F = – 2 × 1.67 × 96500
For Ecell to be positive C2 > C1 or C1 – C2 < 0 = – 322.31 kJ/mole
119. Answer (1) 129. Answer (3)
120. Answer (2) 130. Answer (3)
Upon electrolysis of aq. NaCl, [OH(–)] increases,
so pH of the solution will increase. 1 1 1
nAg : nCu : nPb= : : =4:2:1
1 2 4
121. Answer (3)
131. Answer (1)
Mn2(+) + 2e(–) ⎯→ Mn, ΔG° = –nFE° = 2.36 F...(i)
Mn3(+) + e(–) ⎯→ Mn2(+), Na2 SO4 ⎯⎯→ Na + + SO24−
ΔG° = –nFE° = –1.51 F...(ii) + −


 H + OH
H2 O 
Adding (i) and (ii),
Mn3(+) + 3e(–) ⎯→ Mn, ΔG0 = 2.36 F + (–1.51 F) Cathode : 2H+ + 2e − ⎯⎯→ H2 ↑
∴ ΔG° = –nFE°
1
⇒ 2.36 F – 1.51 F = –3 F × E° Anode : 2OH– ⎯⎯→ H2 O + O2 ↑
2
∴ E° = –0.28 V 132. Answer (1)
122. Answer (3) 2H+ + 2e– ⎯→ H2
When cell stop functioning, Ecell = 0.
0.0591 PH 5
123. Answer (4) E=− lo g +2 2 = −0.0295 lo g –2 2
2 [H ] [10 ]
Fact
124. Answer (4) = –0.0295 [log 5 – log 10–4] = –0.03 [0.7 + 4]

−)
= –0.03 [4.7] = –0.14 volt
FeO2(
4 ⎯⎯⎯
n=3
→ Fe3( + ) ⎯⎯⎯
n =1
→ Fe2( + )
133. Answer (3)
Fe = + 6 Fe = +3 Fe = +2
⇒
0
ERep I2 < Br2 < Cl2
3 × 2.20 + 0.77
E° −) =
FeO2(
4 Fe2( + ) 4 Br2 → Reduction and I2 → Oxidation

7.37 

= = 1.843 V ∴ Cell reaction ⇒ Br2 + I– 
 Br– + I2
4
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Hints & Solutions Electrochemistry 45
SECTION - B ∴ Charge are different.

Assertion and Reason are correct but Reason is

1. Answer (2)
not the correct explanation of Assertion.
Fact.
5. Answer (1)
2. Answer (3)
6. Answer (4)
3. Answer (1)
At anode, oxidation occurs and metal atom from 7. Answer (2)
electrode gets oxidised and electrons are 8. Answer (4)
released at electrode.
∴ It is a negative electrode.
º
This is because EFe 2+
|Fe
> EHº O|H2
2

4. Answer (2)
9. Answer (1)
To deposit 1 mole of Ag, 1F charge is required
Fact.
and to deposit 1 mole Zn, 2F charge is required.

  

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