CHEMISTRY BOOK-3

OBJECTIVE QUESTIONS
SOLUTIONS
ELECTROCHEMISTRY

SOLUTIONS
2
1. (C) MnO 8H 5e Mn 4 H 2O i.e., 5 F
4
1mol 5 mol

Hence, electricity required 5 96500C

482500C 4.83 105 C
W1 E1 Z1.I .t Z E
2. (C) or 1 1
W2 E2 Z 2 .I Z 2 E2
3. (D) Charge of one mole ( 6.023 1023 ) electrons 96500C .
4. (C) In an electrolytic cell, the electrons so not flow themselves. The migration of ions towards oppositely
charged electrodes, indirectly constitutes the flow of electrons from cathode to anode through internal
supply.
3
5. (B) Q it or Q 10 10 t
2 H 2O 2e H 2 2OH
1 mole of H2 is liberated by 0.02 Faraday of charge.
i.e., Q 0.02 96500
from (i) and (ii), 10 103 t 0.02 96500
0.02 96500
t 3
19.3 104 sec
10 10
6. (B) In strong electrolyte, number of ions remains constant so equivalent conductance increases due to
increase in ionic mobility.
M 1
7. (A) Given, concentration C M
32 32
mc 8.0 mho cm 2 ; 0m 400 mho cm 2
cm 8
Degree of dissociation 0.02
0m 400
and dissociation constant,
C 2 1
Kc 0.02 0.02 1 1 1.25 105
1 32
8. (C) On dilution, the volume of the solution increases, thus equivalent as well as molar conductivities
increases. However, the number of current carrying particles per cm 3 decreases on dilution the
solution.
9. (D) According to Debye __ Huckel s theory, for a strong electrolyte (like NaCl), C B C
10. (D) Na+ + 1e Na(s)
11. (B) MnO4 + 2H2O + 3e MnO2 + 4OH
Change required for the reduction of 1 mol of MnO 4 to MnO2 = 3F (as charge = nF).
12. (B) W=ZIt
75
= 4 104 12 3 3600 = 38.8 g
100

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13. (C) Al3+ + 3e Al(s) 3F 1 mole Al
Cu2+ + 2e Cu(s) 3F 1.5 mole Cu
Na+ + e Na(s) 1F 1 mole
3F 3 mole.
14. (B) NaCl aq Na Cl
H 2O H OH
1
H + e H 2
2
Thus, 0.5 mole of H2 is liberated by 1 F = 96500 C.
96500
0.01 mole of H2 will be liberated by charge 0.01 1930C
0.5
Q 1930C
Q I t or t
I 10 1013 A
193000sec 19.3 104 sec
15. (D) When an aqueous solution of NaCl is electrolysed, hydrogen is liberated at cathode.
Specific conductivity and molar conductivity are different terms. Silver nitrate solution cannot be
stored in a copper container as silver will get precipitated because of high reactivity of Cu than Ag.
The addition of liquid bromine to iodide solution turns it violet.
Br2(l) + 2I(aq) 2Br(aq) + I2(l)
16. (D)
17. (D) In the absence of electric field the ions in the solution move randomly due to thermal energy.
18. (B) Mass of silver in coated layer = volume density
= (80 5 103) 1.05 g = 0.42 g
ItE
W =
96500
W 96500 0.42 96500
t 125.09 sec
1 E 3 108
0.108 108
19. (C) ; V0 2 5.6 mL.
V0 2 5.600
W1 E1 W 9 9 19.5
20. (A) 1 W1 4.5 g.
W2 E2 19.5 39 39
21. (C) oBaSO4 oBaCl2 oH2SO4 2oHCl x1 x2 2x3
1000 sp. conductance
oBaSO4
solubility (in saturated solution)
1000 y
x1 x2 2 x3
solubility
1000 y
Solubility (BaSO4) N
x1 x2 2 x3
1000 y
M
2 x1 x2 2 x3
BaSO 4 Ba 2+ SO 24

K sp BaSO4 Ba 2+ SO24 M 2

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 106 y 2

4 x1 x2 2 x3
2

22. (C) (126 Scm2 ) 0NaCl 0Na Cl

0
.....(1)

(152 Scm2 ) 0KBr 0K 0Br .....(2)

(150 Scm2 ) 0KCl 0K Cl

0
.....(3)
By equation (1)+(2) (3)
0NaBr 0Na 0Br
= 126 +152 150 = 128 S cm2 mol1
23. (C) Specific conductance = S m1
24. (A)
25. (C) A cation having highest reduction potential will be reduced first and so on. However, Mg2+ in aqueous

solution will not be reduced E oMg2+ /Mg E 1 . Instead water would be reduced in
2 OH
H O/ H
2
2
preference.
26. (C) The ionic motilities of K+ and NO3 ions are nearly the same. It helps to keep the cathode and anode
half-cells neutral at all times.
27. (C)
28. (A) Basic definition of Daniell cell
29. (A) Zn s 2Haq Zn2aq H 2 g

0.059 Zn 2
Ecell Ecell log 2
2 H

When H 2 SO4 is added then H will increase therefore Ecell will also increase and equilibrium will
shift towards right.
30. (D) Ecell Ecathode
0
Eanode
0
or Ecell Ecathode
0
Eanode
0

(red) (red) (red) (oxid)

Or Ecell Eanode
0
Ecathode
0

(oxide) (oxid)

31. (C) In the cell Zn | Zn 2 || Cu 2 | Cu the negative electrode (anode) is Zn. In electrochemical cell
representation anode is always written on left side while cathode on right side.
32. (A) Strongest oxidizing agent has higher reduction potential. Strongest reducing agent has lowest
reduction potential.
33. (B)
34. (D) emf will decrease
35. (D)
36. (B)
37. (C)
38. (B)
39. (A) Ag Ag+ + e
0.0591
E1 = Eoxid + Ecalomel = Eo log KsP1 Ecalomel
1
0.0591
E2 = Eo log KsP1 Ecalomel
1
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 KsP1 KsP1
E2 E1 = 0.177 = 0.0591 log ; 103
KsP2 KsP2

40. (C) The Ecell is given by

0.0591
Ecell log Keq
n
0.0591
0.591 log Keq
1
or log Keq 11010
41. (B)
42. (D) r G 394.4 2 237.2 166.2 702.6 kJ mol-1
r G 702.6
Efficiency 100 97%
H 726
43. (C) Given, GoH Ol 237.2kJ/mol
2

GoCO2 g 394.4kJ/mol ; G oC5H12g 8.2kJ/mol

C5 H12 8O2 5CO2 6H 2 O

G o 5 G oCO2 6 GoH2O G oC5H12 G Oo 2
5 394.4 6 237.2 8.2 0
3387kJ/mol
In pentane-oxygen fuel cell 32 electrons are involved.
Go nFEo
3387 103 32 96500 Eo 16 O 32e 16O2
3387 103
or E o = 1.0968V
32 96500
44. (B) Zn l Hg s ZnO s Hg l
The cell potential remains constant during its life as the overall reaction does not involve any ion is
solution whose concentration changes during its life time.
45. (B) During the charging of a lead storage battery, the reaction at the anode cathode are
Anode: PbSO 4 2e Pb SO 24
Cathode:
PbSO 4 2H 2O PbO 2 4H + SO 42 e
In Both the reactions H2SO4 is regenerated.
46. (A) The discharged acid cell (lead storage battery or cell) can be recharged by passing a direct current
though it in opposite direction. During recharging of cell, the electrode material are restored in their
original forms. Due to formation of H+ and SO 24 ions the specific gravity of sulphuric acid increases
and it attains the original value (1.3 g/cm3) and also its EMF (voltage) increases.
47. (A) Reactions (ii) is feasible because for this Ecell ve and from G NfE, G ve
48. (D) Calomel electrode reaction,
1
Hg2Cl2 s e Hg(l ) Cl ( aq.)
2
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 Calomel electrode.
ECl / Hg Cl / Hg
2 2

2.303RT
E log[Cl ]
Cl / Hg2Cl2 / Hg F
Thus calomel electrode functions as the reversible chloride electrode.

49. (C) EOP ERP

50. (A) Ecell ve, then

A A e
B e B
A B A B
51. (B) Zn Fe2 Fe Zn2
0.059 Fe2
Ecell Ecell log
2 Zn2
0.059 0.001
0.2905 Ecell log
2 0.01
Ecell 0.2905 0.0295 0.32 V
0.059
Now Ecell log10 Kc
2
0.059
0.32 log10 Kc
2
0.32
K c 10 0.0295

2 4
52. (A) Al2O3 Al O2 , r G 966 kJ mol 1
3 3
Thus, 3O , i.e., 2O O2 , n 4
2 2 2

3
966 103 4 96500 E or E 2.50 V
Thus, minimum potential difference required 2.50 V .
53. (D) E o 3.17 V, n 2
Mg 2+ 0.02
Q 20000
0.001
2 2
Ag +

G o nFE o 2 96500 3.17 611.8kJ

0.059
E Eo log10 Q
n
0.059
3.17 log 20000 3.04 V
2
54. (B)
55. (B)

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 0.059 1
56. (B) 118 103 log
1 H
1 118 103
log 2 ; [H+] = 102 = 0.01 M
H 0.059
57. (B)

0.059 ( Zn )
58. (A) Ecell Ecell
o
log
2 (Cu )
59. (C)
60. (A) G nFE 2 96500 1.10 = 212.3KJ
61. (A)

62. (B) 1000

55 32 I 24 60 60
2 96500
1000 2 96500
I 25.6 A
87 24 60 60
27 25.6
I efficiency = 100 = 100 = 95%.
40.6 27
63. (C)
64. (A) Pb s PbSO4 PbI 2 Pb s
I II

Pb Pb12 2e (Oxidation)
PbII2 2e Pb (Reduction)
Net cell reaction: PbII2 PbI2

0.0592 Pb 2
Ecell Ecell log I
[Nernst equation]
n Pb
2
II

0.0592 Pb 2
Ecell 0 Ecell log II
n Pb 2
I

65. (A) If Q Kc , then E 0

RT
Also E ln Kc
nF
K c e nE F / RT
66. (B) Zn s 2 Ag aq Zn2 aq 2 Ag s
Ecell Ecathode Eanode
EZn2 / Zn EAg /Ag

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 0.76 0.344 1.104 V
n 2 mol , F 96500 C mol 1
G nEFcell
2 96500 1.104
213072CV
213072 J 1 CV 1 J
67. (B) G nFEocell 4 96500 (1.23) 474.78 kJ/mol ; Go H o T S o S o
474.78 285.5 189.28
0.635kJ/K
298 298
68. (A) Nickel-Cadmium battery
Anode Cd;cathode NiO2 ;electrolyte KOH
At anode : Cd(s) 2OH(aq) Cd(OH)2(s) 2e
At cathode : NiO2(s) 2H2O(l) 2e Ni(OH)2(s) 2OH(aq)

Cd (s) NiO 2(s) 2H 2O(l) Cd(OH) 2(s) Ni(OH) 2(s)

0.059 [ H ]2
69. (C) ERP ERP log
1 PH2
70. (B) For The given cell reaction involving formation of 2 moles of H 2O,
G nFEcell 4 96500 1.23 J
474780J 474.78kJ
( n 4 for the given cell reaction)
G H T S
or H G T S
474.78kJ 298K 0.32 kJ K 1
474.8 95.36 kJ 570.16KJ
This is enthalpy change for the formation of 2 moles of H 2 O
Enthalpy change for the formation of 1 mole of

H 2O f H 570.16 285.08kJ .
2
71. (D)
72. (B) HCl is an electrolyte.
73. (A) At cathode: 2 H 2e H 2 ,
1
At anode : 2OH H 2O O2 2e
2
74. (B)
75. (C) C12 H 22O11 is an non-electrolyte.
56
76. (B) Fe2 2e Fe; EFe 28
2
WFe EFe Number of faraday 28 3 84 gm .

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77. (C)
78. (C)
13.6
79. (B) E 2
for He n 1
n
13.6
E 2 13.6 eV .
1
80. (C)
81. (A)
82. (B) C2 H 5OH being non electrolyte so does not ionize.
83. (B) om (C6 H5COOH ) o(C H COO ) o( H )
6 5

42 288.42 330.42
c 12.8
om 3.9%
m 330.42
84. (D) Practically only 60-70% efficiency has been attained.
85. (A) In this reaction 4 electrons are needed for the reaction volume.
86. (B)
87. (B) MnO2 is used in dry batteries cell.
88. (D) Cu FeSO4 No reaction Because Cu has E o 0.34 volt and Fe has E o 0.44 volt.
89. (C) For gold plating, the used electrolyte is K Au(CN )2 .
90. (D)
91. (A) No doubt Be is placed above Mg in the second group of periodic table but it is below Mg in
electrochemical series.
92. (C) At 298 K standard electrode potential of electrode is 0.00 V.
93. (C) Actually the equation is derived from Nernst equation assuming equilibrium condition in a cell
reaction, when E 0 .
94. (A) In galvanic cell anode always made up of negative electrode.
95. (A) OCl Cl , E o 0.94V
1
Cl Cl2 e E o 1.36V
2
adding the two equations, we get
1
OCl Cl2 , E o 0.94 1.36 0.42V .
2
96. (B) E 0 because hydrogen have zero potential.
o

97. (C)

This type of reaction does not occur because

Mg 2 E o 2.37V while Zn2 E o 0.76V .
98. (C) Aluminium forms a protective oxide layer but iron does not.
2 3
99. (D) I get oxidised to I2 hence will form anode and Cr2 O7 get reduced to Cr hence will form cathode.
0
ECell ECathode
0
E Anode
0 0
; ECell ECr O2 EI02
2 7

E 1.33 0.79 ; EI02 1.33 0.79 ; EI02 0.54 V .

0
I2
100. (B)

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