(Physical Chemistry) ELECTROCHEMISTRY

SOLUTION
EXERCISE # (O-I)
1. Chemical reaction produces electrical energy.

2. Reduction takes place at cathode (not anode) in galvanic cell.

3. Standard Hydrogen electrode is universally accepted as reference electrode at all temperatures

and assigned a value of a0 Volt.

4. It is taken as reference, so electrode potential assumed to be zero.

5. Temperature can be varied also in standard Hydrogen Electrode.

6. Zn2+(aq) + 2e–→ Zn(s)

7. E° is independent of balancing of reaction.

10. E° = EoOxyn + EoRe dn

= ESn/Cn 2+ + E
o o
Ag+ /Ag

= 0.80 + 0.14 = 0.94 Volt

11. E° = EoOxyn + EoRe dn

= E Ni/ Ni2+ + EAu3+ /Au

o o

= 0.25 + 1.5 = 1.75 Volt

12. E°cell = E° Co / Co2+ + E°Ce4+ / Ce3+

E° Co / Co2+ = – E°Co2+ / Co = +0.28 V

1.89 = 0.28 + E°Ce4+ / Ce3+

E° Ce4+ / Ce3+ = +1.61 V

E° = EOxdn + E Redn
o o
13.

For option A largest E oCell = 1.25 + 1.25 = 2.5 V

For option B largest E oCell = 1.25 + 0.68 = 0.57 V

For option C largest E oCell = 1.25 + 0.24 = 1.01 V

For option D largest E oCell = 0.68 + 0.24 = 0.92 V

 Clearly, option A has largest E oCell

APNI KAKSHA 1
(Physical Chemistry) ELECTROCHEMISTRY
14. Ecell = E Oxyn + E Re dn

= 0.4 + 0.8 = 1.2

G = –nFE = –2 × 96500 × 1.2 = –231.6 KJ
15. EoCell = EoOxydn + EoRe dn

EoCell = EoI/I2 + EoFe+3 /Fe+2

= –0.536 + 0.771 = 0.235 Volt

; G1
º
16. Au+ + e– ⎯→ Au(s) E° = 1.69 V ...(1)

; G 2
º
Au3+ + 3e– ⎯→ Au(s) E° = 1.40 V ...(2)

From (2) – (1)

; G3
º
Au3+ + 2e– ⎯→ Au+ ...(3)

G3º = Gº2 − G1º

– 2 × F × E° = –3 × F × 1.40 + 1 × 1.69 × F
E° = 1.255 V

17.

18. E oCell = –0.68 + 1.44 = 0.76 V

0.0591
E oCell = log Keq
1
0.76 = 0.0591 log Keq
log Keq = 1012.86 = 7.6 × 1012

1 1
19. H2 + H+ ––→ H+ + H2
2 2
10–3 M 10–8 M
−8
E = 0 – 0.0591 log 10 −3
1 10
E = 0.295 V

APNI KAKSHA 2
(Physical Chemistry) ELECTROCHEMISTRY
20. at eqm E = 0
0.0591
E° = log Keqm
n
0.0591
E° = log (4 × 1012)
n
0.0591
E° = × 12.6 = 0.3717 Volt
n
0.0591
21. E° = log Kc
n
0.0591
E° = log1012
2
E° = 0.354 V
0.0591
22. E° = log Keq
n
0.0591
E° = log106
2
E° = 0.177 V
23. An+ + ne– ––→ A E° = –0.250
To make this reaction spontaneous
Ecell > 0
E redn + E oxyn  0

–0.250 + E oxyn > 0  E oxyn > 0.25 V

Therefore, metal D can displace A from it’s aqueous soln

24. The metal with less reduction potential is strangest reducing agent.
25. Metal with lower reduction potential reduce metal with high reduction potential.
26. 2X– + Y2 ––→ 2Y– + X2  X– can reduce Y
2Z – + X2 ––→ 2X– + Z2  Z– can reduce X
2W– + Y2 ––→X  W– can not reduce Y but y can reduce W
Arrange Reduction potential Z– < X– < Y– < W–
So oxidation potential is reverse Z– < X– < Y– < W–
27. Oxidation reaction  2Cl– ––→ Cl2 + 2e–
Reduction reaction  2Ag+ + 2e– ––→ 2Ag
net Cell reaction 2Ag+ + 2Cl– ––→ 2Ag + Cl2

APNI KAKSHA 3
(Physical Chemistry) ELECTROCHEMISTRY
NERNST EQUATION & ITS APPLICATIONS
28. By Nernst equation
RT [M + ]
E = E° – In
nF [M n +1 ]
29. 2H+ + 2e– ––→ H2 E° = 0
0.1 M 1 atm
0.0591 PH
E = E° – log + 22
n [H ]
E = 0 – 0.0591 log 1 = –0.059 V
2 (0.1) 2

30. Ag+ + e– ––→ Ag

0.1
0.0591 1
E = E Re dn −
o
log
1 0.1
o
E = E Re dn – 0.059
31. Cu2+ + 2e– ––→ Cu
E1 = E° – 0.0591 log 1
2 [Cu 2 + ]

E2 = E° – 0.0591 log 1002+

2 [Cu ]
E2 – E1 = 59 × 10–3 V
32. 2H+(eq) + 2e– ––→ H2(g)
Let PH = 1 bar
2

 When pH = 0  [H+] = 1 M
0.06
E = E° – log 1 = E°
2
& when pH = ?  [H+] = 10–7 M
0.06
E = E° – log 1−7 2 = E° – 0.42
2 (10 )

 Reduction potential decreases by 0.42 V

33. 2H+(eq) + 2e– ––→ H2(g)
When PH = 1 atm
2

0.06 1
E = E° – log 2 = E°
2 1
When PH 2 = 100 atm

0.06 100
E = E° – log 2 = E° – 0.06
2 1

APNI KAKSHA 4
(Physical Chemistry) ELECTROCHEMISTRY
0.0591 [Sn 2+ ]
34. E = E oRe dn − log
2 [Ag + ]2

If [Sn2+]  or [Ag+] , then E

35. 2Ti + Cu2+ ––→ 2Ti+ + Cu

0.1 M 0.01 M
0.0591 [Ti]2
E = E° – log
2 [Cu 2+ ]

TE  [Ti+] or [Cu2+]
36. Cu + 2Ag+ ––→ Cu2+ + 2Ag
0.0591 [Cu 2+ ]
E1 = E° – log
2 [Ag 2+ ]2

0.0592 [Cu 2+ ]  10
E2 = E° – log
2 [Ag 2+ ]2  100
E2 – E1 = 0.0295 V
0.0591 [Zn 2+ ]
37. E = E° – log
2 [Ni 2+ ]

0.0591
0.5105 = E° – log10
2
E° = 0.54 Volt
0.0591 0.1
38. E = E° + log
2 0.1
0.0591
E = 1.1 + log1
2
E = 1.1 V
39. Cl2(g) + 2Br–(eq) ––→ Cl–(eq) + Br2 (g)
[Cl− ]2 PBr2 (0.01) 2  0.01 = 0.01
Q= − 2
=
PCl2 .[Br ] 1  (0.01) 2

0.06
E = E° – log(0.01)
2
= 0.29 – 0.03 log10–2
= 0.35 V

APNI KAKSHA 5
(Physical Chemistry) ELECTROCHEMISTRY
CONCENTRATION CELL
1 1
40. H2 + H+ ––→ H+ + H2
2 2
10–3 M 10–8 M
−8
E = 0 – 0.0591 log 10 −3
1 10
E = 0.295 V
41. Concentration cell has two equivalent half cell
42. G < 0  E > 0
0.0591 C
E = E° – log 1
n C2
If C2 > C1  E > 0
METAL, METAL INSOLUBLE SALT- ION ELECTRODE
43. Pt(s) / H2(g) , 1 bar / 1M HCl (aq) / AgCl (s) / Ag(s)
44. Ag ––→ Ag+ + e–
0.06
E = E° – log[Ag+]
1
–0.209 = –0.799 – 0.06 log Ksp
−
1 [Cl ]

0.06 Ksp
–0.209 = –0.799 – log
1 0.1
 Ksp = 10–11

45. E°I–/AgI/Ag = EAg+/Ag + 0.0591 log 1

1 Ksp

0.0591 1
= 0.8 – log
1 8.3  10–17
17
= 0.8 – 0.591 log 10
8.3
= –0.15 V
dE
46. S = nF
dT
dE S
=
dT nF
used energy G nFEcell
47. efficiency = = =
total energy H H
APNI KAKSHA 6
(Physical Chemistry) ELECTROCHEMISTRY
| G |
48. efficiency = × 100
H
| G |
84 = × 100
285
1
G = –84 × 285 ×
100
G = –239.4 kJ
G = –nFE
–239.4 × 103 = –2 × 96500 × E
E = 1.24 V
dE
49. S = nF
dT
= –2 × 96500 × 0.00065= –125.45 JK–1
50. AgCl, Hg2Cl2 and PbCl2 are sparingly soluble so Cl– will form ppt with silver mercury and lead ,
hence cannot be used.
51. AgCl and PbCl2 are sparingly soluble so Cl– will form ppt with silver and lead, hence can not be
used
52. If cathode is removed from a electro chemical cell. The cell will be not be completed and
polarity of anode end cup.
E
53. Z=
96500
E = equivalent weight
96500 C liberates = E g
E
 1 C will liberate = g
96500
w1 w 2 w1 E1
54. =  =
E1 w 2 w 2 E2
55. equivalent of charge = equivalent of substance deposited
=1
1 equivalent of charge = 1 F = 96500 C
= charge of 1 mol e–
E
56. Z=
96500
E = 0.0006 × 96500 = 57.9

APNI KAKSHA 7
(Physical Chemistry) ELECTROCHEMISTRY
9.65  10  60
57. equivalent of substance = = 0.06
96500
108
58. equivalent of charge = × 1 =1
108
=1F
59. wQ
w1 It
= 11
w 2 I2 t 2
w1 2  2
=  w2 = w
w 2 1 4
60. Snn+ ––→ Sn
nf = 2
9.65  1000
equivalent of Sn = = 0.1
96500
5.95 11.9
× n = 0.1 n = =2
119 5.95
1 1
61. Ag : Cu : Al = 1 : : =6:3:2
2 3
62. 2H+ + 2e– ––→ H2
nf = 2
Mg2+ + 2e– ––→ Mg
nf = 2
w1 E1 2 1
= = =
w 2 E 2 24 12

3 3
= 0.06  E= = 50
E 0.06
63. Ni2+ + 2e– ––→ Ni
nf = 2
Cr3+ + 3e– ––→ Cr
nf = 3
w1 E1
=  0.3 = 59  3
w 2 E2 w2 2 52

0.3  104
w2 = = 0.17 g
177
APNI KAKSHA 8
(Physical Chemistry) ELECTROCHEMISTRY
64. 2H+ + 2e– ––→ H2
nf = 2
I  965 112
=  2  I = 1 amp
96500 22400
1
65. H2O ––→ 2H+ + O2 + 2e–
2
1
2F = 1 mol H2O = mol O2
2
2F = 2 × 96500 C = 1.93 × 105 C
0.108
66. Equivalent of Ag = equivalent of O2= × 1 = 0.001
108
0.001
Moles of O2 =
4
0.001
Vol. of O2 = × 22700 = 5.675 mL
4
67. Mn2O4 ––→ MnO42–
10
nf = 10 nf =
8
10 10
Equivalent of charge = ×1=
8 8
10 10
Equivalent of charge = × 96500 C
8 8
68. equivalent of charge = equivalent of Ag
9.65  t 80  5  10−3  1.08
=
96500 108
t = 40 sec
69. anode 2Br– ––→ Br2 + 2e–
cathode 2e– + 2H2O ––→ H2 + 2OH–
By product NaOH
70. anode 2H2O ––→ O2 + 4H+ + 2e–
cathode Cu2+ + 2e– ––→ Cu
By product NaOH
[H+] , So pH 
71. anode 2H2O ––→ O2 + 4H+ + 4e–
cathode 2e– + 2H2O ––→ H2 + 2OH–
72. anode 2Cl– ––→ Cl2 + 2e–
cathode 2e– + 2H2O ––→ H2 + 2OH–

APNI KAKSHA 9
(Physical Chemistry) ELECTROCHEMISTRY
COMMERCIAL CELLS & CORROSION
73. Voltage of cell increases
74. 2PbSO4(s) + 2H2O( ) ––→ Pb(s) + PbO2(s) + 2H2SO4(aq)
75. At high pH, The passive layer is formed and prevent corrosion
76. Resistance decrease with increase in temp as speed of ions increases
77. K, Molarity
K  1000
78. m =
N
N , m 
1 2.2
79. K=  = 0.01 S cm–1
50 4.4
K  1000 0.01 1000
m = = = 0.2 S cm2 mole–
M 50
1
80. K= × 0.4 = 0.01 S cm–1
40
K  1000 0.01 1000
m = = = 1000 S cm2 mole–1
N 0.01
1
81. K= × 1.5 = 7.5 × 10–3 S cm–1
200
K  1000 7.5  10 −3  1000
eq = = = 750 S cm2 eq–1
N 0.01

82. CH3COOH (eq) + NaOH (eq) ––→ CH3COONa (eq) + H2O ( )

0.015 × V 0.015 × V 0
0 0 0.015 × V
0.015  V 0.015M
 [CH3COONa] = =
2V 2
−4
m = K  1000 = 6.3  10  1000 = 84 S cm2 mole–1
M 0.015 / 2

83. m NaNO3 = m NaCl + m AgNO3 – m AgCl

= 110 + 115 – 120= 105
84. m BaCl2 = eq BaCl2
= eq Ba2+ + eq Cl–= 127 + 76 = 203 S cm2 eq–1

APNI KAKSHA 10
(Physical Chemistry) ELECTROCHEMISTRY
m 80 1
85. = = =
m 400 5
86. m = 10 S cm2 mole–1
m = 200 S cm2 mole–1
10
= = 0.05
200
[H+] = c = 5 × 10–2
pH = 2.2

kc
Ka = c
2
87.  = = 0.04
1−  C
m = m ×  = 380 × 10–4 × 0.04= 1.52 × 10–3 S m2 mole–1
1.52 × 10–3 = K/ (1000 x 0.01)
K = 1.52 × 10–5 S m–1
K  1000
88. m =
s
−6
s = 3.06  10  10 = 2 × 10–3
3

1.53
ksp = s2 = 4 × 10–6

89. K
 m =
1000  Solubility
−6
1.5 × 10–4 × 3 = 9  10
1000  S
S = 2 × 10–5
Ksp = 33 × S4
= 27 × (2 × 10–5)4= 4.32 × 10–18

APNI KAKSHA 11
(Physical Chemistry) ELECTROCHEMISTRY
EXERCISE # S-I
2. 3e– + Cr3+ ––→
Cr (i)
OCl– + H2O + 3e–––→ Cl– + 2OH– (ii)
2Cr3+ + 3H2O + 3OCl– ––→ 2Cr3+ + 3Cl– + 6OH– (iii)
(iii) = –2 × (i) + 3 × (ii)
6E3o = −2  3  E1o + 3  2  Eo2

E 3o = 0.74 + 0.94 = 1.68 V

3. –0.15 = 1.20 + ECl– /Cl
2

ECl– /Cl = –1.35 V

2

E Cl − = 1.35 V
2 /Cl

4. Fe2+ + 2e– ⎯→ Fe E0 = 0.44 V

G1 = –2 × F × (–0.44)
Fe3+ + e– ⎯→ Fe2+ E0 = 0.77 V
G2 = –1 × F × 0.77
By adding above two reactions
Fe3+ + 3e– ⎯→ Fe
G3 = G1 + G2
–3 × F × E0 = 0.88F – 0.77F
E0 = –  0.11  V = –0.0367 V
 3 
5. Cu2+ + e– ⎯→ Cu + G1 = –1 × F × 0.15 ....(1)
Cu +2 + 2e– ⎯→ Cu G2 = –2 × F × 0.34 ....(2)
Cu + + e– ⎯→ Cu ....(3)
(3) =(2) - (1)
G3= G2 – G1
= – 0.68 F + 0.15 F
G3 = –nFE0 = –0.53 F
– 1 × F× E0 = – 0.53 F
E0 = 0.53 V
6. 2e– + 2H+ + SO42– ––→ SO32– + H2O (i)
1 3
3e– + 3H+ + SO32– ––→ S2O32– + H2O (ii)
2 2
1 5
4e– + 5H+ + SO42– ––→ S2O32– + H2O (iii)
2 2
(iii) = (ii) + (i)
G3o = Go2 + G1o
4FE3o = 2FEo2 + 2FE1o

−0.936 − 0.576
= E1 + E 2 =
o o
E 3o = 0.756 V
2 2

APNI KAKSHA 12
(Physical Chemistry) ELECTROCHEMISTRY
8. Mn2+ ––→ Mn3+ + e– (i)
2H2O + Mn3+––→ MnO2 + 4H+ + e– (ii)
2Mn2+ + 2H2O ––→ Mn2+ + MnO2 + 4H+ (iii)
(iii) = (ii) – (i)
E3o = Eo2 − E1o

0.5 = –1.0 + 1.5

E° > 0 , So reaction is spontaneous
G° = –nFE° = –1 × 96500 × 0.5 = –48250 J
9. At equilibrium E=0
0.0591 0.0591
 E = E0 – log K = (–0.68 + 1.44) – logK
n 1
0.0591
0.76 = logK
1
0.76 1
logK = = 12.859
0.0591
K = 1012 × 10-0.859 = 7.6 × 1012
10. (i) E°cell = 2.37 + 0.80
= 3.17 V
0.591
E0 = log K
2
0.591 6.34
3.17 = log K  log K = = 107.275
2 0.0591
K = 10107.275
= 10107 × 100.275
= 1.88 × 10107
(ii) G = 2 × 3.17 × 96500
= –611810 J
= – 611.8 KJ
11. E oCell = E° Zn / Zn2+ + E° Cu2+ / Cu
= 0.76 + 0.34 = 1.1 V
0.0591 [Zn 2+ ]
1.1 = log
2 [Cu 2+ ]

[Zn 2 + ]
log = 37.22
[Cu 2 + ]

APNI KAKSHA 13
(Physical Chemistry) ELECTROCHEMISTRY
12. 2 H2O + 2e–→ H2 + 2OH– E° = -0.84
H2 + 2e → 2 H+ E° = 0
2 H2O → 2H+ + 2OH– K2
2.303RT
2 x Eo = log K2
F
-0.84 = 0.06 log K
log K = – 14
K= 10–14
13. 4 × E° Sn | Sn4+ = 2 × E° Sn | Sn2+ + 2 × E° Sn2+| Sn4+
0.136 − 0.154
E° Sn | Sn4+ = = – 0.009 V
2
Ecell = E° Sn| Sn4+ + E° Cr2O72– | Cr3+
= – 0.009 + 1.33 = 1.321 V
14. rG° = –nFE° = –12 × 96500 × 2.73
= – 3161340
rG° = 4 G ƒ [Al(OH)4-] – 6 G ƒ H2O – 4 G ƒ OH–
0 0 0

–3161.340 = 4 × x – 6 × (–237.2) – 4 × (–157)

= 4x + 1423.2 + 628
x = –1303.13 kJ
15. SRP value , oxidizing power 
Reducing power 
mg is best reducing agent.
16. SRP value , Reducing power 
SRP X>Z>Y
Reducing power Y > Z > X
17. Lower S.R.P. metal can displace higher S.R.P. metals ions from solution.
E° Zn2+ / Zn = –0.763 V
SRP value  , Reducing power ↑
18. Ag ⎯→ Ag+ + e–
1
e– + H+ ⎯→ H2
2
1
Ag+ H+ ⎯→ Ag+ + H2
2
E°cell = –0.8
0.06 1
Ecell = –0.8 – log = –0.8 < 0 (reaction will not spontaneous)
1 1
APNI KAKSHA 14
(Physical Chemistry) ELECTROCHEMISTRY
19. (a) anode Ag ––→ Ag+ + e– × 2
Cathode Cu2+ + 2e– ––→ Cu

2Ag + Cu2+ ––→ 2Ag+ + Cu

(b) anode Fe2+ ––→ Fe3+ + e– × 5

Cathode 5e– + 8H+ + MnO4– ––→ Mn2+ + 4H2O

8H+ + 5Fe2+ + MnO4– ––→ 5Fe3+ + Mn2+ + 4H2O

(c) anode 2Cl– ––→ Cl2 + 2e–
Cathode Ag+ + e– ––→ Ag × 2

2Cl– + 2Ag+ ––→ Cl2 + 2Ag

(d) anode H2 ––→ 2H+ + 2e–
Cathode Cd2+ + 2e– ––→ Cd

H2 + Cd2+ ––→ 2H+ + Cd

20. (a) Zn (s) / Zn2+ (aq) | | Cd2+ (aq) / Cd (s)
(b) Pt / H2 (g) / H+ (aq) | | Ag+ (aq) / Ag (s)
(c) Pt / Fe2+ , Fe3+ | | Cr2O72– , Cr3+ , H+ / Pt
NERNST EQUATION
21. pH = 1 [H+] = 0.1
2H+ ––→ H2 + 2e–
0.0591
E=0– log [H+]2
2
0.0591
E=– log (0.1)2 = 0.0591 V
2
22. Ecell = 0
+2
Ecell = E0 – 0.0591 log [Cu ]
n 1
0.0591 0.0591
E0 = log[Cu +2 ] –0.34 = log[Cu +2 ]
2 2
0.68
log[Cu+2] = – = –11.501
0.0591
log[Cu+2] = –11.501
[Cu+2] = 10–11.501
= 2.97 × 10–12 M
APNI KAKSHA 15
(Physical Chemistry) ELECTROCHEMISTRY
23. Ecell = E0 – ( 0.0591 log 1 )
2 [Zn +2 ]
ZnSO4 ⎯→ Zn+2
0.1×0.8 0.1×0.2
Zn2+ + 2e– ⎯→ Zn
0.0591 1
Ecell = –0.76 – log
2 0.1 0.2
= –0.76 – 0.03 × 1.7 = –0.81V
24. Cu(OH)2 ––→ Cu2+ + 2OH–
[Cu2+] at pH = 14
[Cu2+] × [OH–]2 = 10–19
[Cu2+] × (1)2 = 10–19
[Cu2+] = 10–19 M
Cu+ + 2e– ––→ Cu
E = E° – 0.0591 log 1
2 [Cu 2 + ]

0.0591
= 0.34 – log 1019
2
0.0591
= 0.34 – × 19 = –0.2214 V
2
2+
25. Daniel cell :- Zn (s) ZnSO4 m Cu m2 Cu(s)
1

Zn + Cu+2 ⎯→ Zn+2 + Cu
0.059 0.0591 [Zn +2 ]
E = E0 – log 0  E = E0 – log
n 2 [Cu +2 ]
0.059 001
E = 1.1 – log
2 01
0.59
= 1.1 – log10−2 = 1.1 +0 .059= 1.159 V
2
26. Sn + Pb+2 ⎯→ Pb + Sn2+
E°cell = 0.14V – 0.13V = 0.01V
0.06 [Sn +2 ]
Ecell = E0 – log
2 [Pb+2 ]
0.06 1
= 0.01 – log
2 10−3
0.06
= 0.01 –  3 = 0.01 – 0.09
2
= –0.08 V
Ecell < 0  incorrect
representation should be as
 Pb|Pb+2||Sn+2|Sn
APNI KAKSHA 16
(Physical Chemistry) ELECTROCHEMISTRY
27. (i) anode Zn ––→ Zn2+ + 2e–
Cathode Ag+ + e– ––→ Ag × 2

Zn + Ag ––→ Zn2+ + Ag
(ii) E oCell = E° Zn / Zn2+ + E° Ag2+ / Ag

= 0.76 + 0.8 = 1.56 V

0.0591 [Zn 2+ ]
(iii) 1.6 = 1.56 – log
2 (0.1) 2
[Zn2+] = 4 × 10–4 M
(iv) IF 125 is added then
As+ + I– ––→ AgI
[Ag]  , ECell 
CONCENTRATION CELL
0.0591 .0591
28. E= 0 − 0.0591 log [0.01] = − log10−1 = 1 = 0.0295 V
2 [0.1] 2 2
29. H2 → 2H+ + 2e–
[H a+ ]2 Pa
2H+ + 2e– → H2 =
[H c+ ]2 Pc

0.0591  x 2 1 
0.2367 = 0 − log  
2  1 1 
8 = –log x2
–4 = log x
 x = 10–4

PH = 4

0.0591 [H + ]a2
30. Ecell = – log + 2
2 [H ]c

H2 → + + 2e
2e– + 2H+ → H2+

[H+]a = ka  c = 10−3 c

[H+]c = ka  c = 10−3 c
−3 0.0591 0.0591
Ecell = − 0.0591 log 10−5 c =− log102 =−  2 = –0.0591 V
2 10  c 2 2
APNI KAKSHA 17
(Physical Chemistry) ELECTROCHEMISTRY
0.0591 [H + ]2
31. Ecell = – log + a2
2 [H ]c

[OH]– = k b  c  10−9 10−3 = 10–6

10−14 10−14
[H+] = −
= −6 = 10−8
[OH] 10
50
[H+] = = 10−1
500
−8
E = − 0.0591 log [10 −1 ] = − 0.059 × log(10–7) = − 0.0591 ×(–7) = 0.4137 V
1 10
METAL- METAL INSOLUBLE SALT- ION ELECTRODE
32. (a) anode Cu ––→ Cu+ + 2e–
Cathode 2e– + Hg2Cl2 ––→ 2Hg + 2Cl–

Cu2+ + Hg2Cl2 ––→ Cu2+ + 2Hg + 2Cl–

(b) anode IO3– + Ag ––→ AgIO3 + e– × 2

Cathode Zn2+––→ Zn

2Ag(s) + 2IO3– + Zn2+ ––→ Zn + 2AgIO3

(c) anode Mn + 2OH– ––→ Mn(OH)2 + 2e–

Cathode 2e– + Cu2+ ––→ Cu

Mn + 2OH– + Cu2+ ––→ Mn(OH)2 + Cu

33. Ag | AgBr(s)| KBr (0.001M) || KCl (0.2M)|AgCl(s) |Ag,
Replacing above cell by
Ag / Ag+ | | Ag+ / Ag

0.06  Ag + 
E=0– log a

1  Ag 
+
c

Ksp.AgCl 10−10
[Ag+]c = = = 5 × 10–10 M
[Cl− ] 0.2

Ksp.AgBr 10−13
[Ag+]a = = −3 = 10–10
[Br − ] 10
−10
E = 0.06 log 5  10
−10
= 0.06 × 0.7 = 0.42 V
1 10

APNI KAKSHA 18
(Physical Chemistry) ELECTROCHEMISTRY
34. Ag | Ag I | KI || Ag NO3 | Ag
0.05 M 0.005 M
0.0591 [Ag + ]a
0.788 = 0 – log
1 [Ag + ]c

0.0591 [Ag + ]a
0.788 = − log
1 0.05
[Ag+]a = 2.5 × 10–15
Ksp (AgI) = 0.05 × 2.5 × 10–15
= 1.125 × 10–16
35. Ag |Ag Br(s) | Br– || Cl– | AgCl(s) | Ag(s)
Ag | Ag+ || Ag+ | Ag
Ecell =0

0.0591 [Ag + ]a
Ecell =– log
1 [Ag + ]c

Ksp.AgCl 110−10
[Ag+]a = =
[Cl− ] [Cl− ]
Ksp.AgBr 5 10−13
[Ag+]c = =
[Br − ] [Br − ]
0.0591 −
10 −10 [Br ]
Ecell =– log ×
1 5  10 −13
[Cl− ]
10−10 [Br − ]
=1
5 10−13 [Cl− ]
[Cl− ] 1000 200
= =
[Br − ] 5 1
36. 2e– + PbCl2 ––→ Pb + 2Cl–
E° Cl– / Pb(s) / Pb = E° Pb2+ / Pb – 0.06 log 1
2 Ksp

–0.27 = –0.12 + 0.03 log Ksp

log Ksp = –5
Ksp = 10–5
37. e– + AgI (s) ––→ Ag + I–
E° I– / AgI / Ag = E° Ag+ / Ag – 0.06 log 1
1 Ksp

= 0.8 – 0.06 × 16
= 0.8 – 0.96 = –0.10 V

APNI KAKSHA 19
(Physical Chemistry) ELECTROCHEMISTRY
38. (a) 2Cl– ––→ Cl2 + 2e–
nf = 2
Equivalent of charge = Equivalent of Cl2
355
= × 2 = 0.1
71
Mole of electron = 0.1
No. of electron = 0.1 Na

(b) Cu2+ + 2e– ––→ Cu

nf = 2
Equivalent of charge = Equivalent of Cu= 2
Mole of electron = 2 x 6 × 1023

(c) Al3+ + 3e– ––→ Al

nf = 3
2.7
Equivalent of charge = Equivalent of Al= × 3 = 0.3
27
Mole of electron = 0.3 × NA = 1.8 × 1023
39. (a) equivalent of Al = 0.25 × 3 = 0.75
equivalent of charge = 0.75
1 equivalent charge = 1 F
0.75 equivalent charge = 0.75 F
27.6
(b) equivalent of charge = equivalent of SO32–= × 2 = 0.69
80
0.69 equivalent charge = 0.69 F
(c) equivalent of charge = equivalent of Cu= 1.1 × 0.5 × 2 = 1.1
equivalent charge = 1.1 F
40. 0.5 mole electron = 0.5 F charge
equivalent of charge = equivalent of Zn= equivalent of Ag = 0.5
Moles of Zn × 2 = 0.5
1
Moles of Zn =
4
1
Amount of Zn deposited = 65 × = 16.25 g
4
Moles of Ag × 2 = 0.5
Amount of Ag deposited = 108 × 0.5 = 54 g
APNI KAKSHA 20
(Physical Chemistry) ELECTROCHEMISTRY
41. Pdn+ ––→ Pd
nf = n
equivalent of Pd = equivalent of charge
2.977 3  3600
n =
106.4 96500
n=4
42. 2e– + 2H2O ––→ H2 + 2OH–
nf = 2
2H2O ––→ O2 + 4H+ + 4e–
nf = 4
x x
43. equivalent of Al = ×3=
27 9
x
Equivalent is produced by coast = x Rs
9
1 equivalent will cost = 9 Rs
x x
Equivalent of Mg = ×2=
24 12
x x
Cost to produce equivalent Mg = × 9 = 0.75 x Rs
12 12
44. CrO2(aq) + 6H+ (aq) + 6e– ––→ Ce(s) + 3H2O
nf = 6
24125
(i) equivalent of Cr = equivalent of charge = = 0.25
96500
Moles of Cr × 6 = 0.25
1
Moles of Cr =
24
1
Moles of Cr = × 52 = 2.16 g
24
(ii) equivalent of charge = equivalent of Cr
12.5  t 1.5
= 6
96500 52
t = 1336.15 sec
45. Cu2+ + 2e– ⎯→ Cu
3 3  2  60  60
×2= ×
63.2 96500
 = 0.4221
%  = 42.21 %

APNI KAKSHA 21
(Physical Chemistry) ELECTROCHEMISTRY
46. Mn2+ ––→ MnO2
nf = 2
equivalent of MnO2 = equivalent of charge

25.5  t 1000
× 0.85 = ×2
96500 87
t = 1.023 × 105 sec
47. 2HSO4– ––→ S2O32– + 2H+ + 2e–
nf = 2
equivalent of Ni = equivalent of charge

Q  60  60
× 0.75 = 1 × 2
96500
2  96500
Q= = 71.48 C
3600  0.75
48. (1) molten NaCl
anode 2Cl– ––→ S2O32– + 2H+ + 2e–
cathode Na+ + e– ––→ Na
(2) NaCl (aq)
anode 2Cl– ––→ 2Cl2 + 2e–
cathode 2e– + 2H2O ––→ H2 + 2OH–
(3) Na2SO4 (aq) with pt electrode
anode 2H2O ––→ O2 + 4H+ + 4e–
cathode 2H2O + e– ––→ H2 + 2OH–
(4) AgNO3 (aq) with pt electrode
anode H2O ––→ O2 + 4H+ + 4e–
cathode Ag+ + e– ––→ Ag
(5) CuSO4 (aq) with inest electrode
anode H2O ––→ O2 + 4H+ + 4e–
cathode Cu+ + 2e– ––→ Cu
(6) CuSO4 (aq) with Cu electrode
anode Cu ––→ Cu2+ + 2e–
cathode Cu2+ + 2e– ––→ Cu

APNI KAKSHA 22
(Physical Chemistry) ELECTROCHEMISTRY
49. 2Cl– ––→ Cl2 + 2e–
nf = 2
equivalent of Cl2 = equivalent of charge
30  60  60
moles of Cl2 × 2 =
96500
moles of Cl2 = 0.5%
vol. of Cl2 produced at 1 atm , 273 K = 0.56 × 22.4 = 12.531
equivalent of NaOH = 1.12
moles of NaOH = 1.12
31.75
50. equivalent of Cu = ×2=1
63.5
equivalent of NaOH = equivalent of Cu
=1
Amount of NaOH = 1 × 40 = 40 g
Actual amount of NaOH obtained = 0.6 × 1 = 0.6 mole
0.6
% efficiency = × 100 = 60%
1
51. Ni2+ ––→ Ni
nf = 2
5  20  60
equivalent of Ni = equivalent of charge=
96500
6000 1
Moles of Ni = 
96500 2
6000 1
Amount of Ni =  × 58.5 = 1.82 g
96500 2
52. If active electrodes are used of a metal. Then same metal is oxidized at anode and reduced at
cathode so these is no change in concentration of electrolytic solution.
1
53. K=
R a
1
1.342 = 
170.5 1.86 10–4
 = 1.342 × 170.5 × 1.86 × 10–4
= 4.25 × 10–2 m
54. N = 0.01N, R = 200, (/A) = 0.88 cm–1
K =  1  × 0.88
 200 

0.88 1000
m =  1  × = 440 Scm2 mol–1
200  0.01
APNI KAKSHA 23
(Physical Chemistry) ELECTROCHEMISTRY
55. BaCl2 K = 0.005 ohm– cm–1
Morality = 2.08
3
=
2.08
= 4.16M
500 cm 0.5

0.005 1000 5
m = = = 1.2
4.16 4.16
0.005 1000 5
m = = = 250 Scm2mol-1
0.02 0.02
250
eq = =125 Seq–1 cm2
2
56. K = 1 = 1 = 0.00125 5cm–1 = 1.25 × 10–3 mho cm–1
 800

K 250
eq = = Seq–1 m2
N 1000 2
eq =m = 0.0125 Seq–1 m2
K 1000
57. m = 4 =
0.1
K = 0.4 × 10–3= 0.0004 Scm–1
1 1
Resistivity = = = 2500 ohm cm.
K 0.0004
58.   2cm 1
 = =   cm −1
 A  4cm 2
2

K = 8 × 10–7 Scm–1
(i) R =   

A

R =  1   
 K  A 

R =  1   1  100

−7   = 105 = 6.25 × 10 ohm
5
 8 10   2  16
1
(ii) V = iR  i= = 1.6 × 10–6 amp.
6.25 105
59. Ba(OH)2 = BaCl2 + 2Na OH − 2NaCl
= 280 × 10–4 + 2(240 × 10–4) – (125 × 10–4) × 2 = 510 × 10–4
60. m(CH3COOH) = m(CH3COONa) + mHCl − m NaCl = 425 + 100 – 125 = 400 Scm2 mol–1
For CH3COOH  N=M
eq = m = 48
48
= = 0.12
400
 % = 12

APNI KAKSHA 24
(Physical Chemistry) ELECTROCHEMISTRY
 eq 120
61. = 
= = 0.8
 eq 150
62. HF → H+ + A–
C (1– ) C C
C = 0.002M
 = m = 200 = 0.5
m 400

K = C = 0.002(0.5) = 10 × 10–4
2 2

1−  1 − 0.5
63. K = 1.12 × 10–6 ohm–1 cm–1
  N(AgCl) = 54 + 58 = 112 Scm2/eq
−6
112 = 1.12 10 10
3

S
−6
s = 1.12 10 10
3

112
s= 10–5
AgCl → Ag+ + Cl–
Solubility product = s2 = 10–10 mol/ltr
64. KAgBr = 8.75 × 10–7 – 0.75 × 10–7 = 8× 10–7
m(AgBr) = m(AgNO3 ) + m(K Br) − m(KNO3 ) = 130+140 – 110 = 160
For sparsely soluble like AgBr   = 1
A(AgBr) =  m(AgBr)
−7
160 = 8  10  1000
s
−4
s = 8  10 = 5 × 10–6 M = 188 × 5× 10–6 g/L = 9.48 × 10–4 g/L
160
65.  H2 O = 3.5 × 10–2 + 2 × 10–2= 5.5 × 10–
K = 5.5 × 10–6 Sm–1
−6
 H2 O = 5.5 10 = 5.5 × 10–2
1000  M
5.5  10 −6
M=
10  5.5  10 −2
3

H+  = 10–7
PH = 7
kw = 10–14

APNI KAKSHA 25
(Physical Chemistry) ELECTROCHEMISTRY
EXERCISE # (O-II)
1. dE o = –0.000648 Volt K–1
dT
G° = –nFE
G° = –2 × 96500 × 0.6753
G° = –130332.9 J
G° = H° – T S°
–130332.9 = H° + 298 × 0.000648 x 2 x 96500
H° = –167.6
2. Cell-1 Cell-2 Cell-3
Product O2 Cl2 H2
n-Factor 4 2 2
Equivalent from the 1 3/4 1/4
given resistance
Mol 1/4 3/8 1/8
Volume ratio 2 3 1
6. Specie giving higher reduction potential can oxidize the specie having lower reduction
potential.
7. The metal with less reduction potential is strangest reducing agent.
8. At cathode : 2H+(aq) + 2e– ––→ H2 (g)
At anode : Ag(s) + Cl– (aq) ––→ AgCl (s) + e–
Overall cell rxn : 2Ag(s) + 2H+ (aq) + 2Cl– (aq) ––→ H2(g) + 2AgCl (s)
PH2
Q=
[H + ]2 [Cl− ]2
0.06
E = E° – log Q
2
With increase in value of Q, EMF of cell decrease.
10. (A) : During electrolysis Cu at anode will oxidise as well as Cu2+ of solution will reduce at
cathode.
(B) : During electrolysis
At cathode : 2H+(g) + 2e– ––→ H2(g)
1
At anode : H2O ( ) ––→ O2 (g) + 2H+(g) + 2e–
2
(C) : During electrolysis
At cathode : Na+ + e– ––→ Na
1
At anode : 2OH– ––→ O2 (g) + H2O ( ) + 2e–
2

APNI KAKSHA 26
(Physical Chemistry) ELECTROCHEMISTRY
(D) : During electrolysis
At cathode : 2H+ (aq) + 2e– ––→ H2 (g)
At anode : 2Cl– (aq) ––→ Cl2 (g) + 2e–
1
11. H2O ( ) ––→ H2(g) + O2(g)
2
At cathod At anode
270
Mole of H2O electrolyzed = = 15 mole
18
Equivalent of H2O electrolyzed = 15 × 2 = 30

Equivalent of H2 gas released = Equivalent of O2 gas released = 30

30
mole of H2 gas = = 15 mole
2
30
mole of O2 gas = = 7.5 mole
4
Volume of O2 gas = 7.5 × 22.4 L = 168 L
Total volume of gas = (15 + 7.5) × 22.4 = 504 L
100
Faraday of electricity consumed = 30 × = 40 F
75
12. 2H2SO4 + Pb(s) + PbO2 (s) ⎯→ 2PbSO4(aq) + 2H2O ( )
15. Cathode :Cr2O72– + 6e– + 14 H+ ⎯→ 2Cr+3 + 7H2O
Anode :[Sn2+ ⎯→ Sn+4 + 2e–] × 3
Net cell reaction : Cr2O72– + 3Sn+2 + 14 H+ ⎯→ 3 Sn+4 + 2Cr+3 + 7H2O
Initial conc. 1M 1M 10–1 M – – –
2 2
At completion M – 10–1 M 1M M –
3 3
2
Moles of Cr+3 = ×3=2
3
16. Cathode :Cr2O72– + 6e– + 14 H+ ⎯→ 2Cr+3 + 7H2O
Anode :[Sn2+ ⎯→ Sn+4 + 2e–] × 3
Net cell reaction : Cr2O72– + 3Sn+2 + 14 H+ ⎯→ 3 Sn+4 + 2Cr+3 + 7H2O
Initial conc. 1M 1M 10–1 M – – –
2 2
At completion M – 10–1 M 1M M –
3 3
+3 2
−0.06 [Cr ]
E Cr O−2 /Cr +3 = EoCr O−2 /Cr+3 log
2 7 2 7
6 [Cr2O7 2− ][H + ]14
(2 / 3)2
= 1.33 – 0.01 log = 1.191 Ans.
(2 / 3)(10−1 )14

APNI KAKSHA 27
(Physical Chemistry) ELECTROCHEMISTRY
17. Cr2O72– + 3 Sn+2 + 14 H+ ⎯→ 3 Sn+4 + 2 Cr+3 + 7 H2O
0.06 (0.2)3 (1)2
E = (1.33 – 0.15) – log
6 (0.2)1 (0.1)3 (1)14
= 1.164 V
25. Cells whose cell reaction does not involve any specie whose active mass changes with progress
of reaction gave constant value of EMF.
26. Lower the value of reduction potential higher will be reducing power.
(A): During electrolysis of dil HCl
At cathode: 2e– + H2O ( ) ––→H2 (g) + 2OH–
At anode: 2H2O ( ) ––→ O2 (g) + 4H+ + 4e–
(B) During electrolysis of dil NaCl
At cathode: 2e– + H2O ( ) ––→H2 (g) + 2OH–
At anode: 2H2O ( ) ––→ O2 (g) + 4H+ + 4e–
(C) : During electrolysis of conc. NaCl
At anode: 2Cl–––→Cl2 (g) + 2e–
At cathode: 2H2O ( ) ––→ O2 (g) + 4H+ + 4e–
(D) : During electrolysis of AgNO3
At cathode : 2Ag+ (aq) + e– ––→ Ag
At anode : 2H2O ( ) ––→ O2 (g) + 4H+ + 4e–

APNI KAKSHA 28
(Physical Chemistry) ELECTROCHEMISTRY
EXERCISE # (S-II)
1. 5× E1º = 0.54 × 4 + 0.45 × 1

E1º = 0.522 V

6E º2 = 0.54 × 4 + 0.45 × 1 + 1.07 × 1

E º2 = 0.613 V

2. M/Mn+ (0.02 M) || H+(1M) / H2(g) 1 atm

M ⎯→ Mn+ + ne–
1
e– + H+ ⎯→ H2 × n
2
n
M + nH+ ⎯→ Mn+ + H2
2
0.06 [M n + ](PH2 ) n/ 2
0.81 = 0.76 – log
n [H + ]n

0.06 0.02 1
0.81 = 0.76 – log
n 1
0.06
log 0.02 = –0.05
n
6
n = – log 0.02
5
6
n= log50 = 2
5
0.0591 [Zn 2+ ]a
3. E=0– log
2 [Zn 2+ ]c

0.0591 10
= – log
2 1
= – 0.0295 V
4. H2a ⎯→ 2H a+ + 2e–

2H c+ + 2e– ⎯→ H2c

0.0501
E = E° – log Q
2
[H + ]a2 (PH 2 )c
Q=
[H + ]c2 (PH 2 )a

APNI KAKSHA 29
(Physical Chemistry) ELECTROCHEMISTRY
(PH2)a = (PH2)c = 1 atm

[H+]a = Ka, CH3COOH  C

−5
= 1.8 10  0.1
−5
[OH–]c = 1.8 10  0.01

10−14
[H+]c =
1.8  10−5  0.01

0.0591 (1.8) 2  10−13

E=0– log
2 10−28
= –0.45 V
5. (i) at anode
Fe(s) + 2OH– ⎯→ FeO(s) + H2O() + 2e–
at cathode
Ni2O3(s) + H2O() + 2e– ⎯→ 2 NiO(s) + 20H–
Fe(s) + Ni2O3(s) ⎯→ FeO (s) + 2 NiO(s)
(ii) Ecell = 0.87 + 0.4 = 1.27 v

(iii) G = –nFE°
= –2 × 96500 × 1.27 = –2.45 kJ
|G| = 2.45 kJ
6. Ag |Ag+|| Ag+ | Ag
Ksp. 2.8 10−10
=
AgCl
[Ag+]a = −
[Cl ] 0.2
Ksp AgBr 3.3 10−13
[Ag+]c = =
[Br − ] 0.001

0.0591 2.8 103  0.001

Ecell = 0 – log
1 0.2  3.3

= –0.0591+ log 4.24

= –0.037 V
0.0591
E° Pb |PbCl2| Cl– = E° Pb | Pb2+ – log Ksp
2
0.0591
0.268 = 0.126 – log Ksp
2
Ksp = 1.536 × 10–5

APNI KAKSHA 30
(Physical Chemistry) ELECTROCHEMISTRY
–3
+3
7. C 6 H 5 NO 2 ⎯→ C6H5 NH 2
nf = 6

Equivalent of charge= Eq. of C6H5NO2

= 0.1 × 6 = 0.6
Q
0.6 =  0.2
96500
Q = 115,800 C
E = Q × V = 115,800 × 3 J =347.4 kJ
8. Mass of Ag deposited = 80 × 5 × 10–4 × 10.8 J
= 0.432
0.432
Eq. of Ag = = 0.004
108
2  t(sec)
0.004 =
96500
0.004  96500
t(sec) = = 193 sec
2
9. (i) Eq. of Cu deposit = Eq. of charge = 0.01
0.01
Mole of Cu deposit =
2
0.01
Mass of Cu deposit =  63.5 = 0.3175
2
Mass of Cu remaining = 10 – 0.3175 = 9.6825 g
(ii) Eq. of charge = Eq. of H2O electrolysed
2H2O → 4H+ + O2 + 4e–
nf = 1
Equivalent of H+ = 0.01
10. Amount of Cd deposited
x
100 = 12
x+2
24
x=
88
24 2 5  t(sec)
 =
88 112.4 96500
t = 93.65 sec
11. at cathode
2H+ + 2e– ⎯→ H2(g)
at anode

APNI KAKSHA 31
(Physical Chemistry) ELECTROCHEMISTRY
2SO42- ⎯→ S2O82- + 2e–
2H2O ⎯→ O2 + 4H+ + 4e–
Eq of H2 = Eq of S2O82– + Eq of O2
9.722 2.35 w2
×2= 4+
22.7 22.7 194
w = 42.874 g
Eq of charge/year = 1.5 10  3.15 10 = 4.9 × 108
6 7
12.
96500
Eq of charge = Eq of H2O
n H O × 2 = 4.9 × 10
8
2

n H2O = 2.45 × 108

V(L) = 2.45  10 = 4.41 × 106 L/year

8

55.5

t = 8.2  10 6 = 2 × 106 year

12

4.41 10
K 1000
13. eq =
N
K 1000
97.1 =
0.1
K = 97.1 × 10–4 Scm–1
1
K= .
a R
1 0.5
97.1 × 10–4 = 
R 1.5
104
R= = 34.24 
97.1 3
V 5
I= = = 0.146 amp
R 34.24
14. K total = KSrSO4 + K H2O

1.482 × 10–4 = KSrSO4 + 1.5 × 10–6

KSrSO4 = 148.2 × 10–6 –1.5 × 10–6
= 146.7 × 10–6 s cm–1
m = m Sr2+ +   2–
m SO4

= 139.28 s cm2 mol–1

K 1000 146.7 10 –6 103
m = s=
S 139.28
s = 1.053 × 10–3 M
= 1.053 × 10–3 × 183.6 g/L
= 0.1934 g/L

APNI KAKSHA 32
(Physical Chemistry) ELECTROCHEMISTRY
EXERCISE # (JEE–MAINS)
2− 2−
13. Since S2O8 has highest value of reduction potential among given species therefore S2O8 is
strongest oxidizing agent.
+2 + +3
14. Fe(aq) + Ag(aq) ⎯→ Fe(aq) + Ag(s)
0
Eº = E0Ag+ /Ag – E Fe+3 /Fe+2

Now Eqn.1: Fe+2 + 2e– ⎯→ Fe, Eº = y

Gº = – 2Fy
Eqn.2: Fe+3 + 3e– ⎯→ Fe, Eº = z
Gº = – 3Fz
Eqn.2 – Eqn. 1, We get
Fe+3 + e– ⎯→ Fe+2 , (Eº)1
Gº = – 3Fz + 2Fy
 – 1 × F × (Eº)1 = – 3Fz + 2Fy

0
(Eº)1 = E Fe+3 /Fe+2 = 3z – 2y

Now Eº = E0Ag+ /Ag − E0Fe+3 /Fe+2

= x – (3z – 2y)
= x – 3z + 2y
15. G° = –nFE°
= –2 × 96000 × 2
= –384000 J = –384 kJ
16. Reaction at cathode
Ni2+ + 2e– —→ Ni
0.1 mole
0.1
Deposited moles of Ni = = 0.05
2
17. Conductivity increases with increasing concentration of electrolyte and molar conductivity
decreases with increasing concentration of electrolyte.
18.  m = m º – A C

value of A will be same for NaCl and KCl

So Slope for both curve will be same.
But mº for KCl > mº for NaCl
So m KCl > m NaCl
(for a given Concentration)

APNI KAKSHA 33
(Physical Chemistry) ELECTROCHEMISTRY
19. oxidising power  S.R.P value.
 correct order is : Bi+3 < Ce+4 < Pb+4 < CO+3

Eºred  oxidising power

20. As, Acidic Strength  Ka
 order of Acidic Strength or ka is A > C > B
As, Acidic Strength ()  ka()  electrical conductivity ()
21. Anode
PbSO4 + 2e– ⎯⎯ Pb(s) + SO 24−

Equivalent of PbSO4 electrolysed = 0.05

0.05
Moles of PbSO4 =
2
0.05
Mass of PbSO4 = × 303 = 7.6 g
2
22. Ecell = 2V

As, G° = –nF Ecell ... (1)

and also, G° = –RTlnKC ....(2)

Equating (1) and (2)

 nF E aq =  RTlnKC

2 × 96000 = 8 × 300 lnKC

 KC = e160
 Correct option is 3
23. SRP , Oxidising power ↑
Reducing power 
24. Cell reaction :
→ 2H(+eq ) + 2Ag(s) + 2Cl(eq)
H2(g ) + 2AgCl(s) ⎯⎯ −

[H + ]2 [Cl − ]2 −6 2 −6 2
QC = = (10 ) (10 ) = 10–24
PH 2 1

0.06
E = E° – log Q
n
0.06
0.92 = E° – log 10–24
2
E° = 0.2V

APNI KAKSHA 34
(Physical Chemistry) ELECTROCHEMISTRY
25. Ecell = ( Eox ) + ( Ered )
anode cathode

= 0.76 + (E ) 
red cathode

A electrode having maximum SRP will produce maximum Ecell

26. KC → 10 × 1015
E Cell →?

G° = –nF E Cell ...(1)

Also, G° –RTlnKC ...(2)

Equate (1) and (2)
 nF ECell =  RTlnKC
2.303RT
 2× E Cell = log 1016
F

dE
27. S° = nF
dT
G° = –nFE°
G = H° – T S°
S° = –2 × 96000 × 5 × 10–4 = –96.5 J
G° = –2 × 96000 × 2 = – 384 kJ
G° = H° – T  S°
300  (−96.0)
– 384 = H° –
1000
H° = –384 – 28.8 = – 412.8 kJ mol–1
28. m = m + m – m
HA HCl NaA NaCl

= 425.9 + 100.5 – 126.4 = 400

K 1000 5  10 –5  1000
m = = = 50
M 0.001
29. B2H6+3O2→B2O3+3H2O
Moles of O2 required =3× moles of B2H6 =3

I t
= moles of O2 ×4 =12  t=3.2hrs
96500
30. SRP , Oxidising power ↑
Reducing power 

APNI KAKSHA 35
(Physical Chemistry) ELECTROCHEMISTRY
31. Catnode : 2e– + 2H2O → H2 + 2OH–
nf = 2
CH2 – COO–

CH2 – COO–
Anode : → CH2 = CH2 + 2CO2 + 2e–
nf = 2 nf = 1
Total equivalent of gases (CH2 = CH2 , CO2 , H2) = 0.2 + 0.2 + 0.2 = 0.6
0.2 0.2
Total moles of gases = + 0.2 + = 0.4
2 2
Total Vol. of gases = 0.4 × 22.4 = 8.96 L
32. Cu + ZnSO4 ––→ X
No reaction Cu lies below Zn in electro chemical series.
33. Cu2+ + 2e– → Cu
2F 1 mole = 63.5 g.
34. if Eext > E° Then electron flow from cathode to anode
35. 5e– + 8H+ + MnO4– → Mn2+ + 4H2O
0.06 [H + ]8 f
E = 1.51 – log + 8
5 [H ] i

0.06 (10−3 )8
E = 1.51 – log −7 8
5 (10 )

0.06
E = 1.51 – × 32 = 1.126 V
5
So it will oxidize Br– & I–
36.  = 1.4 S/m.
R = 50 
M = 0.2
1
 = ×
R A

 = 1.4 × 50 m–1.
A
1 1
 = × =  1.4  50 = 0.25 Sm–1
R A 280
 0.25
= = = 5  10−4 Sm2 mol–1
1000  M 1000  0.5
37.  c =  – B C

APNI KAKSHA 36
(Physical Chemistry) ELECTROCHEMISTRY
38. Higher the SRP, better is oxidising agent

Hence MnO4– is strongest oxidising agent

39. X + Y2+→ X2+ + Y
For reaction to be spontaneous Eº must be positive.
40. 2H+ (aq) + 2e– → H2 (g)
0.0591 PH 0.0591 0.0591
Ered = Eºred – log +2 2 ; Ered = 0 – log 2 2 ; Ered = – log2
n (H ) 2 (1) 2
Ered is found to be negative for (3) option
41.  = 1.3 S/m.
R = 50 
M = 0.2
1
 = ×
R A

 = 1.3 × 50 m–1.
A
1 1
 = × =  1.3  50 = 0.25 Sm–1
R A 260
 0.25
= = = 6.25  10−4 Sm2 mol–1
1000  M 1000  0.4
2 4
42. Al2 O3 → Al + O2
3 3
rG = +966 kJ mol–1 = 966 × 103 J mol–1
G = – nFEcell
966 × 103 = – 4 × 96500 × Ecell
Ecell = 2.5 V
43. Fe3+ + 3e– → Fe G1 = –3 × F × E0 3+
Fe /Fe

Fe2+2e–→ Fe G2 = –2 × F × E0 2+
Fe /Fe

Fe3+ + e– →Fe2+ G3 = G1 – G2

G3 = 3 × 0.036F – 2 × 0.439 × F = – 1 × E0 (Fe3+/Fe+2) × F
E0 (Fe3+/Fe+2) = 2 × 0.439 – 3 × 0.036= 0.878 – 0.108= 0.770 V
[Cr +3 ]2
44. Ecell = E0cell – log
[Fe +2 ]3

0.059 (0.1) 2
= 0.3 – log = 0.3 –0.04 = 0.26 V
6 (0.01)3

APNI KAKSHA 37
(Physical Chemistry) ELECTROCHEMISTRY
0.0591 [Zn 2+ ]
45. 0 = + 1.1 – log
2 [Cu 2+ ]
[Zn 2+ ] [Zn 2+ ]
log = 37.3  = 1037.3
[Cu 2+ ] 2+
[Cu ]
0.059
46. 0.152 = – 0.8 – log Ksp  log Ksp = – 16.11
1
47. C = 0.1 M, R = 100 
1
K = 1.29 Sm–1 = ×.
100 A
C = 0.02 M, R = 520 .
1
K= × 129
520
1
 129
M = 520 = 124 × 10–4 Sm2mol-1
1000  0.02
48. CH3COONa + HCI → CH3COOH + NaCI From the reaction,
 0CH3COONa + oHCI =  0CH3COOH + oNaCI or  0CH3COOH =  0CH3COONa + oHCI – oNaCI
Thus to calculate the value of one should know the value of oNaCI along with and oHCI.
5.12  1000 Q
50. 3=
27 96500
Q=54897×103 C = 5.4897×107C
51. Difluoroacetic acid will be strongest acid due to electron withdrawing effect of two fluoring
atoms so as it will show maximum electrical conductivity.
52. ° HOAC = ° NaOAC + ° HCl – ° NaCl
= 91 + 426.2 – 126.5= 390.7
53. E° = E° Sn / Sn2+ + E°Fe3+ / Fe2+= 0.14 + 0.77 = 0.91 V
0.06
54. E° = 10 g Keq
n
0.0591
0.591 = 10 g Keq
1
Keq = 1010
55. °m NaBr = °m KBr + °m NaCl – °m KCl = 152 + 126 – 150 = 12 Scm2 mol–1
56. Zn(s) + 2H+(eq) ––→ Zn2+(eq) + H2(g)
On adding H2SO4, equilibrium shift to right
0.0591 [Zn 2+ ]
E = E° – log + 2
n [H ]
[H+]↑ , E ↑

APNI KAKSHA 38
(Physical Chemistry) ELECTROCHEMISTRY
57. Cr 2+ | Cr 3+ = +0.41V Mn 2+ | Mn 3+ = −1.57V

Fe2+ | Fe3+ = −0.77V Co2+ | Co3+ = −1.97V

As Cr will have maximum oxidation potential value, therefore its oxidation will be easiest.
58. SRP ↑ , Oxidising power ↑
Reducing power 
59. SRP ↑ , Oxidising power ↑
Reducing power 

 0.0591  Zn2+ 
Ecell = E cell − log
n Cu 2+ 
60.
0.0591 1
Ecell = 1.10 − log = 1.07V
2 0.1
9650
61. number of equivalent of of electrons = = 0.1mole
96500
number of equivalent of of Ag = 0.1mole

APNI KAKSHA 39
(Physical Chemistry) ELECTROCHEMISTRY
EXERCISE # (JEE-ADVANCED)
Λ
1. α = Λm
∘
m

cα2
Ka =
1−α
c(Λ m /Λ∘m )2
Ka =
1 − (Λ m /Λ∘m )
cΛ2m
Ka =
Λ∘m (Λ∘m − Λ m )
K a Λ∘m 2 − K a Λ∘m Λ m = cΛ2m
K a Λ∘m
− K a Λ∘m = cΛ m
Λm
K a Λ∘2
m
= cΛ m + K a Λ∘m
Λm
1 cΛ m 1
=( ∘2
)+ ∘
Λm KaΛm Λm
1
P=
Λ∘m
1
S=
K a Λ∘m 2
1
P Λ∘m
=( 1 ) = K a Λ∘m
S
Ka Λ∘2
m

2. (1)
MnO− + ∘
4 (aq) + 4H + 3e → MnO2 (s) + 2H2 O; E = 1.68 V

ΔG1o = −3F(1.68) = −5.04 F

(2)
MnO2 (s) + 4H + + 2e → Mn2+ + 2H2 O; E ∘ = 1.21 V
ΔG2o = −2F(1.21) = −2.42F
(3)
Mn2+ (aq) + 2e → Mn(s); E ∘ = −1.03 V
ΔG3o = −2F(−1.03) = +2.06F
Adding (1), (2) and (3),
MnO− +
4 (aq) + 8H + 7e ⟶ Mn(s) + 4H2 O

ΔG = ΔG1o + ΔG2o + ΔG3o

= (−5.04 − 2.42 + 2.06)F
−7FE ∘ = −5.4 F
E ∘ = 0.77 V
APNI KAKSHA 40
(Physical Chemistry) ELECTROCHEMISTRY
3. λm = λom − A√C
For electrolyte Zm Xn and from given curve
λm (Zm Xn ) = λom (Zm X n ) − A√C
336 − 339 3
−A = =−
0.04 − 0.01 0.03
⇒ A = 100
∴ For λm = 336 S cm2 mol−1
⇒ 336 = λom (Zm Xn ) − 100 × 0.04
λom = 336 + 4 = 340Scm2 mol−1
Zm Xn → mZ n+ + nXX −
∴ 50 m + 80n = 340
⇒ 5 m + 8n = 34 … (i)
Um Yp → mUOp + pYP m−
∴ 25m + 100p = λom (Um Yp ) = 250
⇒ m + 4p = 10 … (ii)
∴ 100 m + 80n = 440
⇒ 5 m + 4n = 22 … (iii)
From equation (i) and (iii)
n=3
m=2
From equation (ii)
p=2
∴ m+n+p =2+3+2= 7
0
4. Ecell = 1.23 volt
0
ΔG0 = −nFEcell {−2 × 96500 × 1.23}J
Since, Work derived from this fuel cell = 70/100 × (−ΔG∘ cell ) × 1.0 × 10−3 = x J
Since insulated vessel, hence q = 0
From equation, for monoatomic gas,
w = ΔU ⇒ x = nCV,m ΔT
3R
{CV,m = }
2
Or
70/100 × 2 × 96500 × 1.23 × 10−3 = 1 × 3/2 × 8.314 × ΔT
ΔT = 13.32

APNI KAKSHA 41
(Physical Chemistry) ELECTROCHEMISTRY
5 & 6. Solution for Questions 5 and 6.
Molar conductivity of HX at infinite dilution
Λ∞
m
= 4 × 102 S cm2 mol−1
Molar conductivity of HX at conc. c1 = y × 102 S cm2 mol−1
c
Λ m1 y × 102 y
α1 = = =
Λ∞m 4 × 102 4
On 20 times dilution of the solution of HX
c
Λ m2 3y × 102 3y c1
α2 = ∞ = 2
= [c2 = ]
Λm 4 × 10 4 20
α1 1
= ⇒ α2 = 3α1
α2 3
HX ⇌ H + + X −
c1 (1 − α1 ) c1 α1 c1 α1
c1 α12 c2 α22 c1 (3α1 )2
Ka = = =
1 − α1 1 − α2 20(1 − 3α1 )
1 9
=
1 − α1 20(1 − 3α1 )
20 − 60α1 = 9 − 9α1
⇒ α1 = 11/51 = 0.215
Y = 4α1 = 0.086

7. Mg (s) + Cu2+ (aq) ––→ Cu (s) + Mg2+ (aq)

Initially : E = 2.7 = E° – RT  1 E° = 2.7
n  
2F  1

When : [Mg2+] = x
E = 2.67 = 2.7 – 300 x
 n 
2  11500 1
n x = 2.3  x = 10
8. 2A (s) + B2n+ (aq) ––→ 2A n+ (aq) + B(s)
Given H° = 2G°
G° = H° – S°
 G° = 2 G° – TS°
G° = TS°
G = G° + RT n Q = 0
 22 
G° = –8.3 × 300 × n   = 300 × S°
 1 
S° = – 8.3 × n 4 = –8.3 × 2 × 0.7 = –11.62 J/K

APNI KAKSHA 42
(Physical Chemistry) ELECTROCHEMISTRY
120
9.  =G× = 5 × 10–7 × = 6 × 10–5 Scm–1
A 1
−4
[H+] = c = 10–4 M  = 10
0.0015

K  1000 6  10−5  1000

m = = = 40 Scm2mol–1
0.0015 0.0015

m m
=  m =
m 

 40 = 6 × 102
 m = −4
10
0.0015

 Z=6
10. Zn (s) + Cu2+(aq) ––→ Zn2+ (aq) + Cu (s)

[Zn 2+ ]
Qc = = 10
[Cu 2+ ]

G° = –2 × F × 1.1
G = G° + RT n Q = –2.2 F + RT n 10= 2.303 RT – 2.2 F
11. H2(g) + M4+(aq) ––→ 2H+(aq) + M2+(aq)
2+
[H + ]2 [M 2 + ] 1  [M ]
Q= = = 10x
PH 2 [M 4 + ] 1  [M 4+ ]

0.059
E = 0.092 = 0.151 – log10x  x=2
2
12. M+ ⎯→ M3+ + 2e–
G0 = –nFE0 For 1 mole of M+
G0 = –2 × 96500 × (–0.25) J
= + 48250 J/mole = 48.25 KJ/mole
Energy released by conversion of 1 mole of
X ⎯→ Y G = –193 KJ

193
Hence mole of M+ convert = =4
48.25

APNI KAKSHA 43
(Physical Chemistry) ELECTROCHEMISTRY
13.  −  −
X Y

  + +  −   + +  −
H X H Y

 
HX 
 HY (1)
m
Also = , So m (HX) = 
m 1 and m (HY) = 
m 2
m 

(Where 1 and 2 are degrees of dissociation of HX and HY respectively.)

Now, Given that
m (HY) = 10 m (HX).
 
m 2 = 10 × 
m 1
2 = 10 1 (2)

Ka = C ,
2
but  << 1, therefore Ka = C2 .
1– 
K a (HX) 0.01 2 1
 = 0.01α12 = ×  1 
 = .
K a (HY) 0.1α 22 0.1  10  1000

 log (Ka (HX)) – log (Ka (HY)) = –3.

 pKa (HX) – pKa (HY) = 3.
14. Salt bridge is introduced to keep the solutions of two electrodes separate, such that the ions in
electrode do not mix freely with each other. But it cannot stop the process of diffusion.
It does not participate in the chemical reaction. However, it is not necessary for occurence of
cell reaction, as we know that designs like lead accumulator, there was no salt bridge, but still
reactions takes place.
X Y
15. (P) (C 2 H 5 )3 N + CH 3COOH ⎯→ CH3COO– (aq) + (C2H5)3NH+ (aq)
As CH3COOH is a weak acid, its conductivity is already less. On
addition of weak base, acid-base reaction takes place and new ions
are created. So conductivity increases.
(Q) KI (0.1 M) + AgNO3 (0.01 M) ⎯→ AgI  (ppt) + KNO3 (aq).
As the only reaction taking place is precipitation of AgI and in
place of Ag+, K+ is coming in the solution, conductivity remain
nearly constant and then increases.
(R) CH3COOH + KOH ⎯→ CH3COOK (aq) + H2O
OH– (aq) is getting replaced by CH3COO–, which has poorer
conductivity. So conductivity dereases and then after the end point,
due to common ion effect, no further creation of ions take place. So,
conductivity remain nearly same.
(S) NaOH + HI ⎯→ NaI (aq) + H2O
As H+ is getting replaced by Na+ conductivity dereases and
after end point, due to OH–, it increases.
So answer of 39 is : (P) – (3) ; (Q) – (4) ; (R) – (2) ; (S) – (1). Answer is (D).
APNI KAKSHA 44
(Physical Chemistry) ELECTROCHEMISTRY
16. (P) EºFe3+, Fe

 1 × 0.77 + 2 × (– 0.44) = 3 × x
0.11
 x=– V ~ – 0.04 V.
3
(Q) 4H2O ⎯→ 4H+ + 4OH–
2H2O ⎯→ O2 + 4H+ + 4e– – 1.23 V
+ O2 + 2H2O + 4e– ⎯→ 4OH– + 0.4 V
_____________________________________
4H2O ⎯→ 4H+ + 4OH– – 0.83 V
(R) Eº(Cu2+ + Cu → 2Cu+)

x × 1 + 0.52 × 1 = 0.34 × 2
x = 0.16 V.
 Cu2+ + e– ⎯→ Cu+ 0.16 V
+ Cu ⎯→ Cu+ + e– – 0.52 V
______________________________________________________________
Cu2+ + Cu ⎯→ 2Cu+ – 0.36 V
However, in the given option, – 0.18 V is printed.
(S) Eº(Cr3+, Cr2+)

x × 1 + 2 × (– 0.91) = 3 × (– 0.74)
x – 1.82 = – 2.22
 x = – 0.4 V
Hence, most appropriate is (D).
(P) – (3) ; (Q) – (4) ; (R) – (1) ; (S) – 2.
17. G = – nFEcell = – 2 × 96500 × 0.059 × 10–3 kJ/mole
= – 11.4 kJ/mole.
18. M|M2+ (aq) || M2+ (aq) | M
0.001 M
Anode : M ⎯→ M2+ (aq) + 2e–
Cathode: M2+ (aq) + 2e– ⎯→ M
____________________________
M2+ (aq)c ⎯→ M2+ (aq)a

APNI KAKSHA 45
(Physical Chemistry) ELECTROCHEMISTRY
0.059  M 2 + (aq) a 
Ecell = 0 – log  −3 
2  10 
0.059  M 2+ (aq)a 
0.059 = − log  −3 
2  10 
 M2+ (aq)a 
– 2 = log  −3 
 10 
10 × 10 = M (aq)a = solubility = s
–2 –3 2+

Ksp = 4s3 = 4 × (10–5)3 = 4 × 10–15

19.

0.059 [Fe 2 + ]2
20. E = Eº – log + 4
4 [H ] PO2
−3 2
0.06 (10 ) 0.03
= 1.67 – log −3 4
= 1.67 – log107
4 (10 )  0.1 2
0.03
= 1.67 – × 7 = 1.67 – 0.105 = 1.565 = 1.57 V.
2
22. M (s) | M+ (aq, 0.05 M) || M+ (aq, 1 M) | M(s)
Anode : M (s) ⎯→ M+ (aq) + e–
Cathode : M+ (aq) + e– ⎯→ M (s)
_____________________
M+ (aq) |c ⎯→ M+ (aq) |a
0.0591 M + (aq) |a
Ecell = E°cell – log
1 M + (aq) |c
0.0591
=0– log
1
= + ve = 70 mV and hence G = – nFEcell = – ve.
0.0591
= 70 mV + log 20 = 140 mV.
1
23. The species having less reduction potential with respect to NO3– (Eº = 0.96 V) will be oxidised
by NO3–. These species are V, Fe, Hg.
  t (sec)
24. Faraday law equivalents of H2 produced =
96500
−3
0.01  2 = 10  10  t = 96500  2=t
96500
t =19.3  104 sec
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(Physical Chemistry) ELECTROCHEMISTRY
25. Cl2 + 2I– ⎯→ I2 + 2Cl– .
Eº = 1.36 + (– 0.54) = 0.82 V (+ ve). Spontaneous.
26. Mn3+ + e– ⎯→ Mn2+, 1.50 volt.
2H2O ⎯→ O2 + 4H+ + 4e–, 1.23 volt.
_____________________________________
4Mn3+ + 2H2O ⎯→ 4Mn2+ + O2 + 4H+, Ecell = 1.5 – 1.23 = 0.27 volt. (+ ve).
So Mn3+ will oxidise H2O.
27. Mol of NaCl = 4 × 0.5 = 2 mol.
1 1
No. of mole of Cl2 evolved = × mol of NaCl = × 2 = 1 mol.
2 2
28. Taking the 1 : 1 molar combination of Na–Hg amalgam.
weight = 2 × 23 + 2 × 200 = 446 g.
29. 2Na+ + 2e– ⎯→ 2Na.
No. of Faraday required = 2.
 total charge = 2 × 96500 = 193000 coulomb.
30. 2Ag+ + C6H12O6 + H2 ⎯→ 2Ag(s) + C6H12O7 + 2H+, Eº = 0.8 + 0.05 = 0.85 volt.
0.0592
0 = 0.85 – log K.
2
ln K = 2.303 × log K = 2.303 × 28.71 = 66.13
31. [H+] = 10–11 M.
0.0591
Eoxide = – 0.05 – log(10–11)2 = – 0.05 + 0.65
2
or, H = 0.65 volt.
32. Standards electrode potential does not depend upon on concentration.
33. AgBr (s) ⎯→ Ag+ + Br–
(s + 10–7) × s = Ksp = 12 × 10–14 .
s = 3 × 10–7 M.
[Ag+] = 4 × 10–7 M ; [Br–] = 3 × 10–7 M ; [NO3–] = 10–7 M.
Ktotal = Ag+ + Br– + NO3–
Ktotal = 4 × 10–4 × 6 × 10–3 + 3 × 10–4 × 8 × 10–3 + 1 × 10–4 × 7 × 10–3.
Ktotal = 24 + 24 + 7.
Ktotal = 55 Scm–1.
34. Fe ⎯→ Fe2+ + 2e–, 0.44 V.
1
2H+ + O2 + 2e– ⎯→ H2O, 1.23 V.
2
____________________________________________
1
Fe + 2H+ + O2 ⎯→ Fe2+ + H2O, Eº = 0.44 + 1.23 = 1.67 volt.
2
Gº = – 2 × 1.67 × 96500 = – 322.3 kJ.

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(Physical Chemistry) ELECTROCHEMISTRY
35. (a) Ag+(aq) + Cl–(aq) ––→ AgCl(s)
Gorxn = –109 – (–129) – 79

= –57 kJ/mole
G° = –nFE°
–57 × 100 = –1 × 96500 × E°
E° = 0.591 V

G° = –RT n 1 = –57 × 100

Ksp

log Ksp = –10

(b) 2Ag+(aq) + Zn(s) ––→ Zn2+(aq) + 2Ag(s)
E° = 0.8 + 0.76 = 1.56 V
0.06
E° = log Kq = 1.56
2
Kq = 1052
36. Zn + Fe2+ ––→ Fe + Zn2+
0.1
Q= = 10
0.01
0.0591
E = E° – logQ
2
0.0591
0.2905 = E° – log(10)
2
E° = 0.32
0.0591
E° = logK = 0.32
2
K = 100.32/0.0295
37. In+ ⎯→ In3+ + 2e–, E° = 0.42 V
In2+ + e ⎯→ In+, E° = – 0.4 V
______________________________
In2+ ⎯→ In3+ + e–
______________________________
Eº = 0.44 V
Eºcell = 0.15 + 0.44 = 0.59 V
0.059
0 = 0.59 – log K.
1
K = 1010 .

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(Physical Chemistry) ELECTROCHEMISTRY
2+
0.06
39. E + 0.03 = Eº – log [Zn ] .
2 0.5
2+
0.06
E = Eº – log [Zn ] . M = 0.05 M.
2 C
40. MnO4– ion can oxidise both Fe2+ to Fe3+ as well as Cl– to Cl2 . So Fe(NO3)2 cannot be estimated
quantitatively with MnO4– ion in HCl.
EºCell for the cell Pt, Cl2(g) (1 atm) | Cl– (aq) | | MnO4– (aq) | Mn2+ (aq). is euqal to (1.51 – 1.4)
= 0.11 V.
41. Disproportionate reaction
42. conductance  1
Hydrated radius of ion

44. (i) H2(g) + 2AgCl(s) ––→ 2Ag(s) + 2H+ (aq) + 2Cl–(aq)

(ii) G° = H° – TS° = –nF°
At 15°C : H° – 288 × S° = –2 × 96500 × 0.23
At 35°C : H° – 308 × S° = –2 × 96500 × 0.21
On solving
H° = –49587 J/mole
S° = –96.5 J/mole-K
45. E°cell = 0.33 + 0.44 = 0.77 Volt
since E°cell is positive therefore reaction is spontaneous.
46. Let initially [Cu2+] = C M
C  250
 moles of Cu2+ in the solution = = 0.25 C moles
1000
After electrolysis
0.25  C
Moles of Cu2+ =
2
0.25  C
Eq. of Cu2+ = × 2 = faraday of electricity.
2
0.25 × C = 2 × 10–3 × 16 × 60/69500
2  10−3  16  60
C= = 7.95 × 10–5 M
0.25  96500
47. Cell reaction :
Fe2+ + Ce4+ ––→ Ce3+ + Fe3+
Q=1
E = E° = 1.61 – 0.77 = 0.84 V
 Direction of flow of current is cathode to anode which will decrease with time.
48. The specie having higher reduction potential oxidizes the specie having lower reduction
potential.
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(Physical Chemistry) ELECTROCHEMISTRY
0.06
49. E° = 0.77 – 0.54 = 0.23 = logK
2
K = 6.26 × 107
50. Ag+(cathode) ––→ Ag+(anode)
0.1 M 2S
2S
Q=
0.1
E = 0.164 = – 0.06 log  2S 
2  0.1 
S = 9.23 × 10–3
Ksp = 4S3 = 2.287 × 10–12

APNI KAKSHA 50