Sheet - 01 (Solution) - Electrochemistry Exercise NJ - 247
Sheet - 01 (Solution) - Electrochemistry Exercise NJ - 247
Sheet - 01 (Solution) - Electrochemistry Exercise NJ - 247
SOLUTION
EXERCISE # (O-I)
1. Chemical reaction produces electrical energy.
= ESn/Cn 2+ + E
o o
Ag+ /Ag
E° = EOxdn + E Redn
o o
13.
APNI KAKSHA 1
(Physical Chemistry) ELECTROCHEMISTRY
14. Ecell = E Oxyn + E Re dn
; G1
º
16. Au+ + e– ⎯→ Au(s) E° = 1.69 V ...(1)
; G 2
º
Au3+ + 3e– ⎯→ Au(s) E° = 1.40 V ...(2)
; G3
º
Au3+ + 2e– ⎯→ Au+ ...(3)
17.
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
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
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 )
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
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
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. wQ
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
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 Cl − = 1.35 V
2 /Cl
−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
[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
Ecell = 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
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
0.0591 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
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–
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
Ecell =0
0.0591 [Ag + ]a
Ecell =– log
1 [Ag + ]c
Ksp.AgCl 110−10
[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
= 0.8 – 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
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 + 2Na OH − 2NaCl
= 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
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
E º2 = 0.613 V
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
−5
= 1.8 10 0.1
−5
[OH–]c = 1.8 10 0.01
10−14
[H+]c =
1.8 10−5 0.01
(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
APNI KAKSHA 30
(Physical Chemistry) ELECTROCHEMISTRY
–3
+3
7. C 6 H 5 NO 2 ⎯→ C6H5 NH 2
nf = 6
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 w2
×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
55.5
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
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
= 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
APNI KAKSHA 33
(Physical Chemistry) ELECTROCHEMISTRY
19. oxidising power S.R.P value.
correct order is : Bi+3 < Ce+4 < Pb+4 < CO+3
[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. Ecell = ( Eox ) + ( Ered )
anode cathode
= 0.76 + (E )
red cathode
26. KC → 10 × 1015
E Cell →?
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
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
= 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
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
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
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
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° = 2G°
G° = H° – S°
G° = 2 G° – TS°
G° = TS°
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
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
Ka = C ,
2
but << 1, therefore Ka = C2 .
1–
K a (HX) 0.01 2 1
= 0.01α12 = × 1
= .
K a (HY) 0.1α 22 0.1 10 1000
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+
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
APNI KAKSHA 46
(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.
APNI KAKSHA 47
(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
APNI KAKSHA 48
(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
APNI KAKSHA 50