Target : JEE (IITs)

CHEMISTRY
COURSE : VIJETA (JP)

TOPIC : ELECTROCHEMISTRY
SOLUTIONS OF ADVANCED LEVEL PROBLEMS
1.

Ecell = 0.77 ( 0.2) = 0.97 V ; Ecell > 0 spontaneous at std state.

2.

Cu can't displace Al3+ ion from aluminium nitrate because Cu is less reactive than Al.

3.

Difference between oxidation potentials of two electrodes should be maximum.

4.

Higher the std. reduction potential, higher is the oxidising power.

5.

Fe Fe2+ + 2e , x1 .....(i)
Fe3+ + 3e Fe, x2 .....(ii)
Fe3+ + e Fe2+ ; E .....(iii)

G1 = ( 2 F x1)
G2 = 3 F x2
G3 = F E

eq. (iii) = eq. (i) + eq. (ii)

G3 = G1 + G2
F E = ( 2 F x1) + 3 F x2
EFe3+ / Fe2+ = 3x2 2x1
6.

E1 =

[ 4 1.47 1 1.6]
5

E1 =

[5 1.496 1.07]
6

= 1.496 V
= 1.425 V

7.

G = (2 0.34 + 2 1.25)
2 x E = (2 0.34 + 2 1.25)
E = 1.59 V. Non-spontanous since E = ve

8.

Zn salt Zn2+
0.1
0.1(1 0.8)
For the reaction :

0
0.02

Zn2+ + 2e Zn
E = 0.76

9.

1
0.059
log
= 0.81 V..
[ Zn2 ]
2

5
4

N O3
+ 2H+ + e N O2 + H2O
5

N O3 + 8H+ + 6e NH3OH+ + 2H2O ;

0.79 volt
0.731 volt

E = 0.79

1
1
0.059
0.059
log
= 0.731
log 8

2
[H ]
[H ]
1
6

0.79 + 2

0.059
0.059
log [H+] = 0.731 +
8 log [H+]
1
6

0.059 = 0.059 (2

RESONANCE

8
) pH
6

pH =

6
= 1.5.
4

Electrochemistry - 1

10.

pH = 14

[OH] = 1 M

Ksp

[AI3+] = [OH ]3 = 1033

Al3+ + 3e Al
E = EAI3 / Al

1
0.0591
log [ AI3 ]
3

E = 2.309 V.
11.
Initially
After reaction

MnO4 +

8H+

0.1
0.10.10.9
0.100.09
0.01

0.8
0.80.098
0.80.72
0.08

[Mn2 ]
0.059
E = E
log10
5
[MnO 4 ] [H ]8

12.

Eo

Ag / Ag

Eo

= 1.51

5e

Mn2+

0
0.09
0.09
0.09

H2O.
0
0.09
0.09
0.09

(0.09 )
0.059
log10
= 1.392 V..
5
(0.01)(0.08 )8

0.46 V

Cu2 / Cu

o
o
(+) E Cu2 / Cu E Zn2 / Zn 1.1V
___________________________

Eo

Ag / Ag

Eo

Zn2 / Zn

1.56 V

Zn/Zn2+ (0.1M) || Ag+ (1.0M) | Ag ; Ecell = 1.56

Ecell = Ecell

0.059
log Q.
n

Cell reaction :
Zn Zn2+ + 2e
+ (Ag+ + e Ag) 2
___________________________
Zn + 2Ag+ Zn2+ + 2Ag
Q=

[ Zn2 ]
2

[ Ag ]

(0.1)

(1) 2

Ecell = Ecell

= 0.1

0.06
log 0.1
2

0.06
1
2
= 1.59 V Ans.
= 1.56

13.

Sn | Sn2+ (1 M) | | Pb2+ (103 M) | Pb.

E(0Sn2 / Sn ) = 0.14 V

and

E(0Pb 2 / Pb ) = 0.13 V..

Ecell = 0.13 + 0.14 = 0.01 V.

Ecell = 0.01

1
0.059
log
= 0.0785 V..
10 3
2

RESONANCE

Electrochemistry - 2

14.

H2(Pt) (1 atm) | H3 O | | Ag+(xM) | Ag

1.0 = (0 + 0.8)

0.06
[H ]
log
1
x

0 .2
[H ]
= log
0.06
x

10
= pH + log x
3

log x = 1.7
x = 2 102 M.
15.

0 = ( 0.7703 + 0.7991)
log X =

16.

0.06
1
log
x
1

0.0288
= 0.48
0.06

Ecell = 3.17

0.059
log Keq.
2

0 = 0.0288 +0.06 log X

X = 0.33 M.

Ecell = 0.

3.17 2
= 107.48.
0.059
Keq. = 3 10107
G = nFE = 2 96500 3.17 = 611810 J = 611.81 kJ.
log Keq. =

17.
t= 0
t = teq

Fe2+ (aq) + Ag+ (aq)

1
1
1x
1x

Fe3+ (aq) + Ag(s)

0
0
x
x

0.059
log Q
1
At eqm.

Ecell = Ecell

Ecell = 0

Ecell = 0.059 log Kc

0.7877 0.77 = 0.059 log Kc

KC = 2

KC =

(1 x )2

=2

x = 0.5

[Fe2+] = 0.5 M, [Fe3+] = 0.5 M, [Ag+] = 0.5 M.

18.

Hg22 + 2e 2Hg , 0.789 Volt

Hg Hg2+ + 2e , 0.854 Volt

Hg22+ Hg + Hg2+ , 0.065 Volt

0.059
log Keq.
2
log Keq = 2.2
Keq.= 6.3 103

0.065 =

19.

At equilibrium
E10 = +

[Cu ]2
0.058
log10
1
[Cu ]

0.058
10 4
log
= 0.2494
1
2

RESONANCE

Electrochemistry - 3

0
E0
E10 = E 2
Cu / Cu

and

Cu / Cu

E10 2E 0

So,

Cu 2 / Cu

20.

E0

0.4547 V

Ecell = Ecell

= 103

[H ]
[ Ag ]

[H+] = 0.6 103 = 6 104

6 10 4
[H ]
=
= 0.4
C
1.5 10 3

Ka =
21.

H+ + OCN
C C

HOCN
C(1)
=

Cu / Cu

[H ]2
0.059
log
2
[ Ag ]2

0.977 = 0.8 0.059 log

[ Ag ]

E0

H2 2H+
2Ag+ + 2e 2Ag
H2 + 2Ag+ 2H+ + 2Ag

Anode :
Cathode

[H ]

Cu 2 / Cu

Cu / Cu

0.4547 V

Cu / Cu

E0

2E0

E0

Cu / Cu

E0 2
Cu / Cu

1.5 10 3 (0.4)2
C 2
=
= 4 104
1 (0 . 4 )
1

Anode :

[Co(CN)6]3 + e [Co(CN)6]4

E0SRP = 0.82 V..

Cathode :

Co3+ + e Co2+

E0SRP = 1.82 V..

So overall cell reaction is,

Co3+ + [Co(CN)6]4 Co2+ + [Co(CN)6]3.
0
E0cell = E0
c Ea = 1.82 ( 0.82) = 2.64 V..
2

ECell = E0cell
Now,

[Co ] [Co(CN)6 ]
0.06
log
.
[Co3 ] [Co(CN)6 ]4
1

Co2+ + 6CN

[Co(CN)6]4

K f1 = 1 1019.

Co3+ + 6CN

[Co(CN)6]3

K f2

at equilibrium, ECell = 0
E0cell =

22.

E1 =
or

K f2
0.06
log K ; solving we get Kf = 1063
f1
1

0.059
1

pH1 =

log [H+]

E1 / 0.059 = pKa + log

RESONANCE

x
y

Electrochemistry - 4

pH2 =

E2 / 0.059 = pKa + log

E1 E2
0.059

= 2 pKa

or

23.

Ecell = Ecell

y
x

or

pKa =

E1 E2
0.118

1
0.0591
log 2 .
[H ]
2

H2 2H+ + 2e.

0.0591
log [H+]2.
2
Lesser the [H+] conc ; greater will be emf.
Ecell =

24.

Pt / H2 / H+ (C6H5NH2) // H+(HCI) / H2 / Pt
H2

2H+(108M) + 2e , C6H5NH2 + H2O

H NH3+ + OH ; [OH] =
6 5

0.5 1014

=106
500 10 9

[H+] = 108 M.
2H+(5102) + 2e

2H+(5102)

2H+(108)

[H+] =

2 .5
= 5 102
500

(108 )2
0.059
0.059
0.059
log
=
log 1014 4 =
[log4 14] = 0.3953 volt.
2
2
2
(5 10 2 )2

E=0
25.

H2

Since both the electrodes are not identical, the given cell is not a concentration cell.
EBr/AgBr/Ag = EAg+/Ag + 0.06 log Ksp
Ecell = EAg+/Ag EBr/AgBr/Ag = 0.06 log Ksp = 0.06 12.3 = 0.738 V

26.

Ag Ag+ + e
E = 0.8 V
AgBr + e Ag + Br
E = 0.0743 V
+

AgBr
Ag + Br
Ecell = 0.0743 0.8 0.059 log [Ag+] [Br]
0.8 0.0743 = 0.059 log Ksp (AgBr)
Ksp = 5 1013
[Ag+] [Br] = 5 1013
[Br] =

5 10 13
= 5 1012
0 .1

Solubility of AgBr = [Br] = 5 1012 M.

27.

ECl / AgCl,Ag = 0.221 V

Anode :

H2 2H+ + 2e

Cathode :

2AgCI 2e 2Ag 2CI

H2 2AgCI 2H 2CI 2Ag

Ecell = ECl / AgCl,Ag

0.059
log [H+]2 [CI]2
2

HCI H+ + CI
[H+] = [CI]
Ecell = 0.221 + 0.059 2 pH = 0.28 V.

RESONANCE

Electrochemistry - 5

28.

Anode : Ag(s) Ag+ (aq) + 1e

Cathode : Ag+ (aq) + 1e Ag

1e
net : Ag ( AgBr )
Ag( Ag2CO 3 )

0=0+

K SP AgBr

[Br ]

K SP Ag2 CO3

0.059
log
1

K SP AgBr

[Br ]

K SP Ag 2CO 3
[CO 32 ]

[CO 23 ]

4 10 13

29.

8 10 12

[Br ]

[Br ]

[CO 32 ]

KSP[Mn(OH)2] = 2 1013
[Mn2+] (1 104)2 = 2 1013

[CO 32 ]

7
2 10

[Mn2+] [OH]2 = 2 1013.

So, [Mn2+] = 2 105.

E0cell = 0.34 ( 1.18) = 1.52

ECell = 1.52

30.

Ka =

[Mn2 ]
0.059
log
2
[Cu2 ]

C 2
1

1
2
=
6
1

1
1
=
M
3
3

[O3] = 1

= 1.52

0.059
2 10 5
log
= 1.52 + 0.13 = 1.65 V..
2
0.675

1
1 1 24
1 (1)2 4 6 1
=
=
3
12
12

[Ag+] =

3 10 8
= 9 108 M
1
3

2e
Now 2Ag + Zn+2
2Ag+ + Zn
Gives
31.

E = 1.56 +
2K+

K2CO3
16
3

1
0.059
log
= 1.147 V = 1147 mV
(9 10 8 )2
2
+

CO32

16
3

16
3

i = 1 + (n 1)

2.5 = 1 + (3 1)
=

3
4

16
3

=4M
3
4
KCl K+ + Cl
i=2
2M
=1

so [Cl ] = 2 M
at anode Ag + Cl AgCl + e

[CO32] =

at cathode

1
1
Ag2CO3 + e Ag + CO32
2
2

Ecell = 0.25

0.059
log
1

(CO32 )
Cl

Ecell = 0.25
Answer in multiple of 102 = 25.

RESONANCE

Electrochemistry - 6

32.

[Ag(NH3)2]+ + e Ag+ + 2 NH3

Kd = 1013
G1 = RT ln Kd

Ag+ + e Ag

G3 = 1 F 0.8

[Ag(NH3)2]+ + e Ag + 2NH3

G3 = G1 + G2

1 F E = RT ln kd 1 F 0.8
RT
ln kd + 0.8
F

E =

0.059 (13) + 0.8

E = 0.033 V.
Cu2+ + 4NH3 [Cu(NH3)4]2+

33.

1
0

a
2

0
1

Kf =

34._

[Cu(NH3 )4 ]2
[Cu2 ] [NH3 ]4
1

or

1 1012 = [Cu2 ] (2)4

Now,

ECell = E0Cell

Pb + SO42

[ Zn2 ]
0.059
log
2
[Cu2 ]

Pb + PbO2 + 2SO42 + 4H+

2SO4

consumed =

Amp hr. =

35.

= 1.1

1
0.059
log
= 0.7106 V..
2
6.25 10 14

PbSO4 + 2e Anode

PbO2 + 4H2 + SO42 + 2e

nH

[Cu2+] = 6.25 1014.

or

PbSO4

+ 2H2O (Cathode)

2PbSO4 + 2H2O

0.292 125
126 0.29
1.3 3500 0.40 1.14 3500 0.20
=
=
= 18 0.58.
3
.
5
3 .5
98

18 0.58 96500
= 279.85 Amp. hr..
3600

dE

= nF dt
p

= 2 96500 [1.25 103] = 241.25 Jk1

= nF Ecell
+ nFT

dEcell
dT

= 2 96500 1.36 + 2 96500 298 ( 1.25 103)

= 193 1.735 = 334.855 kJ

36.

Ecell =

E0cell

[Cu2 ]cathode
0.059

log10
2
[Cu2 ]anode

E0cell = 0.

Ecell =
37.

Ag Ag

0.812

0.059
log10 0.08 = 5.31 mV..
2
0.12

= ECu2

Cu

1
0.059
0.059
1
log [ Ag ] = 0.34
log
1
2
1

Therefore, [Ag+] = 108 M.

RESONANCE

Electrochemistry - 7

38.

2H2SO 4 H2 S 2O 8 2H 2e

Anode
2H2O

O 2 4H 4e
Cathode

{2H2O H2 + 2OH 2e} 3.

Net : 2H2SO4 + 8H2O H2S2O8 + O2 + 3H2 + 6H+ + 6OH

Hence ratio of nO2 and nH2 is 1 : 3.

39.

1
O
2 2
22.4 1000 cm3 H2 2 96500 C

2e
H2O
H2 +

224 cm3 H2
40.

2 96500 224
C = 1930 C.
22.4 1000

NaCIO3 + H2O NaCIO4 + H2

At cathode : 2H+ + 2e H2
For 1 mole of NaCIO4 and H2 we require 2 F of charge
For 0.5 mole of NaCIO4 we require 1 F of charge
Electricity required (assuming 60% efficiency) = 1F 100/60 =

41.

th Area density =
th =

42.

5
F..
3

108 0.2 0.965 3600

;
96500

108 0.2 0.965 3600

cm = 4.32 104 cm
96500 90 10

Number of moles of Cu2+ discharged from anode = number of moles of Cu2+ deposited at cathode. So,
concentration of copper ion remains same.

43.

522 2
19.3 24 3600
=
(55 32)
96500

44.

2HSO4 S2O82 + 2e + 2H+

45.

The number of Faradays =

or

i=

25
= 0.6944 = 69.44%
36

2 96500 9
60 60 5

i = 96.5 Amp.

9.65 60 0.2
= 1.2 103.
96500

At the cathode, reaction is

1
H + OH
2 2
1.2 103 mol of OH are produced.
The concentration = 1.2 10-3 / 0.05 = 0.024 M.
H2O + e

46.
6.15
= 0.05 mole of nitrobenzene
123

v.f. = 6
electricity of charge required if efficiency is 100% = 0.05 6 = 0.3 F
But efficiency is 40%
charge required =

RESONANCE

0.3F
= 0.75F..
0 .4
Electrochemistry - 8

47.

Anode : 2CI Cl2 (g) + 2e

Cathode : 2H2O + 2e H2(g) + 2OH
pH = 12.3 [OH] = 0.02 M
Moles of OH = 0.3 0.02 = 6 103 moles
= Moles of e
Total charge = 6 103 96500 C.
I=

6 10 3 96500
= 1 A.
9.65 60

48.

Q=

m=

49.

25
(25 )
C=
F
4 96500
4

25
108

g = 0.0216 g = 21.6 mg
4 96500
1

Q = 20 4825 = 96500 C
no. of faraday =
Ag

96500
=1
96500
1
Cu++ Ag+
2
2.00
2.00
20.15
2+1

Ecell = ECell

[ Ag ]
0.0591
log
[Cu ]1/ 2
1

E1 = ECell

2.00
0.059
log
(2.00 )1 / 2
1

E2 = ECell

3
0.059
log
(1.5)1/ 2
1

E = E2 E1 =

1
Cu
2

0.059
3 0.059
1
log 2 log
=
[log
]
1
1.5
3
1
=

50.

E = 1.36 V
E = 0.83 V

0.059
0.059
[0 0.24] =
0.125
1
1

With the reverse corrent how, the occuring rex is Cu + Zn2+

No. of Faraday supplied =

[Zn2+] = 1

E = 1.1
= 1.1

1.865

0.0591
2

(5 10 60 60)
96500

m = 0.067 M

log

= 0.01416 V.

Cu2+ + Zn

= 1.865

[Cu2+] = 1

1.865
m = 1.933 M
2

0.067
1.933

0.0591
0.067
log
2
1.933

= 1.143 volt.

RESONANCE

Electrochemistry - 9

51.

Charge passed = 0.01 Faraday

1

At the anode H2 O O 2 2H 2e with 90 % efficientcy 0.01 0.9 F have been used and will
2

1
produce
0.01 0.9 mole of O2 i.e. 0.00225 mol O2 .
4
2e
At the cathode 2H2O H2 + 2OH

0.01 0.8
mol = 0.004 mol
2
Total moles produced of gases = 0.004 + 0.00225 = 0.00625 mol
vol. at STP = 0.00625 22400 mL = 140 mL
moles of H2 produced =

52.

CuSO4 100 ml, M molar.

At Cathode :

Cu2+ + 2e

Cu ] 2

O + 4H+ + 4e
At Anode :
2H2O
2

Over all,
2Cu(s) + O + 4H+
2Cu2+ + 2H2O
2
pH = 1 [H+] = 0.1 H+ = 0.01 mole
Q = 0.01 mole of e = 0.01 96500 coulomb
= 965 coulomb.

duration of electrolysis with 100% efficiencey =

duration of electrolysis with 80% efficiency =

0.7 mmole

965
= 1000 sec.
0.965

1000
sec = 1250 sec.
0 .8

Cu22 + 2

1.4 mmole

2 + 2 Na2S2O3

0.01
mole = 5 m mole.
2

Cu deposited =
2Cu2+ + 4

Q
i

0.7 mmole

Na2S4O6 + 2NaI

0.04 35
= 1.4 mmole

Initial conc. of CuSO4 =

5 1 .4
100

6.4
100

= 0.064 M.

53.

(a) m (Al3+) = v.f. eq (Al3+) = 3 eq (Al3+) ;

(b) m (SO42) = v.f. eq (SO42) = 2 eq (SO42) ;
(c) m (Al2(SO4)3) = v.f. eq (Al2(SO4)3) = 6 eq (Al2(SO4)3)

54.

RA =

1
= 100
0.01

RB =

1
= 200
0.005

1
1
1
Req = R A + RB
Seq = SA + SB = 0.01 + 0.005 = 0.015 S.
55.

K = 1.5 mho metre1

R=

A KA

RESONANCE

R = 150
or

A = 2 104 sec.m.

= R K A = 150 1.5 2 104 = 4.5 102 m.

Electrochemistry - 10

56.

Kwater = 2.6 105 S cm1

KNaCl(aq) = 3.1 105 S cm1.
( 3.1 2.6) 10 5 1000
M

or

M=

1
5 10 3
=
104 mole/L
3
150

585
1
=
104 mole/L
58 .5 V
3

or

V=

585 10 4 3
Liter = 3 105 L = 3 108 cc.
58.5

150 =

or

RESONANCE

Electrochemistry - 11