ELECTROCHEMISTRY (SOLUTION)

21.

PtCl26

contains Pt4+ ion

Pt 4 4e

4F

Pt

1 mole (195g)

195g of Pt will be deposited by = 4 96500C

0.5g of Pt will be deposited by
=

4 96500
0.5C
195

Now Q = It
Q 4 96500
0.5

t
195
5 60 60

Current (I) =
22.

23.

0
Calculate G0 for all these cells using the relation E 0cell E 0cathode E anode
. The cell in which E 0cell is more
has more negative value of G0.

1
H e
H2
2
1

[p H2 ]2

0.059
EE
log
1
[H ]
0

24.

= 0.055 ampere

(b)

0.059
(100) 2
= 0
log
= 0.059 log 10 = 0.059V
1
1

Reactions
Cu2+ + 2e Cu
Cu+ Cu2+ + e
GII0 = F 0.16 = 0.16F
Adding, we get
Cu+ + e Cu

G0 = nFE0
GI0 = 2F 0.34 = 0.68F
G0III = G0I + G0II
= 0.52F = FE0

E0 = 0.52V
25.

At anode: 2Tl 2Tl+ + 2e

At cathode Cu2+ + 2e Cu

Cell reaction 2Tl + Cu+ 2Tl+ + Cu

Using Nernst equation, we get

(c)

E cell E 0cell

2.303RT
[Tl ]2
log
nF
[Cu 2 ]

Thus, Ecell can be increased by decreasing [Tl+] or increasing [Cu2+] or by decreasing

temperature.
26.

Cu 2 2e
Cu(s)
2

E 0 0.33

Cu e
Cu
Cu e
Cu(s)

E 0.153

G1 0.66F
G2 0.153V

G 30 G 2 G1

= + 0.153F 0.66F
27.

E0 = 0.507

During electrolysis of CuSO4 solution using Cu electrodes, the cell reaction is

Anode: Cu(s) Cu++ + 2e
Cathode: Cu++ (aq) + 2e Cu(s)
The loss in weight of anode is equal to gain in weight of cathode.
(D)

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28.

In presence of inert electrode, the cell reaction is

Anode
2H2O 4H+ + 4e + O2
Cathode:
Cu++(aq) + 2e Cu(s)] 2

Net cell reaction 2Cu++ aq. + 2H2O 4H+ + 2Cu(s) + O2

Due to increase in [H+], pH decreases.
(B)
3: The tendency to gain electron is in the order
ZYX
Y + e Y
X X+ + e
(A)

29.

More is the reduction potential, more is the power to get itself reduced or lesser is reducing power or greater
is oxidizing power.
(D)

30.

(D)

31.

(a)
A 349.8 198.5 548.3
1000 5.5 108 1000

M
M
8

M 10.03 10
w H OH 1014

32.

(b)
Cell reaction : Pb s Cu 2aq
Pb2aq Cu s
Ecell E

33.

0
cell

Cu 2
0.0592

log
2
Pb 2

(d) (A) Cathode: Cu 2aq 2e

Cu s

1
Anode: H 2O
2H O 2 2e pH decreases
2
2

(B) Cathode: Cu aq 2e
Cu s
Anode: Cu s
Cu 2aq 2e pH remains unchanged
(C) Cathode: 2H 2O 2e
H 2 2OH aq
Anode: 2Cl
Cl2aq 2e pH increases
34.

(a)
Electrochemical cells or galvanic cells are same thing. Anode is galvanic cells is negative electrode
where oxidation takes place.

35.

(a)
Cell reaction

1
Cathode: H 2O O 2 g 2e aq.
2
Anode: H2 g 2H aq. 2e

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1
H 2 O O 2 g H 2 g 2H aq. 2OH aq.
2
Also we have
1
H 2 g O2 g
H2O
2
f G 0 237.20 kJ mol

H2O
H aq. OH aq.

(1)

(2)

G 80 kJ mol
Hence for cell reaction [eq. (1) + eq. (2) 2]
G 0 237.20 80 2
G0 = 77.20 kJ/mol
G 0
77200

0.40V
So, E0
nF
2 96500
36.

(c)
At anode: Zn Zn 2 2e
At cathode: Cu 2 2e Cu
Cell reaction: Zn Cu 2 Zn 2 Cu
As electricity is withdrawn from the cell, the concentration of Cu2+ decreases while that of Zn2+
increases
Zn 2
0.059
0
Ecell E cell

log 2
n
Cu
Zn 2
0.059
1 1.10
log
2
Cu 2
Zn 2

2453
Cu 2
If x is the amount of Cu2+ that is converted to Cu when the cell potential drops to 1V then
Zn 2 1 x
2452

2453 ; x
0.99918
2
2454
Cu 1 x
To change Cu2+ to Cu and Zn to Zn2+, 2 electrons are required, hence quantity of charge drawn from
the cell
2 0.9992 96500 1.92 105 C

37.

(d)

Ecell

H
0.0591

log a
1
H

For Ecell to be highest H should be lower and [H+]c should be higher and thats why anode
a
compartment should be more basic and cathodic compartment should be more basic and cathodic
compartment should be acidic
38.

(b)
H OH
The ionization of water may be, in a simple way represented as H2 O

H3O OH ]
[of course it is 2H 2O

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G 0 RT ln K w ,

19100 4.18 8.314 298 2.303log K w

log Kw = 13.9923
K w 1.019 10 14
Kh
39.

K w 1.019 1014

7.78 105
10
Ka
1.31 10

(a)
(A) For the cell reaction:
Cd 2 aq 2Ag s
2Ag aq Cd s
E 0cell E 0anode 0.40 0.80 1.20V

Since E 0cell is negative, the reaction will be non spontaneous.

2

Ag
0.1 0.1
(B) Reaction quotient Q

0.1
2
0.1
Cd
2

(C) E cell

Ag
0.0591
0
E cell
log
2
Cd 2

0.0591
0.12
log
1.17V
2
0.1
(D) Cd 2aq 2Ag s
2Ag aq Cd s
120C

0
0
E 0cell E cathode
E anode
0.40 0.80 4.86 1.20V

Since E 0cell is negative, the reaction will be non spontaneous.

40.

(b)

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