1.

Which of the following best explains why concentration cells must be run under non-standard
conditions in order for them to do electrical work?
A) concentration cell cannot do electrical work at 25
o
C.
B)The change in free energy for a concentration cell is always negative under standard
conditions.
C) Concentration cell has a cell potential equal to zero under standard conditions.
D) A concentration cell can only do electrical work when either NH3 or NaOH is added
1.
o
E for two reaction are given below :
2 2 ; 0.94
2
o
OCl H O e Cl OH E V

+ + + =
3
3 ; 0.74
o
Cr e Cr E V
+
+ =
What will be the
o
E for?
3
3 2 3 2 3 6
2
OCl Cr H O Cr Cl OH
+
+ + + +
A) -1.68V * B)1.68V C)-0.20V D)0.20V
16. Alkali metals dissolve in liquid NH
3
and form blue coloured solution which is conductive
due to ammoniated electrons. The conductivity is
A) Lower than that of completely ionized metal salt in water
*B) Higher than that of completely ionized metal salt in water
C) Low than that of fused metal salt
D) Equal to conductivity of liquid metal
17. How many of the following statements are TRUE?
i) use of salt bridge maximizes liquid junction potential
ii) For a spontaneous redox process
0
G 0,E 0 A < >
iii) For a spontaneous redox process G 0,E 0 A > >
iv) A given lead acid storage cell posses constant cell potential.
ANS : 0
19. Which of the following cell(s) can act as concentration cell:
*A)
( )
( )
( )
2 1 2 2
Pt,H P | HCl aq. | H P ,Pt
*B) ( ) ( )
( )
Ag | AgCl s ,KCl aq. || Ag | Ag
aq
+

*C)
( )
( ) ( )
( )
2 1 2 1
Pt,H P |OH || H | H P ,Pt
aq. aq.
+

D)
( )
( )
( )
2 1 2 2
Pt H P | H |O P ,Pt
aq.
+

24. From the following values of electrode potentials,
i)
( ) ( )
2 2
0
2 2 , 0.03
1
fumarate H e succinate E V

+
+ + = and
ii) ( ) ( )
0
2 2 , 0.18
2
pyruvate H e lactate E V

+
+ + = . Calculate
0
G A for the
reaction, ( ) ( ) ( ) ( )
2 2
fumarate lactate succinate pyruvate

+ +
A) -28.95 kJ B) +40.53 kJ C) -75.27 kJ *D) -40.53 Kj
29. Given that = =

+
1.23 ; 1.70
2 /
/
4 2
2
E V E V
MnO MnO
MnO Mn
under
acidic conditions. An acidic solution of MnSO
4
is mixed with KMnO4
solution. The incorrect statement(s) among the following regarding this
system is/are
(I) A stable compound of the stoichiometry Mn(MnO4)2 is formed.
(II) A precipitate of MnO2 is formed.
(III) KMnO4 loses its pink colour.
(IV) A redox reaction with a standard cell potential of +0.47 V
occurs.
*(A) I (B) II, III, IV (C) I, IV (D) II,
III
30. EMF of the following cell is 0.59volts at 298K.
| ( ) , || ( ) |
3 2 3 2
(0.05 ) (2 ) (0.09 )
Cd Cd NO KCN Cd NO Cd
N N N

2NKCN is equilibrium concentration. Coordination no. of Cd is 4. The instability
constant of the complex is
(A)
22
9 10

* (B)
19
2.88 10

(C)
20
1.44 10

(D)
20
2.88 10

35. The voltaic cell using
2
/ Cu Cu
+
and
2
/ Sn Sn
+
half cells is set up at standard
conditions, and each compartment has a volume of 240 mL. The cell delivers 0.15
A for 52.3 h then the concentration in Cu chamber is
x
10
so value of x is : [ Given:
Cu (M. W = 63.5)]
Ans. 4
5. Calculate the cell EMF in mV for

( ) ( )
2
Pt | H 1atm | HCl 0.01M | AgCl(s) | Ag(s) at 298 K
Given :
f
G

A (AgCl) = 109.56 kJmol

1
and
f
G

A (H
+
+ Cl

)
(aq)
= 130.79 kJ mol
1



(A) 456 mV (B) 654 mV
(C)546 mV (D)none of these
Problem 3: The standard reduction potential for the half cell.
NO
3

(aq)
+ 2H
+
(aq)
+ e

NO
2(g)
+ H
2
O
(l)
is 0.78 V
a) Calculate the reduction potential in 8M H
+

b) What will be the reduction potential of the half-cell in a neutral solution? Assume all
other species to be at unit concentration
Solution: For the half cell reaction
NO
3

(aq)
+ 2H
+
(aq)
+ e

NO
2(g)
+ H
2
O
(l)

The Nernst equation is E = E
0

0.059 [Pr oducts]
log
n [Reac tan ts]

= 0.78
2
0.059 1
log
2 (8)
= 0.78 + 0.059 log 8
= 0.833V
Substituting this value for case (b)
E = 0.78
7 2
0.059 1
log
2 (10 )

= 0.78 0.059 7 = 0.367V
7. Calculate the EMF of the cell at 298 K
Pt | H
2
(1 atm) | NaOH (xM), NaCl (xM) | AgCl (s) | Ag (Given
Cl /AgCl/Ag
E 0.222V

= + )
(A) 1.048 V
(B) 0.04 V
(C) 0.604 V
(D) emf depends on x and cannot be determined unless value of x is given
3. At 25C, the emf of the cell
Pb | PbCl
2
.HCl (0.5 M) || HCl (0.5 M) | AgCl
(s)
| Ag is 0.49 volts and its temperature coefficient
4
dE
1.8 10 volt / degree
dT

= . Calculate
a) the entropy change when 1 gm mol of silver is deposited and
b) the heat of formation of AgCl, if the heat of formation of lead chloride is 86000 cal.
3. The net cell reaction

(s) 2
1 1
Pb Agcl Ag PbCl
2 2
+ +

1 96500 0.49
G nFE
4.2

A = =
= 11260 cal [1]

d( G) dE
S nF
dT dT
A
A = =
=
4
96500
( 1.8 10 )
4.2

= 4.14 cal/degree [1]
AH of the reaction
AH = AG + TAS
= 11200 + 298 (4.14)
= 12494 cal [1]
This heat of reaction is the algebraic sum of the heats of formation of the components.

2
As PbCl Pb AgCl
1 1
H H H H H
2 2
A = +

AgCl
1 1
12494 0 86000 0 H
2 2
=

AgCl
H 43000 12494 = + = 30506 cal/mole
12. 25 mL of a solution of HCl (0.1M) is being titrated potentiometrically against 0.1 M NaOH
solution using a hydrogen electrode as the indicator electrode and saturated calomel electrode
(SCE) as the reference electrode. What would be the EMF of the cell initially and after the
addition of 20 mL of alkali at 25C? Given Reduction potential of SCE = 0.2422V. [log 9 = 0.95].
12. The galvanic cell formed in this case is as follows:

+
=
2 2 2(s) (l)
Pt, H (1atm),H (pH ?) || KCl satd. solution, Hg Cl , Hg , Pt [1]

cell
E =
SCE(redn) Hydrogen(redn)
E E
= 0.2422 0.0591 log [
+
[H ]
= 0.2422 + 0.0591 pH at 25 C [1]
Initial pH of the 0.1 HCl:
+
= = = pH log[H ] log(0.1) 1

cell
E = 0.2422 + 0.0591 = 0.3013V [1]
pH after addition of 20 mL alkali:
Amount of HCl initially present = = 25 0.1 2.5 millimole
Amount of NaOH added = = 20 0.1 2 millimole
Amount of HCl left unreached = 2.5 2 = 0.5 millimole
= = =
0.5 0.5
[HCl M pH log 1.95
45 45


cell
E 0.2422 0.0591 1.95 = + = 0.3574V [1]
2. The e.m.f. of the cell
Cd (s) + Hg
2+
(aq) Cd
+2
(aq) + Hg
is given by E = 0.6708 1.02 10
4
(T 25 V) where T is the temperature in C and E in volts. The
entropy change for the reaction is
(A) 19.69 J deg
1
(B) 129.3 kJ
(C) 19.69 kJ deg
1
(D) 9.85 J deg
1

8. Calculate the potential of an indicator electrode versus the standard hydrogen electrode which
originally 0.1M MnO
4

and 0.8M H
+
and which has been treated with 90% of the Fe
2+
necessary to
reduce all the MnO
4

to Mn
2+
.
MnO
4

+ 8H
+
+ 5e

Mn
2+
+ 4H
2
O E = 1.51 V

8. Let us consider Galvanic cell is
H
+
(1M) | H
2
(1atm), Pt || MnO
4

(H
+
) | Mn
+2
, Pt
Anode half cell : 2H
+
(1M) H
2
(1atm) + 2e

Cathode half cell: MnO
4

+ 8H
+
+ 5e

Mn
+2
+ 4H
2
O
Initial Conc.: 0.1 0.8 0 0
Alter Complete
0.1
0.1
100
| |
|
\ .

0.1 90
0.8 8
100
| |

|
\ .

0.1 90
100

reaction with Fe
+2

(0.01) (0.08) (0.09)
So, electrode potential of indicator electrode

2
4
MnO / Mn
E
+
=
2
4
2
o
- 8 MnO / Mn
4
0.0591 [Mn ]
E log
5 [MnO ] [H ]
+
+
+

= 1.51
8
0.0591 (0.09)
log
5 (0.01) (0.08)

= 1.51
9
0.0591 9
log
5 1.67 10

= 1.51
0.0591
log
5
(5.36 10
9
)
= 1.51 0.1149
= 1.395 V
Thus, potential of an indicator electrode versus the SHE is 1.395 V because E
SHE
= 0
12. b) What is the maximum value of ratio
2
[Fe ]
[Fe ]
+
+
for which the following will act as
electrochemical cell?

0 0
2 2+ 3
Cd/ Cd Fe / Fe
E 0.402V, E 0.771V
+ +
= =

2 2 3+
Cd| Cd (10.6M) || Fe , Fe (Pt)
+ +
[log 6 = 0.778] [1 + 4]
12.
b) The cell reaction is
3 2 2
(s)
Cd 2Fe Cd 2Fe
+ + +
+ +

2 2 2
0
cell cell
3 2
0.059 [Cd ][Fe ]
E E log
2 [Fe ]
+ +
+
= [1]
to act as electrochemical cell,
cell
E 0 >

2 2 2
0
cell
2 2
0.059 [Cd ][Fe ]
E log
2 [Fe ]
+ +
+
> [1]
Here
0
cell
E (0.771 0.402) 1.173V = + =

2 2
3 2
0.059 0.6[Fe ]
1.173 log
2 [Fe ]
+
+
>
or,
2
3
[Fe ]
39.76 log0.6 2log[
[Fe ]
+
+
(
> +
(

[1]
or,
2 2
3 3
[Fe ] [Fe ]
log 19.99log 20 (approx.)
[Fe ] [Fe ]
+ +
+ +
< <

2
3
[Fe ]
[Fe ]
+
+
should be less than
20
1 10 [1]
104. When a rod of metallic lead was added to a 0.01 M solution of [Co(en)
3
]
3+
, it was found
that 68% of the cobalt complex was reduced to [Co(en)
3
]
2+
by lead.
i) Find the value of K for Pb + 2[Co(en)
3
]
3+
Pb
2+
+ 2[Co(en)
3
]
2+

ii) What is the value of E
o
[Co(en)
3
]
3+
|[Co(en)
3
]
2+

Given: E
o
(Pb
2+
|Pb) = - 0.126 V

104. i) [Co(en)
3
]
3+
= 0.0032, [Co(en)
3
]
2+
= 0.0068 , [Pb
2+
] = 0..0034
K =
| | ( ) | |
( ) | |
1
3
3
1
2
3
2
en Co
en Co Pb

+
+

On putting the various known values , we get
K = 0.0154
ii) AG
1
0
= -nFE
cell
= -2.303 RT log K.
From here we get, E
cell
= -0.0536 V
From which we can calculate E [Co(en)
3
3+
/[Co(en)
3
2+
] = 0.18V
Problem 6: By how much would the oxidising power of the
+ 2
4
Mn / MnO couple change if the H
+

ions concentration is decreased 100 times?
(a) increases by 189 mV (b) decreases by 189 mV
(c) will increase by 19 mV (d) will decrease by 19 mV
Solution: (b)
4
MnO

+ 5e

+ 8H
+
Mn
2+
+ 4H
2
O
According to Nernst equation,
E
red
=
o
red
E
0.059
5
log
2
8
4
[Mn ]
[MnO ][H ]
+
+
(
(

Let [H
+
]
initial
= X
E
red(initial)
=
2
o
red
8
4
0.0591 [Mn ]
E log
5 [MnO [X]
+

(
(

[H
+
]
final
=
2
10
X
100
X
=
E
red(final)
=
2 16
o
red 8
4
0.0591 [Mn ] 10
E log
5 [MnO ] [X]
+

E
red(final)
E
red(initial)
=
0.0591
5

log 10
16
= 0.1891 V
This E
red
decreases by 0.189 V. The tendency of the half cell to get reduced is its
oxidising power. Hence the oxidising power decreases by 0.189V
Problem 9: The useful work done during the reaction
Ag
(s)
+
1
2
Cl
2(g)
AgCl
(s)

Would be
(a) 110kJ mol
1
(b) 220 kJ mol
1

(c) 55kJ mol
1
(d) 100 kJ mol
1

Given
-
2
0 0
Cl / Cl AgCl/Ag/Cl
E 1.36V, E 0.220V

= = ,
2
Cl
P 1 atm and T = 298K =
Solution: (a) For the cell reaction
Ag
(s)
+
1
2
Cl
2(g)
AgCl
(s)

E
0
= 1.14V
or E = E
0

2
1/ 2
Cl
0.0592
logP
1

Under standard conditions,
2
Cl
P 0 =

2
1/ 2
Cl
logP 0 =
Useful work = W
max
= nFE
= (1) (1.14) 96500 10
3
kJ = 110 kJ mol
1