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SRI SARVANI EDUCATIONAL SOCIETY

SR IPL

ASSIGNMENT

DT:15-04-2014

SINGLE ANSWER TYPE QUESTIONS:

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 25oC.
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

2.

Eo

for two reaction are given below :

OCl H 2O 2e Cl 2OH ; E o 0.94V

Cr 3 3e Cr ;

What will be the

E o 0.74V
Eo

for?

3OCl 2Cr 3H 2O 2Cr 3 3Cl 6OH

A) -1.68V
3.

B)1.68V

C)-0.20V

D)0.20V

The e.m.f. of the cell


Cd (s) + Hg2+ (aq) Cd+2 (aq) + Hg
is given by E = 0.6708 1.02 104 (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 deg1

(B) 129.3 kJ

(C) 19.69 kJ deg1

(D) 9.85 J deg1

4.

Alkali metals dissolve in liquid NH3 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

5.

From the following values of electrode potentials,

fumarate

i)

ii)

pyruvate 2H 2e lactate , E20 0.18V

fumarate

A) -28.95 kJ

6.

2
2 H 2e succinate , E 0 0.03V
1

and

. Calculate

G 0

for the reaction,

lactate succinate pyruvate


B) +40.53 kJ

C) -75.27 kJ

D) -40.53 Kj

Eo
1.23 V ; E o
1.70 V
2

MnO /MnO
MnO /Mn
4
2
2

Given that
under acidic
conditions. An acidic solution of MnSO4 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

Cd | Cd ( NO ) , KCN || Cd ( NO ) | Cd
32
32
(0.05 N ) (2 N ) (0.09 N )
7.

EMF of the following cell is 0.59volts at 298K.

2NKCN

is equilibrium concentration. Coordination no. of


the complex is

9 1022

(B)

(A)
8.

1.88 1019

1.44 1020

is 4. The instability constant of

(D)

2.88 1020

Calculate the cell EMF in mV for


Pt | H 2 1atm | HCl 0.01M | AgCl(s) | Ag(s)

Given :

G f

at 298 K

(AgCl) = 109.56 kJmol1 and

(A) 456 mV

G f

(H+ + Cl)(aq) =

130.79

kJ mol1

(B) 654 mV

(C) 546 mV
9.

(C)

Cd

(D)279.6 mV

Calculate the EMF of the cell at 298 K


E Cl /AgCl/Ag 0.222V

Pt | H2 (1 atm) | NaOH (xM), NaCl (xM) | AgCl (s) | Ag (Given

(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
10.

11.

By how much would the oxidising power of the


concentration is decreased 100 times?

MnO 4 / Mn 2

couple change if the H+ ions

(a) increases by 189 mV

(b) decreases by 189 mV

(c) will increase by 19 mV

(d) will decrease by 19 mV

The useful work done during the reaction

Ag(s) +

1
2

Cl2(g)

AgCl(s)

Would be
(a) 110kJ mol1

(b) 220 kJ mol1

(c) 55kJ mol1

(d) 100 kJ mol1

E 0Cl

2 / Cl

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

Given

PCl2 1 atm and T = 298K

Multiple Answer Type Questions:


12.

Which of the following statements are NOT TRUE?


A) Use of salt bridge maximizes liquid junction potential
B) For a spontaneous redox process
C) For a spontaneous redox process

G 0,E0 0
G 0,E 0

D) A given lead acid storage cell posses constant cell potential.

13. Which of the following cell(s) can act as concentration cell?

Pt,H
A)

B)

Ag | AgCl s ,KCl aq. || Ag aq | Ag

Pt,H

P |OH aq. || H aq. | H P ,Pt


2 1
2 1

Pt H

2 P1 | Haq. |O2 P2 ,Pt

C)

D)

P | HCl aq. | H P ,Pt


2 1
2 2

Integer Type Questions :

Cu / Cu 2

Sn / Sn2

14. The voltaic cell using


and
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
15.

x
10

so value of x is : [ Given: Cu (M. W = 63.5)]

The standard reduction potential for the half cell.(Give your answer as numerical)

NO3(aq) + 2H+(aq) + e

NO2(g) + H2O(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
16.

At 25C, the emf of the cell (Give your answer as numerical)


Pb | PbCl2.HCl (0.5 M) || HCl (0.5 M) | AgCl (s) | Ag is 0.49 volts and its temperature coefficient
dE
1.8 10 4 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.
17.

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]. (Give your answer as numerical)

18.

Calculate the potential of an indicator electrode versus the standard hydrogen electrode which
originally 0.1M MnO4 and 0.8M H+ and which has been treated with 90% of the Fe 2+ necessary
to reduce all the MnO4 to Mn2+.(Give your answer as numerical)
MnO4 + 8H+ + 5e

Mn2+ + 4H2O E = 1.51 V


[Fe2 ]
[Fe ]

19.

b) What is the maximum value of ratio


for which the following will act as
electrochemical cell? (Give your answer as numerical)
E0

Cd / Cd2

0.402V, E0

Fe2+ / Fe3

0.771V

Cd | Cd2 (10.6M) || Fe 2 , Fe 3+ (Pt)

[log 6 = 0.778]
20.

[1 + 4]

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+
Pb2+ + 2[Co(en)3] 2+
ii) What is the value of Eo [Co(en)3]3+|[Co(en)3] 2+
Given: Eo (Pb2+|Pb) = - 0.126 V(Give your answer as numerical)

SOLUTIONS
1. C
10.

2. B
(b)

MnO 4

3. A

4. B

+ 5e + 8H+

5. D

6.A

7.B

Mn2+ + 4H2O

According to Nernst equation,

Ered =

o
Ered

0.059
5

E ored

Ered(initial) =

log

[Mn 2 ]

8
[MnO 4 ][H ]

[Mn 2 ]
0.0591
log

8
5
[MnO 4 [X]

Let [H+]initial = X

[H+]final =

X
X
2
100 10

8.D

9.A

E ored

Ered(final) =

0.0591
[Mn 2 ] 1016
log
5
[MnO 4 ] [X]8

Ered(final) Ered(initial) =

0.0591
5

log 1016 = 0.1891 V

This Ered 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

11.A
(a)For the cell reaction

Ag(s) +

1
2

Cl2(g)

AgCl(s)

E0 = 1.14V

or E = E0

0.0592
log PCl1/22
1
PCl2 0

Under standard conditions,


log PCl1/22 0

Useful work = Wmax = nFE


= (1) (1.14) 96500 103 kJ = 110 kJ mol1
12. ABCD
13. ABC
14. 4
15.

For the half cell reaction


NO3(aq) + 2H+(aq) + e

NO2(g) + H2O(l)
0.059
[Pr oducts]
log
n
[Re ac tan ts]

The Nernst equation is E = E0

0.059
1
log 2
2
(8)

= 0.78

= 0.78 + 0.059 log 8

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

E = 0.78
= 0.78 0.059 7 = 0.367V
16.

The net cell reaction


1
Pb Agcl(s)

G nFE

1
PbCl2
2

Ag

1 96500 0.49
4.2

= 11260 cal
S

[1]

d(G)
dE
nF
dT
dT

96500
( 1.8 10 4 )
4.2

= 4.14 cal/degree

[1]

H of the reaction
H = G + TS
= 11200 + 298 (4.14)
= 12494 cal

[1]

This heat of reaction is the algebraic sum of the heats of formation of the components.
H HAs

1
1
HPbCl2 HPb HAgCl
2
2

12494 0

1
1
86000 0 HAgCl
2
2

HAgCl 43000 12494

= 30506 cal/mole

17. The galvanic cell formed in this case is as follows:


Pt, H2 (1atm),H (pH ?) || KCl satd. solution, Hg2Cl2(s) , Hg(l) , Pt

[1]
Ecell

ESCE(redn) EHydrogen(redn)

=
= 0.2422 0.0591 log [

[H ]

= 0.2422 + 0.0591 pH at

25C

[1]

pH log[H ] log(0.1) 1

Initial pH of the 0.1 HCl:


Ecell

= 0.2422 + 0.0591 = 0.3013V

[1]

pH after addition of 20 mL alkali:


25 0.1 2.5 millimole

Amount of HCl initially present =


Amount of NaOH added =

20 0.1 2 millimole

Amount of HCl left unreached =


[HCl

= 0.5 millimole

0.5
0.5
M pH log
1.95
45
45

Ecell 0.2422 0.0591 1.95

18.

2.5 2

= 0.3574V

[1]

Let us consider Galvanic cell is


H+ (1M) | H2(1atm), Pt || MnO4 (H+) | Mn+2, Pt
Anode half cell :
2H+ (1M)

H2 (1atm) + 2e
Cathode half cell:
MnO4 + 8H+ + 5e

Initial Conc.:
0.1
0.8
0

Alter Complete
reaction with Fe+2

0.1
0.1
100

0.8

0.1 90
8
100

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

Mn+2 + 4H2O
0
0.1 90
100

(0.09)

EoMnO / Mn2

EMnO / Mn2
4

0.0591
[Mn2 ]
log
5
[MnO-4 ] [H ]8

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

= 1.51
= 1.51

0.0591
9
log
5
1.67 10 9

0.0591
log
5

= 1.51
(5.36 109)
= 1.51 0.1149
= 1.395 V
Thus, potential of an indicator electrode versus the SHE is 1.395 V because ESHE = 0
19.
Cd(s) 2Fe3

Cd
2

2Fe2

b) The cell reaction is


0
Ecell Ecell

0.059
[Cd2 ][Fe2 ]2
log
2
[Fe3 ]2

[1]
to act as electrochemical cell,
E0cell

Ecell 0

0.059
[Cd2 ][Fe2 ]2
log
2
[Fe2 ]2

[1]
Here

E0cell (0.771 0.402) 1.173V

1.173

or,

0.059
0.6[Fe2 ]2
log
2
[Fe3 ]2

[Fe2 ]
39.76 log0.6 2log[

[Fe3 ]

log

[1]

[Fe2 ]
[Fe2 ]

19.99log
20 (approx.)
[Fe3 ]
[Fe3 ]

or,

[Fe2 ]
[Fe3 ]

should be less than

1 1020

[1]

20.
i) [Co(en)3]3+ = 0.0032, [Co(en)3]2+ = 0.0068 , [Pb2+] = 0..0034

Pb Co en
2

2 1
3
3 1
3

Co en

K=
On putting the various known values , we get
K = 0.0154
ii) G10 = -nFEcell = -2.303 RT log K.
From here we get, Ecell = -0.0536 V
From which we can calculate E [Co(en)33+/[Co(en)32+] = 0.18V