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Chapter

Electrochemistry
Solutions
SECTION - A
Objective Type Questions (One option is correct)
1.

On passing 3 faradays of electricity through three electrolytic cells connected in series containing Ag+, Ca+2
and Al+3 ion respectively, the molar ratio in which three metal ions are liberated at the electrode is
(1) 1 : 2 : 3

(2) 3 : 2 : 1

(3) 6 : 3 : 2

(4) 3 : 4 : 2

Sol. Answer (3)


i t is same for all the electrolytic solutions

W
it
it
M =
=
(Ag+ + e Ag)
Ag
nF
F
W
it
M =
(Ca2+ + 2e Ca)
Ca
2F
W
it
(Al3+ + 3e Al)
and M =
3F
Al

Molar ratio is 1 :
2.

1
1
:
3
2

or

6:3:2

The molar conductances at infinite dilution of BaCl 2, NaCl and NaOH are respectively 28010 4 ,
126.5 104, 248 104 S m2 mol1. The molar conductance at infinite dilution for Ba(OH)2 is
(1) 523 104 S m2 mol1

(2) 52.3 104 S m2 mol1

(3) 5.23 104 S m2 mol1

(4) 65 104 S m2 mol1

Sol. Answer (1)

BaCl
= Ba2 2Cl
2

...(i)

= Na Cl
NaCl

...(ii)

= Na HO
NaOH

...(iii)

for Ba(OH)2
(i) + 2(iii) 2(ii)
(Ba(OH)2 ) = (280 104) + 2(248 104) 2(126.5 104)
= 523104 Sm2 mol1.
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3.

Electrochemistry

Solution of Assignment (Set-2)

During electrolysis of aqueous solution of a salt, pH in the space near one of the electrode is increased. Which
of the following salt solution was electrolysed?
(1) KCl

(2) CuCl2

(3) Cu(NO3)2

(4) CuSO4

Sol. Answer (1)


In KCl solution the reaction at the electrodes are
2H+ + 2e H2
2Cl Cl2 + 2e
[H+] decreases in the solution because of which [OH] increases hence increasing the pH.
4.

By how much will the potential of half cell Cu+2/Cu change, if the solution is diluted to 100 times at 298 K?
(1) Increases by 59 mV

(2) Decreases by 59 mV

(3) Increases by 29.5 mV

(4) Decreases by 29.5 mV

Sol. Answer (2)


For Cu2+ + 2e Cu(s)
E

Cu2 /Cu

When Cu2+

E'

Cu

/Cu

1
0.0591
log
2
[Cu
]
2
solution is diluted to 100 times [Cu2+] decreases to 1/100

= E

= E

E = E

100
0.0591
log
[Cu2 ]
2

0.0591
[[log 100 log [Cu2+]]
2

E = E

1
0.0591
0.0591
2
log
[Cu2 ]
2
2

E = E

1
0.0591
log
0.0591
[Cu2 ]
2

E = E 0.0591, Hence, Potential decreases by 59 mV.


5.

The Ecell of the reaction

MnO 4 Fe 2 H Mn2 Fe 3 H2O is 0.59 V at 25C. The equilibrium constant for the reaction is
(1) 50

(2) 10

(3) 1050

(4) 105

Sol. Answer (3)

Eocell = 0.59 V
MnO4 + Fe2+ + H+ Mn2+ + Fe3+ + H2O
0.0591
log Qc
5
At equilibrium, E = 0; Qc = Kc

E = Eocell

Eocell =

0.0591
log Kc
5

5 0.59
= log Kc
0.59
50 = log Kc

Kc = 1050.
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Solution of Assignment (Set-2)

6.

Electrochemistry

73

A current of 2.0 A when passed for 5 hrs through a molten salt, deposits 22.2 g of metal (of atomic weight
177). The oxidation state of metal in metal salt is
(1) +1

(2) +2

(3) +3

(4) +4

Sol. Answer (3)


i = 2A, t = 5 hrs = 5 60 60 s
wM = 22.2 g; A = 177
Applying the equation
w=

Eit
Ait
w=
F
nF

n=

177 2 5 60 60
A i t
=
= 2.97
22.2 96500
wF

n=3
M3+ + 3e M
Oxidation state is +3.
7.

Some Indian scientists tried to use a metal x for electroplating iron pillar in Mehrauli but they ended up with
Ecell of the reaction to be negative. They concluded that
(1) Reaction is spontaneous

(2) Reaction is non-spontaneous

(3) Reaction is reversible

(4) Reaction is non-reversible

Sol. Answer (2)


For electroplating Iron a metal x is used.
Ecell is negative, it means that no reaction takes place and the reaction is non-spontaneous.
8.

In the electrolysis of aqueous solution of NaOH, 2.8 litre of oxygen at NTP was liberated at the anode. How
much hydrogen was liberated at cathode?
(1) 5.6 litre

(2) 56 ml

(3) 560 ml

(4) 0.056 litre

Sol. Answer (1)


NaOH is electrolysed.
NaOH Na+ + HO
H2O H+ + HO
At cathode: 2H+ + 2eH2
At anode: 4HO 2H2O + O2 + 4e

w
it w
it
M =
;
=
H2
2F M O2
4F

nH2 : nO2 =
VH2
2.8

2
1

it
it
:
2:1
2F
4F

Volume ratio VH2 : VO2 = 2 : 1

VH2 = 2.8 2 = 5.6 L

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74
9.

Electrochemistry

Solution of Assignment (Set-2)

The equilibrium constant for the reaction Sr (s) + Mg+2 (aq)


The E for a cell made up of Sr/Sr+2 and Mg+2/Mg half cells is
(1) 0.3667 V

(2) 0.7346 V

Sr+2 (aq) + Mg (s) is 2.69 1012 at 25C.

(3) 0.1836 V

(4) 3.667 V

Sol. Answer (1)


The reaction is
Sr(s) + Mg2+(aq) Mg(s) + Sr2+(aq)
Kc = 2.69 1012
At equilibrium, E = 0; Q = Kc
0.0591
log Kc
2
0.0591
0.0591
E =
log Kc =
log (2.69 1012) = 0.3667 V
2
2

0 = E

10. Passage of one ampere current through 0.1 M Ni(NO3)2 solution using Ni electrodes bring in the concentration
of solution to _________ in 60 seconds.
(1) 0.1 M

(2) 0.05 M

(3) 0.2 M

(4) 0.025 M

Sol. Answer (1)


The reaction taking place at the electrodes are
Anode : Ni Ni2+ + 2e
Cathode : Ni2+ + 2e Ni
Hence [Ni2+] does not change.
Concentration of Ni2+ is 0.1M.
11. Which species in each pair is a better oxidising agent under standard conditions?
(1) Br2 & Au+3

(2) H2 & Ag+

(3) Cd+2 & Cr+3

(4) O2 in acidic medium & O2 in basic medium

Sol. Answer (1)


Halogens act as an oxidising agent and in Au3+ the oxidation state of Au is maximum i.e., +3. So, Au3+ also
acts as oxidizing agent.
12. At 25C, the equivalent conductances at infinite dilution of HCl, CH3COONa and NaCl are 426.1, 91.0 and
126.45 cm2 1eq1 respectively. for CH3COOH (in cm2 1eq1) is
(1) 391.6

(2) 390.6

(3) 380.6

(4) 309.6

Sol. Answer (2)


According to given condition:
o
o

= H + Cl
HCl

...(i)

CH
= CH3COO Na
3 COONa

...(ii)

o
o

= Na + Cl
NaCl

...(iii)

Doing the operation


Equation (i) + (ii) (iii)
o
o

+ CH3COONa NaCl
= CH3COO + H
HCl

(426.1 + 91.0 126.45) = CH3COOH

CH
= 390.6 cm2 1/eq
3 COOH

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Solution of Assignment (Set-2)

Electrochemistry

75

13. When electricity is passed through a solution of AlCl3 13.5 g of Al is deposited. The number of faradays must
be
(1) 1.0

(2) 1.5

(3) 0.5

(4) 2

Sol. Answer (2)


The reaction at cathode is
Al3+ + 3e Al (n = 3)
Applying the equation
w=

Eit
w
F
F
E

13.5
13.5

i t = 27 F =
F = 1.5 F
9
3

14. 0.5 faraday of electricity was passed to deposit all the copper present in 500 ml of CuSO4 solution. What was
the molarity of this solution?
(1) 1 M

(2) 0.5 M

(3) 0.25 M

(4) 2.5 M

Sol. Answer (2)


i t = 0.5 F
Applying the equation
w=

w
E it
it
0.5F
=
=
= 0.25 moles
F
2F
2F
M

V molarity = No. of moles


500 x 103 = 0.25
x=

0.25 103
= 0.5
500

Molarity = 0.5 M
15. Cu+ is not stable and undergoes disproportionation E for Cu+ disproportionation
ECu 2 / Cu 0.153 V, ECu / Cu 0.53 V

(1) +0.683 V

(2) 0.367 V

(3) 0.754 V

(4) +0.3415 V

Sol. Answer (3)


Given
EoCu2 /Cu = +0.153 V and EoCu /Cu = 0.53 V
The reaction
2Cu+ Cu + Cu2+

o
o
E oCell = ECu /Cu2 + ECu /Cu

o
we required ECu /Cu2

Cu2+ + 2e Cu; 0.153


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76

Electrochemistry

Solution of Assignment (Set-2)

Cu Cu+ + e; 0.53
Cu2+ + e Cu+
1 F E = [2 F (0.153)] + [F 0.53]
FE = 2F (0.153) + 0.53 F
E = 0.53 + (2 0.153)

EoCu2 /Cu = 0.224

or

EoCu /Cu2 = 0.224

E = 0.224 + 0.53 = 0.754 V


16. 25 g of a metal is deposited on cathode during the electrolysis of metal nitrate solution by a current of 5 A
passing for 4 hours. If atomic weight of the metal is 100. The valency of metal in metal nitrate is
(1) 1

(2) 2

(3) 3

(4) 4

Sol. Answer (3)


wM = 25 g, i = 5 A, t = 5 hrs = 4 60 60 second
A = 100 (metal nitrate was electrolysed)
Applying the equation,
w=

E it
F

25 =

n=

100 5 4 60 60

n
96500

100 5 4 60 60
=3
(96500 25)

Hence, valency = 3
17. A well stirred solution of 0.1 M CuSO4 is electrolysed at 25C using platinum electrodes with a current of 25
mA for 6 hours. If current efficiency is 50%. At the end of the duration what would be the concentration of
copper ions in the solution?
(1) 0.0856 M

(2) 0.092 M

(3) 0.0986 M

(4) 0.1 M

Sol. Answer (3)


18. 50 ml of a buffer of 1 M NH 3 and 1 M NH4+ are placed in two volatic cells separately. A current of
3.0 amp is passed through both cells for 10 min. If electrolysis of water takes place as
2H2O + O2 + 4e 4OH (R.H.S.)
2H2O 4H+ + O2 + 4e (L.H.S.)
then pH of the
(1) L.H.S. will increase

(2) R.H.S. will increase

(3) R.H.S. will decrease

(4) Both side will increase

Sol. Answer (2)


Because of the reactions of electrolysis, [H+] concentration will decrease as a result of which pH will increase.
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Solution of Assignment (Set-2)

Electrochemistry

77

19. 1 M aqueous solution of NaCl undergo electrolysis if 50 mA current is passed for 12 hours. Assume current
efficiency is 25%. The total volume of gas produced at standard state is
(1) 137 ml

(2) 68.5 ml

(3) 125.44 ml

(4) 62.72 ml

Sol. Answer (3)


NaCl aq. solution undergoes electrolysis
NaCl Na+ + Cl
H2O H+ + HO
Reactions :
At cathode : 2H+ + 2e H2(g)
At anode : 2Cl Cl2 + 2e

w
it
it
it
M =
+
=
T
2F
2F
F
3
50 10

25 12 60 60

= nT
100
96500

nT = 0.005595
V = 0.005595 22400
125.44 ml.
20. Vanadium electrode is oxidised electrically. If the mass of electrode decreases by 100 mg during the passage
of 570 coulomb, the oxidation state of vanadium in the product is (At. wt. of V = 51)
(1) 6

(2) 5

(3) 4

(4) 3

Sol. Answer (4)


i t = 570 C
w = 100 mg = 100 103 g
w=

E it
F

570
100 10 3
=
96500 n
51

n=

570 51
100 10 3 96500

=3

21. The specific conductance of a saturated solution of AgCl is K1 cm1. The limiting ionic conductances of Ag+
and Cl are x and y, respectively. The solubility product of AgCl is
1000 K
(1)
xy

(2)

1000 K

xy

1000 143.5 K
(3)
xy

10 3 143.5 K

(4)

xy

Sol. Answer (2)




AgCl 
 Ag+ + Cl
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78

Electrochemistry

Solution of Assignment (Set-2)

Specific conductance = K1cm1

K 1000
C

o
o
AgCl = Ag Cl = (x + y)

(x + y) =

K 1000
C

1000K
C = (x y)

Solubility product =

C2

1000K
=

(x y)

22. The correct order of equivalent conductance at infinite dilution of LiCl, NaCl, KCl is
(1) KCl > NaCl > LiCl

(2) LiCl > NaCl > KCl

(3) LiCl > KCl > NaCl

(4) LiCl ~
NaCl < KCl

Sol. Answer (1)


The ions formed are Li+, Na+ and K+, the hydration is maximum in case of Li+ because of which its mobility
is least and has least conductance.
Hence, the following order.
KCl > NaCl > LiCl
23. The limiting equivalent conductance of NaCl, KCl and KBr are 126.5, 150.0 and 152.0 S cm2 eq1 respectively.
The limiting equivalent ionic conductance of Br is 76 S cm2 eq1. The limiting equivalent ionic conductance
of Na+ is
(1) 25.5

(2) 52.5

(3) 75.5

(4) 57.5

Sol. Answer (2)


o
o

= Na + Cl = 126.5 ...(i)
NaCl
o
o

= K + Cl = 150
KCl

(ii)

o
o

= K + Br = 152
KBr

(iii)

Adding (i) & (iii) subtract (ii)

Na

o
o
o
o
o
o
o
+ Cl + K + Br K Cl = Na + Br

o
= (126.5 + 152 150) = (76) + Na

Na

= 52.5

Equivalent ionic conductance for Na+ is 52.5.


24. The equivalent conductances of CH3COONa, HCl and NaCl at infinite dilution are 91, 426 and 126 S cm2 eq1
respectively at 25C. The equivalent conductance of 1 M CH3COOH solution is 19.55 S cm2 eq1. The pH of
solution is (pKa = 4.74)
(1) 5.3

(2) 4.3

(3) 2.3

(4) 1.3

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Solution of Assignment (Set-2)

Electrochemistry

79

Sol. Answer (4)


o
o

CH
= CH3 COO Na
3 COONa

o
o
o
= H Cl
HCl

o
NaCl
= Na Cl

= CH3COONa HCl NaCl


CH
3 COOH

91 + 426 + (126) = 391 = CH3COOH

C 19.55

=
[H+]

19.55
= 0.05
391

= C = 1 0.05 M

pH = log [H+] = log (5 102)


2log 5 = 2 0.7 =1.3
25.

E(Na /Na) 2.71 V, E(Mg 2 /Mg) 2.37 V


E(Fe 2 /Fe) 0.44 V, E(Cr 3 /Cr) 0.41 V
Based on this data, which is the poorest reducing agent?
(1) Na+

(2) Mg+2

(3) Fe+2

(4) Cr+3

Sol. Answer (4)


Cr3+ is the poorest reducing agent because of least value of oxidation potential.

Vol. of KCl

(4)

Vol. of KCl

Conductance

Vol. of KCl

(3)

Conductance

(2)

Conductance

(1)

Conductance

26. Which of following type of plot would you expect from the titration of AgNO3 against KCl solution?

Vol. of KCl

Sol. Answer (3)


Fact.
27. The standard reduction potential of Cu+2/Cu and Cu+2/Cu+ are 0.337 V and 0.153 V respectively. The standard
reduction potential of Cu+/Cu half cell is
(1) 0.521 V

(2) 0.490 V

(3) 0.321 V

(4) 0.290 V

Sol. Answer (1)


Given (i) ... Cu2+ + 2e Cu(s); E1o = 0.337 V
(ii)... Cu2+ + e Cu+ Eo2 = 0.153 V
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80

Electrochemistry

Solution of Assignment (Set-2)

Reversing equation (ii); we get


Cu+ Cu2+ + e

...(iii)

Adding equation (i) and (iii)


We get, Cu+ + e Cu

o
Go G1o Go2 = (1 F E) = 2 F E1

+ 1 F E
o
2

FE = [ 2 F (0.337)] + [F 0.153]
FE = 2 0.337 F + (0.153) F
E = (20.337) (0.153) = 0.521 V
28. What is G for the following reaction?
Cu+2(aq) + 2Ag(s) Cu(s) + 2Ag+
ECu 2 /Cu 0.34 V, E Ag /Ag 0.8 V
(1) 44.5 kJ

(2) 44.5 kJ

(3) 89 kJ

(4) 89 kJ

Sol. Answer (4)


The reaction given is
Cu2+ (aq) + 2Ag(s) Cu(s) + 2Ag+
o
o
E oCell = E Ag/ Ag ECu2 /Cu

E oCell = ( 0.8) + (0.34) = 0.46

G = n F E = 2 F (0.46)
= 2 0.46 96500 = 88780 J
or G = + 89 kJ.
o

29. For the half cell EQuinhydrone 1.30 V

OH

O
+

+ 2H + 2e
OH

At pH = 3, electrode potential is
(1) 1.48 V

(2) 1.42 V

(3) 1.36 V

(4) 1.3 V

Sol. Answer (1)


For the reaction, on applying Nernst equation
Ecell = EoCell

0.0591
log [H+]2
2

Ecell = 1.30

0.0591
log (103)2
2

0.0591
(6) log 10 + 1.30 = 0.0591 3 + 1.30 = 1.477 1.48
2

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Solution of Assignment (Set-2)

Electrochemistry

81

30. Emf of the cell


Zn | Zn+2(aq) || Cu+2(aq) | Cu is independent of
(1) Quantity of Cu+2 and Zn+2 in solution

(2) Concentration of Cu+2

(3) Concentration of Zn+2

(4) Temperature

Sol. Answer (1)


For the given cell
Zn2

E = E

0.0591
log
2
Cu2

When Zn2+ & Cu2+ quantity is changed the emf does not change because EMF depends upon concentration
and not the quantity.
31. Which is correct increasing order of deposition?
(1) Na+ < Mg+2 < Zn+2 < Ag+

(2) Ag+ < Zn+2 < Mg+2 < Na+

(3) Mg+2 < Na+ < Zn+2 < Ag+

(4) Mg+2 < Zn+2 < Na+ < Ag+

Sol. Answer (1)


Increasing order of deposition is related to the order of reduction and oxidation potential (in accordance with
preferential discharge theory)
Na+ < Mg2+ < Zn2+ < Ag+
32. Which is the correct order of deposition of anion?
(1) SO42 > OH > Cl > Br > I

(2) SO42 < OH < CI < Br < I

(3) SO42 > Cl > Br > I > OH

(4) Br > Cl > I > SO42 > OH

Sol. Answer (2)


It is in the order of discharge potential
In anion order of deposition is

SO2
4 < HO < Cl < Br < I

33. Which metal oxide is thermally unstable?


(1) Al2O3

(2) Na2O

(3) BaO

(4) Ag2O

Sol. Answer (4)


Ag2O decomposes as
1

Ag2O
2Ag + 2 O2.

34. Rate of corrosion is maximum when


(1) An electrolyte is present in water

(2) Metal has low S.R.P.

(3) Metal has high standard oxidation potential

(4) All of these

Sol. Answer (4)


When metal has high standard oxidation potential, it has more tendency to undergo oxidation. In presence
of electrolyte, rate of Corrosion is maximum.
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82

Electrochemistry

Solution of Assignment (Set-2)

35. H2(1 atm) | 2.26 M HCOOH || 0.222 M CH3COOH| (1 atm) H2


Ka(HCOOH) = 1.77 104,
Ka(CH3COOH) = 1.8 105
Emf of the cell is (Neglect the liquid-liquid junction potential)
(1) 0.0591 V

(2) 0.0591 V

(3) 0.02955 V

(4) 0.02955 V

(3) 418.424

(4) 229.284

Sol. Answer (2)




HCOOH 
 HCOO + H+

C1(1 ) C1 C1
[H+]L = C1 =

(Ka)1 C1



CH3 COOH 
 CH3COO + H+
C2(1 )C2
[H+]R =

C2
(Ka)2 C2
[H ]L
0.0591
log
[H ]R
1

E = E

E=0

or E =

E=

K1 C1

0.0591
log
1

K 2 C2

1.77 10 4 2.26
0.0591
log
2
1.8 10 5 0.222

0.0591
log 100 = 0.0591
2

36. Given that


NiO2 + 4H+ + 2e Ni2+ + 2H2O, E = 1.678 V
NiO2 + 2H2O + 2e Ni(OH)2 + 2OH, E = 0.49 V
For the following reaction
Ni(OH)2 + 2H+  Ni2+ + 2H2O
Gibbs free energy change (in kJ mol1) is
(1) 418.424

(2) 229.284

Sol. Answer (3)

NiO2

4H 2e

Ni 2 2H2O

, E1o 1.678 V

Ni(OH)2 2OH 2e

NiO2 2H2O 2e , Eo2 0.49 V

Ni(OH)2 2H

Ni 2 2H2O

, Eo x V

Go = G1o Go2 nF(E1o Eo2 )


= 2 96500 (1.678 + 0.49) J mol1
= 418.424 kJ mol1
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Solution of Assignment (Set-2)

Electrochemistry

83

37. Zn amalgam is prepared by electrolysis of aqueous ZnCl2 using 9 gram Hg cathode. How much current is to
be passed through ZnCl2 solution for 1000 seconds to prepare a Zn amalgam with 25% by weight? (Atomic
mass, Zn = 65.4 g)
(1) 5.6 A

(2) 7.2 A

(3) 6.64 A

(4) 11.2 A

Sol. Answer (3)


Let, x gram of Zn deposited on 9 gram of Hg. % of Zn in amalgam

x
100 25
9x

x = 3 gram
Equivalent of Zn
Current

32
65.4

6
96500

8.85 A
65.4 1000

38. Which of the following cannot be extracted by electrolysis from aqueous solution of their salts?
(1) Zn

(2) Ag

(3) Cu

(4) Pt

Sol. Answer (1)


As EoZn2 / Zn is less than Eo
H /H

39. Emf of cell given, Ag(s), AgCl(s)||KCl(aq)|Hg2Cl2(s)|Hg(s) is 0.05 V at 300 K and temperature coefficient of the
cell is 3.34 104 VK1. Calculate the change in enthalpy of the cell.
(1) 965

(2) 9650

(3) 96500

(4) 96.5

Sol. Answer (2)


2Ag 2Ag+ + 2e

(anode)

Hg22+ + 2e 2Hg

(cathode)

n=2
Ecell
H = nFEcell nFT

T P

= 2 96500(300 3.34 104 0.05)


= 9650 J mol1
40. Given : Ag+ + e Ag ; E = 0.799 V
Dissociation constant for [Ag(NH3)2]+ into Ag+ and NH3 is 6 1014. Then for the following half-cell reaction:
[Ag(NH3)2]+ + e Ag + 2NH3, calculate E.
(1) 0.019 V

(2) 0.03 V

(3) 0.014 V

(4) 0.19 V

Sol. Answer (1)

Ag e ;

o
EOP
0.799 V

Ag(NH3 )2 e

Ag NH3 ;

o
ERP
?

Ag(NH3 )2

Ag

Ag 2NH3

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Electrochemistry

Ecell Ecell

Solution of Assignment (Set-2)

[Ag(NH3 )2 ]
0.0591
0 at equilibrium
log10
1
[Ag ] [NH3 ]2

Eocell 0.0591 log10 K C 0.0591 log10 (6 1014 )


= 0.780 V
o
EoOP( Ag/ Ag ) ERP(
Ag(NH

3 )2 / Ag)

EoAg(NH

0.780 0.799

3 )2 / Ag

= +0.019 V
41. Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milliampere current. The time
[IIT-JEE 2008]
required to liberate 0.01 mol of H2 gas at the cathode is (1 faraday = 96500 C mol1)
(1) 9.65 104 s

(2) 19.3 104 s

(3) 28.95 104 s

(4) 38.6 104 s

Sol. Answer (2)

W it

E F

W
10 103 t
0.01 2
E
96500
t = 19.3 104 s
42. AgNO3(aq.) was added to an aqueous KCl solution gradually and the conductivity of the solution was measured.
[IIT-JEE 2011]
The plot of conductance () versus the volume of AgNO3 is

volume
(P)
(1) (P)

volume
(Q)
(2) (Q)

volume
(R)
(3) (R)

volume
(S)
(4) (S)

Sol. Answer (4)


Ag+ and K+ have nearly same ionic mobility
AgNO3 + KCl AgCl(s) + KNO3

conc. of KCl
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Solution of Assignment (Set-2)

Electrochemistry

85

43. Consider the following cell reaction:

2 2H O(l)
2Fe(s) O2(g) 4H(aq)
2Fe(aq)
;
2

E = 1.67 V

At [Fe2+] = 103 M, P(O2) = 0.1 atm and pH = 3, the cell potential at 25C is
(1) 1.47 V

(2) 1.77 V

(3) 1.87 V

[IIT-JEE 2011]
(4) 1.57 V

Sol. Answer (4)


Ecell 1.67

0.0591
[Fe2 ]2
log
4
pO2 [H ]4

1.67

0.0581
(103 )2
log
4
0.1 (103 )4

1.67

0.0591
10 6
log
4
1013

1.67

0.0591
log107
4

1.67

0.0591
7 1.57
4

SECTION - B
Objective Type Questions (More than one options are correct)
1.

1.0 L of 0.1 M aqueous solution of KCl is electrolysed. A current of 96.50 mA is passed through the solution
for 10 hours. Which is/are correct? (Assume volume of solution remains constant during electrolysis)
(1) After electrolysis molarity of K+ is 0.064 and molarity of Cl is 0.064
(2) After electrolysis molarity of K+ is 0.1 and molarity of Cl is 0.064
(3) At S.T.P. 202 ml of Cl2 produced when current efficiency is 50%
(4) At S.T.P. 606 ml of total gases produced when current efficiency is 50%

Sol. Answer (2, 3)


i = 96.50 A, t = 10 60 60 s
Solution is 1.0 L and 0.1 M
Moles present = 1 0.1 = 0.1 moles
Reactions :
2H+ + 2e H2 : 2Cl Cl2 + 2e

w
it
w
96.50 10 60 60 10 3
=
=
=
= 0.018
2 96500
M
nF
M
For Cl = 0.036; Molarity = 0.1 0.036 = 0.064

VCl2 =

0.018 22.4
= 0.202 L or 202 ml.
2

K+ will not discharge.


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2.

Electrochemistry

Solution of Assignment (Set-2)

1000 ml 2 M CuSO4 is electrolysed by a current of 9.65 amp for 2 hours. Which is/are correct?
(1) After electrolysis remaining concentration of Cu+2 is 1.64 M using Cu electrode
(2) After electrolysis remaining concentration of Cu+2 is 1.64 M using Pt-electrode
(3) When remaining concentration of Cu+2 is 1.822 then volume of solution is reduced by 10% using Ptelectrode
(4) 17.15 g copper deposit when current efficiency is 75% using copper electrode

Sol. Answer (2, 3, 4)


No. of moles of CuSO4
= 1000 2 = 2000 millimoles
= 2 moles
i = 9.65 A; t = 2 hrs = 2 60 60 s
Cu deposited is w =

w=

n=

E it
F

63.5
9.65 2 60 60

= 22.86

96500

W
= 0.36
M

2 0.36 = 1.64
Hence, molarity = 1.64 M using Pt electrode
w=

3.

75 (9.65) 2 60 60
63.5

= 17.15 g
100
96500
2

For the electrolysis of CuSO4 solution which is/are correct?


(1) Cathode reaction : 2H+ + 2e H2 using Pt electrode
(2) Cathode reaction : Cu+2 + 2e Cu using Cu electrode
(3) Anode reaction : Cu Cu+2 + 2e using Cu electrode
(4) Anode reaction : Cu Cu+2 + 2e using Pt electrode

Sol. Answer (2, 3)


CuSO4(aq) forms the ions
Cu2+, H+, HO and SO2
4
Using Pt electrode
At cathode; Cu2+ + 2e Cu
Using Cu electrodes
At anode :
Cu Cu2+ + 2e
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Solution of Assignment (Set-2)

4.

Electrochemistry

87

Daniell cell : Zn|Zn 2(aq) || Cu 2(aq)|Cu operates as electrolysis cell for 60 min and a current of
( 50 ml 1M)

( 50 ml 1M)

0.965 amp is passed. Which is/are correct?

(E Cu 2 /Cu 0.34 V, E Zn 2 /Zn 0.76 V)


(1) After electrolysis Zn+2 concentration is 1.36 M

(2) After electrolysis Cu+2 concentration is 0.64 M

(3) After electrolysis Zn+2 concentration is 0.82 M

(4) After electrolysis Cu+2 concentration is 1.18 M

Sol. Answer (1, 2)


WCu (deposited) =

31.75
0.965 60 60 = 1.143 g
96500

Total weight of copper = 50 103 1 63.5 = 3.175 g


Left weight of copper

5.

= 3.175 1.143 = 2.032 g


2.032 1000

= 0.64 M
63.5
50

Molarity of Cu2+ solution

Molarity of Zn2+ solution

= 1 + 0.36 = 1.36 M

Which compounds have maximum conductivity?


(1) 0.2 M [Cr(NH3)3Cl3]

(2) 0.15 M [Cr(NH3)4Cl2]Cl

(3) 0.1 M [Cr(NH3)5Cl]Cl2

(4) 0.07 M [Cr(NH3)6]Cl3

Sol. Answer (2, 3)


[Cr(NH3)4Cl2]Cl [Cr(NH3)4Cl2]2+ +Cl
0.15 2 = 0.30
and for
[Cr(NH3)5Cl]Cl2 [Cr(NH3)5Cl]2+ + 2Cl
0.1 3 = 0.30
6.

Molar conductance of 2 M H2A acid is 10 S cm2 mol1. Molar conductance of H2A at infinite dilution is 400
S cm2 mol1. Which statement is/are correct?
(1) Degree of dissociation is 2.5% and pH of solution is 1.3
(2) Degree of dissociation is 4 and pH of solution is 1.4
(3) Dissociation constant of H2A is 6.24 105
(4) Dissociation constant of H2A is 2.56 104

Sol. Answer (1)


7.

Which of following is/are correct?


(1) The metallic conduction is due to the movement of electrons in the metal
(2) The electrolytic conduction is due to the movement of ions in the solution
(3) The metallic conduction increases with increase in temperature whereas electrolytic conduction decreases
with increase in temperature
(4) None of these

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88

Electrochemistry

Solution of Assignment (Set-2)

Sol. Answer (1, 2)


The metallic conduction is due to the presence of electrons in the metal and electrolytic conduction is due
to the movement of ions in the solution.
8.

For electrolyte AxBy which is/are not correct relation between molar conductivity (M) and equivalent conductivity
(eq)
(1) M = xy eq

(2) eq = xy M

(3) xM = y eq

(4) yM = x eq

Sol. Answer (2, 3, 4)


For the electrolyte Ax By
n-factor = xy
M = (xy) eq

Only 1st option is correct & others are incorrect option.


9.

The cell constant of a conductivity cell is defined as ( = cell constant, l = length between the electrode, A
= area, R = resistance, G = conductance, K = conductivity)
(1)

l
A

(2)

(3) = (Gr)1

(4)

G
K

Sol. Answer (1, 3)


R=

1 1 l
l

RA
A

K = C

l
A

RA
l
;
and (G)1
l
A

Vol. of NaOH

Vol. of NaOH

(4)

Conductance

(3)

Conductance

(2)

Conductance

(1)

Conductance

10. Which of following plots will not be obtained for a conductometric titration of HCl and NaOH?

Vol. of NaOH

Vol. of NaOH

Sol. Answer (2, 3, 4)


In the conductometric titration of HCl and NaOH conductance first decreases, reaches a minimum value and
then increases.
11. Zn | Zn+2 (1M) || Ni+2 (1 M) | Ni, antilog (0.7411) = 5.5

E Zn 2 /Zn 0.75 V, ENi 2 /Ni 0.24 V


Which statement is/are correct for above cell?
(1) Emf of cell is 0.51 V and cell reaction is spontaneous
(2) Emf of cell is 0.51 V and cell reaction is non-spontaneous
(3) Emf of cell is zero when concentration of Ni+2 is 5.5 1018 M
(4) Cell reaction is non-spontaneous when concentration of Ni+2 is less than 5.5 1018 M
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Solution of Assignment (Set-2)

Electrochemistry

89

Sol. Answer (1, 3, 4)


The given cell is
Zn|Zn2+(1M)||Ni2+(1M)|Ni
E = (0.75) + (0.24) = 0.51V
and cell reaction is spontaneous.
E = E

[Zn2 ]
0.0591
log
[Ni2 ]
2

E = 0; [Ni2+] = 5.5 1018 M


The cell reaction is
Non-spontaneous when concentration of M2+ is less than 5.5 1018 M.
12. Which statement is correct about electrolysis of CuSO4?
(1) At cathode Cu will deposit and at anode O2 will be produced using Pt-electrode
(2) At cathode Cu will not deposit but Cu dissolve at anode using Cu-electrode
(3) At cathode Cu will deposit and at anode O2 will be produced using Cu-electrode
(4) At cathode Cu will deposit and at anode Cu will dissolve using Cu-electrode
Sol. Answer (1, 4)
Using Pt electrodes
CuSO4 Cu2+ + SO2
4
H2O H+ + HO
At cathode : Cu2+ + 2e Cu
Anode : 4HO 2H2O + O2 + 4e
Products are Cu and O2
Using Cu electrodes
Anode : Cu Cu2+ + 2 e
Cathode : Cu2+ + 2 e Cu
13. Aqueous solution of which electrolyte produces H2 gas at cathode?
(1) NaCl

(2) MgCl2

(3) CuCl2

(4) AgCl

Sol. Answer (1, 2)


H+ has lower discharge potential as compared to Na+ and Mg2+
Hence, in case of NaCl and MgCl2 reaction is 2H+ + 2e H2.
14. Which is/are correct?
(1) If temperature coefficient is greater than zero, cell reaction is endothermic
(2) If temperature coefficient is less than zero, cell reaction is endothermic
(3) If temperature coefficient is less than zero, cell reaction is exothermic
(4) If Ecell is negative then G is negative and cell reaction is spontaneous
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90

Electrochemistry

Solution of Assignment (Set-2)

Sol. Answer (1, 3)


It is known fact that H and temperature coefficient are related as,

E
H > 0 for
>0
T
E
and H < 0 for
<0
T
15. Which is/are correct statements about salt bridge?
(1) Velocity of ions of salt bridge are almost equal

(2) Salt bridge completes the electric circuit

(3) Ions of salt bridge discharge at electrode

(4) Ions of salt bridge do not discharge at electrode

Sol. Answer (1, 2, 4)


Salt Bridge contains electrolyte which do not participate in the electrochemical change, completes the cell
circuit and it is also necessary that velocity of ions of salt bridge are almost equal.
16. The standard emf of the cell
Fe | Fe+2(aq) || Cd+2 | Cd is 0.0372 V and temperature coefficient of emf is 0.125 VK1. Which is/are correct
about the cell (at room temperature)?
(1) G = 7.18 kJ, H = 7196.43 kJ

(2) G = 7.18 kJ, H = 7196.43 kJ

(3) G = 7.18 kJ, H = 7196.43 kJ

(4) S = 24.125 kJ K1, reaction is spontaneous

Sol. Answer (3, 4)


The emf of cell
Fe|Fe2+||Cd2+|Cd, E = 0.0372

G = nFE = 2 96500 0.0372

G = 7179.6 J = 7.18 kJ

Ecell
(S) = nF T

P
(S) = 2 F (0.125)
7180 = Ho + 298 {2 96500 0.125}

Ho = 7196.43 kJ

17. Ksp for AgBr = 8 1013


Ag, AgNO3 (1.0 M) || KBr (1.0 M), AgBr, Ag
For above cell which is/are correct?
(1) Ecell = 0.715 V

(2) Ecell = 0.715 V

(3) G = 1 96500 0.715

(4) G = 1 96500 0.715

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Solution of Assignment (Set-2)

Electrochemistry

91

Sol. Answer (2, 4)


For the 1st Half cell
Anode : Ag Ag+ + e
Cathode : Ag+ + e Ag
E=

[Ag ]L
0.0591
log
[Ag ]R
1
1

E = 0.0591 log

[Ag ]

Ksp (AgBr) = [Ag+] [Br]


[Ag+]R =

8 1013
= 8 1013 M
1

E = 0.0591 log

1
8 1013

= 0.0591 log

1013
8

0.0591 log 8 1013.


0.0591 (0.6 13) = 0.715 V
and G = nFE = +1 96500 0.715
18. Which is/are correct about corrosion?
(1) Due to corrosion FeO.xH2O formed
(2) Due to corrosion Fe2O3.xH2O formed
(3) Presence of air and moisture increases the rate of corrosion
(4) Magnesium is used as sacrificial anode
Sol. Answer (2, 3, 4)
In corrosion
Fe Fe2+ + 2e is formed and the formation of oxide i.e., Fe2O3.xH2O takes place and presence of air and
moisture is must.
Mg can be used as sacrificial anode.
19. Which statement is/are correct?
(1) In electrochemical cell electrons flow from anode to cathode
(2) In electrochemical cell, anode is negative electrode and cathode is positive electrode
(3) Oxidation take place at anode and reduction take place at cathode in electrochemical cell
(4) In electrolytic cell oxidation take place at cathode and reduction take place at anode
Sol. Answer (1, 2, 3)
At cathode always reduction takes place and at anode always oxidation takes place.
Hence (4) will not the correct statement.
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92
20.

Electrochemistry

Solution of Assignment (Set-2)

E Zn 2 /Zn 0.76 V, ENi 2 /Ni 0.24 V

EFe 3 /Fe 0.04 V, ECd 2 /Cd 0.40 V


Which is/are correct statements?
(1) Zn+2 + Cd Cd+2 + Zn, spontaneous

(2) Ni+2 + Cd Ni + Cd+2, spontaneous

(3) Fe+3 + Ni Ni+2 + Fe, spontaneous

(4) Cd+2 + Zn Zn+2 + Cd, spontaneous

Sol. Answer (2, 3, 4)


For (1)
Zn2+ + Cd Cd2+ + Zn
o
o
E = ECd/Cd2 EZn2 /Zn = (0.40) + (0.76) = 0.36 < 0

Non-spontaneous
For Ni2+ + Cd Cd2+ + Ni
o
o
E = ECd/Cd2 ENi2 /Ni

= (0.40) + ( 0.24) > 0 is spontaneous


for Fe3+ + Ni Ni2+ + Fe
o
o
E = ENi/Ni2 EFe3 /Fe = (0.24) + (0.04) > 0 i.e. spontaneous

and for reaction


Cd2+ + Zn Zn2+ + Cd
o
o
Eo = EZn/Zn2 ECd2 /Cd = (0.76) + ( 0.40) > 0 is spontaneous.

21. Which of the following cells give the cell potential to their standard values?
(1) Zn|Zn2+(0.01 M)||H3O+(0.1 M)|H2(1 atm), Pt

(2) Cu|Cu2+(0.25 M)||Ag+(0.5 M)|Ag

(3) Cd|Cd2+(0.01 M)||pH = 1|H2(1 atm), Pt

(4) Zn|Zn2+(0.1 M)||pH = 1|H2(1 atm), Pt

Sol. Answer (1, 2, 3)


o
For Ecell Ecell
, K C 1.

22. Which solution(s) become(s) more acidic after the electrolysis using inert electrodes?
(1) NaCl solution

(2) CuSO4 solution

(3) AgNO3 solution

(4) Na2SO4 solution

Sol. Answer (2, 3)


In the electrolysis of CuSO4 solution and AgNO3 solution, H2SO4 and HNO3 are formed respectively.
23. In which of the following cells, reaction quotient is equal to one?
(1) Pb|PbC2O4, CaC2O4, CaCl2(0.1 M)||CuSO4(0.1 M) | Cu
(2) Zn|ZnSO4(0.1 M)||CuSO4(0.1 M)|Cu
(3) Zn|ZnSO4(0.1 M)||Hg2Cl2, KCl(0.1 M)|Hg, Pt
(4) Cu|CuSO4(0.1 M)||SnCl2(0.1 M)|SnCl4(0.1M), Pt
Sol. Answer (1, 2)
In (3), = 10
In (4), = 0.1
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Solution of Assignment (Set-2)

Electrochemistry

93

24. Saturated solution of KNO3 is used to make salt-bridge. Then incorrect option(s) is/are
(1) Velocity of K+ is zero
(2) Velocity of NO3 is zero
(3) Velocity of both K+ and NO3 are nearly the same
(4) KNO3 is highly soluble in water
Sol. Answer (1, 2)
Fact.
25. When a lead-storage battery is discharged, then incorrect option(s) is/are
(1) H2SO4 is consumed

(2) Pb is formed

(3) SO2 is evolved

(4) PbSO4 is consumed

Sol. Answer (2, 3, 4)


Pb is consumed and PbSO4 is formed. SO2 is not evolved.
26. For the reduction of NO3 ion in an aqueous solution, Eo is +0.96 V. Values of Eo for some metal ions are
given below

[IIT-JEE 2009]

V2+ (aq) + 2e V

Eo = 1.19 V

Fe3+ (aq) + 3e Fe

Eo = 0.04 V

Au3+ (aq) + 3e Au

Eo = +1.40 V

Hg2+ (aq) + 2e Hg

Eo = +0.86 V

The pair(s) of metals that is(are) oxidized by NO3 in aqueous solution is(are)
(1) V and Hg

(2) Hg and Fe

(3) Fe and Au

(4) Fe and V

Sol. Answer (1, 2, 4)


Oxidation of V
Eo = 0.96 (1.19) = 2.15 V
For Fe,
Eo = 0.96 (0.04) = 1.0 V
For Au,
Eo = 0.96 1.4 = 0.044 V (not feasible)
For Hg
Eo = 0.96 0.86 = 0.1 V
27. In a galvanic cell, the salt bridge

[JEE(Advanced)2014]

(1) Does not participate chemically in the cell reaction


(2) Stops the diffusion of ions from one electrode to another
(3) Is necessary for the occurrence of the cell reaction
(4) Ensures mixing of the two electrolytic solutions
Sol. Answer (1, 2)
In a galvanic cell, the salt bridge does not participate in the cell reaction, stops diffusion of ions from one
electrode to another and is not necessary for the occurrence of the cell reaction.
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94

Electrochemistry

Solution of Assignment (Set-2)

SECTION - C
Linked Comprehension Type Questions
Comprehension-I
An electrochemical cell is constructed by immersing a piece of copper wire in 50 ml of 0.1 M CuSO4 solution and
zinc strip in 50 ml of 0.1 M ZnSO4 solution
[E Cu 2 /Cu 0.34 V, E Zn 2 /Zn 0.76 V]

1.

The emf of cell is


(1) 1.07 V

(2) 1.1 V

(3) 1.3 V

(4) 1.13 V

Sol. Answer (2)


EoCu2 /Cu = 0.34 V and EoZn2 / Zn = 0.76 V

ECell

[Zn2 ]
0.0591
= E
log
[Cu2 ]
2

[Zn2+] = [Cu2+] = 1M
o
o
E = E = EZn/Zn2 ECu2 /Cu

E = (0.76) + (0.34)
E = E = 1.1 V
2.

The emf of cell increases when small amount of concentrated NH3 is added to
(1) ZnSO4 solution

(2) CuSO4 solution

(3) Both (1) & (2)

(4) Can't say

Sol. Answer (1)


When NH3 is added to ZnSO4 solution, NH3 reacts with Zn2+ in the following manner :
2+


Zn2+ + 4 NH3 
 [Zn(NH3)4]

i.e., [Zn2+] decreases.


In the equation

E = Eo

0.0591
[Zn2 ]
log
2
[Cu2 ]

If [Zn2+] decreases then log

3.

[Zn2 ]
[Cu2 ]

decreases hence, EMF of cell increases.

In a separate experiment, 50 ml of 1.5 M NH3 is added to CuSO4 solution. Emf of the cell is
[Kf ([Cu(NH3)4]+2) = 5.88 1013]
(1) 0.933 V

(2) 1.327 V

(3) 1.467 V

(4) 0.61 V

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Solution of Assignment (Set-2)

Electrochemistry

95

Sol. Answer (4)


Due to the complex formation, [Cu2+] decreases & it can be calculated by the reaction,


Cu2 4HN3 
 [Cu(NH3)4]2+

50 0.1

50 1.5

[Cu2+] =

50 0.1
100
=
= 9.3 1015 M
(0.55)4 5.88 1013

[Cu (NH3 )4 ]2
[NH3 ]4 k f

Ecell = 1.1

0.0591
0.1
log
15
2
9.3 10

= 0.715 V

Thus, the e.m.f. of cell decreases.


Comprehension-II
The ionic mobility for some ions in water at 298 K is given as following

1.

ions

ionic mobility

K+

7.616 104

Ca+2

12.33 104

Br

8.09 104

SO42

16.58 104

The equivalent conductance of CaSO4 at infinite dilution is


(2) 28.51 104

(1) 279

(3) 31.82 104

(4) 306

Sol. Answer (1)


Equivalent conductance of CaSO4 is the sum of ionic conductance of Ca2+ & SO2
4 .

CaSO
= Ca2 SO2
4
4

= UCa2

= USO2

Ca2

SO2
4

Ca2

& USO24 are ionic mobilities

CaSO
= F {12.33 + 16.58} 104
4

CaSO
= 96500 104 28.91 = 278.98 279
4

Equivalent conductance of CaSO4 is 279


2.

If degree of dissociation is 10% then equivalent conductance of CaSO4 is


(1) 27.9

(2) 2.851 104

(3) 3.182 104

(4) 30.6

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96

Electrochemistry

Solution of Assignment (Set-2)

Sol. Answer (1)


We know that
=

(0.1) =

C
(279)

C = 279 (0.1) = 27.9

Equivalent conductance = 27.9


3.

If the equivalent conductance of 0.01 M CaSO4 solution is 13.95, then equilibrium constant is
(1) 5.26 104

(2) 5.26 105

(3) 2.63 104

(4) 2.63 105

Sol. Answer (4)


C = 0.01M; C = 13.95
=

K=

13.95
= (0.05)
279

2C
(0.05)2 (0.01)
=
(1 )
(1 0.05)

K = 2.63 105.
Comprehension-III
Given below are a set of half-cell reactions (in acidic medium) alongwith their E (in volt) values.

1.

I2 2e
2I

E 0.54

Cl2 2e
2CI

E 1.36

Mn3 e
Mn2

E 1.50

Fe3 e
Fe2

E 0.77

O2 4H 4e
2H2 O

E 1.23

Among the following, identify the correct statement


(1) Cl is oxidised by O2

(2) Fe+2 is oxidised by iodine

(3) I is oxidised by chlorine

(4) Mn+2 is oxidised by chlorine

Sol. Answer (3)


2.

While Fe+3 is stable, Mn+3 is not stable in acid solution because


(1) O2 oxidises Mn+2 to Mn+3
(2) O2 oxidises both Mn+2 to Mn+3 and Fe+2 to Fe+3
(3) Fe+3 oxidises H2O to O2
(4) Mn+3 oxidises H2O to O2

Sol. Answer (4)


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Solution of Assignment (Set-2)

3.

Electrochemistry

97

The strongest reducing agent in aqueous solution is


(1) I

(2) Cl

(3) Mn+2

(4) Fe+2

Sol. Answer (1)


Comprehension-IV
Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules
(approximately 6.023 1023) are present in a few grams of any chemical compound varying with their atomic/
molecular masses. To handle such large numbers conveniently, the mole concept was introduced. This concept
has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry and
radiochemistry. The following example illustrates a typical case, involving chemical/electrochemical reaction,
which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to
the evolution of chlorine gas at one of the electrodes (atomic mass: Na = 23, Hg = 200,
1 faraday = 96500 coulomb).
[IIT-JEE 2007]
1.

The total number of moles of chlorine gas evolved is


(1) 0.5

(2) 1.0

(3) 2.0

(4) 3.0

Sol. Answer (2)


nNaCl =

2.

4 500
2
1000

nCl2 1.

If the cathode is a Hg electrode, then the maximum weight (g) of amalgam formed from this solution is
(1) 200

(2) 225

(3) 400

(4) 446

Sol. Answer (4)


nNa deposited = 2
nNaHg formed = 2
Mass = 2 223 = 446.
3.

The total charge (coulomb) required for complete electrolysis is


(1) 24125

(2) 48250

(3) 96500

(4) 193000

Sol. Answer (4)


Total charge required = 2F = 2 96500 = 193000 C.
Comprehension-V
The concentration of potassium ions inside a biological cell is at least twenty times higher than the outside. The
resulting potential difference across the cell is important in several processes such as transmission of nerve impulses
and maintaining the ion balance. A simple model for such a concentration cell involving a metal M is
M(s) | M+(aq; 0.05 molar) || M+ (aq; 1 molar) | M(s)
For the above electrolytic cell the magnitude of the cell potential |Ecell| = 70 mV.

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1.

Electrochemistry

Solution of Assignment (Set-2)

For the above cell


(1) Ecell < 0; G > 0

(2) Ecell > 0; G < 0

(3) Ecell < 0; G > 0

(4) Ecell > 0; G < 0

Sol. Answer (2)


Cell reaction
M
M
(1 M)

(0.05 M)

Apply Nernst equation


E E

2.

0.059
0.05
log
1
1

0.059
log 5 10 2
1

0.059
2 log5
1

If the 0.05 molar solution of M+ is replaced by a 0.0025 molar M+ solution, then the magnitude of the cell
potential would be
(1) 35 mV

(2) 70 mV

(3) 140 mV

(4) 700 mV

Sol. Answer (3)


E1
log0.05

E2 log0.0025
E1
log5 10 2

E2 log25 10 4

E1  70(given)
70 1.3 1

E2 2.6 2

Comprehension-VI
The electrochemical cell shown below is a concentration cell.
M | M2+ (saturated solution of a sparingly soluble salt, MX2) || M2+ (0.001 mol dm3) | M
The emf of the cell depends on the difference in concentrations of M2+ ions at the two electrodes. The emf of the
cell at 298 K is 0.059 V.
[IIT-JEE 2012]
1.

The solubility product (Ksp; mol3 dm9) of MX2 at 298 K based on the information available for the given
concentration cell is (take 2.303 R 298/F = 0.059 V)
(1) 1 1015

(2) 4 1015

(3) 1 1012

(4) 4 1012

Sol. Answer (2)


0.059

0.059
0.001
log 2
2
(M )

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Solution of Assignment (Set-2)

log

Electrochemistry

99

0.001
2
[M2 ]

0.001
100 K sp = 4 (10 5 )3 = 4 10 15
[M2 ]
[M2 ] 105
2.

The value of G (kJ mol1) for the given cell is (take 1 F = 96500 C mol1)
(1) 5.7

(2) 5.7

(3) 11.4

(4) 11.4

Sol. Answer (4)


G = nFE
= 2 96500 0.059
= 11387 joule mol1
11.4 kJ mol1

SECTION - D
Assertion-Reason Type Questions
1.

STATEMENT-1 : The molar conductivity of strong electrolyte decreases with increase in concentration.
and
STATEMENT-2 : At high concentration, migration of ion is slow.

Sol. Answer (1)


Molar conductance is given by the following expression
= (K V) =

K 1000
c

Here c is the concentration


More is the concentration lesser is the molar conductance
Hence, both statements are correct and statement-2 is the correct explanation of statement-1.
2.

STATEMENT-1 : Electrolysis of molten PbBr2 using platinum electrodes produces Br2 at anode.
and
STATEMENT-2 : Br2 is obtained in gaseous state at room temperature.

Sol. Answer (3)


PbBr2 Pb2+ + 2Br
At cathode :
Pb2+ + 2e Pb
At anode :
2Br Br2 + 2e
Br2 obtained in liquid state at room temperature.
Statement-1 is correct and statement-2 is false.
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100
3.

Electrochemistry

Solution of Assignment (Set-2)

STATEMENT-1 : For the concentration cell, Zn(s) Zn 2 (aq) Zn 2 (aq) Zn for spontaneous cell reaction C1 < C2.
C1

C2

and
STATEMENT-2 : For concentration cell, E cell

C
RT
loge 2 for spontaneous reaction Ecell = +ve C2 > C1.
nF
C1

Sol. Answer (1)


The given cell is
Zn|Zn2+(C1) ||Zn2+ (C2)|Zn
Zn(s) Zn2+ + 2e
E

Zn/Zn2

Zn

/Zn

o
= E Zn/ Zn2

= EZn2 /Zn

0.0591
log (C1)
2

1
0.0591
log C
2
2

o
o
E = (E Zn/ Zn2 E Zn2 / Zn )

C1
0.0591
log C
2
2

EMF of cell
E=

C
0.0591
log 1
2
C2

C1
log C < 0 for spontaneity
2
C1
log C < log 1
2

C1 < C2.
Statement-1 and statements-2 is correct and it is also the correct explanation.
4.

STATEMENT-1 : A saturated solution of KCl is used to make salt bridge in concentration cells.
and
STATEMENT-2 : Mobility of K+ and Cl are nearly same.

Sol. Answer (1)


Mobilities of ions involved in salt bridge is same which is used in concentration cells.
5.

STATEMENT-1 : The molar conductance of weak electrolyte at infinite dilution is equal to sum of molar
conductances of cation and anion.
and
STATEMENT-2 : Kohlrauschs law is applicable for both strong and weak electrolytes.

Sol. Answer (3)

AB = A B

Kohlraush law is applicable for weak electrolyte and not for strong electrolyte.
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Solution of Assignment (Set-2)

6.

Electrochemistry

101

STATEMENT-1 : When a copper wire is placed in a solution of AgNO3, the solution acquires blue colour.
and
o
of Cu+2/Cu is lesser than E o
STATEMENT-2 : ERP

Ag / Ag

Sol. Answer (1)


Cu + AgNO3 Cu2+ + Ag
Eo for reaction is positive because Eo

Cu2 /Cu

7.

Eo

Ag / Ag

STATEMENT-1 : G = nFE.
and
STATEMENT-2 : E should be positive for a spontaneous reaction.

Sol. Answer (2)


Go = nFEo
But Go does not decide the spontaneity only G decides the spontaneity of reaction.
Both statements are correct but statement-2 is not the correct explanation.
8.

STATEMENT-1 : One coulomb of electric charge deposits the weight that is equal to electrochemical equivalent
of substance.
and
STATEMENT-2 : One faraday deposits one mole of substance.

Sol. Answer (3)


One faraday deposits one equivalent of substance.
9.

STATEMENT-1 : If an aqueous solution of NaCl is electrolysed, the product obtained at the cathode is H2 gas
and not Na.
and
STATEMENT-2 : Gases are liberated faster than metals.

Sol. Answer (3)




NaCl 
 Na+ + Cl
+



H2O 
 H + OH

Among cations, hydrogen has higher standard electrode potential and among anions chlorine has low
standard electrode potential. Thus, at cathode preferentially H2 gas is evolved, and at anode Cl2 gas is
evolved.
10. STATEMENT-1 : H2 + O2 fuel cell gives a constant voltage throughout its life.
and
STATEMENT-2 : In this fuel cell, H2 reacts with OH ions, yet the overall concentration of OH ions does not
change.
Sol. Answer (1)
In H2 + O2 fuel cell,
Anode : 2H2(g) + 4OH(aq) 4H2O() + 4e
Cathode : O2(g) + 2H2O() + 4e 4OH(aq)
OH consumed is reformed, so [OH] does not change.
Hence, fuel-cell gives constant voltage throughout its life.
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102

Electrochemistry

Solution of Assignment (Set-2)

SECTION - E
Matrix-Match Type Questions
1.

Match the following


Column-I

Column-II
Molar Conductivity (
1)

Complex
(A) CoCl3.6NH3

(p)

97

(B) CoCl3.5NH3

(q)

(C) CoCl3.4NH3

(r)

404

(D) CoCl3.3NH3

(s)

229

Sol. Answer A(r), B(s), C(p), D(q)


[Co(NH 3 ) 6 ] Cl 3 will give maximum number of ions(4) because of which conductivity is maximum
i.e. 404.
In [Co(NH3)3Cl3] no ions are given
Hence molar conductivity is zero.
[Co(NH3)5Cl]Cl2 & [Co(NH3)4Cl2] Cl forms 3 & 2 ions.
2.

Match the following


Column-I

Column-II
(Amount of charge used for diposition/liberation)

(A) 1 mol Al+3

(p)

(B) 2.3 gm of Na+

(q)

3F

(C) 3.6 gm of Mg+2

(r)

0.1 F

(D) 11.2 L H2 at S.T.P.

(s)

0.3 F

Sol. Answer A(q), B(r), C(s), D(p)


(A) 1 mole Al3+
w
it
wF
=
it =
E
F
E

wF
wF
it = 3
= 3F
=
E
M
(B) 2.3 g Na+

it =

2.3
w
F=
F = 0.1 F
23
E

(C) 3.6 g of Mg2+

it =

3.6
F = 0.3 F
12

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Solution of Assignment (Set-2)

(D)

11.2
1
=
22.4
2

Electrochemistry

103

nH
2

w
it
w
=
it =
F
E
F
E

w
1
= 2 F = 2 F = F
M
2

3.

Match the following


Column-I

Column-II
c
m

(A) , specific conductance

(p)

(B) m , molar conductance

(q)

(C) , degree of dissociation

(r)

Decreases with dilution

(D) Kohlrausch law

(s)

Decreases with increase in concentration of strong


electrolytes

Sol. Answer A(r), B(s), C(p), D(q)


(A) Specific conductance decreases with dilution
(B) Molar conductance decreases with increase in concentration of electrolyte
(C)

m
and decreases with dilution
m

(D) Resistance
4.

l
and decreases with dilution
A

Match the following


Column-I

Column-II

(A) Calomel electrode

(p)

Electrolyte concentration cell

(B) Zn-Cd(C1) |CdCl2| Zn-Cd(C2)

(q)

Metal-insoluble anion half cell

(C) Quinhydrone electrode

(r)

Electrode concentration cell

(D) Pt|H2(1 atm)|H+(C1)||H+(C2)|H2(1 atm)|Pt

(s)

Redox half cell

Sol. Answer A(q), B(r), C(s), D(p)


5.

Match the following


Column-I

Column-II

(Electrolysis)

(Observation)

(A) Aqueous solution of NaCl using inert

(p)

Metal loss at anode

(q)

Chlorine gas evolved at anode

(C) CuSO4 using copper electrodes

(r)

Oxygen gas evolved at anode

(D) 50% H2SO4 solution

(s)

A compound with peroxide bond is formed

electrodes
(B) Very dilute aqueous solution of NaCl
using mercury cathode

Sol. Answer A(q), B(r), C(p), D(s)


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104

Electrochemistry

Solution of Assignment (Set-2)

SECTION - F
Integer Answer Type Questions
1.

The half cell potentials of a half cell | A x n , A x | Pt were found to be as follows:


% of reduced form

24.4

48.8

Half cell potential (V)

0.101

0.115

Determine the value of 'n'.


Sol. Answer (2)
A

2.

x n

ne A x

o
0.101 ERP

0.059
75.6
log

n
24.4

o
0.115 ERP

0.059
51.2
log

n
48.8

n2

o
o
The standard reduction potential of EBi3 /Bi and ECu2 /Cu are 0.226 V and 0.344 V respectively. A mixture of

salts of Bi and Cu at unit concentration each is electrolysed at 25C. At what value of log Cu2 does Bismuth
starts to deposit during electrolysis.
Sol. Answer (4)
The passage of current would initially deposit Cu2+ till ECu2 /Cu becomes 0.266 V because then only Bi3+ will
be deposited.
o
Thus, ECu2 /Cu Ecu

2
/Cu

0.266 0.344
3.

0.059
log Cu2
2

0.059
log Cu2 log Cu2 4
2

A cell is containing two H electrodes. The negative electrode is in contact with a solution of pH = 6. EMF of
the cell is 0.118 V at 25C. Calculate pH at positive electrode.

Sol. Answer (4)


Ecell 0.059log

H cathode
H anode

= 0.059 [pH anode pH cathode]


0.118 = 0.059 [6 pH]
pH = 4
4.

How many faradays of electricity is required to deposit 2 mol copper from CuSO4 solution?

Sol. Answer (4)


Equivalent weight of copper = 63.5/2
Hence, 2 mol require 4 F electricity.
5.

A current of 3 ampere has to be passed through a solution of AgNO3 solution to coat a metal surface of
80 cm2 with 0.005 mm thick layer for a duration of approximately (y)3 seconds. What is the value of y?
(Density of Ag is 10.5 g/cm3)

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Solution of Assignment (Set-2)

Electrochemistry

105

Sol. Answer (5)


Volume of surface

= 80 0.0005
= 0.04 cm2

WAg = 0.04 10.5 = 0.42 gram

0.42

Eit
96500

108 3 t
t 125.09 s y 3
96500

y5
6.

The cost at 5 paise per kWh of operating an electric motor for 8 hours, which takes 15 ampere at 110 V, is
11y paise. Calculate y.

Sol. Answer (6)


Total energy consumed for 8 hours = iVt
= 15 110 8 103 kWh
= 13.2 kWh
Total cost = 5 13.2 = 66 paise
11y = 66
y=6

SECTION - G
Multiple True-False Type Questions
1.

STATEMENT-1 : Corrosion of iron is essentially an electrochemical phenomenon.


STATEMENT-2 : Corrosion reaction at anode : 2Fe s 2Fe3 6e
STATEMENT-3 : Corrosion reaction at cathode : O 2 g 4H aq 4e 2H2 O l
(1) T T T

(2)

TFT

(3)

TFF

(4)

FFT

Sol. Answer (2)


Facts about corrosion
Statement 2 : 2Fe s 2Fe2 4e
2.

STATEMENT-1 : Using Kohlrausch's law of independent migration of ions, it is possible to calculate 0 for
any electrolyte from the of individual ions.
STATEMENT-2 : Limiting molar conductivity of an electrolyte can be represented as the sum of the individual
contributions of the anion and cation of the electrolyte.
STATEMENT-3 : When concentration approaches zero, molar conductivity reaches the lowest limit.
(1) T T F

(2)

TTT

(3)

FTT

(4)

FFT

Sol. Answer (1)


Fact.
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106
3.

Electrochemistry

Solution of Assignment (Set-2)

STATEMENT-1 : Electrolysis of acidulated water using inert electrodes results in evolution of gases at cathode
and anode both.
STATEMENT-2 : Al3+ discharges more readily than Zn2+ at cathode.
STATEMENT-3 : In an electrolytic cell, cations move towards anode.
(1) F T T

(2)

TTT

(3)

FTF

(4)

TFF

Sol. Answer (4)


In electrolysis of acidulated water, H2 and O2 is evolved in 2 : 1 volume ratio, at cathode and anode
respectively.
EoAl 3 /Al EoZn2 / Zn Zn2+ discharges more readily at cathode.

In an electrolytic cell, cations move towards cathode, i.e., negative electrode.

SECTION - H
Aakash Challengers Questions
1.

The standard potential of the following cell is 0.23 V at 15C and 0.21 V at 35C.
Pt|H2(g)|HCl (aq)||AgCl(s)|Ag(s)
(i) Write the cell reaction.
(ii) Calculate H and S for the cell reaction by assuming that these quantities remain unchanged in the
range 15C to 35C.
[Given SRP of Ag+(aq)|Ag(s) is 0.80 V at 25C]

Sol. (i)

1
H2 (g) AgCl(s)  H (aq) Ag(s) Cl (aq)
2

E
(ii) S nF T , n 1, F 96500 coulombs
P
E = 0.21 0.23 = 0.02 V, T = 35 15 = 20C

0.02
1
1
S 1 96500
96.5 JK mol
20

o
G15
1 0.23 96500 22195 J mol1
o
H15
G TS

= 22195 288 (96.5)


= 49987 J mol1

S 96.5 J k 1 mol1 , H 49987 J mol1


2.

Calculate Gro of the following reaction


Ag+(aq) + Cl(aq) AgCl(s)
Given: Gro (AgCl) 109 kJ mol1; Gro (Cl ) 129 kJ mol1; Gro (Ag ) 77 kJ mol1
(i) Represent the above reaction in form of a cell.
(ii) Calculate E of the cell.
(iii) Find log10Ksp of AgCl.

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Solution of Assignment (Set-2)

Electrochemistry

107

Sol. (i) Ag(s) | Ag+ | | AgCl | | Cl | Cl2, Pt


o
o
o
o
(ii) Gr GAgCl GAg GCl (Ag+(aq) + Cl(aq) AgCl(s))

= 109 (129) 77
= 57 kJ mol1

G nFE Eocell

57000
1 96500

Eocell 0.59 V
(iii) G = 2.303 RT logK
logK

57000
10
2.303 6.314 298

K = 1010
K sp

3.

1
10 10 log10 K sp 10
K

The following electrochemical cell has been set-up:


Pt1|Fe3+|Fe2+(1M)||Ce4+ | Ce3+ (1M)|Pt2
o
o
EFe
0.77 V and ECe
1.61 V.
3
4
/Fe2
/Ce3

If an ammeter is connected between the two platinum electrodes, predict the direction of flow of current. Will
the current increase or decrease with time?
Sol. SRP of Fe > SRP of Ce
Fe acts as anode and Ce acts as cathode
o
Eocell Ecathode
Eoanode 1.61 0.77 0.84 V

Hence, flow of current is from cathode to anode (right to left)


Current will decrease with time.
4.

An excess of liquid mercury is added to an acidified solution of 1.0 103 M Fe3+. It is found that 5% of Fe3+
o
remains at equilibrium at 25C. Calculate EHg
assuming that the only reaction that occurs is
2
/Hg

2Hg + 2Fe3+ Hg22+ + 2Fe2+ [Given Eo 3 2 0.77 V ] .


Fe /Fe

2Fe3 2Hg

Sol.

At t 0

1 10 3 M

at t(eq)

0.05 10 3 M

2Fe2

0
0.95 10 3 M

Hg22
0
0.95 10 3
M
2

Ecell Eocell

Fe2 [Hg22 ]
0.0591

log10
n
[Fe3 ]2

o
At eqb., 0 0.77 EHg

2
/ Hg

0.0591
(0.95 10 3 )2 (0.475 10 3 )
log10
2
(0.05 10 3 )2

o
EHg
0.792 V
2
/Hg

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108
5.

Electrochemistry

Solution of Assignment (Set-2)

Chromium metal can be plated out from an acidic solution containing CrO3 according to the following equation.
CrO3(aq) + 6H+(aq) + 6e Cr(s) + 3H2O.
(i) How many grams of chromium will be plated out by 24000 coulombs?
(ii) How long will it take to plate out 1.5 g of chromium by using 12.5 ampere current?

Sol. 52 gram of Cr is deposited by passing 6 96500 coulomb


(i) Amount of Cr deposited =

52 24000
= 2.155 g
6 96500

(ii) M = Zit

1.5

52
12.5 t
6 96500

t = 1336.15 s
6.

The specific conductivity of a saturated solution of AgCl is 2.30 106 ohm1 cm1 at 25C. Calculate the
solubility of AgCl at 25C if 61.9 ohm1 cm2 mol1 and 76.3 ohm 1 cm2 mol1.
Ag
Cl

1000
Sol. Dilution = Solubility

oAgCl Ag Cl 61.9 76.3 138.2 ohm1 cm2 mol1


o
Sp. Conductivity dilution = AgCl

2.30 10 6

1000
138.2
s

Solubility (gram per litre) = 2.382 103 g lt1


7.

Neglecting the liquid-liquid junction potential, calculate the emf of the following cell at 25C.
H2(1 atm) | 0.5 M HCOOH | | 1 M CH3COOH | (1 atm)H2
(Ka for HCOOH and CH3COOH are 1.77 104 and 1.8 105 respectively)

Sol. [H ]HCOOH K a C 1.77 104 0.5 0.9407 102 M

[H ]CH3COOH 1.8 10 5 1 4.2426 10 3 M


Ecell 0.0591 log10

[H ]RHS
[H ]LHS

0.0591 log10

4.2426 10 3
0.9407 10 2

Ecell = 0.0204 V
8.

For the cell reaction, Mg | Mg2+(aq) | | Ag+(aq) | Ag.


Calculate the equilibrium constant at 25C and maximum work that can be obtained by operating the cell.
o
[ Given EMg
2.37 V, EoAg / Ag 0.80 V ]
2
/Mg

Sol. Eocell 0.80 2.37 3.17 V


log K c

nEocell
2 3.17

107.2758
0.0591 0.0591

Kc = 1.89 10107
Maximum work = G nFEocell = 2 96500 3.17 = 611.81 kJ
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Solution of Assignment (Set-2)

9.

Electrochemistry

109

Under standard conditions


(i) Will Cu reduces Ag+ to Ag? (Eo 0.799 V, Eo 2 0.337 V)
Ag /Ag
Cu /Cu
o
o
(ii) Will Fe3+ be reduced to Fe2+ by Sn2+? (EFe3 /Fe2 0.771 V, ESn2 / Sn4 0.13 V)

(iii) Would you use a silver spoon to stir a solution of Cu(NO3)2?


Sol. (i) Yes, Eocell of Cu | Cu2+ | | Ag+ | Ag is positive
(ii) Yes, Eocell of Pt, Sn4+ | Sn2+ | | Fe3+ | Fe2+, Pt is positive
(iii) Yes, the reaction between silver and Cu2+ does not occur
10. A weak monobasic acid is 5% dissociated in 0.01 mol/lt solution. The limiting molar conductivity at infinite
dilution is 4 102 ohm1 cm2 mol1. Calculate conductivity of 0.05 molar solution of acid.
Sol. Ka = C2 = 0.01 (0.05)2 = 2.5 105
For C = 0.05 M,

Ka

2.5 105
0.05

= 0.0223

M
o
M

M 0.0223 4 10 2

11. 500 ml CuSO4 solution was electrolysed using a current of 2 amp (efficiency = 75%) for 60 min. Calculate
the pH of solution at the end of electrolysis. (Assume initial pH = 7)
Sol. When CuSO4 solution is electrolysed then H2SO4 is formed.
Equivalents of H2SO4 =

NH2SO4 =

1
75
2
60 60 = 0.0559
96500
100

0.0559
= 1.12 101
500
1000

Now, [H+] = 1.12 101


pH = log [H+] = log 1.12 101
pH = 1 0.05 = 0.95
12. A constant current flowed for 30 min through a solution of KI oxidising the iodide ion to iodine. At the end of
experiment, the iodine was titrated with 10 ml 0.075 M Na2S2O3 solution. Calculate the strength of current.
Sol. t = 30 min = 30 60 = 1800 s
KI K++I
H2O H++HO
(Cathode) 2H+ + 2e H2
(Anode) 2I I2 + 2e
eq. (I2) = eq. (Na2S2O3) = 103 10 0.075 = 0.75 103

w
it
=
E
F

i=

wF
(0.75 10 3 ) (96500)
=
Et
30 60

i = 0.04 A
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110

Electrochemistry

Solution of Assignment (Set-2)

13. A direct current of 3.0 amp (efficiency 75%) was passed through 400 ml 0.2 M Fe2(SO4)3 solution for a period
of 60 min. The resulting solution in cathode chamber was analysed by titrating against acidic KMnO4 solution
20 ml of KMnO4 required to reach the end point. Determine the molarity of KMnO4 solution.
Sol. Equivalents of Fe2+ formed =

1
75
3
60 60 = 0.0839
96500
100

Equivalents of Fe2+ = Equivalents of KMnO4


0.0839 = NKMnO4 20 103

0.0839
103
20

NKMnO4 =

NKMnO4 = 4.195
In acidic medium, n-factor for KMnO4 is 5.

MKMnO4 =

4.195
= 0.84 M
5

14. H2O2 can be produced by successive reactions


2NH4HSO4 H2 + (NH4)2S2O8
60%
(NH4 )2 S 2O 8 2H2O
2NH4HSO 4 H2O 2

The first reaction is an electrolytic reaction and second is steam distillation. What amount of current
would have to be used in first reaction to produce enough (NH4)2S2O8 to yield 100 gm H2O2 per hour?
(Assume current efficiency is 75%)
Sol. Given
(NH4)2S2O8 + H2O 2NH4HSO4 + H2O2
228 g

34g

34 gm of H2O2 is produced by 228 g (NH4)2 S2O8


100 g of H2O2 will be produced by

228
100 = 670 g
34

Since efficiency is 60% hence mass of (NH4)2 S2O8 required will be =

670 100
= 1116.66 gm
60

Equivalent mass of (NH4)2 S2O8 may be calculated


2NH4 SO4 (NH4)2S2O8+2e
ENH S O = M = 228 = 114
4 2 2 8
2
2

From I- law
w=

Ei t
F

1116.66 =

75
3600 114
100
96500

i = 350.09 A
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Solution of Assignment (Set-2)

15

Electrochemistry

111

During discharge of a lead storage battery the density of sulphuric acid fell from 1.3 to 1.15 gm/ml. Sulphuric
acid of density 1.3 gm/ml is 40% H2SO4 by wt and that of density 1.15 gm/ml is 20% by wt. The battery holds
4.0 L of the acid and volume remained practically constant during the discharge. Calculate the number of amphours for which the battery must have been used.
Pb + SO42 PbSO4 + 2e (discharging)
PbO2 + 4H+ + SO42 + 2e PbSO4 + 2H2O (discharging)

Sol. Adding the charging and discharging reactions.


We get
Pb + PbO2 + 4H+ + 2SO2
4 2PbSO4 + 2H2O

NH2SO4 = MH2SO4 (since 2SO2


4 requires 2-electrons)
i.e., Normality = Molarity
Before discharge
40 1.3 1000
= 5.3 M
98 100

MH2SO4 =

Moles of H2SO4 = 5.3 4 = 21.22


After discharge
MH2SO4(ii) =

20 1.15 1000
= 2.34 M
98 100

Moles of H2SO4 = (2.34) (4) = 9.38


Moles or equivalents of H2SO4 Used = 21.22 9.38 = 11.84
i t = (11.84) 96500 = 317 ampere s.
16. A dilute solution of NaCl was placed between two Pt-electrodes 8 cm apart, across which a potential of 4 V
was applied. How far would the Na+ move in 2.5 hours? Ionic conductance of Na+ at infinite dilution at 25C
is 50.11 mho cm2.
Sol. Na+ = 50.11 cm2/eq
Ionic mobility =

50.11
K
=
96500
F

5.19104 cm2 sec1 volt1


Potential gradient applied =

4
= 0.5 volt/cm
8

Speed of Na+ = ionic mobility potential gradient


= (5.19 104) 0.5
= 0.259 103 cm/sec
Distance traveled by Na+ in 2.5 hr
= 0.259 103 2.5 60 60
= 2.33 cm
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112

Electrochemistry

Solution of Assignment (Set-2)

17. The resistance of a conductivity cell filled with 0.01 N KCl at 25C was found to be 500 . The specific
conductance of 0.01 N KCl at 25C is 1.41 103 1 cm 1. The resistance of same cell filled with
0.3 N ZnSO4 at 25C was found to be 69 . Calculate the cell constant, equivalent and molar conductivities
of ZnSO4 solution.
Sol. K =

1
l

R
A

(1.41 103) =

1
l

500
A

l
= 1.41 103 500 = 0.705
A

m =
=

K 1000
1
l
1000
=

M
R
A
M
1
1000
1.41 103 500
69
0.3

= 34.1 1 cm1 eq1.


Molar conductivity = 68.2 1cm1mol1.
18. The equivalent conductance of 0.1 N of H3PO4 at 18C is 96.5 1 cm2 eq1. If HCl = 378.3, NaCl = 109,
NaH2PO 4 70 1 cm 2 eq 1 respectively, calculate the degree of dissociation and dissociation constant for

the reaction :
H+ + H2PO4

H3PO4

o
o
o
o
Sol. H3PO4 = HCl NaH2PO4 NaCl = 378.3 + 70 109 = 339.3

H3PO4
96.5
= o
=
= 0.2844
339.3
H3PO4
K=

C.2
0.1 (.2844)2
=
= 1.13 102
(1 )
(1 .28844)

19. Ag(s) | AgCl (saturated salt), KCl (C = 0.025) || KNO3, AgNO3 (C = 0.2) | Ag
The emf of above cell is 0.43 V.
(a) Write down the cell reaction.
(b) Calculate the solubility product of AgCl.
(Antilog (4.2758) = 1.887 104)
Sol. The given cell
Ag(s) |AgCl (Saturated Salt), KCl (C = 0.025 M)||AgNO3(C=0.2)|Ag
E = 0.43V
(a) Reaction in L.H.C. and R.H.C.
Ag Ag+ + e (Anode)
Ag+ + e Ag (Cathode)
o
(b) E
= E Ag/ Ag
Ag/ Ag

Ag / Ag

o
= E Ag / Ag

0.0591
log [Ag+]L
1
0.0591
1
log
1
[Ag ]R

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Solution of Assignment (Set-2)

EMF of cell = E
(Eo

Ag/ Ag

E=

E=

Ag/ Ag

Electrochemistry

Eo

Ag / Ag

Ag / Ag

[Ag ]L
0.0591

log
[Ag ]R
1

[Ag ]L
0.0591
log
(0.2)
1

[Ag ]
0.43
= log
0.0591
(0.2)

113

0.2
[Ag ]

0.2
0.43
= log
[Ag ]
0.0591

or

= 1.887 106 ;

[Ag+] = 1.05 1010 M.

Therefore, [Ag+] = 1.05 1010 M


K Cl
KCl 0.025
0.025

Ksp (AgCl) = (0.025) (1.05 1010)


Ksp = 2.64 1010
20. Pt | H2(1 bar), H+ || KCl (1.0 M saturated) | Hg2Cl2 | Hg was used to measure the pH of 0.05 M acetic acid
in 0.04 M CH3COONa. Calculate the cell potential.

K a(CH3 COOH) 1.8 10 5 , EHg Cl


2

/Hg, Cl

0.28 V

[Acid]
0.05
= 1.8 105
= 2.25 105
[Salt]
0.04

Sol. [H+] = Ka
o
ECell = (EHg

2Cl2 /Hg, Cl

Eo

H /H2

0.059
[H ]
log
1
1

0.059
log 2.25 105
1
= 0.28 + 0.275 = 0.555 V

ECell = 0.28
ECell
21.

Ag

0.5 M AgNO3

Zn

Salt bridge

Zn(NO3)2
(A)

(B)

(a) If the cell emf is 1.58 V, what is the concentration of Zn+2?


(b) If NH3 added to half cell A, how emf of cell will change?
E Ag /Ag 0.8 V, E Zn 2 /Zn 0.76 V

Antilog (0.6768) = 1.4768

Sol. (a) [Zn+2] = 0.054 M; (b) emf increases


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114
22.

Electrochemistry

Solution of Assignment (Set-2)

ECu2 /Cu 0.34 V, EZn/Zn2 0.76 V


A cell formed by the combination of Cu and Zn.
(a) When CuSO4 is added to Cu+2 compartment what is the effect on emf of cell?
(b) When NH3 is added to Cu+2 compartment what is the effect on emf of cell?
(c) When ZnSO4 is added to Zn+2 compartment what is the effect on emf of cell?
(d) When Zn+2 is diluted what is the effect on emf of cell?

o
o
Sol. ECu2 /Cu = 0.34V; E Zn/ Zn2 = 0.76 V

EMF of the cell is


o
o
E = E Zn/ Zn2 + ECu2 /Cu

(0.34) + (0.76) = 1.1V


(a) According to Nernst equation

[Zn2 ]
0.0591
log
E = E
[Cu2 ]
2
[Cu2+] increases
Hence log terms will decreases and therefore EMF increases.
(b) When NH3 is added it combines with Cu2+ and, hence, [Cu2+] decreases
4NH3 + Cu2+ [Cu (NH3)4]2+.
With decrease in [Cu2+], log tem increase hence EMF decreases.
(c) [Zn2+] will increase as result of which EMF decreases.
(d) Zn2+ dilution means concentration decreases and EMF increases.

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