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Cls Jeead-16-17 Xii Che Target-5 Set-2 Chapter-3
Cls Jeead-16-17 Xii Che Target-5 Set-2 Chapter-3
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
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
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
During electrolysis of aqueous solution of a salt under inert electrodes, 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
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
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
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
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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6.
Electrochemistry
77
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
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
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
w
it w
it
M =
;
=
H2
2F M O2
4F
nH2 : nO2 =
VH2
2.8
2
1
it
it
:
2:1
2F
4F
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78
9.
Electrochemistry
(2) 0.7346 V
(3) 0.1836 V
(4) 3.667 V
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
(2) 390.6
(3) 380.6
(4) 309.6
= H + Cl
HCl
...(i)
CH
= CH3COO Na
3 COONa
...(ii)
o
o
= Na + Cl
NaCl
...(iii)
+ CH3COONa NaCl
= CH3COO + H
HCl
CH
= 390.6 cm2 1/eq
3 COOH
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Electrochemistry
79
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
w=
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
w
E it
it
0.5F
=
=
= 0.25 moles
F
2F
2F
M
w=
0.25 103
= 0.5
500
Molarity = 0.5 M
15. M+ is not stable and undergoes disproportionation to form M and M2+. Calculate E for M+ disproportionation
E 2
M
/M
0.153 V, E
(1) +0.683 V
M /M
0.53 V
(2) 0.367 V
(3) 0.754 V
(4) +0.3415 V
o
o
E oCell = ECu /Cu2 + ECu /Cu
o
we required ECu /Cu2
80
Electrochemistry
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)
or
(2) 2
(3) 3
(4) 4
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 (1 L) solution of 0.1 M CuSO4 is electrolysed at 25C using copper 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
Electrochemistry
81
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
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
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
82
Electrochemistry
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
(4) LiCl ~
NaCl < KCl
(2) 52.5
(3) 75.5
(4) 57.5
= Na + Cl = 126.5 ...(i)
NaCl
o
o
= K + Cl = 150
KCl
(ii)
o
o
= K + Br = 152
KBr
(iii)
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
(2) 4.3
(3) 2.3
(4) 1.3
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Electrochemistry
83
CH
= CH3 COO Na
3 COONa
o
o
o
= H Cl
HCl
o
NaCl
= Na Cl
C 19.55
=
[H+]
19.55
= 0.05
391
= C = 1 0.05 M
(2) Mg+2
(3) Fe+2
(4) Cr+3
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
(2) 0.490 V
(3) 0.321 V
(4) 0.290 V
84
Electrochemistry
...(iii)
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
G = n F E = 2 F (0.46)
= 2 0.46 96500 = 88780 J
or G = + 89 kJ.
o
OH
O
+
+ 2H + 2e
OH
At pH = 3 at 298 K, electrode reduction potential is (Consider quinone and hydroquinone have identical
concentration)
(1) 1.48 V
(2) 1.42 V
(3) 1.36 V
(4) 1.3 V
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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Electrochemistry
85
(4) Temperature
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+
SO2
4 < HO < Cl < Br < I
(2) Na2O
(3) BaO
(4) Ag2O
Ag2O
2Ag + 2 O2.
86
Electrochemistry
(2) 0.0591 V
(3) 0.02955 V
(4) 0.02955 V
(3) 418.424
(4) 229.284
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
(2) 229.284
NiO2
4H 2e
Ni 2 2H2O
, E1o 1.678 V
Ni(OH)2 2OH 2e
Ni(OH)2 2H
Ni 2 2H2O
, Eo x V
Electrochemistry
87
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 20% by weight? (Atomic
mass, Zn = 65.4 g)
(1) 5.6 A
(2) 7.2 A
(3) 8.85 A
(4) 11.2 A
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
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
(anode)
Hg22+ + 2e 2Hg
(cathode)
n=2
Ecell
H = nFEcell nFT
T P
(2) 0.03 V
(3) 0.014 V
(4) 0.19 V
Ag e ;
EoOP 0.799 V
Ag(NH3 )2 e
Ag NH3 ;
o
ERP
?
Ag(NH3 )2
Ag
Ag 2NH3
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Electrochemistry
Ecell Ecell
[Ag(NH3 )2 ]
0.0591
0 at equilibrium
log10
1
[Ag ] [NH3 ]2
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
W it
E F
W
10 103 t
0.01 2
E
96500
t = 19.3 104 s
42. 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
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
106
log
4
1013
1.67
0.0591
log107
4
1.67
0.0591
7 1.57
4
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Electrochemistry
89
43. 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)
volume
(Q)
(1) (P)
volume
(R)
(2) (Q)
(3) (R)
volume
(S)
(4) (S)
conc. of KCl
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%
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
90
2.
Electrochemistry
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
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
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)
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Electrochemistry
91
31.75
0.965 60 60 = 1.143 g
96500
2.032 1000
= 0.64 M
63.5
50
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 1.0
(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 as per H2 A 2H A 2 is 2.56 104
m
0
m
10
1
2.5%
400 40
H2 A
2H A 2
At equation, C(1 )
2C
C
K eq
(2C )2 C
C(1 )
Putting C = 2 M, = 0.025
Keq = 2.56 104
[H+] = 2C = 0.1 = 101
pH = log 101 = 1
7.
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Electrochemistry
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
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) = (G)1
(4)
G
K
1 1 l
l
RA
A
K = C
l
A
RA
l
;
and (G)1
l
A
Vol. of NaOH
Vol. of NaOH
(4)
Vol. of NaOH
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
Electrochemistry
93
(4) Cell reaction is non-spontaneous when concentration of Ni+2 is less than 5.5 1018 M
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.
[Zn2 ]
0.0591
E = E
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, when electrolysed among inert electrodes?
(1) NaCl
(2) MgCl2
(3) CuCl2
(4) AgCl
94
Electrochemistry
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
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
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Electrochemistry
95
[Ag ]L
0.0591
log
[Ag ]R
1
1
E = 0.0591 log
[Ag ]
8 1013
= 8 1013 M
1
E = 0.0591 log
1
8 1013
= 0.0591 log
1013
8
96
20.
Electrochemistry
Non-spontaneous
For Ni2+ + Cd Cd2+ + Ni
o
o
E = ECd/Cd2 ENi2 /Ni
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
Electrochemistry
97
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
[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
[JEE(Advanced)2014]
98
Electrochemistry
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.
(2) 1.1 V
(3) 1.3 V
(4) 1.13 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
E = Eo
0.0591
[Zn2 ]
log
2
[Cu2 ]
3.
[Zn2 ]
[Cu2 ]
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) 0.696 V
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Electrochemistry
99
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
An
An
F (here is the ionic mobility of An+). For electrolytes say A B , molar conductivity is given by
x y
m(A xBy ) x n
1.
An
F ym
Am
F.
ions
ionic mobility
K+
7.616 104
Ca+2
12.33 104
Br
8.09 104
SO42
16.58 104
(1) 279
(4) 306
CaSO
= Ca2 SO2
4
4
= UCa2
= USO2
Ca2
SO2
4
Ca2
CaSO
= F {12.33 + 16.58} 104
4
CaSO
= 96500 104 28.91 = 278.98 279
4
100
2.
Electrochemistry
(1) 27.9
(4) 30.6
(0.1) =
C
(279)
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
(2) Cl
(3) Mn+2
(4) Fe+2
Electrochemistry
101
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.
(2) 1.0
(3) 2.0
(4) 3.0
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
(2) 48250
(3) 96500
(4) 193000
[IIT-JEE 2010]
M
M
(1 M)
(0.05 M)
E E
0.059
0.05
log
1
1
0.059
log 5 10 2
1
0.059
2 log5
1
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102
2.
Electrochemistry
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
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
log
0.059
0.001
log 2
2
(M )
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
Electrochemistry
103
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.
K 1000
c
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.
3.
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
Zn/Zn2
o
= E Zn/ Zn2
Zn2 /Zn
= 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
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104
Electrochemistry
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.
STATEMENT-1 : The molar conductance of weak electrolyte at infinite dilution is equal to sum of molar
conductances of cations and anions.
and
STATEMENT-2 : Kohlrauschs law is applicable for strong electrolytes.
AB = A B
Kohlraush law is applicable for weak electrolyte and not for strong electrolyte.
6.
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
Cu2 /Cu
7.
Eo
Ag / Ag
STATEMENT-1 : G = nFE.
and
STATEMENT-2 : E should be positive for a spontaneous reaction.
8.
Electrochemistry
105
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.
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.
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.
SECTION - E
Matrix-Match Type Questions
1.
Column-II
Maximum molar conductivity (S cm2 mol1)
(p)
97
(B) CoCl3.5NH3
(q)
(C) CoCl3.4NH3
(r)
404
(D) CoCl3.3NH3
(s)
229
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106
Electrochemistry
Column-II
(Amount of charge used for diposition/liberation)
(p)
(q)
3F
(r)
0.1 F
(s)
0.3 F
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
(D)
3.6
F = 0.3 F
12
11.2
1
=
22.4
2
nH
2
w
it
w
=
it =
F
E
F
E
w
= 2 F
M
= 2
1
F=F
2
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3.
Electrochemistry
107
Column-II
c
m
(p)
(q)
(r)
(s)
m
and decreases with dilution
m
(D) Resistance
4.
l
and decreases with dilution
A
Column-II
(p)
(q)
(r)
(s)
(D) Pt|H2(1
atm)|H+(C1)||H+(C2)|H2(1
atm)|Pt
Column-II
(Electrolysis)
(Observation)
(p)
(q)
(r)
(s)
electrodes
(B) Very dilute aqueous solution of NaCl
using mercury cathode
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108
Electrochemistry
Column-II
(p)
0.18 V
(B) E(4H2O
4H+ + 4OH)
(q)
0.4 V
(r)
0.04 V
(s)
0.83 V
Codes :
A
(1) s
(2) q
(3) p
(4) r
Fe
+3
+2
+ e
Fe
G1 = 1F 0.77
Fe
+2
+ 2e
Fe
G2 = + 2F 0.77
Fe
+3
+ 3e
Fe
G3 = 3F EFe+3/Fe
G3 = G1 + G2
0.11 (V)
= 0.036 (V)
3
+
2H2O
(B)
O2 + 4H + 4e
4e + O2 + 2H2O
OH
4 H2O
(C) Cu2+ + 2e
2Cu
2+
Cu
+ Cu
E = + 0.40 V
4H + 4OH
Cu
E = 1.23 V
E = 0.83 V
E = + 0.34 V
2+
Cu + 2eu
+
2Cu
E = 0.52 V
E = 0.18 V
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(D) Cr
Electrochemistry
+ 3e
Cr
Cr
Cr
+ e
Cr
+3
Cr
+2
109
G1 = + 3 F 0.74
+ 2e
G2 = + 2 F 0.91
+2
An aqueous solution of X is added slowly to an aqueous solution of Y as shown in Column-I. The variation in
conductivity of these reactions is given in Column-II. Match Column-I with Column-II and select the correct
answer using the code given below the Columns :
Column-I
(A) (C2H5)3N
[JEE(Advanced)-2013]
Column-II
CH3COOH
(B) KI (0.1M)
+ AgNO3 (0.01M)
change much
(D) NaOH
change much
+ HI
then increases
Codes :
A
(1) r
(2) s
(3) q
(4) p
(A)
Conductivity
(C2H5)3N
Firstly it decreases due to nutrilization of CH3COOH and replacement of H+ by but thereafter buffer
formation takes place and [H+] becomes constant and increases hence conductivity increases but after
equivalence point (C2H5)3N is not ionized due to much higher concentration of in solution.
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Electrochemistry
Conductivity
110
(B)
VKI
Conductivity
Initially only Ag+ is replaced by K+ hence conductivity remain the same thereafter equivalence point
[K+] increases hence conducitity increases.
(C)
VCH3COOH
(D)
Conductivity
Initially conducitity decreases due to replacement of OH by CH3COO and then almost constant due
to buffer formation
VNaOH
Decreases due to removal of H+ by Na+ then increases due to OH.
SECTION - F
Integer Answer Type Questions
1.
24.4
48.8
0.101
0.115
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
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2.
Electrochemistry
111
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.
H cathode
H anode
How many faradays of electricity is required to deposit 2 mol copper from CuSO4 solution?
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)
= 80 0.0005
= 0.04 cm2
0.42
Eit
96500
108 3 t
t 125.09 s y 3
96500
y5
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112
6.
Electrochemistry
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.
[JEE(Advanced)-2015]
rG = 193 kJ mol1
M+ M3+ + 2e
E = 0.25 V
8.
193
mole M 4 mole M
48.25
The molar conductivity of a solution of a weak acid HX (0.01 M) is 10 times smaller than the molar conductivity
0
0,
of a solution of a weak acid HY (0.10 M). If X Y the difference in their pKa values, pKa(HX) pKa(HY),
[JEE(Advanced)-2015]
2 HY
(m )HX
o
m
K a1 C112
0.01
K a1
K a2
(m )HY
o
m
K a2 C2 22
2
(m )HX
0.1
o 2
( m
)
2
0.01(m )HX
2
0.1(m )HY
2
(m )HY
o 2
( m
)
2
( )
0.1 m HX 0.1 1 = 103
(m )HY
10
K a1
K a2
log10 3 = 3
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Electrochemistry
113
SECTION - G
Multiple True-False Type Questions
1.
(2)
TFT
(3)
TFF
(4)
FFT
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
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
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]
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114
Electrochemistry
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
2.
= 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
1
10 10 log10 K sp 10
K
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3.
Electrochemistry
115
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
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
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
5.
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?
52 24000
= 2.155 g
6 96500
(ii) M = Zit
1.5
52
12.5 t
6 96500
t = 1336.15 s
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116
6.
Electrochemistry
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
Neglecting the liquid-liquid junction potential, calculate the emf of the following cell at 25C.
Pt | H2(1 atm) | 0.5 M HCOOH | | 1 M CH3COOH | (1 atm)H2 | Pt
(Ka for HCOOH and CH3COOH are 1.77 104 and 1.8 105 respectively)
[H ]RHS
[H ]LHS
0.0591 log10
4.2426 10 3
0.9407 10 2
Ecell = 0.0204 V
8.
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
9.
Electrochemistry
117
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 at 298 K. (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
w
it
=
E
F
i=
wF
(0.75 10 3 ) (96500)
=
Et
30 60
i = 0.04 A
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118
Electrochemistry
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
0.0839
103
20
NKMnO4 =
NKMnO4 = 4.195
In acidic medium, n-factor for KMnO4 is 5.
MKMnO4 =
4.195
= 0.84 M
5
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
228
100 = 670 g
34
670 100
= 1116.66 gm
60
From I- law
w=
Ei t
F
1116.66 =
75
3600 114
100
96500
i = 350.09 A
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15
Electrochemistry
119
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)
MH2SO4 =
40 1.3 1000
= 5.3 M
98 100
20 1.15 1000
= 2.34 M
98 100
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
120
Electrochemistry
17. 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
=
= 0.2844
= o
339.3
H3PO4
C.2
0.1 (.2844)2
K=
=
= 1.13 102
(1 )
(1 .28844)
18. 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
EMF of cell = E
(Eo
Ag/ Ag
E=
Ag/ Ag
Eo
0.0591
log [Ag+]L
1
0.0591
1
log
1
[Ag ]R
Ag / Ag
Ag / Ag
[Ag ]L
0.0591
log
[Ag ]R
1
[Ag ]L
0.0591
E=
log
(0.2)
1
[Ag ]
0.43
= log
0.0591
(0.2)
or
0.2
0.43
= log
[Ag ]
0.0591
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0.2
[Ag ]
Electrochemistry
= 1.887 106 ;
121
/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
ECell = 0.28
Eo
H /H2
0.059
[H ]
log
1
1
0.059
log 2.25 105
1
20.
Ag
0.5 M AgNO3
Zn
Salt bridge
Zn(NO3)2
(A)
(B)
122
21.
Electrochemistry
o
o
Sol. ECu2 /Cu = 0.34V; E Zn/ Zn2 = 0.76 V
[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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