Chemistry : Electrochemistry

SECTION - I
SUBJECTIVE TYPE PROBLEMS
Problem 1 : State whether Mn2+ ion disproportionates into Mn3+ ion and elemental Mn in solution,
o o
if E Mn2 |Mn3  1.51V and E Mn|Mn2   1.19V . Justify your answer in brief

Solution : Let us suppose Mn2+ ions are not stable in aqueous solution and disproportionate as follows
2Mn2+  Mn3+ + Mn
This shows that some Mn2+ ions are reduced to Mn and rest Mn2+ ions are oxidized to Mn3+.
Thus Mn2+ ions act both as oxidant and reductant

2Mn 2 
 Mn  Mn 3

o o o o
Since E oxidation  E Mn 2 |Mn = –1.19 V is not greater than E reductant  E Mn 3 |Mn 2 = + 1.51V

This disproportionation reaction is not feasible and Mn2+ ion is stable in aqueous solution.
Problem 2 : The standard reduction potential Cu2+/Cu is 0.34 V. Calculate the reduction potential
at pH = 14 for the above couple. K sp(Cu (OH)2 is 1.0  10–19

Solution: K sp(Cu (OH)2 = [Cu2+] [OH–]2

[H+] = 10–14 [OH–] = 100 = 1

K sp 1.0  1019
2+
[Cu ] =   = 1.0  10–19
[OH  ]2 1
Now ERP for the couple Cu2+/Cu is

0.0591 1
ERP = E0RP – log
2 [Cu 2  ]

0.0591 1
= 0.34 – log = – 0.22 V
2 [1  10 19 ]
Problem 3 : The standard reduction potential for the half cell
NO3– + 2H+ + e  NO2(g) + H2O is 0.78 V
(i) Calculate the reduction potential in 8 M H+
(ii) What will be the reduction potential of the neutral solution. Assume all the
species to be at unit concentration.
Solution : (i) In 8M H+ solution, of all other species has conc. of unity.

0.0591 1 1
ERP = E0RP – log  2 = 0.78 – 0.0591 log 2 = + 0.8862 V
1 [H ] (8)
Chemistry : Electrochemistry

(ii) In case of neutral solution, concentration of (H+) = 10–7M and conc,. of all the other
species are unity, then

0.0591 1 0.0591 1
ERP = E0RP – log  2 = 0.78 – log 7 2 = – 0.046 V
1 [H ] 1 (10 )

Problem 4 : The standard potential of the following cell is 0.23 V at 15°C and 0.21 V at 35°C
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 15°C to 35°C.
(iii) Calculate the solubility of AgCl in water at 25°C.
Given : The standard reduction potential of the Ag+ | Ag couple is 0.80 V at 25°C.
Solution : (i) ½H2  H+ + e–
AgCl + e–  Ag + Cl–
AgCl + ½H2  Ag + Cl– + H+
  dE o  o

(ii) H° = nF  T    E 
  dT  

  0.21  0.23  
= 1 × 96500  288    0.23 = – 49987 J mol–1
  20  
G° = – nFE°
= – 1 × 96500 × 0.23 = – 22195 J mol–1
H o  G o 49987  (22195)
S° = = = – 96.5 J mol–1 K–1
T 288
(iii) E°cell for Pt | H2(g) | HCl(aq) | AgCl(s) | Ag(s) is 0.23 volt at 15°C
E 0.02
Since = = – 0.001
T 20
Therefore E°cell at 25°C
E°cell = 0.23 – 0.001 × 10 = 0.22 V
Since E° of anode is zero volt.

 E oCl |AgCl|Ag at 25°C = 0.22 V

AgCl (s) Ag+ (aq) + Cl– (aq) G1° = – RT ln Ksp

Ag+ + e–  Ag G2° = – nFE°
o
AgCl + e–  Ag +Cl– G3° = – nFE Cl |AgCl|Ag
G1° + G2° = G3°
Solving
RT ln Ksp + F × 0.8 = F × 0.22
 Chemistry : Electrochemistry

2.303 RT
log K sp + 0.8 = 0.22
F
0.059 log Ksp + 0.8 = 0.22
Ksp = 1.47 × 10–10
 Solubility of AgCl at 25°C = 1.21 × 10–5 M
Problem 5 : The cell,
Ag(s) | AgCl(s) | HCl (0.1 M) | H2 (1 atm) | Pt ... Pt| H2 (1 atm) | H+ (10–3 M) ||
KCl (0.1 M) | Hg2Cl2(s) | Hg(l)
has the potential 0.0662 V at 25°C. If the E° for Ag | AgCl | Cl– couple is 0.2873 V,
what is the E° for the Hg2Cl2 | Hg couple.
Solution : The cell representation exhibits 2 cells connected in series.
For the first cell, reactions occurring at the electrode are
At anode : Ag + Cl–  AgCl + e–
At cathode : H+ + e–  ½H2
Net reaction : Ag + Cl– + H+  ½H2 + AgCl

o o
(p H2 )1/ 2
(Ecell)1 = E H  / H2  ECl / AgCl / Ag  0.0591 log
[H  ][Cl  ]

1
(Ecell)1 = – 0.2873 – 0.059 log = – 0.4053 V
(0.1) 2

For the second cell, the reactions can be shown as

At anode : H2  2H+ + 2e–
At cathode : Hg2Cl2 + 2e–  2Hg + 2Cl–
Net reaction : Hg2Cl2 + H2  2Hg + 2Cl– + 2H+

o o 0.059 [Cl  ]2 [H  ]2
(Ecell)2 = E Cl / Hg 2 Cl2 / Hg  E H / H2  log
2 p H2

o 0.059 [0.1]2 [10 3 ]2

(Ecell)2 = E Cl / Hg Cl / Hg
 log
2 2 2 1
o
(Ecell)2 = E Cl / Hg 2Cl2 / Hg  0.236

The total cell potential of the overall cell is

Ecell = (Ecell)1 + (Ecell)2
o
0.0662 = – 0.4053 + E Cl / Hg 2Cl2 / Hg  0.236

o
 E Cl / Hg 2Cl2 / Hg = 0.0662 + 0.4053 – 0.236 = 0.2355 V
Chemistry : Electrochemistry

Problem 6 : A cell consists of two hydrogen electrodes dipping into the same 0.1 M solution of HCl.
One electrode is supplied with pure H2 gas at atmospheric pressure, the other with the
mixture of hydrogen and argon also at atmospheric pressure. What is the mole fraction
of hydrogen in this mixture when the emf of the cell is 10 mV at 300 V.
Solution : Let us assume that the cell representation is
Pt | H2 (1 atm) | H+ (0.1 M) |H2 (P atm) | Pt
The reactions occurring at the electrodes are
At anode : H2 (1 atm)  2H+ + 2e–
At cathode : 2H+ + 2e–  H2 (P atm)
Net reaction : H2 (1 atm)  H2 (P atm)

0.0591 (p H2 ) C
 Ecell =  log
2 (pH 2 ) A

0.0591 1
Ecell = log  10  103
2 P
 P = 0.46 atm
Since the pressure of H2 and Ar in the cathode chamber is 1 atm, of which pressure of H2
is 0.456 atm.

0.46
 Pressure fraction of H2 = = 0.46
1
Mole fraction of H2 = 0.46
Problem 7 : The molar conductivity of acetic acid at infinite dilution is 390.7 mho cm2 mol–1 and
that of 0.1 M acetic acid solution is 5.2 mho cm2 mol–1 at 25°C. Calculate the dissociation
constant of the acid at this temperature.
Solution : The degree of dissociation of acetic acid is given by
c 5.2
= = = 0.013
 390.7

CH 3 COOH CH3 COO   H

Initially c 0 0
At equi. c(1  ) c c

Dissociation constant of acetic acid.

Ka = c2
= 0.1 × (0.013)2
= 1.69 × 10–5 M
Problem 8 : The emf of the cell is 0.788V
Ag | AgI, 0.05 M KI || 0.05 M AgNO3| Ag
0
Calculate the solubility product of AgI. E Ag  / Ag  0.80V
 Chemistry : Electrochemistry

Solution : KI is strong electrolyte, hence

[I–]L.H.S. = 0.05 M
AgI(s) is sparingly soluble. If we manage to calculate Ag+ (Ag) in L.H.S.,. half cell, Ksp can
be calculated.
at L.H.S. half cell Ag(s)  Ag+ (xM) + e– E 0ox  0.80V
at R.H.S. half cell Ag+ (0.05) + e–  Ag(s) E 0red  0.080V
R.H.S.
––––––––––––––––––––––
Net Ag+ (0.05)  Ag+ (xM) E 0cell  0.00V
––––––––––––––––––––––
[Ag  ]L.H.S. x
K 

[Ag ]R.H.S. 0.05

0 0.0591
E cell  E cell  log K
n
0.0591  x 
0.788  0  log  
1  0.05 
 x 
log    13.3333  14.6667
 0.05 
x
 4.6416  1014 ; x=2.23110-15 x
0.05
[Ag  ]L.H.S.  2.31 1015 M
[I–]L.H.S. = 0.05M
Ksp = [Ag+] [I–] = 2.31 × 10–15 × 0.05 = 1.16 × 10–16
Problem 9 : The emf of the following cell is – 0.46V
Pt(H2) HSO3 (0.4M), SO32  (6.4 × 10–3M) || Zn2+ (0.3M) | Zn
0
If E Zn 2 / Zn = – 0.76V, calculate pKa of HSO3 i.e. for the equilibrium

HSO3 H   SO32 
Solution : Half cell Reaction E0
L.H.S. H2  2H+ + 2e– E 0ox  0.00V
R.H.S. Zn2+ + 2e–  Zn E 0cell  0.76V
––––––––––––––––––––––––
Net Zn2+ + H2  Zn + 2H+ E 0cell  0.76V
––––––––––––––––––––––––
[H  ]2 0.0591
K  log K
[Zn 2  ] n
Chemistry : Electrochemistry

0.0591
E cell  E 0cell  log K
n
0.0591 [H  ]2
0.46  0.76  log
2 (0.3)
[H+] = 4.60 × 10–6M
HSO3 H  SO32 
0.4M 4.60 × 10–6M 6.4 × 10–3M
[H  ][SO32  ] 4.6  106  6.4  103
K   7.36  108
[HSO3 ] 0.4
pKa = 7.13

Problem 10 : For the following cell

Ag(s) | Ag+ (saturated AgI(aq) || Ag+ (0.10 M) | Ag(s)
Ecell = 0.417. Calculate Ksp of AgI
E 0Ag  / Ag  0.80V

Solution : AgI(s) Ag+(aq) +  I–(aq)

Ksp = [Ag+] [I–]
Since [Ag+] = [I–]
 Ksp= [Ag+]2
If we manage to calculate [Ag+] in saturated in L.H.S. oxidation half cell (anode), then Ksp
can be calculated.
Oxidation Ag(s)  Ag+ [saturated AgI(aq)] + e– E 0ox  0.80V

Reduction Ag+ (0.10 M) + e– Ag(s) E 0red  0.80V

–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Net Ag+ (0.10 M)   Ag+ (saturated AgI)(aq) E 0cell  0.00V
xM
 x 
K  
 0.1 
Ecell = 0.417V (given)
0 0.0591
Using Nernst equation E cell  E cell  log K
n
0.0591  x 
0.417  0.00  log  
1  0.1 
 x  0.417
log    7.0558
 0.1  0.0591
x = [Ag+] in saturated AgI = 8.79 × 10–9
Ksp = [Ag+]2 = (8.79 × 10–9) = 7.73 × 10–17
 Chemistry : Electrochemistry

SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1 : A gas X at one atm is bubbled through a solution containing a mixture of 1 MY– and 1
M Z– at 25°C. If the reduction potential of Z  Y  X, then
(a) Y will oxidize X and not Z (b) Y will oxidize Z not X
(c) Y will oxidize both X and Z (d) Y will reduce both X and Z
Solution: The tendency to gain electron is in the order
ZYX
 Y + e  Y–
X  X+ + e
(a)
Problem 2 : The standard reduction electrode potential values of elements A, B, C are + 0.68, –
2.50, and – 0.50 V respectively. The order of their reducing power is
(a) A B  C (b) A  C  B
(c) C  B  A (d) B  C  A
Solution: More is the reduction potential, more is the power to get itself reduced or lesser is reducing
power or greater is oxidizing power.
(d)
Problem 3 : How much will potential of a hydrogen electrode change when its solution initially at
pH = 0 is neutralized to pH = 7
(a) increase by 0.0591 V (b) decrease by 0.0591 V
(c) increase by 0.413 V (d) decrease by 0.413 V
1
Solution: H++ e– H (g),
2 2
0.0591
[E = E0 – log Q]
n
P1
0.0591 H 22 0.0591 1
= 0.0 – log = log 7
1 [H  ] 1 10
= – 0.0591  7  log10 = – 0.413 V
(d)
Problem 4 : The useful work done during the reaction
1
Ag(s) + Cl  AgCl(s)
2 2(g)
Would be
(a) 110kJ mol –1 (b) 220 kJ mol—1
(c) 55kJ mol –1 (d) 100 kJ mol–1
0 0
Given E Cl2 / Cl  1.36V, E AgCl/Ag/Cl-  0.220V , PCl2  1 atm and T = 298K
Chemistry : Electrochemistry

Solution: For the cell reaction

1
Ag(s) + Cl  AgCl(s)
2 2(g)
E0 = – 1.14V
0.0592
or E = E0 – log PCl1/22
1
Under standard conditions, PCl2  0

 log PCl1/22  0
Useful work = – Wmax = – nFE
= (–1) × (–1.14) × 96500 × 10–3 kJ = 110 kJ mol–1
(a)
Problem 5 : Specific conductance of 0.01 M KCl solution is x ohm–1 cm–1. When conductivity cell
is filled with 0.01 M KCl the conductance observed is y ohm–1. When the same cell is
filled with 0.01 M H2SO4, the observed conductance was Z ohm–1 cm–1. Hence specific
conductance of 0.01 M H2SO4 is:
z
(a) xz (b) xy

xz xy
(c) (d)
y z
Specific conductance x 1
Solution: Cell constant =  cm
Observed conductance y
Specific conductance of 0.01 M H2SO4
x
= Observed conductance  Cell constant = z  y ohm–1 cm–1

(c)
Problem 6 : If the pressure of hydrogen gas is increased from 1 atm to 100 atm, keeping the
hydrogen ion concentration and temperature constant, the voltage of hydrogen half
cell will change by
(a) 0.059 V (b) 0.59 V
(c) 0.118 V (d) 0.0295 V
+
Solution : 2H + 2e  H2
0.059 pH 0.059 1
E H / H = E o   log  2 2 = E oH / H  log  2
2 H / H2
2 [H ] 2 2 [H ]
0.059 100
E 'H  / H = E o   log  2
H /H
2 2 2 [H ]

' 0.059 1 [H  ]2
 E H / H2  E H  / H2 =  log  2   0.059V
2 [H ] 100
(a)
 Chemistry : Electrochemistry

Problem 7 : One litre of 0.1 M CuSO4 solution is electrolysed till whole of the copper is deposited at
cathode. During the electrolysis a gas is released at anode, the volume of the gas at
NTP is
(a) 112 ml (b) 224 ml
(c) 1120 ml (d) 2240 ml
Solution : When copper is deposited at cathode, oxygen gas is released at anode.
Equivalents of Copper = 0.1 × 2 = 0.2
Equivalents of Oxygen = 0.2
Volume of oxygen at NTP = 0.2 × 5600 = 1120 ml
(c)
Problem 8 : In a Copper voltameter, mass deposited in 30 sec. is ‘m’ g. If the time current graph
is as shown in figure, calculate the electrochemical equivalent of Cu.

m
(a) z = m (b) z 
2
m
(c) z  (d) z can’t be calculated from the given data
5
Solution : m =z×i×t
m
z =
it
Total charge passed through copper voltameter
= (100 × 10 × 10–3) + 2(½ × 10 × 100 × 10–3)_ = Area under the curve = 1 + 1 = 2
m
Electrochemical equivalent, z =
2
(b)
Problem 9 : In electrolysis of an aqueous solution of H2SO4 to form perdisulphuric acid (H2S2O8),
O2 and H2 are produced as byproducts on respective electrodes. If 1.4 litre O2 and 5.6
litre of H2 are produced at NTP, the weight of H2S2O8 formed will be
(a) 97 g (b) 46 g
(c) 19.82 g (d) 24.25 g
Solution : The reactions involves are
At anode : 2H2SO4 H2S2O8 + 2H+ + 2e–
2H2O 4H+ + O2 + 4e–
At cathode : 2H2O + 2e– 2OH– + H2
 Equivalents of H2S2O8 + Equivalent of O2 = equivalents of H2
Chemistry : Electrochemistry

2  5.6
Equivalent of H2 = = 0.5 equivalents ( ... 22.4 litre = 1 mole = 2 equivalents of H2)
22.4
1.4  4
Equivalent of O2 = = 0.25 equivalents ( ... 22.4 litre = 1 mole = 4 equivalents of O2)
22.4
Equivalents of H2S2O8 = 0.5 – 0.25 = 0.25 equivalents
m 0.25  194
w H 2S2 O8 = 0.25  =  24.25 g
n 2
(d)
Problem 10 : If the H + concentration is decreased from 1 M to 10 –4 M at 25°C for the couple
MnO4– /Mn2+, then the oxidizing power of the MnO4–/Mn2+ couple decreases by
(a) –0.18 V (b) 0.18 V
(c) 0.38 V (d) –0.38 V
–
Solution : In acidic medium MnO4 acts as oxidising agent as per the reaction
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O
o 0.059 [Mn 2  ]
E1 = E MnO4 / Mn 2  log
5 [MnO 4 ][H  ]8

o 0.059 [Mn 2  ]
= E MnO4 / Mn 2  log
5 [MnO 4 ] (1)8

o 0.059 [Mn 2  ]
E2 = E MnO4 / Mn 2  log
5 [MnO 4 ] (104 )8

0.059  [MnO 4 ] [Mn 2  ] 

 (E1 – E2) =  log 2
  4 8  = 0.3776 V
5  [Mn ] [MnO 4 ] (10 ) 
Thus, the oxidising power of MnO4–/Mn2+ couple decreases by 0.3776 V from its standard
value.

SECTION - III
MULTIPLE CHOICE PROBLEMS
(with one or more than one answer correct)
Problem 1 : What is the difference between galvanic cell and electrolyte cell
(a) In galvanic cell the substance is deposited only to cathod but in electrolytic cell the
substance is deposited at both the electrodes.
(b) In galvanic cell, the two electrodes are placed in different containers but in
electrolytic cell the two electrodes are placed in a same container.
(c) In galvanic cell, anode is negative electrode but in electrolytic cell cathode is
negative electrode.
(d) In galvanic cell electrical energy is produced but electrolytic cell electrical energy
is consumed.
Solution : (a, b, c, d)
 Chemistry : Electrochemistry

C
Problem 2 : For which electrolyte   does not hold good


(a) CH3 COOH (b) HCl

(c) NaCl (d) HClO4

C
Solution : The relation   does not hold good for strong electrolytes.


Problem 3 : Given that

Ni2+/Ni = 0.25 V, Cu2+/Cu = 0.34 V
Ag+/Ag = 0.80 V Zn 2+/Zn = –0.76 V
Which of the following reactions under standard conditions will not take place in
specified direction
2+ 2+ + 2+
(a) Ni(aq) + Cu(s) 
 Ni(s) + Cu(aq) (b) Cu(s) + 2Ag(aq) 
 Cu(aq) + 2Ag(s)

+ 2+ + 2+
(c) Cu(s) + 2H 
 Cu(aq) + H 2 (g) (d) Zn(s) + 2H (aq) 
 Zn(aq) + H 2 (g)

Solution : According to data given, oxidising power is Ag > Cu > Ni > Zn.
Problem 4 : A chemical reaction will be spontaneous if
o
(a) ECell is positive (b) Gº is negative
o
(c) reaction quotient Q < K (d) Eoxid is negative
Solution : (a, b, c, d)
Problem 5 : During electrolysis of AgNO3 (using of electrodes) concentration around cathods as
well as anode falls from 4M to 3M wheel will happen if this happen with Ag
electrodes.
(a) result will remain same
(b) concentration around cathode will fall from 4M to 3M but around anode will
increase from 4M to 5M
(c) Reverse of statement ‘b’
(d) Concentration increases from 4M to 5M on both the electrode.
Solution : (b)
Problem 6 : Which is correct about silver plating
(a) Anode – pure Ag
(b) Cathode – object to be electroplated
(c) Electrolyte – Na[Ag(CN)2 ]
(d) Electrolyte – AgNO3
Solution : (a, b, c)
Chemistry : Electrochemistry

Problem 7 : Which among the following statement are correct

o
(a) If E An+ /A is negative, H+ will be reduced to H2 by element A
(b) Compounds of (Zn, Na, Mg) are reduced by hydrogen (H2) whereas these of
metals (Cu, Ag, Au) are not reducible.
o
(c) If E An+ /A is positive An+ will be reduced to A by H2
o
(d) M/Mn+ | | H+ | H2(Pt) will be spontaneous if E M n+ /M is negative.
Solution : (a, c, d)
Problem 8 : Which of the following statement is/are not correct
(a) Reduction is always followed by decrease in oxidation number of the substance
undergoing reduction
(b) During oxidation, a substance takes out or more electrons
(c) A reducing agent is a substance which itself undergoes reduction
(d) The reaction C + O2 CO2 is a reduction reaction.
Solution : (b, c, d)
Problem 9 : The standard electrode potential of two half cell is given below
Ag + + e - 
 Ag E o = 0.80V

Hg2+ + 2e - 
 2Ag E o = 0.78V
If the two half cells are united together
Solution : (b, c)
Problem 10 : Which of the following aqueous solution turns alkaline after electrolysis
(a) NaCl (b) CuCl2
(c) CH3 COONa (d) H2 SO 4
Solution : (a, c)

SECTION - IV
COMPREHENSION TYPE PROBLEMS
 Write-up I
A acidic solution of Cu+2 salt containing 0.4gm of Cu+2 is electrolysed until all the copper is deposited.
The electrolysis is continued for seven more minutes with the volumes of solution kept at 100 ml and
the current at 1.2 amp.

Problem 1 : In the beginning of the electrolysis the substances evolved at cathode and anode are
respectively
(a) Cu and O2 (b) H2 and O2
(c) Cu and H2 (d) H2 and Cu
Solution : (a)
 Chemistry : Electrochemistry

Problem 2 : During another seven minutes of electrolysis the substances evolved at cathode and anode
are respectively
(a) Cu and O2 (b) H2 and O2
(c) Cu and H2 (d) Only O2 is evolved at cathode
Solution : (b)
Problem 3 : The total volume of gases evolved at STP at cathode during the entire electrolysis
(a) 58.4 ml (b) 48.23 ml
(c) 60.35 ml d) 35.58 ml
Solution : (a)

 Write-up II
The standard potential of the following cell is 0.23 eV at 15°C and 0.21V at 35°C
Pt, | H2(g) | HCl(aq) || AgCl(s) | Ag(s).

Problem 4 : The overall cell reaction is

(a) H2(g) + 2AgCl(s)  2HCl­(aq) + 2Ag(s)
(b) H2(g) + AgCl(s)  HCl(aq) + Ag(s)

1
(c) H + AgCl(s)  HCl(aq) + Ag(s)
2 2(g)
(d) None of these
Solution : (c)
Problem 5 : H0 for the cell reaction is (by assuming that these quantities remain unchanged in the
range 15°C to 35°C)
(a) – 46 kJ mol–1 (b) – 39 kJ mol–1
(c) – 42 kJ mol–1 (d) – 49 kJ mol–1
Solution : (b)
Problem 6 : S0 for the cell reaction is (by assuming that these quantities remain unchanged in the range
15°C to 35°C)
(a) – 96.5 JK–1 mol–1 (b) – 87.8 JK–1 mol–1
(c) –99.2 JK–1 mol–1 (d) – 94.3 JK–1 mol–1
Solution : (a)
Chemistry : Electrochemistry

MATCHING TYPE PROBLEM

Problem 7 : Table (A) Table (B)

(Electrolyte) (pH during Electrolysis)

A – Aq.NaCl (i) remains constant
B – aq CuSO4 (ii) decreases
C – Aq. Na2SO4 (iii) increases
D – Aq. AgNO3 (iv) First increase then decrease
(a) A – ii B – iii C – iv D–i
(b) A – iii B – ii C–i D – ii
(c) A – iii B – ii C – iv D – ii
(d) A – ii B – iii C–i D – iv
Solution : (b)

ASSERTION-REASON TYPE PROBLEMS

The following problems consists of two statements, one labelled as ASSERTION (A) and REASON (R).
Use the following key to chose the correct appropriate answer.
(a) (A) and (R) both are correct and (R) is the correct explanation of (A)
(b) (A) and (R) both are correct but (R) is not the correct explanation of (A)
(c) (A) is correct but (R) is incorrect.
(d) (A) is incorrect but (R) is correct

Problem 8 : ASSERTION (A) : Electrolysis of an aqueous solution of a bromide or iodied gives Br2 and
I2 at the anode where that of NaF gives O2 and F2.
REASONING (R) : F2 is highly reaction where Br2 and I2 are less reactive gas.
Solution : (b)

Problem 9 : ASSERTION (A) : Transport number of Cl– in HCl is less than in NaCl solution.
REASONING (R) : Velocity of H+ in solution is less than the velocity of Na+ ion.
Solution : (b)

Problem 10 : ASSERTION (A) : The aqueous solution H2SO4 give H4S2O8 on electrolysis by high current
density.
REASONING (R) : At high convert density the H2SO4 molecules does not under goes
electrolysis but polymerise.
Solution : (c)
 Chemistry : Electrochemistry

ASSIGNMENTS

SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. Find the charge in coulomb on 1 gm ion of N–3.
2. How many electrons flow when a current of 5 amperes is passed through a solution for 193 seconds
3. Molten aluminium chloride is electrolysed with a carried of 0.5 ampere to produce 27.0 gm of
aluminium. How many litre of chlorine at S.T.P. were produced.
4. Calculate the volume of Cl2 at NTP produced during electrolysis of MgCl2 which produced
6.50 g Mg . [ Atomic weight of Mg = 24.3 ]
5. A cell contains two hydrogen electrodes. The negative electrode is in contact with a solution of
10–6 M hydrogen ion. The EMF of the cell is 0.118 V at 25ºC. Calculate the concentration of hydrogen
ions at the positive electrode.

6. When an aqueous solution of CuSO4 is electrolyzed copper metal is deposited .

Cu+2 + 2 e  Cu .

If a constant current was passed for 5.0 hours and 404 mg of Cu was deposited , what must have
been the current .
7. A current of 20 ampere is passed through dilute sulphuric acid for 80 minutes 27 sec. How many
moles of oxygen gas will be liberated at anode if the current efficiency is only 6 % .
8. A current of 0.250 amper is passed through 400 ml of a 2.0 M solution of NaCl for 35 minutes. What
will be the pH of the solution after the current is turned off.
9. The useful work done during the reaction

1
Ag (s)  d 2(g) 
 AgCl(s)
2

Given : E od / Cl 
 1.36 V
2

E oAgCl/ Ag / Cl  0.22 V

PCl2 = 1 atm and T = 298 K

10. Eo  / Cu  0.34V . Calculate reduction potential at pH = 14 for the Cu 2+/Cu couples K for
Cu 2 sp

Cu(OH)2 = 1.0 × 10–9.

Chemistry : Electrochemistry

LEVEL - II
1. Zinc granules are added in excess to 500 ml of 1.0 M nickel nitrate solution at 25ºC until equilibrium
is reached. If the standard reduction potential of Zn2+/Zn and Ni2+/Ni are –0.75 and –0.24 volt
respectively, find out the concentration of Ni2+ ions in solution at equilibrium.
2. A 100 watt., 100 volt incondescent lamp is connected in series with an electrolytic cell containing
cadmium sulphate solution. What weight of cadmium will be deposited by the current flowing for 10
hours ?
3. A copper cell containing a 5 % solution of CuSO4 . 5 H2O and a silver all containing a 2 % solution
of AgNO3 by weight are connected in a series . A current of 0.01 ampere was passed through the
cell for 30 minutes . What was the ratio of the mass of Cu and Ag deposited at the cathode of the 2
cells .
4. The standard oxidation potential of zinc is 0,76 v and of silver is –0.80 V. Calculate the emf of the
cell Zn | Zn (NO3)2 (0.25 M) || AgNO3 (0.1 M) | Ag
5. The same quantity of electricity is passed between Pt electrodes dipped in the following solutions
(A) 0.03 molar AlCl3 (B) 0.01 molar AlCl3
(C) 0.1 molar AgNO3 (D) 0.1 molar NaOH
If 0.36 g of Ag is deposited in beaker what is the mass of Al deposited in beaker A and B and what
volume of O2 gas is evolved in cell (D) at S.T.P.
6. 19 gm of molten SnCl2 is electrolysed for some time using inert electrodes until 0.119 gm of Sn is
deposited at the cathode. No substance is lost during the electrolysis. Find the ratio of the weight of
SnCl2 : SnCl4 after electrolysis.
7. An acidic solution of Cu+2 salt containing 0.4 g of Cu+2 is electrolysed untill all the copper is deposited
. The electrolysis is continued for seven more minutes with the volume of solution kept at 100 ml and
the current at 1.2 ampere . Calculate the volume of gases evolved at N.T.P. during the entire
electrolysis.
8. The EMF of the following cell 0.265 V at 25ºC and 0.2595 V at 35º. Calculate heat of reaction taking
place at 25ºC
Pt(H 2 ) | HCl(aq) ||AgCl | Ag

 
9. The standard reduction potential for half cell NO3(aq)  2H (aq)  e  
 NO 2  H 2O (l ) is 0.78 V..
(i) Calculate the reduction potential in 8MH+.
(ii) What will be the reduction potential of the half cell in a netural solution ? Assume all other
species to be at unit concentration.
10. Calculate the pH of the following half cell solutions .

(a) Pt H2  HCl E = 0.25 V

(1 atm)

(b) Pt H2  H2SO4 E = 0.25 V

(1 atm)
 Chemistry : Electrochemistry

LEVEL - III
1. Calculate the solubility product constant of AgI from the following values of standard electrode
o
potentials. E oAg  /Ag  0.80 V and E I/ AgI/ Ag  0.15V at 25ºC.
2. A big irregular shaped vessel contained water, the conductivity of which was 2.56 × 10–5 mho
cm–1. 500 gm of NaCl was then added to the water and the conductivity of tetra addition of NaCl,
was found to be 3.10 × 10–5 mho cm–1. Find the capacity of vessel if it is full filled with water
( oNaCl  149.9) .
3. After electrolysis of a sodium chloride solution with inert electrodes for a certain period of time 600
ml of solution was left which was found to be 1N sodium hydroxide. During the same time 31.8 gm
of copper was deposited in a copper voltameter in series with the electrolytic cell. Calculate the
percentage of the theoretical yield of sodium hydroxide obtained.
4. Calculate the EMF of the following cell
Pt (H2, 1atm) | C2H5COOH (0.15M) || (0.01 M) NH4OH | H2, Pt (1atm)
Ka for C2H5COOH = 1.4  10–5; Kb for NH4OH = 1.8  10–5
5. During the discharge of a lead storage battery the density of sulphuric acid fell from 1.294 to 1.139 g/
ml . Sulphuric acid of density 1.294 is 39 % by weight and that of 1.139 g/ml is 20 % H2SO4 by
weight . The battery holds 3.5 litres of the acid and the volume remained practically constant during
the discharge . Calculate the number of ampere-hours for which the battery must have been used .
The charging and discharging reactions are ,
Pb + SO42 = PbSO4 + 2 e (discharging)
PbO2 + 4 H+ + SO42 + 2 e = (charging)
6. When AgCl is dissolved in a large excess of NH3, practically all silver can be assumed to exist in the
form of a single species Ag m (NH 3 ) n m . Compute the values of m and n using the following two cells.
Ag | 0.379  10–3M AgCl, 1M NH3 | | 37.9 10–3M AgCl, 1M NH3 | Ag
Ecell = 0.1185V at 298K
Ag | 3.4 10–3M AgCl, 1M NH3 | | 3.4  10–2M AgCl, 0.1M NH3 | Ag
Ecell = 0.1263V at 298K
7. From the following information, calculate the overall stability constant Ks of
Ag(S2 O3 ) 23 at 25°C
Ag+ + e–  Ag E° = 0.799V
3
Ag  S2 O3 2  e –  Ag + 2S2O3-2; E° = 0.017 volt
8. Calculate the quantity of electricity that would be required to reduce 12.3 gm of nitrobenzene to
aniline if the current efficiency for the process is 50 % . If the potential drop across the cell is 3.0
volts , how much energy will be consumed ?
9. A current of 1.70 ampere is passed through a 300 ml of 0.16 M solution of ZnSO4 for 230 seconds
with a current efficiency 90 % . Find out the molarity of Zn2+ after the deposition of Zn . Assume
solution volume remains same .
10. Electric current is passed through two cells A and B in series . Cell A contains aqueous solution of
Ag2SO4 and platinum electrodes . Cell B contains aqueous solution of CuSO4 and copper electrodes
. The current is passed till 1.6 gm of oxygen is liberated at anode in cell A . Calculate the quantities
of copper and silver deposited at the cathode of the two cells .
[ Atomic weight of O = 16 , Cu = 63.5 , Ag = 108 ]
Chemistry : Electrochemistry

SECTION - II
SINGLE CHOICE QUESTIONS
1. The oxidation number of C in CH 4 , CH3 Cl, CH2 Cl2 , CHCl3 and CCl4 are respectively
(a) +4, +2, 0, –2, –4 (b) +2, +4, 0, –4, –2
(c) –4, –2, 0, +2, +4 (d) –2, –4, 0, +4, +2
2. In which of the following acids the two sulphurs are present in different oxidation states
(a) H2 S 2 O 7 (b) H2 S 2 08
(c) H2 S 2 O 5 (d) all
3. Zn gives H2 gas with H2SO4 and HCl but not with HNO3 because
(a) Zn acts as an oxidising agent when reacts with HNO3
(b) HNO3 weaker acid than HCl or H2SO4
(c) In electrochemical series Zn is above hydrogen
(d) NO3 is reduced in preference to hydronium ion.
4. In an irreversible process taking place at constant T and P and in which only pressure volume work
is being done, the change in Gibbs free energy (dG) and change in entropy (ds) satisfy the criteria.
(a) (ds) v, E  0, (dG)T, P  0 (b) (dG)T ,P  0, (ds) v,E  0

(c) (ds) v, E  0, (dG)T, P  0 (d) (dG)T ,P  0, (ds) v,E  0

5. Hydrogen electrode is dipped in a solution of pH = 3 at 25ºC, the potential of the cell and would be
(a) 0.177 V (b) –0.177 V
(c) 0.087 V (d) 0.059
6. A gas X at 1 atm is bubbled through a solution containing a mixture of 1M Y– and 1M Z– at 25ºC. If
the reduction potential of
Z > Y > X, then
(a) Y will oxidise X not Z (b) Y will oxidise Z not X
(c) Y will oxidise both X and Z (d) Y will reduce both X and Z
7. Which of the following will increase the voltage of the cell
 2
Sn (s )  2Ag (aq ) 
 Sn (aq)  2Ag (s)
(a) Increase in the size of the silver rod
(b) Increase in the concentration of Sn2+ ion
(c) Increase in the concentration of Ag+
(d) None

8. Given : E oAg /Ag  0.80V, E oMg2 /Mg  2.37V

E oCu 2 / Cu  0.34V E oHg 2 /Hg  0.79V

Which of the following statement is correct
(a) AgNO3 can be stored in copper vessel (b) Cu(NO3)2 can be stored in magnesium vessel
(c) CuCl2 can be stored in silver vessel (d) HgCl2 can be stored in copper vessel
 Chemistry : Electrochemistry

9. Cu 2   2C  
 Cu . For this between log (Cu2+) versus Ered is a straight line of intercept 0.34 V
then electrode potential of the half cell Cu/Cu2+ (0.1 M) will be

0.0591 0.0591
(a) 0.34  (b) 0.34 
2 2
0.0591
(c) 0.34 (d) 0.34 
2

 d( G)   dE 
10. G = H – TG and G = H + T   then   is –
 dT  P dT

S nE
(a) (b)
nF S
(c)  nFE cell (d)  nFE cell
11. A solution containing one mole per litre each of Cu(NO3)2, AgNO3, Hg2(NO3)2 and Mg(NO3)2 is
being electrolysed by using inert electrodes. The values of the standard oxidation potential in volts
are Ag/Ag+ = –0.8, Hg/Hg2+ = –0.79, Cu/Cu2+ = –0.34, Mg/Mg2+ = 2.37
The order in which metals will be formed at the cathode, will be
(a) Ag, Cu, Hg, Mg (b) Ag, Hg, Cu, Mg
(c) Ag, Hg, Cu (d) Cu, Hg, Ag
2+ 2+
12. For the cell Zn | Zn (C1) | | Zn (C2) | Zn, G is negative if
(a) C1 = C2 (b) C1 > C2
(c) C2 > C1 (d) none
13. Equivalent conductance of saturated BaSO4 is 400 ohm–1 cm2 eq –1 and specific conductance is 8 ×
10–15 ohm–1 cm–1. Hence Ksp of BaSO4 is
(a) 4 × 10–8 M2 (b) 1 × 10–8 M2
(c) 2 × 10–4 M2 (d) 1 × 10–4 M2
14. Through a solution of CuSO4 a current of three amperes was passed for two hours. At cathode 3 gm
of Cu2+ ions were discharged. The current efficiency is (Atomic weight of Cu = 63.5)
(a) 33% (b) 42.2%
(c) 48.7% (d) 54.4%
15. By removing a salt bridge between the two half cells, the voltage
(a) increase gradually (b) increases rapidly
(c) does not change (d) drops to zero
16. The emf of Daniel cell at 298 K is E, Zn | Zn(SO4)4 (0.01 M) | | CuSO4 (1.0 M) Cu, when the
concentration of ZnSO4 is 1.0 M and that of CuSO4 is 0.01 M, the emf changed to E2. What is the
relationship between E1 and E2.
(a) E1 = E2 (b) E 2  0  E1
(c) E1 > E2 (d) E1 < E2
Chemistry : Electrochemistry

17. An electrochemical cell is set up as

Pt(H2) | HCl (0.1 M) | | CH3COOH (0.1 M) Pt (H2)
the emf of this cell will not be zero because
(a) temperature is constant
(b) pH of 0.1 M HCl and 0.1 M CH3COOH is not same
(c) acid used in two compartments are different
(d) emf depends on molarities of acids used
18. Red hot carbon will remove oxygen from the oxide XO and YO but not from ZO. Y will remove
oxygen from XO. Use this evidence to deduce the order of activity of three metals X, Y and Z
putting the most active first
(a) XYZ (b) ZYX
(c) YXZ (d) ZXY
19. The standard reduction potential at 25ºC of reaction 2H 2 O  2e  
 H 2  2OH  is –0.8277 volt.
Calculate the equilibrium constant for the reaction
2H 2 O H3 O    OH at 25ºC
(a) 1014 (b) 1012
(c) 1011 (d) 1013
20. The ratio of Pb2+ to Sn2+ concentration is needed to reverse the following cell reaction
2 2
Sn (s )  Pb (aq ) 
 Sn (aq )  Pb (s)

standard red potential Sn and lead is – 0.136 and –0.126 volt respectively
(a) [Pb 2  ] / [Sn 2  ]  0.458 (b) [Pb 2  ] / [Sn 2  ]  0.458

(c) [Pb 2  ] / [Sn 2  ]  0.458 (d) [Pb 2  ] / [Sn 2 ]  0

SECTION - III
MULTIPLE CHOICE QUESTIONS
(with one or more than one answer correct)

1. In which of the following cell(s) E cell  E ocell ?

2 
(a) Cu (s) | Cu (0.01M)||Ag (0.1M) |Ag (s )
2
(b) Pt(H 2 ) | pH  1|| Zn (0.01M) | Zn (s)
2
(c) Pt(H 2 ) | pH  1|| Zn (1M) | Zn (s)
 2
(d) Pt(H 2 ) | H (0.01M) || Zn (0.01M) | Zn (s )
 Chemistry : Electrochemistry

2. Fuel cell involves following reactions


 4  OH (aq ) (at cathods)
(a) O 2 (g)  2H 2 O(l )  4e 

 4  OH (aq ) (at anode)
(b) O 2 (g)  2H 2 O(l )  4e 

 4H 2 O(l )  4e (at anode)
(c) 2H 2 (g)  4 OH (aq ) 

 4H 2 O(l )  4e (at cathode)
(d) 2H 2 (g)  4 OH (aq ) 
3. Which of the following statement is / are correct
(a) One Faraday is the charge carried by one mole of electrons
(b) If same quantity of electricity flows through the solutions of 0.1 M AgNO3 and 0.1 M CuSO4
solutions, same weight of silver and copper will be deposited
(c) Electrochemical equivalent has the units of grams per coulomb
(d) Passage of one Faraday of electricity produces one gm of equivalent of substance at the electrode.
4. Consider the sequence
o o
E1 E2
A 0   A b    Ac
| - - - - - - - -E o - - - - - - - 

o E1o  E 2o
Given that E  which of the following might represent correct set of values for a, b and c
2
(a) a = 3b = 2c = 1 (b) a = 5b = 3c = 1
(c) a = 6b = 4c = 4 (d) a = 6b = 4c = 4
5. Consider the standard reduction potentials in acidic medium

1.19 1.21 1.64 1

ClO4  ClO3  HClO 2  Cl
2 2
The species which is(are) likely to disproportionate in the solution are
(a) ClO4 (b) ClO3

(c) HClO 2 (d) Cl2

6. The emf of galvanic cell depends upon
(a) surface area of electrodes (b) concentration of electrolyte
(c) volume of electrolyte (d) temperature
7. The formation of rust on the surface of iron occurs through the reactions
2
(a) Fe(s) 
 Fe(aq)  2e  at anode
 
(b) O 2(q )  4H (aq )  4e 
 2H 2 O(l ) at cathode
2
 2Fe 2 O 3(s )  8H 
(c) 4Fe (aq )  O 2(g )  4H 2 O(l ) 

(d) Fe 2 O3  xH 2 O(l ) 
 Fe 2 O3 .xH 2 O
Chemistry : Electrochemistry

8. Which is/are correct relation for equilibrium constant K.

o 2.303RT log K
(a) G o  2.303 RT log K (b) E cell 
nF

 [Product] H
(c) K  (d) log K  log A 
 [reactants] 2.303
9. If same quantity of electricity is passed through three electrolytic cells containing FeSO4, Fe2(SO4)3,
and Fe(NO3)3, then
(a) The amount of iron deposited in FeSO4 and Fe(SO4)3 are equal
(b) The amount of iron deposited in FeSO4 is 1.5 times of the amount of iron deposited in Fe(NO3)3
(c) The amount of iron deposited in Fe2(SO4)3 and Fe(NO3)3 are equal
(d) The same amount of gas is evolved in cell three cases at the anode
10. Which of the following is/are concentrated cells

(a) Pb(Hg) | Pb 2(aq ) | Pb(Hg) (b) Pt, H 2 (1atm) | HCl | Cl 2 (1atm), Pt

molality m 1 molality m
2

(c) Pt, H 2 (2atm) | HCl | H 2 (1atm), Pt (d) Ag (s) ,AgCl(s ) | KCl ||KCl | AgCl(s ) ,Ag (s)

SECTION - IV
COMPREHENSION TYPE QUESTIONS

I. An electrolyte prepared from H2SO4, CuSO4 and distilled water and its volume is 100 c.c. the
concentration of H+ and Cu2+ in the electrolyte are C   1.0 M and CCu 2  1  10 2 M respectively..
H

Two cubic platinum electrodes are immersed in the electrolyte. Both of the electrode are single,
Crystals with only one face (100) exposed to electrolyte (the two fire faces are blocked physically
by an insulator which is stable in the electrolyte). The exposed surface area of each electrode is
equal to 1.00 c.c. During an electrolysis, a total charge of 2.00 C is passed between the cathode and
anode (Assume ideal gas behaviour) T = 273.15 and PH2  1.01325  10 4 Pa, the volume of H2 is
equal to 2.000 c.c. Note that the lattice constant of Pt is apt = 3.9236 × 10–8 cm
Both Pt and Cu have the f.c.c.
Molar masses and constant
MH = 1.00 795 gm mol–1
Mcu = 63.546 gm mol–1
e = 1.60218 × 10–19 C
F = 96483.3 mol–1
R = 8.314510 JK–1
Vm = 22.4141 litre
1 atm = 1.01325 × 105 Pa
NA = 6.02214 × 1023 mol–1
 Chemistry : Electrochemistry

1. The gas liberated at cathode and anode will be respectively

(a) H2, O2 (b) O2, H2
(c) O3, H2 (d) H2, O3
2. The number of moles of gas generated at the cathode
(a) 8.9230 × 10–6 (b) 4.4615 × 10–6
(c) 2 × 10–4 (d) 1 × 10–4
3. The number of moles of Cu deposited at electrode
(a) 1.4412 × 10–6 (b) 7.206 × 10–7
(c) 2.8824 × 10–6 (d) 4.658 × 10–6

II. Standard reduction potential

Acid Solution (activity of H+ = 1)

+1.39
+1.64

1.19 1.21 1.65 1.61 1 1.36

ClO 4   ClO3   HClO 2   HOCl   Cl2   Cl
2

+1.48
1.45

Basic solution (activity of –OH = 1)

1
ClO4 
36
ClO3 
0.33 0.66
 ClO2   OCl 
40 1.36
Cl2   Cl
2

+0.88

4. What is the standard reduction potential of

1
ClO3 
 Cl2 in acidic medium
2
(a) +1.47 (b) 4.47
(c) +2.235 (d) +2.94
5. What is the standard reduction potential of
ClO3 
 OCl in the basic medium
(a) +5.0 (b) +1.00
(c) 0.99 (d) 0.49
Chemistry : Electrochemistry

6. In basic medium, which of the following reactions will not occur

 OCl  ClO
(a) ClO2  (b) OCl 
 Cl  ClO3

 Cl  OCl
(c) Cl2  (d) ClO3 
 ClO 2  ClO4

MATCHING TYPE QUESTIONS

7. If the following solution are electrolysed using inert electrode, gases liberated are
(A) Na 2 SO 4 (p) Cl2
(B) ZnSO4 (q) O 2
(C) HCl (r) H2
(D) Ag2 SO 4 (s) SO2
(a) (A) – (q, r), (B) – (q, r), (C) – (p, q, r), (d) – (q)
(b) (A) – (p, q), (B) – (p, q, r), (C) – (p, p, s), (d) – (q, r, s)
(c) (A) – (q, r, s), (B) – (q, s), (C) – (p, r, s), (d) – (r, s, q)
(d) (A) – (q, s), (B) – (p, r), (C) – (p, q, s), (d) – (r, s, q)

8. Electrode potential of following reaction in

E Zn 2 /Zn  0.76 V , E Cu 2 /Cu  0.34 V

E Fe3 /Fe2  0.77 V , E Fe/Fe2  0.33V

(A) Zn  Cu 2  
 Zn 2   Cu (p) –0.43 V

(B) Fe3  Fe 
 2Fe2  (q) –spontaneous

(C) Zn 2  Fe 
 Fe 2   Zn (r) non-spontaneous

(D) Fe2   Cu 2 
 Fe3  Cu (s) 1.10 V

(a) (A) – (p, q, r), (B) – (p, q), (C) – (r, s), (d) – (q, r)
(b) (A) – (q, s), (B) – (q, s), (C) – (p, r), (d) – (p, r)
(c) (A) – (p, r), (B) – (p, r), (C) – (q, s), (d) – (q, s)
(d) (A) – (q, r, s), (B) – (p, q), (C) – (q, s), (d) – (p, q, r)
 Chemistry : Electrochemistry

ASSERTION-REASON TYPE QUESTIONS

The following questions consists of two statements, one labelled as ASSERTION (A) and REASON (R).
Use the following key to chose the correct appropriate answer.
(a) (A) and (R) both are correct and (R) is the correct explanation of (A)
(b) (A) and (R) both are correct but (R) is not the correct explanation of (A)
(c) (A) is correct but (R) is incorrect.
(d) (A) is incorrect but (R) is correct

9. ASSERTION (A) : If standard reduction is 0.80 volt, then far the reaction 2Ag+ + 2e– — 2Ag, it
will be 1.60 vol.
REASONING (R) : If concentration of Ag+ is doubled, the electrode potential is also doubled.
10. ASSERTION (A) : Specific conductance decreases with dilution whereas equivalent conductance
increases.
REASONING (R) : On dilution, the number of ions per c.c. decreases but total number of ions
increases considerably.
11. ASSERTION (A) : The ratio of specific conductivity to the observed conductance does not depend
upon the concentration of solution taken in conductivity cell.
REASONING (R) : Specific conductivity decreases with dilution whereas observed conductance
increases with dilution.
12. ASSERTION (A) : In the Daniel cell,if concentration of Cu2+ and Zn2+ ion are doubled, the emf of
the cell will be doubled.
REASONING (R) : If the concentration of ions in contact with the metals is doubled, the electrode
potential is doubled.

dE cell
13. ASSERTION (A) : If  0, then H  nFE cell
dT

  dE  
REASONING (R) : H  nF  T  cell   E cell 
  dT  
14. ASSERTION (A) : For the reactions

Zn  2Ag  Zn 2   2Ag and

1 1 2
Zn  Ag  Zn  Ag the cell potential are different
2 2

REASONING (R) : For the cell reaction, Zn  2Ag  Zn 2   2Ag and

1 1 2
Zn  Ag  Zn  Ag , the free energies are different
2 2
15. ASSERTION (A) : A saturated solution of KCl is used to make salt bridge in concentration cells.
REASONING (R) : Mobilities of velocities of K+ and Cl– are nearly same.
Chemistry : Electrochemistry

SECTION - V
QUESTIONS
OBJECTIVE
A. Fill in the Blanks
1. Galvanization of iron denotes coating with............
2. The more ............ the standard reduction potential, the ............is its ability to displace hydrogen
from acids.
3. The electrical conductivity of a solution of acetic acid will be ............, if a solution of sodium
hydroxide is added.
4. The electrolysis of molten sodium hydride liberates ............ gas at the.............
B. True / False
1. The dependence of electrode potential for the electrode M n+/M with concentration under STP
conditions is given by the expression.
0.0591
E  Eo  log10 [M n  ]
n
C. Only one option is correct (Objective Questions)
1. A solution containing one mole per litre of each Cu(NO3)2, AgNO3, Hg2(NO3)2 is being electrolysed
by using inert electrodes. The values of standard electrode potentials is volts (reduction potential)
are :
Ag/Ag+ = + 0.80, 2Hg/Hg22+ = + 0.79
Cu/Cu2+ = + 0.34, Mg/Mg2+ = – 2.37
With increasing voltage, the sequence of deposition of metals on the cathode will be :
(a) Ag, Hg, Cu, Mg (b) Mg, Cu, Hg, Ag
(c) Ag, Hg, Cu (d) Cu, Hg, Ag
2. The electric charge for electrode deposition of one gram equivalent of a substance is :
(a) one ampere per second (b) 96,500 coulombs per second
(c) one ampere for one hour (d) charge on one mole of electrons
3. The standard reduction potentials E°, for the half reactions are as :
Zn = Zn2+ + 2e–, E° = + 0.76V
Fe = Fe2+ + 2e–, E° = 0.41 V
The e.m.f. for the cell reaction,
Fe2+ + Zn  Zn2+ + Fe is :
(a) – 0.35 V (b) + 0.35 V
(c) + 1.17 V (d) – 1.17 V
 Chemistry : Electrochemistry

4. The standar reduction potentials of Cu2+/Cu and Cu2+/Cu+ are 0.337 V and 0.153 V respectively.
The standard electrode potential of Cu2+/Cu half-cell is :
(a) 0.184 V (b) 0.827 V
(c) 0.521 V (d) 0.490 V
5. The standard reduction potential values of three metallic cations, x, y, z are 0.52, – 3.03 and
– 1.18 V respectively. The order of reducing power of the corresponding metal is :
(a) y > z > x (b) x > y > z
(c) z > y > z (d) z > x > y
6. The gas x at 1 atm is bubbled through a solution containing a mixture of 1 M y– and 1 M z– at 25°C.
If the reduction potential of z > y > x then :
(a) y will oxidise x and not z (b) y will oxidise z and not x
(c) y will oxidise both x and z (d) y will reduce both x and z
7. FOr the electrochemical cell, (M/M )||(X /X), E°(M+/M) = 0.44V and E° (X–/X) = 0.33V. From this
+ –

data one can reduce that :

(a) M + X  M+ + X– is the spontaneous reaction
(b) M+ + X–  M + X is the spontaneous reaction
(c) Ecell = 0.77 V
(d) Ecell = – -.77 V
8. The correct order of equivalent conductance at infinite dilution of LiCl, NaCl and KCl is:
(a) LiCl > NaCl > KCl (b) KCl > NaCl > LiCl
(c) NaCl > KCl > LiCl (d) LiCl > KCl > NaCl
9. Saturated solution of KNO3 is used to make 'salt-bridge' because :
(a) velocity of K+ is greater than that of NO3–
(b) velocity of NO3– is greater than that of K+
(c) velocity of both K+ and NO3– are nearly the same
(d) KNO3 is highly soluble in water
10. Standar electrode potential data are useful for understanding the suitability of an oxidant in a redox
titration. Some half-cell reactions and their standard potentials are given below :
MnO4– (aq) + 8H+ (aq) + 5e–  Mn2+ (aq) + 4H2O(l), E° = 1.51 V
Cr2O72– (aq) + 14H+ (aq) + 6e–  2Cr3+ (aq) + 7H2O(l), E° = 1.38 V
Fe (aq) + e  Fe (aq)
3+ – 2+
E° = 0.77 V
Cl2(g) + 2e–  2Cl– (aq) E° = 1.40 V
Identify the incorect statement regarding the quantitative estimation of gaseous Fe(NO3)2.

(a) MnO4– can be used in aqueous HCl (b) Cr2O72– can be used in aqueous HCl
(c) MnO4– can be used in aqueous H2SO4 (d) Cr2O72– can be used in aqueous H2SO4
Chemistry : Electrochemistry

11. In the electrolytic cell, flow of electrons is from :

(a) cathode to anode in solution (b) cathode to anode through external supply
(c) cathode to anode through internal supply (d) anode to cathode through internal supply
2+ 2+
12. Zn | Zn (a = 0.1 M) || Fe (a = 0.01M)|Fe
The emf of the above cell is 0.2905 V. Equilibrium constant for the cell reaction is :
(a) 100.32/0.0591 (b) 100.32/0.0295
(c) 100.26/0.0295 (d) e0.32/0.295
13. The rusting of iron takes place as follows :

1
2H   2e   O 2 
 H 2 O(l ); E o  1.23V
2
Fe2+ + 2e–  Fe(s); E° = – 0.44 V
Calculate G° for the net process
(a) – 322 kJ mol–1 (b) – 161 kJ mol–1
(c) – 152 kJ mol–1 (d) – 76 kJ mol–1
 Write-up I [Questions 14 to 16]

Ag   e  
 Ag E 0reduction  0.8V

 C6 H12 O 7  2H   2e 
C6 H12 O 6  H 2 O  0
E oxidation  0.5V

[Ag(NH 3 ) 2 ]  e  
 Ag  2NH 3 0
E reduction  0.3V

 F  1
Use    38.9V
 RT 
14. Calculate (ln K) for C6H12O6 + 2Ag+ + H2O  C6H12O7 + 2H+ + 2Ag
(a) 16 (b) 20
(c) 19 (d) 18
15. On adding NH­3 pH of solution increases to 11 then, identify the effect of pH on potential of half-cell

(a) Eox increased from E 0ox by 0.065 (b) Eox decreased from E 0ox by 0.065

(c) Ered increased from E 0red by 0.065 (d) Ered decreased from E 0red by 0.065
16. NH­3 is used in this reaction rather than any other base. Select the wrong statement out of the
following
(a) [Ag(NH3)2]+ is a weaker oxidizing agent than Ag+
(b) NH3 prevents the decomposition of gluconic acids
(c) NH3 has affected the standard reduction potential of glucose/gluconic acid electrode
(d) NH3 combines with Ag+ to form a complex
 Chemistry : Electrochemistry

SUBJECTIVE
1. The standard reduction potential of Cu++/Cu and Ag++/Ag electrodes are 0.337 and 0.799 volt respectively.
Construct a galvanic cell using these electrodes so that its standard e.m.f. is positive . For what
concentration of Ag+ will the e.m.f. of the cell, at 250C, be zero if the concentration of Cu++ is 0.01M ?

2. Zinc granules are added in excess to a 500 ml of 0.1 M nickel nitrate solution at 250C until the
equilibrium is reached . If the standard reduction potential of Zn2+/Zn and Ni2+/ Ni are  0.75V & 
0.24 V respectively , find out the concentration of Ni2+ in solution at equilibrium .

3. For the galvanic cell : AgAgCl (s)KCl (0.2M) K Br (0.001 M)AgBr (s)Ag,
Calculate the e.m.f. generated and assign correct polarity to each electrode for a spontaneous process
after taking into account the cell reaction at 250C .

K AgCl
sp  2.8x10 10 ; K AgBr
sp  3.3x10 13 
4. An aqueous solution of NaCl on electrolysis gives H2(g), Cl2(g) and NaOH according to the reaction:
2Cl(aq) + 2H2O = 2OH(aq) + H2(g) + Cl2(g).
A direct current of 25 amperes with a current efficiency of 62% is passed through
20 liters of NaCl solution (20% by weight) . Write down the reactions taking place at the anode and
the cathode. How long will it take to produce 1 Kg of Cl2 ? What will be the molarity of the solution with
respect to hydroxide ion ?
[ Assume no loss due to evaporation ]

5. The Edison storage cell is represented as , Fe (s)FeO (s)KOH (aq.)Ni2O3 (s)Ni (s)
The half  cell reaction are :
Ni2O3 (s) + H2O (l) + 2 e  2 NiO (s) + 2 OH E0 = + 0.40V
FeO (s) + H2O (l) + 2e  Fe (s) + 2 OH E0 =  0.87V
(i) What is the cell reaction ?
(ii) What is the cell e.m.f. ? How does it depend on the concentration of KOH ?
(iii) What is the maximum amount of electrical energy that can be obtained from one mole of
Ni2O3 ?
6. The standard reduction potential of the Ag+/Ag electrode at 298 K is 0.799 V . Given that for
AgI, Ksp = 8.7 x 1017, evaluate the potential of the Ag+/Ag electrode in a saturated solution of AgI .
Also calculate the standard reduction potential of the I/AgI/Ag electrode .
7. An excess of liquid Hg is added to an acidified solution of 1.0  103 M Fe+3 . It is found that 5 % of
Fe+3 remains at equilibrium at 25°C . Calculate E°(Hg+2/Hg), assuming that the only reaction that
occurs is , 2 Hg + 2 Fe+3  Hg2+ + 2 Fe+2 .
[ Given E° (Fe+3/Fe+2) = 0.77 V ]
Chemistry : Electrochemistry

8. The standard reduction potential for Cu2+ /Cu is 0.34 V. Calculate the reduction potential at pH = 14 for
the above couple . Ksp of Cu(OH)2 is 0.1  1019.
9. Calculate the equilibrium constant for the reaction , Fe2+ + Ce4+  Fe3+ + Ce3+ ,

[ Given : E 0 Ce 4 / Ce3  1.44 V; E 0 Fe 3 / Fe2  0.68 V ]

10. How many grams of silver could be plated out on a serving tray by electrolysis of a solution containing
silver in +1 oxidation state for a period of 8.0 hours at a current of 8.46 Amperes ? What is the area
of the tray if the thickness of the silver plating is 0.00254 cm ? Density of silver is 10.5 g/cm3 .

11. Find the solubility product of a saturated solution of Ag2CrO4 in water at 298 K if the emf of the cell,
AgAg+ (satd. Ag2 CrO4 soln.)  Ag+ (0.1 M)Ag is 0.164 V at 298 K .
12. Calculate the equilibrium constant for the reaction , 2 Fe3+ + 3 I  2 Fe2+ + I3 . The standard
reduction potentials in acidic conditions are 0.77 and 0.54 V respectively for Fe3+/Fe2+ and I3/ I
couples .

13. A cell AgAg+Cu2+Cu initially contains 1 M Ag+ and 1 M Cu2+ ions . Calculate the change in
cell potential aftr the passage of 9.65 ampere of current for 1 hour .
14. Electrolysis of a solution of MnSO4 in aqueous sulphuric acid is a method of preparation of MnO2 as per
reaction , Mn2+ (aq.) + 2 H2O  Mn2O (s) + 2 H+ (aq.) + H2 (g) .
Passing a current of 27 ampere for 24 hours gives only 1 kg of MnO2 . What is the value of current
efficiency . Write the reactions taking place at the cathode and at the anode .
15. The following electrochemical cell has been set up ,

Pt (1)Fe3+ , Fe2+ (a = 1)Ce4+ , Ce3+ (a = 1)Pt (2) .

Eº (Fe3+Fe2+) = 0.72 volts ; Eº (Ce4+Ce3+) = 1.61 volts

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 ?
16. Copper sulphate solution 250 ml was electrolysed using a platinum anode and a copper cathode . A
constant current of 2 milli ampere was passed for 16 minutes . It was found that after electrolysis
absorbance of the solution was reduced to 50 % of its original value . Calculate the concentration of
copper sulphate in the solution to begin with .
17. The standard potential of the following cell is 0.23 V at 15ºC and 0.21 V at 35º C.
Pt / H2(g) / HCl (aq) / AgCl(s) / Ag(s)
(i) Write the cell reaction
(ii) Calculate Hº and Sº for the cell reaction by assuming that these quantities remain unchanged in
the range 15ºC to 35ºC
(iii) Calculate the solubility of AgCl in water at 25ºC.
Given : The standard reduction potentials of the (Ag+ (aq) / Ag(s) is 0.80 V at 25ºC.
 Chemistry : Electrochemistry

18. Two students use same stock solution of ZnSO4 and a solution of CuSO4. The emf of one cell is 0.03 V
higher than the other. The conc. of CuSO4 in the cell with higher emf value is 0.5 M. Fnd out the conc.
of CuSO4 in the other cell 2.303 RT/F = 0.06.
19. Find the equilibrium constant for the reaction

Cu 2  In 2 Cu   In 3
Given that
E oCu 2 / Cu   0.15V, E Ino 2 / In   0.4 V,

E oIn 3 / In   0.42 V,

20. (a) Calculate G or of the following reaction :

Ag (aq )  Cl(aq) 
 AgCl (s)
Given

G of (AgCl) 109 kJ / mol

G of (Cl)  129 kJ / mol
G of (Ag  ) 77 kJ / mol

Represent the above reaction in form of a cell. Calculate Eº of the cell. Find log10 Ksp of AgCl.
(b) 6.539 × 10–2 g of metallic Zn (amu = 65.39) was added to 100 mL of saturated solution of AgCl.

[Zn 2  ]
Calculate log10 , Given that
[Ag  ]2

Ag   e  
 Ag Eº = 0.80 V

Zn 2   2e  
 Zn Eº = –0.78 V
Also find how many moles of Ag will be formed ?
21. We have taken a saturated solution of AgBr is 12  10 14 . If mole of AgNO3 are added to 1 litre of this
solution find conductivity (specific conductivity) of this in terms of 10–7 sm–1 units. Given molar conductivity
of Ag+, Br– and NO3– are 6  103 sm2 mol–1, 8  103 sm2 mol–1 and 7 × 10–3 sm2 mol–1.
Chemistry : Electrochemistry

ANSWERS
EXERCISE-1
1. t = 193 sec. 2. n=4

3.  = 50% 4. Cu2+ = 0.08M, H+ = 0.04M, SO2-4 = 0.1M

5. Ni2+ = 2M 6. A = 114, Q = 5926.8C

EXERCISE-2
1. (a) Zn + Cu2+  Zn2+ + Cu, (b) E0 = 1.113V (c) Yes
2. E = 1.1V 3. Ecell = 0.48V

EXERCISE-3
1. a2 = 0.1006M 2. n=2

3. E = 0.059 4. E = 0.395V

EXERCISE-4
1. E0=-1.59V,non-spontaneous 2. Kc = 2.18 x 1026

3. Kc = 2.864 x 10107, G0 = 611.8 kJ 4. K  10-14 , G0 = +79.89 kJ

5. E0 = 0.7826 V 6. K = 6.26 x 10-3, E0 = 0.919V

7. E0 = 0.88V, G0 =-84.92J

EXERCISE-5
1. 63 –1 cm2 equiv–1 and 1.26  102 –1 cm2 mol–1

2. x = 1.166 cm–1,  = 66.66 ohm–1 cm2

3. 1.80  10–3 g dm–3

4. 523.2  10–4 S m2 mol–1

 Chemistry : Electrochemistry

SECTION-I
SUBJECTIVE QUESTIONS

Level-I

1. 2.89 × 105 coulombs 2. 6.023  1021

3. 33.6 litres 4. 5.99 litres

5. 10–4 M 6. 0.0682 amp

7. 1.5  10 2 moles 8. 12.13

9. 110 Kg Mol–1 10. –0.22 V

Level-II
1. –5.6 × 10–18 M. 2. 19.0598 g

3. Cu : Ag : : 1 : 3.407 4. 1.56 volt

5. 0.03 g of Al will deposit in beaker 6. 71.34 : 1

A and B separately. 1.866 × 10 2 L O2

7. 58.48 ml 8. –82.8 kJ

9. 0.833; 0.367 volt 10. (a) 4.237, (b) 5.08

Level-III
1. 8.4 × 10–17 2. 237258.38 litre

3. 60% 4. –0.46

5. 265.02 ampere hours 6. m = 1, n = 2

7. 1.705 × 1013 8. 115800 coulombs , 347.4 kJ

9. 0.154 M 10. Ag = 21.6 gm , Cu = 6.35 gm

SECTION-II
SINGLE CHOICE QUESTIONS
1. (c) 2. (c) 3. (d) 4. (b) 5. (b)
6. (a) 7. (c) 8. (c) 9. (d) 10. (a)
11. (c) 12. (c) 13. (a) 14. (b) 15. (d)
16. (c) 17. (b) 18. (b) 19. (a) 20. (a)
Chemistry : Electrochemistry

SECTION-III
MULTIPLE CHOICE QUESTIONS
1. (a, b) 2. (a, c) 3. (a, c, d) 4. (a, c) 5. (b, c)
6. (b, d) 7. (a, b, c, d) 8. (b, c, d) 9. (b, c, d) 10. (a, c, d)

SECTION-IV
COMPREHENSION TYPE QUESTIONS
1. (b) 2. (b) 3. (a) 4. (b) 5. (b)
6. (d)

MATCHING TYPE QUESTIONS

7. (a) 8. (b)

ASSERTION-REASON TYPE QUESTIONS

9. (d) 10. (a) 11. (b) 12. (b) 13. (a)
14. (d) 15. (a)

SECTION-V
QUESTIONS
OBJECTIVE
A. Fill in the blanks
1. zinc 2. negative, greater or positive, poorer

3. increased 4. hydrogen, anode

B. True False
1. T

C. Objective Questions with one option correct

1. (c) 2. (d) 3. (b) 4. (c) 5. (a)
6. (a) 7. (b) 8. (b) 9. (c) 10. (a)
11. (c) 12. (b) 13. (a) 14. (a) 15. (a)
16. (c)
 Chemistry : Electrochemistry

SUBJECTIVE

1. 1.48  10 9 M 2. 5.128  10 18 mol l 1

3.  0.037 volts 4. 48.69 hours , 1.408 M

5. (ii) 1.27 volt (iii) 2.45  105 J

6. 0.325 volts , 0.151 volts 7. 0.792 volts

8.  0.22 volts 9. 7.6  1012

10. 1.02  104 cm2 11. 2.44  10 12

12. kC = 6.26  107 13. Echange =  1.01355 volts

14. 94.8 % 15. current will decrease with time

16. 7.95  10 5 mol L 1

17. So  96.5 J / K mol , H o  49987 J / mol ,

Solubility of AgCl = 1.476 × 10–5 mol/L

18. 0.05 M 19. 1010

20. (a) Eº = 0.59 Volts, Ksp = 10–10,

(b) K = 1052.8, Moles of Ag+ precipitated = 10–5.

21. 36