REDOX REACTIONS & ELECTROCHEMISTRY

MULTIPLE CHOICE QUESTIONS

  
1. If E Fe2 / Fe is X1, E Fe3 / Fe is X2 then E Fe3 / Fe2 will be
(a) 3X2 2X1 (b) X2 X1
(c) X2 + X1 (d) 2X1 + 3X2
Sol. (a) G3 = G2G1
  
 n 3 FE 3 =  n 2 FE 2 + n 1 FE 1
   
n 2 FE 2  n1FE1 n 2 E 2  n 1 E1
E3

= = = 3X2 2X1.
Fn 3 n3

2. The half cell reactions for the corrosion are

1
2H   O 2  2e  
 H 2 O E° = 1.23 V
2
Fe 2  2e  
 Fe(s) E° = –0.44 V
Find the G° (in kJ) for the overall reaction.
(a) –76 (b) –322
(c) –161 (d) –152
Sol. (b) Fe  Fe+2 + 2e–
1
2H+ + O 2  2e   H 2 O
2
E Cell = 1.23 + 0.44 = 1.67 J
 G = – 2F (1.67)

cell = –322310 J ~ –322 kJ

1
3. Pure water is saturated with pure solid AgCl, a silver
electrode is placed in the solution and the potential is
measured against normal calomel electrode at 25°C. The
experiment is then repeated with a saturated solution of
AgI. If the difference in potential in the two cases is
0177V. What is the ratio of solubilities of AgCl and AgI at
the temperature of the experiment?
(a) 103 (b) 106
(c) 102 (d) 104
Sol. (a) Ag   e  Ag
( from AgCl)

E1 = E°  0.0591log 1
1 C1

Where C1 is the concentration of Ag+ in saturated AgCl

solution.
0.0591 1
E2 = E°– log
1 C2

Where C2 is the concentration of Ag+ in saturated AgI

solution.
E1–E2 = 0.177 = + 0.059 log C1/C2
log C1/C2 = 3
C1/C2 = 103.

4. For the electrochemical cell, M | M+ || X | X, 

E M | M = 0.44 V

and E X | X = 0.33 V. From this data we can deduce that:
(a) M + X  M+ + X is the spontaneous reaction
(b)M+ + X M + X is the spontaneous reaction
2
 (c) Ecell = 0.77 V
(d) Ecell = 0.77 V
Sol. (b)

5. If the pressure of H2 gas is increased from 1 atm to 100 atm

keeping H+ concentration constant at 1 M, the change in
reduction potential of hydrogen half cell at 25°C will be
(a) – 0.059 V (b) – 0.59 V
(c) – 0.0295 V (d) – 0.118 V
Sol. (a) The half-cell reaction for hydrogen half-cell acting as
cathode is
2H+ + 2e H2
PH
 E H  | H  E oH  | H 
0.059
log  2 2
2 2 2 [H ]
0.059 1
E H | H   log  2
2 2 [H ]

Now, when the pressure of H2 gas is changed to 100 atm

without changing [H+], the reduction potential becomes
 E H  | H  
0.059 100
log  2
2
2 [H ]

Change in reduction potential = EH | H

2
– E H | H
2
=
 0.059  100 [H  ]2 
log   2  

2  [H ] 1 

= –0.059 V

3
6. The electrode reactions for charging of a lead storage
battery are:
Pb SO4 + 2e  Pb + SO42–
Pb SO4 + 2H2O  PbO2 + SO42– + 4H+ + 2e
During charging the battery, which of the following
statement is correct.
(a) The conc. of H2SO4 will be unchanged.
(b) The conc. of H2SO4 will be decreased.
(c) The conc. of H2SO4 will be increased.
(d) The pH of the solution will be increased.
Sol. (c) At anode, H+ ion is generated.

7. The E cell of the reaction MnO 4 + Fe2+ + H+ Mn2+ + Fe3+

+ H2O is 0.59 V at 25°C.
The equilibrium constant for the reaction is
(a) 50 (b) 10
(c) 1050 (d) 105
Sol. (c) For the given halfcell reaction
n F E cell = RT ln Keq
5  96500  0.59
= 2.303  8.314  298 log Keq
Keq1050.

4
8. A 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 Z and X
(d) Y will reduce both X and Z
Sol. (a)

9. Pt | H2 (1 atm) | H+ (pH = 2) || H+ (pH = 3) | H2 (1 atm) | Pt

The cell reaction for the given cell is
(a) spontaneous (b) nonspontaneous
(c) equilibrium (d) none is correct
Sol. (b) As the [H+] increases, the reduction potential of
hydrogen electrode increases.
The reduction potential of anode halfcell is greater than
that of cathode halfcell. The emf of the given cell will be
negative. Therefore, the cell reaction is nonspontaneous.

10. Which of the following statement is correct?

If E oCu | Cu = 0.337 V and E Sno | Sn =  0.136 V.
2 2

(a) Cu2+ ions can be reduced by H2(g)

(b) Cu can be oxidized by H+
(c) Sn2+ ions can be reduced by H2
(d) Cu can reduce Sn2+
5
Sol. (a) Standard reduction potential of H+ (E H | H ) = 0 
2


E Cu 2 | Cu = 0.337 V

E Sn 2 | Sn =  0.136 V.

Since, E Cu 2 |Cu is higher than that of H+,

Cu2+ can be reduced by H2. Also E Sn 2 | Sn is lower than that
of H+, Sn2+cannot be reduced by H2.

11. Calculate the standard potential for the reaction

½ O2 + 2H+ + 2e H2O
If E° for the reaction, ½O2 + H2O + 2e 2OH is + 0.4
V
(a) 1.23 V (b) 1.23 V
(c) 0.828 V (d) 8.28 V
2
Sol. (b) 2H + 2OH+ 
2H2O 
G 1 = RT ln  114 
 10 
1
O2 + H2O + 2e 2OH G 2

= 2F  0.4
2

2H+ + 1 O2 + 2e H2O G 3 = 2FE°

2

 E° = 1.23 V.

6
12. The reduction electrode potential of Cu(s) | Cu2+(aq) 1 M,
electrode when the Cu2+ solution is diluted to 10 times at
30°C,
(a) increases by 0.06 V. (b) decreases by 0.03 V.
(c) increases by 0.03 V. (d) remains constant.
Sol. (b) E = 0.06
log 1
= 0.03 V.
2 10

13. The reaction, ½H2(g) + AgCl(s)  H+(aq) + Cl(aq) +

Ag(s), occurs in the galvanic cell:
(a) Ag(s) | AgCl(s) | KCl (solution) || AgNO3(solution) |
Ag(s)
(b) Pt | H2(g) | HCl (solution) || AgNO3(solution) | Ag(s)
(c) Pt | H2(g) | HCl (solution) || AgCl(s) | Ag(s)
(d) Pt | H2(g) | KCl (solution) || AgCl(s) | Ag(s)
Sol. (c) At anode: ½H2(g)  H+(aq.) + e
At cathode: AgCl(s) + e  Ag(s) + Cl(aq.)
½H2(g) + AgCl(s)  H+(aq) + Cl(aq) + Ag(s).

14. 1 Faraday of electricity is passed through molten Al2O3,

molten CuSO4 and molten NaCl taken in three different
electrolytic cells. The amount of Al, Cu and Na deposited
at the cathodes will be in the ratio of
(a)1 mole : 2 mole : 3 mole
(b) 3 mole : 2 mole : 1 mole
(c)1 mole : 1.5 mole : 3 mole

7
 (d) 1.5 mole : 2 mole : 3 mole
1 1
Sol. (c) (Al 2 )  6  e   Al
6 3
1 1
Cu  2  e   Cu
2 2

Na   e   Na
1 1
ratio = : :1 = 2 : 3 : 6 = 1 : 1.5 : 3
3 2

15. When an aqueous solution of lithium chloride is

electrolysed using graphite electrodes
(a) Cl2 is liberated at the anode.
(b) Li is deposited at the cathode.
(c) as the current flows, pH of the solution around the
cathode increases.
(d) as the current flows, pH of the solution around the
cathode decreases.
Sol. (c) Aqueous solution of LiCl contains Li+, H+, Cl and
OH ions. H+ would be preferentially reduced at cathode
while at anode, OH ions would be oxidised, so H2 and O2
gases are liberated at cathode and anode respectively. As
the current flows, H+ ions around the cathode gets
discharged to give H2 gas, so the pH of the solution around
the cathode increases.

8
16. Through molten AlCl3, a charge equal to the charge of 1
mole N3– ion was passed. Volume of Cl2 evolved at anode
when measured at NTP will be
(a) 22.4 lt. (b) 67.2 lt.
(c) 33.6 lt. (d) 11.2 lt.
Sol. (c) Hence, charge passed
= 1.6  10–19 3  6.02  1023
= 1.63  6.02  104 coulomb.
1.6  3  6.02 104
Number of gm equivalent of Cl2 formed = 3
96500
3
Number of moles of Cl2 formed =
2
3
Volume of Cl2 at NTP =  22.4  3  11.2  33.6 lt.
2

17. Zn rod is dipped in 0.1 M ZnSO4 solution at 298K. The

reduction potential of Zn | Zn2+half cell is (given E oZn |Zn = – 2

0.76V)
(a) + 0.73V (b) – 0.73V
(c) – 0.79V (d) + 0.79V
Sol. (c) Zn 2 + 2e  Zn E = E° – 0.0591
log
1
0.1 2 [ Zn 2 ]

= – 0.76 
0.0591
log
1
2 0.1

=  0.79 ( V )

9
18. For the redox reaction MnO 4  C2O24  H   Mn 2  CO 2  H 2O the
correct coefficients of the reactants for the balanced
equation are
MnO 4 C 2O 24 H 

(a) 2 5 16
(b) 16 5 2
(c) 5 16 2
(d) 2 16 5
Sol. (a) 2MnO 41  5C 2 O 42  16H   2Mn 2  10CO 2  8H 2 O

19. In the acidic medium MnO 4 acts as an oxidising agent.

+ 8H+ + 5e Mn2+ + 4H2O
MnO 4

If the [H+] is reduced to half of its original value, the

electrode potential of the half-cell MnO 4 , Mn2+ | Pt (log 2 =
0.3010)
(a) increases by 14.23 mV
(b) decreases by 14.23 mV
(c) increases by 28.46 mV
(d) decreases by 28.46 mV
Sol. (d) The electrode potential of the half-cell MnO 4 , Mn2+ | Pt
is given by
[Mn 2 ]
E MnO |Mn 2 = E oMnO | Mn 2  
0.059
log
4 4 5 [MnO 4 ] [H  ]8

When the concentration of H+ is reduced to half of its initial

value the electrode potential is given by

10
 [Mn 2 ] 2 8
EMnO |Mn 2 = E oMnO | Mn 2  
0.059
log
4 4 5 [MnO 4 ] [H  ]8

The decrease in electrode potential is given by

E MnO | Mn 2   EMnO |Mn 2 =
0.0591
log 2 8 = 0.02846 V.
4 4 5

 Electrode potential decrease, by 28.46 mV.

20. The reaction, (1/2)H2(g) + AgCl(s)  H+(aq) + Cl(aq) +

Ag(s) occurs in the galvanic cell:
(a) Ag | AgCl(s) | KCl (soln.) | AgNO3(soln.) | Ag
(b) Pt | H2(g) | HCl(soln.) | AgNO3(soln.) | Ag
(c) Pt | H2(g) | HCl(soln.) | AgCl(s) | Ag
(d) Pt | H2(g) | KCl(soln.) | AgCl(s) | Ag
Sol. (c) Anode is H2 / H+, cathode is Ag+/Ag.

21. Which of the following equations is a balanced one

(a) 5 BiO  22 H  Mn  5 Bi  7 H O  MnO

3
 2 3
2

4

(b) 5 BiO  14 H  2 Mn  5 Bi  7 H O  2 MnO


3
 2 3
2

4

(c) 2 BiO  4 H  Mn  2 Bi  2 H O  MnO


3
 2 3
2

4

(d) 6 BiO  12 H  3 Mn  6 Bi  6 H O  3 MnO


3
 2 3
2

4

Sol. (b)
5 BiO  14 H  2 Mn  5 Bi  7 H O  2 MnO is the balanced reaction.

3
 2 3
2

4

22. In the equation

4 M  8 CN   2 H 2 O  O 2  4[M (CN )2 ]  4 OH 

Identify the metal M

11
 (a) Copper (b) Iron
(c) Gold (d) Zinc
Sol. (c)
4 Au  8 CN   2 H 2 O  O 2  4 [ Au (CN )2 ]  4 OH  .

INTEGERS TYPE QUESTIONS

23. To find the standard potential of X+3 | X electrode, the

following cell is constituted
X(s) | X3+ (0.0018 M) || Ag+1(0.01 M) | Ag(s)
The emf of this cell is found to be 0.42 volt. Calculate the
standard potential of the half-cell reaction
X+3 + 3e  X.
Express your answer in millivolts. (Given log 2 = 0.3010,
log 3 = 0.4771 and E oAg | Ag = 0.8V) 

Sol. X + 3Ag+ 3 Ag + X+3

0.591 [X 3 ]
Ecell = E 0cell  log
3 [Ag  ]3
0.0591 [0.0018]
0.42 = E 0cell  log
3 [0.01]3

0.42 = E 0cell – 0.064

E 0cell = 0.484 volt
E 0anode  E 0cathode  E 0cell

= [0.80 – .484] = 0.316 V

E 0anode

= 316 millivolt.
12
24. A Daniel cell originally has 1.0 M Zn2+ in the anode half-
cell and 1.0 M Cu2+ in the cathode half-cell. Estimate the
cell potential of the Daniel cell in milli volt after sufficient
ammonia has been added to the cathode compartment to
make the NH3 concentration 2.0 M. Given that
E Zn | Zn = 0.76 V and E Cu | Cu = 0.34 V. Also equilibrium
o o
2 2

constant for the formation of [Cu(NH3)4]2+ is 1  1012.

Sol. Cu2+ + 4NH3 [Cu(NH3)4]2+
[Cu ( NH 3 ) 4 ] 2
Kf = 1  1012 = = 1 .0
[Cu 2 ] [ NH 3 ] 4 x ( 2 .0 ) 4

x = 6.25  1014 M
Note that due to high value of Kf almost all of the Cu2+ ions
are converted to Cu ( NH ) ion. 2
3 4

  0.059 [Cu 2 ]
Now, Ecell = E Zn .| Zn 2  + E Cu 2  | Cu + log10
2 [ Zn 2 ]

0.059  6.25  1014 

= 0.76 + 0.34 + log10  
2  1 

Ecell= 0.71 V = 710 mV.

25. What is standard reduction potential in millivolt for the half

cell Pt | MnO 4 , MnO2?
Given: E oMnO | Mn = 1.51 V 
4
2

o
E MnO
2 | Mn 2 
= 1.225 V.

13
Sol. MnO 4 + 8H+ + 5e– Mn2+ + 4H2O E° = 1.51 V
MnO2 + 4H+ + 2e– Mn2+ + 2H2O E° = 1.225 V.
Subtracting MnO 4 + 4H+ + 3e– MnO2 + 2H2O
E° = ?
5  1.51  2  1.225
E° = = 7.55  2.45 = 1.70 V
3 3
= 1700 millivolt.

26. Consider the following cell.

Cd | Cd(OH)2(s) | NaOH (0.01 M) | H2 (1 atm) | PtEcell =
0.0V at 298 K and E oCd | Cd  0.4V . Calculate solubility


product of Cd(OH)2 at 298 K. Express your answer as the

multiple of 10–17. [Use 10(13.536) = 3.44 × 1013]
Sol. The given cell representation can be reduced to
Cd|Cd++  K SP 
2 
|| H+ (10–12M) | H2(1 atm)| Pt
[OH] 

The cell reaction is

Cd + 2H+ Cd++ + H2
0.0591 [Cd ]PH 2 

Ecell= E ocell  log  2

2  [H ] 

0.0591 [Cd ][ OH ] PH 2 
  2

0 = 0 – (–0.4)  log  2  2 
2  [H ] [OH ] 
0.0591  K SP PH 2 
0 = 0.4 – log 2 
2  Kw 

or log K 0.4  2

SP
2
 13.536
 K  0.0591
w

14
 K SP  1013.536  K 2w = 3.44 × 10+13 × 10–28= 3.44 × 10–15= 344 ×
10–17 = 344

27. In the electrolysis of KI, I2 is formed at the anode by the

reaction;
2I I2 + 2e
After the passage of current of 0.5 ampere for 9650
seconds, I2 formed required 40 ml of 0.1 M Na2S2O3.5H2O
solution in the reaction;
I2 + 2S2 O32  S4 O 62 + 2I
What is the current efficiency?
MV
Sol. Number of moles of hypo =
1000
0.1  40
= = 4  103
1000

 Number of moles of I2 = 2  103

Mass of I2 = 2  103 254 g
itE
w=
96500
i  9650 127
2  103 254 =
96500
= 0.04 ampere
i

Current efficiency
0.04
=  100 = 8%.
0.50

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28. Calculate G° and S° (at 298 K) for the fuelcell
reaction:
2H2 + O2 2H2O E cell 
= 1.23 V, H  (H2O) f

= 285.8 kJ mol1
Sol. G° =  nFE cell
n = number of electrons exchanged = 4, F = 96500

coulomb, E cell = 1.23 V
 G° = (4  96500  1.23) J =  47480 J
= 474.78 kJ
Also, G° = H°  TS°
474.78= (285.8  2)  (298 S°)
(474.78  571.6)
S° = kJ K1
298

=  0.3249 kJ K1
= 324.9 J K1~ 325 JK1.

29. The oxidation state of sulphur in SO 42  is

Sol. (6)

SO 42 

x  2  4  2

30. The charge on cobalt in [Co (CN )6 ]3  is

Sol. (3)
In [Co (CN )6 ]3  complex Co shows + 3 oxidation state.

16