20 Electrochemical Cells

Chapter 2

ELECTROCHEMICAL CELLS
Redox Reaction :- The reaction in which oxidation and reduction takes place simultaneously.
Gain of 2 electron (Reduction)

Ex. :- Zn + CuSO4 ZnSO4 + Cu

Loss of 2 electron (Oxidation)

Oxidation :- The loss of electron or increase in oxidation number of a substance
Reduction :- The gain of electron or decrease in oxidation number of a substance.
Oxidising Agent or Oxidant :- The substance which oxidise others and itself gets reduced.
Reducing Agent or Reductant :- The substance which reduces others and itself get oxidised.
Oxidation Number (ON):- It is the hypothetical charge that an atom would have if all bonds to atoms of
different elements were 100% ionic.
It represents the number of electrons lost (if O.N is positive) and gain (if O.N is negative) by an atom of that
element in the compound.
Rules to Determine Oxidation Number :-
1. All atomic and molecular species have oxidation number of zero
Ex. : Mg, H 2 , N 2 , Ca, H
2. All element of group one (except H) in a compound has ON of +1
3. All element of group two in a compound have ON of +2.
4. Al has +3 oxidation number in a compound.
5. For an ion, charge number is equal to oxidation number
Ex. : Fe3 , ON  3
Mg 2  , ON  2
CO32 , ON of a anion is –2
6. Flourine has oxidation number of –1
7. Hydrogen will always be +1 except in metal hydrides like NaH, MgH2.
8. Oxygen has ON of –2 except in peroxide O 22  (ON  1) , superoxide O 2 (ON  ½) and
OF2 (ON  2) .
Ex. : Cr2 O 72  MnO 4
2x  7x( 2)  2 x  4( 2)  1
2x  12 x  7
x  6
Electrochemical Cells 21

Electro Chemical Cells

Galvanic Cells Electrolytic Cells

(Chemical Energy  Electrical Energy) (Electrical Energy  Chemical Energy)
Galvanic Cell :-
e e

Anode Cathode
Salt bridge
(Zn) (Cu)

ZnSO4 CuSO4
(1M) (1M)

 Zn 2  aq   2e
Anode (Oxidation) : Zn(s) 

Cathode (Reduction) : Cu 2  aq   2e 

 Cu  s 
Net Reaction : Zn  s   Cu 2 (aq)  Zn 2 (aq)  Cu
Salt Bridge : It is a U-shaped tube containing a solution of an inert electrolyte such as KCl, KNO3 or
NH4NO3.
Characteristics : (i) Mobilities of ions should be same
(ii) Ions should not get oxidised or reduced during the process.
Function : (i) Maintain the flow of current
(ii) Maintain the electrical neutrality of anodic and cathodic compartment
Potential difference develops between electrodes and the electrolyte is called electrode potential.
When half cells are connected by a wire, the difference in the reduction potential of cathode and the reduction
potential of anode is called cell potential.
E cell  E rcathode  E ranode
When pressure is 1 bar, temperature is 298K and the concentration of solution is 1M, the cell potential is called
standard cell potential  E 0cell 

E 0cell  E r0(cathode)  E 0r( anode )

E 0red  O  A  E 0red  R  A 
Reduction Potential : Tendency to reduce. Higher the reduction potential, more easily the species will reduced
Ex.: E 0Ag  |Ag  0.80V 0
E Cu 2
|Cu
 0.34V 0
E Zn 2
|Zn
 0.76V

Reduction Tendency : Ag  Cu  Zn
Oxidation Potential : Tendency to oxidise. Lower the reduction potential, more easily the species will oxidise.
Oxidation Tendency : Zn  Cu  Ag
Strength of Oxidizing Agent :- Higher the reduction potential, strongest the oxidizing agent.
O.A. : Ag  Cu  Zn .
Strength of Reducing Agent :- Lower the reduction potential, strongest the reducing agent
R.A :- Zn  Cu  Ag .
 22 Electrochemical Cells

Note :- E 0red   E 0oxid M   e   M  E 0red 

M  M   e  E 0oxid 
Problem: In which of the following CuSO4 can be stored
(a) Zn pot (b) Ag pot
(c) Fe pot (Eº = –0.44) (d) Al pot (–1.66 v)
0 0
Soln. CuSO4 can be stored in Ag pot as E Ag  |Ag  E Cu 2 |Cu .
Correct option is (b)

Problem: Given that I 2  2e   2I  E 0  0.54 V

Br2  2e  2Br  E 0  1.69 V
Predict which of the following is true
(a) I ions will be able to reduce bromine (b) Br  ions will be able to reduce iodine
(c) Iodine will be able to reduce bromine (d) Bromine will be able to reduce iodide ions
Soln. Since reduction potential of Br2 | Br is greater than reduction potential of I 2 | I  , so I will reduce Br2 .


Correct option is (a)

Problem: E 0A / A  0.3 V E B0  / B  0.7 V E C0  / C  0.7 V

The correct statement is
(a) B can reduce both A and C (b) C can oxidise both A and B
(c) A can oxidise C and reduced B (d) A can oxidise both B and C
Soln. Order of reductional potential :- C  A  B
 order of strength reducting agent :- C  A  B
So, C can reduce both A and B
B can oxidise both A and C
A can oxidise C but will reduce B
Correct option is (c)
Problem: A 19th century iron bridge is protected from corrosion by connecting it to a block of metal (sacritificial
anode), which is replaced annually. The corrosion of iron, represented by the chemical equation :
2Fe  s   2H 2O     O 2  g   2Fe  OH  2 [TIFR-2011]
Which of the following metals is best suited as sacrificial anode ?
(a) Ag : Ag   e  
 Ag  s  , E 0  0.80 V
(b) Cd : Cd 2  2e  
 Cd  s  , E 0  0.40 V
(c) Cu : Cu 2  2e  
 Cu  s  , E 0  0.34 V
(d) Mg : Mg 2  2e    Mg  s  , E 0  2.36 V
Soln. In rusting oxidation of iron takes place. Sacrificial anode is a metal which can act as anode inplace of iron and
itself get oxidised and iron gets protected.
Metal with highest oxidation potential is the most suitable metal for sacrificial anode.
Since Magnesium has lowest reduction potential or highest oxidation potential. So, Mg will be used as sacrifical
anode
Correct option is (d)
Types of Half Cess :-
1. Metal-Metal ion Half Cell :- It consist of a metal rod dipped in a solution of metal ion
Representation :- M n  |M
Electrochemical Cells 23

Mn+

If act as cathode :- M n   ne  M(s)

If act as anode :- M(s)  M n  (aq)  ne 
2. Gas-Electrode :- It consist of a solution containing ions of gas species. In solution, Pt electrode is dipped
on which gas was passed over from outside source.
(i) Hydrogen electrode :- Representation :- H  H 2 Pt
In this, hydrogen gas is passed over a platinum electrode which is dipped in HCl solution
  1
If act as cathode :- H  e  H 2 (g)
2 H2 gas
1  
If act as anode :- H 2  H  e
2
E0red  0 Convention
(ii) Chlorine Electrode :- Representation :- Pt Cl 2 (g) Cl
Pt
In this, Cl2 is passed over a Pt electrode which is dipped in HCl solution
1
If act as cathode :- Cl2  e   Cl 
2 Cl2

 1 
If act as anode :- Cl  Cl 2  e
2

3 Metal-Metal in soluble salt-anion half cell :- Pt

It consist of metal electrode coated with the insoluble salt of metal dipped in a solution containing on ion
common to the anion of metal-salt.
(i) Cl–|AgCl|Ag Half Cell :-
If act as cathode :- Ag(s)
AgCl(s)  Ag  (aq)  Cl (aq) AgCl(s)
Ag   e   Ag
Net Re action :  AgCl(s)  e   Ag  Cl (aq) KCl(aq)

If act as anode:-
Ag(s)  Ag  (aq)  e 
Ag  (aq)  Cl (aq)  AgCl(s)
Net Reaction:- Ag(s)  Cl  (aq)  AgCl  e

(ii) Calomel Electrode :- Representation :- Cl  | Hg 2 Cl 2 | Hg | Pt

24 Electrochemical Cells

If act as Cathode :-
Hg 22   2e   2Hg
Hg 2 Cl2  Hg 22   2Cl 
Net Reaction:- Hg 2Cl2  2e   2Hg  2Cl 
If act as Anode :- Pt
Hg2Cl2
2Hg  Hg 22   2e
Hg
Hg 22  2Cl  Hg 2 Cl2
Net Reaction:- 2Hg  2Cl  Hg 2C 2  2e 

4. Oxidation-Reduction Half Cell (Redox Half Cell)

In this, solution contain metal in more than one oxidation state. This half cell is possible for those metal only
which shows more than one oxidation state. Pt is used as electrode.
Ex:- Fe 2  , Fe3 | Pt
Acting as Cathode :- Fe3  e   Fe 2 
2+ 3+
Acting as Anode :- Fe 2   Fe3  e  Fe , Fe

Pt
Cell Representation :-
Anode || Cathode
In general,
Pt Metal Metal Ion Ion Metal Metal Pt
Salt
(Wherever or insoluble or or insoluble or (Wherever
Bridge
is used) Gas Salt Solution Solution Salt Gas is used)
(i) Salt bridge is represented by || (double dash)
(ii) Single dash ( | ) is used to seperate different phases
(iii) Comma ( , ) is used to seperate ions in solution
Ex:- (i) Zn(s)  Cu 2  (aq)  Zn 2 (aq)  Cu(s)
Anode :- Zn(s)  Zn 2  (aq)  2e
Cathode :- Cu 2   2e   Cu(s)

Cell Representation :- Zn(s) Zn 2  (aq) Cu 2  (aq) Cu(s)

3
(ii) Al(s)  3H  (aq)  Al3 (aq)  H 2 (g)
2
Anode :- Al(s)  Al3 (aq)  3e 
3
Cathode :- 3H (aq)  3e   H 2 (g)
2

Cell Representation :- Al(s) Al3(aq) H  (aq) H 2 (g) Pt

(iii) 2Fe2  (aq)  Cu 2  (aq)  2Fe3 (aq)  Cu(s)

Anode :- 2Fe2  (aq)  2Fe3 (aq)  2e
Cathode :- Cu 2  (aq)  2e   Cu(s)
Electrochemical Cells 25

Cell Representation :- Pt Fe3 , Fe 2  Cu 2  (aq) Cu(s)

(iv) AgCl(s)  Ag  (aq)  Cl (aq)
Cathode
Ag(s) + AgCl(s) Ag+(aq) + Cl–(aq)

Anode

Cell Representation :- Ag(s) Ag  (aq) Cl (aq) AgCl(s) Ag(s)

3 3 
(v) Fe(s)  Cl2 (g)  Fe (aq)  3Cl (aq)
2
Cell Representation :- Fe Fe3 (aq) Cl C 2 (g) Pt
(vi) AgCl(s)  I (aq)  AgI(s)  Cl (aq)
Oxidation

Ag(s) + AgCl(s) + I–(aq) AgI(s) + Cl– + Ag(s)

Reduction

Ag AgI I  (aq) Cl (aq) AgCl Ag

Electric Potential () :- The work done to bring a unit charge from infinity to the point of interest is called
electric potential.
w =  (Unit charge)
A 
w

q

 (Unit charge)
B 
 
A B
w
 A  B  Electric potential difference
q
Escaping Tendency of Charged Particle :-
Let ‘dn’ amount of specie of charge number zi is taken from infinity to the point A.
Let electric potential at A is 
w

q
w  q
or dw   z i F dn .... (1)
Let chemical potential at infinity be i and at point A be  i
26 Electrochemical Cells

Thermodynamically, dG   i dn  i dn .... (2)

Equating (1) and (2)
 i  i   Zi F
 i  i   Zi F
i  chemical potential at infinity (  0)
  Electric potential at point A
zi = Charge number
F = 1 faraday
 i  i   Zi F
  
electrochemical chemical electrical
potential contribution contribution

i will have same value for a species having same composition

(i) For metals :- zi  0
  i  i
(ii) For electron :- zi = –1
 i  i  F
If    ve then  i  or escaping tendency of e  
If    ve then  i  or escaping tendency of e 
 If two half cells having +ve and –ve potential will be connected by a wire then electron will move from –ve
potential electrode to +ve potential electrode.
(higher oxidation potential)  (lower oxidation potential)
So, E cell  E oxid(anode)  E oxid(cathode)
  E red(anode)  E red(cathode)
E cell  E red(cathode)  E red(anode)

Table: Standard Electrode (Reduction) Potentials, T = 25°C:

Half-cell reaction Eº/V Half-cell representation

Li   e  Li –3.045 Li  | Li

K   e  K –2.925 K | K

Na   e  Na –2.714 Na  | Na

Mg 2  2e  Mg –2.37 Mg 2 | Mg

H 2  2e   H 2  2OH  –2.25 H  | H 2 | Pt

Al3  3e   Al –1.66 Al3 | Al

2H 2O  2e   H 2  2OH  –0.828 OH  | H 2 | Pt

Zn 2  2e   Zn –0.763 Zn 2 | Zn
Electrochemical Cells 27

2 2
Cd  NH3 4  2e   Cd  4NH 3 –0.61 Cd  NH3 4 , NH3 | Cd

2CO 2  2H   2e   H 2 C2 O 4 –0.49 H 2C 2O 4 , H  | CO 2 | Pt

Fe 2  2e   Fe –0.44 Fe2 | Fe

Cr3  e  Cr 2 –0.41 Cr 3 , Cr 2 | Pt

Cd 2  2e  Cd –0.40 Cd 2 | Cd
 
Ag  CN  2  e   Ag  2CN  –0.31 Ag  CN 2 , CN  | Ag

Cu  OH  2  2e  Cu  2OH –0.224 OH , Cu  OH 2 | Cu

AgI  e   Ag  I –0.151 I | AgI | Ag

Sn 2  2e   Sn –0.136 Sn 2 | Sn

Pb 2  2e  Pb –0.126 Pb 2 | Pb
2 2
Cu  NH3  4  2e   Cu  4NH 3 –0.12 Cu  NH3 4 , NH 3 | Cu

Fe3  3e  Fe –0.036 Fe3 | Fe

2H   2e   H 2 0.000 H  | H 2 | Pt

AgBr  e  Ag  Br  0.095 Br  | AgBr | Ag

Cu 2  e   Cu  0.153 Cu 2 , Cu  | Pt

Sn 4  2e   Sn 2 0.15 Sn 4 , Sn 2 | Pt

AgCl  e  Ag  Cl 0.222 Cl | AgCl | Ag

Hg 2Cl2  2e  2Hg  2Cl  0.267 Cl | Hg 2Cl2 | Hg  Pt 

Cu 2  2e  Cu 0.337 Cu 2 | Cu
 
Ag  NH 3  2  e   Ag  2NH 3 0.373 Ag  NH3 2 , NH3 | Ag

O 2  g   2H 2O  4e  4OH  0.401 OH  | O2 | Pt

Cu   e   Cu 0.521 Cu  | Cu
1
I2  e   I 0.535 I2 , I  | Pt
2

Fe3  e   Fe 2 0.771 Fe3 , Fe 2 | Pt

1 2 
Hg 2  e  Hg 0.789 Hg 22 | Hg  Pt 
2
Ag   e  Ag 0.799 Ag  | Ag

Br2     2e   2Br  1.086 Br  , Br2 | Pt

28 Electrochemical Cells

O 2  4H   4e  2H 2O 1.229 H  | O2 | Pt

Cr2O72  14H   6e  1.33 Cr2O72 , Cr 3 , H  | Pt

 2Cr 3  7H 2O

1
Cl2  g   e   Cl  1.359 Cl | Cl2 | Pt
2

Ce 4  e   Ce3
1.44 Ce 4 , Ce3 | Pt
1 mol dm3H2SO4 
Au 3  3e   Au 1.455 Au 3 | Au

MnO 4  8H   5e   Mn 2  4H 2O 1.51 MnO 4 , Mn 2 , H  | Pt

Co3  e   Co 2 1.82 Co3 , Co 2 | Pt

Some Important Relations :
(i) Between Ecell and ΔG
w = charge × potential
w = q.Ecell
Work carried out is non-expansion. therefore magnitude of work will be equal to change in gibbs free
energy
w  G  q  E cell
for ‘n’ moles of electron
q  n  Charge of 1 mol of electron
 n  (Zi F)
q   nF
G   nFE cell
or G 0   nFE 0cell
(ii) Relation between ΔS and Ecell

   G  
   S
 T P

or  nFEcell   S
T
 E cell 
or S  nF  T 
 P
 E 
 T   Temperature coefficient of cell.
 P
(iii) Relation between ΔH and Ecell
G  H  TS
Electrochemical Cells 29

 F 
nFE  H  nFT  
 T  P
 E 
H  nFT    nFE
 T  P
  E  
H  nF  T    E
  T  P 
Problem: At 20ºC, the standard EMF of a certain cell is +0.2699 V, and at 30ºC it is +0.2669V. What can
you say about the standard entropy of this reaction ? Assume that the standard H 0 and S0 are independent
of temperature. [TIFR-2012]
(a) S0  0 (b) S0   ve (c) S0   ve (d) Not enough information is given

 E 
Soln. S  nF  
 T  P

 0.2669  0.2699 
S  nF  
 30  20 
 S  0
Correct option is (c)
Problem: The emf of the cell Cd, CdCl2 . 2.5 H2O saturated || AgCl(s), Ag in which the cell reaction is
Cd(s)  2AgCl(s)  aq 
 CdCl2  5 / 2H 2 O(sat)  2Ag(s) is 0.6753 volt at 25°C and 0.6915 volt at 0°C.
Calculate the free energy change ( G ), Enthalpy change ( H ) and entropy change ( S ) for the cell reaction
at 25°C.
Soln: Free energy (G) = –nEF  –2  96500  0.6753  –130.33 kJ
H  E 
We have, E=–  T 
2F  T  P

 E   0.6195V – 0.6753V  –1
     –0.00065 V K
  T P  0  25 K 

H
0.6735   298(–0.00065)
2  96500
H  –167717 Joule  –167.72 kJ

G – H
And S  –  123.8 JK –1
T
Problem: Show that the potentials are additive for the process in which half reactions are added to yield an
overall reaction but they are not additive when added to yield a third half reaction?

 M1n   n1e
M1  – G1  n1E1 F
M 2 n 2  n 2e 
 M2 – G 2  n 2 E 2 F
Soln:
M1  M 2 n 2 
 M1 n1  M 2 +  n1  n 2  e – G 3  n 3E 3 F
 30 Electrochemical Cells

G 3  G1  G 2
n 3E3 F  n1E1 F  n 2 E 2 F
n1E1  n 2 E 2
E3 
n3
0
If n1  n 2  n 3 , then E cell are not additives .
 If n1  n 2  n 3 then E 3  E1  E 2

When two half reactions E0 are added to give an overall reaction, and the number of moles of electrons
involved in each half reaction and the overall reaction is same.
Problem: Calculate E0 for the process
Cu   e   Cu
making use of the following E0 values:
(i) Cu 2   e  Cu  E10  0.153 V (ii) Cu 2   2e   Cu E 02  0.341 V
Soln. As different number of electrons are involved in reactions (i) and (ii). So, simple substraction will not give E 0cell .
0
So, we will use G based method to calculate E 0cell .
Cu 2   e  Cu  G10   nE10 F  1 0.153  F J mol1
Cu 2   2e   Cu G 02   nE 02 F  2  0.341 F J mol 1
The reaction Cu   e   Cu is obtained by subtracting reaction (i) from reaction (ii).
G 0  G 02  G10

G 0   2  0.341 F   1 0.153  F  J mol 1

1.F.E 0   0.153  0.682  F J mol 1
1.F.E 0  0.529  F J mol 1
It follows that, E0 = 0.529 V.
(iv) Nernst Equation :-
G  G 0  RT ln Q
aA  bB  cC  dD
c d

G  G 0
 RT ln
 C  D 
a b
 A   B
nFE nFE 0 RT
0
nFE   nFE  RT ln Q ;   ln Q
nF  nF  nF
RT 2.303 RT
E  E0  ln Q ; E  E 0  log Q
nF nF
At 298 K,
0.0591
E  E0  log Q
n
Electrochemical Cells 31

Problem: For a cell constructed with a Cu  s  | Cu 2 (aq) anode and Ag  | Ag  s  cathode at 25.0ºC,

Calculate the cell potential at 25.0ºC under non-standard conditions:  Cu 2   0.300 M and

 Ag    0.0500 M .
(a) 0.44 V (b) 0.41 V (c) 0.40 V (d) 0.34 V [TIFR-2010]
Soln. Cell reaction :- Cu  s   2Ag   aq  
 Cu 2  aq   2Ag  s 

0.0591
0
 Cu 2  
EE  log 2
2  Ag  

0.0591 0.300
  0.8  0.34   log 2
2  0.05 
 0.46  0.061
Ecell  0.398
Correct option is (c)
Application of Nernst Equation
0
(i) Relation between Ecell and K(equilibrium constant) :-
According to Nernst equation for reaction aA  bB  cC  dD
0.0591
E  E0  log Q
n
At equilibrium, Q  K and E  0
0.0591
E0  log K
n
Problem: The corrosion of iron in contact with an acidic aqueous solution undergoes the following reaction
Fe  s   2H   aq   Fe 2  aq   H 2  g  (1)
in the anaerobic condition, and the following reaction
2Fe  s   O2  aq   4H   aq   Fe2  aq   2H 2O    (2)
in the aerobic condition. during the corrosion, Fe (II) ions are formed in both conditions. If the water is polluted
with Cr(IV), the following reaction may take place.
7H   aq   3Fe 2  aq   HCrO 4  aq   3Fe3  aq   Cr 3  aq   4H 2O    (3)
Reaction (3) be broken down to the following redox half-reactions :
3Fe3  3e   3Fe2  aq  E 0  0.77 V (4)

7H   aq   HCrO 4  aq   3e   Cr 3  aq   4H 2O    E 0  1.38 V (5)

The standard potentials of these reactions are with respect to the normal hydrogen electrode. What would be
the approximate value of the equilibrium constant of reaction 3 at 298K ? [TIFR-2012]
(a) 1011 (b) 1031 (c) 10 31 (d) 10 11
0.0591
Soln. E0  log K
n
 32 Electrochemical Cells

0.0591
1.38  0.77   log K
3
log K  30.96  K  1030.96
Correct option is (b)
Problem: Calculate the equilibrium constant K for the process
1
H 2 +Fe3+  H+ + Fe2+
2 
Soln. The reactions would have been written as
1
H   e  H 2 E0  0
2
Fe3  e   Fe 2 E 0  0.771V
And E0 = 0.771V. In this case n = 1 and
0.771
0.771  0.0257 n K or n K=  30.01
0.0257
And therefore, K  1.1 1013
Problem: Calculate the equilibrium constant for the reaction.

Fe2  Ce 4 
 Fe 3  Ce3

Given: ECe4 /Ce3  1.44 V and E Fe3 /Fe2  0.68 V

0.059
Soln: Ecell  log10 K c
2
Ecell  1.44 – 0.68  0.76 V
0.76
log10 K c   12.8814
0.059
K c  7.6 × 1012

(ii) Calculation of Solubility Pr oduct (K sp)

Let take an example of AgCl
AgCl(s)  Ag  (aq)  Cl (aq)
Reduction (Cathode)
Ag(s) + AgCl(s) Ag+(aq) + Cl–(aq) + Ag(s)

Oxidation (Anode)
For sparingly soluble salt, at equilibrium K  K sp
2.303RT
E 0cell  log K sp
nF
2.303 RT
E 0Cl AgCl Ag  E Ag
0

|Ag
 log K sp
nF
0 0 2.303 RT
In general, E X MX M  E M  |M  log K sp
nF
0 0 0.0591
At 298 K, E X MX M  E M  |M  log K sp
n
Electrochemical Cells 33
Problem: Calculate the solubility product of AgBr in water at 25°C from the cell
Ag|Ag+ Br– (satd. soln) | AgBr (s), Ag
The standard potentials are E AgBr,Ag  0.071V; E °Ag + /Ag = 0.799V..
Soln. The electrode reactions are:
R.H.E. Ag Br ( s)  e –  Ag ( s) + Br – ( aq) : E R  0.0071V

L.H.E.: Ag(s)  Ag + ( aq)  e – EL  0.799V

Hence, for the overall reaction: AgBr(s)  Ag  (aq)  Br – ( aq),

E  = E R – E L  –0.728V
0.0591

1

log Ag    Br – 
  
 eqlib
 0.0591 log K sp

E 0.728
log K sp  – , Hence K sp  4.81  10 –13
0.0591 0.0591
Problem: The EMF of the cell:
Ag| AgCl in 0.1 M KCl || Sat. NH4NO3 || 0.1 M AgNO3|Ag
is 0.45 volt at 25°C. Calculate (i) the solubility product and (ii) the solubility of AgCl. 0.1 M KCl is 85%
dissociated and 0.1 M AgNO3 is 82% dissociated.
Soln. Here the salt bridge has NH4NO3 . Since at 25°C, 0.1 M AgNO3 is 82 per cent dissociated, hence, the Ag+ ion
concentration (c2 ) on the AgNO3 side = 0.1 × 82/100 = 0.082 mol dm–3.
Let c1 be the concentration of Ag+ ions on the AgCl side due to the solubility of AgCl. Then, assuming that
activity coefficients are each equal to unity, the EMF of the cell is given by
0.0591 c
E log 2 (at 25°C)
n c1
Substituting the value of E = 0.45 V, n = 1 and c2 = 0.082 mol dm–3, we get
0.082 mol dm –3
0.45 V = 0.0591 V log
c1
Hence, c1 = 2.008 × 10–9 mol dm–3
Since at 25°C, 0.1 M KCl is 85 per cent dissociated, hence the Cl– ion concentration is given by
0.1  85
[Cl – ] =  0.085 mol dm –3
100
 K sp of AgCl = [Ag+] [Cl–] = 2.008 × 10–9 mol dm–3 × 0.085 mol dm–3
= 1.7068 × 10–10 mol2 dm–6
 Solubility of AgCl = Solubility product of AgCl
= 1.7068 × 10 –10 mol2 dm –6 = 1.308 × 10 –5 mol dm –3
= 1.308 × 10–5 mol dm–3 × 143.5 g mol–1 = 1.875 × 10–3 g dm–3

Problem: The EMF of cell Ag | AgI(s)|0.05 M KI || 0.05 M AgNO3 | Ag is 0.0788 V. Calculate solubility
product of AgI.

0.059 [Ag  ]RHS 0.059 [0.05]

Ecell  log10 ; 0.788  log

1 [Ag ]LHS 1 [Ag  ]LHS
Soln: [Ag  ]LHS  2.203  10 –15
K sp of AgI  [Ag  ] [I – ]  [2.203  10 –15 ] [0.05]  1.10 ×10 –16
34 Electrochemical Cells

(iii) To Calculate pH of Solution

Consider hydrogen electrode,
1
H  e  H 2
2
1/2

E H |H  E 0

0.0591
log
PH2  
H  |H 2
2
n  H  
If PH 2  1 bar then,
1
E H |H  0  0.0591log
2
 H  


E H |H  0.0591  log  H  
2

E H |H  0.0591 pH
2

 Quinhydrone Electrode :- Q, QH 2 , H  | Au
O OH

+ 2H+ + 2e–

O OH

Q  2H   2e   QH 2
Quinone Hydroquinone
O H O

Quinhydrone is slightly soluble in water releasing quinone and hydroquinone in the

O H O

same amount.
Q  2H   2e   QH 2

E  E0 
0.0591
log
QH 2 
2
2 Q H  
0.0591
E  E0 
2

 log  H  
2
 Q  QH  2

E  E0  0.0591 pH
E 0Q,QH H  |Au
 0.6996 V
2,

Problem: The cell pontential for the following electrochemical system at 25ºC is: [TIFR-2013]
Al  s  | Al3  0.01 M  || Fe2  0.1 M  | Fe  s 
(a) 1.23 V (b) 1.21 V (c) 1.22 V (d) –2.10 V
3 
Given : Standard reduction potential of Al  3e  Al is  1.66 V at 25º C
Electrochemical Cells 35

Standard reduction potential of Fe 2   2e  Fe is  0.44 V at 25º C

Soln. Net cell reaction :- 2Al  s   3Fe2  aq  
 2Al3  aq   3Fe  s 
2
0 0.0591  Al3 
E  Ecell  log 3
6  Fe 2  

  0.44   1.66   
0.0591
log
102 
3
6 101 
0.0591
E  1.22  log101
6
0.0591
E  1.22   1.229  1.23 V
6
Correct option is (a)
Problem: According to the Nernst equation, the potential of an electrode changes by 59.2 mV whenever the
ratio of the oxidized and the reduced species changes by a factor of 10 at 25ºC. What would be the corresponding
change in the electrode potential if the experiment is carried out at 30ºC ? [TIFR-2015]
(a) 59.2 mV (b) 71.0 mV (c) 60.2 mV (d) None of the above
Soln. M n   ne 
M
At 298 K,

E1  E 0 
0.0591
log
 Reduced 
n Oxidised 
On changing the ratio by factor 10

E 2  E0 
0.0591
log10
 Reduced 
n  Oxidised 

 E0 
0.0591
log
 Reduced   0.0591 log10
n  Oxidation  n

0.0591
E 2  E1 
n
59.1
or E 2  E1  mV
n
The case taken in the problem has n = 1
E 2  E1  59.1 mV
Correct option is (c)
Problem: The standard redox potential of water oxidation to dioxygen is –1.23 V, [TIFR-2012]
 
2H 2 O  O 2  4H  4e
The redox potential of the same reaction at pH = 7 would be :
(a) -0.41 V (b) -1 V (c) -0.82 V (d) -1.64 V
 
Soln. 2H 2 O 
 O 2  4H  4e E  1.23 V
 36 Electrochemical Cells

0.0591 4
E  E0  log  H  
n
0.0591
E  E0 
4

 log  H  
4

E  E0  0.0591 pH
At pH = 7
E  E 0   0.0591 7   1.23   0.0591 7 
E  0.82 V
Correct option is (c)
Problem: FAD is a redox-active molecule which takes part in many important biological reactions. The redox
potential of FAD at pH = 7.0 is given below [TIFR-2014]
 FADH 2
FAD  2H   2e  
E FADH 2 / FAD  0.180 V
Calculate the redox potential when the media is acidified to pH 0
(a) 0 V (b) 0.24 V (c) 0.12 V (d) none of the above
Soln.  FADH 2
FAD  2H   2e  
0.0591 1
E  E0  log 2
2  H  

0.0591
E  E0 
2

 log  H  
2

E  E0  0.0591 pH
At pH = 7
E  E 0  0.0591 7  E 0  0.4137
E0  0.180  0.4137  0.2337 V
At pH = 0
E  E0  0.2337 V
Correct option is (b)
Pr oblem: Chemical oxidation of water to produce O2 gas is an energy demanding reaction, done routinely by
plants using the process called photosynthesis. By how many eV will it be uphill if the water oxidation reaction
be carried out at pH = 0 versus at pH = 7.0 ? [TIFR-2016]
(a) 0.41 eV (b) –1.6 eV
(c) –0.41 eV (d) cannot be calculated based on the data given.
 O 2  4H   4e 
Soln. Oxidation of water :- 2H 2 O 
0.0591 4
E  E0  log  H  
4
E  E0  0.0591 pH
At pH = 0
E1  E 0
Electrochemical Cells 37
At pH = 7
E 2  E 0  0.0591 7
E 2  E1  0.4137
E 2  E1  0.4137 V
By definition, 1eV is the amount of energy gained or lost by an electron moving across an electric potential
difference of 1 volt
 1 volt corresponds to 1 eV
So, 0.4137 V corresponds to 0.4137 eV
Correct option is (a)

Problem: Given the following E0 values involving both a one electron and a two electron process,
Fe 3  e   Fe 2 E 0  0.771 V
I2  2e  2I  E 0  0.536 V
Find E 0cell for the overall Reaction
2Fe3  2I  2Fe 2  I 2
Soln. 2Fe3  2e   2Fe 2 ... (1)
I2  2e   2I  ... (2)
As net cell reaction is obtained by substraction of equation (2) from (1) and also both equation (1) and (2) have
same number of electrons involved.
So, E 0  0.771  0.536  0.235 V

Problem: If E1 is standard electrode potential for Fe/Fe+2 and E2 for Fe+2/Fe+3 and E3 for Fe/Fe+3. Derive
a relation between E10 , E 02 and E 30 .
Soln:  Fe 2  2e
Fe  – G1  2E1 F ... (1)

Fe2 
 Fe 3  e – G2  1E2 F …(2)

 Fe 3  3e
Fe  – G3  2E3 F …(3)
Susbstracting equation (1) from (3)
Fe2 
 Fe3  e – G 2  G1 – G 3 …(4)

E2 F  3E 3F – 2E1 F

2E1  E 2
E3 
3
3E3  2E1  E 2

Problem: Calculate the emf of the cell,

Co | Co2+ || Ni2+ | Ni
If the concentrations are
(a) [Ni2+] = 1.0 m and [Co2+] = 0.10 m
(b) [Ni2+] = 0.010 m and [Co2+] = 1.0 m
 
Given that, E Ni 2
/ Ni
 –0.257 V and ECo 2
/Co
 –0.280 V
 38 Electrochemical Cells

Soln. The cell reaction is

Co + Ni 2  Co 2  Ni
Half cell reactions are
Ni 2   2e –  Ni E  –0.257 V
Co 2  2e –  Ni E   –0.280 V
The standard emf (E°) is thus –0.257 – (–0.280) = 0.023 V, and n = 2. The cell emf at the first concentrations
specified (a) is

0.0257 [Co 2 ]
E  0.023 – ln
2 [Ni 2 ]
0.0257
 0.023 – ln 0.10  0.023  0.030  0.053 V
2

0.0257 1.0
In (b), E  0.023 – 2
ln
0.010
 0.023 – 0.059  –0.036 V
We see that the cell operates in opposite directions in the two cases.
Problem: At 25°C, the free energy of formation of H2O(l) is – 56700 cal mol–1 with that of its ionisation to (H+
+ OH–) is 19050 cal mol–1. What is the reversible emf of the cell at 25°C?
H 2 1 atm  | H  || O 2  g 1 atm  | OH 

1
Soln: H 2  O2 
 H 2O G1  56700 cal/mol
2
 H   OH 
H 2O  G 2  19050 cal/mol
Addition of above two reactions gives, net cell reaction.
1
 H   OH 
H 2  O 2 
2
G  –56700  19050  –37650 cal mol –1  –158130 Joule mol –1
 G  –nEF
G 158130
 E   0.819 V
nF 2  96500
Problem: A zinc electrode is dipped in a 0.1 M solution of ZnSO4 at 25°C. Assuming that salt is dissociated

to 20% at this dilution. Calculate the electrode potential. E Zn 2 /Zn  –0.76V
Soln:  Zn 2  2e
Zn 

0.1  20
Concentation of [Zn 2 ]  M
100
0.059
E Zn/Zn 2  E0 2 – log[Zn  ]
Zn /Zn 2
0.059 0.1  20
 (–0.76) – log
2 100
0.059 1
 0.76 – log  0.81V
2 50
Electrochemical Cells 39
Problem: Calculate the emf of the following cell at 25°C
Pt | Br– (0.01 M ) | Br 2 (1 atm) || H+ (0.03 M) | H2 (1 atm) | Pt

Given : EBr –  1.08 V E
2 /Br

Soln. Cell reaction, 2Br – + 2H 

 Br2 + H 2

E cell  E RHS – E LHS [  E Hydrogen = 0]

= 0 – 1.08 V = – 1.08 V
0.059 PBr2  PH2
Ecell  Ecell – log
2 [Br – ]2 [H  ]2

0.059 1
 –1.08 – log  –1.08 – 0.208  –1.288V
2 (0.03) (0.01) 2
2

Problem: Calculate the emf of cell

Pt | H 2 1 atm  | CH 3COOH  0.1 M  || NH 4OH  0.01 M  | H 2 1 atm  | Pt
Ka for CH3COOH = 1.8 × 10–5, Kb for NH4OH = 1.8 × 10–5
Soln: At L.H.S.  CH3COO –  H
CH3COOH 

Ka
[H ]  C  C  K a C  1.8  10 –5  0.1  1.34  10 –3 mol litre –1
C

At R.H.S.  NH 4  OH
NH 4 OH 

Kb
[OH – ]  C  C  K b C  1.8  10 –5  0.01  0.42  10 –3 mol litre–1
C

[H  ] [OH – ]  10 –14
10 –14
[H  ]   2.359  10 –11 mol litre –1
–3
0.42  10
Now, for cell,
1
At LHE  H  e –
H 2 
2
1
At RHE H   e 
 H2
2
 0.059 [H  ]LHE
Ecell  Ecell – log
1 [H  ]RHE
0.059 1.34  10 –3
– log  – 0.457 volt
1 2.35  10 –3
2 
Problem: For the cell Mg(s) | Mg(aq) || Ag (aq) | Ag(s), calculate the equilibrium constant at 25°C and maximum
work that can be obtained during operation of cell.
Given : EMg/Mg 2  2.37V and EAg /Ag  0.80V

Soln. Mg  2Ag  
 Mg 2  2Ag

E0cell  E0Mg/Mg2  E Ag
0

/Ag
 2.37  0.80  3.17 V

 Wmax  G  nEF  2  3.17  96500  6.11 105 Joule  6.11× 102 kJ
40 Electrochemical Cells

ELECTROLYTIC CELLS :- The cell in which non spontaneous chemical reaction is carried out using
electrical energy.
Anode :- Oxidation (positive terminal)
Cathode :- Reduction (negative terminal)
1. Electrolysis of Molten NaCl :-

Pt Pt

Molten
+
Na + Cl
– NaCl

Cathode Reduction :- Na   e   Na
1
Anode :- Cl  Cl 2  e 
2
1
Net Reaction :- Na   Cl   Na  Cl 2
2
2. Electrolysis of Aqueous NaCl :-

Anode Cathode
(Pt) (Pt)

Na+,Cl–,H+,OH–

Possible Reactions at cathode :- Na   e   Na

1
H 2O  e H 2  OH 
2
The reaction observed is reduction of water due to high reduction potential.
1
Possible Reactions at anode :- Cl  Cl 2  e 
2
2H 2 O  O 2  4H   4e 
Reaction observed is oxidation of Cl– due to high over potential for oxidation of water even though oxidation
potential of water is higher than oxidation potential of Cl–.
Over Potential / Over Voltage :- It is the difference between the potential at which gas is actually evolved
and the calculate value of potential.
Over potential :- Eactual  E calculated
Value of overpotential depends on
(i) Nature of ion
(ii) Nature of electrode
In the above process, pH increases due to formation of NaOH as by product.