ELECTROCHEMISTRY

Electrochemical cells

Electrochemical cells are classified into:

 Galvanic cells or Voltaic cells

 Electrolytic Cell
 Concentration Cell
 Fuel Cell

An Electrochemical cell is a device in which chemical energy is converted into electrical energy or
vice versa by a spontaneous redox reaction.
Oxidation-Reduction reactions are an important class of chemical reactions.
In Oxidation: A species loses one or more electrons resulting in an increase in the oxidation number.
M  Mn+ + ne-
In Reduction: A species gains one or more electrons resulting in a decrease in the oxidation number.
Mn+ +ne-  M
A reduction process is always accompanied by an oxidation process since electrons can be lost by a
species only when there is another species to receive them. Redox reactions form the basis of
electrochemical cells. An electrochemical cell consists of two electrodes which when connected by a
metallic wire produces electric current as a result of a spontaneous redox reaction.
Each electrode usually consists of a metal in contact with a solution of its own ions. Since the cell is a
combination of two electrodes, each electrode is referred to as a single electrode half cell. A potential
called the electrode potential arises at the electrode in contact with its ionic solution. The difference
between the potentials of the two half cells constitute an electromotive force (emf) of the cell.

Ecell = Ecathode - Eanode

Single electrode potential of an electrode is defined as the tendency of an electrode to undergo reduction with
respect to standard hydrogen electrode.

Nernst Equation

Single electrode potential(E),change in free energy( G)and the concentration,Mn+ are related by
Nernst equation.According to thermodynamics,the decrease in free energy(- G)represents the
maximum amount of work that can be obtained from a chemical reaction.

- G=Wmax---------------(1)

The work performed by an electrochemical cell depends on the number coulombs of electricity that
flow and the energy available per coulomb.
energe available
Work = number of coulombs x
coulomb
The number of coulombs is the product of number of moles (n) of electrons involed in the cell
reaction and the faraday(F).

Number of coulombs=nF

Energy available per coulomb is the cell potential E,since volt is equal to energy per coulomb.The
potential is maximum when the work derived from the cell is maximum.

Thus,

Wmax=nxFxE -------------(2)

-∆ G= nFE-----------------(3)

Under standard conditions

ΔGO=-nFE0-------------(4)
Where E0 is a constant called the standard electrode potential.

For the reaction,

Mn+ + ne M

the equilibrium constant Kc is related to change in free energy by the Vant Hoff equation,

G= G0 + RT ln Kc
[𝑀]
K c= Therefore,
[𝑀𝑛+ ]

[𝑀]
G= G0 + RT ln [𝑀𝑛+ ]

=∆G0+RTln[M ]-RTln[Mn+]

Substituting from Eqs.3&4 for G and G0,

- nFE = -nFE0 + RTln[M]-RTln[Mn+]

Dividing throughout by -nF,

−nFE −nFE0 RTln[M] RTln[Mn+ ]

= + -
−nF −nF −nF −nF

Under standard conditions M=1.Hence the above equation becomes

RT
 E = E0 + ln [Mn+] --------------------(5)
nF
Where E = electrode potential; E0 = standard electrode potential;Substituting the values of R =
Universal Gas Constant [8.314J/K/mol]; T = temperature in Kelvin [298K]; F = Faraday
Constant [96500C/mol]; n=number of electrons involved.
 0.0591
 E = E0 + log[Mn+]
n

This is the Nernst Equation for the Single Electrode Potential.

Nernst Equation for Cell Potential

0.0591 [species at cathode]

Ecell = E0 + log
n [species at anode]

Nernst Equation for Daniel Cell:

Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)

0.0591 [Cu2+ ]
Ecell = E0 + log
2 [Zn2+ ]

REFERENCE ELECTRODES

Reference electrodes are the electrodes with reference to those, electrode potential of any electrode
can be measured. Standard hydrogen electrode is the primary reference electrodes as the electrode
potential value of other electrodes are assigned with respect to it.

Secondary reference electrodes

Secondary reference electrodes are those whose potential is known with respect to SHE. They are
commonly used to determine electrode potentials of other electrodes. Examples – glass electrode,
Ag/AgCl electrode, Calomel Electrode.

Calomel Electrode

It is a metal-metal salt ion electrode.

Construction-

1) The calomel electrode consists of a solid Mercurous chloride in contact with mercury
 placed at the bottom of the long glass tube.
2) Mercurous chloride [Hg2Cl2] and the mercury paste is placed over mercury; the remaining
part of the tube is filled with KCl solution.
3) A platinum wire is dipped in mercury; it is used for external electrical contact.
4) The calomel electrode may act as anode or cathode depending on the nature of the other
electrode.
5) The electrode is represented as-
Hg| Hg2Cl2 (s)| Cl-
If it acts as anode-

2Hg + 2Cl- Hg2Cl2 + 2e-

If it acts as cathode-

Hg2Cl2 + 2e- 2Hg + 2Cl-

The net reversible electrode reaction is

Hg2Cl2(s)+ 2e- 2Hg (l)+ 2Cl-

The potential developed from calomel electrode depends on the concentration of KCl solution.
2.303 RT
E = E0– log[Cl-]2
nF

2.303 RT
E = E0 – log[Cl-]
F

At 298K,

E= E0 – 0.0591 log [Cl-]

The electrode potential is decided by the concentration of chloride ions and the electrode is
reversible with chloride ions.

For saturated KCl  0.241 V ; For 1MKCl 0.280 V

For 0.1M KCl  0.334 V

Applications-

 Used as a reference electrode for the determination of pH.

 It is used in potentiometric titrations.
Determination of single electrode potential:
The test electrode (e.g.,Zn/Zn2+)is coupled with a saturated calomel electrode.
Zn(s)/Zn2+//Cl-/Hg2Cl2(s)/Hg(l)
The emf of the so formed cell is determined experimentally by potentiometric method.
 Then Ecell=Ecathode-Eanode
=Ecal-EZn
=0.2422-EZn
EZn=0.2422-Ecell
Under standard conditions EoZn=0.2422-E0cell

Ag / AgCl electrode

Ag / AgCl electrode is also a metal-metal salt ion electrode. Silver and its sparingly soluble salt
silver chloride are in contact with a solution of Chloride ions.

Construction

 It is prepared by coating thin layer AgCl electronically on to a silver wire.

 A small sheet or wire of platinum is first coated with silver by electrolysis of sodium
argentocyanide solution.
 The silver is then partly converted into silver chloride by making it an anode in KCl
solution and passing a current of low density for 30 minutes.
 The electrode when placed in a solution of KCl with 1 to 2 drops of 1 M silver nitrate
develops potential.
 Potential of 0.1N KCl is 0.29V
1N KCl is 0.223V
Saturated KCl is 0.199V

Cell representation –

Ag / AgCl / Cl-

When it acts as Anode:- Ag(s) + Cl- AgCl + e-

When it acts as Cathode:- AgCl(s) + e- Ag(s) + Cl-

The half cell reaction is

 AgCl(s) + e- Ag(s) + Cl-

Applying Nernst equation,

2.303RT
E = E0 – log[Cl-]
nF

E= E0 – 0.0591 log[Cl-]

Applications:-

 It is used along with glass electrode to find pH of a solution.

 It is non-toxic compared to calomel electrode and inexpensive.
 It is stable and can detect voltages to 1mV.
 Used to determine the uniformity of potential distribution in ships hulls & underground
pipe lines.

ION- SELECTIVE ELECTRODES - These electrodes have the ability to respond to specific ions and
develop a potential in the mixture and ignoring the other ion. The potential developed at the
electrode is a function of the concentration of that ion in the solution.

GLASS ELECTRODE

Principal - When two solutions of different pH are separated by a thin glass membrane, a potential is
developed and this potential is proportional to the pH value.

Glass Electrode

Construction:

 It consist of a long glass tube with a thin glass membrane bulb at the bottom which is made up
of a special type of corning glass(Na2SiO3).
 The corning glass has low melting point and high electrical conductivity.
 The bulb is filled with 0.1M HCl and is inserted with a Ag|AgCl electrode in it. It is also used
for external contact.
  1M HCl is taken in a beaker and the electrode is immersed inside it. They cell is represented as:

Due to the difference in the concentration of ions and the pH a potential is developed at the
membrane- [Ej] junction potential or boundary potential. At first we calculate the junction potential
and then finally the total cell potential.

At equilibrium-

Na+ (glass) + H+(aq)  H+ (glass) + Na+ (aq)

By Nernst equation-
2.303RT C
Ej = log C1
nF 2

2.303RT 2.303RT
Ej = logC1 - log C2
nF nF

At 298 K (250C),
0.0591 0.0591
E= log[C1 ]- log [C2]
n n

0.0591
If [C2] is kept constant, - log [C2] =K
n

0.0591
Ej= log C1 + K
n

Thus total potential EG = Ej + Ereference+Easy(Since Ag/AgCl/Cl- electrode is present within the glass
electrode)
0.0591
EG = log[C1 ] + K + Ereference+Easy Easy -Asymmetric potential arises due to the difference in
n
responses in responses of the inner and outer surface of the glass bulb to changes in H+ ion activity.

[K + Ereference+Easy] = E0G
0.0591
EG = E0G + log[C1 ]
n

0.0591
EG = E0G + n
log [H+] pH = -log [H+]

as n = 1 for H+
 (E0G −EG )
EG = E0G – 0.0591 pH [pH = ]
0.0591

Determination of pH using glass calomel electrodes:

To determine the pH of a given solution, the glass electrode is dipped in a given solution whose pH
needs to be determined.

Hg|Hg2Cl2|Cl- / solution of unknown pH / Glass /Ag|AgCl|Cl-

The glass electrode is coupled with calomel electrode and dipped in the solution whose pH is
determined. Calomel acts as anode and glass acts as cathode.

By general expression-

Ecell = Ecathode - Eanode

Ecell = EG - Ecalomel

Ecell = E0G – 0.0591 pH - Ecalomel

Therefore-

E0 G −Ecell−Ecalomel
pH = 0.0591

(Since, Esat. calomel=0.24V)

Advantages of glass electrodes:

1) Glass electrode can be used in the presence of oxidising and reducing agents.
2) Electrode does not get poisoned.
3) It is simple to operate and is used in industries, agricultural labs, etc.
4) Accurate results are obtained between pH range 1-9. By using special glass electrode pH 1-14
can be measured.
Disadvantage

1) Because of high resistance of glass, simple potentiometers cannot be used. It requires

sensitive electronic potentiometers for emf measurement.
2) The electrode can be used up to a pH 13 but becomes sensitive to Na+ ions above pH 9
resulting in an alkaline error.

Applications of ion selective electrodes

- It is used to find the concentrations of electrolyte solution at anodes and cathodes.

- To measure the level of CO2 in blood sample.

Electrolyte Concentration Cells

It is an electronic cell in which both anode and cathode are made up of the same metal in contact with
same electrolytes but varying concentrations.

Construction-

Two copper electrodes are dipped in copper sulphate solution of different concentrations. The Cu
electrode which is in contact with dilute solution acts as anode and that with concentrated solution
acts as cathode, and the two solutions are connected through a salt bridge.

The flow of electrons takes place from dilute solution to concentrated solution, such a cell is called
concentration cell with transference.

At Anode:-

Cu(s)  Cu+2(aq) [M1] + 2e-

At Cathode:-

Cu2+ (aq) [M2] + 2e-  Cu(s)

Net cell reaction:-

Cu2+(aq)[M2] Cu2+ (aq)[M1]

Concentration cell is represented as-

Cu(s) | Cu2+ [M1] || Cu2+ [M2] | Cu(s)

Applying Nernst equation-

Ecell = Ecathode - Eanode

0.0591
 Eanode = E0 + log[M1]
n

0.0591
 Ecathode = E0 + log[M2]
n

0.0591 0.0591
Ecell = [E0 + log[M2] – (E0 + log[M1])]
n n

0.0591 [M2 ]
Ecell= log
n [M1 ]

By the above equation

 If [M1] = [M2] , emf of the cell is zero (Ecell = 0)

 If [M2] > [M1], emf is positive

[M2]
 If [M1] is large, Ecell is large.

Remember these equations to solve problems-

1) -∆G = nFE
2) Ecell = Ecathode - Eanode
0.0591
3) Ecell = E0 + log [Mn+]
𝑛
0.0591 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
4) Ecell = E0 + log
𝑛 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
0.0591 [𝑆𝑝𝑒𝑐𝑖𝑒𝑠 𝑎𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒]
5) Ecell = E0 + log
𝑛 [𝑆𝑝𝑒𝑐𝑖𝑒𝑠 𝑎𝑡 𝐴𝑛𝑜𝑑𝑒]

Problem: 1.The concentration cell tin/tin ion (0.024M)//tin ion(0.064M)/tin develops a potential of
0.0126V at 250C.Calculate the valency of tin.
0.0591 [M2 ]
Ecell= log
n [M1 ]
 0.0591 [M2 ]
n= log
Ecell [M1 ]

0.0591 0.064
n= 0.0126 log 0.024

=1.998=2

Problem: 2.Two copper rods placed in copper sulphate solutions of equal concentrations are
connected to form a concentration cell

a)What is cell potential?

b)Calculate the cell potential if one of the solutions is diluted to1/5th of its original concentration.
0.0591 [M2 ]
a) Ecell= log
n [M1 ]

Given M1=M2,Hence cell potential=0

b)Assume M2=1M then M1=1/5M

0.0591 [M2 ]
Ecell= log
n [M1 ]

0.0591 1
Ecell= log 1/5
2

0.0591
= log 5
2

=0.02955X0.699=0.0206V

Problem:3 A concentration cell is constructed by dipping copper rods in 0.001M and 0.1M CuSO4
solutions.Calculate the emf of the cell at 298K.

Solution:

The cell is represented as,Cu(s)/Cu2+(0.001M)//Cu2+(0.1M)/Cu(s)

At the anode, Cu→Cu2++2e-

At the cathode, Cu2++2e-→ Cu

0.0591 𝑀2
Ecell = log
𝑛 𝑀1

0.𝑂591 0.1
= log 0.001
2

0.𝑂591
= log100
2

= 0.0591V