Origin of Electrode Potential: If a metal rod or a strip

is dipped in a solution containing its ions, then the

metal has tendency to go into the solution as ions,
conversely the reverse process of deposition of positive
ions on the electrode starts taking place. An equilibrium
is finally reached when rate at which ions are formed is
equal to the rate at which the ions are deposited. The
equilibrium can be represented as;
Mn+(aq) + ne- ⇌ M(s)
According to the modern views, an electrical double of
positive and negative charges is generally formed at the
surface of separation between two phases. At a solid
liquid interphase, this double layer of ions is made up of
a layer of ions, in aqueous solution, which are firmly
held to the solid, and a more diffuse mobile layer,
extending into the solution.

Structure of electrical double layer

The difference of potential between the electrode and

the solution at equilibrium position is called as
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electrode potential or thermodynamic potential. More
precisely, it is the potential difference of the electrical
double layer formed at the contact interface of electrode
metal and the electrolytic solution. It is also called
single electrode potential. It is the measure of the
tendency of an electrode to gain or lose electrons when
it is in contact with its own ions.

Because of the electrical charges, there is a difference of

potential between the dotted line, representing the
separation of fixed and diffuse double layers and the
bulk of the solution is known an electrokinetic potential
or zeta potential, represented by ζ.

Standard electrode potential (E0): The standard

electrode potential is the electrode potential when the
concentration of the solute is 1 moldm-3, the gas
pressures are1 atm and temperature has specified value
(usually 250C).

Electromotive force of a cell: The maximum potential

difference between the electrodes of a voltaic cell is
referred as electromotive force, emf, of a cell, denoted
by Ecell.

Standard emf of a cell: It is the emf of a voltaic cell

operating under standard state conditions (solutes
concentrations 1 mol dm-3, gas pressures 1 atm, and
temperature has a specific value, usually 250C) and
denoted by E0cell.

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Notation for voltaic cell: An electrochemical cell may
be prepared by combining two electrodes of different
types described earlier. Such cells and half cells are
conveniently described by an abbreviated notation
together with appropriate convention so that the
convention will correspond to chemical reaction taking
place in the cell. They can be summarized as follows:
(i) A seat of emf between electrode and electrolyte is
represented by a line, as Ag│Ag+(aq).

(ii) The half-cell written in the sequence electrode

electrolyte represents oxidation, or anode, is always
on the left. If the sequence is electrolyte electrode, or
cathode, is always written on the right.

Ag│Ag+(aq) Ag(s) → Ag+(aq) + e-

Ag, AgCl(s)Cl-(aq) Ag + Cl-(aq) → AgCl(s) +e-

Zn2+(aq)│Zn Zn2+(aq) + 2e- → Zn(s)
(iii) Gas electrodes or oxidation-reduction electrodes
having an inert material such as platinum serves as a
(a) terminal and as an (b) electrode surface on which
half reaction occurs.
Pt, H2(g), H+(aq) ½H2(g) → H+(aq) + e-
Fe3+(aq), Fe2+, Pt Fe3+(aq + e- → Fe2+(aq)

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(iv) A complete cell is written as below:
Zn│Zn2+(aq)│Cu2+(aq)│Cu
Or, Zn, Zn2+(aq)││Cu2+(aq), Cu
Or, Zn, Zn2+(aq) ⁞ Cu2+(aq), Cu
The vertical line in the middle means that two
solutions are in direct contact. Two vertical lines at
that position represents the connection between the
electrodes by a salt bridge, and a dotted single line
shows separation of the electrolytes by a porous
partition.
(iv) The emf of the cell is calculated by subtracting the
electrode potential (reduction) of the left electrode
from the right electrode. An emf will be +ve if there
is a tendency of electron to be driven through the
external circuit from the left the right i.e. oxidation
(release of electron) at left electrode and reduction at
right electrode. If the cell is written such that
reduction is taking place at the left electrode, the emf
will be negative. The emf of the cell
Pt,H2(g)(1atm),HCl(1M)│AgCl(s),Ag is +0.22 volt

But the emf of the same cell of the form

Ag,AgCl(s)│HCl(1M),H2(g)(1atm), Pt is -0.22 volt.
(v) If the emf of the cell has a +ve value the cell
reaction is spontaneous. The cell reaction is
algebraic sum of the reactions at the electrodes.

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Electrode potential and concentration of its ion: The
electrode potential of an electrode is dependent on the
concentration of its ion and temperature. If the
following equilibrium exists at an electrode
M2+(aq) + 2e- ⇋ M(s)
Then the electrode potential (reduction) of the electrode
is given by the Nernst’s equation
RT
E = E0 - nF
ln[M(s)]/[M2+]
RT
E = E0 + nF
ln[M2+] as [M(s)]=1

or, E = E0 + log[M2+]
where, E0- is the standard electrode potential,
R-molar gas constant,
F-Faraday constant, T- temperature in Kelvin
n-number of electron transfer involved in the reaction and
[M2+]–molar concentration of the ion.
At 250C, the value of 2.303RT
F.
is constant and equal to
0.0591, the above equation is can be written as

E = E0 + log[M2+]

The above equation can used to calculate the electrode

potentials of the electrodes at different concentrations of
the ions at 250 C.

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 Figure: Daniel Cell
For the above cell, electrode potential at anode is given
by

E = E0 + ln [Zn2+]

And the electrode potential at the cathode is given by

E = E0 + ln [Cu2+]

So, the emf of the cell is given by

Ecell = ERHE – ELHE

= {E0 Cu2+/Cu + ln [Cu2+]} - {E0 Zn2+/Zn + ln[Zn2+] }

= (E0 Cu2+/Cu - E0 Zn2+/Zn) - RT

nF
ln[Zn2+]/[ Cu2+] …..1

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 = (E0Zn2+/Zn - E0 Cu2+/Cu) - lnQc

Qc-reaction quotient at that time

At 250 C the value of is 0.02568 or value of 2.303RT

F.
is
0.0591
Equation 1 can be used to calculate the emf of cell at
any concentration of the ions at electrodes. If emf of the
cell is known, the value of the reaction quotient or the
feasibility of reaction can be predicted.

*If the emf of the cell is +ve, the reactions at electrodes

will occur spontaneously, oxidation at anode and
reduction at cathode. i.e electron will flow from left
hand electrode to right hand electrode in the external
circuit and current will flow in opposite direction.
*If the emf of the cell is 0.0 V, the reactions at
electrodes are at equilibrium and no current will flow in
circuit.
*If the emf of the cell is -ve, the expected reactions at
electrodes will not occur, but, reverse reactions i.e.
oxidation at right hand electrode and reduction at left
hand electrode will occur spontaneously.
Problem 1: Calculate the emf of a Daniel cell when the
concentrations of Zn2+ and Cu2+ ions are 2.00 and
1.0x10-4 M respectively.

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 RT
Ecell = (E0 Cu2+/Cu - E0 Zn2+/Zn) - nF
ln[Zn2+]/[ Cu2+]

={0.34 - (-0.76)} - ln(2.0/1.0x10-4) V= 0.97 V

Problem 2: Calculate he equilibrium constant at 250 C

between the reaction between zinc metal and acid.
Zn(s) + 2H+(aq)→ Zn2+(aq) +H2(g)
The overall cell potential of above reaction in standard
state is
Zn(s) → Zn2+(aq) + 2e- E0 Cu2+/Cu = -0.7628 V
2H+(aq) + 2e- → H2(g) E0 H+/H2(g) = -0.000 V
_________________________ E0 cell = 0.7628 V
Zn(s) + 2H+(aq)→ Zn2+(aq +H2(g)
0.0={0.000 - (-0.7628)} - lnKc
as Ecell = 0 at equilibrium
lnKc= (2x96485x0.7628)/(8.314x298) = 59.41
Kc=6.3x1025

Battery: A battery is an electrochemical cell, or often a

number of cells connected in series, that can be used as
a source of direct current at a constant voltage.
Although the operation of a battery is similar in
principle to that of the galvanic cells, a battery has the
advantage of being completely self-contained and
requiring no auxiliary components such as salt bridges
is known as battery.

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The dry cell battery: The most common dry cell, that
is, a cell without fluid component, is the Leclanche cell,
used in flashlights and transistor radios. The anode of
the cell consists of a zinc can or container that is in
contact with manganese dioxide (MnO2) and an
electrolyte. The electrolyte consists of ammonium
chloride and zinc chloride is water, to which starch is
added to thicken the solution to a paste-like consistency
so that it is less likely to leak. A carbon rod serves as the
cathode, which is immersed in the electrolyte in the
centre of the cell. The cell reactions are
Anode: Zn(s) → Zn2+(aq) + 2e-
Cathode: 2NH4+(aq) + 2e- → 2NH3(g) + H2(g)
2NH3(g) + 2H2O(l) → 2NH4OH(aq)
H2(g)+2MnO2(s)→Mn2O3(s) + H2O(l)
2NH4+(aq)+H2O(l)+2MnO2(s)→2NH4OH(aq)+Mn2O3(s)

Overall: Zn(s)+2NH4+(aq)+H2O(l)+2MnO2(s)→Zn2+(s)
+2NH4OH(aq)+Mn2O3(s)
Actually, this equation is an oversimplification, because
the reactions that occur in the cell are quite complex.
The voltage produced by a dry cell is about 1.5 V
Brass cap (+ve pole)

Graphite rod

Mixture of MnO2 + powdered carbon

Paste of NH4Cl + starch

Zinc can (–ve pole)

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Alkaline dry cell: It is very similar to the Leclanche
cell, but it has KOH in place of NH4Cl. This cell
performs better under current drain and in cold weather.
The half-reactions are
Zn(s)+2OH-(aq)→ZnO(s)+H2O(l)+2e- (anode)
2MnO2(s)+H2O(l)+2e-→Mn2O3(s)+2OH-(aq) (cathode)
The lead-acid accumulator or the lead storage
battery: The lead storage battery commonly used in
automobiles consists of six identical cells joined
together in series. Each cell consists of two lead plates
dipping into a 30% solution of sulphuric acid both
plates become covered with an insoluble film of lead(II)
sulphate. A direct current of appropriate voltage is
passed through the cell. The processes which take place
are
At positive plate PbSO4(s)+2e- → Pb(s)+SO42-(aq)
At negative plate PbSO4(s)+2H2O(l)→PbO2(s)+4H+(aq)+2e- +SO42-(aq)
___________________________________________
Overall: 2PbSO4(s)+2H2O(l)→Pb(s)+PbO2(s)+2H2SO4(aq)

The plates are now different and therefore have

different potential, so that, when they are connected, an
electric current will between them. When the supplies
electric current, i.e. discharge, the following processes
which take place are
At negative plate Pb(s)+SO42-(aq)→ PbSO4(s)+2e-
At positive plate PbO2(s)+4H+(aq)+SO42-(aq)+2e-→PbSO4(s)+2H2O(l)
_____________________________________________
Overall: Pb(s)+PbO2(s)+2H2SO4(aq)→2PbSO4(s)+2H2O(l)

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When all the PbO2 and Pb have been consumed to
PbSO4, there is no difference between the plates, and
the cell can no longer give a current. It is important to
note that the Pb plate is the positive plate during charge
and the negative plate during discharge. The polarity of
thePbO2 plate is also reversed, from negative during
charge to positive during discharge.

Under normal operating conditions, each cell produces

2V; a total of 12 V from six cells is used to power the
ignition circuit of the automobiles and its other
electrical systems. When the car is in motion, it drives a
generator, which charges the battery. If there is too
much stopping and starting, the battery loses its charge
and become “flat”, until it is recharged by the passage
of a direct current from a transformer.

Electrochemical series or activity series: A table that

lists the elements in order of their ease of losing
electrons during reaction in aqueous solution is known
as electrochemical series or activity series. The
elements at the top of the list are the strongest oxidizing
agents; those at the bottom are the weakest. On the
other hand, the list of the elements arranged in the order
of increasing (becoming more positive) their ion’s
standard electrode potentials (reduction) is known as
electrochemical or activity series.

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 Electrochemical series or activity series
_____________________________________________
Half reaction E0 /V
Li+(aq) + e-→ Li(s) -3.05
K (aq) + e → K(s)
+ -
-2.93
Ba (aq) +2e → Ba(aq)
2+
-2.90
Sr (aq) + 2e → Sr(s)
2+ -
-2.89
Ca (aq) + 2e → Ca(s)
2+ -
-2.87
Na+(aq) + e- → Na(s) -2.71
Mg (aq) + 2e → Mg(s)
2+ -
-2.37
Be (aq) + 2e → Be(s)
2+ -
-1.85
Al (aq) + 3e → Al(s)
3+ -
-1.66
Mn (aq) + 2e → Mn(s)
2+ -
-1.18
H2O(l) + 2e- → H2(g) + 2OH-(aq) -0.83
Zn (aq) + 2e → Zn(s)
2+ -
-0.76
Cr (aq) + 3e → Cr(s)
3+ -
- 0.74
Fe (aq) + 2e → Fe(s)
2+ -
-0.44
Cd (aq) + 2e → Cd(s)
2+ -
-0.40
PbSO4(s) + 2e- → Pb(s) +SO42-(aq) -0.31
Co (aq) + 2e → Co(s)
2+ -
-0.28
Ni (aq) + 2e → CNi(s)
2+ -
-0.25
Sn (aq) + 2e → Sn(s)
2+ -
-0.14
Pb (aq) + 2e → Pb(s)
2+ -
-0.13
2H+(aq) + 2e- → H2(g) 0.00
Sn (aq) + 2e → Sn (aq)
4+ - 2+
0.13
Cu (aq) + 2e → Cu (aq)
2+ - +
0.15
SO4 (aq) + 4H (aq) + 2e → SO2(g) +2H2O(l)
2- + -
0.20
AgCl(s) + e → Ag(s) + Cl (aq)
- -
0.22
Cu2+(aq) + 2e- → Cu(s) 0.34
O2(g) +2H2O(l)+ 4e → OH (aq)
- -
0.40
I2(s) + 2e → 2I (aq)
- -
0.53
MnO4 (aq) + 2H2O(l) + 4e → 4OH (aq)
- - -
0.59
O2(g) +2H (aq)+ 2e → H2O2(aq)
+ -
0.68
Fe3+(aq) + e- → Fe2+(aq) 0.77
Ag (aq) + e → Ag(s)
+ -
0.80
Hg2 (aq) + 2e → 2Hg(l)
2+ -
0.85
2Hg (aq) + 2e → Hg2 (aq)
2+ - 2+
0.92

12
NO3-(aq) + 4H+(aq) + 3e- → NO(g) + 2H2O(l) 0.96
Br2(aq) + 2e- → 2Br-(aq) 1.07
O2(g) + 4H+(aq) + 4e- → 2H2O(l) 1.23
MnO2(s) + 4H+(aq) +2e-→Mn2+(aq)+ 2H2O(l) 1.23
Cr2O72-(aq) + 14H+ 6e-→2Cr3+(aq) + 7H2O(l) 1.33
Cl2(g) + 2e- → 2Cl-(aq) 1.36
Au3+(aq) + 3e- → Au(s) 1.50
MnO4-aq)+8H+(aq)+ 5e→Mn2+(aq) +4H2O(l) 1.51
Ce4+(aq) + e- → Ce3+(aq) 1.61
PbO2(s)+4H (aq)+SO4 (aq)+2e →PbSO4(s)+2H2O(l)
+ 2- -
1.70
H2O2(aq) + 2H (aq) + 2e → 2H2O(l)
+ -
1.77
Co (aq) + e → Co (aq)
3+ - 2+
1.82
O3(g) + 2H (aq) + 2e → O2(g) + H2O(l)
+ -
2.07
F2(g) + 2e- → 2F-(aq) 2.78
______________________________________________

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