Electrochemical cell:

A device which converts chemical energy into electrical energy or electrical energy into
chemical energy or both is called electrochemical cell.
They are of three types.

1. Galvanic cell or voltaic cell

A device used to convert chemical energy of a spontaneous redox reaction into electrical
energy.
Example
When a Zinc rod is placed in copper sulfate solution then redox reaction begins resulted in
dissolution of Zinc rod & precipitation of copper at bottom while solution becomes hot as
chemical energy is converted into heat energy.

Zn0(s) + Cu2+SO42-(aq)
or

Zn

(s)

2+

+ Cu

Zn2+SO42-(aq) + Cu0(s)
2+

Zn

(aq)

(aq)

+ Cu

-H

(s)

This reaction may be split into two half reactions

Zn0(s)
Zn2+(aq) + 2eOxidation Half reaction

2e- + Cu2+(aq)
Cu0(s)
Reduction Half reaction

So if two separate half cells are set up by placing a Zn rod in Zinc sulfate solution in a
beaker and a copper rod in copper sulfate solution in another beaker while two rods are
connected by a wire through an ammeter and two solutions are connected by a salt bridge
than electrons given out by former half cell will be taken up by latter one hence current will
flow.

Zn0(s)

Zn2+(aq) + 2e-

2e- + Cu2+(aq)

Cu0(s)

A salt bridge is a U-shaped tube containing concentrated solution or solidified solution of

an electrolyte in agar or gelatins matrix e.g. KCl, KNO3, K2SO4, NH4NO3 etc. while both
ends of the U-tube plugged with porous material. Salt bridge allow anionic conductance
from one solution to other without mixing of two solutions so when electrons flow in outer
circuit wire, the inner circuit is completed by flow of anions from one solution to other
through salt bridge. Therefore anions of both half cell solutions & of salt bridge should be
identical.
By convention, the electrode at which oxidation occurs is anode and the electrode where
reduction occur is cathode. Thus Zinc rod serves as anode and copper rod as cathode.
In galvanic cell, electrons are released at anode therefore electrons are in excess on it so
it is ve electrode/pole/terminal while electrons are consumed at cathode therefore
electrons are deficient there so it is +ve electrode/pole/terminal of cell.

As external circuit is closed, following changes take place

Electrons flow from anode to cathode as indicated by ammeter.
In oxidation Half cell, Zinc oxidized into Zn2+ ions so that Zn rod get dissolved & Zn2+
ions concentration increases in solution. To maintain electrical neutrality of solution,
SO42- ions migrate from reduction to oxidation half cell through salt bridge hence
solution becomes concentrate in terms of ZnSO4, in oxidation half cell.
In reduction half cell, Cu2+ ions reduced into copper metal so that copper metal cathode
grow in size & Cu2+ ions concentration decreases in solution. As SO42- anions migrated
to oxidation half cell hence solution becomes diluted in terms of CuSO4, in reduction
half cell.
This type of cell called Daniel cell / gravity cell.
So combination of any two-different electrodes constitutes a galvanic cell. The one with
greater tendency to go into the solution by liberating electrons, acts as the anode while
other one with more tendency to get deposited acts as the cathode e.g. Cu-Ag galvanic
cell.

2. Electrolytic Cell
A device used to convert electrical energy into chemical energy, to drive reaction in nonspontaneous direction i.e decomposition of electrolyte solution through electricity.
Example 1: Electrolysis of acidulated water in an electrolytic cell, using platinum or
stainless steel electrodes, resulted in decomposition of water to yield H2 & O2 gases as
follow
At cathode

4H3O+ + 4e-

At Anode

6H2O

O2(g) + 4H3O+ + 4e-

Net electrolytic reaction

2H2O

2H2(g) + O2(g)

2H2(g) + 4H2O

Example 2: Electrolysis of CuCl2 aqueous solution in electrolytic cell while using inert
electrodes (like platinum/ stainless steel) resulted in decomposition of CuCl2 into copper
metal & chlorine gas so that CuCl2 becomes diluted.

At cathode

Cu2+ + 2e-

Cu

At anode

2Cl-

Cl2 + 2e-

Overall electrolytic reaction

CuCl2

Cu + Cl2

In contrast to galvanic cell, in electrolytic cell reduction takes place at ve electrode and
oxidation at +ve electrodes hence they called as cathode & Anode respectively by
convention.

3. ELECTROPLATING CELL
Its a kind of electrolytic cell in which instead of electrolyte anionic part oxidation at anode,
anodic material itself undergoes oxidation. This alteration done by choosing anodic
material metal which readily undergoes oxidation while using electrolyte, which consist of
same metallic part (cations) as anode and have bulky anionic part to reduce anion mobility.
For example electrolysis of CuSO4 solution while using copper metal as anode resulted in
dissolution of copper anode and deposition of copper at cathode. So theoretically
electrolyte solution concentration remains unchanged in electroplating cell while in
electrolysis cell, electrolyte becomes dilute as process proceeds.

Difference b/w Galvanic cell & Electrolytic cell

GALVANIC CELL
It converts chemical energy into electrical
energy
It drives Redox reaction in spontaneous
direction
Two electrodes may be set up in solution
of the same or different electrolytes
+ve & -ve electrodes serve as cathode &
anode respectively
A salt bridge or a porous membrane
separator is used b/w both electrodes
Free energy supplied by cell reaction
system is extracted to do work on
surrounding i.e. G is -ve

ELECTROLYTIC CELL
It converts electrical energy into chemical
energy
It drives Redox reaction in non
spontaneous direction
Two electrodes are setup in the same
electrolytic solution
+ve & -ve electrodes serve as anode &
cathode respectively
No salt bridge or a porous membrane
separator is used
Free energy is supplied in form of electrical
work done on the system by the
surrounding i.e. G is +ve

Faradays Law of Electrolysis

Cation
Atomic mass

Cu+1
63.5

Cu+2
63.5

Fe+2
56

Fe+3
56

Case-I
When Conc. is
1M
1M
1M
1M
then,
a) amount of metal deposited if 48,250 (96,500/2) coulombs charge i.e. half mole of electron
is passed.
31.7 g

15.8 g

14 g

9.3 g

b) amount of metal deposited if 96,500 coulombs charge i.e one mole of electron is passed.
63.5 g

31.7 g

28 g

18.6 g

Case-II
When Conc. is
2M
2M
2M
2M
then,
a) amount of metal deposited if 48,250 (96,500/2) coulombs charge i.e half mole of electron
is passed.
31.7 g

15.8 g

14 g

9.3 g

b) amount of metal deposited if 96,500 coulombs charge i.e one mole of electron is passed.
63.5 g

31.7 g

28 g

18.6 g

Factors affecting amount of metal deposited, are as follow:

iiiiii-

m
m
m

ivv-

m
m

Q
Atomic mass
1 / Valency of cation
as z

Atomic mass / Valency of cation

z
Concentration of electrolyte

First Law: The amount of given metal deposited at an electrode during electrolysis is
directly proportional to the quantity of electricity (i.e. charge), which passes through the
electrolyte solution".
Second Law: "For a constant amount of electricity, the amount of metal deposited is
directly proportional to their electrochemical equivalent.
m Q
As I = Q / t so Q = I t
m It
m = zIt
If I = 1 Ampere
Then

t = 1 Second

m = z

Electrochemical equivalent (z) is that amount of metal, which deposited by 1 ampere

current passing for 1 second (i.e one coulomb) through its electrolyte.
Faraday : (F)
1 F = Charge on one mole of electron
1 F = Numbers in one mole Charge on an electron
1 F = (6.023 x 1023) (1.602 10-19 C)
1 F = 96,500 coulombs
One gram equivalent is the amount of metal deposited by passing one Faraday i.e
96,500 coulombs charge
One gram Equivalent = 96,500 Electrochemical Equivalent
One gram equivalent weight =

Atomic weight
Valency of metal

One gram equivalent w.t of Ag+ = 108

1

= 108 g

One gram Equivalent w.t of Cu2+ = 63.5

2

31.7 g

One gram Equivalent w.t of Al3+ =

9g

27
3

NUMERICAL
1Q. 0.1978 g of copper is deposited by a current of 0.2 ampere in 50 min.
Calculate electrochemical equivalent of copper.
Data:
m = 0.1978 g

I = 0.2 ampere

t = 50 min 60 = 3,000 sec

z=?

Solution:
m =zIt
z =

m
It

0.1978
0.2 3,000

z = 0.003296 g/coulomb
2Q.

How much current in amperes will be required to deposit 10g of silver from
AgNO3 solution in 30 min.

Data:
I =?
m = 10g
t = 30 min 60 = 1800 sec
Solution:
108g of Ag i.e (1g eq. w.t) is deposited by = 96,500 Coulombs
1g of Ag deposited by = 96,500 Coulombs
108
10g of Ag deposited by = 96,500 10 = 8935.18 coulombs
108
I = Q
t
I = 8935.18 coulombs = 4.96 Ampere
1800 sec

Electrode potential
When a metal or a non-metal comes in contact with its electrolyte solution than two types
of reaction are possible for each case.
Case I:
1.
Metal shows tendency to go into solution as metallic cations by loosing electrons.
M
Mn+ + ne2.
Simultaneously metal ions in solution show tendency to get deposited as metal
atoms by gaining electrons.
Mn+ + neM
Case II:
1.
Non metal shows tendency to go into solution as non metal anion by gaining
electrons
XnX + ne2.
Simultaneously non metal anions in solution show tendency to oxidize into non
metal by loosing electrons.
XnX + neIn both cases, competition exist b/w two reactions lead to dominance of more tend
reaction. This net tendency or potential is called electrode potential.
Standard electrode potential (E0)
The potential (tendency) developed at the interface between electrode and solution to
loose or gain electrons when comes in contact with its electrolyte solution of unit activity at
298 K i.e. 25 oC.
Standard Reduction potential (EoRed)
The tendency of an electrode metal cation to reduce itself by gain of electrons from
electrode metal, developed when electrode comes in contact with its 1 M electrolyte
solution at 25 0C. In case of gas electrode conditions further specified as gas at 1 atm
pressure comes in contact with its 1M electrolyte solution at 250C.
+0.521V

0V
+2e

+e
2H+(1M) | H2(1atm)
Cu+(1M) |Cu
Or The tendency of an electrode (usually non metal) to reduce itself by gain of electrons
to form its anion, developed when this electrode (at 1atm pressure if a gas) comes in
contact with its 1 M electrolyte solution at 25 0C.

+2.87V
+2e

+1.359V

F2(1atm) | 2F (1M)

+2e

Cl2(1atm) | 2Cl-(1M)

+ve sign of E0Red shows that reduction is favorable at that electrode system & vice versa

STANDARD OXIDATION POTENTIAL (EOOxd)

Tendency or potential of a metal to go into solution as metal cations by loosing electrons,
developed when comes in contact with its 1 M electrolyte solution at 25 oC.
+0.23V
-

-2e
2+
Ni | Ni (1M)

+2.295V

-e+
K | K (1M)

Or
Potential of a non metal anion in solution to oxidize into non metal by loosing
electrons, developed when non metal electrode (at 1 atm pressure if a gas) comes in
contact with its 1 M electrolyte solution at 25oC.
-1.359V

-2e

2Cl (1M) | Cl2(1atm)

-1.08V

-2e-

2Br (1M) | Br2(1atm)

+ve sign of Eooxd shows that oxidation is spontaneous at that electrode system & vice
versa.

STANDARD HYDROGEN ELECTRODE SCALE FOR ELECTRODE POTENTIAL

The absolute value of individual electrode potential can not be measured experimentally
b/c no electrode itself can oxidize or reduce until connected with another reference
electrode system to maintain electrical neutrality of system. The reference electrode used
is the Standard Hydrogen Electrode (SHE) in which H2 gas at 1 atm pressure is bubbled
around a platinum electrode in 1M HCl solutions at 25oC. SHE arbitrarily fixed at zero.
Hence resulted numerical emf value of cell is assigned as electrode potential of that
electrode with respect to SHE.
Direction of current flow would determine whether measured potential value is for oxidation
or reduction potential. If subject electrode acts as anode than current would flow away
from that electrodes & resulted value is for oxidation potential and vice versa. Voltmeters
indicator tilled opposite to direction of current flow.
According to convention, all electrode potential value should be reported as reduction
tendency of electrodes i.e reduction potential. Since the reduction half reaction is just the
reverse of oxidation half reaction. Therefore reduction potential is obtained from oxidation
potential by simply changing the sign of value.
Reduction potential

-Oxidation potential

Oxidation potential

-Reduction potential

Electromotive force (EMF) of cell

Net force which motivate electrons flow from one (oxidizing) electrode to other
(reducing) electrode in galvanic cell.
As motivation of electron flow cause by difference of potential b/w both electrodes so it is
difference of reduction potential, which causes the current to flow from low reduction
potential electrode to high reduction potential electrode. Its units are volts & represented
by EMF.

Pushing
Force

Pulling
Force

Weight

A
n
o Oxidation potential e Reduction potential
d Tendency to loose esTendency to gain ese

C
a
t
h
o
d
e

Net force = Pushing force + Pulling force

Ecell = Eoxd of oxidation half reaction + ERed of reduction half reaction
but Eoxd of oxidation half reaction = - ERed of oxidation half reaction
so
Thus

Ecell = ERed of reduction half reaction - ERed of oxidation half reaction

Ecell = EMF

Thus emf of a cell is the driving force of cell reaction which thermodynamically correlated
as
G = -FE
Where
G = Free energy change accompanying in cell reaction
n = Number of electrons transfer per cell reaction
F = Faraday constant = 96,500 coulombs/ mole
E = EMF
If G is ve then cell reaction would be spontaneous & if G is +ve then cell reaction
would be non spontaneous. As n & F are always positive, sign of G now depends upon
EMF. So if EMF is +ve then cell reaction would be feasible and spontaneous but if its ve
then cell reaction would be non spontaneous and would not be feasible.
EMF of galvanic cell when the reactants and products of cell reaction are taken as unit
concentration at 298 K temperature and 1 atmospheric pressure is called standard EMF of
cell.
The EMF of a cell can not be measured accurately by using a voltmeter b/c
1. Voltmeter draw some current from the cell thereby alters the concentration of
electrolyte which cause change in emf of cell.
2. A part of the EMF will be utilized to overcome the internal resistance of the cell during
flow of current.
so potentiometer method is used in which emf of a test is opposed by impressed emf from
an external source of emf, and measurements are made when there is no net flow of
current in the circuit.

ELECTROCHEMICAL SERIES OR EMF SERIES

A series comprises different electrode systems, arranged in descending order of
their standard reduction potential at SHE scale.

Electrochemical series with standard reduction potential of redox systems at 25 0C

Reduction half-reaction
F2 (g) + 2e2FO3 (g) + 2H+ + 2eO2 + H2O
3+
2+
CO + e
CO
+
H2O2 + 2H + 2e
2H2O
4+
3+
Ce + e
Ce (In HClO4 solution)
+
MnO4 + 4H + 3e
MnO2 + 2H2O
+
2HClO + 2H + 2e
Cl2(g) + 2H2O
4+
3+
Ce + e
Ce (in HNO3 solution)
+
2HBrO + 2H + 2eBr2 + 2H2O
+
MnO4 + 8H + 5e
Mn2+ + 4H2O
2BrO3 + 12H+ + 10eBr2 + 6H2O
3+
2+
Mn + e
Mn
4+
Ce + e
Ce3+ (in H2SO4 Solution)
Cl2 + 2e2ClCr2O72- + 14H+ + 6e2Cr3+ + 7H2O
Ce4+ + eCe3+ (in HCl solution)
MnO2 + 4H+ + 2eMn2+ + 2H2O
O2 + 4H+ + 2e2H2O
+
ClO4 + 2H + 2e
ClO3- + H2O
2IO3- + 12H+ + 10eI2 + 6H2O
Br2 (g) + 2e
2Br
+
N2O4 + 2H + 2e
2HNO2
+
NO3 + 3H + 2e
HNO2 + H2O
2+
2+
2Hg + 2e
Hg2
+
2NO3 + 4H + 2e
N2O4 + H2O
+
Ag + e
Ag
2+
Hg2 + 2e
2Hg
3+
Fe + e
Fe2+
O2 + 2H+ + 2eH2O2
+
H3AsO4 + 2H + 2e
HAsO2 + 2H2O
I3 + 2e
3I
I2 + 2e
3I-

E0 cell Reduction half-reaction

+2.87 Cu+ + eCu
3+2.07 Fe(CN)6 + e
Fe(CN)64+1.82 Cu2+ + 2eCu
+1.77 Hg2Cl2 + 2e
2Hg + 2Cl+1.70 AgCl + eAg+ + Cl+1.69 Cu2+ + eCu+
+1.63 Sn4+ + 2eSn2+ (in HCl solution)
+1.60 S + 2H+ + 2eH2S
2+1.60 S4O6 + 2e
2S2O32+1.51 2H+ + 2eH2
2+
+1.50 Pb + 2e
Pb
2+
+1.49 Sn + 2e
Sn
2+
+1.44 Ni + 2e
Ni
2+
+1.359 Co + 2e
Co
3+
+1.33 Cr + e
Cr2+ (in HCl solution)
+1.28 Cd2+ + 2eCd
2+
+1.23 Fe + 2e
Fe
+
+1.229 2CO2 + 2H + 2e
H2C2O4
3+
+1.19 Cr + 3e
Cr
2+
+1.19 Zn + 2e
Zn
2+1.087 SO4 + H2O + 2e
SO32- + 2OH+
+1.07 Mn2+ + 2eMn
3+
+0.94 Al + 3e
Al
+0.907 H2 + 2e
2H+0.80 Mg2+ + 2eMg
+
+0.7994 Na + e
Na
2+
+0.792 Ca + 2e
Ca
2+
+0.771 Sr + 2e
Sr
2+
+0.69 Ba + 2e
Ba
+
+0.56 K + e
K
+
+0.545 Rb + e
Rb
+
+0.536 Li + e
Li

E0 cell
+ 0.521
+0.356
+0.337
+0.2680
+0.2224
+0.153
+0.14
+0.14
+0.09
0.0000
-0.126
-0.140
-0.23
-0.28
-0.38
-0.402
-0.440
-0.49
-0.74
-0.7628
-0.93
-0.190
-1.66
-2.25
-2.37
-2.7
-2.87
-2.89
-2.90
-2.925
-2.93
-3.03

Application of ECS
1. To predict the relative ease of oxidation or reduction of various elements.
In ECS, a positive value indicates reduction tendency and a negative value indicates
oxidation tendency with respect to hydrogen. So a substance (element or ion) with greater
electrode potential values in ECS means it will easily reduce or it will be stronger oxidation
agent or weaker reducing agent & vice versa.
Example # 01 In ECS F2 has +2.87 value and Li+ has 3.03 value, So F2 reduced more
easily compared to Li+ ion which reduced with greater difficultly or
F2 is strong oxidizing agent compared to Li+ ion which is weak oxidizing agent or
F2 oxidize more difficulty compared to Li+ ion which oxidize more feasibly or F2 is weak
reducing agent compared to Li+ ion which is strong reducing agent.
2. To predict the spontaneity of a redox reaction.
A reaction is spontaneous if free energy is decreased in that reaction i.e. G is ve but
G = -FE
where E = EMF
As & F has +ve value
So G is negative only if EMF is positive. Hence reaction is spontaneous if EMF is positive
& vice versa
3. To calculate standard EMF of any electrochemical cell
EMF = EoRed of reduction half cell + Eooxd of oxidation half cell
As Eooxd = -EoRed
EMF = EoRed of reduction half cell - EoRed of oxidation half cell
4. To predict whether a metal reacts with acid to give hydrogen gas or not.
A metal would react with an acid to liberate hydrogen gas if emf of that reaction has +ve
value.
M + H+
M+ + H2
[oxidation half reaction]
M
[Reduction half reaction] H+ + e-

M+ + eH2

E ooxd = x
EoRed = 0

EoRed =

EMF = EoH - EoM

EMF = - EoM
So EMF is only +ve if EoM is ve. Thus all metals laying below hydrogen in ECS can react
with acid to give hydrogen gas. Moreover metal with highly ve value, would have highly
+ve reaction emf thus possesses high reactivity & liberates H2 gas vigorously & vice versa.

5. To predict whether metal is able to replace another metal from its solution.
If a metal Ma is dipped in a solution of another metal Mb then if Ma replaces Mb from
solution then reaction will be
Ma + Mbn+
Ma n+ + Mb
[Oxidation half reaction]
[Reduction half reaction]
So

i)
Ma
ii) Mbn+ + ne-

Man+ + neMb

EMF = EoRed of Mb - EoRed of Ma

Therefore if EoRed of Mb > EoRed of Ma then EMF would have +ve sign and above reaction
would occur feasibly that is lower electrode potential metal Ma would replace high
electrode potential metal Mb.
But if EoRed of Mb < EoRed of Ma then EMF would have ve sign & above reaction would not
feasible that is high electrode potential metal Ma would not replace low electrode potential
metal Mb e.g. Electrode potential value for Ag = +0.79 V, Cu = +0.15 V & Zn = -0.76 V so
Zn can displace Cu2+ from CuSO4 solution and Cu can displace Ag+ from AgNO3 solution.