An electrochemical cell is a device that converts chemical

energy into electrical energy, or vice versa, through

chemical reactions:
Galvanic or voltaic cells: Generate an electric current
from spontaneous chemical reactions.
Electrolytic cells: Use an external voltage to drive non-
spontaneous chemical reactions.
Electrochemical cells are made up of two half-cells, each
containing an electrode and an electrolyte:
Anode: The electrode where oxidation occurs
Cathode: The electrode where reduction takes place
Salt bridge: Connects the two half-cells, allowing ions to
move between them
Electrochemical cells are used in many applications,
including: batteries, fuel cells, metal refining, and
electroplating.
TYPES OF ELECTROCHEMICAL CELLS
The two primary types of electrochemical cells are
1. Galvanic cells (also known as Voltaic cells)
2. Electrolytic cells

Galvanic Cell / Voltaic Cell Electrolytic Cell

Chemical energy is
Electrical energy is
transformed into electrical
transformed into chemical
energy in these
energy in these cells.
electrochemical cells.

An input of energy is required

The redox reactions that take for the redox reactions to
place in these cells are proceed in these cells, i.e. the
spontaneous in nature. reactions are non-
spontaneous.

In these electrochemical
These cells feature a positively
cells, the anode is negatively
charged anode and a
charged and the cathode is
negatively charged cathode.
positively charged.
An electrochemical cell is represented in a manner an
illustrated below:
Zn | Zn2+ || Cu2+ | Cu
by convention, the electrode on which oxidation takes
place is written on the left-hand side and the other
electrode on which reduction takes place is written on
the right-hand side. The electrode of the left-hand side is
written by writing the symbol of the metal first followed
by the symbol of the ion with its concentration in
brackets. The electrode on the right-hand side is written
by first writing the ion along with its concentration in
brackets followed by the symbol of the metal.
Electrochemical Cells are made up of two half-cells, each
consisting of an electrode which is dipped in an
electrolyte. The same electrolyte can be used for both
half cells.
These half cells are connected by a salt bridge which
provides the platform for ionic contact between them
without allowing them to mix with each other. An
example of a salt bridge is a filter paper which is dipped
in a potassium nitrate or sodium chloride solution.
One of the half cells of the electrochemical cell loses
electrons due to oxidation and the other gains electrons
in a reduction process. It can be noted that an
equilibrium reaction occurs in both the half cells, and
once the equilibrium is reached, the net voltage becomes
0 and the cell stops producing electricity.
The tendency of an electrode which is in contact with an
electrolyte to lose or gain electrons is described by its
electrode potential. The values of these potentials can be
used to predict the overall cell potential. Generally, the
electrode potentials are measured with the help of the
standard hydrogen electrode as a reference electrode
(an electrode of known potential).

General convention dictates that the cathode must be

represented on the right-hand side whereas the anode is
represented on the left-hand side while denoting an
electrochemical cell.
 Electrochemical cells generally consist of a
cathode and an anode. The key features of the
cathode and the anode are tabulated below.
A salt-bridge is a U-shaped tube containing concentrated
solution of an inert electrolyte like KCl, KNO3, K2SO4 etc.
An inert electrolyte is one whose ions do not take part in
the redox reaction and also do not react with electrolyte
used. The function of the salt bridge is to allow the
movement of the ions from one solution to the other
without mixing of the two solutions. Thus, whereas the
electrons flow in the outer circuit in the wire, the inner
circuit is completed by the flow of ions from one solution
to the other through the salt bridge moreover, it helps to
maintain the electrical neutrality of the solution of the
two half cells.
The salt bridge's functions include:
Maintaining electrical neutrality:
The salt bridge keeps the solutions in the cell neutrally
charged by allowing positive and negative ions to flow
into the solutions.
Preventing cross-contamination:
The salt bridge minimizes cross-contamination between
the two half-cells.
Stabilizing junction potential:
The salt bridge stabilizes the junction potential between
the solutions in the half-cells.
Acting as an alternative electrical pathway:
The salt bridge links the two half-cells as an alternative to
the primary electrical pathway.
Let us see what would happen if the salt bridge were not
used in the cells : Electrons are given out by the zinc
electrode where they will neutralize some of the Cu2+
ions of the solution. Thus SO4 2- ions will not leave and
the solution will acquire a negative charge. At the same
time Zn 2+ ions produced from zinc plate will enter
ZnSO4 solution. After some time, the flow of electrons
will stop and hence the current stops flowing.
A potential difference develops between the electrode
and the electrolyte which is called electrode potential.
When the concentrations of all the species involved in a
half-cell is unity then the electrode potential is known as
standard electrode potential.
According to IUPAC convention, standard reduction
potentials are now called standard electrode potentials.
In a galvanic cell, the half-cell in which oxidation takes
place is called anode and it has a negative potential with
respect to the solution.
The other half-cell in which reduction takes place is
called cathode and it has a positive potential with respect
to the solution.
Thus, there exists a potential difference between the two
electrodes and as soon as the switch is in the on position
the electrons flow from negative electrode to positive
electrode.
The direction of current flow is opposite to that of
electron flow. The potential difference between the two
electrodes of a galvanic cell is called the cell potential
and is measured in volts.
The cell potential is the difference between the electrode
potentials (reduction potentials) of the cathode and
anode.
It is called the cell electromotive force (emf) of the cell
when no current is drawn through the cell.
An electrochemical cell is based on reaction which can be
split into the two half reactions:

Oxidation half reaction

Reduction half reaction
Standard EMF of the cell:
Where,
Ecell = Electrode Potential of the cell
Ecathode = Electrode Potential of the oxidation half
reaction
Eanode= Electrode Potential of the oxidation half
reaction
According to Nernst Equation, the relation between
concentration of electrode and the standard electrode
potential can be given as:

Ecell = Ecathode – Eanode

The Nernst equation provides the relation between the
cell potential of an electrochemical cell, the standard cell
potential, temperature, and the reaction quotient.
Even under non-standard conditions, the cell potentials
of electrochemical cells can be determined with the help
of the Nernst equation.

Ecell = cell potential of the cell

Eo = cell potential under standard conditions
R = universal gas constant
T = temperature
n = number of electrons transferred in the redox reaction
F = Faraday constant
Q = reaction quotient
Mn+ + ne– → nM

E[Mn+/M] = Eo[Mn+/M] – [2.303RT/nF] log [1/[Mn+]]

Where,
R is the gas constant = 8.314 J/K Mole
T = absolute temperature,
n = number of mole of electron involved,
F = 96487 (≈96500) coulomb/mole = charge carried by
one mole of electrons.
[Mn+] = active mass of the ions. For simplicity, it may be
taken as equal to the molar concentration of the salt.

For measurements carried out 298 K, the Nernst

equation can be expressed as follows:

E = Eo – 0.0592/n( log [1/[Mn+])

Electrolytic cells are used in the electrorefining of many
non-ferrous metals. They are also used in the
electrowinning of these metals.
The production of high-purity lead, zinc, aluminium, and
copper involves the use of electrolytic cells.
Metallic sodium can be extracted from molten sodium
chloride by placing it in an electrolytic cell and passing an
electric current through it.
Many commercially important batteries (such as the
lead-acid battery) are made up of Galvanic cells.
Fuel cells are an important class of electrochemical cells
that serve as a source of clean energy in several remote
locations .
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