UNIT 3 : ELECTROCHEMISTRY

Electrochemistry deals with relationship between electrical energy and chemical energy
and their inter-conversion.
Electrochemical cell is a device in which chemical energy is converted into electrical
energy

Electron flow

Anode Cathode

The electrode at which oxidation occurs is called anode and at which reduction occurs is
called cathode.
Salt bridge
It is inverted U like tube containing saturated solution of some electrolyte like KCl,KNO3,
NH4NO3 with agar-agar jelly or gelatine and connects the anode and cathodce in an
electrochemical cell.
Functions of salt bridge:-
 It allows the flow of current by completing the inner circuit.
 It maintains electrical neutrality in both the half cells.

Cell representation:
A cell with the following chemical reaction:

may be represented as

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Electrode potential: - The potential difference set up between the metal and the solution
of its ions is known as electrode potential
Standard electrode potential is the electrode potential of a metal in contact with it’s
ions when the concentration of ions is 1 molar at 1 bar pressure and 298K.It may be
standard reduction potential or standard oxidation potential.
EMF of the cell: - It is defined as the potential difference between the two terminals of
the cell when either no or very little current is drawn from it.

Standard Hydrogen electrode (SHE) OR Normal Hydrogen Electrode (NHE)

H2(g) 2H+ +2e

if SHE acts as anode
+
2H +2e H2(g)
if SHE acts as cathode

Any half cell whose electrode potential is

to be determined is connected to this &
e.m.f measured so is called electrode
potential of that electrode. Presentation
of the cell having SHE and a copper
electrode:
This is a half cell having zero electrode
potential. Electrode potential of any
element is determined in relative term of
it.

Nernst equation:
This equation is used to measure the electrode potential of any half cell at any
concentration with respect to SHE.

The concentration of a solid is unity, so the equation becomes

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Relationship between equilibrium constant and standard electrode potential

Relationship between standard Gibbs free energy and standard electrode

potential
Relationship between standard Gibbs free energy and equilibrium constant

Metallic and Electrolytic Conductance

Metallic or electronic conductance: It isdue to flow of electrons.
Electrolyte or ionic conductance:–It is due to the movement of ions when an electrolyte
decomposes in a solvent.
Metallic conductance depend upon
i) The nature & structure of metal.
ii) The no. of valence electrons per atom.
iii) Temperature ( decreases with increasing temperature.)

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Ionic Conductivity depends upon-
i) The nature of electrolyte & solvent.
ii) size of ion & solvation.
iii) concentration of electrolyte.
iv) temperature ( increases with increasing temperature.)

Molar conductivity

Variation of conductivity and molar

conductivity with concentration:
conductivity always decreases while
Molar conductivity increases with
decrease in concentration for both weak
and strong electrolytes.

Limiting Molar conductivity: When

concentration approaches zero, molar
conductivity is called Limiting molar
conductivity.

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Kohlrauschlaw of independent migration of ions: It states that limiting molar
conductivity of an electrolyte can be represented as the sum of the individual contributions
of the anion and cation of the electrolyte.
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Thus, if  Na+ and  Cl are limiting molar conductivity of the sodium and chloride ions
respectively, then the limiting molar conductivity for sodium chloride is given by the
equation:

Applications of Kohlrausch law: This law is used to measure the limiting molar
conductivity degree of dissociation and dissociation constant of weak electrolytes.

Electrolytic cell In this cell electric energy is used to carry non spontaneous chemical
reaction. An electrochemical cell works as electrolytic cell if external voltage supplied is
more than the emf of the cell.
Faraday’s Laws of Electrolysis
(i) First Law: The amount of chemical reaction occurs at any electrode during electrolysis
proportional to the quantity of electricity passed through the electrolyte (solution or melt).
M = Zit (M=Mass of substance obtained at electrode, i = current in Ampere, t= time in
seconds)
(ii) Second Law: The amounts of different substances liberated by the same quantity of
electricity passing through the electrolytic solution are proportional to their chemical
equivalent weights. (Atomic Mass of Metal ÷ Number of electrons required to reduce the
cation).
Batteries: Any battery (actually it may have one or more than one cell connected in
series) or cell that we use as a source of electrical energy is basically a galvanic cell.
There are mainly two types of batteries.

Primary batteries In the primary batteries, the reaction occurs only once and after use
over a period of time battery becomes dead and cannot be reused
Dry cell or Leclanche cell:

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Mercury or Button cell:

T
The cell potential is 1.35 V and remains constant during its life as the overall reaction
does not involve any ion in solution whose concentration can change during its lifetime.

Secondary Batteries: A secondary cell after use can be recharged by passing current
through it in the opposite direction so that it can be used again.
Lead Storage Cell:
The cell reactions when the battery is in use are

overall cell reaction consisting of cathode and anode reactions is:

On charging the battery the reaction is reversed

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 Nickel Cadmium Cell

Nickel Cadmium cell:

Fuel Cell : fuel cell are galvanic cell that convert energy of combustion of fuel directly
in to electrical energy. Fuel used are hydrogen, methane , methanol. Its efficiency is
about 70% .

Corrosion: the phenomenon of degradation of upper layer of metal in presence of

oxygen, moisture and atmospheric gases etc.
e.g rusting of Iron

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 Prevention of Corrosion-
1. Barrier protection through coating of paints or electroplating.
2. By the use of antirust solutions (bis phenol).
3. By cathodic protection in which a metal is protected from corrosion by
connecting it to another metal that is more easily oxidized.

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