19I203

Industrial Electrochemistry
Dr.J.Ravichandran,
Professor in Chemistry
M: 9790913691
E mail: drjravi@yahoo.co.in
jrc.chem@psgtech.ac.in
 Introduction
• Electrochemistry – is the branch of chemistry which deals with the transformation of electrical
energy into chemical energy and vice versa.

• Use of “electrical energy” to drive chemical reactions.

Example:
• 1.Electrolysis ( process by which electric current is passed through a substance to effect a
chemical change) . Example; water into hydrogen and oxygen
•
2.Electro metallurgy ( is a method in metallurgy that uses electrical energy to produce metals by
electrolysis). Example: aluminium, copper etc.,

• 3.Electroplating (is the process of applying a metal coating on another piece of metal (or another
conductive surface)-through an electro-deposition process). Cu, Ni coating

• Use of “Chemical energy” is transformed into electricity.

• Example
• 1.Galvanic cell or voltaic cell -are electrochemical cells in which spontaneous oxidation-reduction
reactions occurs to produce electrical energy.

• 2.Batteries : A battery is a device that stores chemical energy and converts it into electrical
energy.
• 3. Fuel cells : A fuel cell is an electrochemical cell that converts the chemical energy of a fuel
(often hydrogen) and an oxidising agent (often oxygen) into electricity through a pair of redox
reactions.
• Electronic conductors.

Substance such as metals and alloys conduct electricity, under

the influence of an applied electrical potential through a flow of
electrons and hence are known as electronic conductors.

The flow of electricity in electronic conductors does not cause

any physical and chemical changes in the conductor.

• Electrolytic conductors or electrolytes.

Electrolyte solution and molten salts conduct electricity through

the migration of ions and are known as electrolytic conductors
or electrolytes.

• When direct current is passed through an electrolyte solution,

decomposition and changes occur in the composition of the
electrolyte.
• What is electrolytes?

• Any substance that produce ions when dissolved in a solution (usually

water) is an electrolyte.

• Types of electrolytes:

• Based on the extent of dissociation, electrolytes are classified into two

types

• 1. Strong electrolytes and

• 2. Weak electrolytes

• Strong electrolytes:

• Almost completely dissociated in their aqueous solution and have a large

value of conductance.
• Example NaCl,KCl, HCl, HNO3, NaOH and KOH.
• NaCl + H2O --- Na+ + Cl –
• HCl + H2O --- H3O+ + Cl –
 Weak electrolytes :

• Do not undergo complete dissociation even in their dilute aqueous

solution, and have a low value of conductance.

• Examples

• HCOOH, CH3COOH, NH4OH

• CH3COOH <--- CH3COO- +H+

• In the solution of a weak electrolyte, there is an equilibrium exists

between the un dissociated molecules and their ions.
• Ohm’s law:

• Metallic as well as electrolytic conductor obey ohms’s law.

• Current (I) flowing through a conductor is directly proportional to

the potential difference (V) across the conductor and inversely
proportional to resistance (R) of the conductor.
• Mathematically I = V/R where V– Applied potential
I – Current (A)
R – Solution resistance ( )
between the two
electrodes

Conductance (C):
The degree to which an object conducts electricity, calculated as the ratio of
the current which flows to the potential difference present.
This is the reciprocal of the resistance ( reciprocal ohm-1 and is measured in
(S) siemens or mhos.
C=1/R
• Factors affecting conduction

• 1. Temperature

• In the case of strong electrolytes, increase in temperature,

increases the speed of the ions. This results in increase in
conductivity.
• In the case of weak electrolytes, increase in temperature
increases the degree of dissociation. There is increase in number of
ions and speed. Hence the conductivity increases.

• 2. Concentration:

• Generally conductivity of the solution depends on the number of

ions present in the solution and the speed of the ions.
• At higher concentration, the force of attraction between the ions
increases, which decreases the speed of the ions.
• Hence, the conductance decreases with concentration.
• Mobility of ions or conductivity of solution of electrolytes;
e- flow

+ - Typical electrolytic cell.

A Cl _
Na + C
Electrolyte -
Na + Cl- Con.Nacl

When the electricity is provided by a DC source or a battery,the electrode acquire

electrical charges.
They attract ions of opposite charges which take part in the redox reactions.
Anode : oxidation occurs
For example, in the case of NaCl as electrolyte
Cl- aq  1/2 Cl2 + e-
The e-s from the +ve electrode pumped through the electrical circuit.
These e-s are delivered to the –ve electrode where reduction occurs.
Na+ + e- -- Na
The overall effect is that as redox reactions occur,there is a flow of e- s through
the external wire resulting from the flow of ions in the solution.
The resulting conductance is called the electrolyte conductance.
• Specific conductance (k- kappa)

• Specific Conductance is the ability of a substance to conduct electricity.

• It is the reciprocal of specific resistance.
Specific conductance is defined as the conducting capacity of a solution of the
dissolved electrolyte and the whole solution is being placed between two electrodes
are 1 sq. cm and length 1 cm.

Like any metallic conductor,the electrolytic conductor also offers some resistance
to the flow of current.
let R be the resistance offered by an electrolytic conductor.
If resistance R is directly proportional to the length of the conductor (l) and
inversely proportional to the area of cross section (a) of the conductor.
therefore, [Where P or S is proportionality constant depends upon
the
R l nature of materials and is called specific resistance]
R l/a P is called as row.
R=P l/a. , P= R .a/l , if l = 1m and a = 1m2 , then P=R

Specific resistance P : It is the resistance offered by a conductor of 1 m length and 1m 2

area of cross section. In SI system ,it has unit ohm-meter ( m)

The reciprocal of specific resistance is called the specific conductance (k)

therefore, k = 1/P or k=1/S or k= 1/R x l/a, k= l/a x conductance , K = cm-1
• Cell constant
• The ratio of length to cross sectional area is called the cell constant.
• Cell constant = l/a
• It is the characteristics parameter of conductivity cell used for the
experiments.
• Equivalent conductance ( )
• It is the conductance of an electrolyte solution due to all the ions obtained
from 1 gm. equivalent (g- equivalent mass) of the electrolyte at a given
concentration.
• Therefore
= kV
k = specific conductance of the solution and V is the volume of the solution containing 1 gm
equivalent of the substance.
In terms of concentration = k x 1000/C C= Normality
In Si system, the unit of equivalent conductance = Sm 2 / equivalent.

Molar conductance: m

It is defined as the conductance of an electrolytic solution due to all the ions obtained from
1 mole of electrolyte at a given concentration .

m = k x 1000/C C = 1 molar concentration

In Si system, the unit of molar conductance = Sm 2 /mole
• Ionic conductance:
• The conductance of the solution depends on the number of ions.
• It is observed that molar conductance increases upon dilution. This may be due to
increase in the degree of dissociation of the electrolyte or due to decreased ion –
ion force of attraction .
• With dilution the influence of other ions on the movement of an ion decreases.
• At a particular dilution, the ions become totally independent of other ions. At this
point ,it contributes maximum towards the conductance of the solution.
• The part of the conductance of the solution due to movement of an ion is referred
as ionic conductance.
• Under the conditions, the molar conductance of the solution reaches the maximum
value.
• This value is called molar conductance at infinite dilution o
• Mathematically law expressed as o = o+ + o -

• o+ Ionic conductance of cation at infinite dilution and similarly,

• o - Ionic conductance ofanion at infinite dilution.
• Transport Number: (t)
• During electrolysis, the current is carried by both anions and cations.
• The fraction of total current carried by cation or anion is termed as transport
number.
• Suppose Q is the total current carried through the solution by cations and anions, a
portion of it (q+) is carried by the cation, (q-) carried by the anion.
Therefore , the current carried by the anion is q- = Q - q+
cation is q+ = Q - q-
or t + = Current carried by the cations , so, t + = q+ ----- 1

Total current carried by both the ions Q

Where t + is the transport number of cation.
Similarly t - = q- -------2

Q
Where t- is the transport number of anion.

adding 1 and 2, we get t + + t - = 1

The current carried by an ion depends on the charge (z), speed (V) and molar
concentration (m)of the ion.

Therefore, t + z+m+ V+ and , t- z - m –V- ,

• For an electrolyte z + m + = z - m –

The solution is electrically neutral, but

t + = q+ = V+
q+ + q- V+ + V-

• t- = V–
V+ + V-

• The speed of the ions are proportional to molar conductance ,that is

• t + /t - = V + / V- = +/ -
• Measurement of conductance:

• Conductometry involves the measurement of an electrolytic conductance

under relatively mild conditions of low voltage of about 1 – 100 V. and
frequencies of alternating current of less than 5000 Hz.

• In electrolytic solutions the magnitude of current flowing in the circuit

depends on the number and types of ions present in the electrolyte
solution, their mobility, the nature of the solvent and the voltage applied.
• In a given electrolyte solution of strong electrolytes the number of ions
depends on the concentration.
• While in solutions of weak electrolytes it also dependent on the degree
of dissociation or ionisation and on the temperature.
• Hence, the measurements of conductance provides information on the
concentration of the electrolytic solution.
• The conductance meter for measuring conductance of a solution is based
on a Wheatstone bridge principle.
Electrode potential (V)
• The natural tendency of a metal to undergo oxidation or
reduction reactions, when in contact with an aqueous solution of
its own ions is expressed in terms of electrode potential.

• The oxidation and reduction reactions may occur be represented as

• M → Mn+ + ne− ( oxidation) - oxidation is a reaction that removes an

electron from a substance – loss of electrons.

The species being oxidized is also known as the reducing agent or reductant

• Mn+ + ne− → M (reduction) - reduction is a reaction that adds electrons to a

substance - gain of electron

The species being reduced is called the oxidizing agent or oxidant.

 Electrical double layer:

• Origin of electrode Potential:

An electrode is a metal plate or rod dipped in a solution of its own
ions.
example ;
A galvanic cell is made up of two such electrodes and current flows
from one electrode to another.
This indicates the two electrodes of the cell are at different
potentials.
Also, redox reactions occur in a galvanic cell.

example
Zinc electrodes consists of Zn metal dipped in ZnSO4 solution.
An equilibrium reaction is established within second as
Zn <----> Zn2+ + 2e− ( If oxidation occurs)
• In the case of oxidation, Zn atoms on the surface of the metal undergo
oxidation, leaving behind electrons on the surface.

Metallic surface become – vely charged .the + vely charged ions in the
solution would accumumulate around the metal .
• The Zn+ ions pass into the solution, hence the metal strip become
negatively charged. The positively charged metal ions in the
solution would accumulate around metal and form double layer or
Helmoltz electrical double layer.

• If the other tendency, reduction occurs in this electrode, the Zn+

ion in the solution would undergo reduction by grapping electrons
from the metallic surface. with this, metallic surface become + ve
charged. The – ve charged ions in the solution would accumulate
around the metal.

• Two tendencies happen simultaneously on the same electrode. As

the two tendencies oppose each other, and equilibrium exists
between them.
• Zn <----> Zn2+ + 2e−
• Hence, an electrical double layer called Helmoltz electrical double layer
(HED) is established at the metal – aqueous solution interface.
• The potential difference between the metal and the solution is called the
electrode potential with unit (V) expressed in volts.
ELECTROCHEMICAL CELL ( GALVANIC CELL)

Anion movement

Cation movement
• It consists of anodic half cell –A zinc electrode dipping into a solution of ZnSO4
• Cathodic half cell - A Cu electrode dipping into a solution of CuSO4 .
The two electrodes are connected by an external circuit through a voltmeter and the two
solutions are connected by a salt bridge.
A salt bridge is a tube filled with an electrolyte solution , commonly KCl,KNO3 and fitted
with porous plug at either end.

when the circuit is completed the following reaction takes place.

At anode:
Zn ----> Zn2+ + 2e− ( oxidation )

At cathode:
Cu2+ + 2e− → Cu (reduction)
The e− released by the oxidation of Zn at anode travels through the external
circuit as an electric current to the cathode, where they are picked up by Cu2+
ions and there by get reduced.
 Working of a galvanic cell
• When Zn is oxidised,the solution in the anodic compartment will have more
Zn2+ ions so –ve ions are needed to balances their charge.
• Simlarly when the Cu2+ ions are reduced,the solution in the cathodic
compartment will have more SO42- and + ve ions are needed to balance their
charge.
• To bring about the electrical neutrality in both compartments, salt bridge
serves the purpose.

• Either negative ions can diffuse from the salt bridge into the Zn half cell
or Zn2+ ions leave the solution and enter the salt bridge.
• At the other half cell, +ve ions from the salt bridge can enter or negative
SO42- ions can leave the solution and enter the salt bridge to keep it
electrically neutral.

Anodic part –oxidation Cathodic part –reduction

Half cell Half cell
Salt bridge
• Types of electrodes:

• Electrodes are generally classified into two types.

• 1. Reference electrodes 2. Indicator electrodes

• 1. Reference electrodes

• The electrodes which has a constant emf or constant potential, and that is
used in the measurement of the potential of a given test electrode is known
as reference electrode.

• There are two types of reference electrodes.

• 1. Primary reference electrodes – gas electrodes. ie., Standard or Normal

hydrogen electrodes.

• 2. Secondary reference electrodes – Calomel electrode, quin hydrone

electrode, silver- silver chloride electrode ( metal – Metal salt electrode)
• Standard hydrogen electrodes (SHE) Normal hydrogen electrodes;
• Its potential value is taken as ‘O’ volts, otherwise determination of
potentials of all other electrode is impossible.

Primary electrode

(1 M)
Other types of electrodes
Metal – metal salt ion electrode
Standard electrode potential:
It is the tendency of the metallic electrode to lose or gain e- s when in
contact with 1 molar concentration of its own salt solution at 25o C .
The tendency of a metallic electrode to loose e- s is known as oxidation
potential.
Gain electrons is known as reduction potential.

Cell potential and reduction potential:

The galvanic cell as an ability to push the e- through the external

circuit. The magnitude of this ability is expressed as a potential or
electro motive force (emf).

The maximum potential that a given cell is capable of generating is

called its cell potential. E cell.
In a galvanic cell, each half cell has a certain natural tendency to
undergo reduction reaction, the magnitude of which is expressed by its
reduction potential ( standard reduction potential) when temperature is
25o C , the concentrations are 1.0 M and pressure is 1 atm.
The measured cell potential actually represents the magnitude of difference
between the reduction potential of one half cell and the reduction potential
of the other half cell . ( Only reduction potentials are considered)

Therefore, Eo cell = standard reduction potential of - (substance oxidised)

substance reduced
Eo cell = EoRHE - EoLHE

where, RHE is right hand side electrode,

LHE is left hand side electrode
Eo standard cell potential.

Measurement of electrode potential:

For an isolated half cell there is no way to measure the standard reduction
potential.
Therefore a reference electrode has been chosen whose standard
reduction potential assigned as ‘O’ (zero) volts, so that, when it is combined
with other electrode system form a cell.
But the measured is the reduction potential of the cell ie.,the other
• Sign of Electrode Potential

• 1. If the electrode reaction involved is reduction, when connected to the

SHE,the electrode potential is given as + sign. (SHE is Anode)

• 2. If the electrode reaction involved is oxidation, ( when connected to the

SHE,the electrode potential is given as – sign. (SHE is Cathode)
• Electrochemical series (EMF series)

• Standard electrode (or Reduction) Potential E o

• Using hydrogen electrode as reference, if the metals are arranged in a

series of increasing order (downwards) of their standard electrode
reduction potential is known as emf series.

• Importance of electrochemical series

• The activity series correlates many chemical properties of elements.

• 1. the metals with large ‘negative’ reduction potential at the top of the
series are good reducing agent in the free state,
• ( ie loose electrons during oxidation- are powerful reducing agents).
• They are metals most easily oxidised to their ions by the removal of
electrons (active metals).
• 2. The elements with large ‘positive’ reduction potentials at the bottom
of the series are good oxidising agent.
• ( ie gain electrons during reduction- are powerful oxidising agents).
• The metals are in the form of ions and the non- metals are in the elemental
state.
• 3. The reduced form of any element will reduce the oxidised form of any
element below it.
• For example

• Metallic zinc (- 0.76 V) will reduce copper (II) ions ( + .34 V) according to
the equation.
• Zn + Cu2+ ---Cu+ Zn2+

• Most metal will reduce the halogens that are found at the bottom of the
series and iodide ion ( the reduced form of iodine) will reduce the
elemental bromine forming iodine and bromide ion ( reduced form of
bromine).
anodic

cathodic
Application of emf series:

1. Calculation of standard emf of a galvanic cell and determination of

cell reaction.
_
pressures
Electrolytic cell
Potassium hydrogen phthalate buffer pH – 4.0
Borax buffer pH – 9.0