3.

ELECTROCHEMISTRY
It is a branch of chemistry that deals with
the relationship between chemical energy
and electrical energy and their inter
conversions.

ELECTROCHEMICAL CELLS

These are devices that convert chemical

energy of some redox reactions to
electrical energy. They are also called The reaction taking place in a Daniel cell is
Galvanic cells or Voltaic cells. An
example for Galvanic cell is Daniel cell.

It is constructed by dipping a Zn rod in This reaction is a combination of two half

solution and a Cu rod in reactions:
solution. The two solutions are connected (i) (reduction half
externally by a metallic wire through a reaction)
voltmeter and a switch and internally by a (ii) (oxidation half
salt bridge. A salt bridge is a U-tube reaction)
containing an inert electrolyte like These reactions occur in two different
or in a gelly like substance. The portions of the Daniel cell.
functions of a salt bridge are: The reduction half reaction occurs on the
1. To complete the electrical circuit copper electrode while the oxidation half
reaction occurs on the zinc electrode.
2. To maintain the electrical neutrality These two portions of the cell are
in the two half cells.
also called half-cells or redox couples. The
copper electrode may be called the
reduction half-cell and the zinc electrode,
the oxidation half-cell.

Electrode Potential

The tendency of a metal to lose or gain

electron when it is in contact with its own
solution is called electrode potential. When

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the concentrations of all the species potential of the halfcell on the left hand
involved in a half-cell is unity then the side
electrode potential is known as standard i.e.
electrode potential. According to IUPAC .
convention, standard reduction potential is
taken as the standard electrode potential.

In a galvanic cell, the half-cell in which Measurement of Electrode Potential

oxidation takes place is called anode and it The potential of individual half-cell cannot
has a negative potential. The other half-cell be measured. We can measure only the
in which reduction takes place is called difference between the two half-cell
cathode and it has a positive potential. potentials that gives the emf of the cell.
In a cell, the electrons flow from negative For this purpose a half-cell called
electrode to positive electrode and the Standard Hydrogen Electrode (SHE) or
current flows in opposite direction. Normal Hydrogen Electrode (NHE) is
used.
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.

The cell electromotive force (emf) of the

cell is the potential difference between the
two electrodes, when no current is flow
through the cell.

By convention, while representing a

galvanic cell, the anode is written on the It consists of a platinum electrode coated
left side and the cathode on the right side. with platinum black. The electrode is
Metal and electrolyte solution are dipped in an acidic solution of one molar
separated by putting a vertical line and a concentration and pure hydrogen gas at 1
salt bridge is denoted by putting a double bar pressure and 298 K is bubbled through
vertical line. it. It is represented as
For Daniel cell, the cell representation is .
Under By convention, the electrode potential of
this convention the emf of the cell is SHE is taken as zero.
positive and is given by the potential of the To determine the electrode potential of an
half-cell on the right hand side minus the electrode, it is connected In series with the

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standard hydrogen electrode and the emf of concentration.
the resulting cell is determined by the He showed that for the electrode reaction:
equation,

the electrode potential can be given by:

Since the electrode potential of SHE is
zero, the value of is equal to the [ ]
) )
electrode potential of the given electrode. [ ]

If the standard electrode potential of an Since the concentration of any solid is

electrode is greater than zero (i.e. + ve), taken as unity, the above equation
then its reduced form is more stable becomes:
compared to hydrogen gas. Similarly, if the
standard electrode potential is negative ) ) [ ]
then hydrogen gas is more stable than the
reduced form of the species. Or, ) )
Electrochemical series [ ]
or, [ ]
It is a series in which various electrodes
are arranged in the decreasing order of Where is the standard electrode
their reduction potential. In this table, potential, is the gas constant (
fluorine is at the top indicating that is Faraday constant
fluorine gas has the maximum is temperature in
tendency to get reduced to fluoride ions Kelvin and [ ] is the concentration of
. Therefore fluorine gas is the the species, . In Daniel cell, the
strongest oxidising agent and fluoride ion electrode reactions are:
is the weakest reducing agent.
Lithium has the lowest electrode potential
indicating that lithium ion is the weakest
oxidizing agent while lithium metal is the The electrode potentials are given as
most powerful reducing agent in an For Cathode:
aqueous solution.
) )
Nernst Equation
[ ]
Nernst proposed an equation to relate the
electrode potential of an electrode (or, emf
of a cell) with the electrolytic

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For anode: When the cell reaction attains equilibrium,
[ ]
[ ]
The cell potential, So, [ ]
[ ]
Or, [ ]

[ ]
[ ]
[ ] [ ]
or, But at equilibrium, [ ]
[ ]
So the above equation becomes,
On changing the base of logarithm, we get

[ ]
[ ]
In General,
On substituting the values of
or, at 298 K
at 298 K , the above equation becomes,
Electrochemical Cell and Gibbs Energy
[ ] of the Reaction
[ ]
Electrical work done in one second is
For a general electrochemical reaction of equal to electrical potential multiplied by
the type: total charge passed.
Also the reversible work done by a
galvanic cell is equal to decrease in its
Gibbs energy. Therefore, if the emf of the
Nernst equation can be written as: cell is and is the amount of charge
passed, then the Gibbs energy of the
[ ] [ ]
reaction, If the
[ ] [ ]
concentration of all the reacting species is
Equilibrium Constant from Nernst unity, then . So,
Equation cell Thus, from the measurement
For a Daniel cell, the emf of the cell at 298
of , we can calculate the standard
K is given by:
Gibbs energy of the reaction.
[ ]
[ ]

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Conductance of Electrolvtic Solutions There are of two types of Conductance -
electronic or metallic conductance and
Resistance (R): The electrical resistance is electrolytic or ionic conductance.
the hindrance to the flow of electrons. Its
unit is ohm . The resistance of a Electrical conductance through metals is
conductor is directly proportional to the called metallic or electronic conductance
length of the conductor and inversely and it is due to the movement of electrons.
proportional to the area of cross-section It depends on the nature and structure of
(A) of the conductor. the metal, the no. of valence electrons per
i.e. atoms and temperature. For electronic
or, constant conductance, when temperature increases,
or, , where (rho) is a conduction decreases.
constant called resistivity.
The conductance of electricity by ions
Its unit is ohm-metre ( ) or ohm-
present in solutions is called electrolytic or
centimetre .
ionic conductance. It depends on i) the
nature of electrolyte ii)

Resistivity is defined as the resistance size of the ion produced and their solvation
offered by a conductor having unit length iii) the nature of the solvent and its
and unit area of cross-section. viscosity iv) concentration of the
electrolyte and ) temperature (As
Conductance (G): It is the inverse of temperature increases electrolytic
resistance. conduction also increases).
i.e. . Note: Substances which allow the passage
of electricity in molten state or in solution
Its unit is ohm or mho or Siemens (S)
state are called electrolytes. On the passage
Or, of electricity, they undergo chemical
Or, decomposition.

Where, is called conductivity. It is Measurement of the conductivity of

defined as the conductance of a conductor ionic solutions
having unit length and unit area of cross-
section.
We know that, conductivity
Its unit is ohm or mho or
So conductivity,
.
The quantity is called cell constant
. It depends on the distance between
the electrodes and their area of cross-
section. Its unit is .

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i.e. conductivity conductance cell coated with platinum black. The electrodes
constant are separated by a distance L and their area
of cross-section is A .
So in order to determine the conductivity
of an electrolytic solution, first determine
the resistance by using a Wheatstone
bridge. It consists of two resistances
and , a variable resistance and the
conductivity cell having the unknown
resistance . It is connected to an AC
source (an oscillator, ) and a suitable
detector (a headphone or other electronic
device, P). Direct current (DC) cannot be The cell constant of a conductivity cell is
used since it causes the decomposition of usually determined by measuring the
the solution. resistance of the cell containing a solution
whose conductivity is already known (e.g.
KCl solution).

Molar conductivity ( )

It is the conductivity of 1 mole of an

electrolytic solution kept between two
electrodes with unit area of cross section
and at a distance of unit length. It is related
to conductivity of the solution by the
equation, (where is the
The bridge is balanced, when no current concentration of the solution)
passes through the detector. Under this
Or, (where is the
condition,
molarity)
The unit of molar conductivity is
or .

Therefore, the unknown resistance,

By knowing the resistance, we get the Variation of conductivity and Molar

value of conductance and conductivity. conductivity with concentration
(dilution)
Conductivity cell
It consists of two platinum electrodes

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Both conductivity and molar conductivity increases. So the number of ions and hence
change with the concentration of the the molar conductivity increases.
electrolyte. We know that when a solution
is diluted, its The variation of for strong and weak
electrolytes is shown in the following
concentration decreases. For both strong graphs:
and weak electrolytes, conductivity always
decreases with dilution. This is because
conductivity is the conductance of unit
volume of electrolytic solution. As dilution
increases, the number of ions per unit
volume decreases and hence the
conductivity decreases.

For both strong and weak electrolytes, the

molar conductivity increase with dilution
(or decrease with increase in
concentration), but due to different
For strong electrolytes, the value of
reasons.
can be determined by the extrapolation of
For strong electrolytes, as dilution the graph. But for weak electrolytes, it is
increases, the force of attraction between not possible since the
the ions decreases and hence the ionic
graph is not a straight line. So their
mobility increases. So, molar conductivity
values are calculated by applying
increases. When dilution reaches
Kohlrausch's law of independent migration
maximum or concentration approaches
of ions.
zero, the molar conductivity becomes
maximum and it is called the limiting Kohlrausch's law of independent
molar conductivity ( ). migration of ions
For strong electrolytes, the relation
between and concentration can be The law states that the limiting molar
given as: conductivity of an electrolyte can be
Where ' ' is the concentration and is a represented as the sum of the individual
constant depends on temperature, the contributions of the anion and the cation of
nature of the electrolyte and the nature of the electrolyte.
the solvent. All electrolytes of a particular Thus if an electrolyte on dissociation gives
type have the same value for ' A '. cations and anions, its limiting
molar conductivity is given as:
For weak electrolytes, as dilution
increases, the degree of dissociation

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 By knowing the molar conductivity at a
particular concentration ( ) and
For limiting molar conductivity , we
can calculate the degree of dissociation
For as,

Applications of Kohlrausch's law By using , we can calculate the

dissociation constant of acid as:
1. Determination of of weak
electrolytes

By knowing the values of strong

electrolytes, we can calculate of
weak electrolytes. For e.g. we can Electrolytic Cells and Electrolysis
determine the of acetic acid
by knowing the of
and HCl as follows: In an electrolytic cell, the electrical energy
is converted to chemical energy. The
dissociation of an electrolyte by the
passage of electricity is called electrolysis.
For e.g. when solution is
electrolysed by Cu electrodes, Cu is
deposited at the cathode and ions are
liberated from the anode.

Quantitative Aspects of electrolysis -

Faraday's laws

1. Faraday's first law

It states that the amount of substance
deposited or liberated at the electrodes
is directly proportional to the quantity of
electricity flowing through the
electrolyte.
Mathematically,
Or,
2. Determination of degree of Where is a constant called
dissociation of weak electrolytes electrochemical equivalent (ECE).

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equivalent weight/ 96500 But quantity of At cathode:
electricity is the product of current in At anode:
ampere (I) and time in second ( t ). If NaCl solution is electrolysed, we get
i.e. gas at the cathode and gas at the anode.
NaCl solution contains 4 ions
Therefore, and
1 Faraday is the charge of 1 mole of Cathode reaction:
electron or it is the amount of electricity Anode reaction:
required to deposit one gram equivalent of NaOH is formed in the solution.
any substance. Its value is .
For the deposition of 1 mole of Na , the 2. The type of electrodes used: If the
amount of charge required electrode is inert (e.g. Pt, gold, graphite
Since ) etc.), it does not participate in the electrode
For since reaction. While if the electrode is reactive,
it also participate in the electrode reaction.
2. Faraday's second law

It states that when same quantity of 3. The different oxidising and reducing
electricity is passed through solutions of species present in the electrolytic cell and
different substances, the amount of their standard electrode potentials. Some of
substance deposited or liberated is directly the electrochemical processes are very
proportional to their chemical equivalence. slow and they do not take place at lower
For e.g. when same quantity of electricity voltages. So some extra potential (called
is passed through solutions of two overpotential) has to be applied, which
electrolytes and , then makes such process more difficult to
occur.

For e.g. during the electrolysis of NaCl

Products of electrolysis solution, the possible reactions at anode
The products of electrolysis depend on the are:
following factors:

1 The nature of the electrolyte: The

electrolyte may be in molten state or
At anode, the reaction with lower value of
in aqueous solution state. For e.g. if
molten NaCl is electrolysed, Na is is preferred and so water should get
deposited at the cathode and oxidised in preference to .
chlorine is liberated at the anode. However, on account of overpotential of
oxygen, the first reaction is preferred and
hence is formed at anode.

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Batteries Anode reaction:

Cathode reaction:
A battery is basically a galvanic cell in
which the chemical energy of a redox
The overall reaction is:
reaction is converted to electrical energy.
They are of mainly 2 types - primary
The cell has a constant potential of 1.35 V
batteries and secondary batteries. , since the overall reaction does not involve
a) Primary cells: any ion in solution.

These are cells which cannot be recharged b) Secondary cells

or reused. Here the reaction occurs only
A secondary cell can be recharged and
once and after use over a period of time,
reused again and again. Here the cell
they become dead E.g. Dry cell, mercury
reaction can be reversed by passing current
button cell etc.
through it in the opposite direction. The
1. Dry Cell most important secondary cell is lead
storage cell, which is used in automobiles
It is a compact form of Leclanche cell. It
and invertors.
consists of a zinc container as anode and a
It consists of lead as anode and a grid of
carbon (graphite) rod surrounded by
lead packed with lead dioxide as
powdered manganese dioxide and
the cathode. The electrolyte is
carbon as cathode. The space between the
solution.
electrodes is filled by a moist paste of
The cell reactions are:
ammonium chloride and zinc
Anode:
chloride . The electrode reactions
are:
Cathode:
Anode:
(I)
Cathode:
The overall cell reaction is:
Ammonia produced in this reaction forms
a complex with and thus corrodes the
cell. The cell has a potential of nearly 1.5
V. On charging the battery, the reaction is
2. Mercury cell reversed and on anode and

Here the anode is zinc-mercury amalgam cathode is converted into Pb and ,

and cathode is a paste of HgO and carbon. respectively.
The electrolyte is a paste of KOH and ZnO Another example for a secondary cell is
. The electrode reactions are: nickel - cadmium cell. Here the overall cell

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reaction is 4. Water obtained from fuel
(I) cell can be used for drinking.

Fuel cells
Corrosion
These are galvanic cells which convert the
energy of combustion of fuels like It is the process of formation of oxide or
hydrogen, methane, methanol, etc. directly other compounds of a metal on its surface
into electrical energy. by the action of air, water-vapour, etc.
Some common examples are: The rusting
One example for fuel cell is Hydrogen -
of iron, tarnishing of silver, formation of
Oxygen fuel cell, which is used in the
green coating on copper and bronze
Apollo space programme. Here hydrogen
(verdigris) etc.
and oxygen are bubbled through porous
Most familiar example for corrosion is
carbon electrodes into concentrated
rusting of iron. It occurs in presence of
aqueous sodium hydroxide solution. To
water and air. It is a redox reaction. At a
increase the rate of electrode reactions,
particular spot of the metal, oxidation takes
catalysts like finely divided platinum or
place and that spot behaves as anode. Here
palladium metal are filled into the
Fe is oxidized to .
electrodes.
The electrode reactions are:
Cathode: (g) (I)
Electrons released at anodic spot move
Anode: through the metal and go to another spot
on the metal and reduce oxygen in
Overall reaction is: presence of . This spot behaves as
(l) cathode. The reaction taking place at this
spot is:

Advantages of Fuel cells

1. The cell works continuously as long The overall reaction is:

as the reactants are supplied. The
2. It has higher efficiency as compared ferrous ions are further oxidised to
to other conventional cells. ferric ions and finally to hydrated
3. It is eco-friendly (i.e. pollution free) ferric oxide , which is
since water is the only product called rust.
formed.

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Methods to prevent corrosion

1. By coating the metal surface with

paint, varnish etc.
2. By coating the metal surface with
another electropositive metal like
zinc, magnesium etc. The coating of
metal with zinc is called
galvanisation and the resulting iron
is called galvanized iron.
3. By coating with anti-rust solution.
4. An electrochemical method is to
provide a sacrificial electrode of
another metal (like , etc.)
which corrodes itself but saves the
object (sacrificial protection).

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