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 Galvanic cells
or Voltaic cells. An example for Galvanic cell is Daniel cell.
• It is constructed by dipping a Zn rod in ZnSO4 solution
and a Cu rod in CuSO4 solution. The two solutions are
connected externally by a metallic wire through a
voltmeter and a switch and internally by a salt bridge.

• A salt bridge is a U-tube containing an inert electrolyte

like NaNO3 or KNO3 in a gelly like substance.
The functions of a salt bridge are:
• To complete the electrical circute.
• To maintain the electrical neutrality in the two half cells.
The reaction taking place in a Daniel cell is
Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s)
This reaction is a combination of two half reactions:
• Cu2+ + 2 e- → Cu(s) (reduction half reaction)
• Zn(s) → Zn2+ + 2 e- (oxidation half reaction)
• These reactions occur in two different portions of the Daniel
cell.
• The reduction half reaction occurs on the copper electrode
while the oxidation half reaction occurs on the zinc electrode.

• These two portions of the cell are 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 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 potential

is taken as the standard electrode potential.

• In a galvanic cell, the half-cell in which oxidation takes place

is called anode and it has a negative potential. The other
half-cell in which reduction takes place is called cathode and
it has a positive potential.
• In a cell, the electrons flow from negative electrode to
positive electrode and the current flows in the opposite
direction.

• 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 left side and the cathode on the right side.
• Metal and electrolyte solution are separated by putting a
vertical line and a salt bridge is denoted by putting a double
vertical line.
• [The concentration of the electrolyte is shown in simple
brackette]. For Daniel cell, the cell representation is
• Under this convention the emf of the cell is positive and is given
by the potential of the half-cell on the right hand side minus the
potential of the half-cell on the left hand side.
Measurement of Electrode Potential
• The potential of an individual half-cell cannot be measured.
• We can measure only the difference between the two half-cell
potentials that gives the emf of the cell.
• For this purpose a half-cell called Standard Hydrogen Electrode
(SHE) or Normal Hydrogen Electrode (NHE) is used.
It consists of a platinum foil coated with platinum black (finely divided
Pt).
The electrode is dipped in an acidic solution of one molar concentration
and pure hydrogen gas at 1 bar pressure and 298K is bubbled through it.
It is represented as Pt(s)|H2(g)|H+(aq).
By convention, the electrode potential of SHE is taken as zero.
To determine the electrode potential of an electrode,
it is connected In series with the standard hydrogen electrode
through a volt meter.
Here SHE is always connected on LHS and the emf of the resulting cell is
determined by the Equation
Ecell = ER – EL

Since the electrode potential of SHE is zero, the value of Ecell is equal to
the electrode potential of the given electrode.
If the standard electrode potential of an electrode is greater than zero
(i.e. +ve), then its reduced form is more stable 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
Electrochemical series
• It is a series in which various electrodes are arranged in the decreasing
order of their reduction potential.
• In this table, fluorine is at the top indicating that fluorine gas (F2) has
the maximum tendency to get reduced to fluoride ions (F–).
• Therefore fluorine gas is the strongest oxidizing agent and fluoride ion
is the weakest reducing agent.
• Lithium has the lowest electrode potential indicating that lithium ion is
the weakest oxidising agent while lithium metal is the most powerful
reducing agent in an aqueous solution.
Nernst Equation:
It is an equation relating electrode potential or emf of a cell with
electrolytic concentration
• Nernst equation relating Electrode potential and Electrolytic
concentration:
Consider the electrode reaction: Mn+ (aq) + ne- –→ M(s)

Nernst equation for the electrode potential can be given by:

Since the concentration of any solid is taken as unity, the above equation
becomes:
Where E0el. is the standard electrode potential, R is the universal gas
constant (R = 8.314 JK–1 mol–1),
F is Faraday constant (96500 C/mol), T is temperature in Kelvin and [M n+]
is the concentration of the ion Mn+.On substituting the values of R and F
at 298K, the equation becomes:
(ii) Nernst equation relating emf of a cell and electrolytic concentration:
A Daniel cell can be represented as: Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
The electrode reactions are:
Cu2+ + 2 e- → Cu(s) (cathode reaction)
Zn(s) → Zn2+ + 2e-(anode reaction)
The electrode potentials are:
for cathode:
for anode:
On changing the base of logarithm, we get

On substituting the values of R (8.314 JK–1 mol–1), F (96500 C mol–1) at

298K, the above equation becomes
For a general electrochemical reaction of the type:
Equilibrium Constant from Nernst Equation
For a Daniel cell, the emf of the cell at 298K is given by:

When the cell reaction attains equilibrium, Ecell = 0

On substituting the values of R (8.314 JK–1 mol–1), F (96500 C mol–1)
at 298K, the above equation becomes,
Electrochemical Cell and Gibbs Energy of the Reaction
• Electrical work done in one second is equal to electrical potential
multiplied by 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 cell is Ecell
and nF is the amount of charge passed,

• Then the Gibbs energy of the reaction, ΔG = – nFEcell

• If the concentration of all the reacting species is unity, then E cell =

E0cell .
So, ΔG0 = –nFE0cell

Thus, from the measurement of E0cell, we can calculate the

standard Gibbs energy of the reaction.

By knowing ΔG0, we can calculate equilibrium constant by the

equation:
ΔG0 = – RT ln Kc.
Or,
ΔG0 = – 2.303RT log Kc
Conductance of Electrolytic Solutions
Resistance (R): The electrical resistance is the hindrance to the flow of
electrons. Its unit is ohm (Ω).
The resistance of a conductor is directly proportional to the length of
the conductor (Ɩ) and inversely proportional to the area of cross-
section (A) of the conductor.
i.e. R α Ɩ /A
or, R = a constant x Ɩ/A
or, R = ρ x Ɩ/A,
where ρ (rho) is a constant called resistivity. It is defined as the
resistance offered by a conductor having unit length and unit area of
cross-section.
Its unit is ohm-metre (Ω m) or ohm-centimetre (Ω cm).
1 Ω m = 100 Ω cm, 1 Ω cm = 10-2 Ω m
Conductance (G):
It is the reciprocal of resistance. ( R = ρ x
Ɩ/A)
i.e. G = 1/R.
• Its unit is ohm-1 or mho or siemens (S)

• Where, ƙ is called conductivity. It is defined as the conductance of a

conductor having unit length and unit area of cross-section.
Its unit is ohm-1 m-1 or mho m-1 or S m-1
1 S cm-1 = 100 S m-1
1 S m-1 = 10-2 S cm-1
• There are of two types of conductance - electronic or metallic
conductance and electrolytic or ionic conductance.

• Electrical conductance through metals is called metallic or

electronic conductance and it is due to the movement of electrons.

• It depends on the nature and structure of the metal, the no. of

valence electrons per atoms and temperature.

• For electronic conductance, when temperature increases,

conduction decreases.
• The conductance of electricity by ions present in solutions is called
electrolytic or ionic conductance.

• It depends on i) the nature of electrolyte ii) size of the ion produced

and their solvation iii) the nature of the solvent and its viscosity iv)
concentration of the electrolyte and v) temperature (As temperature
increases electrolytic conduction also increases)

• Note: Substances which allow the passage of electricity in molten state

or in solution state are called electrolytes. On the passage of
electricity, they undergo chemical decomposition.
Measurement of the conductivity(specific conductance) of ionic solution

• The quantity Ɩ/A is called cell constant (G*). It depends on the distance
between the electrodes and their area of cross-section. Its unit is m -1

• i.e. conductivity = conductance x cell constant

• 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 R3 and R4, a variable resistance R1 and
the conductivity cell having the unknown resistance R2.
• It is connected to an AC source (an oscillator, O) and a suitable
detector (a headphone or other electronic device, P). Direct current
(DC) cannot be used since it causes the decomposition of the solution
The bridge is balanced, when no current passes through the detector.
Under this condition,

By knowing the resistance, we get the value of conductance and

conductivity.
Conductivity cell
• It consists of two platinum electrodes coated with platinum black
(finely powdered platinum).
• The electrodes are separated by a distance Ɩ and their area of cross-
section is A.
• The solution confined between the electrodes can be considered as a
column of length l and area of cross section A.
• The cell constant of a conductivity cell is usually determined by
measuring the resistance of the cell containing a solution whose
conductivity is already known (e.g. KCl solution).
Molar conductivity (Λm – lambda m):
• 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.
OR,
• Molar conductivity of a solution at a given concentration is the
conductance of ‘V’ volume of a solution containing one mole of
electrolyte kept between two electrodes with area of cross section A
and distance of unit length.
• It is related to conductivity of the solution by the equation
Variation of conductivity and Molar conductivity with concentration
(dilution)
• Both conductivity and molar conductivity change with the
concentration of the electrolyte.
• We know that when a solution is diluted, its concentration decreases.
For both strong 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
increases with dilution (or decreases with increase in concentration),
• For strong electrolytes, as dilution increases, the force of attraction
between the ions decreases and hence the ionic mobility increases.
So, molar conductivity increases.
• When dilution reaches maximum or concentration approaches zero,
the molar conductivity becomes maximum and it is called the limiting
molar conductivity (Λ0m).

• For strong electrolytes, the relation between Λm and concentration

can be given as: Λm = Λ0m - A√c
• Where ‘c’ is the concentration and A is a constant depending on
temperature, the nature of the electrolyte and the nature of the
solvent. All electrolytes of a particular type have the same value for
‘A’.
• For weak electrolytes, as dilution increases, the degree of
dissociation increases. So the number of ions and hence the molar
conductivity increases.
• The variation of Λm for strong and weak electrolytes is shown in the
following graphs:
• For strong electrolytes, the value of Λ0m can be determined by the
extending the graph to y-axis.
• But for weak electrolytes, it is not possible, since the graph is not a
straight line.
• So their Λ0m values are calculated by applying Kohlrausch’s law of
independent migration of ions.
Kohlrausch’s law of independent migration of ions
• The law states that the limiting molar conductivity of an electrolyte
can be represented as the sum of the individual contributions of the
anion and the cation of the electrolyte.
• Thus if an electrolyte on dissociation gives n(+) cations and n(-) anions,
its limiting molar conductivity is given as:
Applications of Kohlrausch’s law
1) Determination of λ0m of weak electrolytes By knowing the Λ0m values
of strong electrolytes, we can calculate Λ0m of weak electrolytes.

For e.g. we can determine the Λ0m of acetic acid (CH3COOH) by knowing
the Λ0m of CH3COONa, NaCl and HCl as follows:
2) Determination of degree of dissociation of weak electrolytes
• By knowing the molar conductivity at a particular concentration (Λ cm)
and limiting molar conductivity (Λ0m), we can calculate the degree of
dissociation (α) as

• By using α, we can calculate the dissociation constant of weak acid

(Ka) as:
ELECTROLYTIC CELLS AND ELECTROLYSIS
• 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 CuSO4 solution is electrolysed by Cu electrodes
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 (m) is directly proportional to the quantity of electricity (Q) flowing
through the electrolyte. Mathematically

• Where z is a constant called electrochemical equivalent (ECE). Z = equivalent

weight/96500 [Equivalent weight of an ion = Atomic mass/valency.
• But quantity of electricity is the product of current in ampere (I) and time in
second (t).
i.e. Q = It
Therefore, m= zIt
• 1 Faraday is the charge of 1 mole of electron or it is the amount of
electricity required to deposit one gram equivalent of any
substance. Its value is 96487 C/mol or, 96500 C/mol.
• For the deposition of 1 mole of Na, the amount of charge required =
1 F (Since Na+ + e- → Na)
• For Ca, Q = 2F (since Ca2+ + 2e- → Ca)
2) Faraday’s second law
• It states that when same quantity of electricity is passed through
solutions of different substances, the amount of substance
deposited or liberated is directly proportional to their chemical
equivalence.
• For e.g. when same quantity of electricity is passed through
solutions of two electrolytes A and B, then
Products of electrolysis
The products of electrolysis depend on the following factors:
i) The nature of the electrolyte: The electrolyte may be in molten state
or in aqueous solution state.
For e.g. if molten NaCl is electrolysed, Na is deposited at the cathode and
chlorine is liberated at the anode.
• If NaCl solution is electrolysed, we get H2 gas at the cathode and Cl2
gas at the anode.
• NaCl solution contains 4 ions – Na+, Cl-, H+ and OH-

• ii) The type of electrodes used: If the electrode is inert (e.g. Pt, gold,
graphite etc.), it does not participate in the electrode reaction.
While if the electrode is reactive, it also participates in the electrode
reaction.
iii) The different oxidising and reducing species present in the electrolytic
cell and their standard electrode potentials. Some of the electrochemical
processes are very slow and they do not take place at lower voltages. So
some extra potential (called overpotential) has to be applied, which
makes such process
More difficult to occur.
For e.g. during the electrolysis of NaCl solution, the possible reactions at
anode are:
• At anode, the reaction with lower value of E0cell is preferred and so
water should get oxidised in preference to Cl–(aq). However, on
account of overpotential of oxygen, the first reaction is preferred and
hence Cl2 is formed at anode.

• When dilute H2SO4 is electrolysed, O2 gas is liberated from the

anode.

• while if we use conc. H2SO4, peroxodisulphate ion is formed at the

anode.
Batteries
• A battery is basically a galvanic cell in which the chemical energy of
a redox reaction is converted to electrical energy. They are of mainly
2 types – primary batteries and secondary batteries.

a) Primary cells:
• These are cells which cannot be recharged or reused.
• Here the reaction occurs only once and after use over a period of
time, they become dead.
• E.g. Dry cell, mercury button cell etc.
1. Dry Cell
• It is a compact form of Leclanche cell. It consists of a zinc container
as anode and a carbon (graphite) rod surrounded by powdered
manganese dioxide (MnO2) and carbon as cathode.
• The space between the electrodes is filled by a moist paste of
ammonium chloride (NH4Cl) and zinc chloride (ZnCl2).
• The electrode reactions are:

• Ammonia produced in this reaction forms a complex with Zn2+ and

thus corrodes the cell. The cell has a potential of nearly 1.5 V.
2. Mercury cell
• Here the anode is zinc – mercury amalgam and cathode is a paste of
HgO and carbon. The electrolyte is a paste of KOH and ZnO.
• The electrode reactions are:

• The cell has a constant potential of 1.35 V, since the overall reaction
does not involve any ion in solution.
b) Secondary cells
A secondary cell can be recharged and reused again and again. Here
the cell reaction can be reversed by passing current through it in the
opposite direction. E.g.: Lead storage cell, Ni- Cd cell (Nicad cell).
Lead storage cell:
It is used in automobiles and invertors. It consists of lead as anode
and a grid of lead packed with lead dioxide (PbO2) as the cathode. The
electrolyte is 38% H2SO4 solution.
• On charging the battery, the reaction is reversed and PbSO4(s) on
anode and cathode is converted into Pb and PbO2, respectively.

• Another example for a secondary cell is nickel – cadmium cell.

Here the overall cell reaction is
Fuel cells
• These are galvanic cells which convert the energy of combustion of
fuels like hydrogen, methane, methanol, etc. directly into electrical
energy.

• One example for fuel cell is Hydrogen – Oxygen fuel cell, which is
used in the Apollo space programme.
• Here hydrogen and oxygen are bubbled through porous carbon
electrodes into concentrated aqueous sodium hydroxide solution.

• To increase the rate of electrode reactions, catalysts like finely

divided platinum or palladium metal are filled into the electrodes.
Advantages of Fuel cells
1. The cell works continuously as long as the reactants are supplied.
2. It has higher efficiency as compared to other conventional cells.
3. It is eco-friendly (i.e. pollution free) since water is the only product
formed.
4. Water obtained from H2 – O2 fuel cell can be used for drinking
Corrosion:
• It is the process of formation of oxide or other compounds of a metal
on its surface by the action of air, water-vapour, CO2 etc.
• common examples are: The rusting of iron, tarnishing of silver,
formation of green coating on copper and bronze (verdigris) etc.
• Most familiar example for corrosion is rusting of iron.
Chemistry of rusting of iron:
• Rusting of iron is a redox reaction, which occurs in presence of air
and water. At a particular spot of the metal iron, oxidation takes
place and that spot behaves as anode.
Here Fe is oxidized to Fe2+

.
• Electrons released at anodic spot move through the metal and go
to another spot on the metal and reduce oxygen in presence of
H+[H+is formed by dissolving atmospheric CO2 in moisture].

• This spot behaves as cathode. The reaction taking place at the

cathodic spot is:

• The ferrous ions (Fe2+) are further oxidised to ferric ions (Fe3+)
and finally to hydrated ferric oxide (Fe2O3. x H2O), which is called
rust.
Methods used to prevent corrosion
• By coating the metal surface with paint, varnish etc
• 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.

• By coating with anti-rust solution.

• An electrochemical method used is connecting the iron object

with a sacrificial electrode of another metal (like Mg, Zn, etc.),
which corrodes itself but saves the object (sacrificial protection).