Electrochemistry

CLASS XII SIBI REJI

CHAPTER – 3
PART 1
 ELECTROCHEMISTRY

• Electrochemistry is the branch of chemistry

deals with the inter-relationship between
electrical energy and chemical changes.

SIBI REJI
• The chemical reactions occurring due to passage
of electric current is called electrolysis and the
device used to carry out electrolysis is called an
electrolytic cell.
• In electrolytic cells, the electrical energy is
converted into chemical energy.
• The chemical reactions in which electric current is
produced is called an electrochemical
reaction.
(i.e., chemical energy → electrical energy)
• E.g.: galvanic cell or Daniel cell or Voltaic cell
• Batteries and fuels convert chemical energy into
electrical energy.
SIBI REJI
 ELECTROCHEMICAL CELLS
• A device for converting chemical energy into electrical
energy is called electrochemical cell or Galvanic
cell or Voltaic cell.
• In a galvanic cell, redox reaction is carried out in an
indirect manner and the Gibb’s free energy of the
spontaneous redox reaction is converted into electrical
work which may be used for running a motor or other
electrical gadgets like heater, fan, geyser etc.
• An indirect redox reaction is such that reduction and
oxidation processes are carried out in separate vessels.
SIBI REJI
 GALVANIC CELLS
• It consists of 2 half cells.
• One half cell contains a zinc electrode dipped in 1M
ZnSO4 solution, in which oxidation takes place and
it is the anode (negative electrode).
• The other half cell contains a copper electrode
dipped in 1M CuSO4 solution, in which reduction
takes place and it is the cathode (positive electrode).
• When two electrodes are connected externally by a
metallic wire and the solutions are connected by a
salt bridge, a potential difference is developed.
SIBI REJI
• As a result, electrons flow from zinc electrode to
copper electrode.
• The following reaction occurs in the cell:
i. Zn (s) → Zn+2 (aq) + 2e- {oxidation half reaction}
ii. Cu+2 (aq) + 2e- → Cu {reduction half reaction}
• Overall redox reaction is,
Zn + Cu+2 → Zn+2 + Cu
• Disadvantage of the cell: The liquid can easily spill
out and it is inconvenient to carry it from place to
place.

SIBI REJI
SIBI REJI
• Salt bridge: It is a U-shaped glass tube filled with
jelly-like substance (agar-agar) mixed with an
electrolyte like KCl, KNO3, NH4NO3 etc. it
performs the following functions:
1. It permits electrical contact between the
electrode solutions but prevents from mixing.
2. It maintains the electrical neutrality of the
solution by inter-migration of ions into 2 half
cells.
3. It reduces the so called liquid–junction potential.
4. It provides sufficient amount of cations and
anions to replace the ions lost or produced in 2
half cells.
SIBI REJI
SIBI REJI
SIBI REJI
SIBI REJI
SIBI REJI
REPRESENTATION OF GALVANIC CELL
• Cathode on the RHS and anode on the LHS.
• The vertical lines between two half cells, which
indicates salt bridge.
• Sometimes the formula of the electrolyte used in
the salt bridge is written below the vertical lines.

• LOAN – Left Oxidation Anode Negative SIBI REJI

 ELECTRODE POTENTIAL

• When an electrode M is immersed in a solution

containing its own ions (Mn+), the following
changes takes place:
A) metal atom (M) loses ‘n’ electrons to give Mn+
ions. (Oxidation) electrode negative charge
B) Metal ion (Mn+) gains ‘n’ electrons to give metal
atom (reduction) electrode positive charge.
C) no change
SIBI REJI
• A potential difference develops between the electrode
and the electrolyte which is called electrode
potential.
• The electrode potential is a measure of the tendency
of an electrode to gain or lose electrons.
• The tendency of an electrode to gain electrons –
reduction potential.
• The tendency of an electrode to lose electrons –
oxidation potential.
• Oxidation potential is numerically equal to reduction
potential but has a opposite sign.
• According to IUPAC conventions, the reduction
potential is called electrode potential – EMn+/M
SIBI REJI
 STANDARD ELECTRODE POTENTIAL

• The electrode potential at standard conditions

(298K, 1 atm pressure, and 1M conc. solution) is
called Standard Electrode Potential - E°.

SIBI REJI
 CELL POTENTIAL OR EMF OF A CELL
• The potential difference between the 2 electrodes of
a Galvanic cell is called cell potential (EMF) and it is
measured in Volts.
• Electrons flow from the electrode with lower
reduction potential to the electrode with higher
electrode potential.
• EMF = Ecell = redn potential of cathode – redn potential of anode
Ecell = ER – EL
= Ecathode – Eanode
Ecell = ECu+2/Cu – EZn+2/Zn (Daniel Cell)
SIBI REJI
 MEASUREMENT OF ELECTRODE
POTENTIAL
• The electrode potential of a half cell cannot be
directly measured. It is measured in an indirect
manner.
• The electrode whose potential is to be measured
is combined with a reference electrode called
standard hydrogen electrode (SHE).

SIBI REJI
 STANDARD HYDROGEN ELECTRODE
(SHE)
• The electrode potential of SHE is arbitrarily
taken as zero at all temperatures.
• It consists of a platinum electrode coated with Pt
black. The electrode is dipped in 1M HCl
solution and pure H2 gas at 1 bar is bubbled
through it (1M, 1 atm, 298K)
• The concentration of both oxidised and reduced
forms of hydrogen is maintained unity.
SIBI REJI
• The electrode is represented as:
❖Pt(s),H2(g)(1bar)/H+(aq) (1M) -Anode
❖H+(aq) (1M) /Pt(s),H2(g)(1bar)-Cathode
• The cell reactions:
i. H2 → 2H+ + 2e- (oxidation - anode)
ii. 2H+ + 2e- → H2 (reduction - cathode)
SIBI REJI
 MEASUREMENT OF
ELECTRODE POTENTIAL

• According to IUPAC convention, the electrode

potential is given positive sign if the electrode
reaction involves reduction when it is oxidation
when connected to SHE.
• Thus, the electrode in standard conditions is
coupled with a SHE through a voltmeter.
• The reading of a voltmeter indicates the EMF
between the two electrodes.
• Since the potential of SHE is zero, the measured
EMF will numerically be equal to the potential of the SIBI REJI

electrode.
E.g.: when a copper electrode under standard
conditions is connected to SHE, the resulting
galvanic cell is
Pt(s)| H2(g, 1 bar)| H+ (aq, 1 M) || Cu2+ (aq, 1 M) |Cu
The EMF of the cell is 0.34 V.
E0cell = E0R – E0L = 0.34 V
= E0Cu+2/Cu – E0SHE

SIBI REJI
 SIBI REJI

EMF OF DANIEL CELL

 SIBI REJI

ELECTROCHEMICAL SERIES

• The arrangement of various elements in the

increasing or decreasing order of their standard
electrode potential is called electrochemical
series or activity series.
• A negative E0 – redox couple is stronger
reducing agent than H+/H2 couple.
• A positive E0 – redox couple is stronger
oxidising agent than H+/H2 couple.
SIBI REJI
 APPLICATIONS
1. To calculate the EMF an electrochemical cell.
The electrode with higher reduction potential is taken
as cathode and the other as anode.
E0 cell = E0 cathode – E0 anode = E0 R –E0 L

2. To compare the reactivity of elements.

Any metal having lower reduction potential can displace
the metal having higher reduction potential from the
solutions of their salt.
Eg. Zn can displace Cu from CuSo4 from salt solutions
from salt solutions (metals can displace metal ions from
salt solutions which lie above electrochemical series).
Zn + CuSo4 → ZnSo4 + Cu SIBI REJI
3) To predict the feasibility of cell reactions.
If the EMF is positive, the cell reaction is
feasible and if it is negative , the cell reaction is
not feasible.
4) To predict whether the gas will be evolved
by reaction of metal with acids.
All metals which have lower reduction potential
compared to that of H2 electrode can liberate H2
gas from acids (-ve reduction potential can
displace)
5) To predict the product of electrolysis.

SIBI REJI
NOTE:
• Li : lowest electrode potential – powerful reducing
agent/Li+
• F2 : highest electrode potential – powerful
oxidising agent.
• F- - weakest reducing agent
• Electrochemical cells are used in determining the
pH of solutions, solubility product, equilibrium
constant and other thermodynamic properties and
for potentiometric titrations.
SIBI REJI
 SIBI REJI

NEARNST EQUATION

• Nernst derived an equation for the single

electrode potential. It gives a relationship
between the electrode potential and ionic
concentration of the electrolyte solution for the
reduction occurring at an electrode Mn+/M,
• Mn+ (aq) + ne- → M(s)
• The electrode potential at any concentration
measured with respect to SHE can be replaced by
Nernst equation,

SIBI REJI
SIBI REJI

NERNST’S EQUATION FOR GALVANIC CELL

(i.e. DANIEL CELL)
GENERAL REACTION

SIBI REJI
 Equilibrium Constant from
Nernst Equation
At equilibrium,
• [Cu+2], [Zn+2] – no change
• Voltmeter shows zero reading
• Ecell = 0
• T = 298K
• and

SIBI REJI
SIBI REJI
 SIBI REJI

Electrochemical Cell and Gibbs Energy

of the Reaction
• Electrical work done in one second is equal to
electrical potential multiplied by total charge
passed. To get maximum work from a galvanic
cell, the charge has to be passed reversibly.
• the reversible work done by a Galvanic cell =
decrease in Gibbs energy
• And therefore, if the emf of the cell is E and nF is
the amount of charge passed and ∆ Gr is the gibbs
energy of the reaction,
∆ Gr = -nFEcell
SIBI REJI
 SIBI REJI

CONDUCTANCE OF
ELECTROLOYTIC SOLUTIONS

• Conductors – a substance which allows the

passage of electricity through it is called a
conductor.
• Metallic or non-metallic conductors – In
metallic conductors, the conductance is due to the
movement of electrons, which depends on:
i. The nature and structure of the metal.
ii. The number of valence electrons per atom.
iii. Temperature (it decreases with increase in
temperature)
E.g.: Ag, Cu, Al etc.
 SIBI REJI

• Electrolytic conductors – the substances which

conduct electricity in molten state or in solution are
called electrolytes.
• The conductance of electricity by ions present in the
solution is called electrolyte or ionic
conductance and it depends on
1. Nature of electrolyte
2. Size of ions and their solvation
3. Nature of solvent and its viscosity
4. Temperature (it increases with increase in
temperature)
 SIBI REJI

• Like electronic conductors, the electrolytic

conductors also obey Ohm’s Law. Ohm’s Law
states that current passing through the conductor (I)
is directly proportional to the potential difference
(V) applied.
•I V
• V = IR
• R is constant called resistance whose unit is Ohm
(Ω).
• The electrical resistance of any object is directly
proportional to length (l) and inversely proportional
to the area of cross-section(A).
 SIBI REJI

• SI unit of resistivity is Ωm or Ωcm.

• When l = 1m, A = 1m2, Rho = R, i.e., Resistivity
for a substance is its resistance when it is 1m
long and its area of cross section is 1m2.
• 1Ωm = 100 Ωcm
• 1 Ωcm = 0.01 Ωm
 CONDUCTANCE (G)
• The inverse of resistance is called conductance. Or
reciprocal of resistance.
• Unit is Ω-1, mho or Siemen (S).

• The SI units of conductivity are S m–1 but quite

often, κ is expressed in S cm–1.
• Conductivity of a material in S m–1 is its
conductance when it is 1 m long and its area of
cross section is 1m2.
• 1 S cm–1 = 100 S m–1. SIBI REJI
 SIBI REJI

MOLAR CONDUCTANCE

• It is the conductance of a solution containing 1

mol of the electrolyte when placed between two
parallel electrodes 1cm apart.
• It is the product of the specific conductance
(Kappa) and volume (V) in cm3 of the solution
containing 1 mol of the electrolyte.
◦ KV
 SIBI REJI

MEASUREMENT OF CONDUCTIVITY
OF IONIC SOLUTIONS

• The measurement of an unknown resistance can be

done by Wheatstone bridge.
• To measure the resistance of the electrolyte it is
taken in a specially designed vessel called
conductivity cell.
• It consists of two Pt electrodes coated with platinum
black.
• These have an area of cross-section A, and are
separated by a distance l. therefore, solution
confined between these electrodes is a column of
length l and of area of cross-section A.
SIBI REJI
 SIBI REJI

• The resistance of such column of solution is given

by the equation

• The quantity (l/A) is called cell constant denoted

by G*. It depends on the distance between the
electrodes and the area of cross-section A.
MEASUREMENT OF CONDUCTANCE

• We know that
• The value of K could be known if we measure l,
A, R. The value of the resistance of the solution
R between two parallel electrodes is determined
by using ‘Wheatstone bridge’ method.

SIBI REJI
 SIBI REJI

• It consists of two fixed resistances R3 and R4,

variable resistance R1 and the conductivity cell
having the unknown resistance R2.
• The bridge is balanced when no currents passes
through the detector.
• Under these conditions,
 SIBI REJI

VARIATION OF CONDUCTIVITY AND MOLAR

CONDUCTIVITY WITH CONCENTRATION

• Conductivity decreases with decrease in

concentration both for weak and strong electrolytes.
This is because the number of ions per unit volume
that carry the current in the solution decreases on
dilution.
• Molar conductivity increases with decrease in
concentration or increase in dilution. This is because
the total volume V of the solution containing 1 mol
of electrolyte increases. The decrease in K on
dilution of a solution is more compensated by an
increase in its volume.
 SIBI REJI

LIMITING MOLAR CODUCTIVITY

 Strong electrolytes-
DEBYE-HUCKEL ONSAGAR EQUATION

SIBI REJI
 SIBI REJI

KOHLRAUSCH LAW OF INDEPENDENT

MIGRATION OF IONS
 SIBI REJI

Weak Electrolytes
 SIBI REJI

Application of Kohlrausch law

1) Calculation of molar conductivities of weak

electrolytes at infinite dilution
 SIBI REJI

• 2)Determination of degree of dissociation of

weak electrolyte.

• 3)Determination of dissociation constant(Ka) of

a weak electrolyte.
 SIBI REJI

• 4)Determination of solubility of sparingly

soluble salts
=Kx1000/molarity

◦ =Kx1000/solubility
 SIBI REJI

ELECTROLYTIC CELLS AND

ELECTROLYSIS
• In an electrolytic cell external source of voltage
is used to bring about chemical reaction.
• The process of decomposition of an electrolyte
when electric current is passed through its
aqueous solution or fused state is called
electrolysis.
Quantitative Aspects of Electrolysis
• The process of electrolysis of a substance is governed by
Faraday’s laws of electrolysis.
• A)Faraday’s first law of electrolysis
‘The mass of any substance deposited or liberated at any
electrode is directly proportional to quantity of
electricity passed through the electrolyte.’
If ‘w’ grams of the substance is deposited on passing ‘Q’
coulombs of electricity, then
• W∝Q ,
• Q=It,(I=current in A, t=time in seconds)
• w=ZQ=ZIt, where Z is electrochemical equivalent of the
substance deposited
SIBI REJI
 SIBI REJI

• Electrochemical equivalent (Z):

• If I=1A ,t=1sec then w=Z, ie., electrochemical
equivalent may be defined as the amount of
substance deposited by passing 1A current for
1sec or by passing 1C of charge through the
electrolyte.
 SIBI REJI

• B)Faraday’s second law of electrolysis

• ‘When same quantity of electricity is passed through
solutions of different electrolytes connected in series, the
amount of different substances deposited at the
electrodes is directly proportional to their chemical
equivalent weight.’
Equivalent weight of metal =

▫ =
 SIBI REJI

BATTERIES

• The electrochemical cells used to generate electricity

is called batteries.
• There are 2 types of cells:-
i. Primary cells – in which electrode reactions
cannot be reversed by external energy source.
These are not rechargeable.
Eg. Dry cell, mercury cell
ii. Secondary cells – cells which can be recharged
are called secondary cells. The reactions can be
reversed by passing current through them.
Eg. Lead storage cells, Nickel-cadmium cell
 SIBI REJI

PRIMARY CELLS
I. Dry cell- is a compact form of Leclanche cell
• Anode- Zinc container
• Cathode- carbon rod surrounded by powdered
manganese dioxide and carbon
• Electrolyte- moist paste of NH4Cl + ZnCl2
• Emf- 1.45V
• The cell reaction is:
➢Anode - Zn → Zn+2 +2e-
➢Cathode –
2MnO2 + 2NH4+ + 2e- → Mn2O3 + 2NH3 + H2O
• Ammonia produced in the reaction forms a complex
with Zn2+ to give [Zn(NH3)4]+2
 SIBI REJI

II. Mercury cell-

• Anode- Zinc-amalgam (Zn/Hg)
• Cathode- paste of HgO and carbon
• Electrolyte- KOH + ZnO
The cell reactions are-
• Anode- Zn +2OH- → ZnO + H2O +2e-
• Cathode- HgO + H2O + 2e- → Hg + 2OH-
• Overall reaction- Zn + HgO → ZnO +Hg
• Emf- 1.35V
• Uses- digital watches, hearing aids of cameras
 SIBI REJI

SECONDARY CELLS
I. Lead storage cell- commonly used in automobiles
and invertors
• Cathode- a grid of lead packed with lead dioxide
(PbO2)
• Anode- lead
• Electrolyte- 38% solution of H2SO4

The cell reactions are-

Anode- Pb + SO4-2 → PbSO4 + 2e-
Cathode- PbO2 + SO4-2 + 4H+ + 2e- → PbSO4 + 2H2O
Overall reaction- Pb + PbO2 + 2H2SO4 → 2PbSO4 +2H2O
SIBI REJI
 SIBI REJI

• The emf of the cell depends on the concentration of

H2SO4 in solution. In order to recharge the battery, the
reaction occurring on discharge of the battery is applied
externally. during this process Pb is deposited in the
cathode, lead oxide at the anode and H2SO4 is generated
in the cell.
• 2PbSO4 + 2H2O →Pb +PbO2 +2H2SO4
• The lead storage cell act as a galvanic cell when it is
being used and as an electrolytic cell during recharging.
• Thus when it is used to start a motorcar it acts as a
galvanic cell and when the car is running, it acts as an
electrolytic cell (recharging).
 SIBI REJI

II. Nickel-cadmium cell (Nicad)

• Anode- Cd
• Cathode- Ni (IV)oxide/ Ni (OH)3
• Electrolyte- KOH
• The overall reaction during discharge
Cd + Ni (OH)3 → CdO + Ni (OH)2 + H2O
• Emf- 1.4V
• Uses- electronic watches, calculators
• Since it is smaller and lighter, it is used in portable appliances.
 SIBI REJI

FUEL CELLS

• Galvanic cell that are designed to convert the

energy of combustion of fuels like hydrogen,
methane, methanol directly into electrical
energy are known as fuel cells. Such cells convert
74% of chemical energy into electrical energy.
 SIBI REJI

ADVANTAGES

• Fuel cells are more efficient (70%) than

conventional methods of generating energy
(thermal power plants).
• Fuel cells do not cause any pollution problem.
• The electrodes are not affected.
 SIBI REJI

HYDROGEN-OXYGEN FUEL
CELL
• In the cell, hydrogen and
oxygen are bubbled through
porous carbon electrodes
containing catalyst like finely
divided platinum or palladium
metal, to increase the rate of
electrode reaction containing
into concentrated aqueous
KOH or NaOH solution placed
between the electrodes.
 SIBI REJI

• Electrode reactions are:

➢Anode- 2H2 + 4OH- → 4H2O + 4e-
➢Cathode- O2 + 2H2O +4e- → 4OH-
➢Overall reaction - 2H2 + O2 → 2H2O
• The cell runs continuously as long as reactants
are supplied. The emf of the cell is 0.9V.
• The cell has been used for electric power in
Apollo Space Program.
• The product of combustion that is water was
used for drinking by the astronauts.
 SIBI REJI

Corrosion
• Corrosion is a process which involves the slow
destruction of a metal as a result of its reaction
with moisture and other gases present in the
atom.
• The rusting of iron (rust is a hydrated form
of ferric oxide Fe2O3.xH2O), tarnishing of
silver, formation of green coating on copper and
bronze etc are examples of corrosion.
 MECHANISM OF CORROSION SIBI REJI

• Corrosion of iron (rusting) occurs in the

presence of water and air. Impure iron acts
as an electrochemical cell. Iron is oxidised
(lose 2 e- to form Fe2+) and act as an anode.
• Anode- 2Fe → 2Fe+2 + 4e- E0 = -0.44V
• e-s released at the anodic spot move through metal to
another spot and reduce O2 in the presence of H+ (which
acts as a cathode)
• Cathode- O2 + 4H+ + 4e- → 2H2O E0 = 1.23V
• Overall- 2Fe + O2 + 4H+ → 2Fe2+ +2H2O E0 = 1.67V
• The ferrous iron are further oxidised by atom O2 to ferric
ions and form hydrated ferric oxide Fe2O3.xH2O
 SIBI REJI

PREVENTION OF CORROSION
• Barrier protection – coating the surface with paints,
grease, metals like Ni, Cr, Cu etc.
• Sacrificial protection – coating the surface of iron
with a layer of active metals like Zn, Mg, Al etc.
Process of coating a thin film of Zn on iron is
known as galvanisation.
• Anti-rust iron – applying alkaline
phosphate/alkaline chromate on iron objects which
provide a insoluble film.
Also the alkaline nature of the solutions decrease the
availability of H+ iron and then decrease the rate of
corrosion.
 SIBI REJI

PRODUCTS OF ELECTROLYSIS
SIBI REJI