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Electrochemistry
Electrochemistry Electrochemical Cell

The area of chemistry

The devices which
concerned with
convert electrical
the interconversion of energy into chemical
chemical energy energy or vice versa.
and electrical energy.
 Example
Electrochemical cell

A battery is an electrochemical cell

Electrolytic
Galvanic cell
cell

It takes the energy released by a

Also known as spontaneous chemical reaction and
voltaic cell. uses it to produce electricity.
 Galvanic Cell

A galvanic cell is an electrochemical

cell that produces electricity as a
result of the spontaneous reaction Anode Cathode
occurring inside it. (oxidation) (Reduction)

− +
ΔrG < 0

Example Daniel cell

Chemical energy is
converted
into electrical energy. Electron flow
 Electrolytic Cell

An electrolytic cell is an electrochemical

cell in which a non-spontaneous reaction
is driven by an external source of current.

+ −

ΔrG > 0

Electrical energy is converted

into chemical energy.
Current Battery
Electrons
 Important
Redox Couple
Points

Galvanic and electrolytic cells Any redox reaction may be expressed

1 as the difference of two half-reactions,
are reverse of each other.
which are conceptual reactions showing
gain and loss of electrons, i.e., reduction
and oxidation, respectively.

Redox reactions are

2
involved in both cells. The reduced and oxidised species in
a half-reaction form a redox couple.
 Reduction Oxidation

Redox Redox
Half-reaction Half-reaction
couple couple

M+/M M+ (aq) + e− M (s) M/M+ M (s) M+ (aq) + e−

Electrochemical Cell

An electrochemical cell consists of An electrode and its electrolyte

two electrodes, or metallic comprise an electrode
conductors, in contact with an compartment (half cell).The two
electrolyte, an ionic conductor (which electrodes may share
may be a solution, a liquid, or a solid). the same compartment.
 Half Cell

Example
Whenever a metal strip is put
in an electrolyte, the process of
oxidation or reduction takes
place within the system.

Some reactive metals have a

tendency to go into the solution
phase, when placed in contact with
their ions or their salt solution, it is
called oxidation.

Zn rod in ZnSO4 solution

 Electrode Potential

Electrode Potential:

Whenever a metal strip is Oxidation Potential (O.P.)

put in an electrolyte, a
potential difference
developed between metal
electrode and its ions in
solution.
Zn (s) Zn2+ (aq) + 2e‒ E Zn/Zn2+

Electrode potential can be Greater the O.P., greater will

either oxidation potential or be the tendency to get
reduction potential. oxidised.
 Electrode Potential

Cu rod in CuSO4 solution

Some metals (Cu, Ag, Au, etc.)

when in contact with their ions
in the solution have a
tendency to get deposited on
the metal rod.

Reduction
 Electrode Potential

Reduction Potential (R.P.)

Cu2+ (aq) + 2e‒ Cu (s) E Cu2+/Cu

Greater the R.P., greater will

be the tendency to get
reduced.
 Standard Electrode Potential

Electrode reaction in
Potential difference Representation
standard conditions
developed between metal
electrodes and the
solution of its ions at 1 M
Reduction: Zn2+ (aq) + 2e‒ Zn (s) E0 (SRP)
concentration at 1 bar Zn2+/Zn
pressure and at a
particular temperature is
known as standard Oxidation: Zn (s) Zn2+ (aq) + 2e‒ E0 (SOP)
electrode potential (E0). Zn/Zn2+
 Cell Potential

The driving force that pushes the Electromotive force

electrons away from the anode and of a cell is equal to the
pulls them towards the cathode is an potential difference
electrical potential called electromotive between its terminals
force, also known as cell potential when no current is
or the cell voltage. passing through
the circuit.

Unit: Volt
 Cell Potential

SRP of SRP of
= ‒
0
Ecell substance substance
reduced oxidised

The sign of the cell

SRP stands for standard reduction potential tells us the
potential which measures the direction in which the
tendency for a given chemical reaction must shift to
species to be reduced. reach equilibrium.

0
Ecell is a positive number
 Cell Potential

Reactions for which E° cell is The magnitude of the cell

positive. potential

Have equilibrium constants that is a measure of the driving force

favor the formation of the products behind a reaction. The larger the
of the reaction. value of the cell potential.

Occurs naturally and referred The farther is the reaction

to as spontaneous reaction. from equilibrium.
 Relation between ΔrG and Ecell

From thermodynamics
Maximum non-expansion
(electrical) work that a system
dG = dWnon-exp + VdP - SdT (the cell) can do is equal to
decrease in Gibbs free energy
At constant T & P

∫dG = ∫dWnon-exp We, max = |ΔG|

| ΔG | = Wnon-exp, max. ΔG identified with the Gibbs

energy of the cell reaction, ΔrG
 Relation between ΔrG and Ecell

Maximum electrical work Charge present on

obtained from a cell = |ΔrG| 1F = 1 mole of electron

ΔrG = ‒q×V = ‒ nFE

= 96,485 C/mol

where, F is Faraday’s constant

n = Number of moles of electron
≈ 96,500 C/mol
E = Electrode potential or cell EMF
ΔrG = Change in Gibbs energy for
half-cell or cell
 Relation between ΔrG and Ecell

By knowing the Δ rr G at a specified

composition, the cell emf at that
composition can be stated.

Spontaneous
Δ rG < 0 Ecell > 0
cell reaction

Non-spontaneous
Δ G>0 Ecell < 0
cell reaction r
 Calculation of Ecell

Electrode reaction Δ rG

1 Anode: A (s) An+ (aq) + ne‒ ΔrG1 = -nFE

A/An+

2 Cathode: Bm+ (aq) + me‒ B (s) ΔrG2 = -mFE m+

B /B

Multiply eqn (1) by m, & eqn (2) by n and then add both the equations

mA (s) + nBm+ (aq) mAn+ (aq) + nB (s) ΔrG3

Cell reaction Δ rG

ΔrG3 = m ΔrG1 + n ΔrG2

 Calculation of Ecell

When reduction potential of both

electrodes are taken into account:

Reduction Reduction
Ecell = potential ‒ potential
ΔrG3 = m ΔrG1 + n ΔrG2 of cathode of anode

⇒ -nmFEcell= -nmFEA/An+ ‒ nmFE Ered Ered

Bm+/B Ecell = ‒
(cathode) (anode)

Ecell = E + E The difference in electrode

A/An+ Bm+/B
potentials of the two half-cell
reactions (oxidation half-cell and
reduction half-cell) is known
as emf of the cell or cell
potential.
 Electrode potential or cell
Electrode potential depends on:
potential are intensive properties
and does not depend on:

1 Concentration of solution
1 Amount of solution

Thickness of metal
Nature of metal 2
2 rod/plate/wire, etc.

Stoichiometric variation
3
Nature of the electrolyte of a given cell reaction
3

A2+ (aq) + 2e‒ A (s), E = x volt

4
Pressure, temperature
conditions
2A2+ (aq) + 4e‒ 2A (s), E = x volt
 Electrode Potential

An electrode is chosen as a
The potential of a single
reference with respect to which
electrode
all other electrodes are valued.
cannot be determined. But
the potential difference
between two electrodes can
Standard Hydrogen Electrode
be measured accurately.
(SHE) is taken as standard
reference electrode.

The potential of an electrode Its electrode potential

is calculated using a is arbitrarily assumed
reference electrode. to be 0.00 volt.
 Electrode Potential

Electrode potential
of SHE at

Anode Cathode

H2 (g) ⇌ 2H+ (aq) + 2e‒ 2H+ (aq) + 2e‒ ⇌ H2 (g)

O.P. = E R.P. = E
H2/H+ H+/ H2

Under standard state, Under standard state,

E0 S.R.P. E0
S.O.P. = H2/H+
= H+/ H2
 Reference Potential

Electrode potential of SHE is

taken to be zero at all temperature.

S.O.P. = -S.R.P. = 0
 Calculation of Standard Electrode Potential

(at 298 K experimentally)

Example
To calculate standard potential
of any other electrode, it
Construct a cell
is coupled with SHE

Zinc
Anode Cathode SHE
electrode
Its potential is measured and that
gives the value of standard electrode 0
potential of that electrode. Ecell = 0.76 V
 Example

0
=
0 0
Ecell E ‒ E
H+/H2 Zn2+/Zn

0.76 = 0 ‒ E
0
Zn2+/Zn

E0
Zn2+/Zn = -0.76 V

W.r.t. H2, Zn has greater

=
0
E 0.76 V tendency to get oxidised.
Zn/Zn2+
 Measuring SRP of Zinc Electrode

Standard
Zinc Hydrogen
Electrode Electrode
Standard Electrode Potential Electrochemical Series

Similarly, SRP (at 298 K) for many Standard reduction potentials

other electrodes are calculated. (SRP) for various half-cells are
measured at 25℃ w.r.t. SHE

They are arranged in an

decreasing order series known These SRP are
as electrochemical series. arranged in an
decreasing order
 Electrochemical Series

SRP, E0
Half-reaction
(at 298 K)

F2 (g) + 2e− 2F− (aq) 2.87 V

Co3+ (aq) + e− Co2+ (aq) 1.81 V

H2O2 (l ) + 2H+ (aq) + 2e− 2H2O (l ) 1.78 V

−
MnO4 (aq) + 8H+ (aq) + 5e− Mn2+ (aq) + 4H2O (l ) 1.51 V
 Electrochemical Series
SRP, E0
Half-reaction
(at 298 K)

Au3+ (aq) + 3e− Au (s) 1.40 V

Cl2 (g) + 2e− 2Cl− (aq) 1.36 V

2−
Cr2O7 (aq) + 14H+ (aq) + 6e− 2Cr3+ (aq) + 7H2O(l) 1.33 V

O2 (g) + 4H+ (aq) + 4e− 2H2O (l) 1.23 V

MnO2 (s) + 4H+ (aq) + 2e− Mn2+ (aq) + 2H2O (l) 1.23 V
 Electrochemical Series

SRP, E0
Half-reaction
(at 298 K)

Br2 (l ) + 2e− 2Br− (aq) 1.09 V

−
NO3 (aq) + 4H+ (aq) + 3e− NO (g) + 2H2O(l) 0.97 V

2+
2Hg2+ (aq) + 2e− Hg2 (aq) 0.92 V

Ag+ (aq) + e− Ag (s) 0.80 V

Fe3+ (aq) + e− Fe2+ (aq) 0.77 V

 Electrochemical Series

SRP, E0
Half-reaction
(at 298 K)

O2 (g) + 2H+ (aq) + 2e− H2 O 2 0.68 V

I2 (s) + 2e− 2I− (aq) 0.54 V

Cu+ (aq) + e− Cu (s) 0.52 V

Cu2+ (aq) + 2e− Cu (s) 0.34 V

AgCl (s) + e− Ag (s) + Cl− (aq) 0.22 V

 Electrochemical Series

SRP, E0
Half-reaction
(at 298 K)

AgBr (s) + e− Ag (s) + Br− (aq) 0.10 V

2H+ (aq) + 2e− H2 (g) 0.00 V

Pb2+ (aq) + 2e− Pb (s) −0.13 V

Sn2+ (aq) + 2e− Sn (s) −0.14 V

Ni2+ (aq) + 2e− Ni (s) −0.25 V

 Electrochemical Series

SRP, E0
Half-reaction
(at 298 K)

Fe2+ (aq) + 2e− Fe (s) −0.44 V

Cr3+ (aq) + 3e− Cr (s) −0.74 V

Zn2+ (aq) + 2e− Zn (s) −0.76 V

2H2O (l ) + 2e− H2 (g) + 2OH− (aq) −0.83 V

Al3+ (aq) + 3e− Al (s) −1.66 V

 Electrochemical Series

SRP, E0
Half-reaction
(at 298 K)

Mg2+ (aq) + 2e− Mg (s) −2.36 V

Na+ (aq) + e− Na (s) −2.71 V

Ca2+ (aq) + 2e− Ca (s) −2.87 V

K+ (aq) + e− K (s) −2.93 V

Li+ (aq) + e− Li (s) −3.05 V

 Application of Electrochemical Series

Species (particularly metals)

(i) having highly negative SRP
are powerful reducing agents.

Examples Li, Na, Ca etc.

Species having highly +ve SRP

(ii) are powerful oxidising agents.

‒
Examples F2, MnO4 etc.
 Application of Electrochemical Series

More active metals can

(iii) displace less active metals
from their salt solution

CuSO4 (aq) + Zn (s) Cu (s) + ZnSO4 (aq)

ZnSO4 (aq) + Cu (s) No reaction Oxides of active metals

(iv) are thermally stable.

Examples Na2O, Al2O3, CaO

Application of Electrochemical Series

Oxides of less active metals

(v) are thermally less stable.

Δ
1 O (g)
Ag2O (s) 2Ag (s) + 2
2

Δ 1 O (g)
HgO (s) Hg (l) + 2
2
 Galvanic Cell

Daniell cell

Spontaneous redox
reaction is used here It is built by two electrodes
to produce electricity.

Zn rod dipped in Cu rod dipped in

ZnSO4 solution CuSO4 solution

Example Daniell cell

 Daniell Cell

Zn rod in ZnSO4 solutions

Zn atoms will move in the
solution to form Zn2+ ions

An electrical double layer is

developed in the system & hence
a potential difference is created
between the rod and the solution
known as electrode potential.

Zn (s) Zn2+ (aq) + 2e‒

 Daniell Cell

Cu2+ ions will get deposited

to form Cu atoms

Cu2+ (aq) + 2e‒ Cu (s)

 Daniell Cell

From electrochemical series,

E0Cu2+/Cu ＞ E0Zn2+/Zn
On joining the metal strips
through a wire (of negligible
resistance), the current flows as
long as the potential difference
Anode Zn half-cell exists between the metal phase
and the liquid phase.
Construct a cell

Cathode Cu half-cell
 Anode

Zn atoms will move in the Accumulation of extra

solution to form Zn2+ ions positive charge in the solution

After some time, equilibrium Will not allow extra zinc ions
is established to move in the solution.

Zn (s) ⇌ Zn2+ (aq) + 2e−

The solution will be saturated
with Zn2+ ions.
 Anode

Dynamic
equilibrium

−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
 Cathode

Cu2+ ions will get deposited

on electrode to form Cu Accumulation of sufficient
atoms positive charge on the rod will
not allow extra copper
ions to get deposited.

After some time, equilibrium

is established

Cu2+ (aq) + 2e− ⇌ Cu (s)

 Anode Cathode

Oxidation takes place at anode. Reduction takes place at cathode.

It acts as a source of electrons. It acts as a sink of electrons.

It has negative polarity. It has positive polarity.

The electrode potential The electrode potential

is represented by E E
Zn /Zn2+ is represented by Cu2+/Cu
 Cathode

Dynamic equilibrium
 Daniell Cell Metallic wire

Salt bridge

Zinc rod Copper rod

(Anode) (Cathode)

ZnSO4 CuSO4
solution solution

Electron Current
flow
 Salt Bridge

U-shaped inverted tube that contains

a gel permeated with an inert electrolyte
(E.g.: potassium chloride in agar jelly)

Functions of Salt Bridge

It connects the solution

1 of two half-cells to
complete the circuit.

It minimises the
2 liquid junction
potential.
 Liquid Junction Potential

In a cell, if two electrolytic solutions It arises because of the

of different concentrations are difference
in contact with each other, in the rates of diffusion of
positive and negative ions
from more concentrated
solution to less
concentrated solution.
A potential difference develops across
the boundary of the two solutions.

Ions of salt bridge electrolyte

diffuse through the gel-like
This potential difference is known solution and minimise the
as the liquid junction potential.
liquid junction potential.
 Example

0.1 M HCl 0.01 M HCl

H+
Cl−

Porous membrane

0.1 M HCl − + 0.01 M HCl

− +
− +
− +

Excess Cl− Excess H+

 Functions of Salt Bridge
It maintains the electrical
neutrality of the solution in
3 order to give continuous
flow or generation of current.
The simultaneous electrical neutrality
of the anodic oxidation chamber and
cathodic reduction chamber is due to
the same mobility or velocity of K+ and
NO3- ions taken into salt bridge.
Ensures that the two
electrolytic solutions do not
4 mix but slight diffusion of
ions from one electrode to
another is possible.
Salt bridge is not required for
galvanic cell in which a
common electrolyte of anode
half and cathode half is
present.
Example: Concentration cell
 Selection of Electrolyte for Salt Bridge

The electrolyte in salt bridge

Generally tube is filled with a should be such that, speed of its
paste of agar-agar powder cation equals to the speed of its
with a natural electrolyte anion in electrical field.

Generally, not common to

The ions of The ions
anodic/cathodic compartment with
the inert are not
porous plugs at each mouth of tube.
electrolyte do oxidised
not react or reduced
with other ion at the
in the electrodes.
solution.
 Selection of Electrolyte for Salt Bridge

If Ag+, Hg22+, Pb2+, Tl+ ions are present in

a cell, then in salt bridge, KCl is not used

KCl is generally
preferred but KNO3
or NH4NO3 can Because there can be formation of
also be used. precipitate of AgCl, Hg2Cl2, PbCl2
or TlCl at the mouth of the tube which
will prevent the migration
of ions and its functioning will stop.
 Ecell of Daniell Cell

At Anode

Zn (s) Zn2+(aq) + 2e‒

ΔrG1 = -2 × F × EZn/Zn2+
At Cathode

Cu2+(aq) + 2e‒ Cu (s)

ΔrG2 = -2 × F × E Cu2+/Cu
 Ecell of Daniell Cell

Cell reaction

Zn Cu2+ Cu Zn2+
(s) + (aq) (s) + (aq)

ΔrG3 = ΔrG1 + ΔrG2

-2 × F × E cell = -2 × F × E Zn/Zn2+ + -2 × F × E Cu2+/Cu

 Ecell of Daniell Cell

E cell = E
Cu2+/Cu + E Zn/Zn2+

E cell = E
Cu2+/Cu ‒ E
Zn2+/Zn

E0cell = E0Cu2+/Cu ‒ E0Zn2+/Zn

E0cell = 0.34 ‒ ‒ 0.76

E0cell = 1.1 V
 Efficiency of Daniell Cell

|ΔrG| × 100
Efficiency (𝜂) = |ΔrH|

Maximum electrical work

= Heat released in reaction
× 100
 Cell Representation

Oxidation Reduction
half cell + half cell

Electrochemical Cell

A cell can be represented using some

universal conventions and notations.
 Cell Representation

Rule 1

On the left side Anode half cell

On the right
Cathode half cell
side

Rule 2

The separation of two phases

shown by single vertical line (|)
 Cell Representation

Rule 3 Example

Sn(s) | Sn2+(aq), Sn4+(aq)

Various materials present
in the same phase are shown
together with comma (,)

Anode half cell

 Cell Representation

Example

The significant features Zn (s) | Zn2+ (aq, 1 M)

of the substance, like
pressure of a gas,
concentration of ions, etc.
is indicated in brackets
immediately after
writing the substance. Anode half-cell
 Cell Representation

Rule 4 Example

Anode half cell Cathode half cell

The salt bridge is represented by
double slash (||)

Zn (s) | Zn2+ (aq, 1 M) || Cu2+ (aq, 1 M) | Cu (s)

Salt bridge
 Cell Representation

Rule 5 Example

For gas electrode

Pt (s) | H2 (g) | H+ (aq) H+ (aq) | H2 (g) | Pt (s)
Gas indicated after electrode

For anode
For anode For cathode
Gas indicated before electrode

For cathode
 Complete Cell Representation

Pt (s) | H2 (g, 1 bar) | H+ (aq, 1 M) || Cu2+ (aq, 1 M) l Cu (s)

Salt bridge

Cathode half cell

Anode half cell

Phase boundary

Electrode
Factor Affecting Cell Potential

(1) Temperature

(2) Composition of the reaction mixtures

(3) The partial pressure of the gas (if any)

 Nernst Equation

For any reaction,

ΔrG = ΔrG0 + RT ln Q
The dependence
of the concentration and
pressure of the gas
on the cell potential −nFEcell = −nFE0
cell
+ 2.303 RT log Q
can be derived from
thermodynamics.

Q - Reaction quotient
 Reaction Quotient
For any reaction,

aA + bB cC + dD

Where,
R = Universal gas constant
[C]c [D]d T = Temperature
Q = [A]a [B]b
...(1)
n = Number of transferred
electrons
F = Faraday’s constant
2.303 RT Q = Reaction quotient
Ecell = E0cell − nF
log Q ...(2)

Nernst equation
 Nernst Equation
From thermodynamics,

Ecell =
0
Ecell −
0.059
log Q
ΔrG = ΔrG0 + RT ln Q
n

At chemical equilibrium,

0.059 [C]c [D]d

=
0
Ecell − n
log
[A]a [B]b
ΔrG = 0

Ecell = 0

Cell will be of no use

 Equilibrium in Electrochemical Cell

ΔrGO = -RT ln Keq log Keq =

nF
E0cell
2.303 RT

=
0
-nFEcell -2.303 RT log (Keq) T = 298 K,
Take R = 8.314 J/mol K,
F = 96500 C

2.303 RT
E0cell = nF
log Keq
n
log Keq = 0.059
E0cell
Nernst Equation for Different Types of Half-Cells

Based on the constituents,

electrodes are classified as:

Metal-metal soluble salt electrode

Gas electrode

Redox electrode

Metal-metal insoluble salt electrode

Calomel electrode
 Metal–Metal Soluble Salt Electrode

Considering a half-cell reaction,

M
Mn+ (aq)
n+
(aq) + ne‒
ne‒ M (s) Cell representation

Mn+ (aq) | M (s)

Nernst equation for the half-cell,

RT [M(s)]
EMn+/M = 0
EM n+/M − nF
ln
[Mn+(aq)]

2.303RT 1
= 0
EM n+/M − log
nF [Mn+]
 Metal–Metal Soluble Salt Electrode

Similarly for oxidation

B(s) Bm+ (aq) + me‒

2.303RT
= −
0
E B/Bm+ E B/Bm+ log [Bm+ (aq)]
mF

Cell representation: B (s) | Bm+ (aq)

 Metal–Metal Soluble Salt Electrode

Example Zinc half-cell,

Zn2+ (aq) + 2e− Zn (s)

Zinc Rod

Electrode potential

0 0.059 1
EZn2+/Zn = EZn 2+/Zn − 2
log
[Zn2+]

ZnSO4 Solution Cell

Zn2+ (aq) | Zn (s)
representation:
 Standard Hydrogen Electrode (SHE)

At 298 K
Pure H2 gets adsorbed
at Pt surface

A platinum
Pure
foil (platinum
Dipped in hydrogen Which is in contact with
electrode
an acidic gas is H+ ions in the solution
coated with
solution bubbled at
finely
of 1 bar into the
powdered
1 M HCl. solution.
Pt black).
Reduction or oxidation
occurs on Pt foil.
 Standard Hydrogen Electrode (SHE)

If it acts as anode, If it acts as cathode,

2H+(aq)
H2(g) 2H+(aq) + 2e‒ SOP = 0 + 2e− H2 (g) SRP=0

Cell representation Cell representation

Pt (s) | H2 (g, 1 bar) | H+ (aq, 1 M) H+ (aq, 1 M) l H2 (g, 1 bar) l Pt (s)

 Gas Electrode

Cl2 gas
Example
electrode

If it
acts as Pt (s) | Cl2 (g) | Cl‒ (aq)
anode
If it
Cl‒ (aq) | Cl2 (g) | Pt (s) acts as
cathode
 Redox Electrode

Pt wire

The electrode potential results

due to the presence of ions
of the same substance in Fe2+ (aq), Fe3+
different oxidation states. (aq)

If it acts as anode,
Pt wire is used as
electron carrier. Fe2+ (aq) Fe3+ (aq) + e‒

Pt (s) | Fe2+ (aq), Fe3+ (aq)

 If it acts as cathode,

Pt wire
Fe3+ (aq) + e‒ Fe2+ (aq)

Fe3+ (aq), Fe2+ (aq) | Pt (s)

Fe2+ (aq), Fe3+ (aq)

Example: MnO4−(aq) + 8H+ (aq) + 5e− Mn2+ (aq) + 4H2O (l)

0.059 [Mn2+]
EMnO ‒ /Mn2+
4 = E0MnO4‒ /Mn2+ − 5
log −
[MnO4 ][H+]8
 Metal-Metal Insoluble Salt Electrode

Ag rod
It consists of a metal
rod coated with metal
insoluble salt & dipped
into an aq. solution
containing anion of
insoluble salt.

Example:
Ag (s) | AgCl (saturated) in KCl KCl
solution
 Metal-Metal Insoluble Salt Electrode

If it acts as anode, If it acts as cathode,

Ag Cl‒ AgCl AgCl Ag Cl‒

(s) + (aq) (s) + e‒
(s) + e‒
(s) + (aq)

Cell
Cell representation representation

Ag (s) | AgCl (s) | Cl‒ (aq) Cl‒ (aq) | AgCl (s) | Ag (s)
 o
Determination of Ecell

Half-cell: Cl‒ (aq) | AgCl (s) | Ag (s)

AgCl Ag+ Cl−
(s) ⇌ (aq) + (aq)
… (1)

Cell reaction:
0
ΔrG1 = - 2.303RT log Ksp
AgCl Ag Cl‒
(s) + e‒
(s) + (aq)

… (2)
Ag+ (aq) + e− Ag(s)

=
0 0
ΔrG2 - n × F × EAg+ /Ag
 o
Determination of Ecell

AgCl (s) + e− Ag (s) + Cl− (aq)

… (3)

Eq. 3 = Eq. 1 + Eq. 2

Therefore,

ΔrG30 = ΔrG10 + ΔrG02

+
0 0
−nFECl −/AgCl/Ag
= −nFEAg+ /Ag (−2.303RT log Ksp)
Metal-metal Insoluble Salt Electrode

AgCl (s) + e− Ag (s) + Cl− (aq)

0 2.303RT
E
Cl‒/AgCl/Ag = EAg
0
+/Ag + log Ksp
nF

Standard half-cell potential of

metal-metal insoluble salt half cell.
 Determination of Ecell

Half-cell reaction

Cl−
AgCl (s) + e− Ag (s) + (aq)

Applying Nernst equation

0.059
ECl‒/AgCl/Ag = E0Cl‒/AgCl/Ag − n
log [Cl−]
 Determination of Ecell

0.059
E Cl‒/AgCl/Ag = EAg
0
+/Ag + log Ksp − 0.059
log [Cl−]
n n

0.059 [Cl−]
E Cl‒/AgCl/Ag = E0
Ag+/Ag − n
log
Ksp
 Determination of Ecell
Solution is saturated w.r.t. AgCl

+
[Ag+] × [Cl−] = Ksp (AgCl)

[Cl−] 1
Ksp(AgCl)
= [Ag+]

0.059 [Cl−]
E
Cl‒/AgCl/Ag = EAg
0
+/Ag − n
log
Ksp

0.059 1
E Cl‒/AgCl/Ag = E0Ag+/Ag − n
log
[Ag+]
 Calomel Electrode

A calomel electrode consists of a

platinum electrode dipped into
mercury in contact with calomel Movable rubber sleeve
(dimercury (I) chloride, Hg2Cl2) covering filling hole
and KCl solution. Usually, the
solution is saturated with KCl. Hg and Hg2Cl2 paste

Saturated KCl solution

The cell has E0 = 0.28 V

(with respect of SHE) at 25°C Asbestos fibre
 Calomel Electrode

If it acts as anode If it acts as cathode

2Cl‒ Hg2Cl2 2Hg 2Cl‒

2Hg
(l) + (aq)
Hg2Cl2
(s) + 2e‒ (s) + 2e‒
(l) + (aq)

Cell representation Cell representation

Pt (s) | Hg (l) | Hg2Cl2(s) | Cl‒(aq) Cl‒ (aq) | Hg2Cl2(s) | Hg (l) | Pt (s)

E0
Hg/Hg2Cl2/Cl‒ = SOP E0
Cl‒/Hg2Cl2/Hg = SRP
 Calomel Electrode

RT
E
Cl‒/Hg2Cl2/Hg = E0
Cl‒/Hg2Cl2/Hg − F
ln [Cl‒ ]

Standard (normal)
calomel electrode

When [Cl‒ ] = 1 M = 1 N
 Concentration Cells

A concentration
cell consists of two electrodes of Concentration
the same material, each Cells
electrode dipping in a solution
of its own ions.

Difference Difference in the

in the pressure of
electrolytic gases
Current flows in the outer circuit due
concentration at electrodes
to difference in concentration
of solution or partial pressure
of the gases involved.
 Concentration Cells
Example

From Nernst equation,

Cu (s) | Cu2+ (aq., C1) || Cu2+ (aq., C2) | Cu (s)

0.059 C1
=
0
Ecell Ecell − 2
log
C2
…(1)

Two copper electrodes having Cu2+

ions at different concentrations.

Here, n = 2, T = 298 K

C1 & C2 are concentrations

of Cu2+ ions of each half-
cell.
 Concentration Cells

Same metal and

Electrode Half-reaction
its solution

Anode Cu (s) Cu2+ (aq, C1 ) + 2e− As cathode and anode

consist of same electrode.
Cathode Cu2+ (aq, C2 ) + 2e− Cu (s)

Net cell reaction: 0

ECathode = 0
EAnode

Cu2+ (aq, C2) Cu2+ (aq, C1)

 Concentration Cells

0 0.059 C1
0
Ecell
for all Ecell = Ecell − log …(1)
2 C2
concentration cells

Putting values in eq. (1)

0
ECell = 0
ECathode − 0
EAnode Ecell = 0 − 0.059 log C1
2 C2

0
ECell = 0.00 Volt 0.059 C2
Ecell = log
C1
2
 Concentration Cells

C2
Ecell = 0.059 log
2 C1 Concentration Cells

For spontaneous reactions

to take place, Difference Difference in the
in the electrolytic pressure of gases
concentration at electrodes

C1 < C2
 Concentration Cells

Example Electrode Half-reaction

Anode H2 (g, P1) 2H+ (aq, x M) + 2e−

Pt (s) | H2 (g, P1) | HCl (x M) | H2 (g, P2) | Pt (s)

Cathode 2H+ (aq, x M) + 2e− H2 (g, P2)

Two hydrogen electrodes

Net cell reaction:
having hydrogen gas at
different pressures, dipped
in the same electrolytic H2 (g, P1) H2 (g, P2)
solution (x M HCl).

=
0
Ecell 0 Volt
 Concentration Cells

H2 (P1) H2 (P2)
0.059 P1
Ecell = log
Putting values in eq. (1) 2 P2

P2
Ecell =
0
Ecell − 0.059 log
For spontaneous reactions
2 P1
to take place,

0.059 P2
Ecell = 0 − log
2 P1
P1 > P2

0.059 P1
Ecell = 2
log
P2
 Concentration Cells at Equilibrium

At equilibrium
0.059
=
0
Ecell log Keq
n
Ecell = 0

0
nEcell
At 298 K,
Keq = 10
0.059
0.059
Ecell = 0
Ecell − n
log Keq
For concentration cell,
0.059
0 = 0
Ecell − log Keq
=
0
n Ecell 0
Concentration Cells at Equilibrium

Keq = 100

Keq = 1

For concentration cell

at equilibrium,

0
Ecell = 0, Ecell = 0, Keq = 1
Determination of Thermodynamic Functions

Cell reaction:

aA + bB cC + dD Ecell

ΔrG = -nFEcell

For a substance,

dG = VdP ‒ SdT

For a chemical reaction,

d(ΔrG) = (ΔV) dP ‒ (ΔrS) dT

 Determination of Thermodynamic Functions

d
ΔrS = ‒
dT
(‒nFEcell)

dEcell ΔrG = ΔrH ‒ T ΔrS

ΔrS = nF
dT

dEcell
dEcell Temp. coefficient ΔrH = -nFEcell + nFT
of cell reaction dT
dT

Unit: V/K or V/℃

 Electrolytic Cell

Cell reaction:

An electrolytic cell is an 2H2O (l) 2H2 (g) + O2 (g) Ecell = -1.23 V

electrochemical
cell in which a non-
spontaneous reaction
is driven by an external The spontaneous process is actually
source of current. the reverse reaction (i.e., formation
of H2O from H2 and O2)

Converts electrical energy

into chemical energy.
For this at pH = 7, Ecell = 1.23 V
Construction of Electrolytic Cell

Source of current

External Battery

Cathode is attached to negative

terminal of the battery

Reduction occurs at cathode

So, cathode acts as a

negative electrode
 Electrolysis

Electrolysis is a process of
oxidation and reduction due to
current in the electrolytic solution

Electrolyte is a combination
of cations and anions which
in fused state or in aqueous
solution can conduct electricity.
 Construction of Electrolytic Cell

Electrode Half-Reaction
Anode is attached to positive
terminal of the battery Cathode Na+ (l) + e− Na (l)

Anode 2Cl− (l) Cl2 (g) + 2e−

Oxidation occurs at anode

Overall reaction:

2Na+ (l) + 2Cl− (l) 2Na (l) + Cl2 (g)

So, anode acts as a
positive electrode

<
0
Ecell 0V
 Electrolysis of Molten NaCl

Product obtained during electrolysis

depends on following factors:

Sodium metal and

chlorine gas are called 1. Amount of charge passed
product of electrolysis into the electrolyte
of molten NaCl.
2. Nature of the electrolyte

3. Concentration the of
electrolyte

4. Nature of the electrode

Faraday’s First Law

The mass deposited/

released/produced of any
substance during electrolysis
is proportional to the
amount of charge passed
into the electrolyte.
 Faraday’s First Law

W ∝ Q If Q = 1C

W = ZQ W = Z

Mass deposited or liberated

W: Mass deposited or liberated Z when 1 C of charge is
Q: Amount of charge passed passed into the solution
Z: Electrochemical equivalent
of the substance

Unit: kg/C or g/C

 Equivalent Mass (E)

Mass of any Molar mass

substance produced
when 1 mole of
E = No. of e– involved in oxidation/reduction
electrons are passed
through the solution
during electrolysis. M
= n-factor
 Calculating Equivalent Mass (E)

Ag+ (aq) e− Ag (s) 3 Al3+ (aq) 3e− Al (s)

1
+ +
M
E = 1 M
E = 3

2 Cu2+ (aq) + 2e− Cu (s)

M
E = 2
 Faraday’s First Law

We know,
1 C charge E
= g metal deposited
1 mole of e– = 1 F of Charge flow 96500

1F = 96500 C
So, Z =
E
96500

E gram metal
96500 C
charge flow = deposited or Z is the mass deposited or
liberated liberated when 1 C of charge
is passed into the solution.
 Faraday’s First Law

From Faraday’s first law EQ

W = 96500

W = ZQ
M
E= Q=i×t
n-factor

Substituting the value of Z

Molar mass i×t
E
W = n-factor
×
96500
W = 96500
×Q
 Faraday’s Second Law

If equal charge (Q) is passed

through two electrolytic cells and
cells are connected in the series

The mass deposited at electrode will

be in the ratio of their electrochemical
equivalents or in the ratio of the
equivalents masses.
 Faraday’s Second Law

Considering two Since charge passed is

electrolytic cells, 1 & 2 same for both the cells,
connected in series

Applying 1st law,

Q1 = Q2

W1 = Z1 × Q1 W2 = Z2 × Q2

W1 Z1
So, =
W2 Z2
For two cells
 Faraday’s Second Law

E
As, Z = 96500

E1 E2
Z1 = 96500
& Z2 =
96500

W1 E1
W2
= E2

W1 Z1 E1
W2
= Z2
= E2
Nature of the electrolyte

Electrolyte

Molten form Aqueous form

 Aqueous Electrolyte

When electrolysis of aqueous

solution of electrolyte is carried out,
there may be two or more species
present in the solution which may
compete for reduction at cathode
or oxidation at anode.
 Aqueous Electrolyte

For species competing for For species competing for

reduction at cathode, oxidation at anode,

Higher is the SRP, greater Lower is the SRP (or higher in

will be its ease to undergo SOP) greater will be its ease to
reduction at cathode. undergo oxidation at anode.
 Molten Electrolyte

Electrolysis of molten NaF solution

Electrode Half-reaction E0

Cathode Na+ (l) + e− Na (l) E0 = -2.71 V

Anode 2F− F2 + 2e− E0 = -2.87 V

Product of electrolysis:

Anode F2 Cathode Na
 Aqueous Electrolyte

Electrolysis of aq. NaF solution

Possibilities at cathode:

Na+ (aq) + e− Na (s) E0 = -2.71 V

2H2O (l) + 2e− H2 (g) + 2OH‒ (aq) E0 = -0.83 V

Product of
electrolysis at H2
cathode
 Aqueous Electrolyte

Electrolysis of aq. NaF solution

Possibilities at anode:

2F− (aq) F2 (g) + 2e− Eox

0 = -2.87 V

2H2O (l) O2 + 4H+ + 4e− Eox

0 = -1.23 V

Product of
O2
electrolysis at anode
 Aqueous Electrolyte

Electrolysis of aq. NaCl solution

Possibilities at cathode:

Na+ (aq) + e− Na (s) E0 = -2.71 V

2H2O (l) + 2e− H2 (g) + 2OH− (aq) E0 = -0.83 V

Product of
electrolysis at H2
cathode
 Aqueous Electrolyte

Electrolysis of aq. NaCl solution

Possibilities at anode:

2Cl− (aq) Cl2 (g) + 2e− E0ox = -1.36 V

2H2O (l) O2 (g) + 4H+ (aq) + 4e− Eox

0 = -1.23 V

Product of
Cl2
electrolysis at anode
 Aqueous Electrolyte

According to thermodynamics, To increase its rate, the greater

oxidation of H2O to produce potential difference is applied known
O2 should take place on anode. as over voltage or over potential

However, experimentally the But because of this oxidation

rate of oxidation of water is of Cl– ions also become feasible
found to be very slow. and this takes place on anode.
Concentration of electrolyte

Concentration
of electrolyte

Dilute Concentrated
 Dilute Electrolyte

Electrolysis of aq. H2SO4 solution

Possibilities at cathode:

2H+ (aq) + 2e− H2 (g) E0 = 0.00 V

2H2O (l) + 2e− H2 (g) + 2OH− (aq) E0 = -0.83 V

Product of
electrolysis at H2
cathode
 Dilute Electrolyte

Electrolysis of aq. H2SO4 solution

Possibilities at anode:

2SO42− (aq) S2O82− (aq) + 2e− Eox

0 = -2.05 V

2H2O (l) O2 (g) + 4H+ (aq) + 4e− Eox

0 = -1.23 V

Product of
O2
electrolysis at anode
 Concentrated Electrolyte

Electrolysis of highly conc. aq H2SO4 solution

Possibilities at cathode:

2H+ (aq) + 2e− H2 (g) E0 = 0.00 V

2H2O (l) + 2e− H2 (g) + 2OH− (aq) E0 = -0.83 V

Product of
electrolysis at H2
cathode
 Concentrated Electrolyte

Electrolysis of highly conc. aq H2SO4 solution

Possibilities at anode:

2SO42− (aq) S2O82− (aq) + 2e− Eox

0 = -2.05 V

2H2O (l) O2 (g) + 4H+ (aq)+ 4e− Eox

0 = -1.23 V

Product of 2−
S2O8
electrolysis at anode
 Nature of the electrode

Electrode

Inert/ inactive Active

electrode electrode
 Inert Electrode Active Electrode

Electrode that The metal electrodes

conduct electrons in the cell that are
into or out of the cell active, because the
metals themselves are
but cannot take part
components of the
in the half-reactions. half reactions.

e.g. Pt, graphite, etc. E.g. Cu, Ag etc.

 Purification of Metals

Example
Electrolytic cell can be used
for the purification of metals.
Purification of
impure copper

By taking
At anode
impure metal
Obtained by dipping
two Cu strips in aq. CuSO4

Pure metal At cathode

Anode Cathode

CuSO4
solution
 Possibilities at anode

=
0
2H2O (l) O2 (g) + 4H+ (aq) + 4e‒ Eox -1.23 V

0
2-
2SO4 (aq)
2-
S2 O 8 (aq) + 2e‒ Eox = -2.05 V

Cu (s) Cu2+ (aq) + 2e‒

0
Eox = -0.34 V
 At the impure Cu anode

Cu is oxidised along with the more easily

oxidised metallic impurities such as Zn & Fe.

The less easily oxidised impurities such as

Ag, Au, and Pt fall to the bottom of the
cell as anode mud, which is reprocessed
to recover the precious metals.
Possibilities at cathode
At the pure Cu
cathode
2H2O (l) + 2e‒ H2 (g) + 2OH‒ (aq)

E0 = -0.83 V Cu2+ ions get reduced to

pure copper metal

Cu2+ (aq) + 2e‒ Cu (s)

However, the less easily

E0 = 0.34 V reduced metal ions (Zn2+,
Fe2+ and so forth) remain in
the solution.
 The net cell reaction
simply involves
transfer of Cu metal
from the impure
anode to the pure Anode Cathode
cathode. Zn2+
Fe2+
Cu2+
2−
SO4
Anode mud H+ CuSO4
(Au, Ag, solution
Pt, etc)
Cu obtained by this
process is 99.95% pure.
 Electroplating

Object to be
Cathode
electroplated
Electrolytic
deposition of a
thin film of metal Aq. solution of a salt
Electrolyte
on an object. of the plating metal
 Electroplating

For silver plating,

Metal is deposited on the cathode Solution of

Electrolyte
from ions in the electrolyte solution. silver salt

Object to be
Cathode
electroplated

These cations are either supplied by So that metal ions move to it

the added salt or from oxidation at when current is switched on.
anode, which is made of plating
metal
Cathode reaction

Ag+ (aq) + e‒ Ag (s)

 Conductors

Metallic Electrolytic Metallic Electrolytic

conductors conductors conductors conductors

No transfer of
Charge carriers are Charge carriers Transfer of mass
mass
electrons are ions
Resistance is
because of
Decomposition of Resistance is
No chemical collision of ions
electrolyte takes because of
changes with solvent
place collision of
molecules &
electrons with
because of
fixed metal atom.
interionic force of
attraction.
 Conductors

Metallic Electrolytic Metallic Electrolytic

conductors conductors conductors conductors

Metallic Electrolytic T Electrolytic T Electrolytic

conduction conduction conduction conduction
depends on the depends on the
nature nature of
of metal (e.g. no. electrolyte
of valence e- per (strong/ weak),
metal atom, nature of
crystal structure solvent
etc.), and its
temperature, viscosity,
length & area of temperature
cross section. etc.
 Electrical Resistance (R)

The electrical resistance

of a conductor

Directly Inversely
proportional to
proportional
its area of cross
to its length (l)
section (A).

Cross- sectional
area (A)

Length (l)
 Electrical Resistance (R)
Similarly for electrolytic conductors

l
R ∝
A
R = 𝜌 l
A

l l
R = 𝜌
A A
Cell
constant

l Separation between the

Known as electrodes
resistivity/specific
resistance Overlapping area of
A cross-section of electrodes
dipped in the solution
 Resistivity

Platinised Pt Cross
electrodes sectional A
area (A) 𝜌 = R
l
Length (l)

When l = 1 cm,
A = 1 cm2

𝜌 = R

Connectin
g wires
 Resistivity
Ohm
Unit centimetre
(Ω cm)

C.G.S.
Resistivity of a solution is Ohm meter
defined as the resistance (Ω m)
of the solution between
S.I.
the two electrodes of 1 cm2
area of cross-section
and 1 cm apart.

1Ωm = 100 Ω cm

1 Ω cm = 0.01 Ω m
 Conductance

The inverse of the resistance 1

is known as conductance.It is G = R
represented by G.
l
R= 𝜌
A

A
G = l𝜌
Unit mho or Ω-1 or S (siemens)

S.I.
 Factors Affecting Conductance & Resistance

Solute-solute interactions Solute-solvent interaction

(i) (Inter-Ionic force of attraction) (ii) (Hydration of ions)

Greater the force of attraction, Greater the solvation,

greater will be the resistance. greater will be resistance

1
Force ∝ Charge Solvation ∝ Charge ∝
Size
 Factors Affecting Conductance & Resistance

Solvent-solvent interaction
Li+ Hydrated largest (iii) (Viscosity):

Hydrated smallest Cs+ Greater the viscosity,

greater will be resistance

Resistance Resistance
of LiCl > of CsCl
Temperature , Resistance
(iv)
Factors Affecting Conductance & Resistance

Nature of electrolyte
(v)

Electrolyte Conductance

Weak Low

Strong High
 Conductivity (𝞳)

The inverse of resistivity is

known as conductivity/
specific conductance (𝞳).

1
𝞳
= 𝜌 G
= 𝞳 × A
l
1 A Gl
G
= 𝜌 × l
𝞳 = A
 Units of Conductivity (𝞳)

Unit S cm-1 / Ω-1 cm-1

Gl Gl l G l2
𝞳 = A
= A
× =
l V
C.G.S.
S m-1 / Ω-1 m-1

When l = 1 cm, V = 1 cm3

S.I.

𝞳 = G
1 S cm-1 = 100 S m-1
 Conductivity (𝞳)

Conductivity is the conductance

of unit volume of solution filled
between two parallel electrodes
at unit distance.

We know,
Accurate measurement
of resistance (R) performed on a
1 l Wheatstone bridge
𝞳 = R × A

Conductivity is computed by
measuring the resistance (R)
of the electrolyte and cell constant.
 Cell Constant (G*)
Cross-sectional
Area (A)

Length (l)
l Using G* and R of the
solution, conductivity of
the cell is determined.

G*
𝞳 = R
Value of cell constant is written
in the description of cell.
 Note

Conductance is Conductivity is additive

1 extensive property. 4 property when l/A is same.

Conductivity is
2 intensive property. 𝞳total = 𝞳1 + 𝞳2 + 𝞳3 + . . . . + 𝞳water

3 𝞳 ∝ Number of ions
G1 ×
l
+ G2 ×
l
+
l A A
Gtotal ×
A = l l
Conductivity or resistivity G3 × + .... + Gwater ×
of the solution is dependent A A
on its concentration.
 Note

Gtotal = G1 + G2 + G3 + .... + Gwater

1 1 1 1 1
Rtotal = R1
+
R2
+
R3
+....+
Rwater

All electrolytes in solution

are connected in parallel.
 Molar Conductivity (∧m)

l = 1 , and solution contains

Conductance of a solution containing
1 mole of an electrolyte between two 1 mol of electrolyte
electrodes which are unit length
apart
∧m = G

Gl
𝞳 = A
∧m = 𝞳 ×V

𝞳V Volume of solution which

𝞳A l
G = l
× = l
2
contain 1 mol of electrolyte
l
 In C.G.S. Unit

Molarity of
a solution
C mol/L ∧m = 𝞳×V

C mol
electrolyte 103 cm3 solution
𝞳 (S cm-1 ) × 1000
dissolves in ∧m (S cm2 mol−1 ) =
Molarity
1 mol
electrolyte 1000
cm3 solution
will dissolve C
in
 In S.I. Unit

Molarity of
C mol/L ∧m = 𝞳×V
a solution

C mol 𝞳 (S m-1 )
electrolyte 10‒3 m3 solution ∧m (S m2 mol−1 ) =
dissolves in 1000 × Molarity

1 mol
electrolyte 1 1 S m2 mol-1 = 104 S cm2 mol-1
m3 solution
will dissolve 1000 C
in
1 S cm2 mol-1 = 10-4 S m2 mol-1
 Equivalent Conductivity (∧eq)

Normality of
N eq./L
a solution

The conductance of
a solution containing N eq.
1 g-equivalent of electrolyte 103 cm3 solution
the electrolyte dissolves in

1 mol
electrolyte 1000
cm3 solution
will dissolve N
in
 Equivalent Conductivity (∧eq)

∧eq = 𝞳× V
Normality
of N eq./L
𝞳 (S cm-1 ) × 1000 a solution
∧eq (S cm2 eq−1) =
Normality
N eq.
electrolyte 10-3 m3 solution
∧eq = 𝞳 ×V dissolves in

1 eq.
𝞳 (S m-1 ) electrolyte 1 m3
∧eq (S m2 eq−1) = will 1000 N solution
1000 × Normality dissolve in
 Relation between 𝝠eq and 𝝠m

Dividing (eq. 2) by (eq. 1)

1S m2 eq-1 = 104 S cm2 eq-1

Λeq M
Λm = N
1S cm2 eq-1 = 10-4 S m2 eq-1

N = M × n-factor
𝞳 (S cm-1) × 1000 …..(eq. 1)
∧m (S cm2 mol-1) =
M Λm
Λeq = n-factor
𝞳 (S cm-1) × 1000
∧eq (S cm2 eq-1) = …..(eq. 2)
N
 Variation of Conductivity and Molar
Conductivity with Concentration

Effect of concentration
Both conductivity change on
& molar conductivity
change with the
concentration of
the electrolyte.
Molar
Conductivity
conductivity
 Variation of Conductivity (𝞳) with Concentration

Both for weak and

strong electrolytes. On dilution, number of ions
per unit volume decreases.

Concentration Conductivity
Also, conductivity depends
upon the number of ions
per unit volume.

Dilution

Conductivity decreases
Since, conductivity on dilution.
is the conductance
per unit volume of
electrolytic solution.
 Variation of Molar Conductivity (∧m) with Concentration

Molar conductance
increases upon dilution
The variation in Λm
with concentration for
Or decreases on increasing
the concentration.

Weak Strong
electrolytes electrolytes
Reason is different for strong
and weak electrolytes
 The Variation in Λm for Weak Electrolyte
At higher
concentration,
Weak electrolytes like acetic
Increase in the
acid have lower degree of
number of ions in
dissociation
solution

Near lower
With dilution of concentration
an ionic solution

At infinite Steep increase in

dilution, α 1 molar conductance
The degree of
dissociation (α) of
the electrolyte
increases
 Plot of Λm vs. √C

For CH3COOH solution

400

Λm (S cm2 mol-1 )
200

0 0.2 0.4
√C (mol/L)1/2
 The Variation in Λm for Strong Electrolytes

Λm increases slowly with In concentrated solution

dilution.

As strong electrolytes Strong attraction

are mostly in ionised state between oppositely
charged ions

No abrupt change in the Slows down the

number of ions with movement of ions
dilution.
 The Variation in Λm for Strong Electrolytes

With dilution, When concentration

Decrease in approaches zero
distance
interionic
between the
attractions
ions increases

The molar conductivity is

known as limiting molar
Gradual Influence of conductivity
increase in the other ions on
molar the movement
conductivity of of the ion
the solution decreases Molar conductivity
at infinite dilution
 Plot of Λm vs. √C
0
The variation in Λm for strong
Λm
= Λm − A√C

electrolyte is given by

400
For KCl solution

Λm (S cm2 mol-1 )
0
Λm
= Λm − A√C
200 Slope = - A

∧m : Molar conductivity
KCl
0
Λm
∧0m : Limiting molar conductivity
C : Concentration of electrolyte
A : Constant
0 0.2 0.4
√C (mol/L)1/2
 Plot of Λm vs. √C

Value of the constant 'A' for a given

solvent and temperature depends
on the type of electrolyte i.e., the
charges on the cations and anion
produced on the dissociation of
the electrolyte in the solution.
 Types of Electrolytes

Examples

Electrolyte Type

All electrolytes of
a particular type
have the same NaCl 1-1
value of ‘A’.

CaCl2 2-1

MgSO4 2-2
Dielectric constant of solvent ,A

Temperature , Viscosity , A

Λm0 for strong electrolyte can be

determined by extrapolation (as
variation is linear).

But not for weak electrolyte

(as variation is non-linear).
 Ionic Mobility (μ)

Speed
𝝻 =
Electric field
Speed of an
ion per unit
electric field
Speed
(potential gradient). =
Potential gradient

Unit of 𝝻 V-1 cm2 sec-1

Denoted by symbol ‘μ’
 Kohlrausch’s Law

At 298 K,
Kohlrausch examined ∧0m values
0 0 0 0
for ∧m ‒ ∧m ∧m ‒ ∧m
a number of strong electrolytes
(KCl) (NaCl) = (KBr) (NaBr)

and observed certain regularities.

= ∧0m (KI) ‒ ∧0m (NaI) ≃ 23.4 S cm2 mol‒1

Similarly, it was found that

He noted that the difference in
∧m0 of the electrolytes NaX and ∧0m (NaBr) ‒ ∧0m(NaCl) = ∧0m (KBr) ‒ ∧0m (KCl)
KX for any ‘X’ is nearly constant.

≃ 1.8 S cm2 mol‒1

 Kohlrausch’s Law of Independent Migration of Ions

AxBy solution

At infinite dilution or near zero AxBy (aq) xAy+ (aq) + yBx− (aq)
concentration when dissociation is 100%,
each ion makes a definite contribution
towards molar conductivity of electrolyte 0
irrespective of the nature of the other
0
Λm =
0
x λ Ay+ + y λ Bx−
ion.

x and y are the number of

cations and anions, respectively,
after dissociation of the
electrolyte
Kohlrausch’s Law of Independent Migration of Ions

At infinite dilution, when

dissociation is complete,

Each ion makes a definite

contribution towards equivalent
conductance of the electrolyte

Irrespective of the nature of

the ion with which it is associated
 General Case:

y 0 x 0
AxBy (aq) xAy+ (aq) + yBx- (aq) 0
Λ eq = y
λeq (Ay+) + λeq (Bx-)
x

= +
0 0 0
Λm x λm (Ay+)
y λm (Bx-) 0
Λ eq(A B )
x y
= λ0eq (Ay+) + λ0eq (Bx-)

0 Λ0m
Λ eq = n-factor
Al2(SO4)3 solution

0
1 0 1 0
Λ eq = y
λm (Ay+) + x
λm (Bx-) ∧0eq(Al
2(SO4)3)
= λ0eq(Al3+) + 0
λeq(SO
4)
2–
 Applications of Kohlrausch's Law

1
Kohlrausch law is used to evaluate
Λm0 for weak electrolytes.

To calculate limiting
molar conductivity
(Λm0 ) for weak
electrolytes.
From the individual
values of Λm
0 of the ions.
CH3COOH,
NH4OH etc.
Limiting Molar Conductivity of Weak Electrolytes

CH3COOH solution

At infinite dilution,

CH3COOH (aq) CH3COO− (aq) + H+ (aq)

Limiting molar conductivity of CH3COOH,

∧0m [CH3COO−] ∧0m [H+]

= +
0
∧m [CH3COOH] …(1)
 Limiting Molar Conductivity of Weak Electrolytes
The Λm
0 values of strong electrolytes
can be graphically obtained.
The Λ0m values of weak electrolytes
are calculated indirectly by evaluating
Λ0mvalues of selected strong electrolytes.
For different electrolytes having
common ion, limiting molar
conductivity of the common ion remains
same for all such electrolytes.
0
E.g:- λm (H + ) is same for both the
electrolytes, CH3COOH and HCl.
Applications of Kohlrausch’s Law

To determine the
degree of dissociation
(𝛼) and dissociation
constant ‘Ka’ of a
weak electrolyte.
 Degree of Dissociation

Dissociation of weak
electrolyte ‘HA’
∧m ∝ Degree of ionisation
HA ⇌ H+ A‒
+
c
∧m1 𝛼1
t=0 C 0 0 ∧m2
c = 𝛼
2

If C2 0 , 𝛼2 1
t = teq C − C𝛼 C𝛼 C𝛼

∧m
where, C: Initial concentration of HA
𝛼 = 0
…(1)
∧m
 Dissociation Constant (Ka)
Dissociation of weak ‒
electrolyte ‘HA’ [H+] [A ]
So, Ka = [HA]
HA ⇌ H+ + A‒
(C𝛼)(C𝛼)
Ka =
(C − C𝛼)
t=0 C 0 0
C𝛼2
Ka = …(2)
1−𝛼
t = teq C − C𝛼 C𝛼 C𝛼

where,
C: Initial concentration of undissociated electrolyte
𝛼: Degree of dissociation
Dissociation Constant of Weak Electrolyte

∧m C𝛼2
𝛼= …(1) Ka = …(2)
∧0m 1−𝛼

Put eq. (1) in eq. (2)

2
∧m
C 2
∧0m ∧m
Ka = ≃ C
∧m ∧m0
1− 0
∧m
 Application of Kohlrausch’s Law
3

To determine Solubility = Molarity ≃ 0

solubility and
solubility product
constant (Ksp) Solution can be considered
of a sparingly to be of zero concentration
soluble salt. or infinite dilution.

Hence,

Sparingly soluble salt

∧m ≃ 0
∧m

Very small solubility

 Solubility and Ksp

In C.G.S unit

If the conductivity (𝞳) 0 𝞳 × 1000

= =
0
and ∧m of a sparingly ∧m ∧m
Solubility (S)
soluble salt is known,
then solubility & Ksp
of the salt can be
calculated. 𝞳 × 1000
S = 0
∧m

S: Molarity of dissolved electrolyte

Example

AB2 (s) ⇌ A2+ (aq) + 2B− (aq)

𝞳AB2× 1000
S = 0
∧m, (AB )
2

Ksp = S × (2S)2

= 4S3
 Ionic Mobility

Speed of an ion per unit

electric field(potential gradient).

Denoted by symbol ‘μ’

Speed
𝝻
= Electric field

Speed
= Potential gradient

Unit of 𝝻 V-1 cm2 sec-1

 Conductometric Titrations

The principle of conductometric

titrations is based on the fact that
during the titration, one of the ions
is replaced by the other.

H+ (aq) and OH‒ (aq)

ions have
exceptionally high
ionic conductivity.
These two ions differ in the ionic
conductivity with the result that
the conductivity of the solution varies
during the course of the titration.
 Smaller is Greater is the Lesser should be
the ionic size hydrated size ionic mobility

Then why ionic

mobility of H+
is very high?
According to the
Grotthuss mechanism,
there is an effective
motion of a proton
that involves the
rearrangement of
bonds in a group of
water molecules.
Conductometric Titrations

Titrations

Strong acid vs. strong base

Strong acid vs. weak base

Weak acid vs. strong base

Mixture of acids vs. strong base

AgNO3 vs. NaCl

 Plot of Conductance vs. Volume of NaOH

Example HCl (strong acid) with NaOH (strong base)

Conductance (G)

The conductance of
pure HCl is very high, due to
the highly
conducting H+ ions
Equivalence
point

Volume of NaOH
 Strong Acid vs. Strong Base

Conductance (G)
H+ (faster Decreasing
Once the overall
moving) are
we start conductance
replaced
adding till the Volume of NaOH
with Na+
NaOH, equivalence
(slow
moving) point.
By further addition of NaOH,
the OH− conc. in the solution
increases gradually, which
increases the conductivity

This explains first

part of the graph. This explains second
part of the graph.
 Strong Acid vs. Weak Base
Example

NH4OH (weak base)

with HCl (strong acid) Once the addition of
weak base (NH4OH) started, a
replacement of highly
conducting H+ ions by NH4+
causes fall in conductance
Conductance (G)

observed up to the
equivalence point.

Equivalence
point

Volume of NH4OH
 Strong Acid vs. Weak Base

After the equivalence point

The
conductance It’s a weak
remains almost electrolyte,
constant, so further
because addition does
in the solution not increase
only NH4OH is conductance
added now significantly.
 Weak Acid vs. Strong Base

Acetic acid being titrated

Example
against NaOH

CH3COOH (weak acid)

with NaOH (strong base)

Before the addition

of alkali, the solution shows
Conductance (G)

poor conductance
due to feeble ionization of
acetic acid.

Volume of NaOH
 Weak Acid vs. Strong Base
After the addition of alkali,
conductance of the solution
decreases in the
beginning because:
1 Replacement of H+ ions by Na+ ions.
Suppression of dissociation of acetic
2 acid due to the common ion CH COO–.
3
After some time, conductance
starts increasing
Addition of NaOH neutralizes
the undissociated CH3COOH
to CH3COO–Na+
Replacing the non-conducting
CH3COOH with strong-
conducting electrolyte, CH3COO–
Na+
Weak Acid vs. Strong Base

The increase in conductance

continues right up to the
equivalence point.

Beyond this point conductance

increases more rapidly with
the addition of NaOH due to the
highly conducting OH– ions.
 Mixture of Acids vs. Strong Base

Example

HCl (Strong acid) and

CH3COOH (weak acid)

Conductance (G)
with NaOH (strong base)

As, HCl is It first reacts

stronger acid with NaOH

Volume of NaOH

Neutralisation reaction The graph has three parts.

HCl + NaOH NaCl + H2O

 Mixture of Acids vs. Strong Base
Conductance (G)

The conductance of the

solution gradually decreases
Volume of NaOH
due to the replacement
of H+ ions by Na+ ions.

CH3COOH
When HCl is
starts reacting
consumed This explains the first
with NaOH
part of the graph.
Neutralisation reaction

CH3COOH + NaOH CH3COONa + H2O

 Mixtures of Acids vs. Strong Base

Conductance (G)
The feebly ionised weak acid
(CH3COOH) is neutralised.

Volume of NaOH

The conductance increases After the equivalence point

marginally due to the salts
(CH3COONa) produced.
The increase in conductance
is appreciable due to the
added OH− ions
Which explains the second
part of the graph. Which explains the third
part of the graph.
 AgNO3 vs. NaCl

NaCl is added to
a solution of AgNO3,
Conductance (G)

Conductance remains constant

till all AgNO3 is used up as
AgCl is weak electrolyte.

Volume of NaCl
NO3‒ are replaced by Cl‒ ions
AgNO3 vs. NaCl

After AgNO3 is
used completely

There is an increase
in conductance as the
amount of NaCl increases.

Strong electrolyte
 Batteries

Types of batteries
Cell refers to a single
galvanic cell,,Whereas
battery is formed when
two or more cells are Primary Secondary
connected in series or in batteries batteries
series-parallel.

Non-
rechargeable
 Primary Batteries

Primary cells can be used +

only so long the active
materials are present.
Carbon rod
(cathode)
Once these are consumed, the
cell cannot be recharged by MnO2 + carbon
passage of current through it
black + NH4Cl
paste
Hence, it has to be discarded.
Zinc cup
(anode)
Examples ̶
Dry cell or Leclanche cell
Mercury Cell
 Dry Cell

Anode Cathode

Cathode:
Carbon (graphite)
rod surrounded by +
Zinc container powdered MnO2 + NH4 + e− MnO(OH) + NH3
manganese dioxide
and carbon.
Anode:
The space between the Zn (s) Zn2+ + 2e−
electrodes is filled by a moist
paste of ammonium chloride
(NH4Cl) and zinc chloride
(ZnCl2).
 Dry Cell

Ammonia produced in
the reaction forms a
complex with Zn2+

Zn2+ + 4NH3 [Zn(NH3)4]2+

Cell It decreases
1.5 V
potential over use

Used in flashlights,
portable radios, etc.
 Mercury Cell

Anode cap

Zinc - mercury
Anode
amalgam

Paste of HgO
Cathode
and carbon

Paste of KOH Anode Cathode

Electrolyte
and ZnO
Gasket Separator Cell can
 Mercury Cell

At the
anode: ECell = 1.35 V

Zn(Hg) + 2OH− ZnO (s) + H2O + 2e−

Overall reaction does not

At the cathode:
involve any ion in the solution
whose concentration can
HgO + H2O + 2e− Hg (l) + 2OH− change during its life time.

Overall cell reaction

Used in watches, hearing
aids, calculators, etc.
Zn(Hg) + HgO (s) ZnO (s) + Hg (l)
 Secondary Batteries

Examples

A secondary cell after

Lead storage cell
use can be recharged
by passing current
Nickel-cadmium cell
through it in the
opposite direction so
that it can
be used again.
 Lead Storage Cell

Cathode
Lead Anode Anode
̶

Grid of lead
+ Negative
plates: lead
packed with Cathode grids filled
lead dioxide with spongy
(PbO2) lead
Positive plates:
38% solution of lead grids
Electrolyte filled with
sulphuric acid
PbO2
38% sulphuric
acid solution
 Lead Storage Cell

When battery is in use

At the anode:

2−
Pb (s) + SO4 (aq) PbSO4 (s) + 2e−

At the cathode:

2−
PbO2 (s) + SO4 (aq) + 4H+ (aq) + 2e− PbSO4 (s) + 2H2O (l)
 Lead Storage Cell

Overall reaction
Pb (s) + PbO2 (s) + 2H2SO4 (aq) 2PbSO4 (s) + 2H2O (l)
(when in use)

On charging the battery While discharging lead

the reaction is reversed. storage battery

PbSO4 (s) on anode and

If 1 F of electricity is
cathode is converted into
withdrawn from battery,
Pb and PbO2, respectively.
1 mol of H2SO4 is consumed
 During working of cell

H2SO4
[H2SO4] in Density
will be of solution
solution
consumed
Used in automobiles
(cars/bikes) and
inverters.
During charging of cell

PbSO4 will get converted into Pb (s)

and PbO2 (s) and H2SO4 will be
produced.
 Nickel‒Cadmium Cell

Cadmium Anode

Nickel
dioxide Cathode Negative
(NiO2) plate

Separator

KOH Electrolyte Positive

plate
 Nickel‒Cadmium Cell

Anode:

Cd (s) + 2OH‒ (aq) Cd(OH)2 (s) + 2e‒

Cathode:

NiO2 (s) + 2H2O (l) + 2e‒ Ni(OH)2 (s) + 2OH‒ (aq)

 Nickel‒Cadmium Cell

Overall reaction: Cd (s) + NiO2 (s) + 2H2O (l) Cd(OH)2 (s) + Ni(OH)2 (s)

ECell = 1.4 V

Used in cordless razors,

portable electronics, etc. This cell has comparatively
longer life than a lead storage cell.
 Fuel Cell

Here, the cathode and anode

constituents are continually supplied.
Galvanic cell
that are designed
to convert the energy
of combustion of fuels
like H2, CH4, CH3OH, etc, Thus, energy can be withdrawn
directly into electrical indefinitely from a fuel cell as
energy. long as the outside supply
of fuel is maintained.
 H2‒O2 Fuel Cell

Electrodes Electrolyte H2 gas is fed into one

compartment and the O2 gas
is fed into another
compartment.

Made of a conducting
material, such as Aqueous solution
graphite, with a of a base
sprinkling of platinum These gases diffuse slowly
through the electrodes and
react with an electrolyte that
Acts as is in the central
compartment.
catalyst
H2‒O2 Fuel Cell

At the cathode:

O2 (g) + 2H2O (l) + 4e− 4OH− (aq)

At the anode:

2H2 (g) + 4OH− (aq) 4H2O (l) + 4e−

Overall reaction:

2H2 (g) + O2 (g) 2H2O (l)

 H2‒O2 Fuel Cell Advantages of Fuel Cells

Cell used for providing They offer high energy

electrical power in the
Apollo space program
1 conversions (almost 70%).
Compared to thermal plants
whose efficiency is about 40%.

The water vapour produced during

the reaction were condensed and
added to the drinking water supply
for the astronauts.
2 These cells are pollution-free.
 Corrosion

1 Rusting of iron

Slowly coating
of the surfaces of
metallic objects with
2 Tarnishing of silver
oxides or other
salts of the metal.

Development of green coating

3 on copper and bronze
Tarnishing of Silver Green Coating on Copper
 Rusting of Iron

Formation of porous coating

of iron oxide (Fe2O3.xH2O)
on iron surface in moist air

May be considered as an
electrochemical phenomenon
 Water
Iron surface O2 drop

Fe2+ (aq)

Fe Fe2+ + 2e−

O2 + 4H+ + 4e− 2H2O

 Rusted iron
(Fe2O3.xH2O)
 Anode reaction Cathode reaction

Behaves
Electrons released at
as
anodic spot move
cathodic
through the metal
Fe (s) Fe2+ (aq) 2e− region
+ … (1)

Go to another
spot on the metal
Eox
0
= 0.44 V

Reduce oxygen (of air)

in the presence of H+
 Cathode reaction

O2 (g) + 4H+ (aq) + 4e− 2H2O (l) .… (2)

0
E = 1.23 V
H+ available can be from

H2CO3 formed
Dissolution of
due to
other acidic
dissolution of
oxides from the
CO2 from air
atmosphere
into water
 Overall Reaction

Fe (s) Fe2+ (aq) + 2e− …1

O2 (g) + 4H+ (aq) + 4e− 2H2O (l) …2

Overall reaction

2Fe (s) + O2 (g) + 4H+ (aq) 2Fe2+ (aq) + 2H2O (l)

0 0 0
Ecell = Ecathode − Eanode

0
Ecell = 1.23 − − 0.44

=
0
Ecell 1.67 V
 Rusting of Iron

Fe2+ is further oxidised by

atmospheric oxygen to Fe3+.
Due to porous coating of rust

This comes out as rust in the

form of hydrated ferric oxide Further attack of
Strength
with moist air occur
of metal
on iron metal
further production of H+ ions.

Fe2O3. xH2O
 Prevention of Corrosion

Prevention

Using paint
Protective Cathodic
or some
coating protection
chemicals
 Prevention of Corrosion

1. Using Paint or Some Chemicals

Covering the surface with paint or

by some chemicals (e.g. bisphenol)
prevent the surface of the metallic
object to come in contact with the
atmosphere. 2. Protective Coating

Cover the surface by other

metals that are inert or
react to save the object.
Galvanisation: Coating of Zn metal
Galvanised Non-galvanised
 Atmosphere

Zinc layer

Iron slab (to be protected)

Partial corrosion
of zinc layer
 Complete corrosion of
zinc layer and appearance
of rust on Fe surface
 Prevention of Corrosion

3. Cathodic Protection

In cathodic protection, the object is

connected to a metal with a more
negative standard reduction potential A block of magnesium
(E.g.: Mg, E0 = −2.36 V). replaced occasionally is much
cheaper than the ship,
building, or pipeline for which
Mg acts as a sacrificial anode, it is being sacrificed.
supplying
its own electrons to the iron and
becoming oxidised to Mg2+ in the
process.
Cathodic Protection

Other active
Iron
metal

Cathode Anode