CHAPTER 2

ELECTRO CHEMISTRY
Electro chemistry is that branch of chemistry
which deals with the inter-relationship
between electrical energy and chemical
energy.
Electrochemical cell
The chemical reaction in which electric
current is produced is called an
electrochemical reaction and these type of
cells are called as electrochemical cell.
Galvanic cell and electrolytic cell are
examples for electro chemical cell.
Electrolytic cell: -
The chemical reaction occurring due to
the passage of electric current is called
electrolysis and the device to carry out
electrolysis is called an electrolytic cell.
In this cell electrical energy converted
into chemical energy.
Daniel cell (Galvanic cell)
It consists of two half cells contains a Zinc
electrode dipped in a molar solution of
Zinc sulphate- Oxidation takes place. It is
known as anode (negative electrode).

𝑍𝑛 𝑠 → 𝑍𝑛2+
𝑎𝑞 + 2𝑒 − 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 ℎ𝑎𝑙𝑓

Copper electrode dipped in a molar

solution of copper sulphate solution
Reduction takes place. Known as Cathode
(+ve electrode).
𝐶𝑢2+
𝑎𝑞 + 2𝑒 − → 𝐶𝑢
𝑠 𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 ℎ𝑎𝑙𝑓
Net cell reaction
𝑍𝑛 𝑍𝑛2+ 𝐶𝑢2+ 𝐶𝑢
Electrode potential: -
A potential difference develop in between
the electrode and electrolyte is called
electrode potential.
Loss electron - oxidation potential.
Gain electron - reduction potential.
• Oxidation potential and reduction
potential are equal but opposite in sign.
• The reduction potential alone is called
electrode potential.
Standard electrode potential: - The electrode
potential under standard conditions (298 K,
1 atm pressure and 1M conc.) is called
standard electrode potential 𝐸0.
Cell potential or emf cell: -
The difference between the electrode
potential of the cathode and anode of an
electrochemical cell is known as cell
potential of cell.
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
= 𝐸𝑅 − 𝐸𝐿
Standard hydrogen electrode (SHE)
A platinized platinum dipping into a solution
containing 1 molar concentration of H+ ions.
Pure H2 gas at 1 atm pressure is constantly
bubbled through it at constant temperature
of 298 K. The electrode potential is
arbitrarily fixed as zero
𝐴𝑛𝑜𝑑𝑒: 𝐻2 𝑔 → 2𝐻 +𝑎𝑞 + 2𝑒 −
𝐶𝑎𝑡ℎ𝑜𝑑𝑒: 2𝐻 +𝑎𝑞 + 2𝑒 − → 𝐻2 𝑔

𝑁𝑒𝑡 𝑐𝑒𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛: 𝐻2 𝑔 ⇌ 2𝐻 + + 2𝑒 −

Measurement of electrode potential
It is determined by connecting half cell with a
SHE, which taken as zero. eg: measurement of
electrode potential of Cu2+/Cu electrode.
Anode reaction –H2 → 2H+ + 2𝑒̅
Cathode reaction-Cu2+ + 2e̅ → 𝐶𝑢
E0cell = E0cathode − E0anode
E0cell = E0Cu2+/𝐶𝑢 − 𝐸 0 𝐻 +/𝐻2
0.34 = E0 (Cu2+/𝐶𝑢) − 0
E0Cu2+/Cu = 0.34V
Emf of Daniel cell
E0cell = 𝐸𝑅𝑂 − 𝐸𝐿𝑂 = 0.34v − − (0.76) = 1.10v
Electro chemical series:-
The arrangement of element in the increasing
order of their reduction potential value is called
electrochemical series.
Nernst equation
Relationship between single electrode potential
and concentration of electrolyte.
Mn+ + nē →M(s)
Electrode potential at any concentration
𝑅𝑇 𝑀
E= E0 − ln
𝑛𝐹 𝑀𝑛+

E= Electrode reduction potential

E0 = Standard electrode reduction potential
R= Gas constant
n= No. Of electrons involved in the electrode
reaction.
F= Faraday constant
[Mn+ ]= concentration of species
In case of pure solids and liquids, the molar
concentration is taken as unity ie, [M]=1
E=E0 -RT/nF ln [M]/ [Mn+]
1
=E0 -RT/nF ln
𝑀𝑛+
Converting natural log (ln) into log,
=E0+2.303 RT/nF log[Mn+]
(R=8.314 JK-1 mol-1 , T=298K ,F=96500)
We get
0.0591
E= E0 + log[𝑀𝑛+]|
𝑛
Relationship between EMF of the cell and ionic
concentration of the electrolyte solution
In Daniel cell,
Zn |Zn2+ || Cu2+|Cu
E cell = ER – EL= E0Cu2+/Cu – E Zn2+/Zn …(1)
Applying Nernst equation for right hand side
electrode.
2+ 0 2+ 0.0591
E Cu /Cu=E Cu /Cu+ log[Cu2+]...(2)
𝑛
In left hand side electrode
2+ 0 2+ 0.0591
E Zn /Zn=E Zn /Zn+ log[Zn2+]....(3)
𝑛
Substituting eqn (2) and (3) in (1) we get
0 2+ 0.0591
E cell = [E Cu /Cu + log[Cu2+]]–
2
 0.0591
[E0 Zn 2+/Zn + log[Zn2+]]
2
0.0591 𝑐𝑢2+
=(E0 Cu2+/Cu–E0 Zn2+/Zn)+ log at 298k
2 𝑧𝑛2+
E cell = E0 cell +0.0591/2 log[Cu2+ ]/[Zn2+] at 298k.
For general electrochemical reaction,
aA + bB → cC + dD
0 0.0591 𝐴 𝑎 𝐵 𝑏
E cell = E cell + log
2 𝐶 𝑐 𝐷 𝑑
Or
0.0591 𝐶 𝑐 𝐷 𝑑
E cell = E0 cell – log
2 𝐴 𝑎 𝐵 𝑏

For cell reaction in equilibrium E cell = 0

 0.0591
⸫ 0 = cell –
E0 log Kc at 298k
𝑛
0 0.0591
i.e. E cell = log Kc
𝑛
where
Kc = [C]c [D]d/[A]a [B]b
E0 cell = log kc .... equilibrium constant
Electrochemical cell and Gibbs energy of the
reaction.
ΔrG = – nFE cell where,
n - no.of electrons transferred
F - Faraday constant
rG= -2. 303RT log Kc
Kc = Equilibrium constant
Electrochemical cell and Gibbs energy of
the reaction.
ΔrG = – nFE cell
where,
n - no.of electrons transferred
F - Faraday constant
rG= -2. 303RT log Kc
Kc = Equilibrium constant
Conductance of electrolytic solutions
Resistance of a conductor is directly proportional
to it's length (l) and inversely proportional to it's
area of cross section (A) at a given temperature.
𝑙 𝑙
ie, 𝑅 ∝ or 𝑅 = ρ
𝐴 𝐴
ρ = specific resistance
Specific resistance (R) or resistivity
The resistance of a column of solution of
length 1cm and area of cross section 1cm².
ρ = R unit – ohm cm
Conductance (G)
The ease with which current flow through a conductor
is known as its conductance
Unit of G = ohm-1 , mho, Siemens
1 𝐴 𝐴
Conductance, G = = = 𝑘
𝑅 ρ𝑙 1
1
Where 𝑘 = Specific conductivity
ρ
When A = 1cm² and L = 1cm then G = k
Specific conductance (κ) or Conductivity
It is the conductance of a column of solution of
length 1 cm and area of cross section 1cm².
Unit – ohm-1 cm-1 or mho cm-1 or S cm-1
𝐺𝐿
K=
𝐴
Conductivity of electrolytic solutions depends on
1) Nature of electrolyte
2) Concentration of electrolyte
3) Size of ions and solvation of ions
4) Nature of solvent and its Viscosity
5) Temperature (conductivity increases with
temperature)
Equivalent conductance (λ eqv)
It is the conductance of the solution containing
one gram equivalent when placed between two
parallel electrodes 1cm apart.
ie, Λ eqv = κ × V Or Λ = 1000κ/N
N - Normality of solution.
Unit – ohm-1 cm² eqv-1 or S cm 2 eqv-1
Molar conductance (Λ m)
It is the conductance of the solution containing
one mole of the electrolyte when placed
between two parallel electrodes 1cm apart.
Λ m = κv Or Λ = 1000κ/M
M - Molarity of solution.
Unit – ohm -1 cm² mol -1
Relation between Λ eqv and Λ m
Λm = Λeqv × z
z - Total charge of the cations or anions of a
single molecule of the electrolyte.
Cell constant G*
The ratio of the length of conductor and
area of cross section

𝐿
𝐺 ∗ = = RK
𝐴
G * = cell constant / measured resistance
Variation of conductivity and molar
conductance with concentration
a) Variation of conductivity:-
With decrease in concentration or increase in
dilution, the number of ions present per unit
volume of the solution decreases.
Thus conductivity of a solution increases with
increase in concentration or decrease in
dilution.
b) Variation of molar conductivity:-

It increase with decrease in concentration

or increase in dilution. But variation is
different for strong electrolyte and weak
electrolyte.
2) Weak electrolyte
For weak electrolytes the degree of
ionisation is very small in their
concentrated solutions. On dilution degree
of ionisation increases and molar
conductance increases.
1) Strong electrolytes
Partially dissociation .The molar conductivity
increases with decrease in concentration and
reaches a maximum limiting value when the
concentration approaches zero or at infinite dilution.
This is known as Λm or Λm 0 .(limiting molar
conductivity)
Kohlrausch's law of independent migration of
ions
The molar conductance of an electrolyte at infinite
dilution is the sum of the molar ionic conductance
of the cations and anions at infinite dilution.

Application
*Calculate the molar conductance of infinite
dilution for weak electrolyte.
Electrolytic cell and Electrolysis
The electrode connected to the negative pole
of the battery is called cathode and positive
pole is anode. The decomposition of an
electrolyte by the passage of electricity is
called electrolysis.
Electrolysis involving following steps.
a) Ionization and dissolution of electrolyte.
b) Migration of ions to respective electrodes.
c) Discharge of ions at the respective
electrode.
Faraday's first law
The amount of any substance liberated or
deposited at an electrode is directly proportional to
the quantity of electricity passing through the
electrolyte.
W∝Q W - Mass of the substance liberated
W = ZIt Q - Amount of electricity is passed,
Q = It
Z - Electrochemical equivalent.
When I = 1 ampere t = 1 sec W = Z
Electrochemical equivalent of a substance is the
weight of substance liberated or deposited at an
electrode by passing 1ampere current for 1 second.
Faraday's second law
When same quantity of electricity is passed
through different electrolytes, the mass of
different substances produced at the electrode
are proportional to their equivalent masses.
𝑊1 𝐸1
= – Mass and Equivalent mass of first.
𝑊2 𝐸2

W2 E2 W2 and E2 - Mass and equivalent mass

of second.
Equivalent weight of metal = Atomic mass of
metal/No. of ē's required to reduce the cation.
1Faraday = 96500 C
Product of electrolysis
On passing electricity the +ve ions(cations)
move to cathode(-ve) .Cation accepts ē and
become neutral – Reduction
The -ve ions (anions) move to anode(+ve) -
anions lose ē's and become neutral -
Oxidation.
Electrolysis of Nacl
Electricity passed through Nacl
At cathode : Na+ (1) + e – → Na (g) Reduction
At anode : 2Cl-1 (1) → Cl2(g) + 2e– Oxidation
Overall reaction
Na+ + 2Cl– → Na + Cl2(g)
Electrolysis of aqueous solution of Nacl
The aqueous solution of Nacl contains Na+ , Cl- , H + and OH - ions
and solvent H 2O molecule. When we pass electricity Cl2
deposited at anode and H2 is deposited at the cathode and
remaining solution contains NaOH.
At cathode: (Reduction) H 2O + (1) + e- → 1/2 H (2) (g) + OH- (aq)
At anode: (oxidation) Cl- (aq)→ 1/2 Cl2(g) + e-

Overall reaction: Cl- + H 2O(1)→ OH- +1/2 H2(g) +1/2 Cl2 (g)

Net Reaction is written as:

Na+ (aq) + Cl- (g) + H 2O (1)→ Na+ (aq) + OH- + (aq) +1/2 H2 (g) + 1/2Cl2(g)
 Batteries
The electrochemical cells can be used to generate
electricity. Cells used for this purpose are popularly
known as batteries.

Primary cells Secondary cells

Electrode reaction can’t be The reaction can be
reversed reversed by an external
electric energy source
Dry cell: Reaction occur Lead and storage battery
only once and after use
they become dead. Not Rechargeable, storage
changeable. cells.
Anode(Zinc container) Lead storage battery
Zn (s) → Zn2+ + 2ē Rechargeable, storage
cells
Cathode
(Graphiterod) Anode (spongy lead, Pb)
2MnO2(s) + NH4+ + 2ē Pb(s) + S0 4 2-→PbSo4 + 2ē
→MnO(OH) +2NH3 (s)
+ H 20 Cathode (Lead dioxide,
Or PbO2)
Mn(+4) → Mn(+3) Cell PbO2 + 2H+ + S04 2-+
potential = 1.5V eg: 2ē→PbSo4+ 2H 2O
Dry cell, Mercury cell,
Lechlenche cell.
Mercury cell:-Suitable for Overall reaction
low current devices like Pb + PbO2 + 2H2
hearing aids, Watches etc. SO4→PbSO4+ 2H2O
Anode(Zinc amalgam Zn/ Electrolyte - Aqueous
Hg) solution of H 2SO4.
eg: Lead storage battery
Zn (Hg) + 2OH- → ZnO used in automobiles.
+ H 2O + 2ē
Cathode(Paste of H gO + Nickel - Cadmium cell
carbon) It is used in electronic
H gO + H 2O + 2ē → Hg + watches, calculators etc.
2OH- Anode: cd anode
Cathode: Ni(iv) oxide
Electrolyte: KOH solution
Overall reaction Overall reaction
Zn + H gO→ ZnO + Hg Cd(s) + 2Ni(OH)3→CdO +
Electrolyte: Paste of KOH + 2Ni(OH) 2+ H 2O
ZnO
Voltage: 1.4V
Fuel cell
A galvanic cell that converts the chemical energy
from combustion of fuels such as H2, CH4 etc.
into electrical energy is called Fuel cell. eg: H2-O2
Fuel cell. It consist of porous carbon electrodes
with catalyst Pt and conc. KOH or NaOH as
electrolytes. H2 and O2 gases bubbled through it.
At anode - 2H 2(g) +4OH- →4H 2º(1) + 4ē
At cathode – O2(g)+ 2H 2O (aq)+ 4ē→4OH- (1)
Overall reaction - 2H 2(g)+O(2)(g)→2H 2O(1)
*Used in space vehicles.
*There are free from pollution
Corrosion
It 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
atmosphere. Corrosion always occurs at anodic
areas.
eg: Deposition of dark reddish brown on the
iron. The corrosion of iron is called rusting. Rust
is a hydrated form of ferric oxide.
Fe 2O3. xH 2O
Mechanism of corrosion
Impure surface of iron behaves like an
electrochemical cell in presence of water
known as corrosion cell. In corrosion cell pure
iron acts as anode and impure iron as
cathode.
Fe→ Fe 2++ 2ē anode reaction (Oxidation)
At the same time oxygen molecule in the
solution reduced.
O2 + 4H+ + 4ē→2H 2O
cathode reaction (Reduction)
Net cell reaction
2Fe + O2 + 4H+ →2Fe2+ + 2H 2O
The ferrous ion are further oxidised by
atmospheric oxygen to form rust. Fe 2O3. xH 2O.
Prevention of corrosion
1) Barrier protection: -
It can be achieved by coating paint, applying
oil or grease, electroplating with metals or by
chemicals. eg: bisphenol.

2) Sacrificial protection: -
Covering the surface of one metal by applying
with a layer of another metal which is more
active than the metal to be protected and thus
prevent the loss of electron from it. Coating a
thin film of Zinc or iron is called galvanization.
3) Electrical protection (cathodic protection):-
Underground iron water pipes, petrol tank etc.
is connected with more active metal like Mg,
Zn etc. Then more active metal act as anode by
losing electrons. Iron object will act as Cathode
and protected from rusting.