Bal Bharati Public School, Navi Mumbai

Class 12 2022-23
Electrochemistry

Cell/Battery: Source of electrical energy, basically it acts as n Electrochemical cell.

An arrangement is made with a redox reaction which also satisfies the following criterion.
a. It should be light and compact
b. Its voltage should not vary appreciably when in use
c. It should provide power for a longer period.
d. It should be rechargeable.

Classification:

Cell Definition Example

Primary Becomes dead over a period of time and the Dry cell (Compact form of
chemical reaction stops. They cannot be Leclanche Cell)
recharged or used again.
Mercury Cell

Secondary Can be recharged by passing direct current and Lead Storage Cell
can be used repeatedly.
Ni-Cd Storage Cell

Fuel Chemical Energy of the cell is converted to H2-O2 Cell

Electrical energy

A. Primary Cell:

(i) Dry Cell (Compact form of Leclanche Cell)

Anode Zinc Container

Cathode Graphite rod surrounded by powdered MnO2 and C

Electrolyte Paste of NH4Cl and ZnCl2

Reactions Anode: Zn à Zn2+ + 2e

Cathode: MnO2 + NH4+ + e à MnO(OH) + NH3

Zn2+ + 2 NH3 à [Zn(NH3)2]2+

** NH4Cl is acidic so it will corrode Zinc electrode even when not in use.

Cell Potential 1.25 V – 1.5 V

Use In household and portable electronic devices.

 (ii) Mercury Cell

Anode Zinc-Mercury amalgam

Cathode Paste of Mercuric Oxide and Carbon

Electrolyte Moist paste of KOH-ZnO

Reactions Anode: Zn(Hg) +2OH-à ZnO(s) + H2O(l) +2e

Cathode: HgO(s) + H2O(l) + 2e à Hg(l) + 2OH-

Net Rxn: Zn(Hg) + HgO à ZnO(s) + Hg(l)

Cell Potential 1.35 V, Potential is constant throughout its life.

Use Watches, Video cameras, hearing aids and other compact devices.

B. Secondary Cell:

(i) Nickel-Cadmium Storage Cell (Nicad Cell)

Anode Cadmium

Cathode Metal grid containing NiO2

Electrolyte KOH solution

Reactions Anode: Cd(s) +2OH-(aq)à Cd(OH)2(s) +2e

Cathode: NiO2(s) + 2H2O(l) + 2e à Ni(OH)2(s)+ 2OH-(aq)

Net Rxn: Cd(s) + NiO2 (s) + 2H2O(l)à Cd(OH)2(s)+ Ni(OH)2(s)

Cell Potential 1.4 V

Use Electronic Watches and Calculators

 (ii) Lead-Storage Cell

Anode Spongy Lead

Cathode Grid of lead packed with Lead dioxide PbO2

Electrolyte 38% by mass of H2SO4

Reactions Anode: Pb + SO42- à PbSO4 + 2e; E0 =0.36V

Cathode: PbO2 + SO42-+ 4H+ + 2e à PbSO4 + 2H2O; E0 = 1.69V

Net Rxn: Pb + PbO2 + 4H+ + 2SO42- à 2PbSO4 + 2H2O; E0cell = 2.05V

Design and • Anode and Cathode plates are arranged in alternating manner, and
Special they are separated by sheets of insulating material.
Feature • Cathodes and Anodes are separately connected to each other so as
to increase the electrode area in contact with the electrolytic
solution.
• The groups of electrodes constitute one cell.
• Cells are further connected in series.
6V Battery: 3 cells
12V Battery: 6 cells
• During working of the cell, the concentration of H2SO4 decreases
as SO42- are consumed. H2O formed as a byproduct dilutes the
H2SO4. The condition of the battery can be checked by measuring
density of the H2SO4 solution and then cell is to be recharged.
Recharging Connected to external source of direct current with voltage greater then 12
V. During recharging it will behave as electrolytic cell.

Anode: PbSO4 + 2e à Pb + SO42-

Cathode: PbSO4 + 2H2O à PbO2 + SO42-+ 4H+ + 2e

Net Rxn: 2PbSO4 + 2H2O à Pb + PbO2 + 4H+ + 2SO42-

Use Battery in automobiles

Lithium ion Battery (Not required for Board Exam)

Anode Graphite

Cathode Layered oxide of Li such as Lithium Cobalt oxide, LiCoO2

Electrolyte Lithium perchlorate LiClO4 or Lithium hexafluorophosphate LiPF6 in non-

aqueous solvent.
Reactions Anode: LiCoO2 ⇌ Li (1-x) CoO2 + xLi+ + xe

Cathode: xLi+ +xe + 6C ⇌ LixC6

Net Rxn: Zn(Hg) + HgO à ZnO(s) + Hg(l)

Cell Potential 1.35 V, Potential is constant throughout its life.

Use laptop, computer notebook, mobiles etc

C. Fuel Cell: Hydrogen-Oxygen Fuel Cell, Bacon Cell

Electrode Porous Carbon electrode with catalyst (Pt, Ag, CoO), H2 and O2 are
bubbled through the electrode into electrolyte.

Electrolyte Aqueous solution of NaOH, KOH

Reactions Anode: [H2(g) + 2OH-(aq) à 2H2O(l) +2e]x2

Cathode: O2(g) + 2H2O (l) + 4e à 4OH-(aq)

Net Rxn: 2H2(g) + O2(g) à 2H2O(l)

Special • Materials to be oxidized and reduced at the electrodes are stored

Feature outside the cell and are constantly supplied to the electrode.

• This fuel cell is a flow battery that continues to operate as long as

the reactants from outside are fed into it.
Use Apollo Space Mission

Advantages 1. Pollution free working

2. High Efficiency: 70-75%
3. Continuous Source of Energy
4. Water vapour produced can be condensed and used for drinking
purpose.
Corrosion:
Surface of certain metallic object slowly gets coated with oxide or some other salt of the
metal on long exposure to atmosphere.

Factors affecting Corrosion:

(i) Reactivity of the metal
(ii) Presence of Impurities
(iii) Air and Moisture
(iv) Strains in Metal
(v) Presence of Electrolytes

Mechanism of Corrosion:
It is an electrochemical process. Impure Iron surface behaves as the electrochemical cell in
presence of water containing dissolved Oxygen or Carbon dioxide.

Anode: Pure Iron

Cathode: Impurity site

Reaction at Anode: Fe(s) à Fe2+ + 2e; E0 = -0.44 V (**)

Reaction at Cathode: 2H+ + (1/2)O2 + 2e à H2O; E0 = +1.23 V

Net Reaction: Fe(s) + 2H+ + (1/2)O2 à Fe2+ + H2O; E0cell= +1.67 V

**The Fe2+ ion thus formed moved 2Fe2+ + (1/2)O2 +2H2O à Fe2O3 + 4H+
through the electrolyte to the surface of the Fe2O3 + xH2O à Fe2O3.xH2O (Rust)
metallic object and get oxidised to Fe3+ by
atmospheric Oxygen. Fe3+ constitute rust As H+ is involved in the reaction, so pH has an
which is hydrated Ferric Oxide. important role in rusting. Rusting stops at a pH
of 9-10.

Prevention of Corrosion:

• Barrier Protection: Applying oil, paint, electroplating with non-corrosive metal such
as Ni, Cr, Cu.

• Sacrificial Protection: Surface of Iron is covered with more active metal Zn. More
active metal act as anode and loses electron in preference to Iron.

• Electrical Protection: Type of sacrificial protection with more active metals like Mg,
Al, Zn. More active metal act as anode and loses electron in preference to Iron.

• Use of Anti-rust solution: Alkaline solution of phosphate or chromate salts act as

anti-rust solution.
Electrochemical Cell

Standard Cell Potential: E0cell=E0cathode−E0anode

Cathode: Right hand electrode where reduction takes place
Anode: Left hand electrode where oxidation takes place.

Mn+ + ne– → nM
Electrode Potential when concentration is not unity:
Ered = EMn+/M = EoMn+/M – (2.303RT/nF) log [1/[Mn+]
Ecell = Ecathode − Eanode

Now substitute Ecathode and Eanode separately.

Relation between E0 and Equilibrium constant:

E0cell = (RT/nF) ln Kc

Relation between Free energy Change and E0:

DG0 = -nFE0