13-10-2023
Syllabus of Engineering Chemistry (Theory)
Module Module Description Hrs.
No
4 Energy conversion and storage: Fuel cells – 8
Electrochemistry of a H2–O2 fuel cell, Basics of
solid oxide fuel cells-applications; Limitations of
Batteries. Batteries- Chemical change and
Chapter-IV Electrical Work; Electrochemical reactions;
Primary cells: Lechlanche, alkaline and Li-primary
Energy Conservation & Storage cells. Secondary cells - Lead – acid, Ni-Cd, Ni-MH
cells; Rechargeable lithium cells – LiCoO2 and LiC6
By: Dr. Manoj Acharya chemistry and applications.
VIT, Bhopal
Copyright © VIT BHOPAL
Text Books / Reference Books Battery
1) O. G. Palanna, Engineering Chemistry, Tata McGraw Hill Electrochemical Cell is a device which converts chemical
Education energy into electrical energy and vice versa.
2) Jain P. C. and Monica Jain, Engineering Chemistry, A Cell or battery is a source of electrical energy and has
Dhanpat Rai Publishing Company Ltd. two electrodes (or half cells) that generates electrical
energy. The EMF generated depends upon the
magnitude of the electrode potentials of two electrodes.
3) R. L. Madan, Physical Chemistry, McGraw Hill Education
Battery is the arrangement of two or more galvanic cells
4) Dara S. S., Umare S. S., Engineering Chemistry, S. Chand
connected in series. The working principal of battery
& Company Ltd. is the transformation of free energy change of redox
reaction of electrode into electrical energy.
5) Shashi Chawala, Chemistry, Dhanpat Rai & Co. New Delhi
1
13-10-2023
Characteristic of a Battery Capacity: The capacity of battery is the total quantity
Free Energy Change: Whenever reaction takes place of electricity involved in the electrochemical reaction
in a battery then the Gibb’s Free Energy of redox or total number of Ampere hour or Watt hour can be
system decreases. i.e. ΔG = - nFE withdrawn from a fully charged cell or battery.
Q = xnF
EMF of the Battery: The EMF of the battery depends x = No. of moles of reaction
on the total number of cells which constitute a n = No. of electrons transferred/mole of reaction
battery. F = Faraday’s Constant = 96500 columbs
M1 + M2n+ M1n+ + M2
E = Eºcell –
.
log10 (M1n+/M2n+) Power: The power generated by a battery can be
calculated as W = V*I
The EMF of the battery increases with the increase in
V = Cell Voltage
the potential difference between the electrodes and
I = Cell Current
decreases with the increase in concentration of M1n+
Ampere-Hour: Rate at which electron flows in wire. Power Density: Power density is the ratio power
The unit is coulombs/sec. An electron has a charge of delivery by a cell or battery to its weight.
1.602 x 10-19 coulombs & an ampere is 6.24 x 10-18 Power Density = Power / Mass
electrons/sec During discharging the power density decreases.
Energy Density: Energy density is the ratio of
Classification of Batteries
amount of charge that can be stored or the energy
output of a battery to its weight.
Energy Density = Watt Hour / Mass Batteries
Efficiency: Ratio of output of the battery on discharge
to the input required to restore it to initial state of the Secondary Batteries /
Primary Batteries
charge under specified condition. Rechargeable
(Non Rechargeable
Batteries / Galvanic
Batteries)
Shelf Life: The duration of storage at the end of which Battery
a cell or battery still retains the ability to give a
specified performance.
For e.g.: Dry Cell, Alkaline For e.g.: Lead Acid
Primary Cell, Button Type Battery, Ni-Cd Battery
Alkaline Primary Cell,
Primary Lithium Battery
2
13-10-2023
Primary Battery In this cell, anode consist of Zinc container while
The working principal of a primary cell is the conversion cathode is graphite rod surrounded by powdered
of the free energy change of the redox system into Magnese Dioxide (MnO2) and Carbon.
electrical energy. The net cell reaction is irreversible & The space between the electrodes is filled with the paste
they can not be recharged or used again. of NH4Cl and ZnCl2 & whole assembly is wrapped with
Example: Dry Cell (Leclanche Cell), Alkaline Primary polypropylene or cardboard to prevent leakage.
Cell [Mercury Cell or Reuben Mallori (RM) Cell],
Anodic Reaction
Button Type Alkaline Primary Cell
Zn Zn2+ + 2e-
Primary Battery or Dry Cell or Leclanche Cell Cathodic Reaction
2 MnO2 + 2 H2O + 2e- 2 MnO(OH) + 2 OH-
Zn-MnO2 (Dry Cell) Net Cell Reaction
Zn + 2 MnO2 + 2 H2O 2 MnO(OH) + Zn2+ + 2 OH-
Zn/Zn2+//NH4+/MnO2/C
Secondary reaction also takes place inside the cell but
Anode- Zn Cylinder do not contribute to the EMF of the cell
Cathode- MnO2/Carbon 2NH4Cl + 2OH- 2NH3 + 2 H2O + Cl-
Electrolyte-ZnCl2+NH4Cl Zn2+ + 2NH3 + 2 Cl- Zn(NH3)2Cl2
Dry Cell do not have long life as NH4Cl which is acidic,
HgO-Zn Cell
corrode the zinc container even if the cell is not in use. It is also known as Reuben-Mallori Cell.
The Cell potential of dry cell lies in the range 1.25 V to In this cell amalgamated Zinc rod is at the centre which
1.5 V. act as anode of the cell. An absorbent material (cellulose)
Alkaline Primary Cell/ Battery or Reuben-Mallori containing 40% of KOH saturated with ZnO surrounds
anode.
Cell
Anode is surrounded with a paste of 5-10% graphite in
The NH4Cl used in dry cell is acidic and corrode the zinc HgO which is introduced in a steel case which act as
container so it has limited shelf life. In order to overcome cathode. Anode and cathode are separated by a layer of
this problem alkaline KOH is used to obtain better shelf insulating material.
life.
Anodic Reaction
There are two types of alkaline primary cell: Zn +2 OH- ZnO (s) + H2O + 2e-
Cathodic Reaction
1) HgO-Zn Cell HgO + H2O + 2e- 2 Hg(s) + 2 OH-
2) Ag2O-Zn Cell Net Cell Reaction
Zn + HgO ZnO (s) + Hg (s)
3
13-10-2023
The volatage of RM cell is 1.35V. It has high capacity and
the potential remains constant till its shelf life.
Used in electronics watches, electronic gadgets etc.
Ag2O-Zn Cell
Alkaline Primary Cell Battery is commonly known as
Button Type alkaline primary cell. Anodic Reaction
Zn +2 OH- ZnO (s) + H2O + 2e-
Cathodic Reaction
In this cell Ag2O is pressed into thin button type metal Ag2O + H2O + 2e- 2 Ag + 2 OH-
case which act as cathode. Zinc metal is at the centre of Net Cell Reaction
the cell & behaves as Anode. An absorbent material Zn + Ag2O + 2 H2O ZnO (s) + 2 Ag (s)
soaked in KOH is placed between cathodic and anodic
compartments. Electrolyte is KOH solution. The Cell potential of dry cell lies in the range 1.25 V to
1.5 V.
The alkaline battery has better performance due to high Secondary Battery
voltage, longer life, more reliability and non-toxicity.
A rechargeable electric cell that converts chemical
They are used in calculators, electronic watches etc. energy into electrical energy by a reversible chemical
reaction & also called storage cell. Its of two types:
1) Lead-Acid Battery
2) Nickle-Metal Hydride Cell
Lead-Acid Battery
It’s a secondary storage battery and in charged condition
can be represented as
Pb / PbSO4 (s) H2SO4 (aq) // PbSO4 (s) PbO2 (s) / Pb
4
13-10-2023
Discharge Reaction of Lead-Acid Battery
The anode of the cell is a grid filled with spongy Lead,
while cathode is Lead-Antimony grid containing PbO2. During the discharge process of a battery the free energy
The anode and cathode are separated by using porous change of redox reaction converted into electrical energy.
material between them. i.e. ΔG = - nFE
The electrolyte is 28-30% H2SO4 (Specific gravity = 1.2 at
25º C). Anodic Reaction
Pb Pb2+ + 2e-
The whole set up of number of such cells are enclosed in
Pb2+ + SO42- PbSO4
a ebonite case.
____________________________________
Pb + SO42- PbSO4 + 2e- ~ EºPb/ Pb2+ = - 0.36 V
Cathodic Reaction
PbO2 + 4 H+ + SO42- + 2e- Pb2+ + 2 H2O
Pb2+ + SO42- PbSO4 + 2 H2O
_____________________________________________________
PbO2 + 4 H+ + SO42- + 2e- PbSO4 + 2 H2O
~ EºPbO2/ PbSO4 = 1.69 V
Net Cell Reaction Charging Reaction of Lead-Acid Battery
Pb + PbO2 + 2 H2SO4 2 PbSO4 + 2 H2O
The battery can be recharged by connecting it to an
~ Ecell = 2.0 V
external source of direct current with voltage greater
The voltage produced during discharging process is 2 V. than 12 Volt. It forces the electrons to flow in opposite
The Lead Sulphate formed during the discharging direction resulting in the deposition of ‘Pb’ on anode and
process get adhere to the electrodes. The Lead Sulphate PbO2 on cathode.
deposited on the electrode interface is utilised again The battery need charging when the specific gravity of
during the charging process of the battery. H2SO4 acid falls below 1.2 & during recharging it
behaves as electrolytic cell.
During the discharging, water is formed which
dilutes H2SO4. With the decrease in concentration Anodic Reaction
H2SO4 the density of the solution also decreases. PbSO4 (s) + 2 H2O PbO2(s) + SO42-(aq)+ 4 H+(aq) + 2e-
Cathodic Reaction
PbSO4 (s) + 2e- Pb + 2 SO42-
Overall Reaction
2 PbSO4 (s) + 2 H2O Pb (s) + PbO2 + H2SO4
5
13-10-2023
Lead storage battery is used in automobiles, UPS, Secondary (Rechargeable) Lithium Batteries
telephone exchange, trains, laboratories.
The main disadvantage of Lead storage batteries is they
cause environmental hazard & harmful for the human Lithium batteries are of high energy density, power
beings. density, good life cycle, charge retention, high
performance, reliable and safe.
The secondary Lithium batteries are classified into five
categories-
1) Liquid Organic Electrolyte Cells
2) Polymer Electrolyte Cells
3) Lithium Ion Cells
4) Inorganic Electrolyte Cells
5) Lithium Alloy Cells
Liquid Organic Electrolyte Cells (LiCoO2)
It is a solid cell uses intercalation (Reversible inclusion
or insertion of a molecule or ion materials with layered
structure) for cathode, a liquid organic electrolyte and
metallic lithium anode.
The battery consists of a cobalt oxide cathode and a
graphite carbon anode. The cathode has a layered
structure and during discharge, lithium ions move from Its high specific energy makes Li-cobalt the popular
the anode to the cathode. The flow reverses on charge. choice for mobile phones, laptops and digital cameras.
Following material is used for the construction of the cell:
The drawback of Li-cobalt is a relatively short life span, a) Anode: Lithium Metal
low thermal stability and limited load capabilities b) Cathode: LiCoO2, LiNiO2, MnO2, V2O5
(specific power). c) Electrolyte: LiAsF6
d) Separator: Polypropylene
6
13-10-2023
Graphite has layered structure and can be doped with
Anodic Reaction Lithium between the layers so its also known as
Li Li+ + e- Graphite Intercalation Compound.
Cathodic Reaction
Li+ + LiCoO2 + e- LiCoO2 Lithium doping is a charging reaction and undoping
reaction is a discharging.
During charging of LIB, Lithium ions are extracted by
Lithium Ion Cell (LiC6) electrochemical oxidation from LiCoO2 cathode and
extracted Lithium ions are doped by electrochemical
reduction into carbon anode to form LiGIC.
Lithium Ion Battery (LIB) has high energy density. The
cell reaction in LIB is merely the migration of Lithium
ions between anode and cathode.
No chemical changes are observed in the two electrodes
or electrolytes.
During discharging Lithium ions are extracted from the Fuel Cell
anode by electrochemical oxidation and inserted into Fuel cell is a device which convert chemical energy of
cathode by electrochemical reduction. the fuel into electrical energy. It is environmentally
friendly potable power supplies capable of producing
Anode oxidation reaction:
enough energy to run a device and motor vehicles.
LiC6 → Li+ + C6 + e-
Cathodic reduction reaction: These are voltaic cell in which the fuels such as H2 ,
CoO2 + Li+ + e- → LiCoO2 CO, CH4 and C3H8 are used to generate electrical energy
Overall reversible, Redox, cell reaction: without the usage of thermal devices like boiler, turbines
LiC6 + CoO2 C6 + LiCoO2 etc.
Fuel cells are designed in such a way that material to be
The voltage of LIB is 3.6-3.7V. oxidised and reduced at the electrodes are kept outside
the cell and are constantly supplied to the electrodes &
hence it do not require charging.
Fuel cells is a flow battery that continues to operate as
long as the reactants from outside are fed into it.
7
13-10-2023
Fuel |Electrode |Electrolyte |Electrode |Oxidant Alkaline Fuel Cell (AFC)
At anode oxidation takes place and reduction takes place In alkaline fuel cell liquid electrolyte like NaOH / KOH is
at cathode. used. Pure Oxygen or air (free from CO2) is used as
oxidant. The fuel of the cell are hydrogen or any
hydrocarbon.
The working principal of fuel cell is the conversion of free
energy change of redox reaction into electrical energy. Low temperature AFC
operate at 60-80º C &
Types of Fuel Cells highly active catalyst like
Platinum or Ag are used.
Catalyst like Ni require
1) Alkaline Fuel Cell (AFC)
high temperature 200-
2) Phosphoric Acid Fuel Cell (PAFC)
250º C.
3) Molten Carbonate Fuel Cell (MCFC)
4) Polymer Electrolyte Membrane Fuel Cells (PEMFC) H2-O2 cell generates a
5) Solid Oxide Fuel Cell (SOFC) voltage of 1.15V as long
6) Biochemical Fuel Cell (BCFC) as the supply of H2 & O2
is maintained. H2-O2 cell
Electrodes: Porous Carbon or Graphite
Application:
Electrolyte: KOH
Used in US space programme (Apollo Space programme)
Fuel: Hydrogen or Hydrocarbon
to produce electrical energy and water on-board
Catalyst: Platinum
spacecraft.
Charge Carrier: OH-
Operating Temperature: 60-80º C
In AFCs, the oxygen reacts at the cathode to produce
either hydroxide (OH-) or a carbonate ion (CO32-),
depending upon the electrolyte composition. The ion
travels through the electrolyte to react with hydrogen at
the cathode.
Anodic Reaction
H2 + 2 OH- H2O + 2e-
Cathodic Reaction
½ O2 + H2O + 2e- 2 OH-
Overall Reaction
H2 + ½ O 2 2 H 2O
