Sources of Water

1. Rainwater. It is the purest form of natural water. But unfortunately it

dissolves the toxic gases like CO2, SO2, NO2 etc. and other solids.

2. Sea water. It is the most impure form of water containing about 3.5%
dissolved salts of which about 2.6% is NaCl. Other salts present include
sulfates, bicarbonates, bromides of sodium, potassium, magnesium etc.

3. River water. The sources of river water are the springs and the
rainwater. River water while flowing through the land collects lots of
organic matters from falling trees and nearby habitats and also other
soluble and suspended matters from the lands, soils etc.

4. Lake water. It is much purer than river water, dissolved impurities are
less but contains lots of organic matter.

5. Underground water. The rainwater and other surface water percolate

down through the soil and rocks and get filtered and finally collected on
rocky surface or again come out as spring. Though it contains less
suspended matter but the dissolved mineral content is quite high and is
of high organic purity.

Hardness of Water
Hardness of water is the characteristic of preventing lather formation of
water with soap. Generally salts like chlorides, bicarbonates and sulfates
of Ca2+, Mg2+ and Fe2+ make water hard.

This hard water on treatment with soap which is stearic or palmitic acid
salts of sodium or potassium causes white precipitate formation of
calcium or magnesium stearate or palmitate.

Thus the cause of hardness is the precipitation of the soap and hence
prevents lathering at first. When the hardness causing ions are removed
as insoluble soaps, water becomes soft and forms lather.

1
 Types of Hardness

The hardness is of two types:

(i) Temporary hardness is due to the bicarbonates of Ca2+ and Mg2+ and
carbonate of Fe2+. Since bicarbonates readily get precipitated on boiling
the water, the temporary hardness

(ii) Permanent hardness is due to the presence of chlorides and sulfates of

Ca, Mg, Fe, etc. Permanent hardness cannot be removed easily on
boiling.

Units of Hardness
Both temporary and permanent hardnesses are expressed in ppm as
CaCO3. The choice of CaCO3 is due to the fact that its mol. wt. is 100
and equivalent weight is 50 and it is the most insoluble salt in water.
Equivalent of CaCO3

2
 Units of Hardness
Hardness is principally expressed in ppm unit. Other limits include
French degree of hardness, English degree of hardness or Clark, USA
degree of hardness and German degree of hardness.

Scales and Sludges

3
 Priming
During rapid steam production, some liquid water drops are
also carried along with the steam. This wet-steam formation
is called priming.

Priming occurs due to

(i) Presence of large amount of dissolved solids,
(ii) High steam velocities,
(iii)Sudden boiling and
(iv)Sudden increase in steam production.

Priming can be controlled by

(i) Maintaining low water level in boiler,
(ii) Avoiding rapid change in steam rate,
(iii)Softening of boiler water and
(iv)Using mechanical device for steam purification.

Foaming
Foaming is the production of bubbles and foams which do
not break easily.

Foaming occurs due to the presence of oil in the water.

Foaming can be reduced by

(i) removing oil from boiler-feed water and
(ii) adding anti-foaming agents.

• Priming and foaming occur together and they are undesirable

since they wet other mechanical parts of the boiler and
reduce their efficiency.

• Actual height of the water column cannot be judged due to

foaming hence creating difficulty in the maintenance.

4
Lime Soda Process - Reactions of Lime and Soda

5
6
 Hot Lime-Soda Process
Advantages Include:

1. the precipitation reaction becomes almost complete.

2. the reaction takes place faster.
3. the sludge settles rapidly.
4. no coagulant is needed.
5. dissolved gases (which may cause corrosion) are removed.
6. viscosity of soft water is lower, hence filtered easily.
7. Residual hardness is low compared to the cold process.
8. Lime soda process is economical.
9. The process improves the corrosion resistance of the water.
10.Mineral content of the water is reduced.
11.pH of the water rises, which reduces the content of pathogenic
bacteria.

7
8
Ion Exchange resin

9
10
11
 Electroplating
• It is a process by which a coating metal is deposited on
the base metal by passing direct current through an
electrolytic solution, containing the soluble salt of the
coating metal.
• Electroplating is done both for protecting the metal
from corrosion and for decorative purposes.
• A well cleaned and properly pre treated surface of any
material to be electroplated is necessary for obtaining
the coating of long life.
• To get good film complexing agents, organic additives,
levelers, structure modifiers and wetting agents are
added.
• Current density is adjusted to get an adherent film.

12
• The electrolyte is selected in such a way that it is a
good conductor and highly soluble.
• It should not undergo hydrolysis, oxidation, reduction
and other chemical changes.
• It should possess sufficient covering power.
• Hence mixture of two or more electrolytes is used for
preparing electrolytic bath.
• For a good electrodeposit, the pH of the bath must be
properly maintained.For most plating baths, pH
ranges from 4 to 8.
• Electroplating method depends upon the type of
metal to be electroplated,the size and type of article
to be electroplated, its main objectives and
economics involved.

Plating bath
• Normally plating is carried out in rectangular tank
made of wood or steel with a ceramic or polymer
layer inside so as to provide thermal insulation.The
volume varies between 25 to 2000 L.
• Heating if required is provided by heating coils or hot
gases. Air sparger or nitrogen sparger is employed to
introduce convection current in the plating bath
solution. DC source is used for electroplating with a
voltage of 8-12V and a current density of 1-200
mACm-2.
• In large plating operations, pumps and filters are
employed to filter out regularly the metallic particle.
The anode sludge can be retained by anode in cotton
bags.

13
• Pretreatment of surface of substrate is
essential to prepare the surface of the
substrate properly.
• Removal of organic impurities and grease
from the surface are done by employing
organic solvents like trichloroethylene,
methylene chloride and hot aqueous alkalis.
pH increase catalyses the hydrolysis of fatty
impurities.

Thin film coatings

Physical Vapour Deposition (PVD)

• This is a process of depositing some material

by atom by atom or molecule by molecule or
ion by ion.

• The important methods of PVD are thermal

evaporation, sputtering and ion plating.

14
 Thermal evaporation
• Oldest and simplest process. In this method the metal to be
coated is placed in a refractory metal boat or crucible.

• The boat is heated to melt the content or an electron beam is

focused on the contents to melt.

• The contents after melting form an electron cloud in the shape

of ice cream cone with the tip of the cone at the source.

• It coats all surfaces in the line of sight of the boat or crucible.

This process is widely used to produce decorative coatings on
plastic parts those are resembling shiny metal.

• Many automobile parts are plastic with a PVD coating of

aluminium. A lacquer coating is applied over the decorative
coating to provide corrosion protection.

Schematic of thermal evaporation deposition

15
 Sputtering
• High technology coatings such as ceramics, metal alloys and
organic and inorganic compounds are applied by sputtering.

• The substance to be coated is connected to a high voltage dc

power supply.

• When the vacuum chamber has been pumped down, a

controlled amount of argon or another gas is introduced to
establish a pressure of about 10-2 to 10-3 torr.

• On energizing current supply, plasma is established between

the work and the material to be coated.

• The gas atoms are ionized, and they bombard the material to
be coated.

Sputtering
• The energy of impinging ions cause atoms of the target
material to be sputtered off, and they are transported through
the plasma to form a coating.

• Direct current sputtering is used when the target is electrically

conductive.Radio-frequency sputtering, which uses a RF
power supply is used when the target is a non conductor such
as polymer.

• Sputtered coating processes produce microscopic modules of

diameter of several micrometers and they are called macros.

• These macros are undesirable for metal to metal sliding

systems. On the other hand they are usually beneficial to
cutting tools.

16
 Applications

•The PVD coatings most widely used in machine design are titanium nitride

•(TiN), titanium carbonitride (TiCN) and diamond like carbon.

•The latter coatings are also called amorphous hydrogenated carbon coatings,
since they have 30% hydrogen as this is produced from hydrocarbon gas.

•These coatings are applied to punches, cutting tools etc. These are applied to give
extra hardness to a substrate.

•Titanium nitride is gold in colour. The closed coatings are often preferred for many
tool applications.

Chemical Vapour Deposition

17
 Ion implantation

Basic terms in polymer science

Polymer : Polymers are complex and giant molecules which are

made from joining a large number of small and simple molecules
by primary valency linkage.

Monomer : The individual small and simple molecules from which

the polymer is formed are known as monomer.

Polymerization : The process by which the monomer molecules

are linked to form a big polymer molecule is called polymerization.

18
Functionality: The number of bonding sites or active sites in a
monomer is called its functionality.

Degree of polymerization : The number of monomers forming the

polymer chain are called its degree of polymerization

Tacticity : The spatial arrangement of pendent groups of successive

stereocenters (asymmetric carbon) in the main chain is called its
tacticity.

Isotactic Polymer Syndiotactic Polymer

Atactic Polymer

Classification
One classification divides polymers in to condensation and
addition polymers and the other divides them in to step and chain
growth polymers.

Depending on their origin polymers are classified into natural

and synthetic polymers.

Depending on kind of atoms constituting backbone of the polymer

they are classified as organic and inorganic polymers.

Depending upon their ultimate use polymers are classified into

plastics, elastomers, fibres and liquid resins.

19
A polymer which can be reshaped into hard and tough utility articles
by applying heat, pressure or both is said to be a plastics.
Examples : Polystyrene, Poly(vinyl chloride), Poly(methyl
methacrylate), polyester etc.

A polymer which can show good strength and elongatoan upon

vulcanization is called an elastomer.
Examples polyisoprene, polyisobutylene, etc.

A polymer which can be drawn into log tilament like material whose
length is at least 100 times at its diameter is called a fibre.
Examples nylon, terylene, polyester, polyacrylonitrile, etc.

A polymer used as adhesives, potting compounds, sealants etc in a

liquid form is called as liquid resin.
Examples epoxy adhesives, poly sulphides, sealants, etc.

Depending on the number of kinds of monomer used in

polymerization they are classified into homopolymer and copolymer.

Homopolymers are one in which only one kind of monomer is used

to prepare the polymer during polymerization.
Examples, polystyrene, polyacrylamide, etc.

Copolymer is one in which more than one kind of monomers are used
to prepare the polymer during polymerization. Examples poly(vinyl
chloride-co-vinyl acetate), poly(styrene-co--butadiene).

Further homopolymers are sub classified into linear, branched and

crosslinked polymer based on their chain configuration (i.e.
depending on their structure).

20
 Those polymers in which the monomer molecules have been linked
together in one continuous length to form the polymer molecules are
called linear polymers.

Branched polymer molecules are those in which there are side

branches of linked monomer molecules protruding from various
central branch points along the main polymer chain.

21
 Depending on number of kind of atoms forming three main
chain of the polymer they are classified as homochain polymer
and heterochain polymer.

A polymer in which main chain consist of only one kind of

atom is homochain polymer, while heterochain polymers
consist of more than one kind of atoms in their main chain.

Examples of homochain polymer are PE, PP, PS, PVC, etc.

Examples of heterochain polymer are PEO, pester,

nylon(polyamide) polyurethane, polydimethy isicoxane, etc.

Polymers which can be softened on heating and harden on cooling

reversibly, i.e. their hardness is a temporary property subject to
change with rise or fall of temperature are called thermoplastics.
Repeated heating and cooling do not alter the chemical nature of
these materials, because the changes involved are purely of physical
nature.

Examples are polyethylene, polypropylene, poly(vinyl chloride),

polystyrene, nylons, polytetrafluro ethylene (PTFE or Teflon) etc.

Polymers which on heating get hardened and once they have

solidified, they cannot best softened, i.e. they are permanent setting
resins are called thermosetting plastics.

Examples are polyesters, Bakelite and epoxy resins etc.

22
 Thermoplastic
They are formed by addition polymerization
only.
They consist of long chain linear polymers
with negligible cross-links.
They soften on heating readily because
secondary forces between the individual
chain can break easily by heat or pressure.
By re-heating to a suitable temperature, they
can be softened, reshaped and thus reversed.
They are usually soft, weak and less brittle.
These can be reclaimed from wastes.
They are usually soluble in some organic
solvents.
• Cellulose Derivatives
• Polyethylene (PE)
• Polyvinylchloride (PVC)
• TEFLON
• Nylon
Thermosetting
They are formed by condensation
polymerization.
They have three dimensional network
structures, joined by strong covalent bonds.
The cross-links and bonds retain their
strength on heating and hence, they do not
soften on heating on prolonged heating
charring of polymers is caused.
They retain their shape and structure even on
heating. Hence they cannot be reshaped and
reversed.
They are usually, hand, strong and more
brittle.
They cannot be reclaimed from wastes.
Due to storing bonds and crosslinking they
are insoluble in almost all organic solvents.
23
Cotton fiber is mostly cellulose, and
cellulose is made of chains of the sugar,
glucose linked together a certain way.

24
 Cellulose Derivatives

Cellulose derivatives
• Cellulose is a naturally occurring linear polymer
consisting of β-glucose as repeating unit. β-glucose
has three free –OH groups, which may be fully or
partially substituted by chemical reactions.

25
 Cellulose acetate
[C6H7O2(OH)3]n + 3n CH3COOH [C6H7O2(OCOCH3)3]n + 3n H2O
Cellulose triacetate

[C6H7O2(OCOCH3)3]n + n H2O [C6H7O2(OH)(OCOCH3)2]n + n CH3COOH

Cellulose triacetate Cellulose diacetate

• Preparation
• Cellulose acetate is obtained by treating cellulose with
acetic anhydride or glacial acetic acid in the presence
of H2SO4.
• The resulting cellulose triacetate is water insoluble
and hence it is partially hydrolysed into cellulose
diacetate. Cellulose diacetate is soluble in organic
solvents such as acetone.

Properties
1. They are tough and hard materials
2. They have high tensile and dielectric strength
3. They are not affected by any mineral acids

Uses

1. They are used for the manufacture of radio

appliances, windows, combs and non-inflammable
cinematographic films, etc

26
 Cellulose nitrate (or) Nitrocellulose
or Celluloid
3n HNO3
[C6H7O2(NO3)3]n + 3n H2O
H2SO4
Cellulose trinitrate
[C6H7O2(OH)3]n
2n HNO3
[C6H7O2(OH)(NO3)2]n + 2n H2O
H2SO4
Cellulose dinitrate
• Preparation
• It is obtained by reacting cellulose with HNO3 the
presence of H2SO4

Properties
1. Cellulose nitrate is a transparent, tough and
highly inflammable material
2. It is not affected by water but it is affected by
strong acids and alkalis

Uses

1. Cellulose nitrate is used for the manufacture of

toilet articles, pens, table tennis balls, radio-
dials, etc

27
 Addition polymerisation – poly(ethylene)
Five ethene monomer units:
H H H H H H H H H H
C C C C C C C C C C
H H H H H H H H H H
An addition reaction begins when the double bond breaks on each monomer
Two single electrons from Repeating unit of polymer
the broken double bond

H H H H H H H H H H
C C C C C C C C C C
H H H H H H H H H H
n
The polymer poly(ethylene) with five repeating units shown(
n=5)

There are two kinds of polyethylene

• 1. Low Density Polyethylene (LDPE)
• 2. High Density Polyethylene (HDPE)

28
 Addition polymerisation- poly(styrene)
Five styrene monomer units:
C 6H 5 H C 6H 5 H C 6H 5 H C 6H 5 H C 6H 5 H

C C C C C C C C C C
H H H H H H H H H H
An addition reaction begins when the double bond breaks on each monomer
Two single electrons from Repeating unit of polymer
the broken double bond

C 6H 5 H C 6H 5 H C 6H 5 H C 6H 5 H C 6H 5 H

C C C C C C C C C C
H H H H H H H H H H
n
The
Newpolymer poly(styrene)
carbon to carbon with
single bonds arefive repeating
formed joining theunits shown(
monomer units
n=5)
together

Addition polymerisation- poly(propene)

Five propene monomer units:
CH3 H CH3 H CH3 H CH3 H CH3 H
C C C C C C C C C C
H H H H H H H H H H
An addition reaction begins when the double bond breaks on each monomer
Two single electrons from Repeating unit of polymer
the broken double bond

CH3 H CH3 H CH3 H CH3 H CH3 H

C C C C C C C C C C
H H H H H H H H H H
n
The polymer poly(propene) with five repeating units units
New carbon to carbon single bonds are formed joining the monomer
shown(
together n=5)

29
A polymer made form just one monomer is polyethylene. It is the
most common plastic you see.
It is used for bottles, buckets, jugs, containers, toys, even
synthetic lumber, and many other things.

Polyvinyl Chloride
Acetylene
+ H Cl
hydrochloric acid
Cl
Vinylchloride

Polymerisation )
- CH2 - CH )-
n Cl n
Vinylchloride Cl
Polyvinylchloride

• Polyvinyl Chloride (PVC)

Preparation: Preparation of PVC involves the following two steps
I step: Vinyl chloride is prepared by treating acetylene with hydrogen
chloride at 60-80oC in the presence of metal chloride at catalyst

II step: Polyvinylchloride is obtained by heating water emulsion of vinyl

chloride in presence of benzoyl peroxide (or) hydrogen peroxide under
pressure

30
 Properties:
1. PVC is colourless, odourless and chemically inert powder
2. It is insoluble in inorganic acids and alkalis, but soluble in hot chlorinated
hydrocarbons such as ethylchloride
3. It undergoes degradation in presence of heat (or) light

Uses
1. It is used in the production of pipes, cable insulations, table covers and rain-
coasts etc., Polyvinylchloride (PVC)

2. It is also used for making sheets, which are employed for tank-linings, light
fittings, refrigerator components, etc.,

Nylon was discovered

in 1935. The name
nylon is derived from
two cities where it was
discovered namely
New York (NY) and
London (LON).

31
 Preparation of Nylon

Adipoyl chloride
in hexane

Nylon 6,6

Diamine, NaOH, in H2O

Two ingredients are mixed and a solid begins to form

at the junction between the two layers of liquid.

Hot nylon spaghetti can be extracted.

We say certain polymers are man-made, but the truth is they

make themselves. Humans only have to get the ingredients
near each other. The chemicals will assemble themselves.

32
 TEFLON

• It is obtained by the condensation

polymerisation of phenol and formaldehyde
in the presence of acid or alkali catalyst

Preparation
• The reaction involves the following 3 steps

33
 OH

CH2OH
HCHO

Monomethylol phenol

Methylolation OH
OH

HOH2C CH2OH

2HCHO
The first step is
the reaction Dimethylol phenol
between phenol
Phenol OH
and formaldehyde HOH2C CH2OH
forms mono, di 3HCHO
and tri-methylol
phenols
CH2OH
Trimethylol phenol

• When methylol phenols are heated with excess

of formaldehyde in presence of alkaline catalyst.
The methylol phenols condense either through
methylene linkages or through ether linkages to
form resoles.
• Resole is a low molecular weight linear polymer.
It is completely soluble in alkaline solution

34
 OH OH

HOH2C CH2OH H CH2OH

Dimethylol phenol Monomethylol phenol

H2O
Alkaline Catalyst

OH OH

CH2 CH2OH
HOH2C

Resole

OH OH
When methylol phenols are CH2OH H
heated with excess of
phenol in presence of acid +
catalyst, the methylol Phenol
Monomethylol phenol
phenols condense with
phenol through methylene H 2O
linkages to form novolacs. Acid Catalyst

OH OH
OH
Novolac is a high CH2 CH2

molecular weight linear

polymer. It is insoluble in
alkaline solutions. Novolac

35
 Thermo setting Plastics - Bakelite

OH OH
OH
• Further heating of A-stage CH2 CH2

resin or B-stage resin or

both in the presence of a
curing agent
(hexamethylene tetramine) CH2 CH2
CH2

produces hard, rigid,

infusible, cross-linked
polymer called bakelite CH2
CH2
OH OH
OH

Bakelite

Cooker with Bakelite Handles

36
 A Small Segment of Bakelite®

EOS

Properties

1. Bakelite is resistant to acids, salts and most organic

solvents, but it is attacked by alkalis because of the
presence of –OH groups
2. It possesses excellent electrical insulating property

Uses

1. Bakelite is used as an adhesive in plywood

laminations & grinding wheels, etc
2. It is also widely used in paints, varnishes
3. It is used for making electrical insulator parts like
plugs, switches, heater handles, etc.,

37
Amino Resins – Urea Formaldehyde Resins

NHCH2OH
HCHO
O=C
NH2 NH2
O=C Monomethylol Urea
NH2
2 HCHO NHCH2OH
O=C
NHCH2OH
Dimethylol Urea

NHCH2OH NHCH2OH NHCH2OH

O=C + O=C + O=C
NHCH2OH NHCH2OH NHCH2OH

CH2 N CH2 N CH2

N

C=O C=O C=O

CH2 N CH2 N CH2

N
Urea-formaldehyde resin

38
• Properties: Urea-formaldehyde resins give clear,
water-white products of good tensile strength, good
electrical insulation, good chemical-resistance,
great hardness, great light-stability and good
abrasion-resistance

Uses

1. For bonding grinding wheels

2. Binder of glass fibres, rockwool etc
3. Bonding plywood
4. Electrical insulator
5. Decorative articles like plates, drinking glasses,
dishes, etc.

A polymer is a high molar mass molecular compound made up

of many repeating chemical units.

Naturally occurring polymers

•Proteins
•Nucleic acids
•Cellulose
•Rubber
Synthetic polymers
•Nylon
•Dacron
•Lucite
25.1

39
 Moulding Process
• This process involves fabrication of
plastic material into desired shape under
the influence of heat and pressure in a
closed chamber. Some moulding
process is given below
1. Compression Moulding
2. Injection Moulding
3. Transfer Moulding
4. Extrusion Moulding

Compression Moulding
• This method is applied to both thermoplastics and
thermosetting plastics
• Figure shows a typical method used for compression
moulding
• The mould is made up of two halves, the upper and the lower
halves.
• The lower half usually contains a cavity in the shape of the
article to be moulded.
• The upper half has a projection, which fits into the cavity when
the mould is closed.
• The material to be moulded is placed in the cavity of the
mould. Then the mould is closed carefully under low pressure
• Finally the mould is heated to 100-200o C and simultaneously
high pressure (100-500 kg/cm2) is applied on the top of the
mould.
• Curing is done either by heating or cooling. After curing the
moulded article is taken out by opening the mould parts.

40
 Compression Moulding

Compression Moulding Machine

41
 Injection Moulding
1. This method is mainly applicable to thermoplastics.
2. The powdered plastics material is fed into a heated cylinder
through they hopper (Fig).
3. The plastic material melts under the influence of heat and
becomes fluid.
4. The hot fluid is injected at a controlled rate into a tightly locked
mould by means of a screw arrangement or by a piston
5. The mould is kept cold to allow the hot plastic to cure and
becomes rigid. After curing the mould is opened and the object
is ejected.
6. Telephones, buckets etc., are made by this method.

Advantages

1. Low mould cost

2. Low finishing cost
3. Low loss of materials
4. High speed production

Injection Moulding

42
 Injection Moulding Machine

Extrusion Moulding
• This method is mainly used for continuous
moulding of thermoplastic materials into articles
of uniform cross section like rods, tubes etc.
• In this method, the powdered plastic material is
fed into the heated cylinder through the hopper
(Fig).
• The molten plastic material is then pushed by
means of a revolving screw conveyor into a die
having the required shape of the object to be
manufactured. The finished product that
extrudes out is cooled by atmospheric air. A long
conveyor carries away the cooled product.

43
 Extrusion Moulding

Extrusion Moulding Machine

44
 Transfer Moulding
1. This method is used for thermosetting plastics
2. The principle is same as that of the injection moulding
3. The powdered moulding materials is taken in a heated
chamber, maintained at low temperature, at which the
material just begins to become plastic.
4. This plastic is then injected through an orifice into the mould
by a plunger working at high pressure (Fig)
5. Due to the great friction developed at the orifice during
ejection, the temperature of the material rises to such an
extent that the moulding powder becomes almost liquid. So
that it flows quickly and easily into the mould.
6. Then the mould is heated upto the curing temperature
required for setting. Finally the moulded article is ejected
from the mould.

Transfer Moulding

45
 Transfer Moulding Machine

Advantages of Transfer Moulding

1. More complicated shapes can be fabricated
by this method
2. Less expensive
3. Blisters can be eliminated
4. Shrinkage and distortion are minimum
5. Very delicate articles can be made by this
method

46
 Degradable Polymers

Biodegradable Polymers
• The biodegradation of polymer proceeds by hydrolysis and
oxidation.

• The presence of hydrolysable and oxidizable linkages in the

polymer main chain, the presence of suitable substituents, correct
stereoconfiguration, balance of hydrophobicity and
hydrophilicity and conformational flexibility contribute to the
biodegradability of the polymer.

• Biodegradable polymers may be divided into three classes.

• They are natural polymers (eg.Protein),biosynthetic polymers

(eg. Poly-hydroxy alkanoates) and synthetic polymers
(polycaprolacyone and polylactic acid).

47
48
 Lignin
It is a complex constituent of wood connecting cellulose fibers together.

It is brown in colour and largely responsible for the strength and rigidity of
plants.

It is amorphous, aromatic biopolymer and it is obtained from almost all types of

natural wood based resources.

It is byproduct of pulp and paper mills and is conveniently treated as waste material
having low economical usage.

It is separated from the cellulose conventionally either by strong alkaline or acidic

solutions or by high pressure steam treatment followed by solvent extraction.

Unmodified lignin has poor solubility and a thermoplastic melt having flow
characteristic like cellulose.

One method adopted for improving the properties and use of lignin as a
thermoplastic polymer is esterification.

Lignin was found to be useful as a mould lubricant.

Moreover, lignin and its derivatives are bio degradable.

Conducting Polymers

Schematic of PANi/PCL interpolymeric complex,

with PHBSA as the bifunctional linker

49
 Structural formula of undoped PANi (EB)

PANi exists in three forms of oxidation states:

Leucoemeraldine (fully reduced or only benzenoid amine structures),
Emeraldine (neutral or partially reduced and partially oxidized), and
Pernigraniline (fully oxidized or only quinoid imine structures).

Only doped EB PANi is conductive among the three oxidation states.

The emeraldine-based form of PANi is also the most stable of the

three states because leucoemeraldine is easily oxidized when exposed
to air and pernigraniline is easily degraded.

Pure PANi, in the undoped state, is a poor semiconductor with conductivity of about 10-8 S/cm.

However, once it is doped, its conductivity could increase by a factor of 10 S/cm or more
depending on the dopant.

Doping with acid such as PHBSA can increase conductivity because doping forms a
polaron/bipolaron structure that will increase PANi's charge due to increased relocalization.

50
 Bipolaron structure of PANi EB

Polaron structure of PANi EB

APPLICATIONS OF CONDUCTING POLYMERS

51
 APPLICATIONS OF CONDUCTING POLYMERS
Group 1 Group 2
Electrostatic materials Molecular electronics
Conducting adhesives Electrical displays
Electromagnetic shielding Chemical, biochemical and thermal sensors
Printed circuit boards Rechargeable batteries and solid electrolytes
Artificial nerves Drug release systems
Antistatic clothing Optical computers
Piezoceramics Ion exchange membranes
Active electronics(diodes, transistors) Electromechanical actuators
Aircraft structures 'Smart' structures and Switches

The first group utilizes their conductivity as its main property.

The second group utilizes their electroactivity

52
 Fuels and Combustion
• Fuel is a combustible substance, which on combustion
produces a large amount of heat, which can be used for
various domestic and industrial purposes.

• The process of combustion involves oxidation of carbon,

hydrogen etc. of the fuels to CO2, H2O, and the difference in
the energy of reactants and the products are liberated as large
amount of heat energy which is utilized.

Fuel + O2 Products + Heat

• The primary or main source of fuels are coal and petroleum

oils, the amounts of which are dwindling day by day. These
are stored fuels available in earth's crust and are generally
called "fossil fuels".

Classification of fuels

53
 Calorific value of fuels

• The most important property of fuel to be taken into

account is its calorific value or the capacity to supply
heat. The calorific value of a fuel can be defined as
"the total quantity of heat liberated when a unit mass or
volume of the fuel is burnt completely".

Units of heat
1. Calorie - Calorie is the amount of heat
required to raise the temperature of one gram
of water through one degree centigrade.

2. Kilocalorie (or) kilogram centigrade unit -

This is the unit of metric system and is equal
to 1000 calories. This may be defined as
"the quantity of heat required to raise the
temperature of one kilogram of water
through one degree centigrade".
Thus 1 kcal = 1000 cal.

54
 Units of heat
3. British thermal unit (B. Th. U.) - This is
defined as "the quantity of heat required to
raise the temperature of one pound of water
through one degree Fahrenheit". This is
English system unit.
1 B. Th. U. = 252 cal = 0.252 k cal.
1 k cal = 3.968 B. Th. U.
4. Centigrade Heat Unit (C. H. U.) - This is the
"quantity of heat required to raise the
temperature of one pound of water through
one degree centigrade".
Thus, 1 k cal = 3.968 B. Th. U. = 2.2 C. H. U.

Higher or Gross Calorific Value (HCV or GCV)

• Usually, all fuels contain some hydrogen and when the

calorific value of hydrogen containing fuel is determined
experimentally, the hydrogen is converted to steam.

• If the products of combustion are condensed to room

temperature (15°C or 60°F), the latent heat of condensation
of steam also gets included in the measured heat, which is
then called "higher or gross calorific value".

• So gross or higher calorific value may be defined as "the

total amount of heat produced when one unit mass/volume
of the fuel has been burnt completely and the products of
combustion have been cooled to room temperature".

55
 Lower or Net Calorific Value

• In actual use of fuel, the water vapour and moisture etc are
not condensed and escapes as such along with hot
combustion gases. Hence a lesser amount of heat is
available. So, net or lower calorific value may be defined as
"the net heat produced when unit mass / volume of the fuel is
burnt completely and the products are permitted to escape".

• Net or lower calorific value can be found from GCV value

NCV = GCV - Latent heat of water vapour formed
= GCV - Mass of hydrogen x 9 x latent heat of steam

• 1 part by mass of hydrogen produces 9 parts by mass of

water. The latent heat of steam is 587 k cal / kg or 1060 B.
Th. U. / lb of water vapour formed at room temperature. (ie
15°C).

Determination of Calorific Value

Bomb calorimeter

56
 Calculation

m = mass of fuel pellet (g)

W = mass of water in the calorimeter (g)
w = water equivalent of calorimeter (g)
t1 = initial temperature of calorimeter.
t2 = final temperature of calorimeter.
HCV = gross calorific value of fuel.

Corrections
• Fuse wire correction. Heat liberated during sparking
should be subtracted from heat liberated.

• Acid correction. Fuels containing Sulphur and Nitrogen if

oxidised, the heats of formation of H2SO4 and HNO3
should be subtracted (as the acid formations are
exothermic reactions).

• Cooling correction. The rate of cooling of the calorimeter

from maximum temperature to room temperature is noted.
From this rate of cooling (i.e., dt°/min) and the actual time
taken for cooling (t min) then correction (dt × t) is called
cooling correction and is added to the (t2 . t1) term.

57
 Corrections

Dulongs Formula
The approximate calorific value of a fuel can be determined by knowing the
amount of constituents present:

Gross or higher calorific value (HCV) from elemental constituents of a fuel.

H = 34500 kcal/kg; C = 8080 kcal/kg; S = 2240 kcal/kg

Oxygen present in the fuel is assumed to be present as water (fixed

hydrogen).
Available Hydrogen = Total hydrogen - Fixed hydrogen
= Total hydrogen - 1/8 mass of oxygen in fuel.

Dulongs formula for calorific value from the chemical composition of fuel
is,

58
 Knocking
• In an internal combustion engine, a mixture of gasoline vapour and air
is used as a fuel.

• After the initiation of the combustion reaction by spark in the

cylinder, the flame should spread rapidly and smoothly through the
gaseous mixture, thereby the expanding gas drives the piston down
the cylinder.

• The ratio of the gaseous volume in the cylinder at the end of the
suction-stroke to the volume at the end of compression-stroke of the
piston is known as the 'compression ratio'.

• The efficiency of an internal combustion engine increases with the

compression ratio.

• Compression ratio (CR) is defined as the ratio of the cylinder volume

(V1) at the end of the suction stroke to the volume (V2) at the end of
the compression stroke of the piston.

• V1 being greater than V2, the CR is >1.

• The CR indicates the extent of compression of the fuel-air-mixture by

the piston.

• However, successful high compression ratio is dependent on the

nature of the constituents present in the gasoline used.

• In certain circumstances, due to the presence of some constituents in

the gasoline used, the rate of oxidation becomes so great that the last
portion of the fuel-air mixture gets ignited instantaneously producing
an explosive violence, known as 'knocking'.

• The knocking results in loss of efficiency, since this ultimately

decreases the compression ratio.

59
 Chemical structure and knocking
• The tendency of fuel constituents to knock is in the
following order. Straight - chain paraffins > branched - chain
paraffins (isoparaffin) > olefins > cyclo paraffins (naphthenes)
> aromatics.

Octane number
• The most common way of expressing the knocking
characteristics of a combustion engine fuel is by 'octane
number', introduced by Edger. It has been found that n-
heptance, knocks very badly and hence, its anti-knock value
has arbitrarily been given zero.

60
 Octane number
• Octane number is equal to the percentage by volume of iso-
octane (2,2,4-trimethyl pentane) in a mixture of n-heptane and
iso-octane having the same knocking tendency compared to the
sample of gasoline being tested;

• Iso-octane has the best antiknocking properties and assigned an

octane number of 100 whereas n-heptane has poor antiknocking
property and assigned an octane number of zero.

• The hydrocarbons present influence the knocking properties of

gasoline which vary according to the series:

straight chain paraffin > branched chain paraffin > olefin >
cycloparaffin > aromatics.

• The fuel which has same knocking tendency with the mixture
having 80% iso-octance has octane number 80.

H H H H H H H

H C C C C C C C H

H H H H H H H

n-heptane

CH 3

CH 3 C CH 2 CH CH 3

CH 3 CH 3

Isooctane

61
Improvement of anti-knock characteristics of a fuel
• The octane number of many otherwise poor fuels can be raised by the
addition of tetra ethyl lead (C2H5)4Pb or TEL and diethyl telluride
(C2H5)2Te. In motor spirit (Motor fuel) about 0.5ml and in aviation fuel
1.0 - 1.5ml of TEL is added per litre of petrol.

• TEL is converted into a cloud of finely divided lead and lead oxide
particles in the cylinder and these particles react with any hydrocarbon
peroxide molecules formed, thereby slowing down the chain oxidation
reaction and thus decreasing the chances of any early detonation.

• However deposit of lead oxide is harmful to the engine life. In order to

help the simultaneous elimination of lead oxide formed from the
engine, a small amount of ethylene dibromide (or ethylene dichloride)
is also added to petrol.

• The added ethylene dibromide removes lead oxide as volatile lead

bromide along with the exhaust gases. The presence of sulphur
compounds in petrol reduces the effectiveness of the TEL. TEL is
more effective on saturated hydrocarbons than on unsaturated ones.

Other additives

• Oxidation inhibitors - 2,4 - ditertiary butyl - 4 - methyl phenol.

• Rust inhibitors - Organic compounds of phosphorus or

antimony.

• Ignition control additives - tricresyl phosphate which

suppresses pre-ignition of the fuel due to glowing deposits on
spark plug or a hot spot on the cylinder wall.

62
 Diesel Engine Fuels

Characteristics of an ideal diesel oil

• It should have low spontaneous ignition

temperature.
• It should have very little sulphur, aromatic and
ash content.
• The ignition lag should be as short as possible.

Knocking
• In a diesel engine, the fuel is exploded not by a spark, but by the
application of heat and pressure. In the cycle of operations of a
diesel engine, air is first drawn into the cylinder and compressed.

• Towards the end of the compression stroke, the fuel (diesel oil)
is injected as a finely-divided spray into air in the cylinder heated
to about 500°C by compression.

• The oil absorbs the heat from the air and if it attains its ignition
temperature the oil ignites spontaneously. The pressure of the
gases is further increased by the heat accompanying the ignition
of the oil.

• The piston is pushed by the expanding gases and this constitutes

the power stroke.

• Fuel feed and ignition continue during this down stroke. The
fuel injection stops at the exhaust stroke.

63
• The combustion of fuel in a diesel engine is not instantaneous and the
interval between the start of fuel injection and its ignition is called the
'ignition delay' and is an important quality of the diesel fuel.

• This delay is due to the time taken for the vaporization of the individual
droplets and raising of the vapour to its ignition temperature.

• It depends on the engine design, efficiency of mixing of the spray and

air, the injector design and mostly on the chemical nature of the fuel.

• The ignition delay is shorter for paraffinic fuels than for olefinic,
naphthenic and aromatic fuels. Fuels with low carbon residue are
desirable.

• Long ignition delays lead to fuel accumulation in the engine even

before the ignition and when ignited, an explosion results as the
combined effect of increased temperature and pressure. This is
responsible for the diesel knock.

• The diesel fuel should have a spontaneous ignition temperature less than
the temperature produced by compression.

• Diesel engine fuels consist of longer chain hydrocarbons than internal

combustion engine fuels.

• The main characteristic of diesel engine fuel is that it should easily

ignite below compression temperature.

• There should be as short an induction lag as possible. This means that

it is essential that the hydrocarbon molecules in a diesel fuel should be
as far as possible the straight-chain ones with a minimum admixture of
aromatic and side-chain hydrocarbon molecules.

• The suitability of a diesel fuel is determined by its cetane value, which

is the percentage of hexadecane in a mixture of hexadecane and 2-
methyl naphthalene, which has the same ignition characteristics as the
diesel fuel sample, under the same set of conditions.

• The cetane number of a diesel fuel can be raised by the addition of

small quantity of certain "pre-ignition dopes" like alkyl nitrites such as
ethyl nitrite, iso-amyl nitrite, acetone peroxide.

64
 H H H

H C C 14 C H

H H H
n-hexadecane (cetane No.=100)

CH3

2-Methyl naphthalene (cetane No.=0)

Ignition quality decreases among

hydrocarbons is as follows

• n-alkanes > naphthalenes > alkenes > branches

alkanes > aromatics
Cetane number decreases
Ignition quality decreases
Ignition delay increases

65
 Diesel - Index
• On API (American petroleum Institute) scale, the
quality of a diesel fuel is, sometimes, indicated by
diesel-index number which is
Specific gravity (API) X Aniline Point (°F)
D. I= -----------------------------------------
100
• The higher the diesel-index number the better is
the diesel fuel. D. I. = Cetane number + 3.

Liquified Petroleum Gas (LPG) or Bottled

Gas or Refinery Gas
• It is obtained as a by-product during the cracking of heavy oils or
from natural gas.

• LPG is dehydrated desulphurised and traces of odorous organic

sulphides (mercaptans) are added to give warning of gas leak.

• LPG is supplied under pressure in containers under the trade name

like Indane, Bharat gas.

Calorific value - 27,800 k.cal/m3

Composition - n-butane, iso-butane, butylene and propane with little

or no propylene and ethane.
Uses - Domestic, Industrial fuel, Motor fuel.

66
 Natural Gas
• Natural gas is generally associated with petroleum deposits and is
obtained from wells dug in the oil-bearing regions.

• A natural gas containing mainly methane but not higher

hydrocarbons is said to be lean or dry gas whereas that containing
appreciable amounts of propane, butane and other liquid
hydrocarbons like pentane, hexane etc is called rich or wet gas.

• Harmful H2S gas if present in natural gas, is removed by squbbing

with monoethanolamine

(NH2CH2CH2OH) 2HO.CH2.CH2.NH2 + H2S

(HO CH2 CH2 NH2)2.H2S , on heating H2S gas is liberated.

Natural Gas

Calorific value- 12,000 - 14,000 k.cal/m3

Composition - CH4 = 70 - 90%
C2H6 = 5 - 10%
H2 = 3%
CO + CO2 = rest
• Uses - It is an excellent domestic fuel, used in manufacture of
a number of chemicals by synthetic processes.It is the raw
material for the manufacture of carbon black and hydrogen.
Synthetic proteins have been obtained by microbiological
fermentation of methane.

67
 Biogas
• Aquatic plants, organic wastes from domestic, agricultural and
industrial sectors withhigh B.O.D. value (Feed stock) are digested
anaerobically to produce biogas.

• The biogas is totally used as fuel. The chief constituent of biogas is

methane, so the process is also called biomethanation.

• Composition of biogas is given below:

Component Volume%
CH4 52-95
CO2 9-45
H2S 0.001-2
H2 0.01-2
N2 0.1-4
O2 0.02-6.5
CO 0.001
NH3 Small

Biogas

• Conditions for Biomethanation

• Temperature = 35°
• pH = 6.8-8.2
• Anaerobic condition.
• Trace elements = Na+, Co+3, Ni+2 etc.
Arrangements for Biomethanation
Feed stock is mainly cowdung.

68
 Biodiesel
What is bio-diesel?

Biodiesel refers to any diesel-equivalent Biofuel made

from renewable biological materials such as vegetable
oils (Vegetable Oil) or animal fats (Animal Fats).

While there are numerous interpretations being applied to

the term biodiesel, the term Biodiesel usually refers to an
ester, or an oxygenate, made from the oil and methanol
(in other words, the name ‘‘biodiesel’’ can be applied to
any transesterified vegetable oil that makes it suitable for
use as a diesel fuel).

• Technically, as mentioned earlier, biodiesel is vegetable oil methyl

ester or in general the biodiesel consists of mono alkyl-esters.

• It is usually produced by a Transesterification and esterification

reaction of vegetable or waste oil respectively with a low molecular
weight alcohol, such as Ethanol and methanol.

• During this process, the triglyceride molecule from vegetable oil is

removed in the form of glycerin (soap). Once the glycerin is
removed from the oil, the remaining molecules are, to a diesel
engine, somewhat similar to those of petroleum diesel fuel.

• While the petroleum and other fossil fuels contain sulfur, ring
molecules & aromatics, the biodiesel molecules are very simple
hydrocarbon chains, containing no sulfur, ring molecules or
aromatics.

• Biodiesel is thus essentially free of sulfur and aromatics. Biodiesel is

made up of almost 10% oxygen, making it a naturally "oxygenated"
fuel.

69
 Electrochemical energy
systems

Batteries

An Electrochemical cell

• An electrochemical cell is a device in which a

redox reaction is utilized to get electrical
energy.
• Commonly referred to as voltaic or galvanic
cell.
• The electrode where oxidation occurs is
called anode while the electrode where
reduction occurs is called cathode.

70
 Electrochemical cell or galvanic cell
• A device used to convert the chemical energy produced in a redox
reaction to electrical energy is called an electrochemical cell or chemical
cell. Depending upon the changes occuring in the electrochemical cell ,
these can be of two types electrolytic cell and galvanic or voltaic
Voltages generated by such cells have been referred to as electromotive
force.

Electrolytic cell
• A device in which the electrical energy is converted to
chemical energy and resulting in a chemical reaction

71
 Nernst equation

Batteries
• Batteries use a chemical reaction to do work on charge and
produce a voltage between their output terminals.

• The basic element in a battery is called an electrochemical cell

and makes use of an oxidation/reduction reaction.

• An electrochemical cell which produces an external current is

called a voltaic cell. Voltages generated by such cells have
historically been referred to as emf (electromotive force).

• Batteries are devices where several electrochemical systems

are connected together in series.

• And can store chemical energy for later release as electricity

• It is a source of direct electric current at a constant voltage.

72
 Types of
batteries
• Primary battery (Primary cells) in which the cell reaction is not
reversible. When all the reactants have been converted to
product, no more electricity is produced and the battery is
dead.

• Secondary battery (secondary cells) in which cell reactions

can be reversed by passing electric current in the opposite
direction. Thus it can be used for a large number of cycles.

• Flow battery and fuel cell in which materials (reactants,

products, electrolytes) pass through the battery, which is
simply an electrochemical cell that converts chemical to
electrical energy.

Primary batteries

• Dry or lachlanche cell

• Alkaline battery
• Lithium batteries

73
 DRY(or LACLANCHE) CELL

• The venerable
carbon-zinc cell
or Lechlanche' cell
was invented in
1866 by Georges
lachlanche and
was the most
common small
battery throughout
most of the 20th
century

• Dry cell contains Zn, NH4Cl, ZnCl2 and MnO2

• Anodic reaction
• Zn(s) -> Zn2+(aq) + 2e-

• Cathodic reaction
• 2NH4+(aq) + 2MnO2(s) + 2e- -> Mn2O3(s) + H2O(l) + 2NH3(aq)

• Some of the complexity of this reaction comes from the fact that the
reduction of the ammonium ion produces two gaseous products

• 2NH4+(aq) + 2e- -> 2NH3(g) + H2 (g)

• which must be absorbed to prevent the buildup of gas pressure.

• ZnCl2 (aq) + 2NH3 (g) -> Zn(NH3)2Cl2 (s)
• 2MnO2 (s) + H2(g) -> Mn2O3(s) + H2O(l)

74
 Applications and
disadvantages
• Used in flash lights, transistor radios, calculators etc

• Disadvantages of dry cell

• The voltage of this cell is initially about 1.5 volts, but decreases as energy
is taken from the cell. Due to the accumulation of the products on
electrodes. It also has a short shelf life and deteriorates rapidly in cold
weather.

• Oxidation of the zinc wall eventually causes the contents to leak out, so
such batteries should not be left in electric equipment for long periods.

• While these batteries have a long history of usefulness, they are declining
in application since some of their problems are overcome in ALKALINE
BATTERIES.

ALKALINE DRY
CELLS
• Alkaline cells overcome some of the problems
with carbon-zinc batteries by using potassium
hydroxide in place of ammonium chloride in the
electrolyte.

• Potassium hydroxide is a base or alkaline material,

hence "alkaline" batteries. The active materials
used are the same as in the Leclanché cell – zinc
and manganese dioxide.

75
 Chemistr
y
• The zinc anode does not form the container; it is in the form of a
powder instead, giving a large surface area. The following half-cell
reactions take place inside the cell:

• At the anode: Zn + 2OH – → Zn(OH)2 + 2e–

• At the cathode:
2MnO2 + H2 O + 2e – → Mn2 O3 + 2OH –

• Overall: Zn + 2MnO2 + H2 O → Zn(OH)2 + Mn2 O3

Construction : This cell is “inside out” compared to the Leclanché cell

•These cells have much longer shelf life and perform better under drain
and in cold weather.

•They avoid the use of the zinc-corroding ammonium ions and do not
produce any gaseous products.

76
 Advantages and Uses

• Zinc does not dissolve as readily in alkaline

medium
• Long life
• Used in calculators and watches

Lithium batteries
• Main attractions of lithium as an anode material is its position as
the most electronegative metal in the electrochemical series
combined with its low density, thus offering the largest amount of
electrical energy per unit weight among all solid elements.

• Li cannot be used with the traditional aqueous electrolytes due to

the very vigorous corrosive reaction between Li and water with
flammable hydrogen as the product.

• In the 1980s progress was made in the use of Li as an anode

material with MnO2, liquid SO2 or thionyl chlorides as the
cathode, and hexaflurophosphate dissolved in propylene carbonate
as a typical organic electrolyte.

• Li cells are generally properly sealed against contact with air and
moisture Whilst the primary lithium battery has been well
established for nearly two decades,

77
• SystemNominal Cell Voltage (V) Advantages
Disadvantages Applications

• Li/SOCl2 3.60 High Energy density; long shelf life. Only

low to moderate rate applications. Memory devices; standby
electrical power devices

• Li/SO2 3.00 High energy density; best low-temperature

performance; long shelf life. High-cost pressurized system,
Military and special industrial needs

• Li/MnO2 3.00 High energy density; good low-temperature

performance; cost effective. Small in size, only low-drain
applications, Electrical medical devices; memory circuits;

Chemistr
y
• The cell is represented as
Li/Li+(nonaqueous)/KOH(paste)/MnO2,Mn(OH)2,C.

• The anode is lithium. The cathode is carbon in contact with

manganese (III), Manganese(IV) electrode. The electrolyte is a paste
of aqueous KOH

• At anode
Li ---
Li+ + e-

• At cathode
MnO2+2H2O+ e- ---
Mn(OH)2 + OH-

• The overall reaction is

• Li + MnO2+ 2H2O --
Li + + Mn(OH)3 + OH-

78
 Advantages and uses

• High electron density

• Long shelf life
• Low self discharge
• Need less maintenance
• Can provide very high current
• Uses
• Used in auto focus cameras

RECHARGEABLE
BATTERIES
• Lead-acid batteries, invented in 1859 by French
physicist Gaston Plante, are the oldest type of
rechargeable battery.

79
 Lead-Acid Battery
• Batteries use a chemical reaction to do work on charge and produce a
voltage between their output terminals.

Discharging

80
• When the storage cell is operating as a voltaic cell it is
said to be discharging

• In the discharged state both electrodes turn into lead(II)

sulfate (PbSO4) and the electrolyte loses its dissolved
sulfuric acid and becomes primarily water.

• Due to the freezing-point depression of water, as the

battery discharges and the concentration of sulfuric acid
decreases, the electrolyte is more likely to freeze during
winter weather.

• In the charged state, each cell contains electrodes of

elemental lead (Pb) and lead (IV) dioxide (PbO2) in an
electrolyte of approximately 33.5% v/v (6 Molar)
sulfuric acid (H2SO4).

Charging the Lead-Acid Battery

•The discharge reaction can be reversed by applying a voltage

from a charging source.

•During discharge process the concentration of sulfuric acid

decreases and while charging the concentration may attain their
initial values.

•In the charged state, each cell contains electrodes of elemental

lead (Pb) and lead (IV) dioxide (PbO2) in an electrolyte of
approximately 33.5% v/v (6 Molar) sulfuric acid (H2SO4).

81
 Overcharging

• Because of the open cells with liquid electrolyte

in most lead-acid batteries, overcharging with
high charging voltages will generate oxygen and
hydrogen gas by electrolysis of water, forming
an explosive mix. The acid electrolyte is also
corrosive.

Uses
•For constant power supply for electrical vehicles,
•gas engine ignition,
•in telephone exchangers,
•trains,
•mines,
•laboratories,
•hospitals,
•automobiles and in power stations

82
 Nickel Cadmium battery

• The nickel-cadmium battery (commonly

abbreviated NiCd or nicad) is a type of
rechargeable battery using nickel oxide
hydroxide (NiOOH) and metallic cadmium (Cd)
as electrodes and an alkaline potassium
hydroxide KOH electrolyte.

• The first NiCd battery was created by of

Sweden in 1899. But only introduced in the early
1960's

Characteristics

• 1.4 Volt
• Energy density about double that of lead acid
batteries.
• Their small size and high rate discharge capacity
made portable tools and other consumer
applications practical for the first time.

83
 Chemistry

• At anode
Cd + 2OH- --
Cd(OH)2 +2e-

• At cathode
2NiO(OH) +2H2O +2e- --
2Ni(OH)2+2OH-

• Net reaction
2NiO(OH) + Cd +2H2O-
Cd(OH)2 + 2Ni(OH)2

Advantages
• Constant voltage(1.4V)
• No gaseous products
• Wide temperature range (Up to 70°C)

• Charging process is strongly endothermic-the battery cools

during charging. This makes it possible to charge very
quickly

• Rapid charge typically 2 hours, but can be as low as 10 to

15 minutes.

• The sealed nickel-cadmium cell can be stored in the

charged or discharged state without damage.

• Available in a large variety of sizes and capacities

84
 Applications
• Motorised equipment
• Power tools
• Transistors
• Electronic calculators
• Commercial and industrial portable products
• Medical instrumentation
• Emergency lighting
• Toys
• Cordless and wireless telephones

Disadvantages
• NiCad batteries are also prone to damage by
overcharging.

• Low cell voltage of 1.4 Volts compared with primary

alkaline cells 1.5 Volts and only quarter of the capacity
of the alkaline cells.

• Self re-sealing safety vents must be incorporated to

prevent damage due to overheating and pressure build
up.

• The use of Cadmium in consumer products is now

deprecated on environmental grounds.

85
 Problem with NiCad
• Overcharging must be considered in the design of most
rechargeable batteries. In the case of NiCds, there are two
possible results of overcharging:

• If the negative electrode is overcharged, hydrogen gas is

produced.

• If the positive electrode is overcharged, oxygen gas is

produced.

• NiCd cells are vented, with seals that fail at high internal
gas pressures. The sealing mechanism must allow gas to
escape from inside the cell, and seal again properly when
the gas is expelled. This complex mechanism, unnecessary
in alkaline batteries, contributes to their higher cost.

Nickel Metal Hydride Batteries

• Their basic structure is identical to that of Ni-Cd

• The NiMH battery was patented in 1986 by Stanford

Ovshinsky.

• Now NiMH batteries have begun to find use in high

voltage automotive applications. The energy density is
more than double that of Lead acid and 40% higher than
that of NiCads

86
 Anode
• Instead of cadmium, hydrogen is used as the
active element at a hydrogen-absorbing negative
electrode (anode).
• This electrode is made from a metal hydride
usually alloys of Lanthanum and rare earths that
serve as a solid source of reduced hydrogen that
can be oxidized to form protons.

Components

• The components of NiMH batteries include a

cathode of Nickel-hydroxide, an anode of
Hydrogen absorbing alloys
• Potassium-hydroxide (KOH) electrolyte.
• They are more expensive than Lead-acid and
NiCd batteries, but they are considered better
for the environment.
• The electrolyte is alkaline potassium hydroxide.
Cell voltage is 1.2 Volts

87
 Advantages

• High energy density

• Rapid charge possible in 1 hour
• overcharging can cause deterioration of the battery. Chargers
should therefore incorporate a timer to prevent overcharging.
• Because of potential pressure build up due to gassing they
usually incorporate a re-sealable vent valve
• Reconditioning is possible.
• Environmentally friendly (No cadmium mercury or lead)

Applications
• Low cost consumer applications
• Electric razors
• Cameras
• Mobile phones
• Pagers
• Medical instruments and equipment
• Automotive batteries

88
 Lithium batteries

Lithium batteries
• The main attractions of lithium as an anode
material is
– It is the most electronegative metal in the
electrochemical series
– It has very low density,
– Means, the largest amount of electrical energy
per unit weight

• But Li cannot be used with the traditional

aqueous electrolytes
– due to the very vigorous corrosive reaction
between Li and water
– with flammable hydrogen as the product.

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 Li batteries
• In the 1980s progress was made in the use of Li
as an anode material with MnO2, liquid SO2 or
thionyl chlorides as the cathode, and
hexaflurophosphate dissolved in propylene
carbonate as a typical organic electrolyte.

• Li cells are generally properly sealed against

contact with air and moisture

• Cathode materials

• The most common compounds used for

cathode materials are LiCoO2, LiNiO2 and
LiMn2O4.
• Of these, LiCoO2 has the best
performance but is very high in cost, is
toxic and has a limited lithium content
range over which it is stable.
• LiNiO2 is more stable, however the nickel
ions can disorder.
• LiMn2O4 is generally the best value for
money, and is also better for the
environment.

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 Anode material and
electrolyte
• The anode material is carbon based, usually with
composition Li0.5C6.
• This lithium content is lower than would be ideal,
however higher capacity carbons pose safety issues.

• Electrolyte
• Since lithium reacts violently with water, and the cell
voltage is so high that water would decompose, a
non-aqueous electrolyte must be used.
• A typical electrolyte is LiPF6 dissolved in an ethylene
carbonate and dimethyl carbonate mixture.

Discharging

• The following reactions take place upon discharge:

• At the anode: LixC6→ xLi+ + 6C + xe-
• At the cathode: xLi+ + Mn2O4 +xe-→ LixMn2O4
• Overall: LixMn2O4 + 6C → LixC6 + LixC6

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 Chemistry and construction
• Anode here is a non-metallic compound, e.g. carbon,
which can store and exchange lithium ions.
• A lithium ion-accepting material, for example CoO2,
is then used as the cathode material, and lithium ions
are exchanged back and forth between the two during
discharging and charging. These are called
intercalation electrodes.
• This type of battery is known as a “rocking chair
battery” as the ions simply “rock” back and forth
between the two electrodes.

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 Lithium ion Cells
Charging Discharging

Anode: lithium ions in the carbon material

Cathode: lithium ions in the layered material (lithium compound)

Anode Cathode
Li1-XCoO2+ CnLix → LiCoO2 + Cn LiCoO2+ Cn → Li1-XCoO2 + CnLix

The lithium ion moves from the anode to the cathode during
discharge and from the cathode to the anode when charging.

Applications: Laptops, cellular phones, electric vehicles

Lithium Polymer batteries are better than Lithium ion batteries

Exploded laptop
• Li-ion batteries use organic solvents to suspend the lithium ions.
• In situations where the structure of the battery is compromised, that
solvent can ignite and vent from the pressurized battery.
• The result is a dangerous explosion
• The main advantage of Li-poly batteries that has been discussed in
the press recently is their reluctance to explode under duress

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 Lithium Polymer Battery
• Electrolyte is a polymer

Lithium polymer (Poly-Carbon Monofluoride)

batteries
← Charging

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 Lithium battery-battery of the
future
• Imagine your electrical equipment powered by
Lithium ion battery refuse to die out of charge.

• Imagine your 2 hour battery backup of your

laptop increases to 20 hours.

• 6 days of standby time of cell phones increases to

60 days i.e 2 months ( charging a mobile just 6
times a year !!!

• Now !! stop imagining because its going to happen

very soon. scientists from Stanford University have
found a way to use silicon nanowires to produces 10
times the amount of electricity of existing lithium-
ion, known as Li-ion, batteries that power laptops,
iPods, video cameras, cell phones, and countless
other devices. A laptop that now runs on battery
for two hours could operate for 20 hours.

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 Solid Oxide Fuel Cells
• Anode Reaction:2 H2 + 2 O2- => 2 H2O + 4 e-
• Cathode Reaction:O2 + 4 e- => 2 O2-
• Overall Cell Reaction:2 H2 + O2 => 2 H2O

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