18CH101-ENGINEERING

CHEMISTRY
 Module 1
Water chemistry and Corrosion: Water treatment-
characteristics of water-hardness-types and estimation of
hardness by EDTA method with numerical problems. Boiler
feed water–requirements-disadvantages of hard water.
Domestic water treatment-disinfection methods
(chlorination, Ozonation, UV treatment)-demineralization
process–desalination- reverse osmosis.

Corrosion-types–mechanism of dry and wet corrosion-

galvanic corrosion- differential aeration corrosion-protective
coatings-electroplating of gold-electro less plating of nickel.
 Module 2
Electrochemistry and Energy sources: Electrochemical cells-
electrolytic cell-reversible and irreversible cells - Free energy
and emf, cell potentials, Nernst equation and applications.
Oxidation and reduction potentials-standard hydrogen
electrode, saturated calomel electrode, glass electrode-pH
measurement.

Energy Sources-Nuclear energy- reactor-breeder reactor-

Photovoltaic cells-Fuel cells. Storage Devices-Batteries-
alkaline-Lead acid and nickel cadmium batteries.
 Module 3
Polymer chemistry, Spectroscopic techniques and Synthesis
of drug molecules:
Introduction-monomers and polymers-classification of
polymers-Polymerization-types. Mechanism of addition
polymerization (free radical mechanism). Plastics-
classification- preparation, properties and uses of Nylon 6,6,
Nylon 6, PVC, Bakelite and PET. Moulding methods-
Compression moulding, Injection moulding and Blow
moulding.
Spectroscopy-Beer Lambert’s law, principle, instrumentation
and applications of Electronic spectroscopy (UV- visible),
Vibrational and rotational spectroscopy (IR) and Flame
emission spectroscopy (FES). Synthesis of a commonly used
drug molecule-Asprin, p-nitroaniline from acetanilide.
 SRI KRISHNA COLLEGE OF ENGINEERING AND TECHNOLOGY
(AN AUTONOMOUS INSTITUTION, AFFILIATED TO ANNA UNIVERSITY, ACCREDITED BY NAAC WITH ‘A’ GRADE)
ACCREDITED BY NBA (CSE, IT,ECE,EEE,MECH,MCT &CIVIL)

CLASS LECTURE

SUBJECT : 18CH101 - ENGINEERING CHEMISTRY

(Common to all first year B.E./ B.Tech students)

MODULE : I - WATER CHEMISTRY AND CORROSION

FACULTY : Dr. M.SANGEETHA

www.skcet.ac.in
 Module 1
Water chemistry and corrosion
 Introduction

Water is the most important compound for the

existence of human beings, animals and plants. About 80% of
the earth’s surface is occupied by water. The main sources of
water are
(i) rain,
(ii) rivers and lakes
(surface water),
(iii) wells and springs
(underground water),
(iv) sea water.
 Sources of water

Rain - purest form of water

Rivers and lakes

(surface water) Wells
and springs
(underground
water)Sea water.
  Among the above sources of water, rain water is the
purest form of water but it is very difficult to collect,
 Sea water is the most impure and not fit for drinking
 Surface and underground water are normally used
for domestic and industrial purposes. Such water
must be free from undesirable impurities.
The process of removing all types of impurities from
water and making it fit for domestic or industrial purposes
is called water technology (or) water treatment process.
Before treating the water, we should know the nature
as well as the amount of impurities.
 Types of impurities present in water

Physical impurities
⮚Suspended impurities – sand, oil droplets, vegetables, animal
matters – Imparts turbidity to water
⮚Collidal impurities – silica, clay, organic waste- imparts
colour, odour and taste to water.
Chemical impurities
⮚Dissolved salts - bicarbonates , sulphates of Ca and Mg –
hardness causing
bicarbonates , sulphates of Na and K – alkalinity causing.
⮚Dissolved Gases – O2, CO2, H2S, SO2, NO2 –Acidic causing
Biological impurities
Fungi , bacteria, other micro organisms – harmful diseases
 Characteristics of Potable water

 It should be clear, colourless and odourless.

 It should be cool and pleasant to taste.
 Free from harmful bacteria and suspended impurities.
 Free from dissolved gases like CO2, H2S, NH3 etc., and
 It should be free from the poisonous minerals like lead,
arsenic, manganese, etc.,
 Hardness should be less than 500 ppm.
 Chloride content should be less than 250 ppm.
 Fluoride content should be less than 1.5 ppm
 Total Dissolved Solids (TDS) content should be
less than 500 ppm.
 pH of the potable water should be 6.5 - 8.5
 Unique Properties of water

Polarity and hydrogen bonding

A hydrogen bond (abbreviated H-bond) is a partial
intermolecular bonding interaction between a lone pair on
an electron rich donor atom
 Cohesion and Adhesion

Water is attracted to
water

Water is attracted to other substances

 Capillary action and surface tension

Capillary action is the

ability of a liquid to flow in
narrow spaces without the
assistance of, or even in
opposition to, external
forces like gravity.

Surface tension is the tendency

of liquid surfaces to shrink into
the minimum surface area
possible.
 Hard Water and Soft Water

Hard water
Hardness is the property of water which do not produce
lather with soap, instead it produces white precipitate
(scum) due to the presence of dissolved salts of Ca &
Mg salts.
Soft water
The Water, which readily produces lather with the soap
solution is called soft water.
Scum
This is due to the absence of Ca and Mg salts.
Hardness of water is a measure of the total
concentration of the calcium and magnesium ions
expressed as calcium carbonate.
 Detection /Simple test for hardness

1. Soap Test: The hardness causing salt forms white

scum precipitate with sodium salt of fatty acids (Soap)

2C17H35COONa + CaCl2−−−> (C17H35COO)2 Ca + 2NaCl

Soap White scum ppt
Sodium Soap Hardness Calcium Soap
water soluble causing Ions water insoluble
2. EBT Test: The Water containing hardness, gives wine red colour
with Eriochrome Black-T indicator at pH 9-10.
Structure of
EBT
 Types of Hardness

Based on the dissolved salts present in water, hardness can

be classified into two types
 Temporary hardness (called as Carbonate
Hardness).
 Permanent hardness (known as Non-Carbonate
Hardness).
 Total hardness is the sum of Temporary and Permanent
hardness
Carbonate hardness Non- Carbonate hardness
Compounds compounds
Calcium Carbonate -CaCO3 Calcium Sulphate –CaSO4
Magnesium Carbonate -MgCO3 Magnesium Sulphate –
MgSO4
Calcium bicarbonate -(Ca(HCO3)2 Calcium chloride – CaCl2
Magnesium bicarbonate - Magnesium chloride – MgCl2
 Temporary Hardness

This is due to the presence of bicarbonates of calcium

and magnesium compound. It can be removed by the following
methods
(i) By Boiling
(ii) By adding lime to the water.
The above two processes convert the bicarbonates
into insoluble carbonates and hydroxides, which can be
removed by filtering.

Ca(HCO3)2 −−> CaCO3↓ + H2O + CO2

Mg(HCO3)2 + 2Ca(OH)2 −−−> Mg(OH)2↓ + 2CaCO3↓ + 2H2O

(lime)
 Permanent Hardness

This is caused by the presence of chlorides,

sulphates and hydroxides of calcium and magnesium. It
cannot be removed by boiling the water. But, it can be
removed by the following external water treatment
process,
 Zeolite Process
 Lime soda process
 Ion-exchange process
 Reverse Osmosis
 Electro-dialysis
 Units of Hardness (CaCO3 Equivalents)

The concentration of hardness producing salts are

usually expressed in terms of CaCO 3 equivalent.
Because of the following reasons,
 Its molecular weight is 100 and its equivalent
weight is 50 as a whole number. So the calculations in
water analysis can be simplified.
 It is the most insoluble salt, that can be
precipitated in water treatment.
 Expression of CaCO3 equivalent using the
formula
If the concentration of hardness producing salt is
x mgs/lit, then
 Problem
A Hard water sample contains 285 mg of MgCl 2. Express its
hardness in terms of CaCO3 equivalents. (Nov 2019)

Amount equivalent to CaCO3 = X x 100/m.wt MgCl2

= 285 x 100 / 95
= 300 mg/L
Molecular weight of MgCl2
Mg : 24.31+(2X 35.45) = 24.31+70.90 = 95
 Problems

Calculate the hardness of 5 L of water when it contains

333mg/ L of CaCl2 (Nov 2018)
Amount equivalent to CaCO3 = X x 100/m.wt CaCl2
= 333x 100 / 110.90
= 300 mg/L
Molecular weight of CaCl2
CaCl2 : 40+(2X 35.45) = 40+70.90 = 110.90

Amount of hardness for 5L water = 300*5=1500ppm

 Units of Hardness

1. Parts per million (ppm)

It is defined as the number of parts of
CaCO3 equivalent hardness per 106 parts of water.
2. Milligrams per liter (mg/lit)
It is defined as the number of milligrams of CaCO3
equivalent hardness per 1 litre of water.
3. Clarke's degree (°Cl)
It is defined as the number of parts of CaCO3
equivalent hardness per 70,000 parts of water.
4. French degree (°Fr)
It is defined as the number of parts of CaCO3
equivalent hardness per 105 parts of water.
Molecular weights of some hardness producing salts

Hardness Molecular Hardness Molecular

producing salt weight producing salt weight

Ca(HCO3)2 162 MgSO4 120

Mg(HCO3)2 146 MgCO3 84
Mg(NO3)2 148 MgCl2 95
Ca(NO3)2 164 CaCl2 111
CaCO3 100 Ca2+ 40
CaSO4 136 Mg2+ 24

Relationship between various units of hardness

1 ppm = 1 mg/lit = 0.1° Fr = 0.07° Cl
Estimation of Hardness by EDTA method
Amount of hardness present in water can be estimated by
EDTA method. The EDTA method is more accurate, easy and
widely used.
Ethylene Di-amine Tetra Acetic acid (EDTA)
It is a chelating/complexing agent
It can easily forms complex with the divalent metal cations
such as Ca2+ and Mg2+

EDTA is insoluble in water so its disodium salts are used as

a complexing agent.
 Principle
The amount of hardness causing ions Ca 2+/Mg2+ can be
estimated by titrating the water sample against EDTA using
Eriochrome–BlackT indicator at pH 8-10.
In order to maintain the pH buffer solution(NH4Cl + NH4OH)
Only at this pH complexation is possible
When EBT indicator is added to the water sample, it forms
wine red colour weak complex with Ca 2+/Mg2+ ions present
in the hard water.
When this solution is titrated against EDTA, it replaces the
indicator from the weak complex and form stable EDTA
complex.
Ca2+ pH = 8 - 10 Ca2+
2+ + EBT 2+ EBT
Mg Mg

wine red coloured

weak complex
+ EDTA
pH = 8 - 10

Ca2+ EDTA
Mg2+ + EBT
(steel blue colour)
stable and colourless complex
 Estimation of
Hardness
 This method involves in the complexometric titration
between EDTA and water sample using EBT indicator.
Complexometric Titration
Standardization of EDTA
Titration I (EDTA Vs Standard Hard Water)
Burette Solution : EDTA Solution
Pipette Solution : 50 ml Standard Hard water
Additional solution : 10 ml of Buffer
Indicator : Erio Chrome Black T (EBT)
End Point : Wine Red to Steel Blue Color
Let the volume of EDTA consumed be V1 ml
Calculation
1 ml of standard hard water = 1mg of CaCO3
50 ml of standard hard water = 50mg of CaCO3
50 ml of standard hard water consumes = V1 ml of EDTA
1 ml of EDTA = 50 mg of CaCO3
V1
 Estimation of
Hardness
Estimation of total hardness
Titration II (EDTA Vs Hard Water Sample)
Burette Solution : EDTA Solution
Pipette Solution : 50 ml Hard water Sample
Additional solution : 10 ml of Buffer (NH 4OH + NH4Cl)
Indicator : Erio Chrome BlackT (EBT)
End Point : Wine Red to Steel Blue Color
Let the volume of EDTA consumed be V2 ml.
Total hardness
50ml of sample hard water = V2 X 1 ml of EDTA
= V2X 50 mg of CaCO3
V1
1 ml of given sample hard V2 X 50 X 1 mg of CaCO3
water contains V1 50

Total hardness of water

1000 ml of hard water = 1000 x V2 mg of CaCO3
V1
Estimation of permanent hardness
Titration II (EDTA Vs Hard Water Sample)
Burette Solution : EDTA Solution
Pipette Solution : 50 ml Boiled waterSample
Additional solution : 10 ml of Buffer (NH4OH + NH4Cl)
Indicator : Erio Chrome BlackT (EBT)
End Point : Wine Red to Steel Blue Color
Let the volume of EDTA consumed be V3 ml.
Permanent hardness
50ml of boiled water sample = V 3 X 1 ml of EDTA
1 ml of boiled water sample
Contains (permanent hardness)

1000 ml of boiled water sample

Contains (permanent hardness)
Temporary Hardness = Total Hardness – Permanent Hardness

V2 x 1000 mg of CaCO3 - V3 X 1000 mg of CaCO3

V1 V1
 Hardness Problems
Calculate the carbonate and non-carbonate hardness of a
water sample containing the Dissolved salts as given below in
mg/l.
Mg(HCO3)2 =7.3 ; Ca(HCO3)2 =40.5 ; CaSO4 = 13.6, MgCl2 =
21.75 and NaCl =50
Solution
Amount of Hardness of Mg(HCO3)2 in terms of CaCO3 equivalent

Amount of Hardness of Ca(HCO3)2 in terms of CaCO3 equivalent

Amount of Hardness of CaSO4 in terms of CaCO3 equivalent

Amount of Hardness of MgCl2 in terms of CaCO3 equivalent

Carbonate hardness = Mg (HCO3)2+ Ca(HCO3)2= 5+25 = 30 mg/l

Non-Carbonate hardness = CaSO4 +MgCl2 = 10+22.9 =32.9 mg/l

Total Hardness = Carbonate hardness + Non-carbonate hardness

= 30 + 32.9 = 62.9 mg/l

 Boiler Feed Water

The water feed into the boiler for the production of

steam is called boiler feed water.
Boiler feed water should be free from turbidity,
oil, dissolved gases, alkali and hardness causing
substances.
If the hard water obtained from natural sources is fed
directly into the boilers, the following boiler troubles
may arise.
Boiler troubles/Disadvantages of using hard
water in boilers

1. Scale and sludge formation,

2. Priming and foaming (carry over),

3. Caustic embrittlement,

4. Boiler corrosion.
 Scale and Sludge Formation in boilers

 When water is continuously converted into

steam in boilers, the concentration of dissolved salts
in water increases progressively.
 When the concentration of the salts reaches
their saturation point, they are thrown out in the form
of precipitates on the inner walls of the boilers. The
least soluble one gets precipitated first.
Schematic Representation of Scales and Sludges

a) Sludge in boiler b) Scale in boiler

Sludge
If the precipitate is loose and slimy it is called sludge.
Sludges are formed by substances like MgCl 2, MgCO3,
MgSO4 and CaCl2. They have greater solubility in hot
water than cold water.
Scales
if the precipitate forms hard and adherent coating on the
inner walls of the boiler, it is called scale. Scales are
formed by substances like Ca(HCO 3)2, CaSO4 and
Mg(OH)2.
 Comparison of Sludges and Scales

Sludges Scales
Sludge is a loose, slimmy Scale is hard and adherent
and non adherent coating
precipitate
The main sludge forming The main scale forming
substances are MgCO3, substances are Ca(HCO3)2
MgCl2, MgSO4, CaCl2 Mg(OH)2, CaSO4.

Sludges can be removed Scales can be removed by

by blow down operation External treatment
Internal treatment
Process of removing They can also removed by
concentrated water by fresh applying thermal shocks,
water frequently from the scribers and wire brush
boiler during steam
production
Disadvantages Disadvantages
Sludge's are poor conductor Scales act as insulator,
of heat. Excess formation decreases the boiler
decreases boiler efficiency efficiency. Any crack
developed on the scale lead
to explosion
Prevention Prevention
By using Soft water Dissolving using acids like
HCl and H2SO4
 Priming and Foaming (Carry Over)

 During the production of steam in the boiler, due

to rapid boiling, some droplets of liquid water are
carried along with steam.
Steam containing droplets of liquid water is called
wet steam.
 These droplets of liquid water carry with them
some dissolved salts and suspended impurities.
 This phenomenon is called carry over. It occurs
due to priming and foaming.
 Priming
Priming is the process of production of wet steam.
Priming is caused by
The presence of large amount of dissolved salts
High steam velocity
Very high water level in the boiler
Sudden boiling of water
Very poor boiler design
Sudden increase in steam production rate
Priming can be controlled by
 Avoiding rapid change in the steam production rate
 Controlling the velocity of steam
Maintaining the water level lower
Good boiler design
Using treated water
 Foaming
 The formation of stable bubbles above the
surface of water is called foaming.
These bubbles are carried over by steam
leading to excessive priming.
Foaming is caused by the
(i) presence of oil, and grease
(ii)presence of finely divided particles.
Foaming can be prevented by
By adding coagulants like sodium aluminate,
aluminium hydroxide
By adding anti-foaming agents like synthetic poly
amides.
 Caustic Embrittlement /
Intercrystalline Cracking

Caustic embrittlement means intercrystalline

cracking of boiler metal by caustic action.
 Boiler water usually contains a small
proportion of Na2CO3. In high pressure
boilers this Na2CO3 undergoes decomposition to
give NaOH.
Na2CO3 + H2O 2NaOH + CO2
This NaOH flows into the minute hair cracks and
crevices, usually present on the boiler material, by
capillary action and dissolves the surrounding area of
iron as sodium ferrate.
 Fe + 2NaOH Na2FeO2 + H2
This causes brittlement of boiler parts, particularly
stressed parts like bends, joints, rivets, etc., causing
even failure of the boiler.
 Prevention of caustic embrittlement

It can be prevented by the following methods,

By using sodium phosphate as softening agent instead
of sodium carbonate.
By adding tannin, lignin to the boiler water, which
blocks the hair cracks.
 Boiler Corrosion
The decay of boiler material by the dissolved gasses,
dissolved salts and dissolved acids are called boiler
corrosion

Corrosion in boilers are due to the presence of

1. Dissolved Oxygen.
2. Dissolved Carbon Dioxide.
3. Dissolved Salts.
4. Dissolved acids
 1. Dissolved Oxygen

Dissolved oxygen in water is mainly responsible

for the corrosion of boiler. The dissolved oxygen in water
attacks the boiler material at higher temperature.
4Fe + 6H2O + 3O2 4Fe(OH)3 = Fe2O3 3H2O
(Rust)
Removal of Dissolved Oxygen
Chemical Method
Sodium sulphite and hydrazine are the chemical
reagents used to remove the dissolved oxygen

2Na2SO3 + O2 −−−> 2Na2SO4

N2H4 + O2 −−−> N2 + 2H2O

 Hydrazine is found to be an ideal compound for
removing dissolved oxygen; since the products are
water and inert N2 gas.
Mechanical Method: Mechanical De – aeration
Dissolved oxygen can also be removed from water
by mechanical deaeration – it is shown in the below
figure
Mechanical Deaeration Method
 In this process,
water is allowed to fall
slowly on the perforated
plates fitted inside the
tower.
 The sides of the
tower are heated by
heating coil, and a vacuum
pump is also attached to
produce low pressure.
 The high
temperature and low
pressure produced inside
the tower reduce the
dissolved oxygen content
 2. Dissolved Carbon Dioxide
Dissolved carbon dioxide in water produces carbonic
acid, which is acidic and corrosive in nature
CO2 + H2O −−−> H2CO3
Carbon dioxide gas is also produced from the
decomposition of bicarbonate salts present in water.

Removal of Dissolved Carbon Dioxide

Chemical Method
Carbon dioxide can be removed from water by
adding a calculated amount of NH4OH into water.

2NH4OH + CO2 −−−> (NH4)2CO3 + H2O

 3. Dissolved Salts
Dissolved salts in water, are also mainly
responsible for the corrosion of boilers. Salts like MgCl 2,
CaCl2, etc, undergo hydrolysis at higher temperature to
give HCl, which corrodes the boiler.

Removal of Acids
Corrosion by acids can be prevented by the addition of
alkali to the boiler water.
HCl + NaOH NaCl + H2O
Boiler Corrosion Images
 Requirements Of Boiler Feed Water

S Specifications Disadvantages
No
1 Boiler water should Scales and Sludge will be
have zero hardness produced which prevent
efficient heat transfer
2 It must be free from It leads boiler corrosion
dissolved gases like
CO2,O2
3 It must be free from Produces wet steam
suspended impurities
4 It should be free from Produces Caustic
dissolved salts and embrittlement causes
Alkalinity brittlement of boiler parts
 Treatment of water for domestic supply

 Rivers and lakes are the most common sources

of water used by municipalities.
 These water should be free from colloidal
impurities, domestic sewages, industrial effluents
and disease producing bacteria's.
 Hence domestic supply of water involves the
following stages of purification processes.
 Purified/Treated water is supplied by
municipalities for drinking.
 Water treatment Process

Source of Water Screening Aeration

Filtration Sedimentation Coagulation

Sterilisation Domestic water supply

(or)
Disinfection
 Screening
It is a process of removing the floating materials like,
leaves, wood pieces, etc. from water. The raw water is
allowed to pass through a screen, having large number
of holes, which retains the floating materials and allows
the water to pass.
Aeration
The process of mixing water with air is known as aeration
and its main purpose is
To remove dissolved gases like CO 2, H2S and
other volatile impurities present in the water
To remove ferrous and manganous salts
as insoluble ferric and manganic salts.
Sedimentation
It is the process of removal of suspended impurities by
allowing the water to stand undisturbed for 2-6 hours in
a tank.
Most of the suspended particles settle down at the
bottom due to forces of gravity are removed.
Sedimentation removes only 75% of the suspended
impurities.
Demerits
It cannot remove the finely divided particles like
silica and clay.
Sedimentation Process
Coagulation
Finely divided clay, silica, etc. do not settle down
easily and hence cannot be removed by sedimentation.
Such impurities are removed by coagulation method.
In this method certain chemicals, called
coagulants, like alum, Al2(SO4)3 etc., are added to water.
Al2(SO4)3 +6H2O 2 Al(OH)3 + 3H2SO4

When the Al2(SO4)3 is added to water, it gets

hydrolyzed to form a gelatinous precipitate of Al(OH) 3.
The gelatinous precipitate of Al(OH) 3 entraps the finely
divided and colloidal impurities, settles to the bottom
and can be removed easily.
 Filtration  It is the process of
removing bacteria, colour, taste,
odour and suspended particles,
etc., by passing the water
through filter beds containing
fine sand, coarse sand
and gravel and it is shown in the
figure.
 The sand filter consists of
a tank containing a thick top layer
of fine sand followed by coarse
sand, fine gravel and coarse
gravel.
The rate of filtration decreases
slowly due to the clogging of
impurities in the pores of the
The rate of filtration becomes very slow, the filtration is stopped and
sand bed.
the thick top layer of fine sand is scrapped off and replaced with
clean sand. Bacteria are also partly removed by this process
 Sterilization / Disinfection

The process of destroying the harmful bacteria's

is known as sterilization or disinfection. The chemicals
used for this purpose are called disinfectants.
Methods of sterilization

1. By Boiling
2. By Ozonation (using ozone)
3. By Using Ultraviolet Radiations
4. By Chlorination
 Method of
sterilization

Chemical methods
Physical methods 1.Ozonation
Heat (Boling) 2. Adding chlorine
 Chlorine gas
Radiation (UV) Chloramines
Bleaching powder
Boiling
When water is boiled for 10-15 minutes, all the
harmful bacteria's are killed and water becomes safe for
use.
Disadvantages
Boiling alters the taste of drinking water.
It is impossible to employ it in municipal water-works.
Ozonation
Ozone is a powerful disinfectant and is readily
absorbed by water. Ozone is highly unstable and breaks
down to give nascent oxygen.
O3 −−−> O2 + [O]
The nascent oxygen is a powerful oxidizing agent
and kills the bacteria's.
Disadvantages
This process is costly and cannot be used in large
scale.
Ozone is unstable and cannot be stored for
long time.
Ultraviolet Radiation
UV rays are produced by passing electric current
through mercury vapour lamp. This is particularly useful
for sterilizing water in large scale methods employed for
municipal water/domestic water supply.
Disadvantages
 It is costly.
 Turbid water cannot be treated.
Chlorination
The process of adding chlorine to water is called
chlorination. Chlorination can be done by the following
methods.
(i) By Adding Chlorine Gas
Chlorine gas can be bubbled in the water as a very
good disinfectant.
Cl2 + H2O −−−> HCl + HOCl
(ii) By Adding Chloramine
When chlorine and ammonia are mixed in the
ratio 2:1, a compound chloramine is formed.

Cl2 +NH3 ClNH2 +HCl

Chloramine

ClNH2 +H2O HOCl + NH3

Disinfectant

Chloramine compounds decompose slowly to

give chlorine. It is a better disinfectant than chlorine.
Chloramine gives good taste to the treated water.
(iii) By Adding Bleaching Powder
When bleaching powder is added to water, it
produces hypochlorous acid (HOCl). HOCl is a powerful
germicide.
CaOCl2 + H2O Ca(OH)2 +Cl2
Bleaching powder

Cl2 +H2O HCl +HOCl

Hypochlorous acid

HOCl + Bacterias Bacterias are killed

Break point Chlorination
Breakpoint chlorination is the point where the
demand for chlorine has been fully satisfied in terms of
chlorine addition to the water.
When chlorine is added to water, a reaction is
produced in the compounds present in the water. These
compounds utilize the chlorine, resulting in zero chlorine
residual.
The following compounds such as organic
impurities, reducing substances (Fe2+, H2S, etc.) and
free ammonia and harmful bacterial are removed by the
addition of chlorine to water (i.e these compounds
utilize the chlorine)
  The graph depicts that
initially the applied chlorine is
used to kill the bacteria and
oxidizes all the reducing
substances present in the
water and there is no free
residual chlorine.

 As the amount of
applied chlorine increases, the
amount of combined residual
chlorine also increases and
Break Point Chlorination this is due to the formation of
chloramine and other chloro
compounds.
 Mechanism of Chlorination Process

At one point, on further chlorination, the oxidation of

chloramines and other impurities starts and there is a fall
in the combined chlorine content.
Thus the combined residual chlorine decreases to a
minimum point at which oxidation of chloramines and
other impurities complete and free residual chlorine
begins to appear this minimum point is known as, “break
point chlorination”.
Significance: The break point chlorination
eliminates bacterias, reducing substances, organic
substances responsible for the bad taste and odour,
from the water.
Demineralized
water
Vs
Soft water
 External Water Conditioning methods

It involves the removal of permanent hardness

producing salts from the water by the following
methods,
 Demineralisation or Ion-exchange process
 Lime soda process
 Zeolite process / Permutit Process.
 De-Salination Methods
Reverse Osmosis
Electrodialysis
 Ion Exchange/Demineralisation process

 This process removes almost all the ions (both

anions and cations) present in the hard water.
The soft water, produced by lime-soda and zeolite
processes, does not contain hardness
producing Ca2+ and Mg2+ ions, but it will contain
other ions like Na+, K+, SO42-, Cl- etc.,
(De-mineralised) water does not contain both
anions and cations. Thus a soft water is not de-
mineralised water whereas de-mineralised water is soft
water.
This process is carried out by using ion exchange
resins, which are long chain, cross linked, insoluble
organic polymers
 Ion Exchange Process

Principle: It is based on the principle of exchanging ions

with membrane

(i) The hard water is first passed into cation exchange

column; which absorbs all the cations like Ca 2+, Mg2+,
Na+, K+, etc., present in the hard water and releases an
equivalent amount of H+ ion from the resin.

2RH++ Ca2+ R2Ca + 2H+

2RH++ Mg2+ R2Mg + 2H+
RH++ Na+ RNa + H+

2RH++ K+ RK + H+
(ii) The cation free water is then passed into the anion
exchange column and it absorbs all the anions like Cl −,
SO42−, HCO3−, etc., present in the water and releases an
equivalent amount of OH – ions from the resins.
ROH + Cl- RCl + OH-
2ROH + SO42- R2SO4 +2OH-

2ROH + CO32- R2CO3 +2OH-

ROH +HCO3- RHCO3 +OH-

H+ and OH- ions released from cation and anion
exchanger are combined to produce water molecules
H+ + OH- H2O Ion free water
Deionised water
Cation Exchanger Demineralised water

It consists of resins containing acidic functional

groups (−COOH, −SO3H) are capable of exchanging
their H+ ions with other cations of hard water. Cation
exchange resin is represented as RH+.
(i) Sulphonated coals.
(ii) Sulphonated polystyrene.
R − SO3H ; R − COOH ≡ RH2
 Anion Exchanger

Resins containing basic functional groups (−NH 2,

−OH) are capable of exchanging their anions with
anions present in hard water. Anion exchange resin is
represented as ROH.
(i) Cross-linked quaternary ammonium salts.
(ii) Urea-formaldehyde resin.
R − NR3OH ; R−OH ; R−NH2 ≡ R(OH)2
Schematic diagram of Demineralization Process
 Regeneration
When the cation exchange resin is exhausted, it
can be regenerated by passing a solution of dil HCl or dil
H2SO4.
R2Ca +2HCl −−−> 2RH+ + CaCl2
RNa + HCl −−−> RH + NaCl

Similarly, when the anion exchange resin is

exhausted, it can be regenerated by passing a
solution of dil NaOH.
RCl + NaOH −−−> ROH + 2NaCl
R2SO4 + NaOH −−−> 2ROH + Na2SO4
 Advantages of ion-exchange process

(i) Highly acidic or alkaline water can be treated

(ii) The water obtained by this process will have very

low hardness (nearly 2 ppm).
Disadvantages

(i) Water containing turbidity, Fe and Mn cannot be

treated, because turbidity reduces the output and Fe, Mn
form stable compound with the resin.
(ii) The equipment is costly and more expensive
chemicals are needed.
 Desalination

 The process of removing common salt (sodium

chloride) from the water is known as desalination.
 The water containing dissolved salts with a
peculiar salty or brackish taste is called brackish
water.
 The process of desalination can be carried out
by Reverse osmosis and Electro-dialysis method.
Water Specification

(i) Fresh Water –

Contains < 1000 ppm of dissolved solids.
(ii) Brackish water –
Contains > 1000 but < 35,000 ppm of dissolved
solids.
(iii) Sea water –
Contains > 35,000 ppm of dissolved solids.
 Osmosis
 Osmosis: When two solutions of different
concentrations are separated by a semi-permeable
membrane, solvent (water) flows from a region of
lower concentration to higher concentration. This
process is called osmosis.
The driving force in this phenomenon is called
osmotic pressure.
Osmosis Vs Reverse Osmosis:
 Reverse Osmosis: If a hydrostatic pressure in excess
of osmotic pressure is applied on the higher
concentration side, the solvent flow is reversed i.e
solvent
flows from higher concentration to lower concentration.
This process is called reverse osmosis. Thus, in the
process of reverse osmosis pure water is separated
from salt water.

 This process is also known as super-filtration.

 The membranes used are cellulose acetate,

cellulose butyrate.
Schematic Diagram of Reverse osmosis
Reverse Osmosis Home
Systems
 Advantages

 The life time of the membrane is high, and it

can be replaced within few minutes.
 It removes ionic as well as non-ionic, colloidal

impurities.
 Due to low capital cost, simplicity, low
operating, this process is used for converting sea
water into drinking water.
 water obtained by this method is used as boiler
feed water in high pressure boilers.
 INTRODUCTION

Metals and alloys are generally used as fabrication or

construction materials in engineering.
The metal or alloy structures are not properly
maintained, they deteriorate slowly by the action of
atmospheric gases, moisture and other chemicals.
 This phenomenon of deterioration or destruction
of metals and alloys is known as corrosion.
 CAUSES OF CORROSION
Metals occur in nature in two different forms.
1. Native state. 2. Combined state.
Native State
The metals occur in native (or) free (or) uncombined
state are non-reactive with the environment.
They are noble metals exist as such in the earth crust.
They have very good corrosion resistance.
Example : Au, Ag, Pt
 Combined State
Except noble metals, all other metals are reactive
and react with environment and form stable
compounds, as their oxides, sulphides, chlorides and
carbonates. They exist in their form of stable
compounds called ores and minerals.
Examples : Fe, Zn, Pb, Ca etc
 How and Why Corrosion Occurs

 The metals are extracted from these compounds

(ores).
 During the extraction, these ores are reduced to
their metallic states.
In the pure metallic state, the metals are unstable as
they are considered in excited state ie., higher energy
state.
Therefore, as soon as the metals are extracted from
their ores, the reverse process begins and form
metal compounds, which are thermodynamically
stable, ie., lower energy state.
Corrosion and oxidation process
 When metals are used in various forms, they are
exposed to environment, (such as dry gases, moisture,
etc.,) the exposed metal surface begins to decay ie.,
conversion into more stable compound. This is the basic
reason for metallic corrosion.

Due to corrosion, some useful properties of metals

such as electrical conductivity, ductility and malleability
etc., are lost.
 Consequences Of Corrosion

1.Due to formation of corrosion product over the

machinery, the efficiency of the machine gets lost.

2.The products gets contaminated due to corrosion.

3. The corroded equipment must be replaced frequently.

4. Plant gets failure due to corrosion.

5.It is necessary for over design to compensate for the

corrosion.

6.Corrosion releases toxic products, health hazard, etc.

 CLASSIFICATION OF CORROSION
Based on the environment, corrosion is classified into

 Corrosion by
Oxygen
 Corrosion by
Hydrogen
 Liquid metal
corrosion
 DRY (or) CHEMICAL CORROSION

Dry corrosion is due to the direct attack on metal

surfaces by the atmospheric gases such as oxygen,
hydrogen sulphide, sulphur dioxide, nitrogen, etc.
There are 3 main types of dry corrosion.
1. Oxidation corrosion (or) corrosion by
oxygen.
2.Corrosion by hydrogen.
3.Liquid-metal corrosion.
 Oxidation Corrosion / Corrosion by Oxygen

Oxidation corrosion occurs by the direct attack of

oxygen at low or high temperatures on metal surface
in the absence of moisture. Alkali metals (Li, Na, K,
etc.) Alkaline-earth metals (Mg, Ca, Sn, etc.) are rapidly
oxidized at low temperature.
 At high temperature, almost all metals (except, Ag, Au
and Pt) are oxidized.
Mechanism of dry corrosion
 Mechanism of Dry Corrosion

(i) Oxidation occurs first at the surface of the metal

resulting in the formation of metal ions (M2+), which
occurs at the metal / oxide interface.

M −−−−−> M2+ + 2e−

(ii) Oxygen changes to ionic form (O2−) due to the transfer of
electron from metal, which occurs at the oxides
film / environment interface
½ O2 + 2e− −−−−−> O2−
(iii) Oxide ions reacts with the metal ion to form the metal-
oxide film.
M + ½ O2 −−−−−> M2+ + O2− ≡ MO
(Metal-oxide film)
 Identify the type of
corrosion

Before After
 Nature Of Oxide Film

Once the metal surface is converted to a

monolayer of metal-oxide, for further corrosion
(oxidation) to occur, the metal ion diffuses outward
through the metal-oxide barrier. Thus the growth of
oxide film commences perpendicular to the metal
surface.
The nature of oxide film formed on the metal
surface plays an important role in oxidation corrosion.
A stable oxide layer
 a fine-grained in structure,
 gets adsorbed tightly to the metal surface.
 impervious in nature (no diffusion)
 stops further oxygen attack through diffusion.
 film behaves as a protective coating
 no further corrosion can develop.
Example: Oxides of Al, Sn, Pb, Cu, etc., are stable
oxide layers.
(ii) Unstable Oxide Layer
Unstable oxide layer is mainly produced on the
surface of noble metals, which decomposes back into
the metal and oxygen.
Metal Oxide Metal + Oxygen
Examples: Oxides of Pt, Ag, etc., are unstable oxide
layers.
(iii) Volatile Oxide Layer
The oxide layer volatilizes as soon as it is formed,
leaving the metal surface for further corrosion
Example :MoO3
(iv) Protective (or) Non-Protective oxide film
(Pilling- Bedworth rule)

(a) According to Pilling-Bedworth rule, if the volume of

the oxide layer formed is less than the volume of the
metal, the oxide layer is porous and non-protective.
Examples: Alkali and Alkaline earth metals such as
Na, Mg, Ca, etc.

(b) on the other hand, if the volume of the oxide layer

formed is greater than the volume of the metal, the oxide
layer is non-porous and protective.
Example: Heavy metals such as Pb, Sn, etc.
 Pilling-Bedworth Ratio

The ratio of the volume of the oxide formed to the

volume of the metal consumed is called “Pilling-
Bedworth ratio”

If PB ratio > 1; Protective and Non porous in nature

If PB ratio < 1; Non-Protective and porous in nature
 Corrosion by Hydrogen

(a) Hydrogen embrittlement (at ordinary

temperature) When metals contact to H 2S at ordinary
temperature causes evolution of atomic hydrogen.
Fe + H2S −−−−−> FeS + 2H
This atomic hydrogen diffuses readily into the
metal and collects in the voids, where it recombines to
form molecular hydrogen and collection of these
hydrogen gases in the voids develop very high pressure,
which causes cracks and blisters on metal.
H + H −−−−−> H2↑
Thus, the process of formation of cracks and
blisters on the metal surface, due to high pressure of
hydrogen gas is called hydrogen embrittlement.
 (b) Decarburization (at Higher Temperature)

At higher temperature atomic hydrogen is

formed by the thermal dissociation of molecular
hydrogen. H 2  Heat
  2H
When steel is exposed to this environment, the atomic
hydrogen readily combines with carbon of steel and
produces methane gas.

C + 4H −−−−−> CH4↑
Collection of these gases in the voids develop very high
pressure, which causes cracking. Thus the process of
decrease in carbon content in steel is termed as
“decarburisation” of steel
 Liquid - Metal Corrosion

This is due to the chemical action of flowing liquid

metal at high temperature. The corrosion reaction
involves,
(i) Either dissolution of a solid metal by a liquid metal.
(ii) Liquid metal may penetrate into the solid metal.
 WET ELECTROCHEMICAL CORROSION

Wet corrosion occurs under the following conditions.

(i) When two dissimilar metals or alloys are in
contact with each other in the presence of an aqueous
solution or moisture.
(ii) When a metal is exposed to varying
concentration of oxygen or any electrolyte.
 (a) Hydrogen Evolution Type Corrosion

“All metals above hydrogen in the electrochemical

series have a tendency to get dissolved in acidic solution with
simultaneous evolution of hydrogen gas”
 When iron metal contacts with non-oxidizing acid
like HCl, H2 evolution occurs.
At Anode
Iron undergoes dissolution to give Fe 2+ ions with
the liberation of electrons.
Fe −−−−−> Fe2+ + 2e− (Oxidation)
At Cathode
The liberated electrons flow from anodic to
cathodic part, where H+ ions get reduced to H2.

2H+ + 2e− −−−−−> H2↑ (Reduction)

Electrochemical Series
A series of electrodes or half cells arranged in order of
their in decreasing order of their standard reduction
potentials is called as electromotive force series
(e.m.f series) or electrochemical series

Reduction potential
A measure of the tendency of a chemical species to
acquire (accept) electrons
Electrochemical Series

Accept
electrons
cathode

Reactivity

loss electrons
anode
 Corrosion by Oxygen Absorption
(or) Formation of hydroxide type
The surface of iron is usually, coated with a thin
film of iron oxide. However, if the oxide film develops,
some crack will come and anodic areas are created on
the surface while the remaining part acts as cathode.
When iron metal contacts with a neutral
solution of an electrolyte in presence of
oxygen, OH− ions are formed.
 At Anode
Iron dissolves as Fe2+ with the liberation of
electrons.
Fe −−−−−> Fe2+ + 2e− (oxidation)
At Cathode

The liberated electrons flow from anodic to

cathodic part through metal, where the electrons are
taken up by the dissolved oxygen to form OH − ions.
½ O2 + H2O + 2e− −−−−−> 2OH−
The net corrosion reaction is
Fe2+ + 2OH− −−−−−> Fe(OH)2↓

4Fe(OH)2 + O2 + 2H2O −−−−−> 4Fe(OH)3 Rust formation

Difference between Chemical and Electro
Chemical Corrosion
Identify the type of corrosion
in the pictures and write the
mechanism
 Types of Electrochemical Corrosion

1. Galvanic Corrosion
2. Differential Aeration (or) Concentration Cell Corrosion

Galvanic Corrosion
When two different metals are in contact with each
other in presence of an aqueous solution or moisture,
galvanic corrosion occurs.

The more active metal (with more negative

electrode potential) acts as anode (undergoes corrosion)
and the less active metal (with less negative electrode
potential) acts as cathode.
Standard reduction potential value for
Zn = - 0.76
Fe = -0.44
Cu = +0.34
 Example Zn – Fe Couple
The above example represents Zn-Fe couple, in
which zinc (more active or higher in emf series)
dissolves in preference to iron (less active metal) i.e.,
Zn acts as anode and undergoes corrosion and Fe
acts as cathode.
Cu – Fe Couple
The above example represents Fe − Cu couple,
in which iron (more active, when compared to Cu)
dissolves in preference to copper (less active) i.e., Fe
acts as anode and undergoes corrosion and Cu acts as
cathode.
 Examples for Galvanic Corrosion

Steel screw in a brass marine hardware corrodes

This is due to galvanic corrosion. Iron (lower position in
electrochemical series) becomes anodic and is
attacked and corroded, while brass (higher in
electrochemical series) acts as cathodic and is not
Boldattacked.
and Nut made of the same metal is preferred
It is preferred in practice, because galvanic corrosion is
avoided due to homogeneous metals (no anodic and
cathodic part)
Prevention
Galvanic corrosion can be minimized by providing an
insulating material between the two metals
 Galvanic corrosion in Screw

Galvanic Corrosion in lighting Protection

 Differential aeration (or) concentration cell corrosion

This type of corrosion occurs when a metal is

exposed to varying concentration of oxygen or any
electrolyte on the surface of the base metal.
Metals partially immersed in water (or)conducting
solution (called water line corrosion).
 If a metal is partially immersed in a conducting
solution the metal part above the solution is more
aerated and become cathodic.
On the other hand, the metal part inside the
solution is less aerated and thus, become anodic and
suffers corrosion.
At anode (less aerated) corrosion occurs
M −−−−−> M2+ + 2e−
At cathode (more aerated part) OH− ions are
produced
½ O2 + H2O + 2e− −−−−−> 2OH−
 Differential Aeration Corrosion
–Various types
a) Pitting or localized corrosion.
b) Crevice corrosion.
c) Pipeline corrosion.
d) Corrosion on wire fence.
 Pitting or Localized Corrosion

Pitting is a localized attack, resulting in the

formation of a hole around which the metal is relatively .

Pitting Corrosion
 Let us consider a drop of water or aqueous NaCl
resting on a metal surface. The area covered by the
drop of water acts as an anode due to less oxygen
concentration and suffers corrosion. The uncovered
area (freely exposed to air) acts as a cathode due to
high oxygen concentration.
The rate of corrosion will be more, when the area
of cathode is larger and the area of anode is smaller.
Therefore, more and more material is removed from the
same spot. Thus a small hole or pit is formed on the
surface of the metal.
 At Anode
Iron is oxidized to Fe2+ ions
Fe −−−−−> Fe2+ + 2e−
At Cathode
Oxygen is converted to OH− ions.
½ O2 + H2O + 2e− −−−−−> 2OH−
Net Reaction
(o)
Fe2+ +2OH- Fe(OH)2 Fe(OH)3

This type of corrosion is called Pitting Corrosion

 Crevice Corrosion

If a crevice (Space) between different metallic

objects or between metal and non-metallic material is in
contact with liquids, the crevice becomes the anodic
region and suffers corrosion. This is due to less oxygen
in crevice area. The exposed areas act as the cathode .
Pipeline Corrosion
 Differential aeration corrosion may also occur
in different parts of pipeline.
 Buried pipelines or cables passing from one
type of soil to another say, from clay (less aerated)
to sand (more aerated) may get corroded due to
differential aeration.
 Corrosion on Wire - Fence

A wire fence in which the areas where the wires

cross are less aerated than the rest of the fence and
hence corrosion occurs at the wire crossings, which
are anodic.
 Factors Influencing the Rate of Corrosion

Factors affecting corrosion

Nature of metal Nature of environment

1.Position of electro 1.Temperature

chemical series 2.Humidity
2.Purity of the metal 3.Presence of corrosive
3.Over voltage gases
4.Relative cathodic area to 4.Presence of suspended
anodic area particles
5.Nature of surface film 5.Effect of pH
PROTECTIVE COATINGS
INTRODUCTION
Protective coatings are used to protect the metals from
corrosion.
 Protective coatings act as physical barrier between the
coated metal surface and the environment.
 However, they are also used for decorative purpose.
 In addition to corrosion protection and decoration,
they impart some special properties such as hardness,
electrical properties, oxidation- resistance and
thermal insulating properties to the protected surface.
 FUNCTION OF PROTECTIVE COATINGS
 The function of protective coatings is to prevent highly
corrosive industrial fumes, liquids, solids, or gases from
contacting the reactive underlying substrate of the
structure.
 This physical separation of two highly reactive materials,
the atmosphere and the substrate, is extremely important.
 That coatings are, in general, a relatively thin film
separating the two reactive materials indicates the vital
importance of the coating and the concept of a corrosion
free structure.
 The coating must be, according to this concept a
completely continuous film in order to fulfill its function.
 Any imperfection becomes a focal point for corrosion and
the breakdown of the structure.
 PROPERTIES OF PROTECTIVE COATINGS

Corrosion resistant coatings must be characterized by

many essential properties. These may very, depending upon
the specific use of the coating, but there are several basic

characteristics required by all coating materials.

TYPES OF PROTECTIVE COATINGS
COPPER ELECTROPLATING
GOLD ELECTROPLATING
 METALLIC COATINGS

Electroplating (or) Electro-Deposition

Electroplating is the process in which the coating
metal is deposited on the base metal by passing a direct
current through an electrolytic solution containing the
soluble salt of the coating metal.
 Objectives of Electroplating

1. On Metals

(i) To increase the resistance to corrosion of the coated

metal.
(ii) To improve the hardness and physical appearance of
the article.
(iii) To increase the decorative and commercial values
of the article.
(iv) To increase resistance to chemical attack.
(v) To improve the properties of the surface of the
article.
 Objectives of Electroplating on non-metals

2. On Non-Metals
(i) To increase strength.
(ii) To preserve and decorate the surfaces of non-
metals like plastics, wood, glass, etc.
(iii) For making the surface conductivity by utilization
of light weight, non-metallic materials.
Electroplating of gold over copper object
Process
The copper object, to be plated, is first treated with
dil.HCl or dil. H2SO4. The cleaned object is then made cathode
of an electrolytic cell and gold foil as the anode. AuCl 3 solution
is taken as the electrolyte.
When the current is passed from the battery through
the solution, gold dissolves in the electrolyte and deposits
uniformly on the copper object.
 Various Chemical Reactions
AuCl3 −−−−−> Au3+ + 3Cl−
AuCl3 ionises as
At Cathode
On passing current, Au3+ ions move to the
cathode and get deposited there as Au metal.
Au3+ + 3e− −−−−−> Au
At Anode
The free chloride ions migrate to the gold anode and dissolves
an equivalent amount of Au to form AuCl3.
Au + 3Cl− −−−−−> AuCl3 + 3e−
 In order to get strong, adherent and smooth deposit
certain additives (glue, gelatin, etc.,) are added to the
electrolytic bath.
 To improve the brightness of deposit, brightening
agents are added in the electrolytic bath.
 The favorable conditions for a good electro-deposit
are optimum temperature (60oC), optimum current density
(1-10 mA/cm2) and low metal ion concentrations.
 Application of Gold Plating
(i) The deposits of gold are used for electrical and
electronic applications.
(ii) It is used for high quality decorations and high
oxidation resistant coatings.
(iii) For jewellery very thin coating is given (0.05 -1.0
microns).
 Electro less Plating
Principle
Electro less plating is a technique of depositing a noble
metal (from its salt solution) on a catalytically active surface of
the metal, to be protected, by using a suitable reducing agent
without using electrical energy.
The reducing agent reduces the metallic ions to metal,
which gets plated over the catalytically activated surface giving
a uniform thin coating.

Metal ions + Reducing agent −−−−−> Metal + Oxidized Product

(Deposited)
 Electroless Nickel Plating

Step : 1
Pretreatment and activation of the surface

The surface to be plated is first degreased by using

organic solvents or alkali, followed by acid treatment.
Activation depend on the type of metal (or) alloy (or) non-
metal used
(i) The surface of the stainless steel is activated by dipping in hot
solution of 50% dil H2SO4.
(ii) The surface of Mg alloy is activated by thin coating of Zn and
Cu over it.

(ii) Metals and alloys like Al, Cu, Fe, brass, etc., can be directly Ni −
plated without activation.

(iii) Non-metallic articles (like plastics, glass, etc.,) are activated by

dipping them in the solution containing SnCl2+ HCl,
followed by dipping in palladium chloride solution. On drying a
thin layer of Pd is formed on the surface.
 Step II
Preparation of Plating bath
The plating bath consists of the following ingredients
 Step III
Procedure for Plating
The pretreated object is immersed in the plating
bath for the required time. During which the following
reduction reaction will occur and the Ni gets coated
over the object.
Various Reactions

At Cathode
Ni2+ + 2e− −−−−−> Ni
At Anode
H2PO2− + H2O −−−−−> H2PO3− + 2H+ + 2e-

Net reaction
Ni2+ + H2PO2−+H2O −−−−−> Ni + H2PO3−+ 2H+
 Applications

1. Electro less Ni–plating is extensively used in

electronic appliances.
2. Electro less Ni–plating is used in domestic as well as
automotive fields (eg., jewellery, tops of perfume bottles.).
3. Electro less Ni-coated polymers are used in decorative and
functional works.
4. Electro less Cu & Ni coated plastic cabinets are used in
digital as well as electronic instruments.
 Advantages of Electroless Plating Over
Electroplating
1. No electricity is required.
2. Electro less plating on insulators (like plastics, glass) and
semiconductors can be easily carried out.
3. Complicated parts can also be plated uniformly.
4. Electro less coatings possess good mechanical, chemical
and magnetic properties.
Differences Between Electroplating and Electroless Plating
 SRI KRISHNA COLLEGE OF ENGINEERING AND TECHNOLOGY
(AN AUTONOMOUS INSTITUTION, AFFILIATED TO ANNA UNIVERSITY, ACCREDITED BY NAAC WITH ‘A’ GRADE)
ACCREDITED BY NBA (CSE, IT,ECE,EEE,MECH,MCT &CIVIL)

CLASS LECTURE

SUBJECT : 18CH101 - ENGINEERING CHEMISTRY

(Common to all first year B.E./ B.Tech students)

MODULE : II – ELECTROCHEMISTRY AND ENERGY

SOURCES

FACULTY : Dr. M.SANGEETHA

www.skcet.ac.in
Introduction
Electrochemistry is a branch of chemistry, which
deals with the chemical applications of electricity.
Electrochemistry deals with the chemical reactions produced
by passing electric current through an electrolyte or the
production of electric current through chemical reactions.
Conductors
 A substance or material that allows electric current
to pass through it is called a conductor. The ability of a
material to conduct electric current is called conductance.
 All metals, graphite, fused salts, aqueous solutions of
acids, bases, etc.,
Non-Conductors (or) Insulators
 Materials which do not conduct electric current are called
non-conductors or insulators.
 Plastics, wood, most of the non metals, etc.,
 Types of Conductors
The conductors are broadly classified into two types
1. Metallic conductors (or) Electronic conductors
Metallic conductors are solid substances, which conduct
electric current due to the movement of electrons from one end
to another end. The conduction decreases with increase of
temperature.
All metals, graphite.
2. Electrolytic Conductors
Electrolytic conductors conduct electric current due to the
movement of ions in solution or in fused state. The conduction
increases with increase of temperature.
Acids, bases, electrovalent substances.
S.
Metallic conduction Electrolytic conduction
No.
1. It i n v o l v e s t h e It involves the movement
f l o w of electrons in a of ions in a solution.
2. conductor.
It does not involve any It involves transfer of
transfer of matter. electrolyte in the form of
3. Conduction decreases ions.
Conduction increases with
with increase in increase in temperature.
temperature.
4. No change in chemical Chemical reactions occur
properties of the at the two electrodes.
conductor.
CELLS
A cell is a device consisting two half cell.
Each half cell consists of an electrode dipped in an
electrolytic solution. The two half cells are
connected through one wire.
TYPES OF CELLS
1. Electrolytic cells.
2. Electrochemical cells (or)voltaic cells
(or) galvanic cells.
 ELECTROLYTIC CELLS
Electrolytic cells are cells in which electrical energy
is used to bring about the chemical reaction.
Electrolysis, electroplating, etc.,
ELECTROCHEMICAL CELLS OR GALVANIC CELLS
Electrochemical cells are entirely different from
electrolytic cells. The cells used for electrolysis (where
electrical energy is converted to chemical energy) are
called electrolytic cells, whereas in electrochemical cells,
chemical energy is converted to electrical energy.
Galvanic cells are electrochemical cells in which the
electrons, transferred due to redox reaction, are
converted to electrical energy.
Cell device (Construction)
Daniel cell consists of a zinc electrode dipped in 1
M ZnSO4 solution and a copper electrode dipped
in 1 M CuSO4 solution. Each electrode is known as a
half cell. The two solutions are inter connected by a salt
bridge and the two electrodes are connected by a wire
through the voltmeter.
 Reactions occurring in the cell
At anode: Oxidation takes place in the zinc electrode by
the liberation of electrons, so this electrode is called
negative electrode or anode.
At cathode: Reduction takes place in the copper
electrode by the acceptance of electrons, so this electrode
is called the positive electrode or cathode.
Zn −−−−−> Zn2+ + 2e− (at anode)
Cu2+ + 2e− −−−−−> Cu (at cathode)
Cu2+ + Zn −−−−−> Zn2+ + Cu (net cell reaction)
The electrons liberated by the oxidation reaction flow
through the external wire and are consumed by the copper
ions at the cathode.
 Salt bridge
It consists of a U-tube containing saturated solution
of KCl or NaNO3 in agar-agar gel. It connects the two half
cells of the galvanic cells.
Functions of salt bridge
• It eliminates liquid junction potential.
• It provides the electrical continuity between the two half
cells.
Conditions for a cell to act as standard cell
The conditions for an electrochemical cell to act as a
standard cell are
• The e.m.f of the cell is reproductive.
• The temperature-coefficient of emf should be very low.
Representation of a galvanic cell (or) Cell diagram

(i) A galvanic cell consists of two electrodes anode and cathode.

(ii) The anode is written on the left hand side while the
cathode is written on the right hand side.

(iii)The anode must be written by writing electrode metal first

and then electrolyte. These two are separated by a vertical line
or a semicolon. The electrolyte may be written by the formula
of the compound (or) by ionic species.

Zn / Zn2+ (or) Zn / ZnSO4 (or) Zn; Zn2+

 IV) The cathode must be written by writing electrolyte
first and then the electrode metal. These two are
separated by a vertical line or a semicolon.
Cu2+ / Cu (or) CuSO4 / Cu (or) Cu2+; Cu

(v) The two half cells are separated by a salt bridge,

which is indicated by two vertical lines.
Zn / ZnSO4 (1 M) // CuSO4 (1 M) / Cu (or)
Zn / Zn2+ (1 M) // Cu2+ (1 M) / Cu (or)
Zn ; Zn2+ (1 M) // Cu2+ (1 M) ; Cu
 REVERSIBLE AND IRREVERSIBLE CELLS
1. Reversible Cells
Daniel cell, secondary batteries (rechargeable batteries).Daniel
cell is a very good example for a reversible cell. Its emf is 1.1
volt. It is represented as Zn/ZnSO4(1 M)//CuSO4 (1 M)/Cu

A cell which obey the following three conditions of

thermodynamic reversibility is called reversible cell.
(i) If the daniel cell is connected to an external
source of emf equal to 1.1 volt, no current flows and
also no chemical reaction takes place in the cell.

(ii) If the external emf is made slightly less than 1.1

volt, small amount of current flows from the cell and
small chemical reaction occurs.
(iii) If the external emf is made slightly greater than 1.1
volt, the current will flow in the opposite direction.
Copper will pass into the solution as copper ions
and zinc will get deposited on the zinc electrode.

2. Irreversible Cells
Zinc – silver cell, Dry cell (Primary Cells)

Cells which do not obey the conditions of

thermodynamic reversibility are called irreversible
cells. Zinc-Silver cell is an example for a irreversible
cell.
It is represented as
Zn/H2SO4(aq)/Ag
The cell reactions occur at anode and cathode are,
Zn + H2SO4 −−−> ZnSO4 + H2↑ (at anode)
2Ag+ + 2e− −−−> 2Ag (at cathode)
 When the two electrodes are connected, zinc dissolves
with the liberation of hydrogen gas.
 When the external emf, slightly greater than the actual
emf of the cell, is applied to it, the above reactions are
not reversed.
 Because one of the product, H2 gas, is already escaped.
Such a cell, which does not obey the conditions of
thermodynamic reversibility is called an irreversible cell.
 Gibbs free energy:

The difference between the enthalpy of a system and the

product of its entropy and absolute temperature; a measure of
the useful work obtainable from a thermodynamic system at
constant temperature and pressure.
In a galvanic cell, the Gibbs free energy is related to the
potential by: ΔG°cell = −nFE°cell
If E°cell > 0, then the process is spontaneous (galvanic cell).
If E°cell < 0, then the process is nonspontaneous (electrolytic
cell).
EMF OF A CELL:
Definition
Electromotive force is defined as, "the difference of
potential which causes flow of current from one electrode of
higher potential to the other electrode of lower potential.
Thus, the emf of a galvanic cell can be calculated using
the following relationship.

Standard reduction  Standard reduction 

   
EMF potential of right hand    potential of left 
side electrode  hand side electrode
   
Measurement of emf of a cell:
The potential difference or emf of a cell can be
measured on the basis of poggendorff’s
compensation principle. Here the emf of the cell is
just opposed or balanced by an emf of standard cell
(external emf), so that no current flows in the circuit.
 The potentiometer consists of a uniform wire
AB . A storage battery (K) is connected to the ends A
and B of the wire through a rheostat (R). The cell of
unknown emf (x) is connected in the circuit by
connecting its positive pole to A and the negative pole
is connected to a sliding contact (D) through a
galvanometer G. The sliding contact is freely moved
along the wire AB till no current flows through the
galvanometer. Then the distance AD is measured. The
emf of unknown cell is directly proportional to the
distance AD.
Ex  AD
 Then the unknown cell (x) is replaced by a
standard cell (s) in the circuit. The sliding contact is
again moved till there is null deflection in the
galvanometer. Then the distance AD′ is measured. The
emf of standard cell Es is directly proportional to the
distance AD′. Es  AD′
The emf of the unknown cell can be calculated from the
following equation. E x AD

Es AD'
AD
 Emf of the unknown cell E x  X Es
AD'
Factors affecting emf of a cell
1. Nature of the electrolytes and electrodes.
2. Concentration and composition of the electrolytes.
3. pH and temperature of the solution.
Applications of emf measurements
 Determination of standard free energy change and equilibrium
constant.
 Determination of pH by using a standard hydrogen electrode.
 Solubility of a sparingly soluble salt can be determined.
 Valence of an ion can be determined
Differences between electrolytic cells and electrochemical cel
Nernst equation for electrode potential
Consider the following redox reaction
Mn+ + ne− −−−−−> M
For such a redox reversible reaction, the free
energy change (∆G) and its equilibrium constant (K) are
inter related as
∆G = − RT ln K + RT ln [ Product ]
[ Reactant]
= ∆G° + RT ln [ Product ] ........ (1)
[ Reactant ]
where,
∆G° = Standard free energy change
 The above equation (1) is known as Van’t
Hoff isotherm. The decrease in free energy (− ∆G) in the
above reaction involves transfer of ‘n’ number of electrons,
then ‘n’ faraday of electricity will flow. If E is the emf of the
cell, then the total electrical energy (nEF) produced in the
cell is
− ∆G = nEF
(or)
− ∆G° = nE°F
........ (2)
where,
− ∆G = decrease in free energy change.
(or) − ∆G° = decrease in standard free energy change.
Comparing equation 1 and 2, it becomes
− nEF = − nE°F + RT ln [ M ]
[ Mn+] . .......(3)
Dividing the above equation (3) by − nF
[  the activity of solid metal [M] = 1 ]
E = E° − RT ln 1
nF [ Mn+ ]

In general, E = E° − RT ln [Product]
nF [Reactant]
(or)
E = E° + RT ln [ Mn+ ]
nF
 2.303RT
E E o  log[M n  ]
nF
When, R = 8.314 J/K/mole; F = 96500
coulombs ;
T = 298 K (25°C),o the0.0591
above equation
n
becomes
E E red  log[M ]
In general, n

o0.0591
E E oxi  log C
n
Similarly for oxidation potential
0.0591
E E o oxi  log[M n  ]
n
“Nernst equation for single electrode
potential”.
Applications of Nernst equations

1. Nernst equation is used to calculate electrode

potential of unknown metal.

2. Corrosion tendency of metals can be predicted.

Oxidation and Reduction potential
The tendency of an electrode to lose electrons is
called the oxidation potential, and the tendency of an
electrode to gain electrons is called the reduction
potential.

Factors affecting electrode potential

The rate of the above reactions depend on
i. The nature of the metal.
ii.The temperature.
iii.The concentration of metal ions in solution.
Single electrode potential (E)
It is the measure of tendency of a metallic
electrode to lose or gain electrons, when it is in
contact with a solution of its own salt.

Standard electrode potential (E°)

It is the measure of tendency of a metallic
electrode to lose or gain electrons, when it is in
contact with a solution
of its own salt of 1 molar concentration at 25°C.
REFERENCE ELECTRODES (STANDARD ELECTRODES)

The electrode potential is found out by coupling

the electrode with another reference electrode, the
potential of which is known or arbitrarily fixed as zero.
The important primary reference electrode used is a
standard hydrogen electrode, standard electrode potential of
which is taken as zero.
It is very difficult to set up a hydrogen electrode.
So other electrodes called secondary reference electrodes
like calomel electrodes are used.
 Primary Reference Electrode
(Standard Hydrogen electrode)
Construction:
Hydrogen electrode consists of platinum foil, that
is connected to a platinum wire and sealed in a
glass tube. Hydrogen gas is passed through the side
arm of the glass tube. This electrode, when dipped in a
1N HCl and hydrogen gas at 1 atmospheric pressure is
passed forms a standard hydrogen electrode. The
electrode potential of SHE is zero at all temperatures.
(Fig. 1.2).
It is represented as,
Pt , H2 (1 atm)/H+ (1 M); E° = 0 V

In a cell, when this electrode acts as anode, the

electrode reaction can be written as
H2 (g) −−−−−> 2H+ + 2e−
When this electrode acts as cathode, the
electrode reaction can be written as

2H++2e- −−−−−> H2(g)

Limitations
i. It requires hydrogen
gas and is difficult to
set up and transport.
ii. It requires considerable
volume of test solution.
iii. The solution may
poison the surface of
the platinum electrode.
iv. The potential of the
electrode is altered
by changes in
barometric pressure.
Secondary Reference Electrode
(Saturated Calomel Electrode)
Construction:

Calomel electrode consists of a glass tube containing

mercury at the bottom over which mercurous chloride is
placed. The remaining portion of the tube is filled with a
saturated solution of KCl. The bottom of the tube is
sealed with a platinum wire (Fig. 1.3). The side tube is used
for making electrical contact with a salt bridge. The
electrode potential of the calomel electrode is + 0.2422 V.
It is represented as,
Hg , Hg2Cl2 (s) , KCl (sat.solution); E° = 0.2422 V
If the electrode acts as anode the reaction is
2Hg(l) −−−−−> Hg22+ + 2e−

Hg22+ + 2Cl−−−−−−>Hg2Cl2 (s)

2Hg(l) + 2Cl− Hg2Cl2 (s) + 2e−

If the electrode acts as cathode the reaction is

Hg2 Cl2 (s) −−−−−>Hg22+ + 2Cl−

Hg22+ + 2e−−−−−−> 2Hg(l)

The electrode potential is given by (for example
cathode)
o RT
E (calomel) E (calomel) - In a c1 -
2F
The electrode potential depends on the
activity of the chloride ions and it decreases as the
activity of the chloride ions increases. The single
electrode potential of the three calomel electrodes
on the hydrogen scale at 298 K are given as

0.1 N KCl = + 0.3338 V

1.0 N KCl = + 0.2800 V
Saturated KCl = + 0.2422 V.
Measurement of single electrode potential of Zn using
saturated calomel electrode
The saturated calomel
electrode is coupled with
another Zn electrode, the
potential of which is to be
determined (Fig. 1.4). Since the
reduction potential of the
coupled Zn electrode is less
than E° of calomel electrode (+
0.2422 V), the calomel electrode
will act as cathode and the
reaction is
At Anode:
Zn Zn2+ + 2e− (Oxidation)
At Cathode:
Hg2Cl2 (s) + 2e− 2Hg(l) + 2Cl−
(Reduction)
Zn + Hg2Cl2 (s) ZnCl2 + 2Hg (l)

Ecell = E°right − E°left

Ecell = E°cal − E°Zn
E°Zn = E°cal − Ecell
= + 0.2422 − 1.0025
Ion-Selective Electrodes (ISE)
Ion-selective electrodes are the electrodes having the
ability to respond only to a particular ions, and develop
potential, ignoring the other ions in a mixture totally. The
potential developed by an ion-selective electrode depends
only on the concentration of particular ions.

Glass Electrode
The glass membrane of the glass electrode is only
selective to H+ ions only in a mixture.
Glass Electrode (Internal Reference
Electrode)
Construction:
A glass electrode consists of thin-walled glass bulb
(the glass is a special type having low melting point and
high electrical conductivity) containing a Pt wire in 0.1M
HCl (Fig.1.5). The glass electrode is represented as

Pt, 0.1 M HCl / Glass

HCl in the bulb furnishes a constant H+ ion concentration.
 Glass electrode is used as the “internal reference
electrode”. The pH of the solutions, especially colored solutions
containing oxidizing or reducing agents can be determined. The
thin walled glass bulb called glass membrane functions as an ion-
exchange resin, and an equilibrium is set up between the Na+ ions
of glass and H+ ions in solution. The potential difference varies
with the H+ ion concentration, and its emf is given by the
expression

EG = E°G + 0.0592 pH
Determination of pH of a Solution using Glass Electrode
The glass electrode is placed in the solution under test
and is coupled with saturated calomel electrode as shown
in the figure 1.6.
 The emf of the cell is measured. From the emf, the pH of
the solution is calculated as follows
Ecell = Eright − Eleft
Ecell = Ecal − EG
Ecell = Ecal − (E°G + 0.0592 pH)
Ecell = Ecal − E°G − 0.0592 pH

pH = Ecal − E°G − Ecell  Ecal = 0.2422 V

0.0592
 pH = 0.2422 – EoG – Ecell
0.0592
Advantages of Glass Electrode:
i. It can be easily constructed and readily used.
ii. The results are accurate.
iii. It is not easily poisoned.
iv. Equilibrium is rapidly achieved.
Disadvantages (Limitations):
i) Since the resistance is quite high, special electronic
potentiometers are employed for measurement.
ii) The glass electrode can be used in solutions only with pH
range of 0 to 10. However above the pH 12 (high alkalinity),
cations of the solution affect the glass and make the
electrode useless.
Applications of ISEs:

(i) ISEs are used in determining the concentrations of

cations like H+, Na+, K+, Ag+, Li+.
(ii) ISEs are used for the determination of hardness
Ca2+ and Mg2+ ions).
(iii) Concentrations of anions like NO3−, CN−, S2−, halides
(X−) can be determined.
(iv) ISEs are used in the determination of concentration
of a gas by using gas-sensing electrodes.
(v) pH of the solution can be measured by using glass
electrode.
ENERGY SOURCES AND
STORAGE DEVICES
NUCLEAR FISSION
When 92 U235
is bombarded by thermal neutron (low energy
neutron), it splits into two approximately equal parts with the
liberation of a large amount of energy.
Enormous amount of Energy
Neutron

Neutron
U-235
U-236
Intermediate Smaller Nuclei
Definition
Nuclear fission is defined as "the process of splitting of
heavier nucleus into two (or) more smaller nuclei with
simultaneous liberation of large amount of energy".
Mechanism of nuclear fission
When 92 U235
is bombarded by thermal neutron

(slow moving), unstable 92U236 is formed. The unstable U

then divides into two approximately equal nuclei with the
release of neutrons and large amount of energy.
 CHARACTERISTICS OF NUCLEAR FISSION
A heavy nucleus (U235 (or) Pu239), bombarded by
slow moving neutrons, split into two or more nuclei.
Two or more neutrons are produced by fission of each
nucleus.
Large quantities of energy is produced as a result of
conversion of small mass of nucleus into energy.
All the fission fragments are radioactive, giving off  and
-radiations.
The atomic weights of fission product ranges from about
70 to 160.
All the fission reactions are a self-propagating chain-
reactions because fission products contain neutrons
(secondary neutrons) which further cause fission in other
nuclei
 CHARACTERISTICS OF NUCLEAR FISSION
• The nuclear chain reactions can be controlled and
maintained steadily by absorbing a desired number of
neutrons. This process is used in nuclear reactor.

• Every secondary neutron, released in the fission process,

does not strike a nucleus, some escape into air and hence a
chain reaction cannot be maintained.

• Multiplication factor: The number of neutrons, resulting

from a single fission, is known as the multiplication factor.
When the multiplication factor is less than 1, a chain
reaction does not take place.
 NUCLEAR FUSION

Nuclear fusion is defined as, "the process of combination of

lighter nuclei into heavier nuclei, with simultaneous liberation of

large amount of energy". Nuclear fusion occurs in sun.

S. No Nuclear fission Nuclear fusion
1. It is the process of breaking It is the process of
a heavier nucleus. combination a lighter nucleus.
2. It does not emits any
It emits radioactive rays.
radioactive rays.
3. It occurs at high temperature
It occurs at ordinary
(>106K).
temperature.
4. The mass number and atomic The mass number and atomic
number of new elements are number of product is higher
lower than that of parent than that of starting elements.
nucleus.
5. It gives rise to chain reaction. It does not give rise to chain
reaction.
6. It emits neutrons. It emits positrons.
7. It can be controlled. It cannot be controlled.
NUCLEAR CHAIN REACTIONS

In the nuclear fission reaction the neutrons emitted from

the fission of U235 atom may hit another U235 nuclei and
cause fission producing more neutrons and so on.

A chain of self sustaining nuclear reactions will be set up

with the release of enormous amount of energy.

But the amount of energy released will be less than

expected.

Thus the fission of U by slow moving neutrons is a chain

reaction.
Illustration
When U235 nucleus is hit by a thermal neutron, it undergoes the
following reaction with the release of three neutrons.

Each of the three neutrons, produced in the above reaction,

strikes another U235 nucleus causing (3x3) 9 subsequent reactions.
These 9 reactions further give rise to (3 x 9) 27 reactions. This process
of propagation of the reaction by multiplication in threes at each
fission is called chain reaction.
Definition
A fission reaction, where the neutrons from the previous step
continue to propagate and repeat the reaction is called nuclear chain
reaction.

Reason for less energy

Some of the neutrons, released in the fission of U235 may escape
from the surface to the surroundings or may be absorbed by U238
present as impurity. This will result in breaking of the chain and the
amount of energy released will be less than expected.

Criteria for nuclear chain reaction

For a nuclear chain reaction to continue, sufficient
amount of U235 must be present to capture the neutrons, otherwise
neutrons will escape from the surface.
Critical mass
The minimum amount of fissionable material (U235) required
to continue the nuclear chain reaction is called critical mass

(a) Super critical mass

If the mass of the fissionable material (U235) is more the
critical mass, it is called super critical mass.

(b) Sub-critical mass

If the mass of the fissionable material is smaller than the
critical mass, it is called sub-critical mass. Thus the mass greater or
lesser than the critical mass will hinder the propagation of the chain
reaction.
 NUCLEAR ENERGY
The enormous amount of energy released during the nuclear
chain reaction of heavy isotope like U235 (or) Pu239 is called nuclear
energy.

Definition
The energy released by the nuclear fission is called nuclear
fission energy (or) nuclear energy.

Illustration
The fission of U or Pu239 occurs instantaneously, producing
enormous amount of energy in the form of heat and radiation.
Cause of the release of energy

The enormous amount of energy released during the nuclear fission is

due to the loss in some mass, when the reaction takes place.

It has been observed that during nuclear fission, the sum of the masses
of the products formed is slightly less than the sum of masses of target
species and bombarding neutron.

The loss in mass gets converted into energy according to Einstein

equation
E = mc2
Where, c = velocity; m = loss in mass and E = energy.
 NUCLEAR REACTOR OR PILE
If a nuclear fission reaction is made to occur in a controlled manner,
then the energy released can be used for many constructive purposes.
Definition
The arrangement or equipment used to carry out fission reaction
under controlled conditions is called a nuclear reactor.
Example
The energy released (due to the controlled fission of U235in a nuclear
reactor) can be used to produce steam, which can run turbines and
produce electricity.
Components of a nuclear reactor
The main components of the nuclear reactor are
 1. Fuel rods
The fissionable materials used in the nuclear reactor is enriched U 235.
The enriched fuel is used in the reactor in the form of rods or strips.
Example : U235, P239
Function: It produces heat energy and neutrons, that starts nuclear
chain reaction.
2. Control rods
To control the fission reaction (rate), movable rods, made of
cadmium (or) boron, are suspended between fuel rods. These rods can be
lowered or raised to control the fission reaction by absorbing excess
neutrons.
If the rods are deeply inserted inside the reactor, they will absorb
more neutrons and the reaction becomes very slow. On the other hand, if
the rods are pushed outwards, they will absorb less neutrons and the
reaction will be very fast.
 Example : Cd113 ,B10
Function: It controls the nuclear chain-reaction and avoids the damage
of the reactors.

3. Moderators
The substances used to slow down the fast neutrons are called
moderators.

When the fast-moving neutrons collide with moderator they lose

energy and gets slow down.
Example: Ordinary water, heavy water, graphite, beryllium
Function: The kinetic energy of fast moving neutrons
(2 meV) is reduced to slow neutrons (0.025 eV).
4. Coolants
In order to absorb the heat produced during fission, a liquid called
coolant is circulated in the reactor core. It enters the base of the
reactor and leaves at the top. The heat carried by out-going liquid is
used to produce steam.
Example: Water (act as moderator & coolant), heavy water, liquid
metal (Na or K), air (CO2).

Function: It cools the fuel core.

5. Pressure vessel
It encloses the core and also provides the entrance and exit passages
for coolant.
Function: It withstands the pressure as high as 200 kg/cm2.

6. Protective shield
The nuclear reactor is enclosed in a thick massive concrete shield
(more than 10 meters thick).
Function: The environment and operating personnel are
protected from destruction in case of leakage of radiation.
 Light Water Nuclear-Power Plant

Definition
Light-water nuclear-power plant is the one, in whichU 235 fuel rods are
submerged in water. Here the water acts as coolant and moderator
Working
The fission reaction is controlled by inserting or removing the control
rods of B10 automatically from the spaces in between the fuel rods.
The heat emitted by fission of U 235 in the fuel core is absorbed by the
coolant (light water). The heated coolant (water at 300°C) then goes to the
heat exchanger containing sea water. The coolant here, transfers heat to
sea water, which is converted into steam. The steam then drives the
turbines, generating electricity.
Pollution
Though nuclear power plants are very important for production of
electricity, they will cause a serious danger to environments.

Problem on disposal of reactor waste

Disposal of reactor waste is another important problem because the

fission products viz., Ba139&Kr92 are themselves radioactive. They emit
dangerous radiation for several hundred years. So the waste is packed
in concrete barrels, which are buried deep in the sea.
BREEDER REACTOR
Breeder reactor is the one which converts non-
fissionable material (U238, Th232) into fissionable material (U235,
Pu239). Thus the reactor produces or breeds more fissionable material
than it consumes.
 In breeder reactor, of the three neutrons emitted in the fission of
U235, only one is used in propagating the fission chain with U 235.

The other two are allowed to react with U238.

Thus, two fissionable atoms of Pu239 are produced for each atom of
U235consumed.

Therefore, the breeder reactor produces more fissionable material

than it uses.

Hence Pu239is a manmade nuclear fuel and is known as secondary

nuclear fuel.
Significance
The non-fissionable nucleides, such as U238&Th232, called fertile
nucleides are converted into fissile nucleides.
The fissionable nucleides such as U235& Pu239 are called fissile
nucleides.
As regeneration of fissile nucleided takes place, its efficiency is
more.
 FUEL CELLS
Definition
Fuel cell is a voltaic cell, which converts the chemical energy
of the fuels directly into electricity without combustion. It converts the
energy of the fuel directly into electricity. In these cells, the reactants,
products and electrolytes pass through the cell.

Fuel + oxygen  Oxidation products + Electricity

Examples : Hydrogen-oxygen fuel cell; Methyl alcohol-oxygen fuel

Hydrogen-Oxygen fuel cell
Hydrogen-oxygen fuel cell is
the simplest and most successful fuel
cell, in which the fuel-hydrogen and
the oxidizer-oxygen and the liquid
electrolyte are continuously passed
through the cell.
Description
It consists of two porous electrodes anode and cathode.

These porous electrodes are made of compressed carbon

containing a small amount of catalyst (Pt, Pd, Ag).

 In between the two electrodes an electrolytic solution such as

25% KOH or NaOH is filled.

 The two electrodes are connected through the volt meter.

Working
Hydrogen (the fuel) is bubbled through the anode compartment,
where it is oxidized. The oxygen (oxidizer) is bubbled through the
cathode compartment, where it is reduced.
Various reactions
At Anode:
Hydrogen gas, passed through the anode, is oxidised with the
liberation of electrons which then combine with hydroxide ions to
form water.
At cathode:
The electrons, produced at the anode, pass through the external wire
to the cathode where it is absorbed by oxygen and water to produce
hydroxide ions.
Fuel Battery
When a large number of fuel cells are connected in series, it forms fuel battery .

Advantages of Fuel cells

Fuel cells are efficient (75%) and take less time for operation.
It is pollution free technique.
It produces electric current directly from the reaction of a fuel and an oxidizer.
It produces drinking water.
Disadvantages
Fuel cells can not store electric energy as other cells do.
Electrodes are expensive and short lived.
Storage and handling of hydrogen gas is dangerous.

Applications
H2-O2 fuel cells are used as auxiliary energy source in space

vehicles, submarines or other military-vehicles.

In case of H2-O2 fuel cells, the product of water is proved to be a
valuable source of fresh water by the astronauts.
 BATTERIES
INTRODUCTION
In electrochemical cells, the chemical energy is converted into
electrical energy.
The cell potential is related to free energy change (G).
 In an electrochemical cell, the system does work by transferring
electrical energy through an electric circuit.
Thus G for a reaction is a measure of the maximum useful work, that
can be obtained from a chemical reaction.

ie., G = maximum useful work

 But we know that maximum useful work = nFE
When a cell operates, work is done on the surroundings (flow of
electricity).
G = -nFE or G < 0
Decrease in free energy is indicated by (-)ve sign.

One of the main uses of the galvanic cells is the generation of

portable electrical energy. These cells are known as batteries.
Battery
A battery is an arrangement of several electrochemical cells connected in series, that
can be used as a source of direct electric current)
A Cell: It contains only one anode and cathode.
A Battery: It contains several anodes and cathodes.
Requirements of a battery
A useful battery should fulfill the following requirements
1. It should be light and compact for easy transport.
2. It should have long life both when it is being used and when it is not used.
3. The voltage of the battery should not vary appreciably during its
use.
 TYPES OF BATTERY
1. Primary Battery (or) Primary cells(or) Non-reversible Battery
In these cells, the electrode and the electrode reactions cannot be reversed by passing
an external electrical energy.
The reactions occur only once and after use they become dead. Therefore, they are
not chargeable
Examples: Dry cell, mercury cell.
2. Secondary Battery (or) Secondary cells(or) Reversible Battery
In these cells, the electrode reactions can be reversed by passing an external electrical
energy.
Therefore, they can be recharged by passing electric current and used again and
again. These are also called Storage cells (or) Accumulators.
Examples : Lead acid storage cell, Nickel-cadmium cell.
3. Flow battery (or) Fuel cells
In these cells, the reactants, products and electrolytes are
continuously passing through the cell. In this chemical
energy gets converted into electrical energy. Eg.:
Hydrogen-oxygen fuel cell.
ALKALINE BATTERY
Description
 Alkaline battery is improved form of the dry cell, in

which the electrolyte NH4C1 is replaced by KOH.

 Alkaline battery consists of a zinc cylinder filled with an

electrolyte consisting of powdered Zn, KOH and MnO 2

in the form of paste using starch and water.

 A carbon rod (graphite), acts as cathode, is immersed in
the electrolyte in the centre of the cell. The outside
cylindrical zinc body acts as anode.
 LEAD STORAGE CELL OR LEAD ACCUMULATOR OR
ACID STORAGE CELL

A lead acid storage cell is a

secondary battery, which can operate both
as a voltaic cell and as an electrolytic cell.
When it acts as a voltaic cell, it supplies
electrical energy and becomes "run down".
When it is recharged, the cell operates as
an electrolytic cell.
Description
 A lead-acid storage battery consists of a number of (3 to 6) voltaic cells connected in
series to get 6 to 12 V battery.
 The anode is made of lead. The cathode is made of lead dioxide PbO 2 or a grid made of

lead, packed with PbO2.

 A number of lead plates (anodes) are connected in parallel and a number of PbO 2 plates

(cathodes) are also connected in parallel.

 Various plates are separated from the adjacent ones by insulators like rubber or glass
fibre.
 The entire combinations is then immersed in dil. H2SO4 (38% by mass) having a density

of 1.30 gm/ml.
The cell may be represented as;
Pb | PbSO | | H SO | PbO | Pb
Working (Discharging)
When the lead-acid storage battery operates, the
following reaction occurs.
At anode: Lead is oxidized to Pb ions, which further
combines with SO4 forms insoluble PbSO4.
 PbSO4 is precipitated at both the electrodes and H2SO4 is used up.

As a result, the concentration of H2SO4 decreases and hence the density of

H2SO4 falls below 1.2 gm/ml. So the battery needs recharging.

Recharging of batteries: The cell can be charged by passing

electric current in the opposite direction. The electrode reaction gets
reversed. As a result, Pb is deposited on anode and PbO2 on the cathode. The

density of H2SO4 also increases. The net reaction during charging is

Advantages of lead-acid batteries
(i) it is made easily.
(ii) it produces very high current.
(iii) the self-discharging rate is low when compared to other rechargeable batteries.
(iv) it also acts effectively at low temperature.
Disadvantages of lead-acid batteries
(i) recycling of this battery causes environmental hazards.
(ii) mechanical strain and normal bumping reduces battery capacity.
Uses
lead storage cell is used to supply current mainly in automobiles such as cars, buses,
trucks, etc.,
It is also used in gas engine ignition, telephone exchanges, hospitals, power
stations, etc.,
 NICKEL-CADMIUM CELL (or) NICAD BATTERY

This is also a rechargeable battery.

Description
Nickel-cadmium cell consists of a cadmium anode and a metal grid containing
a paste of NiO2 acting as a cathode the electrolyte in this cell is KOH.

It is represented as: Cd | Cd(OH)2 11 KOH(aq) | NiO2 | Ni

Working (discharging)
When the NICAD battery operates, at the anode cadmium is oxidized to Cd 2+
ions and insoluble Cd(OH)2 is formed. It produces about 1.4v.
At anode: Cadmium is oxidized to Cd 2+ and further it combines with OH-
ions to form Cd(OH)2
 There is no formation of gaseous products, the products Cd (OH) 2 and

Ni(OH)2adhere well to the surfaces. This can be reconverted by recharging the

cell.
Recharging the battery
The recharging process is similar to lead storage battery. When the
current is passed in the opposite direction, the electrode reaction gets reversed.
As a result, Cd gets deposited on anode and NiO2 on the cathode.
Advantages
It is smaller and lighter.
It has longer life than lead storage cell.
 Disadvantage
it is more expensive than lead storage battery.
Uses
it is used in calculators, electronic flash units, transistors and cordless
appliances.
 SRI KRISHNA COLLEGE OF ENGINEERING AND TECHNOLOGY
(AN AUTONOMOUS INSTITUTION, AFFILIATED TO ANNA UNIVERSITY, ACCREDITED BY NAAC WITH ‘A’ GRADE)
ACCREDITED BY NBA (CSE, IT,ECE,EEE,MECH,MCT &CIVIL)

CLASS LECTURE

SUBJECT : 18CH101 - ENGINEERING CHEMISTRY

(Common to all first year B.E./ B.Tech students)

MODULE : III – POLYMER CHEMISTRY, SPECTROSCOPIC

TECHNIQUES AND SYNTHESIS OF DRUG
MOLECULES

FACULTY : Dr. M.SANGEETHA

www.skcet.ac.in
 Module III - Polymer Chemistry

⮚ Introduction
⮚ Classification of Polymers
⮚ Polymerization Types
⮚ Tacticity of Polymers
⮚ Functionality of polymer types
⮚ Mechanism of Addition polymerization
⮚ Thermoplastics & Thermosetting plastics
⮚ Preparation, Properties and Uses of Polymers
⮚ Moulding Methods
 DEFINITIONS
• Polymer: a long chain molecule made up
of many small identical units.
• Monomer: the smallest repeating unit of
a polymer (propene in polypropylene).
.

Many + Parts
What is a polymer?

•A long molecule made up

from lots of small molecules
called monomers.
Representation of Polymerization
 Common examples
Monomer Polymer
CH3
H3C
Polyethylene n
Ethylene Repeat unit
CH3
CH3 n
Polypropylene CH3 CH3 CH3 CH3 CH3 CH3 CH3
Propylene

CH3
Ph n
Polystyrene Ph Ph Ph Ph Ph Ph Ph
Styrene

CH3
Cl n
Poly(vinyl chloride) Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
F2 F2 F2 F2 F2 F2
F2C CF2 C C C C C C CF3
F3C C C C C C C
F2 F2 F2 nF F2 F2
Tetrafluoroethylene Poly(tetrafluoroethylene): Teflon 2
 Nomenclature of polymer

• Homo polymer
• Hetero polymer (or) co polymer
• Homo chain polymer
• Hetero chain polymer
 Homo polymer
• A polymer containing same type of
monomers is known as homo polymers.
• Example : polyethylene
-CH2-CH2-CH2-CH2-CH2-CH2
 Co polymer (or) hetero polymer
• A polymer containing more than one type of
monomers is known as co polymers.
• Example : Nylon 6:6
 Homo chain polymer

• If the main chain is made is up of same

species of atoms in the polymers is called
homo chain polymer.
• Example poly vinyl chloride
 Hetero chain polymer

• If the main chain of a polymers is made up

of different atoms it is called hetero chain
polymer.
• Example: C-C-O-C-C-O-C-C-O-C-C-

main chain
 TACTICITY
• The orientation of monomeric units in a polymer
molecule can take place in an orderly or disorderly
manner with respect to the main chain.
• Isotactic polymer
• Atactic polymer
• Syndiotactic polymer
 FUNCTIONALITY

• The number of bonding sites or reactive sites

or functional groups present in a monomer is
known as its functionality
 FUNCTIONALITY
Example functionality
• CH2=CH2 • -2 (two bonding sites are
(Ethylene) due to the presence of one
double bond in the
monomer .therefore
ethylene is a bi-functional
NH2-(CH2)6-NH2 monomer)
• -2(this monomer contains
Hexamethylene diamine
two functional
groups ,hence it is a bi
functional monomer.)
 Example Functionality
• CH2-OH • -3(this monomer contains
three functional groups
CH-OH hence it is a tri functional
monomer.)
CH2-OH
glycerol
 POLYMERIZATION
• Polymerization is a chemical reaction in
which large number of smaller molecules
combine to give a macro molecules with
or without elimination of small molecules
like water, HCl
Polymerisation -Example
 Degree of Polymerization, DP
DP = average number of repeat units per chain
Mn
DP 
m
molecular weight of the polymeric network
Mn -

m- molecular weight of the repeating unit

The number of repeating units (n) or monomer present in the
polymer chain is called the degree of polymerization.
Degree of polymerization is the ratio between molecular weight of
the polymeric network and molecular weight of the repeating unit.
 DP- example
• 2 CH2=CH2 -(CH2-CH2)- (CH2-CH2)-

in this example 2 repeating units are present in the polymer

chain . So the degree of polymerization is 2.
Oligo polymer –low degree of polymerization
their M.Wt ranges from 500-5000
High polymer- high degree of polymerization
their M.Wt ranges from 10,000-2,00,000
 TYPES OF POLYMERIZATION

• Addition polymerization
• Condensation polymerization
• Co polymerization
 Addition polymerization
• It is the reaction that yields a polymer, which is
an exact multiple of the original monomeric
molecule.
Monomers contain C=C bonds
• Double bond opens to (link) bond to next
monomer molecule
• Chain forms when same basic unit is repeated
over and over.
 Addition Polymers
• Addition polymerization: a reaction in which
unsaturated monomers combine with each other to form
a polymer
• Example: 1 Tetra fluoroethene can be polymerized to
form polytetrafluoroethene, commonly known as Teflon
 Addition Polymers
• Polyvinyl chloride

• Polyvinyl chloride or
PVC is wide used for
pipes and other
structural materials
• Vinyl chloride is also
known as
chloroethene
Some Common Addition Polymers
 Condensation Polymers

• Condensation polymers form from condensation

reactions.
• In a condensation polymer a smaller molecule

such as water, CH3OH is eliminated

• In order to form a condensation polymer the

monomer must have two functional groups
Condensation (Step) Polymerization ( example)
 Example of a Condensation
Polymer 2
• Dacron is also a condensation polymer

Ethylene Glycol (1,2ethanediol) para Terephthalic acid

Dacron is an example of a polyester

• It is also a copolymer since it is made from two

different monomers
Some Condensation Polymers
 Copolymerisation

• It is the joint polymerisation in which two

(or) more different monomers combine to give a
polymer. High molecular weight polymers
obtained by co polymerisation are called co
polymers.
 Co polymerization example

• Butadiene and styrene co polymerize to give

GR-S rubber.
• nCH2=CH-CH=CH2 + n CH2=CH-C6H5
butadiene styrene

-(CH2-CH=CH-CH2-CH2-CH-C6H5)n
Styrene butadiene rubber - SBR
 Addition polymerization Condensation polymerization

The monomer must have at The monomer must have at

least one multiple bond. least two identical (or)
Example : different functional groups.
Ethylene CH2=CH2 Example
Acetylene CH≡CH glycol CH2-OH

CH2-OH
6-amino hexanoic acid
H2N-(CH2)6-COOH
Monomers add on to give a Monomers condense to give a
polymer and no other by polymer and by product such
product is formed. as H2O, CH3OH are formed.

Homo chain polymer is Hetero chain polymer is

obtained obtained
Addition polymerization Condensation polymerization

Molecular weight of the Molecular weight of the

polymer is an integral multiple polymer need not be an
of molecular weight of integral multiple of monomer.
monomer.
Thermoplastics are produced Thermosetting plastics are
produced

high molecular weight polymer Molecular weight of the

is formed at once. polymer rises steadily
throughout the reaction
 Mechanism of Addition Polymerization

The mechanism of addition polymerization can be

explained by any one of the following three types.
Free Radical mechanism
Ionic mechanism
Co ordination mechanism
 Free Radical Polymerization - Mechanism
Free radical Reaction Mechanism

Additional polymerization reaction proceeds via free

radical route with the help of reactive peroxide
catalyst and hence it is known as free radical
polymerization

It proceeds through following three steps

(i) Initiation
(ii) Propagation
(iii) Termination
 Free Radical Mechanism Step I
Step 1-Initiation
Initiation can be proceed through initiators.
Initiators are compounds used to generate free
radicals by homolytic disassociation.
Peroxides are used as the initiators. Hydrogen
Peroxide and Benzoyl peroxides are most widely to
initiation the reaction
 Free Radical Mechanism Step II
Step-2 Propagation (Chain growth step)
Free radical generated during initiation attacks
the double bond of new monomer molecule and
propagates the polymeric chain reaction.
 Free Radical Mechanism – Step III
Step 3: Termination
Termination is the final step of the polymeric chain reaction
and it can be carried out by coupling or Dis-
proportionation.
Terminators are chemical compounds inhibit the chain
growth by combining with free radicals and forms
either stable products or inactive free radical species.
(e.g.) Hydroquinone, Nitrobenzene
 – Initiation

– Propagation

– Termination

340
 PREPARATION OF NYLON-6
Nylon-6 is produced by the ring opening / Self
condensation polymerization of caprolactum.
 Properties of Nylon-6
⮚ Nylons are highly translucent
⮚ White horny and high melting polymers.
⮚ High temperature stability
⮚ Good abrasion resistance.
⮚ High chemical resistance
⮚ Corrosion resistance
⮚ High tensile strength
⮚ Moisture resistant
 Uses of Nylon-6
⮚ Gears, Fittings and bearings in automotive industries
⮚ Bristles in toothbrushes and cleaning brushes
⮚ Surgical sutures
⮚ Strings for musical instruments
⮚ Threads, Ropes & Filaments
⮚ Nets and Tyre cords
⮚ Hoisery & Knitted Garments
⮚ Moulded products Gun frames and skated board wheels
⮚ Fabric yarn and cordage
Application - Nylon-6 Products
 Synthesis of Poly vinyl Chloride (PVC)

PVC is produced by addition polymerization from the vinyl

chloride monomer.
 Properties of PVC Polymeric material
⮚ It is a colourless, odourless and chemically inert powder

⮚ High chemical resistant

⮚ It undergoes degradation in presence of sunlight
⮚ PVC is amorphous with partially crystalline
⮚ PVC (rigid) decomposes at 212 F
⮚ Chemically stable, Neutral and Non-toxic
⮚ Excellent electrical insulation
⮚ Good Impact strength
⮚ Better weather proof properties
⮚ Good Moisture resistant
⮚ Ease of fabrication into various shapes
 USES OF PVC & PVC PRODUCTS
⮚ Bio-Medical Applications
⮚ Transportation
⮚ Building and Construction
⮚ Toys, Structural Yard and Garden Structures
⮚ Consumer Goods in Everyday Life
⮚ Packaging
⮚ Art and Design
⮚ Pipes
PVC PRODUCTS
 Preparation properties and uses of Bakelite
It is prepared by the condensation polymerisation
reaction between formaldehyde and phenol. It is a
thermosetting polymer having strong covalent links.
 PROPERTIES OF BAKELITE

⮚ Good electrical insulation – Act as insulators

⮚ Better Thermal resistance
⮚ Three dimensional network structure
⮚ High molecular weight polymer
⮚ High Moisture resistance
⮚ High chemical resistance
⮚ Due to presence –OH group-easily attacked by alkalis
⮚ Rigid, hard and scratch resistant
⮚ Excellent adhesive properties
⮚ It is thermosetting network polymer
⮚ It cannot be recycled
⮚ Excellent Corrosion resistance
 Applications of Bakelite

⮚ Telephone cases, cabinets parts and Heater Handle

⮚ Phonograph record (Audio recording in olden days)
⮚ Electrical switches and Switch gears
⮚ Bearings used in propeller shafts in paper industry
⮚ Uses as resin in wooden laminates & Plywood
⮚ Bakelite resin used in varnishes
⮚ Sulphonated bakelite used an ion exchange resins
⮚ For impregnating, fabrics, wood and paper
⮚ Bank lockers
Bakelite Condensed Polymer products
 Preparation properties & uses of PET
It is prepared by the transesterification reaction between
ethylene glycol and terephthalic acid.
 Properties of PET
⮚ High clarity & transparent
⮚ Good chemical resistance
⮚ Excellent moisture and gas resistance
⮚ High impact resistance
⮚ Medium rigidity
⮚ Moderate scratch resistance
⮚ Food grade safety
⮚ Temperature resistance upto 100 degree F
⮚ Ease of fabrication
⮚ Woven as fabric in garments industry
⮚ Recyclable polymer
 USES OF PET PLASTICS
• Cosmetic packaging items
• PET water bottles
• Pharmaceutical pet bottles
• Water containers
• Juices and carbonated drink containers
• Food graded plastics
• Tupperware
• Health care items
• Frozen food containers
PET Polymer Products
 Plastics
Advantages Disadvantages
• Light weight • Very high softness
• Low melting point • Embrittlement at low temperature
• Good strength • Deformation under load
• Easily moulded • Easily combustible
• corrosion resistant & • non- bio degradable
chemically inert
• Good water resistance
 Classification of plastics
Based on structure Based on usage

• Thermoplastics • General purpose plastics

eg polyethylene eg poly ethylene, poly propylene
• Thermosetting plastics • Engineering plastics
eg bakelite, polyester eg pvc, teflon
 There are two main types of plastics( based on structure

thermoplastic plastics
thermosetting plastics. The word ‘plastic’
means ‘easily shaped
or moulded’.
Thermoplastic plastics:
Formed by heat

Soften when heated

Made of long polymer
chains with few cross
links

Can be reheated and

reshaped
Mostly recyclable
 Plastics
Thermosetting plastics
Initially set by heat

Consist of polymer Cannot be reshaped

chains with strong once set
bonds between each
chain

Strong and durable Common in powder or

resin forms

What items do you have in your possession that are made of plastic?
Are they made from thermoplastic or thermosetting plastics?
Thermoplastic plastics are made of long chains of polymers which
don’t cross over very often. When heated, the molecules slip easily
over one another.
Thermosetting plastics also have lots of long chain molecules, but
there are links between them. These cross links prevent the
molecules from moving over one another.

individual monomer molecule individual monomer molecule

 Thermoplastic plastics
The majority of common plastics are thermoplastics.

Thermoplastics can be heated and reshaped because of the ways

in which the molecules are joined together.

This can be repeated many times (as long as no damage is caused

by overheating). Heat

Harden
Soften

Cool
 Thermosetting plastics
Thermosetting plastics are those which are set with heat and have
little elasticity. Once set, they cannot be reheated and reformed.
Burn

They are heated and moulded

during manufacture. Heat

Once cooled, they will not soften

again when heated. This breaks
the potentially unending cycle Harden Soften

that thermoplastic plastics are

capable of.
Cool
If heated too much, they burn.
 Uses of plastics (thermoplastics)
Here are some common products made from thermoplastics.

Polystyrene
High density
polythene Low density polythene

Polypropylene

Acrylic

What other uses do these thermoplastics have?

 Plastics classification (based on usage)

General purpose plastics Engineering plastics

• They have low to medium • They have high mechanical

mechanical properties strength, abrasion
• Used to prepare resistance.
commodity items • High load bearing capacity
• They account for 80-85% • High dielectric constants
of polymer production . • Readily moldable properties
• Ex : polypropylene, • Cant broken easily
polyvinyl chloride • Ex : PVC .Nylon 6,6 ,Teflon
 Engineering plastics applications

• They can be used alone or in conjunction with metals,

ceramics or glasses etc.
• They find applications in and demanding areas like
automobiles, defence, electrical and electronics
telecommunications, textiles, satellite, robots,
computer components.
• Important engineering plastics are PVC, Teflon,
Nylon6:6
 Molding
• Molding is the process of manufacturing by shaping liquid
or pliable raw material using a rigid frame called a mold or
matrix.
• A mold is a hollowed-out block that is filled with a liquid or
pliable material such plastic, glass, metal, ceramic raw
material. The liquid hardens or sets inside the mold,
adopting its shape. The very common bi-valve molding
process uses two molds, one for each half of the object.
Types
 Injection Molding
 Blow Molding
 Extrusion Molding
 Compression Molding
 INJECTION MOLDING
Injection molding is a manufacturing process for
producing parts from both thermoplastics and
thermosetting plastics or other materials
 MAIN COMPONENTS
Hopper
Thermoplastic material is supplied in form of small
palates. The gravity fed into the barrel and the screw
assembly
Barrel
This is a chamber in which the reciprocating screw is
located. The barrel is heated by electric heater.
Nozzle
The nozzle forms a sealed connection between the barrel
and the spruce bushing of the mold. Temperature of the
nozzle is set neat the plastic melt temperature.
Reciprocating Screw
It Compress and melt the plastic material and also moves
the material towards the die.
There are three main zones
1. Feeding Zone
2. Transition (Compressing)Zone
3. Metering Zone
Steps involved
 Material Preparation
 Feeding into the Hopper
 Injection
 Mould Holding and Cooling
 Ejection
Process
 Materials granules are fed into hopper then melted
down in barrel which is surrounded by heaters.
 The moulded material is injected into mould cavity and
mold is held under pressure until the material cools and
hardens.
 Once the material hardens, the mold is opened and the
component is ejected by runner plate.
 And the process can be repeated.
Most Commonly used Materials
PVC, ABS (Acrylonitrile Butadiene Styrene),
Polypropylene, Poly Styrene, HDPE, LDPE, Epoxy,
Rubber Thermoplastic.
Injection molding is used for
 Plastic Injection molding
 Rubber Injection molding
 Metal Injection molding
Metal Injection Rubber Injection
molding molding

Plastic Injection
molding
 INJECTION MOLDING
APPLICATIONS IN CAR PARTS
AND BOTTLE CAPS
 TYPICAL PRODUCTS MADE WITH
PLASTIC INJECTION MOLDING
Plastic bottles are the most common product manufactured by
the billions each year, ranging in multiple shapes and sizes.
Electronic housings are also quite commonly fabricated with
injection molding services. Used in devices such as remote
controls, computers, televisions, medical equipment, and other
consumer electronic components, housings are all produced by
injection molding process.
Toys: The Lego brand of building block recognized by all is
made of firmer plastic granules which are heated until liquefied
and then injected into metal molds in which the plastic cools and
solidifies into a studded brick or other shape
Machinery and Automotive Components: Bumpers,
dashboards, radio controls, cup holders, and many other
elements found in cars and transportation vehicles, both interior
and exterior, are made by the injection molding process.
 BLOW MOLDING

• Blow molding (also blow forming) is a manufacturing process by which

hollow plastic parts are formed.
• In general, there are three main types of blow molding:
– Extrusion blow molding
– Injection blow molding
– Stretch blow molding

Swimming pool ladder

 BLOW MOLDING PROCESS

1. A hollow length of plastic, 2. The mould closes.

called a parison, is extruded
down between the two halves of
the mould.
 BLOW MOLDING PROCESS

3. Compressed air is blown into 4. The mould is then opened the

the inside of the parison which molding ejected and the waste
inflates it, pushing the soft plastic (called flash) is trimmed off
hard against the cold surfaces of with a knife.
the mould.
 STEPS IN PROCESS OF INJECTION
BLOW MOLDING
Injection Blowing Ejection
• The injection blow molding • The preform consists of a • After a cooling period the
• .
machine is based on an fully formed bottle/jar neck blow mold opens and the
extruder barrel and screw with a thick tube of core rod is rotated to
assembly which melts the polymer attached, which will the ejection position.
polymer. form the body. • The finished article is
• The molten polymer is fed • The preform mold opens and stripped off the core rod and
into a manifold where it is the core rod is rotated and leak-tested prior to packing.
injected through nozzles into clamped into the hollow, • The preform and blow mold
a hollow, heated preform chilled blow mold.
can have many cavities,
mold. • The core rod opens and typically three to
• The preform mold forms allows compressed air into sixteen depending on the
the external the preform, which article size and the required
shape and is inflates it to the finished article output.
clamped shape.
• There are three sets of core
around a rods, which allow concurrent
mandrel (the core rod) preform injection, blow
which forms the internal molding and ejection.
shape of the preform

Vaccum cleaner Insecticide sprayers Dust bins

 MATERIALS USED IN BLOW MOLDING

• High density polyethylene (HDPE) and low density

polyethylene (LDPE) are both commonly used for blow
molding as are other types of thermoplastics.
• The thermoplastic used in blow molding needs to be more
viscous (flow less easily) than that used for injection
molding as the parison must retain its form before the
mould closes around it.
• Used extensively to make bottles and other lightweight ,
hollow parts .

Cane Toy
Fuel tank
 APPLICATIONS OF BLOW MOLDING

• The main applications are bottles, jars and

other containers.
• The stretching of some polymers, such as PET (polyethylene teraphthalate)
results in strain hardening of the resin, allowing the bottles to resist
deforming under the pressures formed by carbonated beverages, which
typically approach 60 psi.
• Advantages of blow molding include: low tool and die cost; fast production
rates; ability to mold complex part; produces recyclable parts
• Disadvantages of blowhttps://www.youtube.com/watch?v=YWzaZYHXS9s
molding include: limited to hollow parts,
wall thickness is hard to control.
Hockey stick

Snow board

Spa pillow
 EXAMPLES OF BLOW MOLDING

Boat fenders Seats of tricycles kayaks

Copier tonner
Totes Mannequin parts Hosiery forms
bottle
 EXTRUSION MOLDING PROCESS
FOR PLASTIC MACHINING
• It is process to make parts of continuous length and uniform cross-
section.
• A characteristic that often differentiates extruded from injection-molded
plastics is the viscosity of the plastic at normal processing temperatures.
• Extruded plastics often have a higher melt viscosity, which allows the
extrudate to retain the shape imparted to it by the die while the extrudate
is in the quenching stages.

Hoses
 EXTRUSION MOLDING PROCESS FOR
PLASTIC MACHINING
 The extrusion molding is a common method for making of Pipe, Rods, Hoses,
Driking Staws and more.
 The die is main part of extrusion molding process, because of the product cross
section depends on the Die Cross section. The Screw part is inside a barrel.
 First the extrusion of plastic is form of powder, it fed into screw from hopper. It
conveyed through barrel and heated by Heater Conduction process.
 In this extrusion process the shear force made by screw movement. Finally, the
end of extruder the extrusion of plastics passed through die to make the require
shape object.

Schematic diagram for extrusion of plastics

• They have mainly three zone:
• (i) Feed Zone for extrusion molding process:
• In this process the plastic is pre heated and convey to subsequent zone.
The Raw material is pass to feed zone from hopper. The heater is heated by the
materiel. The screw will be designed in constant depth and supply some
sufficient amount of material to the metering zone.
• (ii) Compression Zone For extrusion of plastics:
• In this Zone, The cross Section of screw depth will be gradually
decrease, so compact the plastic. The Compaction process any trapped air back
into feed zone and thickness of material reduced by heat transfer from heater.
• (iii) Metering zone for extrusion process
The metering zone, again the screw depth will be decrease and it much
lower than the feed zone. The melton metal pass to the die with constant rate,
uniform pressure and temperature .
• Advantages :
• Extrusion molding is to make long shape of object the machining cost will be
low Efficient of melting Process Mass production volume Good mixing of
Metal (compounding)
Disadvantages :
• Limited complexity of parts
Strings

EXTRUSION MOLDING
Pipes/Tubes
• The die for producing a tube or pipe consists of a circular
orifice with a carefully centered mandrel or torpedo,
which is held, in the die orifice by, supports at the back
end.
• Generally the mandrel is constructed so that compressed
air can be blown through it into the hot extorted tube
with the object of preventing the tube from collapsing.
• At the front of the barrel, the molten plastic leaves the
screw and travels through a screen pack to remove any
contaminants in the melt.

• The screens are reinforced by a breaker plate (a thick metal puck with many holes
drilled through it) since the pressure at this point can exceed 5000 psi (34 MPa).
• The screen pack/breaker plate assembly also serves to create back pressure
in the barrel.
• Back pressure is required for uniform melting and proper mixing of the polymer,
and how much pressure is generated can be 'tweaked' by varying screen pack
composition (the number of screens, their wire weave size, and other parameters).
 EXTRUSION
MOLDING
Wires
• The coating of wire with thermoplastic material is carried out by
using a special die, which extrudes the plastic material at right
angles to the screw direction.
• Wire is continually fed through the die from which it energies
evenly
coated with the plastic material.

Film tape
 COMPRESSION

MOLDING
Compression molding is a method of molding in which the molding material, generally
preheated, is first placed in an open, heated mold cavity.
 The mould is closed with a top force or plug member, pressure is applied to force the
material into contact with all mould areas, while heat and pressure are maintained until the
molding material has cured.
 The process employs thermosetting resins in a partially cured stage, either in the form of
granules, putty-like masses, or preforms.
 Compression molding is a high-volume, high-pressure method suitable for molding
complex, high-strength fiberglass reinforcements.
 Advanced composite thermoplastics can also be compression molded with unidirectional
tapes, woven fabrics, randomly oriented fiber mat or chopped strand.
 The advantage of compression molding is its ability to mold large, fairly intricate parts.
Also, it is one of the lowest cost molding methods compared with other methods such
as transfer molding and injection molding; moreover it wastes relatively little material,
giving it an advantage when working with expensive compounds.
 COMPRESSION
MOLDING

1. The mould is charged with a 2. When the two halves of the mould
measured amount of powder or are brought together the plastic
granules ready to be compressed. material is forced under compression
Sometimes plastic charge is first to flow rapidly around the cavity. heat
compacted into a shape called a from the platens causes the plastic to
preform. cure resulting in a permanent change
in shape.
 COMPRESSION MOLDING

The component is
ejected from the
mould and any
excess material
formed at edges
(flash) is removed.

Materials used.
Typical thermosetting plastics used in
compression molding are urea formaldehyde and
phenol formaldehyde.
 COMPRESSION MOLDING
Compression molding uses heated steel tooling in high-
pressure presses to produce more complex, high volume parts with
fast cycle times.
This process produces high strength, complex parts in a
wide variety of sizes. Matched metal dies are mounted in a
hydraulic molding press. The material charge is manually or
robotically placed in the mold, heated mold halves are closed, and
up to 2,000psi of pressure is applied. Cycle time ranges from 1-5
minutes depending on part size and thickness. Features such as
ribs, bosses, and inserts can be molded in.
Compression molding is a high volume molding method that yields fast cycle times, high part
uniformity, and allows for metal inserts, ribs, and bosses to be molded in the part. In the compression
molding process, the heated matched metal mold set is mounted in a large hydraulic press. A pre-weighed
charge of molding compound is loaded into the mold and the press is closed. Under the pressure and
temperature of the toolset, the material cures rapidly. Subsequent machining and finishing operations are
minimal in compression molding so labor costs are reduced.
 E S
Q U
N I
C H
T E
A L
I C
Y T
A L
A N
 Spectroscopy
one of the most powerful tools available for the study of

the atomic and molecular structure and is used in the

analysis of a most of the samples.

Spectroscopy is used to study the interactions of

electromagnetic radiation with matter.

 The interaction of electromagnetic radiation of an atom
or a molecule results in transition of electrons from one
energy level to another level.
If this interaction happens in atomic levels it is atomic
Spectroscopy. If this happens in molecular level it is
molecular spectroscopy.
The measure of absorption of electromagnetic
radiation for the transition of electrons - Absorption
Spectroscopy.
The measure of emission - Emission Spectroscopy.
The electromagnetic spectrum consist of a range of
spectrum of electromagnetic radiation with different
energies - measured by frequency or wavelength or wave
number.
TYPES OF SPECTROSCOPY
Atomic spectroscopy –
interaction of the electromagnetic radiation with
atoms - atoms absorb radiation and gets excited
from the ground state electronic energy level to
another.
Molecular spectroscopy
It deals with the interaction of electromagnetic radiation
with molecules. This results in transition between
rotational, vibrational and electronic energy levels.
 Difference between Atomic Spectroscopy
and Molecular Spectroscopy

Atomic Spectroscopy Molecular Spectroscopy

It occurs due to the interaction It occurs due to the interaction of

of atoms with electromagnetic molecules with electromagnetic
radiation radiation

Molecular spectra is a
Atomic spectra is a line spectra
complicated spectra

It is due to vibrational, rotational

It is due to electronic transition
and electronic transition in a
of an atom
molecule
 SPECTRU
M
E2 (E.S)

hv hv

E1 (G.S)

Absorption Spectrum Emission Spectrum

 PHOTOPHYSICAL LAW
Lambert’s Law
when a beam of monochromatic radiation is
passed through a homogeneous absorbing
medium the rate of decrease of intensity of the
radiation dI with a thickness of absorbing medium
‘dx’ is proportional to the intensity of the incident
radiation ‘I’.
Incident light Transmitted light

Sample
 Lambert’s Law
it is mathematically expressed as
dI = kI
(1)
dx
where dI = infinitesimally small decrease in the
intensity of the radiation
dx = thickness of the absorping medium
k absorption coeffient
on integrating the equation (1) between the limit I =I0 at
x=0 and I=I at x=x x
I dI
= kI
dx o
Io
ln I = - kx (2)
I0
This equation(2) is know as Lamberts law
Beer’s law (or) Beer-Lambert’s Law
• when a beam of monochromatic radiation is passed
through a homogeneous absorbing medium the rate
of decrease of intensity of the radiation dI with a
thickness of absorbing medium ‘dx’ is proportional
to the intensity of the incident radiation ‘I’ as well
as concentration of the solution
Beer’s law (or) Beer-Lambert’s Law
it is mathematically expressed as
dI = kIC
(3)
dx
Where k absorption coef f ient
on integrating the equation (3) between the limit I =I0 at
x=0 and I=I at x=x
I x
dI
= kIC
Io dx o
 -ln I = kCx or 2.303 log I = -kCx
I0 I0
I0
log = k Cx or A = Cx (4)
I 2.303

where k = molar absorpivity or molar extinction coeffcient

=
2.303
log I0 =A =Absorption or optical density
I
This equation(4) is know as Beers-Lamberts law
Application of Beer-Lambert’s law
Determination of unknown concentration
As = Cs x
As (5)
= x
Cs
The f irst absorbance 'Au' of a unkown solution of unknown concentration
'Cu' is measured,
Au (6)
= x
Cu

From equation (5) and (6)

As Au
= Cu
Cs
Au (7)
Cu = As x Cs

Since the values As and Au can be experimentally determined and Cs is known

The value of Cu can be calculated f rom the equation (7)
Limitations of Beer-Lambert’s law
Beer-Lambert’s law is not obeyed if the radiation
used is not monochromatic.
It is applicable only for dilute solutions.
The temperature of the system should not be
allowed to vary to a large extent.
It is not applied to suspensions.
The deviation may occur, if the solution contains
impurities.
Deviation also occurs if the solution undergoes
polymerization (or) dissociation.
 ULTRAVIOLET (UV) AND VISIBLE
SPECTROSCOPY
Principle
Ultraviolet (UV) and visible spectra arise from the
transition of valence electrons within a molecule or ion
from a lower electronic energy level (ground state E 0)
to higher electronic energy level (excited state E 1).
 This transition occurs due to the absorption of UV
(wavelength 100-400 nm) or visible (wavelength 400-
750 nm) region of the electronic spectrum by a
molecule (or) ion.
 The actual amount of energy required depends on the
difference in energy between the ground state and the
excited state of the electrons.
E1 – E0= hν
Types of electrons involved in organic molecule
S.No Electron Examples Energy to require Present In

1 σ Saturated long Absorption appears Single

electrons chain below 200 nm bonded
Hydrocarbons (large energy) compounds
Eg Methane
125 nm

2 π Unsaturated Absorption appears Double bond

electrons hydrocarbons UV to visible and triple
Alkenes, Alkynes bonded
and aromatic compounds
compounds

3 n Organic UV radiation Unshared or

electrons compounds non bonded
containing N, O electrons
and Halogens
Three types of electrons present in the HCHO
(Formaldehyde)

H n
C O
H
The energy values for different transitions are in the
following order.
n → π∗ < π → π∗ < n → σ∗ << σ → σ∗ * (Antibonding)

* (Antibonding)

n * n *
Energy

* *

n (non -bonding)

(Bonding)

(Bonding)
σ → σ∗ electrons
the electrons are involved is single bond there is no
lone pair of electrons
The energy required for the transition is very large.
The absorption band appears in the far UV region.
Example
Saturated Hydrocarbons
CH4, CH3-CH3, CH3-CH2-CH3 (alkanes)
CH4 for σ → σ∗ λmax = 121 nm
CH3-CH3 for σ → σ∗ λmax = 135 nm
π → π∗ transitions
This transitions occurs due to the transitions of an electron
from bonding π orbital to anti bonding orbital π*.
This transitions occur in any molecule having π electron
system.
Example
Ethylene CH2=CH2
It shows intense band at 174 nm (allowed transitions) and
weak band at 200 nm.
Both are due to π → π∗
n → π∗ transitions
n → π∗ transitions are shown by unsaturated
molecules containing hetero atoms like N, O & S. It
occurs due to the transition of non-bonding lone pair of
electrons to the anti bonding orbitals. This transition
shows a weak band, and occurs in longer wavelength
with low intensity.
Example O O
H3C C CH3 H3C C H

Ketones Aldehydes
Having no C=C C≡C
(n → π∗ transitions occurs in the range of 270-300 nm)
 H3C HC HC C CH3
O

Having double bond

(n → π∗ transitions occurs in the range of 300-350nm)
(π → π∗ transitions occurs in the range of 250 - 300nm)
n →σ* Transitions
Saturated compounds containing atoms with lone
pairs (non-bonding electrons) are capable
of n→σ* transitions.
These transitions usually need less energy than
σ →σ* transitions. They can be initiated by light whose
wavelength is in the range 150 - 250 nm. The number of
organic functional groups with n →σ* peaks in the UV
region is small.
CH3- OH

Low intensity band at 183 nm is due to n → σ∗

H3C Cl

High intensity band at 173 nm is due to n → σ∗

Important term used in UV Spectroscopy
Chromophores (colour producing groups)
The presence of one or more unsaturated linkages (π
electrons) in a compound is responsible for the colour of
the compound. This linkages are referred to as
Chromophores.
Examples

C C C C C N N N C O
Alkene Alkyne Nitrile Diazene Ketone

Chromophore undergoes π→π∗ transitions in shorter

wavelength regions of UV radiations.
Auxochrome (colour intensifying group)
It refers to an atom or a group which does not gives rise to
absorption band on its own. But when conjugate to
chromophore will cause red shift.
Example -OH, -NH2, -Cl, -Br, -I etc
Chromophore Auxochrome
NH2

Benzene Amino benzene (aniline)

λmax = 225nm λmax
= 280 nm
Colourless compound
λ = 250 - 270 nm

λ = 400 – 500 nm
Difference between Chromophore and Auxochrome
S.No Chromophore Auxochrome

1 This group is responsible It does not impart colour , but

for the colour of the
compound when conjugate with
chromophore produce colour

2 It does not form salt But it forms salt

3 It contains at least one It contains lone pair of

multiple bond electrons
Example –NO2, -NO, - Example
N=N -OH, -NH2, -NR2
Some important definition related its change in
wavelength and intensity

1 Bathochromic Shift Shift to higher wavelength

(red shift) (lower frequencies)
2 Hypsochromic Shift Shift to lower wavelength
(blue shift) (Higher frequencies)
3 Hyperchromic effect An increase in intensity
4 Hypochromic effect A decrease in intensity
Intensity
INSTRUMENTATION
I. Components
1. Radiations source
Invisible – UV spectrometers, the most commonly used
radiation sources are hydrogen (or) deuterium
lamps.
2. Monochromators
The monochromator is used to disperse the radiation
according to the wavelength. The essential elements
of a monochromator are an entrance slit, a dispersing
element and an exit slit. The dispersing element may
be a prism or grating (or) a filter.
3. Cells (sample cell and reference cell)
The cells, containing samples or reference for analysis,
should fulfill the following conditions.
 They must be uniform in construction.
The material of construction should be inert to solvents.
They must transmit the light of the wavelength used.
4. Detectors
Three common types of detectors.
They are Barrier layer cell, Photomultiplier tube, Photocell.
The detector converts the radiation, falling on which, into
the current. The current is directly proportional to the
concentration of the solution.
5. Recording system
The signal from the detector is finally received by
the recording system. The recording is done by
recorder pen.

https://www.youtube.com/watch?
II Working of Visible and UV spectrophotometer

Source Monochromator Sample

Recorder

Reference
Beam
Spliter

Block diagram of visible UV spectrophotometer

Applications
1. Predicting relationship between different groups
 Between two or more C–C multiple bonds(= (or) ≡
bonds).
 Between C – C & C – O double bonds.
 Between C – C double bonds and the aromatic
benzene ring.
the structure of several vitamins and steric hindrance of the
molecule – determined
2. Qualitative analysis
identification of aromatic compounds and conjugated
olefins –comparing sample with the same of known
compounds available in reference books.
3. Detection of impurities
UV absorption spectroscopy is the best method for
detecting impurities in organic compounds, because
The bands due to impurities are very intense.
Saturated compounds have little absorption band and
unsaturated compounds have strong absorption band.
4. Quantitative analysis
UV absorption spectroscopy is used for the quantitative
determination of compounds, which absorbs UV light.
This determination is based on Beer’s law.
5. Determination of molecular weight
The molecular weight of a compound can be determined if
it can be converted into a suitable derivative, which gives
an absorption band.
6. Dissociation constants of Acid and Base
The dissociation constant (Pka) of an acid (HA) can be
determined by determining the ratio of [HA]/[A]
spectrophotometerically from the graph plotted between
absorbance Vs wavelength at different pH values. The
values substituted in the equation.
HA
Pka =pH + log
A
7. Study of tautomeric equilibrium
The percentage of various keto enol forms present in a
tautomeric equilibrium can be determined by measuring the
strength of the respective absorption band using UV
spectroscopy.
Example
Ethyl Acetoacetate
H3C C CH2COOC2H5 H3C C CHCOOC2H5
O OH
Keto Form Enol form
λmax = 275nm λmax = 244 nm
8. Determination of calcium in blood serum
Calcium in the blood can be determined by converting the
‘Ca’ present in 1 ml of the serum as its oxalate and
redissolving it in H2SO4 and treating it with dilute ceric
sulphate solution. The absorption of the solution is
measured at 315 nm. Thus, the amount of ‘Ca’ in the blood
serum can be calculated.
UV 315 nm
 INFRARED SPECTROSCOPY
Principle
IR spectra are produced by the absorption of energy by a
molecule in the infrared region and the transitions occur
between vibrational levels. So, IR spectroscopy is also
known as vibrational spectroscopy.
Range of Infrared Radiation
The range of the electromagnetic spectrum extending
from 12500 to 50 cm− 1 (0.8 to 200 μ) is commonly
referred to as the infrared. This region is further divided
into three sub-regions.
 λ = 0.8 2.5 15 20 μ

Near IR IR Far IR

γ = 12500 4000 667 50 cm-1

•Near infrared : The region is from 12500 to 4000cm -1

•Infrared (or) ordinary IR : The region is from 4000 to 667
cm-1
• Far infrared : The region is from 667 to 50 cm-1
Molecular Vibrations and Origin of IR Spectrum

1. Stretching vibrations: During stretching the distance

between two atoms decreases or increases, but bond
angle remains unaltered.
2. Bending (or) deformation vibrations: During bending
bond angle increases and decreases but bond distance
remains unaltered.
Vibrational changes depend on the masses of the atoms
and their spatial arrangement in the molecule.
Finger Print Region
The vibrational spectral (IR spectra) region at 1400 − 700
cm− 1 gives very rich and intense absorption bands. This
region is termed as fingerprint region. The region 4000 −
1430 cm− 1 is known as a Group frequency region.
Uses of fingerprint region
1. IR spectra are often characterized as molecular
fingerprints, which detect the presence of functional
groups.
2. Fingerprint region is also used to identify and
characterize the molecular just as a fingerprint can be used
to identify a person.
Types of stretching and bending vibrations
The number of fundamental (or) normal vibrational
modes of a molecule can be calculated as follows.
1. For Non-linear molecule
A non-linear molecule containing ‘n’ atoms has (3n − 6)
fundamental vibrational modes.
H2O = (3 x 3- 6) = 3 fundamental vibrational
modes
CH4 = (3 x 5 -6) = 9 fundamental vibrational
modes
C6H6 = (3 x12- 6) = 30 fundamental vibrational
modes.
2. For linear molecules
A linear molecules containing ‘n’ atoms has (3n-5)
 Symmetric Asymmetric elongation Bending
elongation 3756 cm-1 1596 cm-1
3652 cm-1

Thus, for a vibration to be active in IR, the dipolemoment

of the molecule must Change
IR spectrum of Water
Carbon dioxide
Carbon dioxide is a linear triatomic molecule and has 3n −
5 = (3 × 3 − 5) = 4 fundamental vibrational modes.
Out of the four normal modes of vibration of CO 2, only the
asymmetric stretching and bending vibrations ie., (ii),
(iii) and (iv) involve a change in dipole moment (all are
IR - active) and (i) no change in dipole moment (IR
inactive)
Thus, though there are three active vibrations, two of
them ((iii) and (iv)) have the same frequency, so the IR
spectrum of CO2 exhibits only two bands ie., one at 526
cm− 1 and another at 2565 cm− 1.
O C O

Symmetric Strecthing
1480 cm-1
(i)

Antisymmetric Strecthing
2565 cm-1
(ii)

Inplane bending
526 cm-1

(iii)
Out of plane bending
526 cm-1

(iv)
INSTRUMENTATION
1. Radiation Source
The main source of IR radiation.
Nichrome wire Nernst glower, which is a filament
containing oxides of Zr, Th, Ce, held together with a
binder.
When they are heated electrically at 1200 to 2000°C,
they glow and produce IR radiation.
2.Monochromator
It allows the light of the required wavelength to pass
through but absorbs the light of another wavelength.
3. Sample Cell
The cell, holding the test sample, must be transparent to
IR radiation.
4. Detector
IR detectors generally convert thermal radiant energy
into electrical energy. There are so many detectors, of
which the followings are important.
Photoconductivity cell.
Thermocouple
Pyroelectric detectors.
5. Recorder
The recorder records the signal coming out from the
detector.
II. Working of IR Spectrophotometer

Source Monochromator Sample Recorder

Detector

Reference
Beam
Spliter

Block diagram of double beam IR spectrophotometer

https://www.youtube.com/watch?v=DDTIJgIh86E
Applications of IR spectroscopy
Identity of the compound can be established
The IR spectrum of the compound is compared with that of
known compounds. From the resemblance of the two
spectra, the nature of the compound can be established.
This is because a particular group of atoms gives a
characteristic absorption band in the IR spectrum.
Example :

C6H5 C H C6H5 C CH3

O O
Benzaldehyde Acetophenone
Sharp Absorption peak at 1700cm-1
(presence of Carbonyl group)
Detection of Functional groups
(i) In a given environment a certain functional group will
absorb IR energy of nearly same wavelength in all the
molecule.
H3C C CH3 C2H5 C C2H5
O O
Acetone Diethyl ketone

Absorption peak at 1750 and 3000 cm -1

IR Spectrum of Acetone
IR Spectrum of Diethyl ketone
(ii) But acetic acid and cyclo butanone gives absorption
peaks at different wavelength

IR spectrum of Acetic Acid

IR spectrum of Cyclobutanone
3. Testing Purity of the sample
Pure sample will give sharp and well resolved peak. But
impure will give broad and poorly resolved absorption
bands. Thus by comparing IR spectra of pure compound,
presence of impurity can be detected.
4. Study of progress of a chemical reaction
The progress of a chemical reaction can be easily
followed by examining the IR spectrum of test solution at
different time intervals.
IR Spectrum of Secondary Alcohol
IR spectrum of ketone
5. Determination of shape (or) Symmetry of a molecule
Whether the molecule is linear (or) non-linear (bend
molecule) can be found out by IR spectra.
Example
IR spectra of NO2 gives three peaks at 750, 1323, and
1616 cm− 1. According to the following calculations,
For non-linear molecule = (3n − 6) = 3 peaks.
For linear molecule = (3n − 5) = 4 peaks.
Since the spectra show only 3 peaks, it is confirmed that
NO2 molecule is a non-linear (bend) molecule
6. To study tautomerism
Tautomeric equilibrium can be studied with the help of IR
spectroscopy.
Example
The common systems such as keto-enol, lacto-lactum,
mercapto- thioamide contain groups like C=O, -OH, -NH
or C=S. These groups show a characteristics absorption
band in the IR spectrum, which enable us to find at which
form predominates in the equilibrium.

HN CH2 HN CH HN CH2
C C C
O OH OH
Industrial applications
Determination of structure of chemical products
During the polymerization the bulk structure can be
determined using IR spectra.
(b) Determination of molecular weight
Molecular weight, of a compound, can be determined by
measuring end group concentrations, using IR
spectroscopy.
(c) Crystallinity
The physical structure like crystallinity can be studied
through changes in IR spectra.
FLAME PHOTOMETRY (OR) FLAME EMISSION
SPECTROSCOPY
Flame photometry is a method in which, the intensity of
the emitted light is measured when a atomized metal is
introduced into a flame. The wavelength of the colour
tells us what the element is, and the intensity of the colour
tells us how much of the element is present.
Theory (or) Principle
When a metallic salt solution is introduced into a flame,
the following processes will occur.
The solvent is evaporated, leaving behind the solid salt
particle.
 The salt is vaporized into the gaseous state and
dissociated into atoms.
Some of the atoms from the ground state are excited to a
higher energy state by absorbing thermal energy from the
flame.

M X Evaporation MX Vapourisation MX Dissociation

M X
Solution Solid Gas Gas Gas

Thermal Excitation
hv
M* M
Gas emission
(excired State)
INSTRUMENTATION
I. Components
1. Burner
The flame must possess the following characteristics.
 It should evaporate the solvent from the sample
solution.
 It should dissociate the solid into atoms.
 It should excite the atoms and cause them to emit
radiant energy.
2. Mirror
The radiation from the flame is emitted in all directions
in space. In order to increase the amount of radiation
reaching the detector, a convex mirror is used which is set
behind the burner.
3. Slits
Entrance slits : It is kept between the flame and
monochromator. It permits only the radiation coming
from the flame and a mirror.
Exit slit: It is kept between the monochromator and
detector. It prevents the entry of interfering lines.
4. Monochromator (or) Prism (or) Grating (or) Filter
It allows the light of the required wavelength to pass
through but absorbs the light of other wavelengths.
5. Detector
The radiation coming out from the filter is allowed to
fall on the detector, which measures the intensity of the
radiation falling on it. Photomultiplier (or) photocell is
used as a detector, which converts the radiation into an
electrical current.
 Lens Filter
Detector Amplif ier
(photocell) &
Burner Recorder

Fuel Gas

Mixing Chamber

Drain Air

Sample solution
Layout of Simple f lame photometer
 Fuel

Recorder
Amplif ier
Detector
Flame Spectral
Excitation Isolator
Unit (Lens
Filter)

Air Block diagram of Flame Photometer

Sample
6. Amplifier & Recorder
The current coming out of the detector is weak, so it is
amplified and recorded.
Working of Flame photometer
Air, at a given pressure, is passed into an atomiser. The
suction so-produced draws some solution of the sample
into the atomiser.
Air + sample solution is then mixed with fuel gas in the
mixing chamber. The Air + sample solution + fuel gas
mixture is then burnt in the burner.
The radiation, emitted by burner flame, is passed
successively through the lens, filter, detector, amplifier and
finally into a recorder.
intensity of emitted light

Concentration of
unknown solution
Concentration (mgs/lit)
Calibration Curve
Applications of flame photometry
1. Estimation of sodium by flame photometry
The instrument is switched on. Air supply and gas supply
are regulated. First distilled water is sent and ignition is
started.
After the instrument is warmed up for 10 min, the
instrument is adjusted for zero reading in the display.
Since sodium produces a characteristic yellow emission at
589 nm, the instrument is set at λ = 589 nm and the
readings are noted.
2. Qualitative Analysis
The elements of group I & II. (K, Na, Li, Ca, Mg, etc)
can be detected visually from the colour of the flame.
Non-radiating elements such as carbon, hydrogen and
halides cannot be detected using this method.
Quantitative analysis
The amount of the elements in a group I & II (alkali &
alkaline-earth metals) can be determined from the sample.
Certain transition elements, such as Cu, Fe & Mn can
also be determined using flame photometry.
Other applications
 The measurement of these elements is very useful in
medicine, agriculture and plant science.
Flame photometry is extensively used in the analysis of
biological fluids and tissues.
 In soil analysis, the elements like Na, K, Al, Ca, Fe, etc.,
are determined. Industrial and natural waters, petroleum
products, cement, glass, and metallurgical products can
also be analysed by this method.
Limitations of flame photometry
It cannot be used for the determination of all metal
atoms and inert gases.
Only liquid samples must be used.
It does not provide information about the molecular
form of the metal present in the original sample.

https://www.youtube.com/watch?v=DueH4LFJf
hQ
 Drug
A drug is any substance (other than food that
provides nutritional support) that, when inhaled,
injected, smoked, consumed, absorbed via a patch on
the skin, or dissolved under the tongue causes a
temporary psychological change in the body.
A pharmaceutical drug, also called a medication or
medicine, is a chemical substance used to treat, cure,
prevent or diagnose a disease or to promote well-
being.
Traditionally drugs were obtained through extraction
from medicinal plants, but more recently also
by organic synthesis.
Asprin
Asprin
Aspirin is an effective analgesic (pain reliever),
antipyretic (fever reducer) and anti-inflammatory agent and
is one of the most widely used non-prescription drugs

The use of aspirin had its origin in the 18th century, when it
was found that an extract from the bark of willow trees
was useful in reducing pain and fever.

The active ingredient in willow bark was later found to be

salicylic acid.
Although salicylic acid was effective at reducing pain
and fever, it also had some unpleasant side effects. It is
irritating to the lining of the mouth, esophagus, and
stomach, and can cause hemorrhaging of the stomach
lining.

In 1899, the Bayer Company in Germany patented a

drug they called aspirin, which was a modification of
salicylic acid.
 O O

C C
OH OH

OH O C CH3

O
Salicylic acid Acetyl salicylic acid (Asprin)

Salicylic acid contains a phenol group, and phenols are

known to be irritating. The Bayer company replaced the

phenol group with an ester group. This esterified

compound (acetylsalicylic acid, also known as aspirin)

was shown to be much less irritating than salicylic acid.

Aspirin can be made by reacting salicylic acid with
acetic acid in the presence of an acid catalyst

The phenol group on the salicylic acid forms an ester

with the carboxyl group on the acetic acid. However,
this reaction is slow and has a relatively low yield.

If acetic anhydride is used instead of acetic acid, the

reaction is much faster and has a higher yield (since
acetic anhydride is much more reactive than acetic acid)
Synthesis of Asprin

O O
O

C C
C CH3 H +
OH OH
CH3COOH
O

C CH3 O C CH3
OH
O
O
Salicylic acid Acetic anhydride Acetyl salicylic acid (Asprin)
Synthesis of p-nitroaniline

In the first step electrophilic aromatic substituion

(nitration) of nitronium ion is occurring towards
para position of acetanilide more than ortho
position due to steric reasons. Nitronium ion is the
electrophilc generates from fuming nitric acid in
presence of fuming Sulphuric acid.
In the second step p-nitro aniline is prepared from
p- nitro acetanilide due to the hydrolysis of acetate
ion from acetoamido functional group in the
presence of Sulphuric acid.

It is an intermediate for dyes, pigments,

pharmaceuticals, pesticides and rubber chemicals
Synthesis of p-nitroaniline
NHCOCH3 NHCOCH3 NHCOCH3

NO2
f uming H2SO4

fuming HNO3

NO2
Acetanilide o- nitro acetanilde p - nitroacetanilide
NHCOCH3
(major product)
NH2

70% H2SO4

10% NaOH

NO2
NO2
p - nitroacetanilide
(major product) p -nitroaniline