NEW EDITION

A TEXT BOOK OF

ENGINEERING
CHEMISTRY
For I Semester B.E. / B.Tech. Students
(As per the SSN College of Engineering (Autonomous) Syllabus)
COMMON TO ALL BRANCHES

Dr. Arun Luiz T

Dr. Davis Presley S I
Dr. Murugesan A
Dr. Tamilmani V
Department of Chemistry
SSN COLLEGE OF ENGINEERING
Kalavakkam, Chennai

DHANAM PUBLICATIONS
Chennai - 600 042
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Mobile: 99406 41496 / 98401 25695
Email [email protected]
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First Edition – August 2024

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ii
 PREFACE

This book has been written to cater the needs of first semester B.E./ B.Tech.

students according to the new syllabus (Regulation 2024) prescribed followed by SSN

College of Engineering (Autonomous affiliated to Anna University).

This book comprises of five units which covers the entire syllabus. Topics like

water technology, electrochemistry, corrosion, polymers and analytical techniques

have been written in a simple and lucid manner. Most of these topics are traditionally

taught in engineering chemistry courses in several universities and institutes. Figures

and tables are incorporated wherever necessary to make the concept clearer. Authors

hope that this book will be useful for both students and faculty alike.

Despite all precautions and care, some error or misprints might have been left in

advertently. The author welcomes comments, suggestions and criticisms for the

improvement of the book.

- Authors

iii
 Course Code Course Title L T P C
ENGINEERING CHEMISTRY
XXXX 3 0 2 4
(THEORY CUM PRACTICE)
OBJECTIVES:
 To impart knowledge on various aspects of chemistry
 To improve the ability of students to think logically and solve the problems in
industries and day-to-day life efficiently

Unit I WATER AND ITS TREATMENT 9+6

Theory: Hardness of water – types – expression of hardness – units – estimation
of hardness of water by EDTA – numerical, Water quality parameters - WHO
guidelines and BIS guidelines.
Industry water treatment - External treatment – Ion exchange process, zeolite
process. Domestic water treatment - Reverse Osmosis-Working of RO system –
Advantages/limitations.

Practical:
Exp.1: Estimation of hardness of water
Exp.2: Hardness of different sources of water
Laboratory Demonstration:
 Ion Exchange process

Unit II ELECTROCHEMISTRY 9+6

Theory: Conductance- Conductometric titration and its applications - estimation
of strong acid, estimation of mixture of strong and weak acids (numerical based
on conductance).
Electrochemistry-redox reaction - types of Electrode-Ion selective electrodes –
Glass electrodes-measurement of pH-potentiometry
Energy storage systems for electric vehicles – Principle & Electrochemistry of a
H2–O2 fuel cell, Li-ion battery, Na-ion battery.

Practical:
Exp.3: Conductometric titrations- strength of mixture of acids
Exp.4: Estimation of strong acid-pH
Exp.5: Estimation of ferrous ion by potentiometry
iv
 Unit III CORROSION 9+6
Theory: Corrosion - Types of corrosion - wet corrosion – mechanism –galvanic
corrosion -differential aeration- Rate of corrosion, Corrosion control –Cathodic
protection-electroless plating (Printed Circuit Board), Corrosion in different
industries –concrete (reinforcing steel in concrete), boilers, electronic components

Practical:
Exp.6: Rate of corrosion
Industrial visit:
 Plating industry- Electroless plating
Unit IV POLYMERS IN EVERY DAY LIFE 9+6
Theory: Polymers and Polymerization: types of polymerization: addition and
condensation – Properties: Crystallinity, Glass Transition temperature (Tg),
Average Molecular weight-viscosity method &PDI, tacticity, polymer recycling-
biodegradable polymers.

Practical:
Exp.7 : Molecular weight of water soluble polymer by viscosity method
Exp.8: Finding the Tg point of different polymer.
Laboratory Demonstration:
Chemical recycling of post consumed polymer
Unit V ANALYTICAL TECHNIQUES 9+6
Theory: Spectroscopy: Beer-Lambert’s law. Colorimetric estimation of Fe3+,
Principle, working and applications of IR, UV-Visible spectroscopy and
Chromatography (TLC and column)

Practical:
Experiment 9: Colorimetric estimation of Fe3+ ions
Laboratory Demonstration:
Thin Layer Chromatography

Theory Periods 45
Practical Periods 30
Total Periods 75

v
 Course Outcomes:

Upon successful completion of the course, students will be able to

CO1: Analyze the water samples, categorize based on the nature of impurities and
suggest suitable method of treatment for domestic and industrial usage
(BL:L3).
CO2: Understand the principles of electrochemistry and apply the principles for
zero-emission vehicles (BL: L3).
CO3: Identify the type of corrosion and analyze different preventive methods of
corrosion in various industries (BL: L3).
CO4: Acquire sound knowledge on polymeric material and understand the need
for sustainable polymeric materials (BL: L3)
CO5: Apply analytical skills of techniques such as chromatography, spectroscopy
to characterize materials to solve real life problems (BL: L3)

Text Books:
1. Jain P.C. and Monika Jain, ‘Engineering Chemistry’ 17th edition, Dhanpat Rai
Publishing Company (P) Ltd, New Delhi, 2023.
2. S.S.Dara, ‘The Text Book of Engineering Chemistry, S.Chand & Co.Ltd, New
Delhi, 2011

References:
1. N.F. Gray, ‘Water Technology-An Introduction for Environmental Scientists
and Engineers’ Third Edition, Taylor & Francis, USA, 2010
2. S. Glasstone, ‘An Introduction to Electrochemistry’ East-West Press Pvt. Ltd.,
New Delhi, 2007
3. Bengt Sundén, ‘Hydrogen, Batteries and Fuel Cells’ Academic Press Inc, USA,
2019
4. R. Gowariker, N. V. Viswanathan, Jayadev Sreedhar, ‘Polymer Science’ New
Age International (P) Ltd, New Delhi, reprint, 2005
4. R. Gopalan, K. Rangarajan, P.S. Subramanian, “Elements of Analytical
Chemistry” Sultan Chand & Sons, 2003
5. B.Viswanath, B, P.S. Raghavan, ‘Practical Physical Chemistry’, ViVa Books
PVT. Ltd., New Delhi, 2012

vi
CO to PO Mapping

COs POs PSOs

1 2 3 4 5 6 7 8 9 10 11 12
1 3 1 1 1 1

2 3 1 1 1

3 3 1 1 1 1 1

4 3 1 1 1 1 1

5 3 1 1

PO1: Engineering knowledge: Apply the knowledge of mathematics, science,

engineering fundamentals, and an engineering specialization for the solution of
complex engineering problems.

PO4: Conduct investigations of complex problems: Use research-based knowledge

and research methods including design of experiments, analysis and interpretation of
data, and synthesis of the information to provide valid conclusions.

PO6: The engineer and society: Apply reasoning informed by the contextual
knowledge to assess societal, health, safety, legal, and cultural issues and the
consequent responsibilities relevant to the professional engineering practice.

PO7: Environment and sustainability: Understand the impact of the professional

engineering solutions in societal and environmental contexts, and demonstrate the
knowledge of, and the need for sustainable development.

PO9: Individual and team work: Function effectively as an individual, and as a

member or leader in diverse teams, and in multidisciplinary settings.

PO12: Life-long learning: Recognize the need for, and have the preparation and
ability to engage in independent and life-long learning in the broadest context of
technological change.

vii
 CONTENTS

Unit – 1 Page Nos.

Water and its Treatment ………………………………………. 1.1 – 1.24

Unit – 2

Electrochemistry ……………………………………………… 2.1 – 2.42

Unit – 3

Corrosion ……………………………………………………... 3.1 – 3.27

Unit – 4

Polymers in Every Day Life ………………………………….. 4.1 – 4.32

Unit – 5

Analytical Techniques ………………………………………… 5.1 – 5.45

viii
Water and its treatment 1.1

UNIT - 1
WATER AND ITS TREATMENT

Hardness of water – types – expression of hardness – units – estimation of

hardness of water by EDTA – numerical, Water quality parameters - WHO
guidelines and BIS guidelines. Industry water treatment - External treatment – Ion
exchange process, zeolite process. Domestic water treatment - Reverse Osmosis-
Working of RO system – Advantages/limitations.

1.1. INTRODUCTION
Earth is the only planet containing water. Hence it is known as “blue planet”.
About 71% of the earth’s surface is covered by water, out of which only 0.014% can
be used for domestic, agriculture and industrial purposes and rest is locked in oceans,
polar ice caps, giant glaciers and rock crevices. Nearly 70% of human body is made
up of water. Water is one of the most widely used and abundant chemical in nature.
Water is so essential part of plant and animal life that without which life cannot
survive. Hence, water is also known as “elixir of life”.
Impurities in Water
Water dissolves many salts and gases. So it is known as an “universal solvent”. So
many undesirable impurities are present in water. These impurities can be classified
as
1. Dissolved impurities: The following impurities may be present in the water in
the dissolved form.
a) Inorganic salts: Cations like Ca2+, Mg2+, Na+, K+, Fe2+, Al3+ and sometimes
traces of Cu2+ and Zn2+ salts. Anions like Cl-, SO42-, HCO3-, NO3- and
sometimes F- and NO2-.
b) Organic compounds: Hydrocarbon, phenols etc.
1.2 Engineering Chemistry
c) Dissolved gases: Like O2, CO2, N2, oxides of nitrogen and sulphur, and
sometimes NH3 and H2S.
2. Colloidal impurities: Like clay, silica, Al(OH)3, Fe(OH)3, organic waste
products, humic acids, amino acids, proteins etc.
3. Suspended impurities: Inorganic matter like clay and sand; organic matter like
oil globules.
4. Biological impurities: Bacteria and other microorganism like virus, algae, fungi,
phytoplanktons etc.
These impurities may give water a bad taste, odour, turbidity, etc. and cause hardness,
frothing, corrosiveness, staining etc.

1.2. HARDNESS
Water which does not produce lather with soap is known as hard water. It is
due to the presence of bicarbonates, chlorides and sulphates of calcium and
magnesium. Salts of Fe, Mn and other heavy metals also can cause hardness.
Soap is sodium or potassium salts of higher fatty acids like oleic, palmetic stearic acid
etc. Sodium salt is soluble in water while corresponding calcium and magnesium salts
are insoluble in water. When soap is added to soft water, it dissolves and forms lather
easily. When a hard water sample is treated with soap, it does not form lather but it
gets precipitated in the form of insoluble salts (scum/precipitate) of calcium and
magnesium.
CaCl2 + 2C17 H35 COONa → (C17 H35 COO)2Ca + 2NaCl

CaSO4 + 2C17 H35 COONa → (C17 H35 COO)2Ca + 2Na2SO4

Mg(HCO3)2 + 2C17 H35 COONa → (C17 H35 COO)2Mg + 2NaHCO3

(From hard water) (Soap) (Insoluble ppt)

In case of hard water, initially soap is used to precipitate out the hardness causing
ions. No lather is formed until all the hardness causing ions are removed. So, large
amounts of soap is consumed unnecessarily. Anions associated with these metal ions
Water and its treatment 1.3

include chloride, sulphate, bicarbonate but these do not contribute to the hardness of
water.
TYPES OF HARDNESS:
Temporary Hardness (Carbonate hardness or alkaline hardness): It is due to the
presence of bicarbonates of calcium and magnesium. It can be easily removed by
boiling. On boiling, bicarbonates are decomposed to insoluble carbonates and
hydroxides.
Ca(HCO3)2 → CaCO3  + H2O + CO2 
Mg(HCO3)2 → Mg(OH)2  + 2 CO2 
Permanent Hardness (Non-carbonate hardness or non-alkaline hardness): This
is due to the presence of chlorides and sulphates of calcium and magnesium. This
type of hardness cannot be removed by boiling. The hardness can be removed by lime
soda process, zeolite process and ion exchange process.
1.3. CALCIUM CARBONATE EQUIVALENT
(Degree of hardness)
The concentration of hardness producing salts or ions such as bicarbonates, chlorides
and sulphates of Ca, Mg, etc. is measured in terms of equivalent amounts of calcium
carbonate. The weights of different salts causing hardness are converted to weights
equivalents to that of CaCO3
CaCO3 eq. of hardness = Mass of hardness producing substance (in mg) x Mol. mass of CaCO3
Molecular mass of hardness producing
saltCaCO3 is particularly selected to express the hardness of water because:
1. CaCO3 is the most insoluble salt which can be precipitated during the water
treatment.
2. Since the molecular mass of CaCO3 is 100 (eq. weight = 50), the calculation
becomes easy.
1.4 Engineering Chemistry

Hardness causing Salt Molecular Weight

Ca(HCO3)2 162
Mg(HCO3)2 146
CaSO4 136
CaCl2 111
MgSO4 120
MgCl2 95
Ca(NO3)2 164
Mg(NO3)2 148

Units of hardness

1. Parts per million (ppm)

It is the parts of calcium carbonate equivalent hardness per 106 parts of water.
i.e. 1ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water.

2. Milligrams per litre (mg/L)

It is the number of milligrams of calcium carbonate equivalent hardness present per

litre of water.

Thus,
1 mg/L = 1 mg of CaCO3 equivalent hardness per1 L of water

But 1 L water = 1 kg = 1000g = 106 mg

1 mg/L = 1 mg of CaCO3 equivalent per 106 mg of water

= 1 part of CaCO3 equivalent per 106 parts of water = 1 ppm

3. Degree Clark (0Cl)

It is the number of grains of CaCO3 equivalent hardness per gallon of water (or) it is
the parts CaCO3 equivalent hardness per 70,000 parts of water.
Water and its treatment 1.5

1°Cl = 1 grain of CaCO3 equivalent hardness per gallon of water

1°Cl = 1 part of CaCO3 equivalent hardness per 70,000 parts of water
4. Degree French (0Fr)
It is the parts of calcium carbonate equivalent hardness per 105 parts of water.
i.e. 10Fr = 1 part of CaCO3 equivalent hardness in 105 parts of water.
Relationship between various units of hardness

1ppm = 1 mg/L = 0.1 0Fr = 0.07 0Cl

1.4. ESTIMATION OF HARDNESS OF WATER

Hardness in water is due to the presence of dissolved salts of calcium and
magnesium. It is unfit for drinking, bathing, washing and it also forms scales in
boilers. Hence it is necessary to estimate the amount of hardness producing
substances present in the water sample. The estimation of hardness is based on
complexometric titration.

Aim: To estimate the amount of total hardness present in the given sample of water
by EDTA titration method.

Apparatus required: 50 ml Burette, 20 ml Pipette, 250 ml Conical flask, 100 ml

Beaker, 250 ml beaker, Glass funnel.

Reagents: EDTA solution, Standard CaCO3 solution, Eriochrome Black–T indicator,

Buffer solution.

Principle : EDTA ( Ethylene diamine tetra acetic acid) forms colourless stable
complexes with Ca2+ and Mg2+ ions present in water at pH = 9-10. To maintain the
pH of the solution at 9-10, buffer solution (NH4Cl + NH4OH) is used. Eriochrome
Black-T (E.B.T) is used as an indicator. The sample of hard water is first treated with
buffer solution and EBT indicator which forms unstable, wine-red coloured
complexes with Ca2+ and Mg2+ present in water. Now this wine red complex is
1.6 Engineering Chemistry
titrated against EDTA solution (of known strength) the colour of the sample changes
from wine red to steel blue showing the endpoint.

Preparation of Solutions

Following solutions are prepared for estimation of various types of hardness

1. Standard Hard Water (SHW): Dissolve 1 gram of pure CaCO3 in minimum

quantity of dil. HCl and dilute to 1L with distilled water.
1mL of SHW  1mg of CaCO3 equivalent hardness

2. EDTA solution: 4 gram of pure EDTA crystal along with 0.1 gram of MgCl2 in
1L of distilled water
3. Indicator: 0.5 gram of EBT in 100 mL of alcohol.
4. Buffer solution: Add 67.5 gram of NH4Cl in 570 mL of concentrated ammonia
solution and further dilute to 1L with distilled water
Water and its treatment 1.7

PROCUDERE

Titration I: Standardization of EDTA

20 mL of standard hard water (SHW) is pipetted out into a clean conical flask.
5 mL of ammonia buffer and few drops of EBT indicator are added. The solution
turned wine red in colour and is titrated against EDTA taken in the burette. The end
point is the change in colour from wine red to steel blue. The titration is repeated for
concordant value and readings are tabulated. Let the volume of EDTA consumed by
SHW be V1 mL. From the titre value, EDTA equivalence is calculated.
Titration II: Estimation of Total Hardness

20 mL of given water sample is pipette out into a conical flask and 5 mL of

ammonia buffer and few drops of EBT indicator are added and the titration is carried
out as before. Let the volume of EDTA consumed by sample water be V2 mL. From
the titre value the total hardness of the given sample(s) can be calculated.

Titration III: Estimation of Permanent Hardness

20 mL of boiled water sample is pipette out into a conical flask and 5 mL of

ammonia buffer and few drops of EBT indicator are added and the titration is carried
out as before. Let the volume of EDTA consumed by boiled sample water be V3 mL.

From the titre value the permanent hardness of the given sample can be calculated.

The difference between the Total and Permanent hardness gives the Temporary
Hardness of the water sample.

Calculation for Titration I

1mL of SHW  1mg of CaCO3 equivalent hardness
20 mL of SHW  20 mg of CaCO3 equivalent hardness
20 mL of SHW = V1 mL of EDTA
 20 mg of CaCO3 = V1 mL of EDTA

 1 mL of EDTA = 20/ V1 mg of EDTA (This is known as EDTA equivalence)

1.8 Engineering Chemistry

Calculation for Titration II and III

20 mL of given water sample require V2 mL of EDTA

V2  20
Total Hardness in 20 mL of water sample = mg of CaCO3
V1

V2  20 1000
1L (1000 mL) of given water contains = mg of CaCO3
V1  20

V2 ×1000
Total hardness = ppm of CaCO3 equivalents
V1

Similarly,

20 mL of boiled water sample require V3 mL of EDTA

V  20
Permanent Hardness in 20 mL of water sample = 3 mg of CaCO3
V1

V3  20 1000
1L (1000mL) of given water contains = mg of CaCO3
V1  20

V3 ×1000
Permanent hardness = ppm of CaCO3 equivalents
V1

Temporary Hardness = Total Hardness – Permanent Hardness

1000(V2  V3 )
= ppm of CaCO3 eq.
V1
Water and its treatment 1.9

PROBLEMS

1. Calculate the total hardness of water containing 16.8mg/L of

Mg(HCO3)2,19.0mg/L of MgCl2,24.0mg/L of MgSO4 and 22.2 mg/L of CaCl2.
Multiplication
Constituent Amount CaCO3 Equivalent
Factor
Mg(HCO3)2 16.8mg/L 100/146 16.8x100/145=11.5mg/L

MgCl2 19.0mg/L 100/95 19.0X100/95=10.0mg/L

MgSO4 24.0mg/L 100/120 24.0X100/120=20.0mg/L

CaCl2 22.2mg/L 100/111 22.2X100/111= 20.0mg/L

Total Hardness = (11.5+10.0+20.0+20.0)mg/L = 61.5mg/L

2. A sample of water on analysis has been found to contain following in ppm.

Ca(HCO3)2= 10.5, Mg(HCO3)2= 12.5,CaSO4=7.5 CaCl2= 8.5,MgSO4=2.6
Calculate the temporary and permanent hardness.
Multiplication
Constituent Amount CaCO3 Equivalent
Factor
Ca(HCO3)2 10.5 ppm 100/162 10.5x100/162=6.48 ppm

Mg(HCO3)2 12.5 ppm 100/146 12.5X100/146=8.56 ppm

CaSO4 7.5 ppm 100/136 7.5X100/136=5.15ppm

CaCl2 8.2ppm 100/111 8.2.2X100/111= 7.38ppm

MgSO4 2.6 ppm 100/120 2.6X100/120= 2.16 ppm

Temporary hardness = 6.48+8.56= 15.04ppm

Permanent hardness = 5.15+7.38+2.16= 14.69ppm

1.10 Engineering Chemistry
3. A sample of water on analysis was found to contain the following impurities
expressed in mg/litre Ca(HCO3)2 =10.0mg/L , Mg(HCO3)2 = 8.5mg/L, CaSO4
= 12.0 mg/L, MgSO4 = 14.0 mg/L. Calculate the temporary and permanent
hardness and express the total hardness in degree French.

Multiplication CaCO3 Equivalent

Constituent Amount
Factor
Ca(HCO3)2 10.0 mg/L 100/162 10.0x100/162=6.17mg/L

Mg(HCO3)2 8.5 mg/L 100/146 8.5X100/146=4.45mg/L

CaSO4 12.0mg/L 100/136 12.0X100/136=8.82mg/L

MgSO4 14.0mg/L 100/120 14.0X100/120= 11.67mg/L

Temporary hardness = 6.17 +4.45= 10.62mg/L

Permanent hardness = 8.82+11.67 = 20.49 mg/L
Total hardness = 10.62 + 20.49 = 31.11 mg/LX 0.1OFr = 3.111 OFr

1.5. WATER QUALITY PARAMETERS

The water we consume must adhere to specific quality standards. In industrial

settings, water often requires treatment to achieve a quality suitable for various
essential processes. To assess water quality, physical, chemical, and biological
parameters are checked. Physical parameters include colour, taste, odour, and
turbidity. Chemical parameters include pH, acidity, alkalinity, chloride, and hardness.
Biological parameters involve the presence of bacteria, algae, and viruses.

Colour

Pure water contains no colour because it is essentially colourless. Colour of the

water is affected by materials that decay from organic matter and inorganic matter
such as rock, soil and stones. Common sources of contamination comes from organic
Water and its treatment 1.11

dyes and inorganic compounds like Fe, Mn, and Cr etc. The colour of the water is
measured in terms of Hazen units. Yellowish tinge in water indicates the presence of
chromium whereas yellowish red indicates the presence of iron. Colour can be
removed by coagulation, settling and filtration.

Taste and Odour

The taste of water can change and odours can develop when foreign substances are
introduced. These substances may include organic materials, dissolved gases, and
inorganic compounds, often originating from agricultural, natural, and domestic
sources. Water can have a salty taste due to high levels of sodium, potassium and
magnesium. Bacteria growing in your sink drain or hot water heater may cause odour.
Naturally occurring hydrogen sulfide in your water supply can also cause rotten egg
odour .Taste and odour can be improved by aeration or by activated charcoal
treatment.

Turbidity

Turbidity refers to how cloudy a water is. Turbidity occurs due to higher
concentration of silt, clay, and organic materials. Additional problems that are caused
due to turbidity include high water treatment costs, affects the aquatic life, increases
the water temperature because suspended particles absorb more heat. Turbidity of
water can be removed by coagulation, settling and filtering.

Total Dissolved Solids (TDS)

TDS represents the total concentration of dissolved substances in water. TDS is

made up of inorganic salts as well as small amounts of organic matter. Common
inorganic salts that can be found in water include calcium, magnesium, potassium and
sodium, which are all cations, and carbonates, nitrates, bicarbonates, chlorides and
sulfates, which are all anions. Cations are positively charged ions and anions are
negatively charged ions. These minerals can originate from a number of sources, both
1.12 Engineering Chemistry
natural and as a result of human activities. TDS can be removed by Reverse Osmosis.
Permissible limits of TDS is given below.

Level of TDS( mg/L) Rating

Less than 300 Excellent
300-600 Good
600-900 Fair
900-1200 Poor
Above 1200 Unacceptable

Fluoride (F-)

Fluoride occur normally in water, its source is only natural, soluble fluoride
minerals from the soil get dissolved in water. F- prevents tooth decay at levels around
1mg/L in drinking water. However when the fluoride content of drinking water is
high greater than 10mg/L it causes fluorosis, which damages teeth and bones, the
teeth become stained with colours. Fluoride contents in water can be removed by a
process called Defluoridation. This process involves treating water with Ca2+ (aq)
which combines with F- to form insoluble CaF2.

pH

pH value of a water is a measure of its acidity and alkalinity. The pH level is a

measurement of the activity of the hydrogen atom, because the hydrogen activity is a
good representation of the acidity or alkalinity of the water. The hydrogen ion
concentration is represented by

pH = - log10[H+]

The pH scale, as shown below, ranges from 0 to 14, with 7.0 being neutral.
Water with a low pH is said to be acidic, and water with a high pH is basic, or
alkaline
Water and its treatment 1.13

Fig. 1.1. The pH scale

The pH scale is logarithmic, which means that each step on the pH scale
represents a ten-fold change in acidity. For example, a water body with a pH of 5.0 is
ten times more acidic than water with a pH of 6.0. And water with a pH of 4.0 is 100
times more acidic than water with a pH of 6.0.

Alkalinity

Alkalinity is a chemical measurement of a water’s ability to neutralize acids. It

can measure the bicarbonate, hydroxide ions, and carbonate naturally present in the
water. The majority of alkalinity in the surface water is from calcium carbonate,
leached from soil and rocks. High alkalinity values are harmful to aquatic organisms
where as low alkalinity values can contribute to the corrosion of pipes.

Chemical oxygen Demand (COD)

Chemical Oxygen Demand (COD) measures the amount of oxygen, in

milligrams, needed to oxidize all the organic pollutants in water into carbon dioxide
and water. The test involves boiling the water sample with potassium dichromate in a
1.14 Engineering Chemistry
strongly acidic medium under reflux, which oxidizes the organic compounds present.
The COD test is commonly used to assess the efficiency of water treatment plants and
to quantify pollutants in water, wastewater, and aqueous hazardous wastes

Biological Oxygen Demand (BOD)

Biochemical Oxygen Demand (BOD) is the amount of dissolved oxygen

needed by bacteria to biologically oxidize organic matter under aerobic conditions at
20°C over a period of 5 days. BOD is calculated by measuring the oxygen consumed
by bacterial and chemical action in a closed sample of water maintained at 20°C over
a period of 5 days. A lower BOD value indicates better water quality. Water with a
BOD of less than 3 ppm is considered pure, while a BOD greater than 4 ppm suggests
the water is polluted.

1.6. DRINKING WATER SPECIFICATIONS

World Health organization (WHO) and Bureau of Indian standards (BIS)
produces norms on water quality in form of guidelines that are used as basis for
regulation. Assurance of drinking water safety is the foundation for the prevention
and control of water borne diseases. Table 1 gives the guidelines for drinking water

WHO and BIS guidelines for drinking water

Standard limits as per Standard limit as per

Parameter
WHO in (mg/L) BIS in (mg/L)

Colour in Hazen units No visible colour 5

Odour and taste Odourless and tasteless Unobjectionable and

agreeable

Turbidity ---- 5

pH Value ---- 6.5-8.5

Total hardness as CaCO3 ---- 300

Water and its treatment 1.15

Alkalinity ---- 200

Iron as Fe ---- 0.3

Chlorides as Cl 200-300 250

Total dissolved solids ---- 500

Nitrate 50 45

Fluoride 1.5 1.0

Lead 0.01 0.05

Arsenic 0.01 0.05

Cyanide 0.07 0.01

Mercury 0.006 0.001

1.7. INDUSTRY WATER TREATMENT

Industrial water treatment addresses four main issues: scaling, corrosion,
microbial activity, and the disposal of residual wastewater.
Industrial waste water treatment Involves both Internal and external treatment.
Internal treatment is done by adding chemicals to the water and the impurities are
removed in the form of precipitates.
External treatment of water
External Treatment is the reduction or removal of impurities from feed water used in
boilers. Common Industrial water treatment methods are
1. Filtration
2. Softening
3. Reverse osmosis
4. Ion exchange
5. Zeolite Process
1.16 Engineering Chemistry
1.8. DEMINERALIZATION OR ION EXCHANGE OR
DEIONIZATION METHOD
Demineralization is an external conditioning method. In this method cations are
exchanged by H+ and anions are exchanged by OH-. Ion exchange resins are
insoluble, cross linked, organic polymers with micro porous structure. Functional
groups attached to the polymer chains are responsible for ion exchange properties.
The ion exchange resins may be classified as cation exchange resins and anion
exchange resins. Both have a network of divinyl benzene co-polymer.
 Cation exchange resins (R-H): Cation exchange resins have –COOH or –SO3H
group in their structure so that they can easily exchange H+ ions with cations of
the water. Cation exchange resins can be represented as R-H
Eg: Sulphonated or carboxylated styrene divinyl benzene copolymer.
Commercially available cation exchangers are Amberlite IR-120 and
Dowex-50.
 Anion exchange resins (R-OH): Anion exchange resins have quarternary
ammonium hydroxide [–NH3+OH-]. They are capable of exchanging OH- with
anions present in hard water. Anion exchange resins can be represented as R-OH.
Eg: Styrene divinyl benzene copolymer containing amino or quarternary ammo-
nium salts. Commercially available anion exchangers are AG-1, AG-2.

Fig. 1.2. Structures of cation and anion exchange resins

Water and its treatment 1.17

Method: Cation and anion exchange resins are packed in separate cylindrical
containers and hard water is passed through each of these consecutively. Hard water
is first passed through cation exchange resin. The cations (Ca2+, Mg2+, Na+, K+ etc)
present in the water get exchanged with H+ ions of the resin as shown by the reaction
given below.
Ca2+ + 2 R-H  R2 Ca + 2 H+
Mg2+ + 2 R-H  R2 Mg + 2 H+
(Hard water) (Cation exchanger)
The water coming out of the first chamber contains free H+ ions and hence acidic in
nature. Now it is passed through the anion exchange resin. Anion exchange resin
exchanges anions (Cl-, SO42-, HCO3- etc) with OH- ions.
Cl- + R-OH  RCl + OH-
HCO3- + R-OH  R HCO3 + OH-
(Anion exchanger)
The OH- ions liberated from the chamber now react with free H+ ions (coming from
the first chamber) to form water.
H+ + OH-  H2 O
Thus the water coming out from the second chamber is free from all cations and
anions that were initially present in hard water. Hence it is generally known as
demineralized water or deionized water. Thus water becomes soft after this
process.
Regeneration of resin:
As the continuous use of demineralization makes the resin exhausted, therefore for
the future use, resins must be regenerated.
Exhausted cation exchange resin is regenerated by passing a moderately concentrated
(10-20%) hydrochloric acid or sulphuric acid solution through the chamber.
R2 Ca + 2 HCl  2 R-H + CaCl2
(Exhausted cation (Regenerated resin)
exchange resin)
1.18 Engineering Chemistry
Exhausted anion exchange resin is regenerated by passing a moderately concentrated
(10-20%) sodium hydroxide solution through the chamber.

R-Cl + NaOH  R-OH + NaCl

(Exhausted anion (Regenerated resin)
exchange resin)

Fig. 1.3. Demineralization process

Advantages
 Highly acidic and highly alkaline water can be treated.
 Treated water has very low hardness (~ 2 ppm) and is suitable for high pressure
boilers.
Disadvantages
 Ion exchange resins are expensive.
 If water is turbid, efficiency of the process is reduced as the pores are blocked
by turbid impurities.
 Water containing Fe, Pb and Mn cannot be treated as they form stable
complexes with resins and it becomes difficult to regenerate the resins.
 For effective water treatment, ion exchanger should possess following
properties.
Water and its treatment 1.19

 They should be non-toxic.

 They should not discolour the water being treated.
 They should possess high ion-exchange capacity.
 They should be resistant to chemical attack.
 They must be capable of being regenerated and back washed easily.
 They should have large surface area since ion-exchange is a surface
phenomenon (adsorption).
1.9. ZEOLITE PROCESS OR PERMUTIT PROCESS
Zeolites are naturally occurring hydrated sodium aluminosilicate minerals. The
term "zeolite" comes from the Greek for "boiling stone," as zeolites released water
when heated. Zeolites do not have a fixed composition and are examples of
nonstoichiometric compounds. Artificial zeolite known as permutit is widely used for
water softening. It has the general formula Na2O. Al2O3.xSiO2.yH2O (x= 5-13; y =
3-4) but is generally represented by Na2Ze.
Zeolites are highly porous and they have three dimensional tunnels and cavities of
different sizes. Zeolites are insoluble in water and are capable of reversibly
exchanging its sodium ions with the alkaline earth group cations generally present in
water.
Process
A cylindrical column is initially packed with a layer of coarse gravel followed
by a layer of fine gravel. Above this permutit or zeolites are packed as shown in the
figure. A slow stream of hard water is passed through this material. As a result,
calcium and magnesium ions present in the hard water are exchanged with sodium
ions in the permutit. The water that flows out from the zeolite bed contains sodium
ions which do not cause hardness.
Na2Ze + CaCl2 → CaZe + 2 NaCl
Na2Ze + MgSO4 → MgZe + Na2SO4
1.20 Engineering Chemistry

Fig. 1.4. Zeolite process

Regeneration
Over a period of time, permutit bed loses its sodium exchange capacity as it gets
converted into a mixture of calcium and magnesium aluminosilicates. The zeolite bed
is said to be “exhausted”. Exhausted zeolite bed can be regenerated by treating with
5-10% brine.
CaZe + 2NaCl → Na2Ze + CaCl2
Resulting calcium or magnesium chloride produced are washed out through the tap at
the bottom. Regenerated permutit is reused for softening of water.

Advantages
 Water of very low hardness (~10 ppm hardness) is obtained.
 This method is very cheap as exhausted zeolite can be regenerated.
 No sludge is formed during this process.
 The equipment used is compact and uses little space.
 Easy operation.
 The process can be made automatic and continuous.
Water and its treatment 1.21

Disadvantages
 Zeolite process cannot be used for acidic water as it may destroy the zeolite
bed.
 Turbid water or water with suspended impurities cannot be used as these may
clog the fine pores in the zeolites.
 This treatment only replaces only the cations leaving all anions like HCO3-,
CO32- etc. in soft water. Presence of these impurities may result in boiler
corrosion (caustic embrittlement).
 Zeolite process cannot be used for brackish water because brackish water also
contains Na+ ions. So the ion exchange reaction will not take place.
 Water containing manganese, iron and lead ions cannot be used as they bind
irreversibly with zeolite. Such zeolites cannot be regenerated back to sodium
zeolites
1.10. DESALINATION OF BRACKISH WATER
Water contains large amount of salts dissolved in it. The process of removal of these
dissolved salts present in the water is known as desalination. Salinity of water is primarily
due to dissolved sodium chloride and to smaller extent due to other inorganic salts (mostly of
calcium and magnesium).The salinity of water is expressed in terms of mg/L of dissolved
salts. On the basis of salinity, water is divided into three categories.
(i) Fresh water: Water having salinity less than 1000 mg/L
(ii) Brackish water: Water having salinity in the range 1000 – 35000 mg/L. Brackish
water has a peculiar salty taste.
(iii) Sea water: Water having salinity greater than 35000 mg/L.
Desalination can be achieved by two methods. a) removal of water from salt (eg:
distillation or evaporation, solvent extraction, reverse osmosis etc) b) removal of salt from
water (eg: electrodialysis). Reverse osmosis and electrodialysis are most commonly used for
the desalination on a large scale.
1.22 Engineering Chemistry
Reverse Osmosis
When two solutions of different concentrations are separated by a semi permeable
membrane, the flow of solvent takes place from a region of low (solute) concentration
to a high (solute) concentration until the concentration of the both solutions is equal.
This process is known as osmosis. The driving force for this phenomenon is known
as osmotic pressure. But when a greater pressure, in excess of osmotic pressure is
applied on the higher concentration side, the solvent flow reverses, i.e. the solvent is
forced to move from higher (solute) concentration to lower (solute) concentration.
This is known as reverse osmosis.
Principle:
Brackish water contains large amounts of dissolved salts and is more concentrated as
compared to fresh water. Thus, if sea water is kept in contact with fresh water through
a semi permeable membrane, then a pressure of 15-40 kg/cm2 is applied on sea water,
then water will pass thorough the semi permeable membrane leaving behind the salts.
Thus, reverse osmosis separates water from dissolved salts. Pressure is usually
applied by a pump. Charcoal pre filters are placed before the membrane unit to filter
out the suspended matter which would otherwise clog the pores of the membrane.
Membrane used for reverse osmosis
Earlier semi permeable membranes used were made up of cellulose acetate. More
recently superior membranes made up of polymethacrylate and polyamide polymers
have been introduced. The membrane consists of a skin of about 0.25 μ and a support
layer 100 μ in width.

Fig. 1.5. Reverse osmosis

Water and its treatment 1.23

Advantages:
 Reverse osmosis is known as the finest hyper filtration technique known. This
process will allow the removal of particles as small as ions.
 This process is very economical and convenient. It can be used at room
temperature.
 The membrane will last for more than 2 years. Replacement of membrane will
take only few minutes.
 It gives water, as and when required without any interruption.
 RO process removes ionic and non-ionic impurities easily.
 It is effective in removing colloidal impurities present in water.
 Suitable for converting sea water into drinking water.
Disadvantage:
 The membrane must be strong enough to withstand high pressure without
breaking.

DID YOU KNOW?

Chemicals can create monsters, foreign agents such as chemicals can enter a body
of pregnant woman and can cause defects for the baby. The study of this subject is
called teratology. Teratogens are substances that may cause birth defects. The
word has been derived from the French word terat, meaning “monster”. Several
environmental pollutants today have been proved to be the potential teratogens.
CO, Cd, Pb, Hg are teratogenic to animals.
1.24 Engineering Chemistry
QUESTIONS
1. What is meant by hardness of water?
2. Why Hardness is expressed in terms of Calcium carbonate?
3. What is temporary hardness and permanent hardness?
4. Identify the hardness causing salts among the following:
NaHCO3, Ca(HCO3)2, Na2CO3, NaCl, MgCl2 and Al2(SO4)3.
5. What is Eriochrome Black-T? Write its Molecular structure
6. Identify the colours of the following chemical species Ca-EDTA, Mg-EDTA,
Ca-EBT,EBT.
7. How is water softened by ion exchange method? Explain in detail with a neat
diagram
8. What are zeolites? How do they function in removing the hardness of water?
9. What are cation and anion exchangers? Give one example?
10. A sample of water drawn by a jute mill near Calcutta has the following analytical
data. Calculate the temporary and permanent hardness of the sample of water.
Mg(HCO3)2 = 16.8 ppm, MgCl2 = 19ppm, Mg(NO3)2 = 29.6ppm ,
CaCO3 = 20 ppm, MgSO4 = 24 ppm, KOH = 0.9 ppm.
11. How hardness of water is determined by EDTA method?
12. What is reverse osmosis? How is it useful for desalination of brackish water?
Explain with a diagram.
13. What is meant by desalination?
14. Enumerate the merits and demerits of reverse osmosis technique for desalination
of water.
15. Define and give the importance of following: i) COD ii) Alkalinity iii) pH
16. Explain the significance of fluoride content in water
17. What is meant by exhaustion of zeolite?
18. What is semi-permeable membrane?
19. What is meant by exhaustion of cation and anion exchangers? How they are
regenerated?
Electrochemistry 2.1

UNIT - 2
ELECTROCHEMISTRY
Conductance - Conductometric titration and its applications -estimation of strong
acid, estimation of mixture of strong and weak acids (numerical based on
conductance).

Electrochemistry-redox reaction- types of Electrode-Ion selective electrodes –

Glass electrodes-measurement of pH - potentiometry

Green hydrogen-Energy storage systems for electric vehicles – Principle &

Electrochemistry of a H2–O2 fuel cell, Li-ion battery, Na-ion battery.

2.1. INTRODUCTION
Electrochemistry is a branch of chemistry that explores the relationship
between electrical energy and chemical reactions. Electrochemical cell (also called
Galvanic cell or Voltaic cell) deals with the conversion of chemical energy to
electrical energy. While electrolytic cell deals with conversion of electrical energy
into chemical energy.

Fig. 2.1. Electrochemical cell Vs Electrolytic cell

2.2 Engineering Chemistry
2.2. APPLICATIONS OF ELECTROCHEMISTRY
Electrochemistry has a vast array of applications that impact our daily lives and drive
technological advancements:
1. Batteries and Fuel Cells: Electrochemical cells are at the heart of batteries and
fuel cells. Lithium-ion batteries power a multitude of devices, from smartphones
to electric vehicles. Fuel cells, which convert chemical energy from fuels like
hydrogen into electricity, are being developed for clean energy applications.
2. Electroplating and Surface Coating: Electroplating involves coating a metal
object with a thin layer of another metal using electrochemical processes. This
technique is used to enhance the appearance, durability, and corrosion resistance
of items ranging from jewellery to automotive parts.
3. Electrolysis: Electrolysis is used in various industrial processes, such as the
extraction of metals from ores (e.g., aluminium production) and the electrolysis of
water to produce hydrogen and oxygen gases, which have applications in energy
storage and fuel.
4. Sensors and Analytical Devices: Electrochemical sensors detect and quantify
chemical substances, playing a critical role in environmental monitoring, food
safety, and medical diagnostics. For instance, glucose sensors are widely used by
diabetic patients to monitor blood sugar levels.
5. Corrosion Prevention: Understanding electrochemical principles is essential for
preventing and controlling corrosion, which is a major challenge in many
industries, including construction, transportation, and marine engineering.
Techniques such as cathodic protection and anodic inhibitors are employed to
protect structures and materials from degradation.
6. Environmental Applications: Electrochemical methods are employed in water
purification, waste treatment, and pollution control. Electrocoagulation and
electrochemical oxidation are techniques used to remove contaminants from water
and industrial effluents, contributing to environmental sustainability.
Electrochemistry 2.3

Fig. 2.2. Applications of Electrochemistry

DID YOU KNOW?

Fig. 2.3. Electric Eel

The electric eel (Electrophorus electricus), native to South America, can generate
powerful electric shocks up to 600 volts. This ability comes from specialized organs
that make up 80% of its body length, containing thousands of electrocytes (battery-
like cells).
2.4 Engineering Chemistry
How They Generate Electricity?

Electric eels use electrocytes to create electricity. When signaled by the eel, these
cells move ions across their membranes, generating a voltage difference. When many
electrocytes discharge simultaneously, they produce a significant electric shock.

2.3. CONDUCTANCE
Electrolytic conductance refers to the ability of an electrolyte solution to
conduct electricity. It is a fundamental concept in electrochemistry and plays a crucial
role in various industrial and scientific applications.
What is Electrolytic Conductance?
When an electrolyte (a substance that dissolves in water to produce ions) dissolves in
water, it dissociates into its constituent ions. These ions are responsible for
conducting electric current through the solution. Electrolytic conductance is measured
by the ease with which these ions move under the influence of an electric field.
The electrolytic conductance, G, of a medium is equal to the reciprocal of its
electrical resistance (Resistance is the measure of how much the material opposes the
flow of current) R in ohms:
1 1
R=G So, G = R (i)

In a qualitative sense, the resistance tells us how difficult it is for an electrical current
to pass.
Since a solution is a three-dimensional conductor, the exact resistance will
depend on the spacing l and area A of the electrodes (cell constant). The resistance of
the solution in such situation is directly proportional to the distance between the
electrodes and inversely proportional to the electrode surface area. If we consider the
electrolytic cell with two electrodes having a cross sectional area of A [m2] and
separated by l [m], then the resistance R of the electrolyte solution present between
the electrodes is
𝑙
R=𝐴 (ii)
Electrochemistry 2.5

where  is the proportionality constant called specific resistance and it is a

characteristic property of material. Substituting the value of R from Eq. (ii ) in Eq. (i),
the expression for the conductance, G , is
1𝐴 𝐴
G= 𝑙 = (iii)
𝑙

Where  is the reciprocal of specific resistance called specific conductance or

conductivity. It is defined as the conductance of one cm3 of a solution of electrolyte.
In the SI system, the unit of conductance is “Siemens”, (S) hence the unit for
conductivity will be [S cm-1] (1S = 1  -1).

Fig. 2.4. Specific conductance

In order to compare quantitatively the conductivities of electrolytes, a quantity
called molar conductance is frequently used. The molar conductance, m, is the
conductivity per unit molar concentration of a dissolved electrolyte. It is connected
with specific conductivity, , by the relation

m =𝑐 (iv)

where c is the concentration in [mol m-3]. The molar conductivity is usually expressed
in [S m2 mol-1] or [S cm2 mol-1].
Molarity = (moles/volume) ×1000
Since, we are working with 1 mole, Volume=1000/molarity
Therefore, molar conductance =m = 1000 
M
Where, M is the number of moles of the electrolyte present in 1000 cc of electrolyte.
2.6 Engineering Chemistry
Equivalent conductance is the conductance of a volume of solution containing one
equivalent weight of dissolved substance.
Normality = (gram equivalent/volume) × 1000
Since gram equivalent here is 1g
Therefore, Volume = 1000/Normality
So, equivalent conductance = e = 1000 
N
COMPARISON:
Specific conductance Equivalent Molar conductance
() conductance (e) (m)
Conducting power of Conducting power of Conducting power of
ions present in one cm3 ions produced by ions produced by
of the solution dissolving one gram dissolving one gram
equivalent of the mole of the electrolyte
electrolyte

Decreases with dilution Increases with dilution Increases with dilution

Unit: Ohm-1cm-1 or Unit: Ohm-1cm2 equi-1 Unit: Ohm-1cm2 mol-1 or

Sm-1 or S m2 equi-1 S m2 mol-1

2.4. EFFECT OF DILUTION ON CONDUCTANCE

Specific conductance is the conductance of one cm3 of a solution of an
electrolyte. If we dilute the solution the specific conductance decreases. On diluting
the solution, the concentration of ions per cm3 decreases. Hence the specific
conductance decreases.
Equivalent or molar conductance and molar conductance increases with
dilution. But it varies for strong electrolytes and weak electrolytes. For strong
electrolytes (e.g., NaCl, HCl), which completely dissociate in solution, molar
Electrochemistry 2.7

conductance increases with dilution due to reduced ion-ion interactions. Dilution

decreases ion interactions, allowing ions to move more freely. For weak electrolytes
(e.g., acetic acid), which partially dissociate, molar conductance increases more
sharply with dilution due to increase in degree of dissociation.
Graphical Representation
 Strong Electrolytes: Linear increase in Λm Vs √c, showing moderate rise with
dilution. This is because, with increased dilution, the number of ions per unit
volume decreases, but the mobility of each ion increases due to less inter ionic
attraction. This increase in mobility generally results in an increase in the overall
conductance of the solution.
 Weak Electrolytes: Steep, nonlinear increase, indicating significant rise in
ionization. As the solution is diluted, the degree of dissociation of the weak
electrolyte increases, leading to a more significant increase in the number of ions
available for conduction.

Fig. 2.5. Variation of molar conductance with dilution

2.8 Engineering Chemistry
2.5. FACTORS AFFECTING ELECTROLYTIC CONDUCTANCE
(i) Nature of electrolyte
The strong electrolytes undergo complete ionization and hence show higher
conductivities since they furnish more number of ions. Example: HCl, H2SO4, HNO3,
HBr, NaOH, KOH, NaCl, KCl etc.
Whereas weak electrolytes undergo partial ionization and hence show
comparatively low conductivities in their solutions. Examples: Acetic acid, Oxalic
acid, Alkyl amines, Mercury(II) chloride, Lead acetate etc.
(ii) Concentration of ions
The sole reason for the conductivity of electrolytes is the ions present in them.
The conductivity of electrolytes increases with increase in the concentration (number)
of ions as there will be more charge carriers. As explained earlier for weak
electrolytes and strong electrolytes, molar (or equivalent) conductance increases with
dilution.
(iii)Ionic size and mobility
Ionic mobility decreases with increase in ionic size and extent of hydration.
Hence, conductivity decreases. Example: In molten state, the conductivities of
lithium salts are greater than those of cesium salts since the size of Li + ion is smaller
than that of Cs+ ion.

Fig. 2.6. Size and mobility of free ions

However, in aqueous solutions the extent of hydration affects the mobility of
the ion, which in turn affects the conductivity. Heavily hydrated ions show low
conductance values due to larger size.
Electrochemistry 2.9

Example: In aqueous solutions Li+ ion with high charge density is heavily
hydrated than Cs+ ion with low charge density. Hence hydrated Li+ bigger than
hydrated Cs+. As a result, lithium salts show lower conductivities compared to those
of cesium salts in water. The ionic mobility is reduced in more viscous solvents.
Hence, the conductivity decreases.

Fig. 2.7. Size and mobility of hydrated ions

(iv) Temperature
The conductance of an electrolyte solution increases with increase in the
temperature due to increase in the extent of ionization. Increasing the temperature of
an electrolyte solution always increases the conductivity. The increase is significant,
between 2-3 % per °C. With rise in temperature viscosity of the solvent decreases
which makes ions to move freely to the electrode.
2.6. CONDUCTOMETRIC TITRATIONS
Conductometric titrations are a type of titration where the conductance
(or conductivity) of the solution is measured as a function of the volume of titrant
added.
PRINCIPLE
Conductometric titration is based on the fact that the conductance of a solution
at a constant temperature depends on the i) number of ions present in the solution ii)
charge on the ions iii) mobility of ions.
During the titration, one type of ions are replaced by the another kind of ions
which differ in their mobilities. At the equivalence point, there is a sharp change in
2.10 Engineering Chemistry
the conductance. The equivalence point can be located graphically by plotting the
changes of conductance as a function of the volume of the added titrant.
PROCEDURE
A known volume of one of the reactant solutions is pipetted out into a beaker.
Conductivity cell is dipped in this beaker and initial conductance is noted after
stirring. Now, equal volumes of titrant (say 0.5 mL or 1 mL) is added to beaker,
stirred well and conductance of the solution is measured after every addition of the
titrant.

Fig. 2.8. Conductometric titration set up

Advantages:
 Conductometric titration is simple and has wide selectivity.
 Precise results with minimal errors
 The conductometric titration is also suitable for weak acids and more dilute
solutions.
 Conductometric titration can be used to find out the endpoint of some samples
such as coloured or turbid solutions
 The temperature remains constant throughout the process.
Disadvantages:
 It is not possible to measure samples with high concentrations.
 Changes in salt levels can increase the conductivity of the solution.
 Only a limited number of redox titrations can be performed.
Electrochemistry 2.11

DID YOU KNOW?

H+ and OH- ions indeed have unusually high mobilities in aqueous solutions
(water) compared to other ions.
For H+ ions:
Proton hopping: This hydronium ion can then transfer its proton very quickly
to another water molecule due to the unique hydrogen bonding network in
water. The proton essentially jumps between water molecules, effectively
moving the H+ very fast.

Fig. 2.9. H+ migration in water

For OH- ions:
OH⁻ ions can form when water dissociates into H⁺ and OH⁻. The hydroxide ion
can then accept a proton from a neighbouring water molecule, creating a new
OH⁻ ion and leaving behind a proton vacancy. This effectively allows the OH⁻
ion to move through the solution.

Fig. 2.10. OH- migration in water

2.12 Engineering Chemistry
1. STRONG ACID WITH A STRONG BASE
Let us consider a titration between strong acid (HCl) and strong base (NaOH).
Here, a definite amount of HCl is pipetted into the beaker and conductivity cell is
inserted. Initially high conductance is observed due to the complete ionization of
strong acid (HCl) and high mobility of hydrogen ions. When the strong base (NaOH)
is added as titrant, the conductance decreases due to the replacement of H+ ions by the
added Na+ ions and replaced H+ ions react with OH- ions to form undissociated water.
This decrease in the conductance given by line AB. The decrease continues till the
equivalence point O is reached. After the equivalence point, addition of NaOH is
continued, and the conductance increases due to the high conductivity of OH- ions
given by line CD.
H+ + Cl - + Na+ + OH - → Na+ + Cl- + H2O

Fig. 2.11. Strong acid Vs Strong base – Conductometric graph

Electrochemistry 2.13

2. MIXTURE OF A STRONG ACID (HNO3) AND A WEAK ACID

(CH3COOH) Vs STRONG BASE
In this type of titration, a mixture of strong acid and weak acid is pipetted out into
the beaker. Conductivity cell is dipped, and conductance is measured. Now strong
base is added from the burette as small aliquots (say 0.5 mL), stirred and conductance
is noted. In the mixture, first strong acid reacts, after complete reaction of strong
acid, weak acid begins to react. So, initial curve is similar to strong acid Vs strong
base titration. First conductance decreases and reaches a minimum. The first break
point (x) corresponds to the neutralization of strong acid.
Once equivalence point for strong acid is reached, conductance increases
slowly. The second break point (y) corresponds to the neutralization of weak acid and
after that the conductance increases due to the excess of OH- ions in the case of a
strong base as the titrant.
H+ + Cl - + Na+ + OH - → Na+ + Cl- + H2O
CH3COO-+ H+ + Na+ + OH - → CH3COO- +Na+ + H2O

Fig. 2.12. Strong base Vs Strong acid+ Weak acid mixture – Conductometric
graph
2.14 Engineering Chemistry

ACTIVITY:
Draw the conductance vs volume curve for
(i) Strong acid Vs Weak base (ii) Weak acid Vs Strong base (iii) Weak acid
Vs Weak base

CHECK YOUR UNDERSTANDING:

Consider conductometric titration between Na2SO4 (burette) and BaCl2.
Precipitate BaSO4 is formed during the process. Predict the nature of the
conductometric titration curve.

2.7. ELECTROCHEMICAL GLOSSARY

Oxidation describes the loss of electrons.
Zn(s)  Zn2+(aq) + 2 e-
Reduction describes the gain of electrons
Cu2+(aq)+ 2 e- Cu (s)
Current is defined as flow of electricity which results from the ordered
directional movement of electrically charged particles called electrons or ions.
Electrode is a material which allows the electrons to pass through. It is used
in the form of rod / bar / foil.
Anode is the metal at which oxidation takes place. It is the electrode through
which electrons leave the cell. It has a negative sign in electrochemical cell and
positive sign in electrolytic cell.
Cathode is the metal at which reduction takes place. It is the electrode
through which electrons enter the cell. It has a positive sign in electrochemical cell
and negative sign in electrolytic cell.
Half-cell is a part of the cell containing electrode immersed in an electrolytic
solution. If oxidation occurs at the electrode it is called oxidation half cell (anode
Electrochemistry 2.15

compartment) and if reduction occurs it is called reduction half cell(cathode

compartment).
Redox reaction is the process in which oxidation and reduction occurs
simultaneously. Oxidation-reduction reactions involve the transfer of electrons
between substances. The gain of electrons is called reduction and the loss of electrons
is called oxidation. The substance which loses electron is said to have undergone
oxidation while the one which gains electron is said to have undergone reduction.
Single Electrode Potential (E)
The measure of tendency of an electrode to lose or gain electrons when it is
contact with a solution of its own ion is called single electrode potential.
Standard Electrode Potential (Eo)
The measure of the tendency of the electrode to lose or gain electrons when it
is dipped in its own salt solution of unit concentration (1M), at 25oC and 1atm is
called standard single electrode potential.
Oxidation potential (Eox)
The measure of tendency of an electrode to lose electrons when it is contact
with a solution of its own ion is called oxidation potential.
Standard oxidation Potential (Eoox)
The measure of the tendency of the electrodes loose electrons when it is
dipped in its own salt solution of unit concentration (1M), at 25oC and 1atm is called
standard oxidation potential.
Reduction potential (Ered)
The measure of tendency of an electrode to gain electrons when it is contact
with a solution of its own ion is called reduction potential.
Standard reduction Potential (Eored)
The measure of the tendency of the electrode to gain electrons when it is
dipped in its own salt solution of unit concentration (1M), at 25oC and 1atm is called
standard reduction potential.
2.16 Engineering Chemistry
Nernst equation for a single electrode
For the reaction, M n+ (aq) + ne-  M (s) Nernst equation is given by

Ered = Eored + 0.0591 log [M n+]

n
Nernst equation for a cell
Nernst equation for a cell is given by
Ecell= Eocell + 0.0591 log [R]
n [P]

2.8. TYPES OF ELECTRODES

Depending on the species involved in electron transfer reactions at the metal-
electrolyte interface, the following types of electrodes are known
i) Metal-metal ion electrode
This process takes place within the very thin interfacial region at the electrode
surface. It consists of a metal rod in contact with a solution of its own ion or ions
(cations), with which the electrode is reversible. The potential of this electrode
depends on the concentration of the metal ions in the solution and the temperature.
Electrode representation (M/Mn+) Electrode reaction
i) Zn(s) | Zn2+(aq) Zn → Zn2+ + 2e-
ii) Cu(s) |Cu2+(aq) Cu → Cu2+ + 2e-
ii) Redox or Ion-ion electrodes
Many electrode reactions involve only ionic species, such as Fe2+ and Fe3. This type
of electrodes consists of an inert metal like platinum in contact with an aqueous
solution of the salt of an element in different oxidation state. The potential of this
electrode depends on the concentration of the activities of the metal into in different
oxidation state.
Electrode representation Electrode reaction
Fe3+aq| Fe2+ aq |Pt Fe3+(aq) + e- → Fe2+(aq)
Electrochemistry 2.17

iii) Insoluble–salt or Metal- Metal sparingly salt electrodes

This type of electrode consists of a metal in contact with one of the sparingly soluble
salts and a solution containing a negative ion of the salt. The electrode involves a
reversible reaction between the metal and the negative ion to form sparingly soluble
salt with the liberation of electrons. A typical electrode of this kind consists of a silver
wire covered with a thin coating of silver chloride, which is insoluble in water. The
electrode reaction consists in the oxidation and reduction of the silver.
Example: SCE and silver electrode
Electrode representation (M|MX||X-) Electrode reaction
Ag(s) | AgCl(s)| KCl AgCl(s) + e- → Ag(s) + Cl-
Hg |Hg2Cl2(s)| KCl aq Hg2Cl2(s) + 2e- → 2Hg(l) + 2Cl-
iv) Gas electrode:
It consists of a gas bubbled around an inert metal like platinized platinum
dipped in a solution containing ions to which the gas is reversible. The gas gets
adsorbed on the inert metal and an equilibrium is established between the gas and its
own ions in the solution. The potential of the gas electrode depends on the pressure of
the gas, the concentration of the solution and the pressure
Examples: Hydrogen gas electrode (SHE), Oxygen gas electrode, Chlorine gas
electrode
Electrode representation Electrode reaction
+
H │ H2(g) (1atm)│Pt H + + e- → ½ H2(g)
Cl- │ Cl2(g)(1atm)│Pt ½ Cl2(g) + e- → Cl-

2.9. ION-SELECTIVE ELECTRODES

An Ion selective electrode (ISE) is an indicator electrode that responds
(produces a potential) when it is placed in a solution containing a certain ion. It
responds to only one species of ions ignoring all other ions present in the solution.
Potential developed at ion selective sensor is a measure of the concentration of the
2.18 Engineering Chemistry
ionic species of interest. Now a large variety of ion-selective electrodes are available
commercially which selectively respond to particular cations and anions, and certain
gases. Most widely used among ion selective electrodes are pH electrodes.
The main features of ISE are
 Selectivity
 Accuracy
 Fast Response
 Reproducibility of data.
 Long Lifetime
Construction:
The three main components of making a measurement at an ISE are
• an inner reference, or standard solution
• an outer analyte, or sample,
• solution separated by a thin membrane.
The potential developed at the membrane is the result of either an ion exchange
process or an ion transport process occurring at each interface between the membrane
and solution.
2.10. GLASS ELECTRODE
Construction of glass electrode:
1. Glass Membrane:
The core component of a glass electrode is a thin-walled glass bulb made of a
special type of glass that is sensitive to hydrogen ions (H+). Special glass of low
melting point and high electrical conductance is used for the purpose.
2. Internal Solution:
Inside the glass bulb, there is an internal solution of known and constant pH,
typically a dilute hydrochloric acid (HCl) solution. This internal solution ensures a
constant internal potential.
Electrochemistry 2.19

3. Internal Electrode:
An internal reference electrode, usually a silver/silver chloride (Ag/AgCl)
electrode, is immersed in the internal solution. The purpose of this electrode is to
maintain a stable reference potential.
4. External Electrode and Junction:
The glass electrode is usually paired with a reference electrode (Ag/AgCl
electrode) that is placed in the solution being tested. This reference electrode
provides a stable reference potential.

Fig. 2.13. Measurement of pH using glass electrode

Principle
When a glass surface is kept in contact with a solution, a potential is
established between the glass and the solution. The value of the potential is a function
of H+ ion concentration of solution and the nature of the glass electrode.
The magnitude of the potential difference at 25 C is given by
0
Eg = E - 0.0591 pH
g
0
E determined using solution of known pH
g
2.20 Engineering Chemistry
When glass electrode is dipped into an analyte solution, there is a change in
composition of the glass membrane due to ion exchange process involving solution
and the membrane.
[H+] + Na+Gl- → Na+ + H+Gl-
(membrane) (membrane)

A corresponding change in membrane potential, proportional to pH is measured. All

other potentials are constant. In short, the membrane potential (variable) is measured
against two standard external and internal Ag/AgCl reference electrodes.
2.11. ACID-BASE TITRATION-DETERMINATION OF pH
During a chemical reaction, if a change in the concentration of anion (H+ in
case of neutralization) causes a change in potential of a suitable electrode, then the
progress of the reaction can be monitored by change in potential of electrodes. For an
acid-base titration, hydrogen electrode or a pH-sensitive glass electrode may be used
as the indicator electrode.
 Reference electrode: Saturated Calomel Electrode (SCE)
 Indicator electrode : Glass electrode
Combined glass electrode which is commercially available has the combination of
these two electrodes.
Cell representation is
Pt, H2 (1 atm), H+ (unknown concentration C) II KCl solution, Hg2Cl2(s), Hg
Emf is measured by potentiometer which is connected to both electrodes while base is
added slowly from the burette.
Ecell = Ecathode – Eanode
= ESCE –E glass
= 0.2422 – (E0G - 0.0591 log [H+])
Ecell = 0.2422 + 0.0591 pH
pH = Ecell – 0.2422 + E0G
0.0591V
By knowing emf of the cell, we can find the pH of the solution.
Electrochemistry 2.21

Procedure
Pipette solution: unknown acid solution
Burette solution: standard base
Base is slowly added from burette. During the addition of base from the
burette concentration of H+ keeps on decreasing (pH increasing). From the earlier
equation, it is clear that Ecell increases with pH. A graph is plotted with electrode
potential against volume of base added. The curve is steep near endpoint. More
accurate end point can be determined by plotting pH/V Vs volume of base.

Fig. 2.14. pH metry titration curves

Advantages of glass electrode
 It is very easy to construct and simple to operate.
 The potential developed remains constant for long time.
 It can be used with very small amount of the test solution.
 It can be used even in the presence of oxidizing impurities, reducing impurities
etc.
 Results are accurate.
 Equilibrium is easily achieved.
2.22 Engineering Chemistry
Limitations of glass electrode
 Very fragile and to be used with care
 Can measure pH 0-10 only
2.12. POTENTIOMETRY
Potentiometry is an electroanalytical technique in which amount of the
substance in solution is determined by placing two electrodes in a test solution. A
potential difference is set up between two electrodes by the addition of the titrant.
Since this is an equilibrium measurement, therefore, the Nernst equation is applicable.
A potentiometer is used to measure the emf of the cell and emf is measured no
current passes through the circuit under equilibrium condition (i.e.), when neither the
current is drawn from the cell nor it passes through the cell.
Applications of potentiometry
 Determination of concentration of analyte (redox active species)
 Determination of concentration of H+ (pH)
 Determination of concentration of one particular ion in presence of other ions
Principle
Potentiometric measurement system consists of two electrodes called
reference electrode and indicator electrode, potentiometer and a solution of analyte.
 Reference electrode is an electrode whose potential is accurately known and
constant. Its potential does not change to whichever solution it is dipped. It should
maintain a constant potential on passing small current and follows Nernst
equation. Most widely used reference electrodes are Saturated Calomel Electrode
(SCE) and Ag-AgCl electrode.
 Indicator electrode is an electrode whose potential depends upon the
concentration of the analyte ions. Ideally it must respond to changes in
concentration of an analyte or group of analytes rapidly and reproducibly. During
the course of the titration, the electrode potential of indicator electrode changes
with the concentration of active ion in the analyte according to Nernst equation. A
Electrochemistry 2.23

digital potentiometer is used to measure the potential difference between indicator

and reference electrodes.
Ecell= Eindicator − Ereference

Fig. 2.15. Potentiometry electrodes

Potentiometric titrations can be used for redox titrations, acid-base titrations,
precipitation titrations etc.
Redox titration
Any redox reaction (reduction- oxidation reaction) can be studied using a
potentiometer. The most common system is the ferrous- ferric system. Ferrous ion can
be oxidized to Ferric ion by an oxidizing agent viz., KMnO4, K2Cr2O7 etc. The
reaction can be represented as
2KMnO4+10FeSO4+8H2SO4  2MnSO4 + 5Fe2(SO4)3 + 8H2O+ K2SO4
K2Cr2O7 + 7H2SO4 + 6FeSO4 Cr2(SO4)3 + 3Fe2(SO4)3 +7H2O + K2SO4
 Reference electrode: Saturated Calomel Electrode (SCE)
 Indicator electrode: Pt
Oxidation of Fe2+ to Fe3+ happens in the test solution and indicator electrode measures
the change in potential The cell is represented as SCE // Pt / Fe2+ - Fe3+
Since the potential of the reference SCE remains fixed throughout the
experiment, the variation of potential of the indicator electrode for a particular redox
system could be described as,
2.24 Engineering Chemistry

For this system,

On reaching the end point, entire Fe2+ is converted to Fe3+, thus the
denominator term decreases drastically, the potential increases drastically which is
observed as a jump.
Procedure
Pipette solution : Ferrous salt solution
Additional solution: dil.H2SO4
Burette solution : standard KMnO4 or K2Cr2O7

Fig. 2.16. Potentiometry set up

20 ml Fe2+ salt solution is pipetted out into a beaker. Equal volume of
dil.H2SO4 is added and a working Pt electrode and a reference calomel electrode are
Electrochemistry 2.25

placed into it in such a way that the Pt foil is completely immersed. The other end of
the electrodes is connected to appropriate terminals of the potentiometer (Pt electrode
to +ve terminal). Solution is stirred uniformly by a magnetic stirrer bit. The emf of the
made up solution is measured before adding oxidizing agent. Oxidizing agent is
added from a burette, aliquots of 1ml at a time. The solution is stirred and emf is
noted. The titration is carried out till the end point is reached which is indicated by a
sudden increase in the emf. Titration is continued for another 4-5 ml after the sudden
rise. First graph is plotted volume of oxidizing agent vs emf. Second graph is drawn
with volume of oxidizing agent vs. E/V. Volume corresponding to the peak of
the second graph gives the end point.

Fig. 2.17. Potentiometry curves

Advantages of potentiometric titrations
 Even coloured solutions can be used.
 Accurate and fast results.
 Can be conducted even in microscale.
2.26 Engineering Chemistry

2.13. GREEN HYDROGEN

Green hydrogen refers to hydrogen produced through the process of electrolysis
using renewable energy sources, which results in no greenhouse gas emissions. It is a
key component in the transition to a sustainable and low-carbon energy system.
Methods of Producing Green Hydrogen
Green hydrogen is produced exclusively through electrolysis, a process that splits
water into hydrogen and oxygen using electricity. However, the source of electricity
is what differentiates green hydrogen from other types.
Electrolysis Powered by Renewable Energy
The core principle of green hydrogen production is the use of renewable energy
sources to power the electrolysis process. Here are the primary methods:
1. Electrolysis with Solar Power:
o Solar panels generate electricity from sunlight. This electricity is then used to
power the electrolyzer, splitting water into hydrogen and oxygen.

Fig. 2.18. Solar green hydrogen production

Electrochemistry 2.27

2. Electrolysis with Wind Power:

o Wind turbines convert wind energy into electricity. This electricity is fed into
the electrolyzer to produce hydrogen.

Fig. 2.19. Wind green hydrogen production

3. Electrolysis with Hydropower:
o Hydropower plants harness the energy of flowing water to generate
electricity. This electricity is used for electrolysis.
Applications of Green Hydrogen as energy source
1. Transportation:
 Hydrogen Fuel Cell Vehicles (FCVs): Companies like Toyota, Honda, and
Hyundai have developed hydrogen fuel cell vehicles (e.g., Toyota Mirai, Honda
Clarity, Hyundai Nexo) that emit only water vapor. These vehicles are being
used in various regions with growing hydrogen infrastructure, like California,
Japan, and parts of Europe.
 Buses and Trucks: Green hydrogen is being used in public transport. For
instance, the European Clean Hydrogen Alliance has been promoting
hydrogen-powered buses across the EU. Similarly, companies like Nikola
Motors are developing hydrogen-powered trucks.
2.28 Engineering Chemistry
2. Industrial Applications:
 Steel Production: Companies like SSAB in Sweden are using green hydrogen
in a project called HYBRIT to replace coal in steel production, aiming to
produce fossil-free steel.
 Chemical Industry: Green hydrogen is used to produce ammonia for
fertilizers through a cleaner process. Projects like Yara in Norway are
developing green ammonia plants using renewable energy sources.
3. Energy Storage and Grid Balancing:
 Power-to-Gas: Green hydrogen can be produced from surplus renewable
electricity (from wind or solar) and stored for later use. For example,
Germany's "Energiepark Mainz" uses excess wind power to produce hydrogen,
which can be injected into the natural gas grid or used as fuel.
 Hydrogen-Powered Backup Generators: Data centers and remote facilities
are exploring hydrogen fuel cells as backup power sources. For instance,
Microsoft has experimented with hydrogen fuel cells as a backup power option
for its data centers.
4. Maritime Applications:
 Hydrogen-Powered Ships: The shipping industry is exploring green hydrogen
as a fuel alternative to reduce emissions. Projects like the “HySeas III” in
Scotland aim to develop the world's first sea-going vehicle and passenger ferry
powered by hydrogen fuel cells.
5. Residential Heating:
 Hydrogen Blending in Natural Gas Grids: Some countries are testing the
blending of green hydrogen into existing natural gas grids to reduce carbon
emissions from residential heating. The UK has projects like the HyDeploy
project, which blends hydrogen into the natural gas supply for homes.
Electrochemistry 2.29

DID YOU KNOW?

Fig. 2.20. Schematics of green hydrogen mission

Indian government took major initiative on the production of green hydrogen to
the capacity of 5 million metric tons per annum by 2030, thanks to its favorable
geographic location with the abundance of sunlight and wind energy. The mission
leads to the reduction to the worth of 1 lakh crore of the fossil fuel imports and an
abatement of annual greenhouse gas emissions (~ 50 MT).

Advantages of Green Hydrogen

 Zero Emissions: Produces no greenhouse gases during production if renewable
energy is used, making it a clean energy source.
 Energy Storage: Acts as a means to store excess renewable energy for use
when renewable sources are not available.
 Versatility: Can be used across various sectors, including transportation,
industry, and power generation.
 Energy Carrier: Can transport energy over long distances, useful for regions
rich in renewable resources but far from demand centres.
Challenges
1. Cost: Currently more expensive than hydrogen produced from fossil fuels (grey
or blue hydrogen).
2. Infrastructure: Requires development of production, storage, transportation, and
distribution infrastructure.
2.30 Engineering Chemistry
3. Efficiency: Overall efficiency of production, storage, and conversion processes
needs improvement.
4. Materials: Dependence on expensive and rare materials for certain electrolysis
technologies.
2.14. ENERGY STORAGE SYSTEMS FOR ELECTRIC VEHICLES
Energy storage systems are critical for the performance, range, and overall
viability of electric vehicles (EVs). Here’s an overview of the primary types of energy
storage systems and key considerations:
Types of Energy Storage Systems
1. Hydrogen Fuel Cells
 Description: Convert hydrogen gas into electricity through a chemical reaction
with oxygen.
 Advantages: High energy density, fast refuelling, and no direct emissions (only
water vapor).
 Limitations: Infrastructure challenges, high production and storage costs for
hydrogen, and lower efficiency compared to battery-electric systems.
2. Lithium-Ion Batteries:
 Description: The most widely used battery type in EVs due to its high energy
density and long cycle life.
 Advantages: High efficiency, good power-to-weight ratio, relatively fast
charging, and decreasing costs.
 Limitations: Safety concerns such as thermal runaway, environmental impact
of mining lithium and cobalt, and recycling challenges.
3. Sodium-Ion Batteries
 Description: Sodium-ion (Na-ion) batteries are an emerging alternative to
lithium-ion batteries, operating similarly but using sodium-ions as charge
carriers. They are gaining attention due to the abundance and low cost of
sodium.
Electrochemistry 2.31

 Advantages: Use of abundant and inexpensive materials, lower environmental

impact compared to lithium-ion batteries, improved safety with a lower risk of
thermal runaway, and potential for lower overall costs.
 Limitations: Currently lower energy density than lithium-ion batteries,
resulting in shorter driving ranges for EVs, technology is less mature with
ongoing research needed to improve performance and cycle life, and potentially
heavier batteries due to the larger size of sodium-ions.
Features:
1. Energy Density: Determines the driving range of the EV. Higher energy density
means longer range.
2. Power Density: Affects the vehicle's acceleration and the ability to handle
regenerative braking.
3. Cycle Life: The number of charge and discharge cycles a battery can undergo
before significant degradation. Longer cycle life means longer battery lifespan.
4. Charging Time: The time required to recharge the battery. Faster charging is
crucial for the convenience and adoption of EVs.
5. Safety: Concerns such as the risk of thermal runaway, fire, or explosion. Safety
features and stable chemistries are essential.
6. Cost: Includes manufacturing, raw materials, and recycling. Reducing costs is
critical for making EVs affordable.
7. Environmental Impact: The impact of raw material extraction, battery
manufacturing, and disposal. Sustainable practices and recycling are increasingly
important.
2.15. FUEL CELLS
Fuel cells are electrochemical cells in which chemical energy present in
the fuel is converted into electrical energy without burning. Fuel is oxidized at the
anode by electrochemical process.
Fuel + oxygen  Oxidized products + electricity
2.32 Engineering Chemistry
Like any other electrochemical cell, the fuel cell has two electrodes and
electrolyte. Fuel and oxidant are continuously and separately supplied to the two
electrodes of the fuel cell, where they undergo reactions. Fuel cell can supply current
as long as they are supplied with reactants.
A fuel cell essentially consists of the following arrangement.
Fuel/electrode//electrolyte/electrode oxidant
At anode electrochemical oxidation of the fuel happens
Fuel  Oxidant product + ne-
At cathode, the oxidant gets reduced
Oxidant + ne-  Reduction products
The electrons produced by the oxidation process at anode can perform useful
work when they pass through the external circuit to the cathode.
HYDROGEN-OXYGEN FUEL CELL
Hydrogen-oxygen fuel cell is the simplest type of fuel cell in which hydrogen gas is
used as the fuel and oxygen gas as oxidant. A schematic diagram of H2-O2 fuel cell is
shown in the figure below.

Fig. 2.21. H2-O2 fuel cell

Electrochemistry 2.33

Construction:
The cell consists of a porous carbon (graphite) electrodes (both anode and cathode)
impregnated with catalysts such as finely divided platinum or palladium. Electrolyte
is an aqueous solution of KOH (25-30%).
Working:
Hydrogen fuel is continuously supplied at anode and oxygen gas is supplied at the
cathode. As hydrogen gas diffuses through the anode, it is adsorbed on the electrode
surface, gets oxidized to H+ ions. It reacts with hydroxyl ions to form water. The
electrons produced moves through the external circuit, reaches cathode where oxygen
gas is passed. The adsorbed oxygen gas is reduced to hydroxyl ions. Thus, electrolyte
is regenerated.
The electrode reactions are summarized as below:
Anode:
2H2 → 4H++ 4e-
4H++ 4OH- → 4 H2O
------------------------------------
2H2 + 4 OH- → 4 H2O + 4e-

Cathode:
O2 + 4e- → 2 O2-
2O2- + 2 H2O → 4 OH-
-----------------------------------
O2 + 2 H2O +4e- → 4 OH-
Overall reaction:
2H2 + O2 → 2 H2O
A typical fuel cell produces a voltage from 0.6 V to 0.7 V
2.34 Engineering Chemistry
Advantages of fuel cell:
 High efficiency (50-80% efficiency)
 Pollution free
 High power density
 Quiet operation
 No moving parts, so elimination of wear and tear
Disadvantages of fuel cell:
 Fuel cells were large and extremely expensive to manufacture
 Energy cannot be stored
 Power output is moderate
 Fuels in the form of gases and oxygen need to be stored
in tanks under high pressure.

2.16. LITHIUM-ION BATTERIES

Lithium-ion batteries are a type of rechargeable battery powering everything
from smartphones and laptops to electric vehicles and grid-scale energy storage
systems. Their high energy density, long lifespan, and lightweight design have made
them the preferred choice for a vast array of applications.
How Do They Work?
A lithium-ion battery consists of several components:
 Anode: Typically made of graphite, it stores lithium-ions during charging.
 Cathode: Composed of materials like lithium cobalt oxide or lithium iron
phosphate, it receives lithium-ions during charging.
 Separator: A porous membrane that prevents the anode and cathode from
touching but allows lithium-ions to pass through.
 Electrolyte: A liquid or gel-like substance that conducts ions between the anode
and cathode.
Electrochemistry 2.35

Fig. 2.22. Lithium ion battery

 Charging: LiCoO2+C6→LiC6+CoO2 During charging, lithium-ions move from
the cathode (LiCoO₂) to the anode (graphite,C6) through the electrolyte, while
electrons flow through the external circuit to balance the charge.
 Discharging: : LiC6+CoO2→C6+LiCoO2 During discharging, lithium-ions move
back from the anode to the cathode, releasing energy that can be used to power
electronic devices.
Advantages
 High Energy Density: Lithium-ion batteries can store a large amount of energy
in a compact and lightweight package, making them ideal for portable
applications.
 Long Cycle Life: They can be recharged many times without significant loss of
capacity, providing a long operational lifespan.
2.36 Engineering Chemistry

 Low Self-Discharge: Lithium-ion batteries have a low rate of self-discharge

compared to other rechargeable batteries, retaining their charge for longer
periods.
 Fast Charging: Advanced lithium-ion batteries support rapid charging,
reducing downtime for users.
Applications
 Consumer Electronics: Widely used in smartphones, laptops, tablets, and
wearable devices due to their high energy density and compact size.
 Electric Vehicles (EVs): Powering electric cars, buses, and bikes, contributing
to the reduction of greenhouse gas emissions and reliance on fossil fuels.
 Grid Energy Storage: Used for storing renewable energy from sources like
solar and wind, helping to stabilize the grid and provide backup power.
 Portable Power Tools: Providing reliable and powerful energy for cordless
tools, enhancing mobility and convenience.

2.17. SODIUM-ION BATTERIES

Sodium-ion batteries are emerging as a promising alternative to lithium-ion
batteries, particularly for large-scale energy storage applications. Utilizing sodium, a
more abundant and less expensive element than lithium, these batteries have the
potential to offer sustainable and cost-effective energy storage solutions.
Components of a Sodium-Ion Battery
1. Anode: Often made of hard carbon or other sodium-intercalation materials.
2. Cathode: Typically composed of sodium metal oxides, such as sodium cobalt
oxide (NaCoO2).
3. Electrolyte: A sodium salt dissolved in an organic solvent, facilitating the
movement of sodium-ions between the anode and cathode.
4. Separator: A porous membrane that prevents direct contact between the anode
and cathode while allowing sodium-ions to pass through.
Electrochemistry 2.37

Fig. 2.23. Sodium ion battery

Working Principle
Sodium-ion batteries operate similarly to lithium-ion batteries, with sodium-ions
moving between the anode and cathode through an electrolyte during charge and
discharge cycles.
1. Charging: Nax+yMO2+C→NaxC+NayMO2 During charging, sodium-ions are
extracted from the cathode (typically a sodium metal oxide, NaMO₂) and
intercalated into the anode (such as hard carbon, C) through the electrolyte.
2. Discharging: NaxC+NayMO2→C+ Nax+yMO2During discharging, sodium-ions
move back from the anode to the cathode, releasing energy that can be used to
power devices.
2.38 Engineering Chemistry

DID YOU KNOW?

Fig.2.24. Schematics depicting intercalation mechanism in graphite anode

Graphite, which is the state-of-art anode material for lithium-ion batteries renders very
low capacity, when used as a sodium-ion battery anode. Relatively larger ionic size of
sodium-ion (~0.102 nm) in comparison to lithium-ion (0.076 nm) and lower interlayer
spacing of graphite (~0.335 nm) is responsible for the insufficient sodium-ion storage in
graphite anodes.

Advantages
 Abundance of Sodium: Sodium is much more abundant and widely distributed
than lithium, reducing concerns about resource scarcity and cost.
 Cost-Effective: The raw materials for sodium-ion batteries are cheaper,
potentially lowering the overall cost of battery production.
 Environmental Impact: Sodium-ion batteries can offer a more
environmentally friendly alternative due to the reduced need for mining and
processing of scarce elements.
 Scalability: Suitable for large-scale applications, such as grid energy storage,
due to their potential cost advantages and material availability.
Applications
 Grid Energy Storage: Ideal for storing renewable energy from sources like
solar and wind, helping to stabilize the grid and provide backup power.
 Consumer Electronics: While not as energy-dense as lithium-ion batteries,
sodium-ion batteries can still be used in various electronic devices where lower
energy density is acceptable.
Electrochemistry 2.39

 Electric Vehicles (EVs): Research is ongoing to make sodium-ion batteries a

viable option for electric vehicles, focusing on improving energy density and
cycle life.
 Industrial and Commercial Energy Storage: Used in large-scale storage
systems for industries and commercial operations to manage energy
consumption and reduce costs.
Comparison Table: Lithium-Ion vs. Sodium-Ion Batteries

Aspect Lithium-Ion Batteries Sodium-Ion Batteries

Materials: Sodium, carbon

Materials: Lithium, cobalt,
(hard carbon), metal oxides
nickel, manganese, graphite
(e.g., sodium cobalt oxide)
Material Abundance: Scarcer,
Abundance: Abundant,
Abundance concentrated in specific
widely distributed, easily
and Cost regions
obtainable
Cost: Higher due to scarcity
Cost: Lower due to abundance
and extraction complexity
and ease of extraction

Energy High Energy Density: 150- Lower Energy Density: 100-

Density 250 Wh/kg 150 Wh/kg

Long Cycle Life: Hundreds Developing Cycle Life:

Cycle Life to thousands of cycles Shorter than lithium-ion, but
depending on usage improving

Safety Concerns: Risk of Enhanced Safety: Lower risk

Safety thermal runaway, of thermal runaway, less
overheating, fire/explosion flammable
2.40 Engineering Chemistry

Aspect Lithium-Ion Batteries Sodium-Ion Batteries

Concerns: Significant Lower Impact: Less

environmental and social environmental damage,
Environmental
impacts from mining. abundant materials
Impact
Recycling: Complex, not Recycling: Easier and less
widely practiced yet costly

Large-Scale Storage: Ideal

for grid energy storage, cost-
Versatile Applications:
sensitive applications
Applications Consumer electronics, EVs,
Emerging Applications:
grid storage
Potential in consumer
electronics, industrial uses

PROBLEMS ON CONDUCTANCE

1. A conductivity cell has two platinum electrodes separated by a distance 1.5 cm

and the cross-sectional area of each electrode is 4.5 sq cm. Using this cell, the
resistance of 0.5 N electrolytic solution was measured as 15 Ω . Find the specific
conductance of the solution.

Answer:

1 𝑙
 = 𝑅 .𝐴
1 1.5
= 15 . 4.5

= 0.022 S cm-1
Electrochemistry 2.41

2. The molar conductivity of 0.05 M BaCl2 solution at 250C is 223 Ω-1 cm2 mol-1.
What is its conductivity?
Answer:

𝑚 𝐶
= 1000
223 𝑋 0.05
= 1000

= 0.01115 Ω-1 cm-1

3. A conductivity cell containing 0.02% KCl solution offers a resistance of 550

ohms at a definite temperature. The specific conductivity of 0.02 N solution at
that temperature is 0.002768 ohm-1 cm-1. If the cell is now filled with 0.2 N
ZnSO4, the observed resistance of the cell is 72.18 ohm. Calculate the equivalent
and molar conductivities of the ZnSO4 solution.

Answer:

Cell constant = R x 

= 550 x 0.002768 = 1.522 cm-1

 of ZnSO4 = 1/R x cell constant

= 1.522 = 0.0210 ohm-1 cm-1

72.18
e =  x 1000
C
= 0.0210 x 1000 = 105 ohm-1 cm2
0.2
m =  x 1000
M
= 0.0210 x 1000 = 210 ohm-1 cm2
0.1
2.42 Engineering Chemistry
QUESTIONS
1. Define conductance. What is its unit?
2. What is specific conductance?
3. Define equivalent conductance and molar conductance.
4. Describe the effect of dilution on specific conductance and molar conductance.
5. What are factors affecting conductance?
6. Explain the principle of conductometric titrations.
7. Explain the nature of graph for a conductometric titration for
(a) strong acid Vs strong base (b) strong acid + weak acid Vs strong base
8. What is electrode potential? How is it developed?
9. What are ion selective electrodes? Mention its applications
10. Describe the construction and working of combined glass electrode.
11. Explain the principle of potentiometric titrations.
12. Explain how ferrous ion is estimated by potentiometry.
13. Write a note about production of green hydrogen and its applications.
14. Explain the construction, working and applications of lithium-ion batteries.
15. Explain the construction, working and applications of lithium-ion batteries.
Corrosion 3.1

UNIT - 3
CORROSION
Corrosion - Types of corrosion - wet corrosion – mechanism – galvanic corrosion
- differential aeration - Rate of corrosion, Corrosion control – Cathodic protection
- electroless plating (Printed Circuit Board), Corrosion in different industries –
concrete (reinforcing steel in concrete), boilers, electronic components

3.1. INTRODUCTION
Corrosion defined as slow destruction or deterioration of metals/ alloys due to
the chemical interaction with their environment. Corrosion is exactly reverse of
extraction of metals. For example, silver tarnishes, copper develops green coating on
surface, iron rusts etc. The word corrode is derived from the Latin corrodere, which
means “to gnaw to pieces”.

Examples: Rusting of iron (Fe2O3 .n H2O (n = 1-3), green patina (Copper

oxide) on copper sheets, tarnishing of Ag (due to the formation of Ag2S), pitting of
stainless Steel etc.

Almost all metals except less reactive metals such as gold, platinum,
palladium undergo corrosion. Materials that undergo corrosion can be metals and
alloys, polymers (plastics, rubbers, etc.), ceramics (concrete, brick, etc.) or
composites.

Why do metals corrode?

Materials always occur in the lowest energy state. Metals in the combined
state (ores) are more thermodynamically stable than the pure elements. Hence, most
of the metals (except noble metals Au, Pt etc) in the nature are found in the form of
3.2 Engineering Materials
minerals and ores (oxides, sulphides, carbonates, halides, sulphates, etc.), i.e., in the
lower energy state.

On the other hand, pure metal is in higher energy state and tends to go to
lower energy state by reacting with the environmental elements chemically or
electrochemically, i.e., metal undergoes corrosion to obtain thermodynamic stability.

Fig. 3.1. Corrosion and metallurgy

Thus, energy is required for the extraction of metals (ΔG is positive) and
corrosion is reverse of extractive metallurgy (ΔG is negative). Corrosion is a
spontaneous process (Fig 3.1).

Consequences / Effects of corrosion

The process of corrosion is slow and occurs at the surface only, but the losses
incurred are enormous. It leads to destruction of machines, equipment, resulting in
economic and life loss. The following are measurable losses of corrosion

 Plant shut down (due to failure)

 Increase in maintenance cost
 Loss of efficiency
 Contamination or loss of product (from the corroded container)
 Safety (fire due to release of toxic product or collapse of construction)
 Corrosion may contaminate stored food, dairy products etc.
 Corrosion products cause pollution
 Environmental degradation due to both corrosion and methods adopted to control
it.
Corrosion 3.3

It is essential to understand the mechanism and the factors that influence the
rate of corrosion to combat it and minimize the loss incurred due to corrosion. No
engineering design would be complete without consideration for issues related to
corrosion.

DID YOU KNOW?

The Statue of Liberty is green because of corrosion! The outer layer is made of
copper, and over time, it reacted with oxygen, carbon dioxide, and water in the
atmosphere, forming a green patina that actually protects the metal underneath
from further corrosion.

3.2. TYPES OF CORROSION

Based on the environment leading to corrosion and the mechanism of corrosion,

corrosion is classified into two major types

1. Dry or Chemical Corrosion: Corrosion due to interaction of metal with dry

gases like oxygen, hydrogen, chlorine etc in the absence of moisture. This is less
common, and we will not discuss here.
2. Wet or Electrochemical Corrosion: This is the most common form of corrosion,
which happens in the presence of water/moisture/electrolyte. We will discuss in
detail here.
3.3. WET CORROSION
Electrochemical corrosion occurs when two dissimilar metals are in contact with
each other in presence of an aqueous solution or moisture. Among the two metals one
metal acts as a cathode while other acts as an anode. The anodic metal undergoes
oxidation and further corrosion depends on the nature of the corrosion product. If the
corrosion product is insoluble in the corroding medium, it sticks on the surface and
insulates the metal from electrolyte. If the corrosion product is soluble, a fresh surface
of metal comes in contact with the electrolyte.
3.4 Engineering Materials

Conditions for wet corrosion

 Two dissimilar metals or alloys are in contact with each other in the presence of
aqueous solution or moisture.
 Metal is exposed to varying concentration of oxygen or any electrolyte.
 Metal surface is heterogeneous
 Formation of separate anodic and cathodic area/parts between which the current
flow through a conducting medium.
 The anodic reaction is the oxidation at the anodic metal part.
 The cathodic reaction is influenced by the pH of the corroding medium. If the
electrolyte pH is < 7 (Acidic medium) reduction proceeds by evolution of
hydrogen.
 If the electrolyte pH is ≥7 (Neutral medium and / or alkaline medium),
reduction proceeds by absorption of oxygen. Whatever may be the pH of the
medium, product will be the same for a given metal.
 The metallic ions formed at the anodic part and non-metallic ions formed at
the cathodic part diffuse towards each other through the conducting medium
and form a corrosion product. The product gets accumulated somewhere
between the anode and cathode nearer to cathode, as the mobility of cation
will be greater than that of the anion.
Mechanism

At Anode: Corrosion takes place by the dissolution of the metal.

M  M n+ + n e-
At cathode:

1. Acidic Medium: Evolution of Hydrogen

If the corrosive environment is acidic, hydrogen evolution occurs at cathodic part.

H2O + H+  H3O++ 2e-  OH − + H2↑

Corrosion 3.5

Fig. 3.2. Hydrogen evolution

2. Neutral / Alkaline medium: Absorption of oxygen

If the corrosive environment is slightly alkaline or neutral, hydroxide ion forms at

cathode by the absorption of oxygen.
H2O + ½O2 + 2e-  2OH –

Fig. 3.3. Hydrogen evolution

Overall Reaction at both acidic and alkaline pH

M2+ + 2(OH)−  M(OH)2
3.6 Engineering Materials

Wet corrosion mechanism

Anode:
Fe  Fe 2+ + 2e-
Cathode:
1. Acidic Medium: Evolution of Hydrogen
H2O + H+  H3O+
H3O+ + 2 e-  OH − + H2↑
2. Neutral / Alkaline medium : Absorption of Oxygen
H2O + ½O2 + 2e- 2 (OH)−

Overall Reaction: for all pH

OH−
−
2Fe 2+
+ 4(OH)  2 Fe(OH)2  2 Fe (OH)3  Fe2O3.3H2O
Rusting of Iron

3.4. TYPES OF ELECTROCHEMICAL CORROSION

Electrochemical corrosion is classified into two,

a) Galvanic (bimetallic) corrosion and
b) Differential aeration / concentration cell corrosion.
1. Galvanic Corrosion / Bimetallic Corrosion
When two different metals are in contact with each other, in the presence of
an electrolyte or just moisture, the more anodic metal corrodes preferentially. The
corrosion reaction initiated due to the potential gradient is called galvanic corrosion.
The metal which is at higher position in galvanic series (with more negative electrode
potential) acts as anode and undergoes corrosion, while less active metal at lower
position in galvanic series (with less negative electrode potential) acts as cathode. The
greater the potential difference between the two metals greater is the rate of corrosion.
Corrosion 3.7

Example 1: Thermocouple made with Zn and Cu dipped in water or conducting

solution

Fig. 3.4. Galvanic corrosion

(a). In Fe-Cu couple, in which iron (more active) dissolves in preference to copper
(less active) i.e., Fe acts as anode and undergoes corrosion and Cu acts as cathode.
(b). In Zn- Fe couple, zinc (more active or anodic) dissolve in preference to iron (less
active or cathodic) i.e., Zn acts as anode and undergoes corrosion, and Fe acts as
cathode.
3.8 Engineering Materials
Example 2: When a brass name plate is fixed on door with nails made of iron, a tiny
galvanic cell is formed at the area of contact between the iron and brass. The nail is
anodic with respect to brass hence it starts corroding. Rust is visible around the nail
on the brass plate (cathode).
Factors that affect galvanic corrosion:
1. Potential difference between the two metals: Greater the potential difference
between the metals in contact greater (faster) is the corrosion.
2. Conductivity of the medium: Greater the conductivity of the medium, faster the
rate of galvanic corrosion.
3. Surface area of the metals: Corrosion is greater at rough and uneven surfaces. If
the area of contact between the metals is greater, more faster the corrosion.
4. Anode to cathode ratio: Large anode connected to a small cathode result in low
corrosion rate.
Prevention:
Galvanic corrosion can be minimized by
 Using only single metal (eg: bolt and nut of the same metal)
 Selecting metals and alloys that are very close together in the galvanic series.
 Insulating the dissimilar metals whenever possible.
 Using corrosion inhibitors to reduce the aggressiveness of the environment.
 Applying cathodic protection. Install a third metal which is anodic to both metals
in galvanic contact.
2. Differential aeration corrosion / Concentration cell corrosion
Differential aeration corrosion occurs due to the concentration difference in
various parts of the metal. When the metal is exposed to an electrolyte of varying
concentration or exposed to different atmospheric conditions, the part exposed to
lower concentration becomes anodic with respect to the part exposed to higher
concentration. Anodic reaction is independent of pH but cathodic reaction is
dependent on pH.
Corrosion 3.9

Example: A Zn rod partial exposed to salt water (pH =7). The Zn metal above the
water level is in contact with atmospheric oxygen while that under water is in contact
with dissolved oxygen. This difference in the concentration of oxygen leads to the
development of a concentration gradient and corrosion is initiated slowly. The part of
Zn above water acts as cathode while the part immersed in water becomes anodic.
The corrosion product zinc hydroxide is sparingly soluble in water and hence gets
accumulated on the part of the zinc rod which is at the interface of water and air.
Reactions
At anode: Zn Zn2+ + 2e-
At cathode: ½ O2 + 2e- + H2O 2OH-
Net reaction: Zn2+ + ½ O2 + H2O Zn (OH) 2

Fig. 3.5 Differential Aeration Corrosion

Examples for differential aeration corrosion:

a. Pitting corrosion
b. Crevice corrosion
c. Waterline corrosion
d. Corrosion on the wire fence
e. Pipeline/soil corrosion
3.10 Engineering Materials
a. Pitting corrosion
Pitting is a localized attack resulting in the formation of a pit (hole) on the
surface of the metal. Presence of water droplet, sand, dust, scale etc on the surface of
metals can result in intense localized corrosion. Pitting corrosion is usually the result
of the breakdown or cracking of the protective film on a metal at specific points by
various mechanical factors or by chemical attack. Metals or alloys having non porous
protective oxide film at their surface are prone to pitting corrosion when passivity is
destroyed. Examples are aluminum, titanium, stainless steel.

Fig. 3.6. Pitting Corrosion

Consider a drop of water or salt solution on iron surface. The area covered by a
drop of water acts as an anode due to less oxygen concentration and suffers corrosion.
The uncovered area acts as cathode due to high oxygen concentration.

Rate of corrosion will be more, when area of cathode is larger and 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. Thus, corrosion takes place
just under the impurity. This type of intense corrosion is called pitting corrosion.
Pitting corrosion is influenced by pH and temperature of the corrosive medium.

Reactions:
At anode: Fe  Fe 2+ + 2e-
At cathode: ½O2 + H2O + 2e-  2 OH−
Overall reaction:Fe +H2O +½ O2Fe(OH)2
Fe(OH)2will lead to the formation of rust as explained earlier.
Corrosion 3.11

Reasons for pitting corrosion

• Non-homogenous and non-uniform metal surface.
• Non uniform protective film.
• Presence of cavities, sharp bends or corners on the metal surface.
• Corrosive environment is not homogeneous.
Prevention and control
Pitting corrosion can be minimized by
• cleaning the metal surface to prevent the accumulation of dust, water droplets etc.
• avoiding in homogenities both in the metal and in the corrosive environment.
• proper designing of the metal.
• using protective coating on the metal surface.
b. Crevice corrosion
Crevice corrosion is a corrosion occurring in gaps. These spaces are generally
called crevices. The Corrosion resulting due to the presence of a small gap or cleft or
crack on the surface of the metal is called crevice corrosion. If a crevice between
different metallic objects 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
area acts as the cathode. Thus, crevice corrosion is due to the lack of oxygen in the
crevice.
Examples of crevices are gaps and contact areas between parts, bolts ,rivets, under
gaskets or seals, inside cracks and seams, spaces filled with deposits and under sludge
piles.
Reactions:
At anode: Fe  Fe 2+ + 2e-

At cathode: ½O2 + H2O + 2e-  2 OH−

Overall reaction: Fe + H2O + ½ O2  Fe(OH)2

Fe(OH)2 will lead to the formation of rust as explained earlier.

3.12 Engineering Materials
Crevices may be formed due to
• geometry of the surface
• contact of the metal with non-metallic solids eg: plastics, rubber, glass etc.
• deposition of sand, dirt or corrosion products on the metal surface.

Fig. 3.7. Crevice Corrosion

Prevention and control
Crevice corrosion can be minimized by
• maintaining a clean surface
• selection of corrosion resistant materials.
• proper design of the materials.
• using protective coating on the metal surface.
c. Waterline corrosion
This type of corrosion occurs when a metal is partially immersed in water.
Corrosion happens just below the waterline and hence known as waterline corrosion.
The principle is exactly similar to the example described in differential aeration
described earlier. When a metal is partially immersed in 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.

Fig. 3.8. Waterline Corrosion

Corrosion 3.13

Example: When water is stored in a steel or iron tank for long time, corrosion
happens just below the waterline. Waterline corrosion also happens in boilers.

d. Corrosion on the wire fence

The fence wire is usually made up of mild steel. Corrosion on a wire fence
occurs in areas where the wires inter cross with one another. This area seems to be
less aerated and acts as an anode. The rest of the fence acts as a cathode. For reactions
refer wet corrosion.

Fig. 3.9. Corrosion on a wire fence

e. Pipeline/soil corrosion
This type of corrosion occurs at the external surface of the pipes lying under
the ground. Buried pipelines and cables laid for long distances are exposed to
different type of environment. For example at some places they may run under sand
and at some places under clay. The texture and moisture content in these two types of
soil is totally different. Sand is porous and has poor water retention while clay is non
porous (porosity is related to particle size) and has high water retention capacity. For
reactions refer wet corrosion.

Fig. 3.10. Pipelene Corrosion

3.14 Engineering Materials
This creates a difference in the oxygen accessibility of the underground pipe
line. The part of pipe under sand is most oxygenated and the part under clay is least
oxygenated. Hence the pipe line under clay is anodic. In addition to this if the amount
of moisture present in clay is high then corrosion starts and proceeds fast.

GALVANIC SERIES
In galvanic series metals and alloys are arranged according to their tendency
to corrode. In the galvanic series, metals are listed from most noble (least likely to
corrode) to least noble (most likely to corrode). It is more of real and practical series.
This series can be used to determine whether galvanic corrosion is likely to occur and
how strong the corrosion reaction will be. However, the position of a metal or alloy is
not fixed in this series.
Most active (Anodic) Magnesium
Likely to corrode
Zinc
Aluminum
Brass
Copper
Stainless steel 304
Graphite
Titanium
Gold
Least active (Cathodic)
Platinum
Less likely to corrode

Importance of galvanic series

 It provides practical information on the relative corrosion tendencies of different
metals and alloys
 The rate and severity of corrosion depends on the potential difference existing
within the system greater the potential difference. Greater is the rate of corrosion
Corrosion 3.15

3.5. RATE OF CORROSION

The rate of corrosion refers to how quickly a material, typically a metal,
deteriorates due to chemical reactions with its environment. This rate is influenced by
several factors, including:
1. Material Composition: Different metals and alloys have varying resistance to
corrosion. For example, gold doesn’t corrode and iron corrodes. Stainless steel is
also resistant to corrosion.
2. Environmental Conditions: The presence of water, oxygen, salts, acids, or other
corrosive agents can accelerate corrosion. Humid or marine environments tend to
increase corrosion rates.
3. Temperature: Higher temperatures generally increase the rate of corrosion by
accelerating chemical reactions.
4. pH Levels: Acidity or alkalinity of the environment can significantly affect
corrosion rates. Metals tend to corrode faster in acidic environments.
5. Electrochemical Factors: In electrochemical corrosion, the presence of an
electrolyte and the difference in electric potential between different areas of the
metal can lead to corrosion.
6. Mechanical Stress: Stressed areas of a material might corrode faster, especially
in a process known as stress corrosion cracking.
3.6. CORROSION CONTROL
Corrosion is a very undesirable process, which cause the disintegration of metals
and alloys. Corrosion leads to huge loss, plant failure or shutdowns. So, it is necessary
that metals or alloys are protected against corrosion.
Corrosion cannot be prevented but onset can be delayed. As the corrosion is a
reaction between the metal or alloy and the environment, any method of corrosion
control can be minimized by either modifying the metal or the environment. Cathodic
protection is widely used for corrosion control.
3.16 Engineering Materials

Cathodic Protection
Cathodic protection (CP) is an electrochemical technique used to prevent or minimize
corrosion on metal surfaces by converting them into the cathode of an electrochemical
cell. It is widely employed in various industries to protect structures such as pipelines,
ships, offshore platforms, and storage tanks.
In short, the metal to be protected is made to behave like a cathode. This is
done by two methods namely
1. Sacrificial anodic protection
2. Impressed current.

1. SACRIFICIAL ANODIC PROTECTION METHOD

In this method, the metallic structure to be protected is made cathode by

connecting it with more active metal (anodic metal). So that the corrosion will happen
only on the active metal. The artificially made anode thus gradually gets corroded
protecting the original metallic structure. Hence this process is otherwise known as
sacrificial anodic protection. Since a galvanic cell is deliberately constituted, it is
also termed as galvanic protection. The sacrificial anodes must be periodically
inspected and replaced when consumed.

For example corrosion of iron pipes can be prevented by connecting it to Zn

or Mg. Both Zn and Mg are anodic compared to iron so they behave as anode and
undergo oxidation while the iron is unaffected.

It is also used to protect steel rods used in construction of large buildings, hull
of the moving ships, pipes carrying water, underground cables, marine structures,
water tanks etc.
Corrosion 3.17

Fig. 3.11. Sacrificial anodic protection

Advantages of sacrificial anodic protection

 No external power is required.
 No regulation is required.
 Easy to install.
 Minimum or no maintenance.
Disadvantages of sacrificial anodic protection
 Poorly coated structure may require many anodes.
 Periodic replacement is required.
 Installation can be expensive if installed after construction.
2. IMPRESSED CURRENT CATHODIC PROTECTION METHOD (ICCP)
In this method the corrosion current is suppressed by impressing (applying) a
DC current on the base metal. The metal structure to be protected is connected to the
negative terminal of a rectifier. The positive terminal is connected to an inert material
like Graphite / Pt / high iron silica which is immersed in a back fill consisting of a
mixture of Coke breeze / gypsum / graphite and moist sodium chloride. The role of
the back fill is to increase the conductivity of the soil. Coke breeze being a good
absorbent absorbs water from the soil and NaCl dissolves in the water. This method
3.18 Engineering Materials
is adopted to protect stationary structures like transmission line towers, laid up ships,
pipe lines in petrol pumps and huge buildings

Fig. 3.12. Impressed current cathodic protection

Applications of impressed current cathodic protection:
Impressed current cathodic protection is usually used in buried structures such as
tanks and pipelines, transmission line towers, underground water/oil pipe lines
Advantages of impressed current cathodic protection
 Can be designed for wide range of voltage and current.
 No or very less maintenance is required.
 Large areas can be protected by single installation.
 Applicable in high resistivity environments.
 Effective in coating uncoated and poorly coated structures.
Disadvantages of impressed current cathodic protection
 Subject to power failure.
 Require external power, resulting in monthly power costs.
 Overprotection can cause coating damage.
 It may increase the corrosion of adjacent unprotected pipes due to stray current
 The capital investment and maintenance cost of this protection is high.
Corrosion 3.19

Differences between the different methods of cathodic protection

Sacrificial anodic Impressed current

No external power supply is

External power supply is required
required

Requires periodical replacement of Anodes are stable and do not

sacrificial anodic material disintegrate

Investment is low Investment is high

For short term protection it is Method is suitable for large structures

economical and long-term operations

Suitable when the current Suitable when current requirement and

requirements and the resistivity of the resistivity of the electrolytes are
the electrolytes are relatively low. relatively high.

DID YOU KNOW?

The Iron Pillar at Qutb Minar, over 1,600 years old, is renowned for its
exceptional resistance to corrosion, a feat of ancient Indian metallurgy. Despite
being exposed to the rain and sun for centuries, it shows minimal signs of rust, a
phenomenon that has puzzled scientists and metallurgists for years. It is made of
nearly pure wrought iron with a high phosphorus content.
3.20 Engineering Materials

3.7. ELECTRO LESS PLATING

In 1940 Brenner and Riddell used redox reaction to coat one metal over
another without using electricity. The importance of electroless plating is due to its
ability to provide uniform coat at the inner surfaces of pipes, valves, tubes etc.

Electroless plating is a technique of depositing a noble metal from its salt

solution on a catalytically active surface of the metal or nonmetal by using a suitable
reducing agent without using electrical energy. The reducing agent reduces the
metallic ions to metal, which gets deposited over catalytically active surface giving a
uniform coating.

Metal ions + reducing agent  Metal (deposit) + Oxidized products

Pretreatment of the material has to be done before carrying out electroless plating
to ensure that surface is homogeneous. Pretreatment for electroless plating is different
for different substrates. A general scheme for metallic and non-metallic substrate is
given in the flowchart.

General method of pretreatment for Electroless plating

Metallic Non-Metallic
Substrate

Degreasing Degreasing

Acid Cleaning Activation

Washing
Corrosion 3.21

Electroless Nickel Plating (EN)

Electroless Ni plating (EN) is a technique used to deposit a layer of Ni-P alloy

on a solid work piece. It is autocatalytic method i.e. once an initial layer of Ni is
coated, it catalyses the reaction leading to the formation of a thick coating. Electro
less deposit are functional (not decorative). Ni coated substrates have a shiny silver
coloured appearance and are resistant to wear and corrosion. Ni coating is also given
to improve hardness, lubricity and machinability.

EN is more popular commercially due to its low cost, ease of control and
excellent mechanical properties .It is extremely versatile and can be carried out for all
kinds of materials.

Ni can be plated on metals like Al, Cu, Fe, alloys like mild steel, brass,
stainless steel and nonmetals like plastics, glass and quartz.

Pretreatment process for Metals and Alloys

Step 1: Degreasing to remove oil and grease

Step 2: Acid cleaning to remove scales

Step 3: Weak acid etching or Ni strike to activate

Pretreatment process for Non-metals

Step1: Degreasing to remove oil and grease

Step 2: Activation is done by dipping the substrate in a solution of SnCl2-HCl,

followed by dipping in PdCl2 solution.
3.22 Engineering Materials

Plating Bath for Electroless Nickel Plating

Composition of the bath

Content

Coating solution
NiCl2 / NiSO4
(Coating metal)
Reducing agent
Sodium hypophosphite
(Metal ions reduced)
Buffer
Sodium acetate
(controls the pH)
Complexing agent
Sodium succinate
(Improves the quality)
Optimum pH 4.5
Optimum Temperature 93oC
Oxidation (Anode) NaH2PO2+H2O NaH2PO3 + 2H+ + 2e-
NiCl2 + 2e-  Ni + 2Cl-
Reduction (Cathode)
2H+ + 2Cl- 2HCl

Net reaction NiCl2 + NaH2PO2 + H2O → NaH2PO3 + 2HCl + Ni

Applications
Electroless Ni-plating is used
 in electronic appliances
 in jewellery, decorative articles and caps of perfume bottles
 on components used in oil field, pressure vessels, hydraulic compressors,
marine aviation and aerospace application.
Corrosion 3.23

Advantages

 Metallic and nonmetallic substrates can be coated

 Shape of the substrate does not have any influence on the thickness of the coat
unlike electroplating
 Matte, Semi- bright and bright finishes can be obtained
 Electricity is not required
 Complicated parts can also be plated uniformly

Limitations

 The chemicals used have limited life span

 Waste treatment cost is high

Electroless Plating in Printed Circuit Boards (PCBs)

Electroless plating is a crucial process in PCB manufacturing.

Conductive Pathways:
 Used for through-hole plating in PCBs, creating conductive paths between layers
by coating via walls with electroless copper.
 Ideal for complex geometries, ensuring uniform metal deposition without the need
for an external electrical current.

Surface Finishing:
 Electroless Nickel Immersion Gold (ENIG) is a common finish that deposits
nickel and gold layers, providing corrosion protection and enhanced solderability.
 Ensures reliability and performance in high-density PCB applications through
consistent and precise coatings.
3.24 Engineering Materials
3.8. CORROSION IN DIFFERENT INDUSTRIES
Corrosion poses a significant challenge across various industries. Let's explore its
impact on some industries.
1. Corrosion in Concrete: Reinforcing Steel
Concrete is a remarkably durable material. Usually, reinforcing steel embedded
within it which is susceptible to corrosion. Once the steel corrodes, it forms rust,
which has a greater volume than the original metal, leading to expansion and cracking
of the surrounding concrete.
The reasons for corrosion are:
 Chloride Ions: These ions, often present in water, penetrate the concrete and
accelerate corrosion.
 Carbonation: Carbon dioxide from the atmosphere reacts with concrete,
reducing its alkalinity, which protects the steel.
 Oxygen: The presence of oxygen is essential for corrosion to occur.
The consequences of reinforcing steel corrosion are severe:
 Loss of Structural Integrity: Corroded steel weakens the concrete, leading to
cracks and reduced load-bearing capacity.
 Increased Maintenance Costs: Repairing or replacing corroded concrete
structures can be expensive.
Preventive Measures:
 Using corrosion-resistant steel.
 Employing concrete with low permeability to chloride ions.
 Applying protective coatings to the concrete surface.
 Implementing cathodic protection systems.
2. Corrosion in Boilers
Boilers operate in harsh environments characterized by high temperatures, pressures,
and exposure to water and chemicals. These conditions create an ideal breeding
ground for corrosion.
Corrosion 3.25

 Types of Corrosion:
o General corrosion: Uniform attack on the boiler metal.
o Caustic embrittlement : Highly alkaline conditions can cause boiler material
brittle.
o Pitting corrosion: Localized attack resulting in small holes.
o Stress corrosion cracking: Combination of tensile stress and corrosive
environment.
o Erosion corrosion: Combined action of corrosion and mechanical wear.
 Consequences:
o Reduced boiler efficiency.
o Increased maintenance costs.
o Risk of equipment failure and safety hazards.
Preventive Measures:
 Water treatment to maintain appropriate pH and chemical balance.
o Regular inspections and cleaning.
o Use of corrosion-resistant materials.
o Applying protective coatings.
3. Corrosion in Electronic Components
Corrosion in electronics is a silent killer, often leading to equipment failure and data
loss. Even trace amounts of moisture and contaminants can cause significant
damage.
 Causes:
o Humidity.
o Electrolytic corrosion (when dissimilar metals are in contact with an
electrolyte).
o Sulfur-induced corrosion.
 Consequences:
o Equipment malfunction.
3.26 Engineering Materials
o Data loss.
o Increased repair costs.
Preventive Measures:
o Proper packaging and storage.
o Use of corrosion inhibitors.
o Controlled environments with low humidity.
o Application of protective coatings.
By understanding the causes and consequences of corrosion in these industries,
effective prevention strategies can be implemented to protect assets, ensure
safety, and extend equipment life.
Corrosion 3.27

QUESTIONS
1. Define corrosion.
2. Why certain metals undergo corrosion while others don’t?
3. What is electrochemical corrosion?
4. What is galvanic cell corrosion? How is it prevented?
5. Bolt and nut of the same metal is preferred in practice. Why?
6. What is differential aeration corrosion?
7. How does a drop of water, oil, dust, rusting on an iron surface lead to
corrosion of the metal?
8. What type of corrosion occurs in the following cases (i) Wire fence (ii) Riveted
joints (iii) Iron tanks used for storing water.
9. Iron is corroded faster than aluminium even though Fe is placed below Al in
electrochemical series. Why?
10. What is water line corrosion?
11. Explain why magnesium corrodes faster when it is in contact with copper
than when it is in contact with iron.
12. What is a sacrificial anode? How does it protect a submerged pipeline?
13. Which of the following metals could provide cathodic protection to iron: Al,
Zn, Cu, Ni
14. Explain the chemical reactions involved in the electroless plating of nickel.
15. List the advantages of electroless plating
16. Corrosion is a billion-dollar thief. Explain corrosion problems faced by various
industries.
Polymers in Every Day Life 4.1

UNIT - 4
POLYMERS IN EVERY DAY LIFE

Polymers and Polymerization: types of polymerizations: addition and

condensation – Properties: Crystallinity, Glass Transition temperature (Tg),
Average Molecular weight-viscosity method &PDI, tacticity, polymer recycling-
biodegradable polymers.

4.1. INTRODUCTION
The word polymer is derived from Greek words “poly” means many and “mer”
means unit or part. Polymers are macromolecules built up by linking together large
number of smaller molecule (repeating units) in the polymer chain. The small
molecules that combine with each other to form polymers are termed monomers.

Fig. 4.1. Polymerization

Polymers can contain hundreds, thousands, or even tens of thousands of

monomeric repeating units. They are essential commodity products in the industrial
sector, widely utilized in automobiles, defense, electronics, and computer
components.
4.2. POLYMERS
Polymers are macromolecules (giant molecules of higher molecular weight) formed
by repeated linking of large number of smaller molecules (monomers).
Example: Polyethylene is formed by the combination reaction of large number of
ethylene monomers.
4.2 Engineering Chemistry

Where n is the number of monomeric repeating units present in the polymer chain via
polymerization.
Some commonly used polymers and their uses are given below
Monomer Polymer Uses

Plastic bags, bottles,

toys

Milk cartons, rope,

carpets

Plastic glasses,
containers

Pipes, tubes,
raincoats

Nonstick vessel
coatings

and Plastic bottles

Polymers in Every Day Life 4.3

Differences between monomers and polymers

Monomer Polymer
A single molecule A collection of molecules, which are
joined together.
Molecular weight is low Molecular weight is high, which is many
times of the weight of a monomer.
Have lower viscosity, boiling Have higher viscosity, boiling points,
points, mechanical strength etc. mechanical strength etc.
Chemically more reactive. Reacts slowly when compared to
monomers.

How are polymers different from other compounds?

 High molecular weight

 Polymers are made up of small repeating units.
 The molecular weight of a polymer is expressed in a range.
 Polymer solids don’t have a sharp melting point
 Viscosity of polymer liquids are high
 Structure/shape of the polymer is quite complex
Advantages of polymers (over metals or ceramics)

 Low density (specific gravity = 1.0 – 1.4) (7.85 for steel)

 Corrosion resistance
 Easy to manufacture and mould
 Electrical insulator
 Low thermal conductivity
 Toughness, ductility
 Can be transparent
4.4 Engineering Chemistry
Disadvantages of polymers (relative to metals or ceramics)

 Low temperature usage (Melts/decomposes at high temperature).

 Low stiffness (Modulus, E  E of a metal/100)
 Low strength (strength might be improved using composite structures)
 Fatigue sensitivity
 May swell with water
 Toxicity, flammable
 Solvent sensitivity (may be soluble or properties may change)
 U.V. light sensitivity (can break covalent bonds for some polymers)

4.3. POLYMERIZATION
Polymerization is a process in which a large number of monomers combine to
form large chain like network called polymer.

Degree of Polymerization (DP)

The number of monomeric units (n) present in a polymeric chain is known as the
degree of polymerization. It is represented by the following relationship.

Example:

In this example, five monomeric units are present in the polymer chain. So,
the DP is 5.

Depending upon the value of ‘n’ – polymers are broadly categorized into
Polymers in Every Day Life 4.5

 Oligomers (n is small; average molecular weight (100-1000)

 Macromolecule or high polymers (n is large; average molecular weight
(104-106)

Importance of Degree of polymerization

Physical properties such as solubility, viscosity, surface tension, density,
crystallinity, morphology etc., varies with degree of polymerization. The strength of
the polymer increases with the degree of polymerization. Chemical reactivity of the
polymer also varies according to DP.

Molecular weight (hence DP) of a polymer can be determined using osmometry,

viscometry, sedimentation method etc.

ACTIVITY:
Find the DP of polyvinyl chloride (Molecular weight of polyvinyl chloride
is 1,20,000).

Functionality of a Monomer

The number of active bonding sites or reactive functional groups present in a

monomer is known as its functionality. Bonding sites are due to the presence of
carbon-carbon double bond (C=C) or triple bonds (C≡C) in the monomers. Two or
more functional groups (like –OH, -COOH, -NH2, -SH, -NCO, etc) present in the
molecule gives functionality of monomers.

Note: All monomers are molecules, but not all molecules are monomers.

Based on the bonding sites or functional groups present in a molecule, three types of
functionalities can be classified, such as bifunctional, trifunctional and polyfunctional.
4.6 Engineering Chemistry
1) Bifunctional monomer: Two bonding sites or functional groups.
Bifunctional monomers mainly form linear or straight chain polymers. Linear
chain is linked by strong covalent bonds (primary bonds) and the different chain are
held together by weak vanderwaal’s force of attraction (secondary bonds).

 No restriction to movement of one chain over another.

 Soft and flexible and possess less strength, low heat resistance.
 Soluble in organic solvents.
Example: Ethylene glycol, Ethylene.

2) Trifunctional monomer: Contains three active sites

When trifunctional monomers are mixed in small amounts with bifunctional
monomers, they form branched chain polymer.

 Movement of chain molecules are restricted due to presence of side chain.

Example: Glycerol, Dimethylol phenol, phenol

3) Polyfunctional monomer: Containing more than three functional groups.

Polyfunctional monomers from cross-linked polymers (3D network polymers).

All the monomers are connected to each other by strong covalent bonds in the
polymer structure.
Polymers in Every Day Life 4.7

 The movement of polymer chain is totally restricted

 Hard and brittle and possess very high strength, heat resistance
 Insoluble in almost all organic solvents
Example: Si (OH)4
Functionality of some compounds

Compound Structure Functionality

Methane CH4 Zero
Methanol CH3OH One
Acetic acid CH3COOH One
Ethylene CH2=CH2 Two
Styrene C6H5CH=CH2 Two
Glycol HOCH2-CH2OH Two
Malonic acid HOOC-CH2-COOH Two
Glycerol HOCH2-CH(OH)-CH2OH Three
Phenol C6H5OH Three*
Acetylene CH≡CH Four*

*In phenol, o- and p- hydrogens are also functionally active. So, maximum
functionality is three. In the case of acetylene both double bonds can be
functionalized.
4.8 Engineering Chemistry

4.4. TYPES OF POLYMERIZATION

The process of formation of polymer from monomers is known as

polymerization. Depending upon the mode and mechanism of polymerization
reaction, it can be of two types,

1. Addition polymerization.
2. Condensation polymerization.

1. Addition polymerization (chain growth polymerization):

The molecules of same monomer or different monomers undergoes simple

addition reaction to form macromolecules without the elimination of small molecules
is known as “addition polymerization”. The unsaturated compounds such as
alkenes, alkynes, dienes and their derivatives are used as monomers in the addition
polymerization reaction.

Addition polymerization is also called chain growth polymerization because it

takes place through stages leading to an increase of chain length. Here, each stage
produces reactive species which is used in the next step. Since there is no elimination
of small molecules, the molecular weight of the polymer is an integral multiple of the
monomer.

Polymerization happens in presence of catalyst at high temperature and pressures.

Addition polymerization is initiated by radical or ionic (anionic or cationic) catalysts.
A very important group of compounds which undergo addition polymerization is of
the type CH2=CHY, where Y= H, X (halogen), COOR, CN etc.

Mechanism of addition polymerization

Mechanism of polymerization is of four types – free radical, cationic, anionic and

coordination based on the reactive species involved.
Polymers in Every Day Life 4.9

Some of the industrial polymer synthesis via addition polymerization

i) Poly Vinyl Chloride (PVC)

Preparation:

PVC is obtained by heating a water emulsion of vinyl chloride in presence of

small amount of benzoyl peroxide or hydrogen per oxide in an autoclave under
pressure.

Step 1: Preparation of Vinyl Chloride monomer.

Step 2: Polymerization of monomer.

Properties
 Non-flammable with a high softening point (145-150°C).

 Colourless, Odourless and chemically inert.

 Resistant to atmospheric oxygen, light and inorganic acids and alkalis but
soluble in halogenated hydrocarbons (ethyl chloride and THF).
 Stiff, rigid and brittle.
 Uses
 PVC is commonly used as the insulation on electrical cables.
 PVC pipes are used to transport water.
 Plasticized PVC fabric is water-resistant, used for making raincoats, skiing
equipment, shoes, jackets and sports bags.
 PVC containers are used to collect biological test samples (blood, urine etc.).
4.10 Engineering Chemistry
ii) Poly Styrene (PS)

Preparation:

PS is prepared by the addition polymerization of styrene in presence of

benzoyl peroxide

Properties

 Amorphous with low specific gravity (1.054).

 Hard, Brittle and Transparent with high refractive index (1.592).
 Softening temperature is 90±10oC.
 It is nonpolar but soluble in oil.
 On combining with elastomers its impact strength increases and the product is
generally called HIPS (High Impact PS).
Uses

 It is used to make talcum powder container, Comb, Bottle cap and Brush.
 Expanded or Foamed PS is used as false ceiling and packing material
(thermocole).
 HIPS is used for making TV cabinets, inner liners for refrigerators, disposable
cups and plates.
Features of addition polymerization

 Monomer molecules get added up in presence of catalyst at high temperature

and pressure to yield the polymer.
 No molecules are eliminated during the process.
Polymers in Every Day Life 4.11

 The molecular weight of the polymer is an integral multiple of the monomer.

 The time required for the completion of polymerization reaction is very less.
The reaction will be over in few minutes.
 Degree of polymerization of a polymer formed via addition polymerization is
very high.
 Results in the formation of thermoplastics.

What the types of polymerization and monomers are involved in the

following polymers?
i) polyacrylonitrile
ii) polyvinyl alcohol

2. Condensation polymerization (Step-growth polymerization)

The process by which monomers undergo a series of condensation reactions in a

controlled stepwise manner with the elimination of small molecules (like water,
ammonia, methanol etc) to form polymers is called condensation polymerization.
The process takes place in a step wise manner, so it is also called step-growth
polymerization.

The monomers for condensation polymerization must have at least two functional
groups (like alcohol, amine, carboxylic acid etc). Polymerization starts by the
condensation reaction of two reactant molecules and forms dimer. A small molecule
like water is eliminated during this process. This dimer again reacts with another
monomer to form trimer and so on. The monomer must have at least two functional
groups. If the two functional groups are different (H2N-R-COOH), the monomer can
undergo polymerization. However, if the two functional groups are the same (H2N-R-
NH2), it cannot polymerize alone but can react with other bifunctional monomers
(HOOC-R-COOH). Polymerization can progress step by step.
4.12 Engineering Chemistry

Mechanism of condensation

 Step growth polymers

 Bi-functional monomers involves with catalyst
 Eliminate byproducts of small molecule like H2O, HCl, NH3, CH3OH, etc.,
 Molecular weight of polymer is lesser than the weight of monomers
 Stable intermediates formed such as dimer, trimer, tetramer, etc.,
 Cross-link and fibrous polymers are formed
O O

HO C (CH 2 ) 4 C OH + H 2N (CH 2 ) 6 NH 2

M onom er M onom er

O O H O O

HO C (CH 2 ) 4 C N (CH 2 ) 6 NH2 + HO C (CH 2 ) 4 C OH

M onom er
Dimer

O O H O O
H

+ H 2N (CH 2 ) 6 NH 2
HO C (CH 2 ) 4 C N (CH 2 ) 6 N C (CH 2 ) 4 C OH

Trim er M onom er

O O H O O H
H

HO C (CH 2 ) 4 C N (CH 2 ) 6 N C (CH 2 ) 4 C N (CH 2 ) 6 NH 2

Tetramer

O O H
H

* C (CH 2 ) 4 C N (CH 2 ) 6 N *
n
Polym ers

Fig. 4.2. Mechanism of condensation polymerization

Polymers in Every Day Life 4.13

Some of the industrial polymer synthesis via condensation polymerization

i) Nylon 6.6

Preparation

It is obtained by condensation polymerization of adipic acid and hexamethylene

diamine.

Fig. 4.3. Synthesis of Nylon 6,6

Properties

• High Melting point (255oC)

• Translucent
• Good thermal stability
• Good abrasion resistance
• Insoluble in common organic solvents
• Soluble in organic acids and phenol
• High impact strength
• Self-lubricating
4.14 Engineering Chemistry

Uses
Nylon 6:6 fibres are used for making
• Socks
• Carpets
• Dresses
• Ropes
• Upholstery
• Tooth brush bristles
• Due to self-lubricating property, used in making bearings and gears.

ii) Polyethylene terephthalate (PET)

Preparation

PET is prepared for the condensation reaction between terephthalic acid and
ethylenediol.

Fig. 4.4. Synthesis of PET

Properties

 High tensile strength

 Low moisture absorption
 Resistant to acids

 Food safe material

Uses

 Packing food materials

 Water bottles
Polymers in Every Day Life 4.15

Features of condensation polymers

• Monomers undergo a series of condensation reactions with the elimination of
small molecules (like water, ammonia, methanol etc.).
• The process takes place in a controlled step wise manner.
• Since small molecules are eliminated during polymerization, the molecular
weight of the polymer is NOT an integral multiple of the monomer.
• Molecular weight of the polymer increases steadily throughout the reaction.
• Longer reaction times are required to obtain polymer. It is a slow process and
takes hours or even days to complete.
• Results in the formation of thermosetting plastics.

Differences between addition and condensation of polymerization

Addition polymerization Condensation polymerization
(Chain growth polymerization) (Step-growth polymerization)
Involves repeated addition of Involved series of condensation
monomers to give polymer. between monomers to give polymers
Monomer must have minimum two Monomers must have at least two
bonding sites identical or different functional
groups.
Reaction proceeds via inter Reaction proceeds via chemical
molecular rearrangement of bonds. reaction between functional groups of
monomers which result in loss of
small molecules likes H2O, NH3 , etc.
Mostly results in homo chain Mostly results in heterochain
polymer. polymer
Reaction mixture contains only By-products are formed and by
monomer and polymer- no other products are present at any stage.
products.
4.16 Engineering Chemistry

Molecular weight of the polymer is Molecular weight is not an exact

exact multiple of molecular weight multiple of molecular weight of the
of monomers. monomer.

Results in linear polymer and mostly Results in branched and cross-linked

thermoplastics. polymer-mostly thermosetting plastics.
Longer reaction time has little effect Molecular mass or DP rises steadily
on the molecular weight but gives throughout the reaction and hence
higher yields. longer reaction time is essential.
Mechanism of polymerization can be Follows mechanism of condensation or
free radical, cationic, anionic or esterification.
coordination
Radical initiators, or Lewis’s acid Mineral acids or bases are used as
and base are used. catalyst.
Examples: Examples:
Polyethylene (PE), Polyvinyl Nylon 6,6, Polyethylene Terephthalate
chloride (PVC), Polystyrene (PS) (PET)

4.5. PROPERTIES OF POLYMERS

1. Crystallinity

The structure of a polymer is defined by its crystallinity. Most polymers are either
amorphous or semi crystalline. Crystalline polymers have a distinct melting point
(Tm), while amorphous polymers exhibit a glass transition temperature (Tg). Semi
crystalline polymers possess both Tg and Tm due to their combination of crystalline
and amorphous regions.
Polymers in Every Day Life 4.17

Fig. 4.5. Crystallinity of polymers

Crystallinity in polymers refers to the organized arrangement of molecular

chains within the polymer structure. It significantly affects a polymer's optical,
mechanical, thermal, and chemical properties. The degree of crystallinity, typically
between 10% and 80%, is measured through various analytical techniques; polymers
with this feature are known as "semi-crystalline." The properties of semi-crystalline
polymers are influenced by their crystallinity as well as the size and orientation of
their molecular chains.
Crystalline polymers have a specific shape, with ions, molecules, or atoms
orderly arranged in a three-dimensional crystal lattice and uniform intermolecular
forces. In contrast, amorphous polymers do not have a distinct shape and exhibit a
4.18 Engineering Chemistry
disordered arrangement of bulky groups, leading to varying intermolecular forces and
distances.

2. Glass Transition Temperature (Tg)

It is a property related to the amorphous regions and not the crystalline regions
of a polymer.

Definition: The temperature below which an amorphous polymer becomes hard

and brittle and above which it is soft and rubbery is called glass transition
temperature.

Fig. 4.6. Glass Transition temperature of polymers

Explanation:

On cooling the polymer, temperature decreases and the extended polymer

chains come closer therefore the inter chain mobility decreases. This makes the
polymer hard and brittle.
Polymers in Every Day Life 4.19

On heating, temperature increases, and the intermolecular forces are overcome.

Hence interchain mobility increases. This makes the polymer soft and elastic
(rubbery).

Approximate glass transition temperatures of a few polymers are given in the

table.

Polymer Tg (oC)

Polyethylene (LDPE) -125

Poly(ethyleneterephthalate) (PET) 69

Poly(vinyl alcohol) (PVA) 85

Poly(vinyl chloride) (PVC) 81

Factors influencing GTT

 Extent of crystallization (Crystallinity): Crystallinity has a direct bearing on

GTT. Greater the crystalline nature of the polymer greater is the glass transition
temperature.
 Molecular weight: As molecular weight increases there is an increase in GTT
till a particular mass (saturation point) beyond that the GTT remains constant.
 The presence of a side chain decreases the inter chain mobility hence increases
Tg.
 Addition of plasticizers also neutralizes the inter chain attraction and hence
decreases GTT.
4.20 Engineering Chemistry

3. Molecular weight

Molecular weight plays a crucial role in the physical and mechanical properties of
polymers. Polymers usually contain a mixture of varying length of chains hence their
molecular weights are not constants. Statistical methods are adopted to express the
molecular weight of polymers. The three most important ways of expressing
molecular weights of polymers are

i) Number average molecular weight (Mn)

ii) Weight average molecular weight (Mw)
iii) Viscosity average molecular weight (Mv)

i) Number average molecular weight

Definition: It is the ratio of the sum of the molar masses of individual

molecules to the total number of molecules present in the mixture

It is determined by measuring the colligative properties such as depression in freezing

point, elevation in boiling point, osmotic pressure.

Let us consider that in a polymer mixture there are n1 molecules with a molar
mass M1, n2 molecules have a molar mass M2 and so on and so forth

The number average molecular weight is given by the expression

n1M1  n 2 M 2  ...n i Mi
Mn 
n1  n 2  ...n i

 n i Mi
Mn 
 ni
Polymers in Every Day Life 4.21

ii) Weight Average molecular weight:

Ultra-centrifugation and light scattering studies are employed to determine weight

average molecular weight.

Let us consider that w1 is the weight of molecules with a molar mass M1, w2 is
the weight of molecules that have a molar mass M2 and so on and so forth.

The weight average molecular weight is given by the expression.

w1M1  w 2 M 2  ...w i Mi
Mw 
w1  w 2  ...w i
We know that n = w/M

Substituting w as nM in the above

Hence Mn is usually less than Mw

(n1M1 )M1  (n 2 M 2 )M 2  ....(n i Mi )Mi

Mw 
n1M1  n 2 M 2  ...n i Mi

Mw 
 n i Mi2
 n i Mi

Fig. 4.7. Molecular weight of a polymer

4.22 Engineering Chemistry

A polymer has following two different moles and molecular weight

9 moles, molecular weight (Mw) = 30,000
5 moles, molecular weight (Mw) = 50,000
Determine the Number and weight average molecular weight of the polymer.

Determination of average molecular weight and degree of polymerization by

viscosity method
The force of friction between two layers of fluid having the area in square
centimeter and separated by distance will have a velocity is given by:

F∝A (or) F = A

Here, η is coefficient of viscosity and is velocity gradient

If dx is 1cm, A is 1cm2 and dV is 1cm/s Then, f = η

The coefficient of viscosity is defined as the force of friction that is required to
maintain a difference of velocity of 1cm/s between parallel layers of fluid. The unit is
usually expressed in poise or centipoise.
Each solvent has its own viscosity. Addition of a polymer to a solvent of low
viscosity results in a sharp increase in its viscosity. The extent of increase in its
viscosity depends on the molecular weight and amount of the polymer added. If 0

and  are the viscosities of the solvent and the solution respectively, then is

called relative viscosity,r. Also, the ratio, = r – 1, known as the

specific viscosity, sp. It is the ratio referred to as the reduced viscosity. It is

relative increase in viscosity per unit concentration of polymer which is a function of
the molecular weight of polymer. Since this ratio varies with concentration, it is
Polymers in Every Day Life 4.23

necessary to extrapolate a plot of against C to infinite dilution and the value

thus obtained is called the intrinsic viscosity [], so that = []

Since sp is dimensionless, [] has the units of reciprocal concentration and
Since C is usually expressed in grams per litre of solution, [] is given in deciliter per
gram. The relationship between the intrinsic viscosity and molecular weight of the
dispersed polymer is given by Mark Houwink empirical equation, []= K x M,
where K is a constant for a given polymer-solvent system and M is the molecular
weight of the polymer and  depends on the shape of the molecule. [] is obtained

from the graph by plotting vs C. Knowing the values of K and ‘a’ (constants
for a particular polymer, solvent, system at a given temperature), M can be calculated.

Polydispersity index (PDI)

Poly dispersity index is a measure of broadness of molecular weight

distribution of a polymer.

It is the ratio of weight average molecular weight to number average

molecular weight (Mw/Mn). The larger the polydispersity index, the broader the range
of molecular weight. A mono disperse polymer where all the chain lengths are equal
(such as a protein) has PDI = 1. The best controlled synthetic polymers (narrow range
molecular weight polymers are used for calibrations) have PDI of 1.02 to 1.10.
4.24 Engineering Chemistry
Condensation polymerization typically yield polymers with PDI ≈ 2, whereas addition
polymerization yield polymers whose PDI varies from 1.5 to 20.

Fig. 4.8. PDI of a polymer

 Condensation polymer (PDI = 1 to 2)

 Addition polymer (PDI = 11)

Solve
1. Number and weight average molecular weight of polymers are 24000
and 43000 g/mol respectively. Determine the PDI of polymer and
predict the types of polymerization of that polymer.
2. Number and weight average molecular weight of polymers are 12000
and 152000 g/mol respectively. Determine the PDI of polymer and
predict the types of polymerization of that polymer.

Tacticity

Tacticity is the arrangement of bulky groups in polymer main chain backbone.

Ex: Poly Styrene

If all of the phenyl groups are on the same side of the chain, the polymer is
isotactic.
Polymers in Every Day Life 4.25

If the phenyl groups are arranged on alternative sides of the chain, the polymer
is syndiotactic.

If the phenyl groups are on both sides and right and left following no
particular order, in a random fashion, then the polymer is atactic.

Fig. 4.9. Tacticity of a polymer

An orderly arrangement makes the polymer crystalline and strong. In any

polymer, a definite part is crystalline while the rest is amorphous. If the crystalline
part accounts for > 50% of polymer then it is said to be a crystalline polymer. A 50%
amorphous polymer is classified as amorphous polymer.

 Isotactic and Snydiotactic polymers having regular arrangement of pendant

groups - crystalline or semi-crystalline – dense, stronger, less solubility and low
permeability

 Atactic polymers having irregular or random arrangement of pendant groups –

amorphous - soft and more elastic, higher solubility and permeability.
4.26 Engineering Chemistry
Ex:
 HDPE, isotatic PVC and PP – highly crystalline
 Atactic PVC and PP – amorphous .

Draw the structures of isotactic, syndiotactic and atactic polyacrylonitrile.

4.6. POLYMER RECYCLING

The global use of plastic materials is rising due to their durability, cost-
effectiveness, and lightweight nature. However, this unchecked usage is leading to
significant disposal and environmental challenges. Recent and traditional methods for
recovering and recycling plastic waste are categorized into two types: thermoplastics
and thermosets.

Thermoplastics:

 Softened on heating and hardened on cooling

 Can be remoulded

 Prepared by addition polymerization

 Straight chain (or) branched polymers by Vanderwaal’s forces

Ex: Polyethylene, Polyvinyl chloride, Polysulphone, etc

a) Thermosets
 Get harden on heating and once harden – cannot be softened again
 Cannot be remoulded
 Prepared by condensation polymerization
 Various polymer chain are held together by strong covalent bonds
Polymers in Every Day Life 4.27

Ex: Bakelite, Urea-formaldehyde, Epoxy resins, etc

Differences between thermoplastics and thermosetting plastics

Thermoplastics Thermosetting plastics

Soften on heating and harden on Do not soften; they burn on heating.
cooling.
Can be remoulded recast and Cannot be remoulded or reshaped.
reshaped.
Soft, weak and less brittle. Hard, strong and more brittle.

Soluble in some organic solvents. Insoluble in organic solvents.

Formed by addition polymerization. Formed by condensation
polymerisation.
Have usually linear structures. Have three-dimensional cross-linked
structures.
Can be reclaimed from wastes. Cannot be reclaimed from wastes.

Ex: Polyethylene, PVC, teflon. Ex: Bakelite, epoxy resins.

Recycling of polymers

Thermoplastic polymers are easily recycled due to their ability to melt and
reform, though their properties deteriorate with each reuse, but thermosetting
polymers are more challenging to recycle. Environmental concerns regarding post-
consumer polymers can be addressed through two main approaches: recycling and
4.28 Engineering Chemistry
biodegradable polymers. Recycling of polymer is a process to recover value added
products such as monomers or chemicals or energy from post-consumer plastics.
Recycling is the best approach to manage and prevent plastic waste accumulation in
the environment. The enhancement of polymers for better performance complicates
their reuse and recycling. The recycling process aims to reduce plastic output by 80%
and to create a circular economy for plastic production and use.

Types of Recycling

There are mainly two important approaches used in the recycling of post-consumer
plastic such as thermal and chemical recycling process.

i) Thermal recycling process (pyrolysis)

This technological approach focuses on catalytic pyrolysis as a method to convert

polymeric waste into energy products, offering an innovative waste management
solution that fosters a sustainable environment. Pyrolysis involves the controlled
thermal decomposition of non-biodegradable polymers in an oxygen-free setting,
breaking down macromolecules into lower molecular weight compounds and
producing a variety of products, including hydrogen, hydrocarbons, and coke.

Example: Catalytic pyrolysis of polypropylene (PP) and polyethylene (LDPE or

HDPE) into light oils, heavy oils and other hydrocarbons

ii) Chemical recycling process

Chemical recycling is an innovative method that breaks down polymers into basic
monomers or other molecules. This process alters the polymer's chemistry, allowing
the raw materials to be reconstituted and reused to produce new polymers or
petrochemical feedstock.

Example: Chemical depolymerization of PET bottle into their monomers

(terephthalic acid) or other molecules
Polymers in Every Day Life 4.29

Identify and recommend an appropriate recycling process for the polymers

you use in daily life.

4.7. BIODEGRADABLE POLYMERS

Biodegradable polymers are those that can be decomposed by naturally occurring
microorganisms like bacteria, fungi, and algae. Utilizing these polymers as matrices
would give wood-plastic composites a 100% green label on a large scale. They break
down into non-toxic compounds such as CO2, H2O, N2, biomass, and inorganic salts.
For a polymer to be biodegradable, it must be hydrophilic. The degradation process
involves hydrolysis and photo-oxidation or microbial oxidation, occurring under both
aerobic and anaerobic conditions. The general aerobic (1) and anaerobic (2)
degradation can be represented as given below.

Cpolymer + O2 → Cresidue + Cbiomass + CO2 + H2O ------- (1)

Cpolymer → Cresidue + Cbiomass + CO2 + CH4 + H2O ------- (2)

During anaerobic oxidation, in addition to water and carbon dioxide, Methane is

formed which can be used as a fuel.

Synthetic polymers, in general are non-biodegradable. However, polymers with

hydrolysable backbones are susceptible for enzymatic biodegradation.

Examples are polycaprolactone, polyamides, polyurethanes, polyureas and

polyanhydrides.

Application of biodegradable polymers

Biodegradable polymers have been widely used.

 in vascular and orthopedic surgery as implantable matrices for the controlled

long-term release of drugs inside the body.

 as absorbable surgical sutures and plastic staples, various pins and screws,
ligature clips and vascular grafts, artificial skin and bone fixation devices.
4.30 Engineering Chemistry
 as agricultural mulches, agricultural planting containers, and in controlled
release of agricultural chemicals.

 Woven and non-woven fabrics, made from biodegradable polymers are used as
industrial wipes, filters etc.

 Personal hygiene products, such as disposable diapers with a biodegradable

plastic liner or tampon applicators are made from biodegradable resins.

Identify examples of biodegradable polymers that you encounter in your

daily life.
Polymers in Every Day Life 4.31

QUESTIONS

1. What is the functionality of (a) propylene (b) Phenol towards polymerisation?

2. Define polydispersity index.
3. What are thermoplastics?
4. Find the functionality of i) phenol ii) styrene iii) ethylene glycol iv) acetylene
5. What is functionality of polymers?
6. Mention any two uses of Nylon6,6.
7. What is meant by degree of polymerization?
8. Mention any two uses of epoxy resin.
9. Define degree of polymerization.
10. How are polymers classified based on their tacticity?
11. How is polymerization classified? Give one example for each class.
12. Mention the monomers used for the preparation of Nylon 6,6.
13. Explain functionality of a monomer with an example.
14. Explain condensation polymerization with a suitable example.
15. Can thermosetting plastics be remoulded? Justify.
16. Define polymerization.
17. Differentiate between addition and condensation polymerization techniques.
18. Define (a) functionality of a molecule and (b) degree of polymerization
19. What are the differences between thermoplastic polymers and thermosetting
polymers?
20. Explain any four important properties of polymers.
21. Define the crystallinity of polymers.
22. What is PDI of polymers?
4.32 Engineering Chemistry
23. Write down the preparation properties and uses of Nylon 6:6
24. Distinguish thermoplastics and thermosetting plastics.
25. Explain condensation polymerization taking one example.
26. What is functionality of a monomer? Explain its significance with a suitable
example.
27. Write briefly about the following properties of polymers- Tg, weight average
molecular weight, tacticity and polydispersity index.
28. Define the terms monomer and functionality. Explain condensation
polymerization with a suitable example. How does it differ from chain
polymerization?
29. What are thermoplastics and thermosetting plastics? Distinguish between the two?
30. What is polymer recycling?
31. Explain the types of depolymerization with an example.
32. What you mean by biodegradable of polymers?
33. Define the process of aerobic and anaerobic degradation of polymers.
34. Discuss about biodegradable polymers and its functions.
Analytical Techniques 5.1

UNIT - 5
ANALYTICAL TECHNIQUES

Spectroscopy: Beer-Lambert’s law, Colorimetric estimation of Fe3+, Principle,

working and applications of UV-Visible, IR spectroscopy and Chromatography
(TLC and Column)

.
5.1. INTRODUCTION
Analytical chemistry is an effective and accurate tool for determining
qualitative and quantitative compositions of substances and chemical species.
Analytical chemistry is integrated with other scientific and industrial disciplines.
“Analytical chemistry may be defined as the branch of science which deals with the
study of determination of composition of materials in terms of the elements or
compounds contained”. It is also considered as the art of determining the quality and
purity of the materials. Spectroscopy is one of the most widely used analytical
methods.
5.2. SPECTROSCOPY
Spectroscopy is one of the most powerful tools used to derive information
about atomic and molecular structures. Spectroscopy is the study of the interaction
between matter and electromagnetic radiation. It involves the study of radiation
emitted, absorbed or scattered by the matter under study. It provides valuable
information regarding chemical structure such as functional groups, unsaturation,
bond strength, molecular structure such as molecular symmetry, bond distances, bond
angles etc.
Electromagnetic radiation:

Electromagnetic radiations (EMR) are the radiations in which the electric and the
magnetic field oscillate perpendicular to each other, and both are perpendicular to the
5.2 Engineering Chemistry
direction of propagation of wave. It is also a form of energy transmitted through space
at very high velocities.

a)

b)

Fig. 5.1. (a) Electric and magnetic field components of electromagnetic waves
and (b) Electromagnetic induction to HOOPRA (Battery-free radio receiver).

Characteristic features of wave:

A wave has five important characteristics, such as

1. Wavelength (λ)
2. Frequency (ν)
3. Velocity (c)
4. Wave number (ν̅)
5. Amplitude (a)
Analytical Techniques 5.3

1. Wavelength (λ):
The distance between two successive troughs or crests is known as wavelength of
light. It is denoted by ‘λ’ and is commonly expressed in nanometers (1 nm = 10–9
m) or Angstrom (1 Å = 10–10 m).

2. Frequency (ν):
The frequency of a wave is the number of waves (or number of crests) passes
through a given point in a medium every second.
𝑺𝒑𝒆𝒆𝒅 𝒐𝒇 𝒍𝒊𝒈𝒉𝒕 (𝒄𝒎. 𝒔−𝟏 )
Frequency (ν)= = c/λ
𝑾𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉 (𝒄𝒎)

3. Velocity(c):
The distance travelled by the wave in one second is called its velocity. It is
denoted by ‘c’ and expressed in ms–1.
c = νλ or λ = c/ν (Velocity of light, c= 3×108 ms–1)

4. Wavenumber (𝛎̅):
It is defined as the number of waves spread per cm and denoted by ‘𝛎̅’. It is
expressed in cm–1.
Wavenumber, 𝛎̅ = 1/λ or ν/c

5. Amplitude(a):
It is the height of a crest or depth of a trough of a wave and denoted by ‘a’. It also
determines the intensity or brightness of the light beam.

5.3. ELECTROMAGNETIC SPECTRUM:

The electromagnetic spectrum is the distribution of electromagnetic radiation
according to frequency or wavelength. The types of electromagnetic radiation are
broadly classified as Gamma, X-ray, Ultraviolet, Visible, Infrared, Microwave,
and Radiowaves.
5.4 Engineering Chemistry

Wavelength Frequency Energy

Region
(Å) (Hz) (eV)
9 9 –5
Radio >10 <3×10 <10
9 6 12 –5
Microwave 10 –10 3×10–3×10 10 –0.01
6 12 14
Infrared 10 –7000 3×10 –4.3×10 0.01–2
14 14
Visible 7000–4000 4.3×10 –7.5×10 2–3
14 17 3
Ultraviolet 4000–10 7.5×10 –3×10 3–10
17 19 3 5
X-Rays 10–0.1 3×10 –3×10 10 –10
19 5
Gamma Rays < 0.1 >3×10 >10

Fig. 5.2. Electromagnetic spectrum in the increasing order of frequency

(decreasing wavelength order).
Analytical Techniques 5.5

Types of EM waves Source Applications

Radio Transmitter Radio Communication,
Transmitting TV programs
Microwave Microwave Microwave Ovens, Radio
Transmitter Telescopes, Radar
Infrared Stars and Other Thermal imaging, Night Vision
Hot Objects Camera, Remote Control Security
System
Visible Stars, Hot Normal Vision, Photography,
Objects, Flame Photosynthesis
Ultraviolet Stars, Special Astronomical Observations,
Lamps Killing Microbes, Document
Security
X-Rays X-ray Machine Medical Imaging and Diagnosis,
Defects in metals, Security
System
Gamma Rays Radioactive Food Sterilization, Medical
Decay Tracers/Water Flow Monitor, Kills
Cancer Cells

Fig 5.3: Electromagnetic Radiation type sources and depiction of daily

commercial and household radiation sources with corresponding operational
frequency ranges.
5.6 Engineering Chemistry

DID YOU KNOW?

Why does UV-b cause sunburn yet UV-a does not? (Electromagnetic
spectrum)

UV-a comprises wavelengths in the range 320–400 nm. Such light penetrates the
top, outermost layer of skin, causing photolytic damage to the layers beneath, as
seen by premature aging, sagging, wrinkles and colored blotches. UV-a can
contribute to the onset of skin cancer (melanoma) but is otherwise relatively safe
provided that suitable protection is taken.

Origin of Spectra
Spectrum can originate from atoms or molecules due to absorption or emission of
radiation.

(a) Atomic spectra:

The atomic spectrum is obtained when atoms interact with electromagnetic
radiation. During this interaction, the atoms absorb radiation and get excited from
ground state electronic energy level to higher excited energy level.
A typical example of atomic spectra is hydrogen spectra. The hydrogen spectrum
consists of several lines.

(b) Molecular spectra:

The molecular spectrum arises when molecules interact with electromagnetic
radiation. Absorption of radiation in molecules will result in changes in rotational,
vibrational and electronic energy levels.
Analytical Techniques 5.7

Atomic spectra Vs Molecular spectra

Atomic spectra Molecular spectra

Atoms interact with Molecules interact with
electromagnetic radiation electromagnetic radiation
Simple line spectra are observed Complex band (Broad) spectra are
observed
Due to electronic transition only Due to vibrational, rotational and
(UV region) electronic transitions. (Visible region)
Tells about the nature Tells about the nature of bonds,
(characteristic) of element functional
groups etc.,
Example: Spectra of hydrogen Example: UV-Visible spectra of
molecules

Spectra can be differentiated as absorption and emission spectra due to absorption and
emission of light by atoms or molecules.
(a) Absorption spectra:
When electromagnetic radiation is passed through a medium, certain photon of
energy (“hν”) are absorbed. Due to this absorption, an atom or a molecule from a
lower energy level is promoted to a higher energy level. The spectrum thus obtained
due to absorption of radiation is known as absorption spectra. The measurement of
decrease in intensity (based on Lambert-Beer’s law) of the incident radiation is the
basis for absorption spectroscopy.
5.8 Engineering Chemistry

Since the energy levels are quantized, the energy of the photon absorbed should be
exactly equal to E2-E1.
Example: UV-Visible spectra
An absorption spectrum is usually a plot of absorbance versus wavelength.
Absorption spectra can be of two types: atomic absorption spectra and molecular
absorption spectra.
(b) Emission spectra:
When a beam of radiation is allowed to pass through a molecule in ground
state, the molecule absorbs energy and undergoes a transition from ground state to
excited state energy level. Molecule in the excited state is highly unstable and it
returns to ground state with emission of photon of energy “hν”. This emitted radiation
is plotted as a function of frequency or wavelength, and then it is called an emission
spectrum. The energy of the photon emitted will be exactly equal to E2-E1.

Example: Laser Assisted Stimulated Emission of Radiation (LASER), Fluorescence,

Phosphorescence.
Analytical Techniques 5.9

Each element emits specific radiation depending on the energy gap between the
ground state and the excited state. Therefore, emission spectra can be used to identify
the chemical species.

DID YOU KNOW?

Why do neon streetlights glow? (Absorption and emission of light)
Neon lights glow because they emit light under suitable conditions. The principal
difference between neon lights and the colors seen in daylight is that neon light
emits light, whereas wine, paint and chromophores, in general, absorb light.

Energy Levels in a Molecule:

In atoms, energy levels are determined by the motion of electrons. Molecules
are formed when atoms combine chemically. The sum of the energy levels of
involved atoms in molecules are lower than unbound atoms.

Molecules have different energy levels. They are

Translational energy (Etrans): This energy is concerned with the translational motion
of molecules along three axes. It is significant only in gases and to a lesser extent in
liquids. In solids, molecules have fixed position, so generally solids are not associated
with translational energy.
Rotational energy (ERot): This energy involves the spinning of molecules about the
axes passing through centre of gravity.
Vibrational energy (EVib): This energy is associated with the to and fro motion
(vibrations) of the molecule. Examples of such vibrations are stretching and bending.
Electronic energy (EElec): Electronic energy deals with the transition of an electron
from ground state to an excited state due to the absorption of energy.
Total energy (ETot) of a molecule can be expressed as the sum of all these energies.
ETot = EElec + EVib + ERot + ETrans
5.10 Engineering Chemistry

Translational energy levels are so close together that they are essentially continuous
(not quantized) and can be ignored.

Fig. 5.4. Energy level diagram of molecule.

The energy requirements for various energy level changes and radiation which cause
these transitions are given below.

Transitions Energy Radiation causing

(KJmol–1) transition
Rotational 0.01-1.0 Microwave

Vibrational 1-100 Infrared

Electronic 100-10,000 Ultraviolet-visible

Absorption of light:
Light interacts with matter in several ways, including absorption, reflection,
refraction, emission, and scattering. Here, we will focus on two of these: absorption
and emission. Absorption of light occurs when the matter is in resonance with
Analytical Techniques 5.11

frequency of the light – i.e., when the frequencies match (νlight = νmatter). As a result,
knowing the frequencies of light that are absorbed by a particular atom or molecule
can give us information about its structure.

5.4. BEER’S LAW OR LAMBERT-BEER’S LAW

Lambert-Beer’s law gives the relationship between intensity of light with
concentration and path length.

Fig. 5.5. Transmission of light through a sample solution in a cuvette.

Lambert-Beer’s law states that “When a beam of monochromatic radiation

passes through a homogeneous solution of an absorbing substance, the rate of
decrease of intensity of radiation dI, with the thickness of absorbing solution dx is
proportional to the intensity of the incident radiation I, as well as the concentration of
the solution c”.
Mathematically,

𝒅𝑰
− 𝒅𝒙 = 𝒌. 𝒄. 𝑰𝟎 , Where k is a constant

𝒅𝑰
= −𝒌. 𝒄. 𝒅𝒙
𝑰𝟎
5.12 Engineering Chemistry

Integrating between limits,

𝑰 𝒙
𝒅𝑰
∫ = − ∫ 𝒌. 𝒄. 𝒅𝒙
𝑰𝟎 𝑰𝟎 𝟎

𝑰
𝒍𝒏 𝑰 = −𝒌. 𝒄. 𝒙
𝟎

𝑰 𝒌
𝒍𝒐𝒈 =− . 𝒄. 𝒙
𝑰𝟎 𝟐. 𝟑𝟎𝟑

𝑰𝟎 𝒌
𝒍𝒐𝒈 = . 𝒄. 𝒙
𝑰 𝟐. 𝟑𝟎𝟑

𝑰𝟎
𝒍𝒐𝒈 = 𝜺. 𝒄. 𝒙
𝑰

A = 𝜺. 𝒄. 𝒙

Where ‘𝜀’ is a new constant called molar absorptivity or molar extinction coefficient.
Its value depends upon the units of concentration. The concentration is expressed in
mol. dm–3 and x in centimetres.

Where Absorbance (A) or Optical Density (O.D) =log I0/I

𝜀 = Molar absorptivity or molar extinction coefficient. (𝜀 = k/2.303)

c = Concentration of absorbing species
x = length of absorbing medium (path length)
A=𝜺. 𝒄. 𝒙
When c = 1 mol. dm–3 and x = 1cm, then,
𝜺=A
Molar absorption coefficient is the absorbance of the solution when concentration is
1 mol.dm-3 and path length is 1 cm.
Analytical Techniques 5.13

Ratio I/I0 is known as transmittance (T)

A = –log T
Applications of Lambert-Beer’s law:
1. Determination of unknown concentration:
By knowing the absorbance of a standard solution, the unknown concentration of
another solution can be found out,
As = ε. Cs. x (for standard)
Au = ε. Cu. x (for unknown solution)
Where, As and Au are the absorbance of standard and unknown solution, respectively.
Cs and Cu are the concentrations of the standard and unknown solution, respectively. ε
is the molar absorptivity of the solution.
𝐴𝑠 ε. 𝐶𝑠 . 𝑥
=
𝐴𝑢 ε. 𝐶𝑢 . 𝑥
𝑨𝒔
𝑪𝒖 = ∗ 𝑪𝒔
𝑨𝒖
2. Identification of sample:
ε, the molar extinction coefficient is a physical constant. Therefore, by knowing or
comparing ε values, the chemical identity of a sample can be found out.
3. Determining rate of a reaction:
The change in concentration can be followed by measuring absorbance (A) as a
function of time. This is useful in chemical kinetics for determining the rate of
chemical reactions.
4. Colorimetric estimation of metal ions:
Lambert-Beer’s law is the principle of colorimetric estimation. Metals like Fe, Co, Ni,
Cu etc., can be estimated even in low concentrations using colorimetry. Basic
principle of colorimetry is that absorbance of a solution varies with concentration.
Colour of the solution is measured using a spectrophotometer.
5.14 Engineering Chemistry

Ferric ion reacts with thiocyanate ion, forming a deep blood red coloured complex
which can be estimated by colorimetry.
Fe3+ + 6KSCN → [Fe(SCN)6]3– + 6K+
Colourless Colourless Red

Fig. 5.6. Calibration plot to determine the concentration of an unknown

metal ion by colorimetry.
Limitations of Lambert-Beer’s law:
 The law is obeyed when radiation is monochromatic.
 It is applicable only for dilute solutions.
 The temperature of the system should not vary significantly.
 It is applicable only for true solutions (non-colloidal solutions)
 Impurities present in the solution can cause deviation.
 The law is not obeyed, if there is association or dissociation of sample in
solution.
Analytical Techniques 5.15

DID YOU KNOW?

How does breathalyzer work? (Beer Lamberts law)
When you exhale into the mouthpiece, your breath enters a chamber filled with
potassium dichromate and other chemicals, which are a red-orange color. Alcohol
reacts to this solution and changes the liquid's color to green. The degree of color
change is related to the level of alcohol in your exhaled breath.

5.5. ULTRAVIOLET AND VISIBLE SPECTROSCOPY

The study of interaction of electromagnetic radiation with matter in the
ultraviolet region (200–400 nm) and visible region (400–800 nm) is called UV-
Visible spectroscopy. Molecules absorb in the UV-Visible region and get excited to
higher electronic excited states (electronic transitions) from the ground state.
Therefore, UV-Visible spectroscopy is also called electronic spectroscopy.

Types of electrons involved in electronic transitions:

When a molecule absorbs UV or visible light, valence electrons get promoted to
higher energy levels. The following three types of electrons are involved in this
transition.
 Sigma (σ)-electrons: These electrons are found in sigma orbitals. σ-bonds are
very strong so that high energy is required for the promotion of these electrons.
Ex: Saturated hydrocarbons [CH4, CH3-CH3, CH3–CH2–CH3]

 Pi ()-electrons: These are electrons present in Π orbitals or molecules having

unsaturated (double and triple) bonds.
Ex: Unsaturated compounds (CH2 = CH2), Aromatic compounds (C6H6)

 Non-bonding (n)-electrons: These non-bonding electrons are not involved in any

kind of bonding.
Ex: Organic compounds containing heteroatoms (N, O, S etc.). Such heteroatoms
have one or more lone pairs of electrons which are not involved in any bonding.
5.16 Engineering Chemistry

Electronic Transitions:
The absorption of UV or visible radiation corresponds to the excitation of valence
electrons to higher energy orbitals. Various electronic transitions involving σ,  and n
electrons are highlighted in the Figure 7. There are six types of transitions can be
considered: σ→σ*, σ→*, →*, →σ*, n→σ* and n→*.

Fig. 5.7. Different electronic transitions involving σ and n electrons

Types of possible electronic transitions:

 σ→σ* transitions:
An electron in a bonding σ orbital is excited to the corresponding anti bonding σ*
orbital. The energy required is large as sigma bonds are stronger.

Ex: Saturated hydrocarbons [CH4, CH3-CH3, CH3–CH2–CH3, etc]

CH4: σ→σ* transition, λmax=122 nm

CH3-CH3: σ→σ* transition, λmax=135 nm

 n→σ* transitions:
Saturated compounds containing atoms with lone pairs (non-bonding electrons) are
capable of n→σ* transitions. These transitions require less energy when compared to
σ→σ* transitions.
Analytical Techniques 5.17

Some examples of molecules with n→σ* peaks with their λmax values are listed
below.
λmax εmax
Molecule
(nm) L. mol–1. cm–1
H2O 167 7000

CH3OH 183 500

1-Hexanethiol 224 126

n-Butyl iodide 257 486

 →* transitions:
→* transitions occur in unsaturated compounds having electrons. Electrons are
promoted from bonding orbital to * antibonding orbital. These absorption peaks
are found in the region 200–700 nm. →* transitions of olefinic systems are called
K-bands. These →* absorption bands are shifted to longer wavelengths when
double bonds are in conjugation or double bond of an alkene is in conjugation with a
carbonyl group of an aldehyde or ketone.

→* transitions of benzenoid molecules are called B-bands.

Some examples of molecules with →* peaks with their λmax values are given
below.
λmax εmax
Molecule
(nm) L. mol–1. cm–1
CH2=CH2 165 10000
CH2=CH–CH=CH2 217 21000
CH2=CH–CHO 210 11500
CH2=CH–CO–CH3 212 7079
C6H5COCH3 240 13000 (K-Band)
278 1110 (B-Band)
5.18 Engineering Chemistry
 n→* transitions:
These transitions are restricted to unsaturated molecules containing heteroatoms like
N, O and S. The non-bonding electrons present in the lone pair of heteroatoms are
promoted to * orbitals. Non-bonding electrons are weakly held, and energy essential
for excitation is much less. n→* transition is always less intense because the
electrons present in n-orbital are situated perpendicular to the plane of bond (and
hence to the plane of * orbital).

Important terms in UV-Visible Spectroscopy:

 Chromophores:
The functional groups having one or more double or triple bonds (unsaturated linkage
with electrons) which are responsible for absorption of UV-Visible light are known
as “chromophores”. Chromophores impart colour to the molecules. A compound
containing chromophore is known as chromogen.

Ex: Compounds containing –C=C–, –C≡C–, –C≡N, –N=N– etc. Chromophores

undergo →* transitions in UV-Visible region.

Chromophores are of two kinds.

1. Chromophores which contain  electrons only and undergo →* transition.

Ex: CH2=CH2, CH≡CH

2. Chromophores which contain electrons and n electrons. Such chromophores can

undergo both →* and n→* transitions.
Ex: Carbonyl compounds, Nitro compounds, Azo compounds etc.
 Auxochromes:
Functional groups like –OH, –NH2, –SH etc. which do not absorb radiation but
enhance the absorption due to presence of lone pairs electrons on heteroatom are
called “auxochromes”. Auxochromes have at least one lone pair of electrons which
extends  conjugated system of chromophore by resonance. This may increase the
Analytical Techniques 5.19

wavelength at which the light is absorbed and increase the intensity of absorption.
Auxochromes do not impart colour to a compound but intensify the colouring power
of chromophores.

Ex: Benzene is colourless but nitrobenzene is pale yellow in colour due to the
presence of the nitro group. p-hydroxy nitrobenzene is deep yellow in colour.

There are mainly two types of auxochromes:

Acidic: –COOH, –OH, –SO3H

Basic: –NHR, –NR2, –NH2, –CONH2

Chromophore Auxochrome
Auxochrome conjugates with chromo-
Chromophore is directly responsible
phores to impart (or intensify) colour to
for the colour of the molecule.
the molecule.
It contains one or more lone pair of
It contains at least one multiple bonds.
electrons.
They do not form salts. They form salts.
Ex: –NO2, –NO, –N=N– Ex: –OH, –NH2

 Bathochromic shift:
The increase in absorption intensity due to the shifting of wavelength from lower to
higher region (lower energy) is called bathochromic or red shift.

λmax εmax
Molecule
(nm) L. mol–1. cm–1
CH2=CH2 165 10,000
CH2=CH–CH=CH2 217 21,000
CH2=CH–CH=CH–CH=CH2 258 35,000
5.20 Engineering Chemistry
 Hypsochromic shift:
The decrease in absorption intensity due to the shifting of wavelength from higher to
lower region (higher energy) is called hypsochromic or blue shift. Blue shift results in
weakening of colour. This is usually caused due to the substitution or solvent effect
(polarity).

Ex: Aniline shows an absorption band at λmax 280 nm while anilinium ion (in acidic
medium) shows λmax at 254 nm. In acidic medium, the nitrogen atom in aniline is
protonated and hence a lone pair of electrons is not able to enter conjugation with
benzene ring.

 Hyperchromic shift: This refers to the increase in intensity of an absorption

band.
 Hypochromic shift: This refers to the decrease in intensity of an absorption band.

A typical UV-Visible spectrum is a plot of absorbance vs wavelength. The

wavelength corresponding to maximum absorbance is known as λmax.

Fig. 5.8. UV-Visible spectrum of a molecule.

Analytical Techniques 5.21

Instrumentation and working of UV-Visible Spectrometer:

The instrument, which is used for the production, observation and recording spectra is
called spectrometer. The basic components of a UV-Visible spectrometer are

1. Radiation source
2. Monochromator
3. Beam splitter
4. Sample cell
5. Detector
6. Recorder

A typical block diagram of UV-Visible spectrometer is shown in Figure 9.

Fig. 5.9. Block Diagram of UV-Visible spectrometer

1. Radiation source: Hydrogen discharge lamp or deuterium lamp or high-pressure

mercury lamp is used as a source for ultraviolet region. A second light source,
tungsten lamp is used for the visible region.
2. Monochromator: The monochromator is used to disperse radiation into different
wavelengths. A narrow band of wavelengths is selected according to the
requirement. A prism or grating is usually used as a monochromator.
3. Beam splitter: Each monochromatic wavelength (single wavelength) beam is
split into two equal intensity beams by a half-mirrored device. The half-mirrored
device is a rotating disc (chopper) which splits each beam into two beams of equal
intensity.
5.22 Engineering Chemistry
4. Cells: The sample container is a matched pair of silica or quartz (for UV region)
and glass (for visible region).
5. Detectors: The intensities of light coming out from the sample and the blank is
measured using a detector. A detector is usually a photomultiplier tube or a
photocell. The detector converts the incident radiation into current. The current is
directly proportional to the concentration of the solution.
6. Recorder: Signal from the detector is amplified and recorded by the recording
system. The recording is done by a recorder pen and spectrum is obtained on a
graph paper.
Working of a UV-Visible spectrometer:
The radiation from the source of light is passed through the monochromator. The
monochromator allows a narrow-desired range of wavelengths to pass through. The
beam of radiation coming out of the monochromator is split into two identical beams
by a beam splitter. One half of the beam (the sample beam) passes through the
reference cell containing the solution of the substance to be analyzed. The other half
of the beam passes through an identical cell containing only solvent. The instrument
is so designed that it compares the intensities of the sample beam (I) and reference
beam (I0) using a detector. The instrument gives the output graph of absorbance, log
(I0/I) vs wavelength. The plot is called UV-Visible (or electronic) spectrum of the
sample. Different compounds have very different absorption maximum and
absorbance. The absorbance of the sample is proportional to molar concentration of
the sample.

Applications of UV-Visible Spectroscopy:

1. Structure of organic compounds: UV spectroscopy is useful in finding the

structure of organic molecules, the presence or absence of unsaturation,
conjugated double bonds, and the presence of heteroatoms etc.
2. Detection of impurities: Additional peaks are observed due to impurities in the
sample, and it can be compared with that of standard compound.
Analytical Techniques 5.23

3. Quantitative analysis: UV-Visible spectroscopy can be used for the quantitative

determination of compounds that absorb UV-Visible radiation. This determination
is based on Beer’s law.
4. Identification of geometrical isomers: Among cis- and trans-isomers, generally
trans-isomer absorbs at a longer wavelength when compared to cis-isomer. ε value
is also higher for the trans-isomer. For example, in cis-stilbene, the two phenyl
groups are not planar due to steric effect and delocalization is remarkably
reduced.

5. Study of kinetics of a chemical reaction: Kinetics of the reaction can be

followed by using UV. This is very useful when reactants and products have
different λmax.
6. Percentage of tautomers: Keto form and enol form absorbs at different
wavelengths. Thus, the keto-enol forms are present in a solution and their
percentage can be found out.
5.24 Engineering Chemistry

DID YOU KNOW?

How does a suntan protect against sunlight? (Absorbance as a function of

wavelength)

The color of our skin is caused by the presence of pigments (i.e. Melanin is a
complicated mixture of optically absorbing materials chromophores), of which
melanin is the most important. The increase in the concentration of melanin
following exposure to the sun is more obvious for fair-skinned people, although
darker people usually tan more quickly because melanin is produced more
efficiently in their skins.

5.6. INFRARED/VIBRATIONAL SPECTROSCOPY

Absorption of radiant energy in the infrared region by a molecule causes
transitions between vibrational energy levels. Therefore, this spectroscopy is known
as vibrational/infrared spectroscopy. Vibrational energy level change is accompanied
by a change in large number of rotational energy levels. So, it is also known as
vibrational–rotational spectroscopy. The energy change between vibrational levels is
of the order of 1 to 100 KJ mol-1.

The infrared portion of electromagnetic spectrum is divided into three regions: the
near-mid- and far- infrared.

Region Wavenumber (cm–1)

Far Infrared 400–10

Infrared (Mid) 4000–400

Near Infrared 14000–4000

Analytical Techniques 5.25

Condition for a molecule to absorb infrared radiation:

All types of molecules cannot interact with infrared radiation. The essential
condition for a molecule to absorb infrared radiation is given below.

“For a vibration to be IR active there should be a change in dipole

moment of the molecule, or the molecule should have permanent dipole
moment”.

Molecules Dipole moment Infrared absorption

H2, N2, O2 No dipole moment No infrared absorption

CH4, CO2, H2O Have dipole moment Absorb infrared

Modes of Molecular Vibrations:

A molecule is not rigid. Atoms in a molecule can be considered as balls of
different masses connected by tiny weightless springs.

Fig. 5.10. Ball and spring representation of a diatomic molecule

When a molecule absorbs infrared radiation, it results in vibrations. The two

modes fundamental molecular vibrations known are

1. Stretching vibrations: In stretching vibrations, bond distance between two atoms

increases or decreases but the bond angle remains constant. There are two types of
stretching vibrations.

* CO2 does not have a permanent dipole moment, but its dipole moment
changes during asymmetric stretching and bending.
5.26 Engineering Chemistry
(a) Symmetric stretching: Atoms of the molecule move symmetrically with respect
to the central atom.
(b) Asymmetric stretching: Atoms of the molecule move in the opposite direction
with respect to central atom.

Fig. 5.11. Stretching vibrations of a molecule.

2. Bending vibrations: In bending vibrations, the bond length remains constant, but
the bond angle varies. The energy required for bending is less than energy required
for stretching vibration. Four types of bending vibration are known.

(a) Scissoring: The atoms move away and closer like the movement of scissors. This
happens in a plane.
(b) Rocking: In this vibration, movement of atoms takes place in the same direction
within a plane.
(c) Wagging: In this vibration, two atoms simultaneously move up and down the
plane with respect to the central atom.
(d) Twisting: In this vibration, one atom moves up the plane and the other atom
moves down the plane with respect to the central atom.

Fig. 5.12. Bending vibrations of a molecule.

Analytical Techniques 5.27

The number of fundamentals vibrational modes for a polyatomic molecule can be

calculated as follows.

(a) For a non-linear molecule containing N atoms has (3N–6) fundamental vibrational
modes.
(i). Water, H2O triatomic, non-linear. Therefore (3N–6) = (3×3–6) = 3
fundamental modes of vibration. They are symmetric stretching, asymmetric
stretching, and bending vibrations.

(ii). Methane, CH4→(3×5–6 ) = 9 fundamental vibrational modes

(iii) Benzene, C6H6→(3×12–6) = 30 fundamental vibrational modes

(b) For a linear molecule containing N atoms has (3N–5) fundamental vibration
modes.
(i). CO2 triatomic linear
Therefore (3N–5) = (3×3–5) = 4 fundamental modes of vibration. They are
symmetric stretching, asymmetric stretching, in plane bending and out of plane
bending.
5.28 Engineering Chemistry
Of the four normal modes of vibration of CO2, only the symmetric stretching is not
infrared active as there is no net change in dipole moment during stretching. The
other three vibrations (asymmetric stretching, twisting and wagging) are all infrared
active.

Instrumentation and Working of Infrared Spectrophotometer:

The basic components of an infrared spectrophotometer are

1. Radiation source
2. Monochromator
3. Sample cell
4. Detector
5. Recorder
A typical block diagram of infrared spectrometer is shown in Fig 5.13.

Fig. 5.13. Block Diagram of Infrared Spectrometer

1. Radiation source: The common radiation sources for infrared spectrometer is an

inert solid heated electrically to 1000 to 1800° C. Three popular sources of
radiation are
(a) Nichrome wire.

(b) Nernst Glower (a rod made from mixture of oxides of Zr, Th and Ce).

(c) Globar (silicon carbide rod).

They all produce continuous radiation, but with different energy profiles.

2. Monochromator: Monochromator is used to disperse the radiation into different

wavelengths. A narrow band of wavelengths is selected according to the
Analytical Techniques 5.29

requirement. Optical prisms made of NaCl, KBr and grating help to choose the
wavelength.
3. Sample cell: Solid samples are usually mixed with dry KBr and made into
transparent disk at high pressure. Liquid samples can be either recorded neat or as
solutions in CCl4, CHCl3 or CS2.
4. Detectors: It converts thermal energy into electrical energy. Thermocouple
detectors or photoconductivity cells are used.
5. Recorder: The output is recorded on a computer and is plotted on a graph.
Usually, transmittance or absorbance is plotted against wavenumber.

Working of infrared spectrophotometer:

Radiation sources produce infrared radiation. Monochromator converts this
light into energy of desired wavelength. When the infrared beam passes through the
sample, transmitted light becomes less intense due to absorption of certain
wavelengths. Different bonds and functional groups absorb different energy regions.
The changes are electronically compared with the reference beam and detected by the
detector. The signal from the detector is passed to the recording unit and recorded.
Usually, transmittance or absorbance is plotted against wavenumber.

Representative IR Spectrum of a sample is shown below

5.30 Engineering Chemistry

Analysis of the Spectra:

The entire infrared spectrum is divided into group frequency region and fingerprint
region.

 Group frequency region: (4000–1400 cm–1)

In the group frequency region, the peaks corresponding to different functional
groups can be observed. Functional groups can be determined as different functional
groups absorb at different frequencies.

Representative stretching frequencies of some common functional groups are given

below.
Stretching frequencies
Functional group
(in cm–1)

C–H 2900–3100

C=C 1600–1700

O–H 3100–3500

C=O 1700–1800

N–H 3300–3400

 Fingerprint region: (1400–700 cm–1)

In this region molecules give very rich and intense absorption bands which are
unique and characteristic of the molecule. No two organic compounds (except
enantiomers) will have an identical absorption band in the fingerprint region. Hence
this region can be considered as a fingerprint of a molecule.
Analytical Techniques 5.31

Fig. 5.14. Typical Infrared absorption values for various types of bonds

Applications of Infrared Spectroscopy:

1. Detection of functional groups:

Various functional groups can be detected from the functional group region of
the infrared spectrum. Each functional group absorbs at different wavenumbers. For
example, C=O stretching occurs around 1700 cm–1 while O–H stretching occurs
around 3200 cm– 1.

2. Identification and characterization of compounds:

Fingerprint region can be used for the identification of compounds. No two
compounds can have the same set of peaks in the fingerprint region.

3. Studying the progress of the reaction:

Progress of chemical reaction can be determined by examining the small
portion of the reaction mixture withdrawn from time to time. For example, when an
alcohol is oxidized to corresponding aldehyde or ketone, the absorption band ~3300
cm–1 due to O–H stretching diminishes and a new absorption band appears
~1700 cm–1 due to C=O stretching.
5.32 Engineering Chemistry

4. Detection of impurities:
The infrared spectrum of the test sample to be determined is compared with
the standard compound. Impure samples generally give broad and poorly resolved
bands.

5. Intermolecular and intramolecular H-bonding in molecules:

Free O-H and hydrogen bonded O–H absorbs at different frequencies. Infrared
spectra can be used to identify between intermolecular and intramolecular hydrogen
bonding.

6. Moisture content in samples:

If a sample contains moisture, it shows absorption bands around 3300 cm–1
due to O–H stretching. If moisture is absent, no such peak will be present. This can be
used to ensure the dryness of the samples.

5.7. CHROMATOGRAPHY
Chromatography is an analytical technique that can be used for qualitative or
quantitative analysis. It can both identify components in a mixture and determine how
much of each component is present. It is a useful form of separation science that uses
intermolecular forces, to separate the components of a mixture according to their
properties.

Chromatography has a wide range of uses, including in:

 Pharmaceuticals Science – identifying elements and molecules in drugs as well
as measuring the purity of medicines
 Environmental Science – analyzing water quality and gases in the air and the
impact they may have on Earth
 Police Work – analysis such as breathalyzers and drug detection
 Forensic science and archaeology – analyzing material such as blood and hair
samples
Analytical Techniques 5.33

 Biomedical Research – analyzing material such as proteins in cancer research

 Food Science – analyzing the nutritional quality of food and food spoilage

In chromatography technique, a mixture of solute is allowed to interact with two

physically distinct entities, that is, the stationary phase and the mobile phase. The
mixture of solutes is dissolved in a common solvent and is separated from one another
by a differential distribution of solutes between the stationary and the mobile phase.
The stationary phase can be the solid/gel/liquid/solid-liquid mixture that is
immobilized, and it may have the ability to bind some type of solutes on to it. And the
mobile phase can be liquid or gas which passes over the stationary phase.
General Principle of Chromatography:

All forms of chromatography work on the same principle. All chromatography

uses two phases to separate a mixture. They have a stationary phase (a solid or liquid
supported on a solid) and a mobile phase (a liquid or a gas).

Mobile phase, which is a solvent moves over or through the stationary phase.
Stationary phase, which is either a solid with a high surface area or a liquid coated
onto a solid support. It always stays still. The mobile phase moves through and carries
a sample (solute) over the stationary phase. Components of the sample are more
attracted to either the mobile or the stationary phase, depending on their
intermolecular forces. This makes the components move at different rates and
separates them.

Several key terms are used to describe this attraction

Affinity: Components of a sample are attracted, by intermolecular forces, to the

mobile or stationary phase. High affinity means that the component interacts strongly
with the mobile or stationary phase.

Adsorption: Components of the sample adsorb onto the stationary phase from the
mobile phase if they are attracted to, or have an affinity for, the stationary phase.
5.34 Engineering Chemistry

Desorption: components of the sample desorb off the stationary phase into the
mobile phase if they are attracted to, or have an affinity for, the mobile phase.
During the process, the sample containing many molecular components comes
into contact with the stationary phase and the components distribute themselves
between the stationary and the mobile phase. If some components in the sample are
bound to the stationary phase, then they will spend more time in stationary phase and
hence their movement in the chromatographic system will be retarded.
On the other hand, the molecules that show weak affinity/interaction with the
stationary phase spend more time with the mobile phase and are rapidly removed and
eluted from the system. Thus, the rate of migration of the solute depends on the rate
of interaction of it with the stationary and mobile phase. Distribution or Partition
coefficient (Kd) describes the way an analyte distributes between the two immiscible
phases.
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒊𝒏 𝒔𝒕𝒂𝒕𝒊𝒐𝒏𝒂𝒓𝒚 𝒑𝒉𝒂𝒔𝒆
𝐊𝐝 =
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒊𝒏 𝒎𝒐𝒃𝒊𝒍𝒆 𝒑𝒉𝒂𝒔𝒆
Thus, the difference in Kd value of the components results in their separation. And the
general process of moving a solute mixture through a chromatographic system is
called development.

Classification of Chromatography:
a) Based on mechanism of separation:
I. Adsorption chromatography
II. Partition chromatography
b) Based on phases:
I. Solid phase chromatography
(i) solid- liquid chromatography
(ii) solid-gas chromatography
II. Liquid phase chromatography
(i) Liquid- liquid chromatography
(ii) Liquid-gas chromatography
Analytical Techniques 5.35

c) Based on shape of chromatographic bed:

I. Planner chromatography
(i) Paper chromatography
(ii) Thin layer chromatography

II. Column chromatography

(i) Packed column chromatography
(ii) Open tubular column chromatography

5.8. THIN LAYER CHROMATOGRAPHY (TLC)

Thin layer chromatography (TLC) is the separation technique used to separate non-
volatile organic compounds present in chemical mixtures. The method is based on a
polarity interplay between the sample and two other constituents namely the
stationary (solid) phase, and the mobile phase (liquid or gas). The relative affinity of
the organic compound towards the mobile and stationary phase is the deciding factor
for the separation of individual components of the chemical mixture using TLC. The
compounds with higher affinity towards stationary phase move at lower speed, when
compound with lower affinity during the uphill of mobile phase in the TLC. The
schematic representation depicting the overview of the steps followed in the
qualitative separation of organic mixture using TLC is shown below.

Fig. 5.15. Schematic representation of the steps followed in the qualitative

separation of organic mixture using TLC.
5.36 Engineering Chemistry

The scientific measure of the chromatographic separation in the TLC is the retention
factor (Rf value), which is the ratio of the distance travelled by the compound to the
distance travelled by the solvent. Rf values are always less than 1. Effective
separation of the organic compounds from the organic mixture can be made by the
proper choice of solvent with optimal polarity relevant to the individual components
of the organic mixture.

Basic components of TLC

The basic components of TLC are as follows

TLC Plate: One of the main components of thin layer chromatography (TLC) is the
TLC plate that consists of the thin layer of adsorbents such as silica gel or activated
alumina coated onto the glass plates or plastic films. Generally, the coated thin layers
are inert and stable in nature. For better analysis, the coating of the stationary phase
must be done throughout the plate. Spotting is the process in which organic mixture is
spotted using micro syringe or capillaries on the pre-lined TLC plates.

Mobile Phase: The second important component of the thin layer chromatography is
the mobile phase, which is generally a solvent or mixture of solvents. The solvent to
be used as the mobile phase should be particulate free and chemically inert with high
purity. Generally, the solvents used as the mobile phase are termed as eluting
Analytical Techniques 5.37

solvents. Wide range of solvents with varying degree of polarity can be used as the
mobile phase in the TLC procedure.

TLC chamber: The third main component of the thin layer chromatography is the
TLC chamber, where the chromatographic separation of organic compounds takes
place. TLC chamber keeps away the dust particles and prevents the solvent
evaporation during the entire process. For the development of the spots, a uniform
environment needs to be maintained inside the chamber.

Model image of TLC chamber with TLC plate and filter paper

Filter paper: To ensure uniform uphill of mobile phase (solvent) throughout the TLC
plates, it is mandated to keep a filter paper moistened with the solvent

Iodine Staining test: Iodine staining technique is employed to visualize the

developed TLC to corroborate the separation of organic compounds from the mixture,
since most of the organic compounds react with the sublimed iodine forming yellow-
brown spots. Alternatively, UV chamber can also be used to identify the separation of
organic compounds.

The detailed procedure of executing the TLC experiment in separating organic

compounds from the mixture is highlighted below. The steps involve three stages as
listed below;
5.38 Engineering Chemistry

1) Running the TLC

2) Visualizing the spots
3) Evaluating the TLC
Running the TLC:
1) Mark two lines on the white surface of the TLC plates using pencil. Refrain using
pen as the ink, which is mainly of dye may interfere with the results of developing
spots in the TLC plate.
2) The second step is the spotting of the organic mixture on the TLC plate using
capillary or micro syringe. Approximately 1 µL of the sample may be spotted on
the bottom line of the TLC. For multiple spotting, use separate capillaries.
Suitable solvent may be used, if the test sample is solid or high viscous liquid.
3) Allow the TLC to air dry for 10 min.
4) Take 10 mL of mobile phase (solvent) in the TLC chamber and keep for 10
minutes in room temperature.
5) Using clean forceps, place the TLC plate inside the chamber in straight position
with the spotted samples near to the solvent. Placing TLC in straight position
ensures the uniform uphill of the solvent in the plate.
6) Place a solvent moistened filter paper wick on the chamber for the uniform rise of
solvent in the TLC plate.
7) Once the solvent rise reaches the top line, take out the TLC plates.
Visualizing the spots:
8) Prepare Iodine chamber by adding few crystals of Iodine in the glass vial
containing 1~2 g of powdered silica gel.
9) Insert the air dried TLC plates into the glass vial using clean forceps and close the
lids.
10) Gently shake the chamber to bury the TLC plate in the iodine-stained silica.
Yellow brown coloured spots will appear immediately.
11) Record the observations by encircling the spots using pencil.
Analytical Techniques 5.39

Evaluating the TLC:

12) Calculate the distance between the top and bottom line made in the TLC plate. It
corresponds to the distance travelled by the mobile phase (solvent).
13) Calculate the distance between the bottom line and the spots that appeared after
the iodine staining test. It corresponds to the distance travelled by the separated
organic compound.
14) Calculate the retention factor, Rf by taking the ratio of distance travelled by the
organic compound to that of the mobile phase (solvent).
15) Record the observations for the future reference.

Detection of Analytes:
If the compounds are colorless, then the detection can be done in several ways.

1) By spraying the plate with a specific reagent that converts the analyte to a colored
product. For example, during the separation of a mixture of amino acids, ninhydrin is
sprayed on the dried chromatogram. Ninhydrin reacts with amino acids to give
colored compounds, mainly brown or purple. So, after spraying ninhydrin the spots of
amino acids will be visible.

Fig 5.16: Separation of a mixture of amino acids by ninhydrin.

5.40 Engineering Chemistry

2) By incorporating a fluorescent dye into the stationary phase so that when the plate
is examined under ultraviolet light the analytes show as blue, green or black spots
against a fluorescent background and thus the separated components can be visually
detected.

3) By using radiolabeled analytes and subjecting the developed plate to

autoradiography using an X-ray film or by scanning the plate with a radio-
chromatograph scanner.

Application of Thin Layer Chromatography:

 Detection of purity of sample can be carried out by TLC. If any impurity is

detected, then it shows extra spots and thus can be detected easily.
 It can be employed in purification, isolation and identification of natural products
like volatile oil or essential oil, fixed oil, waxes, terpenes, alkaloids, glycosides,
steroids etc.
 Reaction mixture can be examined by TLC to assess whether the reaction is
complete or not. This method is also used in checking other separational processes
and purification processes like distillation, molecular distillation etc.

5.9. COLUMN CHROMATOGRAPHY

Column chromatography is described as the useful technique in which the
substances to be isolated are presented onto the highest point of a column loaded with
an adsorbent (stationary phase), go through the column at various rates that rely upon
the affinity of every substance for the adsorbent and the solvent or solvent mixture,
and are typically gathered in solution as they pass from the column at various time.

The two most common examples of stationary phases for column chromatography are
silica gel and alumina while organic solvents are regarded as the most common
mobile phases.
Analytical Techniques 5.41

Column Chromatography Principle:

The main principle involved in column chromatography is the adsorption of the

solutes of the solution with the help of a stationary phase and afterward separates the
mixture into independent components.

At the point when the mobile phase together with the mixture that requires being
isolated is brought in from the top of the column, and the movement of the individual
components of the mixture takes place at various rates.

The components with lower adsorption and affinity to the stationary phase head out
quicker when contrasted with the greater adsorption and affinity with the stationary
phase. The components that move rapidly are taken out first through the components
that move slowly are eluted out last.

The adsorption of solute molecules to the column happens reversibly.

Fig. 5.17. Column chromatography diagram

5.42 Engineering Chemistry

Column Chromatography Components:

Components of a typical chromatographic system using a gas or liquid mobile phase
include:

Stationary phase: Generally, it is a solid material having a good adsorption property

and should be suitable for the analytes to be separate. It should not cause any
hindrance in the flow of the mobile phase.

Mobile phase and delivery system: This phase is made up of solvents that
complement the stationary phase. The mobile phase acts as a solvent, a developing
agent (promotes separation of components in the sample to form bands), and an
eluting agent (to remove the components from the column that are separated during
the experiment).

Column:
 Liquid chromatography: 2-50 cm long and 4 mm internal diameter, fabricated
with stainless steel
 Gas chromatography: 1-3 m long and 2-4 mm internal diameter, fabricated
either with glass or stainless steel
A column’s material and its dimension are very crucial to support the stationary phase
and promote effective separations.

Injector System: Responsible for delivering test samples to the column’s top in a
reproducible pattern.

Detector and Chart Recorder: This gives a continuous record of the presence of
analytes in the elute as they come out from the column. Detection relies on the
measurement of a physical parameter (like visible or UV adsorption). On the chart
recorder, each separated analyte is represented by a peak.

A collector at the bottom is placed at the bottom end of the column set up to collect
the separated analytes.
Analytical Techniques 5.43

Column chromatography Procedure:

The steps included in the column chromatography are

Preparation of the Column:

Mostly the column is comprised of a glass tube with an appropriate stationary phase.
The bottom end of the column is packed with glass wool/cotton wool or an asbestos
pad after which the stationary phase is packed.

After packing the column, a paper disc is placed on the top to avoid the disturbance of
the stationary phase during the introduction of the sample or mobile phase.
The disturbance in the stationary phase (adsorbent layer) leads to the irregular bands
of separation.

The column should be properly washed and completely dried before in-use.

Introduction of the Sample:

The sample (a mixture of components) is dissolved in the minimum amount of the
mobile phase. At one instant, the sample is introduced into the column and on the top
portion of the column, it is absorbed. Through the elution process, the individual
sample can be isolated from this zone.

Elution technique:
Through this technique, the individual components are separated completely from the
column.

Detection of Components:
In case the mixture separated in a column chromatography procedure are colored
compounds, then monitoring the separation progress is simple.

In case the compounds undergoing separation are colorless, then small fractions of the
eluent are sequentially collected in tubes that are labeled. Through TLC, the
composition of each fraction is determined.
5.44 Engineering Chemistry

Column Chromatography Uses:

Column chromatography is one of the versatile methods for purifying and separating
both solids and liquids.

Major applications:

 To isolate active constituents

 To separate compound mixtures

 To remove impurities or carry purification process

 To isolate metabolites from biological fluids

 To estimate drugs in drug formulations or crude extracts

Analytical Techniques 5.45

QUESTIONS
1. Define spectroscopy
2. Derive Beer-Lambert’s law. What are its applications?
3. Explain the principle and instrumentation of UV-Visible spectroscopy photometer
with neat block diagram.
4. Explain the various electronic transitions possible on the absorption of UV-
Visible radiation.
5. Explain the principle and instrumentation of IR spectroscopy photometer with
neat block diagram.
6. Explain the various vibrations possible when a molecule absorbs infrared
radiation.
7. Define the working principle of chromatography
8. Define (i) Partition coefficient (ii) Retention factor
9. Discuss the TLC separation procedure
10. Explain in detail about column chromatography