12/1/2022

Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
• Introduction to the Course
• Syllabus overview
• Water Pollution
• Causes of Water Pollution
• Effects of Water Pollution
• Summary

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Introduction to the Course

Course Code - CYC102
Course Title - Engineering Chemistry
Number of Credits - 4
Course Type – General Institute Requirements (GIR) Course

OBJECTIVES

To learn about hard-soft water and solve problems based on hardness estimation.

To comprehend the structure, properties, synthesis and applications of polymers.

To investigate engineering materials such as nanomaterials, fuels and lubricants.
To understand the structure and properties of compounds using IR, UV, NMR, Thermal
analysis and chromatography.
To acquire skills to perform laboratory experiments, demonstrate safe and proper use of
standard chemistry glassware and equipment.

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Syllabus Overview
UNIT I: Water and its Treatment
Sources, hard and soft water, estimation of hardness by EDTA method, softening of water, boiler
feed water, treatment methods, specifications for drinking water, BIS and WHO standards,
desalination processes.
Unit-II: Polymer and Composites
Introduction, functionality, classification, mechanism of polymerization, molecular weight,
structure property relationship, molding techniques, synthesis, properties and application of
commercially important polymers, conducting polymers, Composites: Introduction
classification, constituents, advantages and applications.
Unit-III: Engineering Materials
Introduction to Nano chemistry, synthesis, characteristics and applications of carbon
nanostructures, Fuels- Classification, types of coal, determination of calorific value of solid fuels,
Bomb calorimeter, theoretical oxygen, proximate and ultimate analysis of coal, manufacture of
metallurgical coke, flue gas analysis, Lubricants-Definition, theories, characteristics, additives to
lubricants, solid lubricants.
Unit-IV: Characterization Techniques
Introduction to spectroscopy, UV-Visible spectroscopy: Principle, Instrumentation and
application, IR spectroscopy: Principle and applications, NMR: Principle, Instrumentation,
applications of NMR, Thermal method: Instrumentation, fundamental principles and
applications of TGA, DTA and DSC, Introduction to chromatographic techniques.
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Syllabus Overview (Contd.)

Text Books
1. Vairam, S., “Engineering Chemistry- A textbook of chemistry for engineers”,
Wiley India Pvt. Ltd., 2018.
2. Palanna, O. G., “Engineering Chemistry”, Tata McGraw-Hill Publishing
Company Ltd., 2017.
3. Jain, P.C., “Engineering Chemistry- Chemistry of Engineering Materials. A
Modern Approach”, Dhanpat Rai Publishing Company (P) Ltd., 2022.

Reference Books
1. Dara, S. S. and Umare, S. S., “A Text Book of Engineering Chemistry”, S.
Chand Publishing, 2011.
2. Poole, Jr, Charles, P., and Frank J. Owens., “Introduction to
nanotechnology”, John Wiley and Sons, 2009.

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Water Pollution

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Water Pollution (Contd.)

Waterless countries- just 10 countries
account for 60 % of the world
population without access to clean
water (WaterAid, 2018)

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Water Pollution (Contd.)

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Water Pollution (Contd.)

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Introduction
What is Water Pollution?
• The World Health Organisation (WHO) says that polluted water is water
whose composition has been changed to the extent that it is unusable. In
other words, it is toxic water that cannot be drunk or used for essential
purposes like agriculture, and which also causes diseases like diarrhoea,
cholera, dysentery, typhoid and poliomyelitis that kill more than 500,000
people worldwide every year.
• The main water pollutants include bacteria, viruses, parasites, fertilisers,
pesticides, pharmaceutical products, nitrates, phosphates, plastics, faecal
waste and even radioactive substances. These substances do not always
change the colour of the water, meaning that they are often invisible
pollutants. That's why small amounts of water and aquatic organisms are
tested to determine water quality.

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Causes of Water Pollution

Main causes of Water Pollution
The most common cause of poor quality water is human activity and its
consequences, which we will now go on to explain:

Global warming
Rising global temperatures caused by CO2 emissions heat the water, reducing
its oxygen content.

Deforestation
Felling forests can exhaust water resources and generate organic residue
which becomes a breeding ground for harmful bacteria.

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Causes of Water Pollution (Contd.)

Industry, agriculture and livestock farming
Chemical dumping from these sectors is one of the main causes
of eutrophication of water.

Rubbish and faecal water dumping

The UN says that more than 80% of the world's sewage finds its way into
seas and rivers untreated.

Maritime traffic
Much of the plastic pollution in the ocean comes from fishing boats,
tankers and cargo shipping.

Fuel spillages
The transportation and storage of oil and its derivatives is subject
to leakage that pollutes our water resources.

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Effects of Water Pollution

Deteriorating water quality is damaging the environment, health conditions and
the global economy. Here are some of the other consequences:

 Destruction of biodiversity. Water pollution depletes aquatic ecosystems and

triggers uncontrolled proliferation of phytoplankton in lakes — eutrophication —.
 Contamination of the food chain. Fishing in polluted waters and the use of waste
water for livestock farming and agriculture can introduce toxins into foods which
are harmful to our health when eaten –Biomagnification-.
 Lack of potable water. The UN says that billions of people around the world have
no access to clean water to drink or sanitation, particularly in rural areas.
 Disease. The WHO estimates that about 2 billion people have no option but to
drink water contaminated by excrement, exposing them to diseases such as
cholera, hepatitis A and dysentery.
 Infant mortality. According to the UN, diarrhoeal diseases linked to lack of
hygiene cause the death of about 1,000 children a day worldwide.

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Summary
The waters of the River Ganges flow clear and clean through the
Indian city of Rishikesh at the gateway to the Himalayas. In these
mountains, nobody would guess that this water will be transformed
into one of the most heavily polluted rivers in the world, with faecal
bacteria levels up to 31 million per 100 millilitres. This is according to
reports from Sankat Mochan Foundation, an organisation struggling
to restore the Ganges to its former glory. These levels mean that the
sacred river has become synonymous with water pollution, a
worldwide problem affecting one in every three people on the
planet, according to the United Nations (UN).
Half of the world's inhabitants will live in water-scarce areas by 2025,
so every drop of polluted water today is an irreparable loss for
tomorrow.

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Thank You!
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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
• Introduction
• Sources of Water
• Characteristics imparted by impurities in water
• Hardness of Water

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Introduction
What is Water?
 Water is made up of tiny molecules of hydrogen and oxygen.
 Each molecule is so small (0.275 nm) that you cannot see it with the
most powerful microscope.
 Pure water has no taste, no color and does not smell of anything.
 Water exists in three forms on earth:
 Solid (Ice, Hail, Snow or Frost)
 Liquid (In lakes, oceans, rain, dew, fog or mist)
 Gas (Steam or water vapour -“invisible” water in the air)
 Its most important use as an engineering material is in the “ STEAM
GENERATION”
 It is also used as a COOLANT in power an chemical plants.
 Besides, water is used predominantly in drinking, bathing, sanitary,
washing irrigation, textiles, chemicals, paper, etc.

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Introduction (Contd.)
One estimate of global water distribution (Percents are rounded, so will not add to 100)

Source: Igor Shiklomanov's chapter "World fresh water resources" in Peter H. Gleick (editor), 1993, Water in Crisis: A Guide to the World's Fresh
Water Resources (Oxford University Press, New York).

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Introduction (Contd.)
This image shows blue spheres representing
relative amounts of Earth's water in
comparison to the size of the Earth.
The largest sphere represents all of Earth's
water. Its diameter is about 860 miles. This
sphere includes all of the water in the oceans,
ice caps, lakes, rivers, groundwater,
atmospheric water, and even the water in you,
your dog, and your tomato plant.
The world's liquid fresh water constitutes of
99 percent is groundwater, much of which is
not accessible to humans. The diameter of
this small bubble is about 169.5 miles.
The tiny dot represents fresh water in all the
lakes and rivers on the planet. Most of the
water people and life of earth need every day
comes from these surface-water sources. The
diameter of this sphere is about 34.9 miles.

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Sources of Water
Purest form of natural water.
Contains suspended matter Obtained due to evaporation from
with disease causing earth’s surface. on its journey down
pathogenic bacteria. gets loaded with industrial gases
Therefore not suitable for Rain Water and suspended solid particles.
direct human consumption. Fed by rain and spring water.
Contains dissolved minerals of the
River Water soil such as chlorides, sulphates,
bicarbonates of Na, Ca, Mg, Fe. Also
Surface contain organic matter, small
Water particles of rock and sand, other
Lake Water suspended impurities.
Has constant chemical composition.
Source Contain less dissolved minerals but
Sea Water more organic matter.

Most impure form of water.

Contains dissolved salts (eg NaCl,
Underground Spring and Na2SO4, KHCO3, Mg(HCO3),
Water Well Water Ca(HCO3)2, KBr, MgBr2, etc.

Percolates into soil. Comes in contact with a Clearer in appearance due to

number of mineral salts. filtering action of soil. Contain more
dissolved salts. Thus has more
hardness.
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Characteristics
Characteristics imparted by impurities in water

Physical Impurities Chemical Impurities Biological Impurities

 Dissolved mineral matter

 Colour Microorganisms such
Hardness
 Taste as algae, bacteria,
Alkalinity
 Odour fungi, viruses,
Total solids
 Turbidity pathogens, parasitic
Corrosion
worms, etc.
 Dissolved gases

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Characteristics (Contd.)
PHYSICAL IMPURITIES
COLOUR

 Colour caused by metallic substances like salts of Fe, Mn, humus materials,
algae, weeds, protozoans, tannins, etc.
 Colour is due to dissolved substances and substances present as fine
colloids.
 Change in colour is fine unless associated with any chemical of toxic nature.
 Usually variation of water colour is often used as an indicator of water
quality. E.g.
Yellowish tinge: Presence of chromium and appreciable amount of
organic matter.
Yellowish red colour: Presence of Fe.
Red-Brown colour: Presence of peaty matter
 Removal or reduction of colour and organic matter is generally accomplished
by coagulation, settling, adsorption, filtration and sometimes chlorination.

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Characteristics (Contd.)
PHYSICAL IMPURITIES
COLOUR
Laguna Colorada
The shallow salt lake in Bolivia is also known as
Red Lagoon because of the blood-like deep red
colour it exhibits. The red colour is due to the
presence of algae and rich minerals in the
water. While massive deposits of borax gives
the white colour as a contrast.

Masazir Lake
Situated in Azerbaijan, this lake is known for
salt farming. At times, salt forms huge blocks
on its waters. Large volumes of chloride and
sulphate can be found concentrated in the ion
composition of the water of the lake.
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Characteristics (Contd.)
PHYSICAL IMPURITIES
TASTE

 It is usually directly interlinked with odour.

 However, in some waste water, taste is not accompanied by odour. Thus
presence of dissolved mineral in water produces taste, but not odour.
E.g.
 Bitter taste can be due to the presence of Fe, Al, Mn, SO42-, or excess
of lime.
 Soapy taste can be due to the presence of unusual amount of
NaHCO3.
 Brackish taste is due to the presence of unusual amount of salts.
 Palatable taste is due to the presence of dissolved gases (CO2) and
minerals (like Nitrates) in water.
 Organic tastes may be removed by means of activated carbon and
aeration.

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Characteristics (Contd.)
PHYSICAL IMPURITIES
ODOUR
 Disagreeable odour in water may be due to presence of living organism,
decaying vegetation including algae, bacteria, fungi and weeds; and even
due to industrial effluents.
 Common causes include:
 Presence of inorganic and organic compounds of N,S and P and the
putrefaction of proteins and other organic materials present in sewage;
 Industrial effluents containing organic substances such as alcohols,
aldehydes, phenols, esters, ketones, etc. flowing into the water bodies. For
e.g.
 Algae gives a grassy odour due to liberation of essential oils from their
bodies.
 Colloidal vegetable matter gives a peaty odour.
 Growth of Fe and S bacteria produces an offensive odour.

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Characteristics (Contd.)
PHYSICAL IMPURITIES
TURBIDITY
 It is due to colloidal, extremely fine suspension such as clay, slit, finely
divided matter (organic and inorganic), micro-organism like plankton, etc.
 Turbidity expresses the optical properties of water containing insoluble
substances, which scatter light rather than to transmit in straight lines.
 It depends not only on the quantity of insoluble substances but also on their
shape, size and reflective index.
 Turbidity in water can be removed by sedimentation, followed by
coagulation, filtration, etc.

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Characteristics (Contd.)
BIOLOGICAL IMPURITIES
 The source of biological impurities is usually the discharge of domestic and
sewage wastes, excreta, etc.
 Micro-organisms are abundant on the surface instead of deep waters.
 They have high growth in the temperature range of 20-35°C.
 The commonest type of microorganism – algae, fungi and bacteria form
“slime” which causes fouling as well as corrosion. It is the common cause of
clogging. Therefore, chemical treatment like chlorination is done to tackle
biological impurities.
 Even the bottle sludge and
phytoplanktons on the surface are the
breeding grounds of worms like flat
worms, hair worms, tin round worms,
etc. They are parasitic in nature and
affects fishes as well as human
health.

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Characteristics (Contd.)
CHEMICAL IMPURITIES
 DISSOLVED MINERAL MATTER
HARDNESS
ALKALINITY
TOTAL SOLIDS
CORROSION
 DISSOLVED GASES (such as CO2 , O2 , NH3 , etc.)

 Inorganic and organic chemicals discharged from domestic and industrial

effluents alters the characteristics of water. Mineral matters have origin from
rocks and industrial effluents. They include mineral acids, Ca2+ , Mg2+ , Na+ ,
K+, Fe2+ , F-, etc.
 Further, the presence of free CO2, mineral acids e.g. H2SO4, and weakly
dissociated acids leads to Acidity in water which determines the power to
neutralize the hydroxyl ions.

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Hardness of Water
 Hardness of water is that characteristic, which “prevents the lathering of
soap”.
 This is due to the presence in water of certain salts of Calcium, magnesium
and other heavy metals dissolved in it.
 A sample of hard water, when treated with soap does not produce lather, but
on the other hand forms a white scum or precipitate. This precipitate if due to
the formation of insoluble soaps of calcium and magnesium.

Depending on the hardness of your water,

after using soap to wash hands you may
have felt like there was a film of residue left
on your hands. In hard water, soap reacts
with the calcium (which is relatively high in
hard water) to form "scum". When using
hard water, more soap or detergent is
needed to get things clean, be it your
hands, hair, or your laundry.

1 December 2022 <CYC102—Theory Lecture No. 2> 15

Hardness of Water (Contd.)

A typical reaction involves:

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

Sodium Stearate Calcium Stearate
(Soap) (Insoluble)

2C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

Magnesium Stearate
(Insoluble)

HARD WATER SOFT WATER

Water which does not Water which lathers easily on
produce lather with soap shaking with soap solution is
solution readily, but forms a called as Soft Water.
white curd is called as Hard
Water.

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Hardness of Water (Contd.)

TEMPORARY HARD WATER PERMANENT HARD WATER
Presence of chlorides and sulfates of
Presence of bicarbonates of calcium
calcium and magnesium,
and magnesium, i.e. Ca(HCO3)2 and
i.e. CaCl2, CaSO4, MgCl2, and MgSO4
Mg(HCO3)2 makes the water,
makes the water, permanent hard
temporary hard water.
water.
It is called temporary hardness as it It is called permanent hardness as it
can be easily removed by simple cannot be easily removed by simple
boiling and filtering the water. boiling and filtering the water.
It can be also called Carbonate It can be also called Non-Carbonate
hardness. hardness.

Ca(HCO3)2 CaCO3 + H2 O + CO2

Calcium bicarbonate Calcium carbonate
(insoluble)

Mg(HCO3)2 Mg(OH)2 + 2CO2

Magnesium bicarbonate Magnesium Hydroxide
(insoluble)
1 December 2022 <CYC102—Theory Lecture No. 2> 17

Hardness of Water (Contd.)

Descriptions of hardness correspond roughly with ranges of mineral concentrations:
Soft: 0–20 mg/L as calcium
Moderately soft: 20–40 mg/L as calcium
Slightly hard: 40–60 mg/L as calcium
Moderately hard: 60–80 mg/L as calcium
Hard: 80:120 mg/L as calcium
Very Hard: >120 mg/L as calcium

Unit of hardness
(i) Parts per million (ppm): It is defined as parts of calcium carbonate equivalent
hardness per 106 parts of water.
That is 1 ppm = 1 part of calcium carbonate equivalent hardness in 106 parts of
water.
(ii) Milligrams per litre (mg/L): It is the number of milligrams of CaCO3 equivalent
hardness present per litre of water.
Thus, 1 mg/L = 1 mg of CaCO3 equivalent hardness in 1 L of water.
1 Litre = 1 kg = 1000 g = 1000 x 1000 mg = 106 mg
1 mg/L = 1 mg of CaCO3 equivalent hardness in 106 mg of water or = 1 ppm.

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Effects of Water Pollution

Disadvantages of hardness of water
The disadvantages of using hard water for domestic and industrial purposes are
plenty.
(I) For domestic use
(i) Washing—Presence of hardness causes wastage of soap, etc.
(ii) Drinking—Excess calcium content in drinking water may be injurious to health.
(iii) Cooking—It may affect the utensils if the water is hard. Effect the cooking
process due to the presence of mineral contaminants.
(iv) Bathing—Lack of foaming soap leads to uneasiness of bathing and wastage of
soap.
(II) For industrial use
(a) Paper—The presence of calcium and magnesium has impact on the properties
and quality of paper and their products.
(b) Textile—During dyeing process of cloths, the calcium and magnesium
contaminants induce poor quality of shades.
(c) Sugar—Causes hindrance to crystallization of sugar, if nitrates and sulphates of
calcium and magnesium are present.
(d) Boilers—Formation of scales corrodes the boilers. Wastages of fuel, etc.
1 December 2022 <CYC102—Theory Lecture No. 2> 19

Thank You!
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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
• Estimation of Hardness of Water
• Numerical Problems

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Hardness of Water
Hardness is expressed in terms of degree of hardness which is defined as the
number of parts by weight of Calcium Carbonate hardness per particular
number of parts of water, depending upon the units employed.

Mathematically it can be expressed as-

Chemical equivalent
Hardness of substance Strength of of CaCO3
in terms of CaCO3 substance (mg/l)
Chemical equivalent
of substance

For e.g. for CaSO4:

Strength of 100
Hardness of CaSO4 in
terms of CaCO3 substance (mg/l)
136

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Hardness of Water (Contd.)

Calculate the Temporary hardness, Permanent Magnesium Hardness,
Permanent Hardness, and Total Hardness in terms of Calcium carbonate
equivalents in a water sample containing following dissolved salts per liter:
 Calcium Bicarbonate (12.2 mg)
 Magnesium Bicarbonate (8.2 mg)
 Magnesium Sulphate (5.6 mg)
 Magnesium Chloride (6.2 mg)
 Calcium Sulphate (10.3 mg)
Given that the atomic weight of Mg= 24 amu, Ca=40 amu, S=32 amu, O=16
amu, Cl=35.5 amu and C=12 amu.
Chemical equivalent
Hardness of substance Strength of of CaCO3
in terms of CaCO3 substance (mg/l)
Chemical equivalent
of substance
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Hardness of Water (Contd.)

What is the Hardness of a solution containing 0.585 gms of NaCl and 0.6
gms of MgSO4 per liter?

Chemical equivalent
Hardness of substance Strength of of CaCO3
in terms of CaCO3 substance (mg/l)
Chemical equivalent
of substance

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Hardness of Water (Contd.)

Determination of Hardness of Water by EDTA Method
Ethylenediamine Tetraacetic acid (EDTA) is a reagent which reacts with metal
ions like Ca2+ , Mg2+ forming complex compounds and therefore can be used
to determine the concentration of hardness causing substances.

The stochiometric reaction takes places in which

1000 ml of 1M EDTA = 1g atomic weight of metal
It cane be expressed in terms of equivalent amount of calcium carbonate in
ppm or mg/l as
1 ml of 1M EDTA = 100 mg of CaCO3

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Hardness of Water (Contd.)

 A 100 ml sample of water required 13.5 ml of 0.02 M EDTA solution for
titration using EBT as indicator.
 Another 100 ml of water from the same source was boiled and precipitate
removed by filtration. The filtrate required 6 ml of 0.02 M EDTA for titration.
 Calculate the Total Hardness, Permanent hardness and Temporary
hardness of water sample.

It cane be expressed in terms of equivalent amount of calcium carbonate in

ppm or mg/l as
1 ml of 1M EDTA = 100 mg of CaCO3

1 December 2022 <CYC102—Theory Lecture No. 3> 7

Hardness of Water (Contd.)

 0.28 gm of CaCO3 was dissolved in HCl and the solution was made up to
one liter with distilled water. 100 ml of the above solution required 28 ml of
the EDTA solution on titration.
 100 ml of a hard water sample required 33 ml of same EDTA solution on
titration.
 Another 100 ml of the same water, after boiling, cooling and filtering required
10 ml of EDTA solution on titration.
 Calculate Temporary and Permanent Hardness of Water?

It cane be expressed in terms of equivalent amount of calcium carbonate in

ppm or mg/l as
1 ml of 1M EDTA = 100 mg of CaCO3

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Thank You!
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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
• Alkalinity
• Hard Water Treatment for Domestic and Industrial
Purpose
• Water Softening
• Cold Soda: Lime Process
• Hot Lime Soda Process
• Calgon Process
• Zeolite or Permutit Process
• Ion-Exchange Resins

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Alkalinity
 Alkalinity measures the acid-neutralizing capacity of a water sample.
 The alkalinity of surface water is primarily due to the carbonate,
bicarbonate and hydroxide content and is often interpreted in terms of
the concentrations of these constituents.
 Alkalinity may also include contributions from borates, phosphates,
silicates or other bases if they are present.
 Alkalinity is used to determine the suitability of water for irrigation,
industrial use, raw water characterization and water and wastewater
monitoring.
 Alkalinity is also important as an indicator of water body’s ability to
resist pH change with the addition of acid from an accidental spill or
acid precipitation.

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Hard Water Treatment for Domestic and

Industrial Purpose
The consumers of water have different perceptions about pure water. They are
as follows:
 Home owners concerned with domestic water problems related to colour,
odour, taste and safety to family health, as well as the cost of soap,
detergents, ‘softening,’ or other treatments required for improving the
water quality.
 Chemists and engineers working for industry are concerned with the purity
of water as it relates to the scale deposition and pipe corrosion.
 Farmers are interested in the effects of irrigation waters on the chemical,
physical and osmotic properties of soils, particularly as they influence crop
production.
 Therefore, demand for high quality water is growing around the world.

Contaminated water is unfit for domestic and industrial uses. Water in such
cases is subjected to softening process.

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Water Softening
(External Treatment Process)

 The process of removal of inorganic contaminants like calcium and

magnesium from hard water by any technique is referred to as Softening of
water.
 Hard water cannot be used for domestic as well as for industrial purposes. It
has to be subjected to softening process.
 There are various softening processes. They are mainly:
Cold soda: lime process
Hot lime-soda process
Calgon process
Zeolite or permutit process
Softening water by ion-exchange resins

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Cold Soda: Lime Process

The basic principle involved in softening of hard water, preferably, removal of salts of calcium
and magnesium of temporary hardness, is to neutralize and precipitate as their insoluble
salts by the addition of adequate amounts of Na2CO3 (soda ash) [S] and Ca(OH)2 (lime) [L]
which get deposited at the bottom.

When requisite amounts of soda ash and lime are treated, the soluble calcium and
magnesium salts of hard water chemically interact and get transformed to insoluble salts of
calcium and magnesium.

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Cold Soda: Lime Process (Contd.)

Water drawn from natural sources have temporary hardness that is conveniently
and economically removed by lime treatment, as lime is cheap and removes
efficiently without adding soluble salts in water.

Thus, net outcome of soda-lime treatment is:

 It eliminates both temporary and permanent hardness by precipitating
dissolved impurities as insoluble carbonates which is filtered off.
 Sodium salts of the acid radicals (NaCl, Na2SO4, etc.) are formed after the
treatment.
 Since the reactions are slow during mixing of soda ash and lime, there may be
the possibility deposition/corrosion of the metals due to the deposition of
products like Mg(OH)2 and fine CaCO3.

5 December 2022 <CYC102—Theory Lecture No. 4> 7

Cold Soda: Lime Process (Contd.)

 Requisite quantities of both soda ash and
lime as desired in equivalents are fed
through the hopper into the inner cylinder.
 A stirrer attached to a motor swirls the raw
water continuously along with the soda ash
and lime. As a result of chemical interaction,
carbonates of the metal ions are
precipitated as a fine powder that settles
down very slowly.
 A coagulant like NaAlO2, aluminium
sulphate, sodium aluminate are introduced
to grow the size of the carbonates of
calcium and magnesium particles and to
settle quickly at the bottom, as sludge that
can be easily removed.
 The soft water moves to the outer cylinder
and passes through a filter that filters out
unwanted materials.

5 December 2022 <CYC102—Theory Lecture No. 4> 8

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Hot Lime Soda Process

This method is similar to Cold Lime Soda Process except the temperature is
maintained at 80-110°C and there is no need for coagulants.

The advantages of this method are

 Soda ash and lime interacts with calcium and magnesium ions of hard water
quickly at this temperature and settles down easily and hence there is no
need for the addition of coagulants.
 Softening rate of water is faster.
 Calcium and magnesium contents in water are reduced to 15–25 ppm.
 Sludge settles rapidly and can be removed.
 Filtration process of water is easier.

5 December 2022 <CYC102—Theory Lecture No. 4> 9

Hot Lime Soda Process (Contd.)

 Super-heated steam is sent
simultaneously along with lime and soda
ash at 110°C into the conical reaction
chamber.
 Reaction occurs at a faster rate at this
temperature yielding soft water and the
carbonates of metal ions settles rapidly
as sludge and collects at the bottom and
can be removed.
 The soft water thus got passes through
another, known as filtration unit.
 The filtration unit consists of layers of
fine sand, coarse sand and gravel which
is employed to remove other unwanted
impurities of water.
 Softened water is collected and stored in
tank for industrial use.

5 December 2022 <CYC102—Theory Lecture No. 4> 10

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Calgon Process
Calgon is a trade name of a complex salt, sodium hexametaphosphate (NaPO3)6.
It is used for softening hard water. Calgon ionizes to give a complex anion:

The addition of calgon to hard water causes the calcium and magnesium ions of
hard water to displace sodium ions from the anions of calgon.

This results in the removal of calcium and magnesium ions from hard water in
the form of a complex with Calgon. The water is softened and sodium ions are
released into water.

5 December 2022 <CYC102—Theory Lecture No. 4> 11

Zeolite or Permutit Process

Permutit or Sodium Aluminium Silicate is a complex chemical compound which
occurs as a natural mineral called Zeolite. Permutit or zeolites are insoluble in
water and have the property of exchanging ions present in them with the ions
present in the solution.
A cylindrical column is initially packed
with a layer of course gravel followed by
a layer of fine gravel. Above this,
permutit or zeolites layer is packed. A
slow stream of hard water is passed
through this material. As a result,
calcium and magnesium ions present in
hard water are exchanged with sodium
ions in the permutit (Na+Al-silicate–).
The outgoing water contains sodium
salts that do not cause hardness.

5 December 2022 <CYC102—Theory Lecture No. 4> 12

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Zeolite or Permutit Process (Contd.)

Regeneration:
Over a period of time permutit gets converted into a mixture of calcium and
magnesium aluminium-silicates and permutit has to be regenerated for further use.
This is done by packing brine—a concentrated solution of sodium chloride, through
the column packed with spent permutit.
The following reactions take place-

The resulting calcium chloride and magnesium chloride produced are washed out
through a tap at the bottom. The regenerated permutit is reused for softening water.

5 December 2022 <CYC102—Theory Lecture No. 4> 13

Ion-Exchange Resins
 Ions can exist with either a positive charge or a negative charge. A
positive charge ion is called a cation. A negative charge ion is called an
anion.
 Calcium (Ca) and magnesium (Mg), the principle elements causing
hardness, are typically positive charged cations. Therefore, the basic
premise of which ion-exchange softening uses is trading one ion for
another.
 Giant organic molecules having acidic or basic groups are known as Ion-
exchange resins.
 Acid resins contain the acid group (–COOH). Basic resins contain the basic
group [(–NH3+)OH–], that is substituted ammonium hydroxide group.
 Acid and basic ion exchange resins are represented as RCOO–H+ and
RNH3+ + OH–, respectively.
 An ion-exchange water softener has two main units: one containing
cation exchange resin and the other containing anion exchange resin.

5 December 2022 <CYC102—Theory Lecture No. 4> 14

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Ion-Exchange Resins (Contd.)

5 December 2022 <CYC102—Theory Lecture No. 4> 15

Ion-Exchange Resins (Contd.)

Hard water is sent to the first compartment containing a layer of gravel and cation exchange
resin. When water percolates through the resin, cations like Ca2+ , Mg2+ , Na+ , K+ , etc. present
in the hard water get exchanged with H.

It is observed that the water emerging out from the cationic compartment is acidic in
nature. In order to eliminate both H+ and anions from water that is received from the first
column, the water is made to pass through the second anionic resin column. The resin
interacts with anions present in hard water.

5 December 2022 <CYC102—Theory Lecture No. 4> 16

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Ion-Exchange Resins (Contd.)

The water that is collected from the second resin column is free from both cations and
anions. The H+ and OH– ions combine during the softening process and give water
molecules. The water obtained after passing through the ion-exchangers is called deionized
water or demineralized water. This is as good as distilled water. The water becomes soft
after this process.

Regeneration:
After some time, the resins require regeneration as they become ineffective. Adding a strong
acid regenerates cation resin and the anion resin is regenerated by treating it with a solution
of a strong base.

The regenerated resins are washed to remove Ca2+ , Na+ , SO42– , Cl– , etc. The resins can be
used again. The water treated by ion-exchange process not only becomes soft but also free
from all dissolved mineral impurities. It gets completely demineralized.

5 December 2022 <CYC102—Theory Lecture No. 4> 17

Thank You!
5 December 2022 <CYC102—Theory Lecture No. 4> 18

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
• Internal Conditioning: Phosphate, Calgon, Carbonate, Sodium
Aluminate and colloidal
• Boiler Feedwater
Priming
Foaming
Scale formation
Sludge formation
Boiler corrosion
Caustic embrittlement

9 December 2022 <CYC102—Theory Lecture No. 5> 2

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Internal Conditioning
Even after subjecting water to external treatment for hardness removal, the
residual hardness has to be removed using conditioning agents. This treatment
can be carried out inside the boiler itself, and is called as Internal Treatment.

The reagents added can act in 2 ways:

1. They can precipitate scale-forming impurities, and the sludge formed can
be removed by blow-down operation.
2. These can convert the scale-forming impurities to form more soluble
complexes, which stay in dissolved form without causing any harm.

The various conditioning treatments are:

 Phosphate Conditioning
 Calgon Conditioning
 Carbonate Conditioning
 Treatment with Sodium Aluminate
 Colloidal conditioning

9 December 2022 <CYC102—Theory Lecture No. 5> 3

Phosphate Conditioning
Mono-, di- or tri-sodium phosphate and sodium polyphosphate can be added to treat boiler
feedwater and buffer the water to minimize pH fluctuation. This involves addition of phosphate salts
that convert scale forming calcium salts into water insoluble calcium phosphate Ca3(PO4)2 which can
be removed as sludge by blow-down operation.
The 3 main orthophosphates used in this conditioning treatment are:
 alkaline Trisodium Phosphate Na3PO4 (For acidic waters);
 acidic Sodium Dihydrogen phosphate NaH2PO4 (For alkaline waters) and
 neutral disodium hydrogen sulphate Na2HPO4 (for neutral waters).

3Na3PO4 + 3CaSO4 Ca3(PO4)2 + 3Na2SO4

The addition of these orthophopshates is carried out in the boiler itself because addition to feed
water will cause calcium phosphate to precipitate out and clog the water feed pipes.
If phosphate conditioning is to be carried out in feed water, it is treated with either sodium
pyrophosphate (Na2P2O7) or Sodium Metaphosphate (NaPO3) both of which form soluble Calcium
salts that do not clog feed pipes.

Phosphates used to be the main conditioning chemical, but nowadays chelate and polymer type
chemicals are mostly used. These new chemicals have the advantage over phosphates of
maintaining scale-free metal surfaces.

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Calgon Conditioning
Calgon, or Sodium Hexametaphosphate on addition to hard water forms soluble
complexes with Calcium and Magnesium ions at pH 10, thus preventing the
formation of scales or sludge and ensuring the smooth running of the boiler.

2Ca2+ + Na2[Na4(PO3)6] 4Na+ + Na2[Ca2(PO3)6]2-

9 December 2022 <CYC102—Theory Lecture No. 5> 5

Carbonate Conditioning

Addition of Sodium carbonate prevents the precipitation of scale-forming

calcium sulphate. Instead, by increasing the concentration of carbonate ions,
the equilibrium can be shifted to facilitate precipitation of calcium carbonate.

Na2CO3 + CaSO4 CaCO3 + Na2SO4

This forms a loose precipitate which can be easily removed by blow down
operation. The pH of the boiler water should be between 10 and 11 to
maintain the required concentration of carbonate ions.

However, this method cannot be used in high-pressure boilers, since sodium

carbonate gets hydrolysed to sodium hydroxide that causes caustic
embrittlement.

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Treatment with Sodium Aluminate

Sodium Aluminate is a good coagulating agent. When it is added to water, it gets
hydrolysed yielding NaOH and a gelatinous precipitate of aluminium hydroxide
according to the following reaction.

NaAlO2 + 2H2O NaOH + Al(OH)3

Sodium Hydroxide thus forms precipitate with some of Magnesium as hydroxides.

This reaction is as-

MgCl2 + 2NaOH Mg(OH)2 + 2NaCl

The precipitate of Mg(OH)2 and Al(OH)3 produced inside the boiler entraps
suspended and colloidal impurities including oil drops and silica. In Water
treatment, it is used an additional reagent with other softening agents.

9 December 2022 <CYC102—Theory Lecture No. 5> 7

Colloidal Conditioning
This treatment involves addition of conditioning agents such as glue, seaweed
extract, agar-agar, tannin, etc. to hold the boiler water.

The residual precipitates get surrounded by molecules of the conditioners and are
effectively maintained in the colloidal state.

Once the colloidal solution becomes concentrated, the colloids can be removed by
blow-down operations.

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Boiler Feed Water

A boiler is an enclosed vessel that provides a means for combustion heat to be
transferred into water until it becomes heated water or steam. The hot water or steam
under pressure is then usable for transferring the heat to a process.
Water is a useful and cheap medium for transferring heat to a process. When water is
boiled into steam its volume increases about 1600 times, producing a force that is almost
as explosive as gunpowder. This causes the boiler to be extremely dangerous equipment
that must be treated with utmost care.

THE BOILER SYSTEM:

It comprises a feed water system, steam system and fuel system. The feed water system
provides water to the boiler and regulates it automatically to meet the steam demand.

The water supplied to the boiler which is converted into steam is called feed water. The
two sources of feed water are:
 Condensate or condensed steam returned from the processes and
 Makeup water (treated raw water) that must come from outside the boiler room and
plant processes.

9 December 2022 <CYC102—Theory Lecture No. 5> 9

Importance of Feedwater
Maintaining good feedwater is an important and fundamental aspect of any steam
boilers.
A plant that maintains good feedwater achieves the following three benefits:
 Help to ensure maximum life out of its boilers, steam turbines, condensers and
pumps.
 Reduce maintenance expenses.
 Maintain optimal thermal performance.
There is a definite legal and moral responsibility on the part of the management to
ensure reliable, continuous and efficient operation of the steam boiler and to ensure
that no damage to equipment or physical hazard occurs.

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Problems due to impurities in Boiler

feedwater
Problems Arise due to Impurities in Water for Boilers
In treatment of water, complete elimination of all the impurities is not
possible. The impurity that gives rise to certain troubles will be removed to
certain extent. In modern pressure boilers and laboratories, water purer than
the distilled water is required. Some of the boiler troubles caused by the use of
unsuitable water are:
 Priming and foaming
 Scale and sludge formation
 Boiler corrosion
 Caustic embrittlement

9 December 2022 <CYC102—Theory Lecture No. 5> 11

Priming
Priming is the carryover of varying amounts of droplets of water in the steam (due to high
level of water in the boiler), which lowers the energy efficiency of the steam and leads to
the deposition of salt crystals on the super heaters and in the turbines. This process of wet
steam formation is called priming. Priming is common cause of high levels of boiler water
carryover. These conditions often lead to super heater tube failures as well. Priming is related
to the viscosity of the water and its tendency to foam.
The cause for priming may be due to the following:
 Dissolved solids in water
 High steam velocities
 Sudden increase in steam production rate
 Sudden fluctuations in steam demand
 Due to improper boiler design

Priming in a boiler can be controlled by the following

 Maintaining the concentration of solids (TDS) in the boiler water at reasonably low levels
 Avoiding high water levels and rapid change in steam rate.
 Proper boiler design and using fitted mechanical steam purifier
 Uniform distribution of fuel and providing anti-priming pipes
 Keeping the water level low and avoid sudden steam demands and
 Efficient softening and filtration of the boiler feed water
9 December 2022 <CYC102—Theory Lecture No. 5> 12

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Foaming
The contamination of the steam in the boiler carryover is the impurities of water.
Bubbles or froth actually build up on the surface of the boiler water and pass out with
the steam. This is called foaming and it is caused by high concentration of any solids in
the boiler water.
It is generally believed, however, that specific substances such as alkalis, oils, fats,
greases, certain types of organic matter and suspended solids are particularly conducive
to foaming. In theory, suspended solids collect in the surface film surrounding a steam
bubble and make it tougher. The steam bubble therefore resists breaking and builds up
foam. It is believed that the finer the suspended particles the greater their collection in
the bubble.

Foaming in boilers can be controlled by the following:

 Using anti-foaming chemicals
 Removal of concentrated boiler water containing
impurities and replacing it by fresh feed water
 Removing oil from boiler water by adding compounds
like sodium aluminate

9 December 2022 <CYC102—Theory Lecture No. 5> 13

Scale Formation
Scales are hard, adhering precipitates formed on the inner walls of the boilers. They
stick very firmly onto the inner wall surface and are difficult to remove with chisel and
hammer. Generally, scales are formed due to decomposition of calcium bicarbonates,
decomposition of calcium sulphates, presence of silica and hydrolysis of magnesium
salts.
Scales formation can be prevented by external treatment of boiler feed water, internal
treatment of water in boiler and blowdown process

Scale and sludge deposit in boiler.

9 December 2022 <CYC102—Theory Lecture No. 5> 14

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Scale Formation (Contd.)

Reasons of scale formation
(a) Following are the causes
decomposition of calcium bicarbonate:
Ca(HCO3)2 CaCO3 + H2O + CO2
In low pressure boilers, CaCO3 causes scale formation.
In high pressure boilers, CaCO3 becomes soluble.
CaCO3 + H2O Ca(OH)2 + CO2
(b) Decomposition of calcium sulphate:
The solubility of CaSO4 in water decreases with rise of temperature. In super-heated
water, CaSO4 is insoluble. This is the main cause in high-pressure boilers.
(c) Hydrolysis of magnesium salts:
Dissolved magnesium salts undergo hydrolysis forming Mg(OH)2 precipitate.
MgCl2 + 2H2O Mg(OH)2 + 2HCl
Mg(OH)2 so found by hydrolysis of magnesium salts is a soft type of scale.
(d) Presence of silica:
Silica is present in small quantity deposits as silicates like CaSiO3 and MgSiO3
to remove

9 December 2022 <CYC102—Theory Lecture No. 5> 15

Scale Formation (Contd.)

Problems Caused by Scale in Boilers
The biggest problem caused by scale is overheating and failure of boiler tubes. The thermal
conductivity of porous boiler scale is similar to insulating brick. The scale acts as an insulating
layer and prevents an efficient transfer of heat through the tubes to the circulating water. The
reduction in thermal conductivity means lower boiler efficiency which in turn leads to
overheating and may result in the softening, bulging or even fracturing of the boiler tubes.
Boiler scale can also cause plugging or partial obstruction of circulating tubes in a water tube
boiler, which again causes starvation and overheating of the tubes. Another important aspect
is that corrosion may occur under the boiler scale.
In general, boiler scale causes:
 increased fuel bill by decreasing the operating efficiency
 thermal damage
 unscheduled down-time
 increased cleaning time and cleaning costs
 reduced working life of a boiler

Prevention
 External treatment: efficient softening of water is to be carried out.
 Internal treatment: Suitable chemicals are added to the boiler water either to precipitate
or to convert the scale into compounds.
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Sludge Formation
In boilers, because of continuous evaporation of water, the concentration of salts
increase progressively and after the saturation point is reached, precipitate forms on the
inner walls of boiler.
Sludge is a soft, loose and slimy precipitate formed within the boiler. It is formed at
comparatively colder portions of the boiler and collects in the area where flow rate is
slow.
These are formed by substances which have greater solubilities in hot water than in cold
water.

Examples: MgCO , MgCl , CaCl , MgSO

3 2 2 4, etc.

Disadvantages
 As the sludge is poor conductor of heat, it causes loss of heat.
 The working of the boiler is disturbed because of chocking of pipes by the sludge.
Prevention
 By using well softened water.
 By drawing off a portion of concentrated water frequently

9 December 2022 <CYC102—Theory Lecture No. 5> 17

Boiler Corrosion
The process of corrosion is actually not so simple, it is a complex electro-chemical reaction.
Corrosion may generally be over a large metal surface but sometimes it results in pinpoint
penetration of metal. Though basic corrosion is usually due to reaction of the metal with
oxygen, other factors including stresses produce different forms of attack.
Corrosion may occur in the feedwater system as a result of low pH water and the presence
of dissolved oxygen and carbon dioxide. Corrosion in the boiler itself normally occurs when
boiler water’s alkalinity is too low or too high or when the metal is exposed to oxygen-
bearing water during either operation or idle periods.

Dissolved oxygen:
As water is heated, dissolved oxygen is liberated and iron is corroded.

9 December 2022 <CYC102—Theory Lecture No. 5> 18

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Boiler Corrosion (Contd.)

Dissolved Carbon dioxide:
Bicarbonates produce CO2 which in turn produces carbonic acid and it causes local
corrosion or pitting

Mineral acids:
Acidic waste or inorganic salts produce acids which causes corrosion. These acids
react with iron to produce hydrogen which leads to embrittlement.

PREVENTION
 Mechanical deaeration
 Chemical treatment: Adding reducing agents (hydrazine, sodium sulphite for
oxygen) and adding lime or NH3 for carbon dioxide.
 Ion exchange techniques to reduce oxygen at very low concentration.

9 December 2022 <CYC102—Theory Lecture No. 5> 19

Caustic Embrittlement
The formation of brittle and in-crystalline cracks in the boiler shell is called caustic
embrittlement. It is a type of boiler corrosion and the main reason for this is the
presence of alkali-metal carbonates and bicarbonates in feed water and also the
presence of sodium sulphate. In lime-soda process, it is likely that, some residual Na2CO3
is still present in the softened water. This Na2CO3 decomposes to give NaOH and CO2,
due to which the boiler water becomes ‘Caustic’.
Na2CO3+ H2O 2NaOH + CO2

This caustic water flows inside the boiler and

causes some minute hair-cracks by capillary
action. On evaporation of water, the dissolved
caustic soda increases its concentration which
attacks the surrounding area, thereby
dissolving iron of boiler as sodium ferroate.
This causes embrittlement of boiler parts such
as bends, joints, reverts, etc., due to which
the boiler gets fail.

9 December 2022 <CYC102—Theory Lecture No. 5> 20

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Caustic Embrittlement (Contd.)

Prevention
Therefore, caustic embrittlement can be prevented
 By maintaining the pH value of water and neutralization of alkali
 By using sodium phosphate as softening reagents, in the external treatment of
boilers.
 Caustic embrittlement can also be prevented by adding tannin or lignin which
prevents the infiltration of caustic soda solution blocking the hair cracks.

9 December 2022 <CYC102—Theory Lecture No. 5> 21

Boiler explosion
(Muzaffarpur May 2021)

9 December 2022 <CYC102—Theory Lecture No. 5> 22

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Thank You!
9 December 2022 <CYC102—Theory Lecture No. 5> 23

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
• Desalination
• Reverse Osmosis
• Electrodialysis

9 December 2022 <CYC102—Theory Lecture No. 6> 2 1

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Overview
The water containing dissolved salts and having very salty taste is called
Brackish water, like the sea water and it is not suitable for drinking. The
process of removal of common salt from this brackish water is called as
Desalination.

Desalination can be done by the following two methods:

 Reverse Osmosis
 Electrodialysis

9 December 2022 <CYC102—Theory Lecture No. 6> 3

Reverse Osmosis
 Reverse osmosis (RO) is a process that uses a membrane under pressure to separate
relatively pure water (or other solvent) from a less pure solution.
 When two aqueous solutions of different concentrations are separated by a semi -
permeable membrane, water passes through the membrane in the direction of more
concentrated solution as a result of osmotic pressure.
 If enough counter pressure is applied to the concentrated solution to overcome the
osmotic pressure, the flow of water will be reversed.
 Reverse osmosis is known as the finest hyper-filtration technique.

Water molecules can form hydrogen bonds in the RO membrane and fit into the
membrane matrix. The water molecules that enter the membrane by hydrogen bonding
can be pushed through under pressure. Most organic substances with a molecular
weight over 100 are sieved out, i.e. oils, pyrogens and particulates including bacteria and
viruses. Salt ions, on the other hand, are rejected by a mechanism related to the valence
of the ions. Ions are repelled by dielectric interactions; ions with higher charges are
repelled to a greater distance from the membrane surface.

9 December 2022 <CYC102—Theory Lecture No. 6> 4 2

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Reverse Osmosis (Contd.)

9 December 2022 <CYC102—Theory Lecture No. 6> 5

Reverse Osmosis (Contd.)

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Reverse Osmosis (Contd.)

Membrane for reverse osmosis
The majority of the commercially manufactured RO membranes are usually made from
cellulose acetate, polysulphonate and polyamide. The membrane consists of a skin about
0.25 microns and a support layer about 100 microns. The skin is the active barrier and
primarily allows water to pass through. The process of reverse osmosis requires a driving
force to push the fluid through the membrane, and the most common force is pressure
from a pump.

Advantages
 Removal of solutes (ionic, non-ionic, colloidal and high molecular weight) from water.
 Regeneration of the process involves the easy replacement of the semi-permeable
membrane
 Easy maintenance and economical, as membrane lifespan is high
 Uninterupted supply of large volume of water for industrial or domestic purpose can
be obtained.
 Low capital and low cost for converting sea water into drinking water.

9 December 2022 <CYC102—Theory Lecture No. 6> 7

Electrodialysis
Electrodialysis depends on the following general principles:
 Most salts dissolved in water are ionic, being positively (cationic) or negatively
(anionic) charged. These ions are attracted to electrodes with an opposite electric
charge.
 Membranes can be constructed to permit selective passage of either anions or
cations.

The dissolved ionic constituents in a saline solution such as Na+, Ca2+ and CO32- are
dispersed in water, effectively neutralizing their individual charges. When
electrodes connected to an outside source of direct current like a battery are
placed in a container of saline water, electrical current is carried through the
solution, with the ions tending to migrate to the electrode with the opposite
charge.

Electrodialysis is an electro-membrane process in which ions are transported

through ion permeable membranes from one solution to another under the
influence of potential gradient.

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Electrodialysis (Contd.)

9 December 2022 <CYC102—Theory Lecture No. 6> 9

Electrodialysis (Contd.)

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Electrodialysis (Contd.)
Overview of Electrodialysis:
 Electrodialysis requires a large amount of electricity to produce a current in
the water strong enough to manipulate the impure ions.
 Electrodialysis also has a limited range of contaminates with which it can filter.
It cannot remove organics, pyrogens and elemental metals.
 Electrodialysis can remove salts from food, dairy and other products, waste
streams and other solutions, as well as concentrate salts, acids or bases.

9 December 2022 <CYC102—Theory Lecture No. 6> 11

Thank You!
9 December 2022 <CYC102—Theory Lecture No. 6> 12 6
 12/12/2022

Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
• Dissolved oxygen
• BOD
• COD
• BIS and WHO standards of water

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Overview
 Oxygen is important to all lives. Dissolved oxygen is the form of oxygen in water
that is freely available to aquatic plants and animals.
 Oxygen is transferred from the atmosphere into surface waters, as well as being
produced by aquatic plants, algae and phytoplankton as a by-product of
photosynthesis.
 Oxygen, in water, is measured as dissolved oxygen (D.O). One unit of measure of
dissolved oxygen in water is parts per million (ppm) which is the number of
oxygen (O2 ) molecules per million total molecules in a sample.
 It is also defined as the number of moles of molecular oxygen (O2) dissolved in a
litre of water at a temperature, expressed as mg O2/L.
 A high percentage of dissolved oxygen is conducive to supporting aquatic flora
and fauna, such as algae, plants, fish, mollusks and invertebrates.

12 December 2022 <CYC102—Theory Lecture No. 7> 3

Factors affecting DO
Dissolved Oxygen Levels are affected by
 Water temperature: when temperature decreases, more oxygen dissolves in
water; when temperature increases, dissolved oxygen decreases.
 Aquatic plant populations
 Stream Flow
 Altitude/atmospheric pressure
 Human activities
 Water discharge: when water discharge (flow) increases, dissolved oxygen
increases.
 Organic waste (such as leaves, sewage, industrial waste, agricultural/fertilizer
runoff and faecal matter) build up when it increases and dissolved oxygen
decreases.

Weather, temperature and salinity affect amounts of dissolved oxygen (DO). Cold and
fresh water holds more oxygen than warm or salty water. If DO levels are severely
low, large quantities of fish may die. Low DO is also caused by fertilizer and manure
runoff from streets, lawns and farms. Fertilizers and faecal matter encourage
the growth of too much algae which uses up the oxygen quickly. Plants and animals
die and are decayed by bacteria which also uses up a great deal of oxygen.
12 December 2022 <CYC102—Theory Lecture No. 7> 4 2
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Sources of DO
Dissolved oxygen concentrations in water arise from the interaction between:
 oxygen produced by photosynthesis;
 oxygen consumed by aerobic respiration, nitrification and chemical oxidation
within the water environment; and
 the exchange of oxygen with the atmosphere.

Natural processes (e.g. weather, tides and currents) and human pollution
(particularly organic matter) can result in severe reductions in dissolved oxygen
levels. Both anoxia (no oxygen) and hypoxia (very low oxygen) are harmful to most
marine animals causing:
 animal kill,
 a decrease in the available habitat, and
 limiting animal movements.

12 December 2022 <CYC102—Theory Lecture No. 7> 5

Biochemical Oxygen Demand

(BOD)
 The BOD is an important measure of water quality. It is a measure of the amount of
oxygen needed (in milligrams per litre or ppm) by bacteria and other microorganisms
to oxidize the organic matter present in a water sample over a period of 5 days.
 The BOD of drinking water should be less than 1. That of raw sewage may run to
several hundreds. It is also called the ‘biological’ oxygen demand.

 When organic matter decomposes, microorganisms (such as bacteria and fungi) feed
upon this decaying material and eventually it becomes oxidized.
 When this happens, much of the available dissolved oxygen is consumed by aerobic
bacteria, robbing other aquatic organisms of the oxygen they need to live.
 BOD directly affects the amount of dissolved oxygen in rivers and streams. The more
rapidly oxygen is depleted in the stream, the greater the BOD. This means less oxygen
is available. The detriment of high BOD is same as low dissolved oxygen; aquatic
organisms become stressed, suffocate and die.

12 December 2022 <CYC102—Theory Lecture No. 7> 6 3

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BOD (Contd.)
 The temperature of the water can also
contribute to high BOD levels. For example,
warmer water usually will have a higher
BOD level than colder water. As water
temperature increases, the rate of
photosynthesis by algae and other plant life
in the water also increases. When this
happens, plants grow faster and also die
faster.
 When the plants die, they fall to the bottom
where they are decomposed by bacteria.
The bacteria require oxygen for this process
so the BOD is high at this location.
Therefore, increased water temperatures
will speed up bacterial decomposition and
result in higher BOD levels.

12 December 2022 <CYC102—Theory Lecture No. 7> 7

Chemical Oxygen Demand (COD)

 In environmental chemistry, the chemical oxygen demand (COD) test is commonly
used to indirectly measure the amount of organic compound in water.
 Most applications of COD determine the amount of organic pollutants found in
surface water (e.g. lakes and rivers), making COD a useful measure of water quality.
 It is expressed in milligrams per litre (mg/L) which indicates the mass of oxygen
consumed per litre of solution. Older references may express the units as parts per
million (ppm).
 COD of wastewater is the number of milligrams of oxygen required to oxidize the
impurities present in 1000 ml of wastewater using a strong oxidizing agents like
acidified K2Cr2O7.
 COD represents the total amount of oxygen required to oxidize all oxidizable
impunities in a sample of sewage wastes.
 COD is always greater than BOD since in COD measurement both biodegradable and
nonbiodegradable load are completely oxidized.
 The difference in COD and BOD is equivalent to the quantity of biologically resistant
organic matter.

12 December 2022 <CYC102—Theory Lecture No. 7> 8 4

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Bod Vs COD
BOD COD
It is a biological oxidation process. It is a chemical oxidation process.
BOD is performed by aerobic BOD is performed by chemical
organisms. reagents.
BOD value is determined in 5 days. COD value is measured in few
hours (1-3 hrs).
Breakdown of organic matter. Breakdown of both organic and
inorganic constituents.
It is a slow method. It is much faster and accurate
method.
BOD value is lower than COD. COD Value is greater than BOD.

12 December 2022 <CYC102—Theory Lecture No. 7> 9

WHO and BIS

12 December 2022 <CYC102—Theory Lecture No. 7> 10 5

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WHO and BIS (Contd.)

The Bureau of Indian Standards is the National Standards Body of India under
Department of Consumer affairs, Ministry of Consumer Affairs, Food & Public
Distribution, Government of India. It is established by the Bureau of Indian
Standards Act, 2016 which came into effect on 12 October 2017.

12 December 2022 <CYC102—Theory Lecture No. 7> 11

WHO and BIS (Contd.)

The World Health Organization (WHO) is a specialized agency of the United
Nations responsible for international public health.The WHO Constitution states its
main objective as "the attainment by all peoples of the highest possible level of
health".
The WHO's mandate seeks and includes: working worldwide to promote health,
keeping the world safe, and serve the vulnerable. It provides technical assistance to
countries, sets international health standards, and collects data on global health issues.

12 December 2022 <CYC102—Theory Lecture No. 7> 12 6

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WHO and BIS (Contd.)

https://cpcb.nic.in/who-guidelines-for-drinking-water-quality/

12 December 2022 <CYC102—Theory Lecture No. 7> 13

WHO and BIS (Contd.)

https://cpcb.nic.in/wqm/Primary_Water_Quality_Criteria.pdf

12 December 2022 <CYC102—Theory Lecture No. 7> 14 7

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WHO and BIS (Contd.)

12 December 2022 <CYC102—Theory Lecture No. 7> 15

Thank You!
12 December 2022 <CYC102—Theory Lecture No. 5> 16 8
 12/29/2022

Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
• Polymers
• Functionality
• Degree of Polymerization
• Molar masses of polymers
• Numerical based on molar masses

29 December 2022 <CYC102—Theory Lecture No. 8> 2 1

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Polymers
 A polymer is a large molecule built by the repetition of small and simple
chemical unit called monomer. The repeating chemical units are covalently
linked to each other in a macromolecule.
 The properties of a polymer are entirely different from those of the
chemicals (monomers) from which it is formed.

 Monomer: it is defined as a simple molecule with two or more binding

sites through which it forms covalent linkages with other monomer
molecules to form the macromolecule.
 Monomers are thus building blocks of polymers.
 All simple molecules cannot behave as monomers but only those with two
or more bonding sites can act as monomers.
 Thus molecules like ammonia, water, ethanol, etc. are not monomers.
 Alkenes, vinyl chloride, adipic acid and glycol with two bonding sites act as
monomers.

29 December 2022 <CYC102—Theory Lecture No. 8> 3

Functionality

 Functionality of a monomer is defined as the number of bonding sites

present in a molecule of the monomer.

 E.g.

Ethene CH2=CH2 2 bonding sites (Bifunctional)

Glycol HO-CH2-CH2-OH Bifunctional
Phenol C6H5-OH 2,4,6 positions act as active centers and is trifunctional

29 December 2022 <CYC102—Theory Lecture No. 8> 4 2

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Polymerization
 Polymerization is defined as the chemical reaction in which monomer is
converted to the polymer under specific conditions.
 Monomer alone cannot undergo polymerization, but requires the presence of a
chemical called initiator.

Required temperature
Monomer + Initiator Polymer
Pressure

29 December 2022 <CYC102—Theory Lecture No. 8> 5

Polymers
ADDITION POLYMERS

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Polymers
CONDENSATION POLYMERS

29 December 2022 <CYC102—Theory Lecture No. 8> 7

Degree of Polymerization
Degree of Polymerization is defined as the number of repeating units present in
a polymer molecule.

Here, ‘n’ is a whole number and is called as the degree of polymerization.

Molar mass of addition polymer = Degree of polymerization x molar mass of

monomer

Polymers produced in a reaction do not have the same degree of polymerization

and show variation in molar mass. Hence, Normally only average degree of
polymerization (𝐷𝑃) and average molar mass (𝑀 ) are used

𝑴𝒏 = 𝑫𝑷 X Molar mass of Monomer

29 December 2022 <CYC102—Theory Lecture No. 8> 8 4

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Degree of Polymerization (Contd.)

29 December 2022 <CYC102—Theory Lecture No. 8> 9

Molecular weight of Polymers

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Molecular weight of Polymers (Contd.)

29 December 2022 <CYC102—Theory Lecture No. 8> 11

Numericals (Contd.)
Numerical:
If polymer sample has population as:
10 molecules of molecular mass each = 5,000
20 molecules of molecular mass each = 7,500
20 molecules of molecular mass each = 10,000
25 molecules of molecular mass each = 15,000
20 molecules of molecular mass each = 20,000
5 molecules of molecular mass each = 25,000
Calculate its number-average (𝑀 ) and weight-average (𝑀 ) molecule mass of polymer.

29 December 2022 <CYC102—Theory Lecture No. 8> 12 6

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Numericals (Contd.)
Numerical:
A Polymer sample contains:

Polymer of DP 400 500 600 800 1000

Percentage 10 15 35 15 25

Calculate its average degree of polymerization.

29 December 2022 <CYC102—Theory Lecture No. 8> 13

Numericals (Contd.)
Numerical:
Calculate the number average and weight average molecular masses of
polypropylene polymer with the following composition:
-CH2-CH(CH3)n- where n=400 (25%); n=800 (35%); n=600 (40%)
Solution:

Molar mass of repeating unit: 42

No. of repeating unit (n) 400 800 600
Molar mass (=42n) 16800 33600 25200
No. of molecules in 100 25 35 40

∑
𝑀 = ∑

∑
𝑀 = ∑

29 December 2022 <CYC102—Theory Lecture No. 8> 14 7

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Thank You!
29 December 2022 <CYC102—Theory Lecture No. 8> 15

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Types of Polymerization
 Addition Polymerization
 Mechanism of Addition Polymerization
 Condensation Polymerization
 Co Polymerization
 Visual representation of Polymerization

9 January 2023 <CYC102—Theory Lecture No. 10> 2

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Types of Polymerization
Polymerization

Addition Polymerization Co-polymerization Condensation polymerization

(Chain Growth Polymerization) (Step Growth Polymerization)

Free Radical Polymerization

Cationic Mechanism
Ionic Polymerization
Anionic Mechanism
A generic representation of a
step-growth polymerization.
Coordination Polymerization or Ziegler-Natta Polymerization (Single white dots represent
monomers and black chains
represent oligomers and
polymers)

9 January 2023 <CYC102—Theory Lecture No. 10> 3

Types of Polymerization (Contd.)

Chain-growth polymerization Step-growth polymerization
CHAIN GROWTH PROFILE Growth by addition of monomer Growth throughout matrix
only at one end or both ends of
chain
USAGE OF MONOMER IN THE Some monomer remains even at Rapid loss of monomer early
REACTION long reaction times in the reaction
REACTION STEPS Different steps operate at different Similar steps repeated
stages of mechanism (i.e. initiation, throughout reaction process
propagation, termination, and
chain transfer)
AVERAGE MOLECULAR WEIGHT Molar mass of backbone chain Average molecular weight
increases rapidly at early stage and increases slowly at low
remains approximately the same conversion and high extents of
throughout the polymerization reaction are required to obtain
high chain length
ACTIVE CHAIN REMAINS AFTER Chains not active after termination Ends remain active (no
REACTION? termination)
INITIATORS REQUIRED? Initiator required No initiator necessary

9 January 2023 <CYC102—Theory Lecture No. 10> 4

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Addition Polymerization
Monomers (M) having the general formula, CH2=CHY (Y=X, CO2R, CN, etc.)
undergoes polymerization, i.e., these monomers having double or triple bonds
polymerize without the liberation of small molecules.
Head Tail
There are three ways of addition polymerization:
CH2=CH
Y
Head to tail type

Head to head type

Random type

9 January 2023 <CYC102—Theory Lecture No. 10> 5

Mechanism of Addition Polymerization

FREE RADICAL POLYMERIZATION
A free radical is simply a molecule with an unpaired electron. The tendency for this
radical to gain an additional electron in order to form a pair make sit highly reactive so
that it breaks the bond on another molecule by stealing an electron, leading that
molecule with an unpaired electron (i.e. free radical)

The decomposition of the initiator to

form free radicals can be induced either
by:
 Heat energy
 Light energy
 Catalyst

9 January 2023 <CYC102—Theory Lecture No. 10> 6

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Mechanism of Addition Polymerization (Contd.)

FREE RADICAL POLYMERIZATION
 Initiation

R-R 2R C C
(Initiator) (Radical) x
C C
H H H
R C R C C C C
CH 2

Y H Y C C x

9 January 2023 <CYC102—Theory Lecture No. 10> 7

Mechanism of Addition Polymerization (Contd.)

FREE RADICAL POLYMERIZATION
 Propagation

H H H H H H H
R C C H2C C R C C C C
H Y Y H Y H Y

n (CH2=CHY)

H H H H
R C C C C
H Y H Y
n

9 January 2023 <CYC102—Theory Lecture No. 10> 8

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Mechanism of Addition Polymerization (Contd.)

FREE RADICAL POLYMERIZATION
 Termination
Coupling/ Combination Disproportionation

H H H H H H H H H H H H H H H H
R C C C C C C C C R R C C C C C C C C R
H Y H Y Y H Y H H Y H Y Y H Y H

H H H H H H H H H H H H H H H H
R C C C C C C C C R R C C C CH C C C C R
H Y H Y Y H Y H H Y H Y Y Y H

(Saturated) (unsaturated)

9 January 2023 <CYC102—Theory Lecture No. 10> 9

Mechanism of Addition Polymerization (Contd.)

CATIONIC POLYMERIZATION
 Initiation The initiators are Lewis acids like AlCl3, BF3, H2SO4, etc.
H H H
X H2C C X C C
An acid (cation) Carbocation
Y H Y

 Propagation
H H H H H H H H H H H
n (CH2=CHY)
X C C H2 C C X C C C C X C C C C

H Y Y H Y H Y H Y H Y
n

 Termination
H H H H H H H H
Z
X C C C C X C C C C Z Polymer
(Anion)
H Y H Y H Y H Y
n n

9 January 2023 <CYC102—Theory Lecture No. 10> 10

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Mechanism of Addition Polymerization (Contd.)

ANIONIC POLYMERIZATION
 Initiation The initiators are Lewis bases like Sodium ethoxide, etc.
H H H
Z H2C C Z C C
A base (anion) Y H Y Carbanion

 Propagation
H H H H H H H H H H H
n (CH2=CHY)
Z C C H2C C Z C C C C Z C C C C
H Y Y H Y H Y H Y H Y
n

 Termination
H H H H H H H H
H+
Z C C C C Z C C C C H Polymer
(Cation)
H Y H Y H Y H Y
n n

9 January 2023 <CYC102—Theory Lecture No. 10> 11

Mechanism of Addition Polymerization (Contd.)

Coordination Polymerization or Ziegler-Natta Polymerization
Ziegler (1953) and Natta (1955) discovered that in the presence of a combination
of a transition-metal halide (like TiCl4 or TiCl3, ZrBr3, TiCl2, halides of V, Zr, Cr, Mo
and W) with an organo-metallic compounds (like triethyl aluminium, trimethyl
aluminium), stereospecific polymerization can be carried out.

9 January 2023 <CYC102—Theory Lecture No. 10> 12

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Mechanism of Addition Polymerization (Contd.)

COORDINATION POLYMERIZATION OR ZIEGLER-NATTA POLYMERIZATION
 Initiation
H H H
Cat-R' H2C C Cat C C R'
Complex R H R
Catalyst Monomer

 Propagation H H H H H H H
Cat C C R' n H2 C C Cat C C C C R'
H R R H R H R
n

 Termination
H H H H H H H H

Cat C C C C R' HX Cat-X H C C C C R'

Polymer
H R H R H R H R
n n

9 January 2023 <CYC102—Theory Lecture No. 10> 13

Mechanism of Addition Polymerization (Contd.)

Coordination Polymerization or Ziegler-Natta Polymerization

9 January 2023 <CYC102—Theory Lecture No. 10> 14

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Condensation Polymerization
A Polymer formed by the condensation of two or more monomers (similar or different)
with the elimination of molecules like water, HCl, Ammonia, alcohol, etc. is called
Condensation polymer.

The monomers that are involved have two special characteristics:

 Instead of double bonds they should have functional groups.
 Each monomer should have atleast two reactive sites i.e. two functional groups.
NH2(CH2)6NH2 + HOOC(CH2)4COOH
(1,6-Diaminohexane) (Adipic acid)
Linkages?
NH(CH2)6NH C (CH2)4C
O O n Product?
(Nylon-6,6)

9 January 2023 <CYC102—Theory Lecture No. 10> 15

Co Polymerization
 A specific type of addition polymerization process.
 Two or more monomers undergoing joint polymerization is called as copolymerization
reaction
HC CH2
COPOLYMER: Since it is made of atleast
two types of repeating units, it can be
n H2C C C CH2 + n
classified based on arrangement. H H
(Butadiene)
Random Copolymer (Styrene)
-A-A-B-B-A-A-A-B-A-A-B-B-B-A-B-B-A-A-

Alternate Copolymer H2 H2 H 2 H
-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B- C C C C C C
H H

Block Polymer
-A-A-A-A-B-B-B-B-A-A-A-A-B-B-B-B-A-A-
n
Graft Copolymer (Styrene Butadiene Rubber -SBR)
-A-A-A-A-A-A-A-A-A-A-A-A-A-B-B-B-B-B-

9 January 2023 <CYC102—Theory Lecture No. 10> 16

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Visual Representation of Polymerization

9 January 2023 <CYC102—Theory Lecture No. 10> 17

Thank You!
9 January 2023 <CYC102—Theory Lecture No. 10> 18

9
 1/18/2023

Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Structure property relationship
 Stress strain analysis
 Glass transition temperature

16 January 2023 <CYC102—Theory Lecture No. 11> 2

1
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Structure Property Relationship

Effect on Chemical Properties
 Effect on solubility/swelling Behavior  Polarity
 Chemical reactivity  Molecular weight
 Ageing and weathering  Degree of Crosslinking
 Diffusion
Effect on Mechanical Properties
 Toughness
 Strength
 Elasticity

Effect on Electrical Properties

 Electrical conductivity

Effect on Optical Properties

 Amorphous and Crystalline

16 January 2023 <CYC102—Theory Lecture No. 11> 3

Structure Property Relationship

Effect on Chemical Properties
 Effect on solubility/swelling Behavior  Polarity
 Molecular weight
 Degree of Crosslinking

16 January 2023 <CYC102—Theory Lecture No. 11> 4

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Effect on chemical properties

1) Effect on solubility or swelling behavior:
A . Polarity:
 Polymers having polar groups (OH- ,COOH- etc.) will dissolve easily in polar solvents like
water, alcohol, aldehydes and ketones etc.
 Polymers having non polar groups (alkyl, aryl, etc.) will be more soluble in non polar
solvents like benzene, toluene etc.
B . Molecular weight:
 Solubility of a polymer in a particular solvent decreases with increase in molecular
weight of polymer.
C . Degree of cross linking:
 More the degree of cross linking in the polymer ,lesser will be the solubility.

2) Chemical reactivity of a polymer changes by changing the nature of functional group in

the polymers.
Example:
 Nylon and polyester can undergo hydrolysis because they have amide and esteric
linkage.
 Teflon is chemically inert because it has only C-C and C-F bonds.
 Rubber have C=C, which can easily be attacked by oxygen and ozone.

16 January 2023 <CYC102—Theory Lecture No. 11> 5

Effect on chemical properties (Contd.)

3) Ageing and weathering.(light and heat)
 Different polymers shows different resistance power against weathering.
 Example-Teflon has more resistance power towards heat than PVC.
 Teflon and cellulose degraded under high energy radiations.

4) Diffusion:
 Amorphous polymers are non uniform in arrangement of monomers, while crystalline
polymers have regular arrangement.
 So amorphous polymers have more free space ,hence more diffusion is possible in
Amorphous polymers.

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Effect on mechanical properties

1) Effect on strength and toughness:
 Strength of polymer depend upon magnitude of intermolecular force of attraction
between monomers.
 More the magnitude of intermolecular force of attraction more will be the strength of
the polymer.
 Intermolecular force of attraction is of the order of
Cross linked ≥ Branched ≥ linear
Order of strength is also same.
 The movement of molecules over each other decreasing due to increase in the no. of
bulky groups (side groups),so the strength of polymer also increases.
 Intermolecular force are more in polymers having polar groups than in polymers with
non polar groups.
 Crystalline polymers have high strength than amorphous.
2) Effect on stress(load bearing capacity):
The extent of stress is determined by stress/strain ratio.
(Where stress=Applied force strain =Extent of stretch)
3) Effect on elasticity:
Amorphous polymers are more elastic than crystalline.

16 January 2023 <CYC102—Theory Lecture No. 11> 7

Effect on mechanical properties

16 January 2023 <CYC102—Theory Lecture No. 11> 8

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Effect on electrical properties

Plastic substances act as electrical insulators –
Insulation property of polar polymers destroy in humidity because water has high dielectric
constant , which raise the over all dielectric constant of polymer-water mixture. So
resistivity decreases and electrical conductivity increases.
In case of nonpolar polymer vice-a- versa is true.

Effect on optical properties

Amorphous polymers are generally transparent
because they have non-uniform arrangement of
monomers.
Crystalline polymers may or may not be transparent
because they have uniform arrangement of
monomers.

16 January 2023 <CYC102—Theory Lecture No. 11> 9

Stress-Strain analysis
The internal arrangement of the long-
chain molecules provides the forms in
which the polymer may form i.e., fibres,
plastics and rubbers. If the internal
forces between the molecules are low:
molecules becomes bulky, form random
arrangement and show rubbery
character. If the internal forces are high
they ultimately give rise to orderly
arrangement and form fibrous nature.
Intermediate nature gives rise to plastic
nature.
Stress-strain graphs
Stress is the force per cross-sectional area that a material withstands. Strain is
the percent change in the length of the material. The stress-strain curve is the simplest
way to describe the mechanical properties of the material. The stress-strain curve can
provide information about a material’s strength, toughness, stiffness, ductility, and
more.
16 January 2023 <CYC102—Theory Lecture No. 11> 10

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Stress-Strain analysis (Contd.)

Once the material yields, it enters the “plastic” regime. (Polymer plastics are named so
because they have a very large plastic regime).
In the plastic regime, atomic bonds are broken and reformed. Surprisingly, the material
strength increases during this time because of dislocation pile-up.
16 January 2023 <CYC102—Theory Lecture No. 11> 11

Stress-Strain analysis (Contd.)

16 January 2023 <CYC102—Theory Lecture No. 11> 12

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Stress-Strain analysis (Contd.)

16 January 2023 <CYC102—Theory Lecture No. 11> 13

Glass Transition Temperature

Glass transition temperature is defined as the temperature below which an
amorphous polymer is brittle, hard and glassy and above the temperature it becomes
flexible, soft and rubbery.

In the glassy state the polymer is neither in molecular nor segmental motion. When
all chain motions are not possible the rigid solid results. On heating beyond Tg,
segmental motion becomes possible but molecular mobility is disallowed. Hence,
flexible and sift rubbery state is reached. On heating much above Tg both
segmental and molecular motion becomes possible and the polymer flows like a
viscous liquid. This temperature is usually called a glow temperature since any
polymer is only a mixture and has no sharp melting point.

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Factors affecting Tg
A number of factors affect the value of Tg:
 Crystallinity: In crystalline polymers the polymer chains are arranged in a
regular parallel fashion. Each chain is bound to the other by strong forces like
H-bonding. Hence, crystalline polymers have higher Tg than amorphous
polymers.
 Molecular mass: Generally Tg of a polymer increases with molar mass up to a
particular value and beyond that there is no change.
 The presence of side chain which hinders free rotation also increases Tg.
 The presence of plasticizers’ reduces Tg of a polymer (like impurities on melting
point of pure solid.
 Stereo regularity of polymers increases Tg.
Thus Tg of an Isotactic polymer is greater than that of syndiotactic polymer whose
Tg is greater than a tactic polymer.

16 January 2023 <CYC102—Theory Lecture No. 11> 15

Some definitions
Ductility:
The physical property of a metal that can be drawn into the thin wire is called ductility
or ductility is the property of metal associated with the ability to be hammered thin or
stretched into wire without breaking. The degree of ductility occurs due to metallic
bonds.
Brittle:
A material that experiences very little or no permanent, non-recoverable
deformation before it fractures or breaks is called a brittle material. Ceramics are
much more brittle than metals.
Tensile strength:
Maximum load that a material can support without fracture when being stretched,
divided by the original cross-sectional area of the material.

16 January 2023 <CYC102—Theory Lecture No. 11> 16

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Thank You!
16 January 2023 <CYC102—Theory Lecture No. 11> 17

9
 1/19/2023

Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Plastics
 Polyethylene
 Some Commercially important plastics
 Techniques for plastic moulding
 Calendering  Compression Moulding  Extrusion Moulding
 Die Casting  Injection Moulding  Thermoforming
 Film Casting  Blown Film Moulding

19 January 2023 <CYC102—Theory Lecture No. 12> 2

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Plastics
Plastics are macromolecules, formed by polymerization and having the ability to be shaped
by the application of reasonable amount of heat and pressure or some other form of force.

A plastic material should possess sufficient rigidity, dimensional stability and mechanical
strength at room temperature to serve as a useful household article, gadget or structural
part and still be of such a character that it may be moulded into shape by the application of
reasonable temperature and pressure.
Types of Plastics

Thermoplastic Plastics Thermosetting Plastics

Effect of heat on Thermoplastic

19 January 2023 <CYC102—Theory Lecture No. 12> 3

Polyethylene
Polyethylene (Polythene)
 It is the simplest and inexpensive homopolymer.
 Waxy and chemically inert Plastic.
 Formed by addition polymerization of ethylene.
 It is of two types:
1. Low Density Polyethylene (LDPE)
Manufactured by chain polymerization of ethylene gas at 350°C at a pressure of 1000-
2500 atmospheres in presence of oxygen or any peroxide as catalyst.

2. High Density Polyethylene (HDPE)

Mnaufactured by the coordination of ethylene in a hydrocarbon solvent using Titanium
Tetrachloride and aluminium triethyl at 50-70°C.

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Polyethylene (Contd.)
A comparative analysis of properties and applications of LDPE and HDPE

 Small parts  Construction materials like cement or sand

 Food items  Bulk dry goods like rice or grain
 Pallet covers  Auto parts and tools
 Grocery and produce
bags
Additionally, with effect from December 31, 2022, the thickness of plastic carry bags must be increased from 75
microns to 120 microns to allow their re-use. Indian Government had earlier banned polythene bags under 75
microns in September 2021, widening the limit from the earlier 50 microns.

19 January 2023 <CYC102—Theory Lecture No. 12> 5

Few Commercially important

polymers
THERMOPLASTIC POLYMER THERMOSETTING POLYMER
Polyethylene Phenol-Formaldehyde
Polytetrafluoroethylene PTFE Urea-Formaldehyde
(Teflon)
Poly (methyl-methacrylate) Novolacs
PMMA (Plexiglass)
Polyurethane (PU) Resoles
Polycarbonate (PC)
Polyvinyl Chloride (PVC)
Nylon 66

Preparation Properties Application

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Techniques for Plastic Moulding

Compounding material run between two metallic rollers rotating in opposite
Calendering direction, gets compressed and forms sheets based on thickness of gaps.
Engraving can also be done.

Compounded material is poured into die cavities made up of metals or POP and
Die Casting
is heated to form crosslinking and finally the material is cooled down.

Compounded solution in a suitable solvent is continuously dropped on a moving

Film Casting belt, solvent evaporated and films are formed. E.g. Cellophane papers and
photographic films

Compression Moulding
Injection Moulding
Blown Film Moulding
Extrusion Preparation
Moulding Properties

Thermoforming

19 January 2023 <CYC102—Theory Lecture No. 12> 7

Techniques for Plastic Moulding

(Contd.)
Compression Moulding

 The process for forming thermosets by applying heat and pressure.

 A measured amount of thermoset powder, granules or pellets is fed into the mould
cavity.
 Heat softens the material and pressure fills the cavity, then the material is cured.
 Heat actually causes the polymer to transform into a highly cross-linked and network
structure.
 Process is of limited use for the thermosets because of the requirement of cooling
time of the mould.
 Typical products include electrical insulators, pot handles and some locomotive parts.

Preparation Properties

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Techniques for Plastic Moulding

(Contd.)
Compression Moulding

19 January 2023 <CYC102—Theory Lecture No. 12> 9

Techniques for Plastic Moulding

(Contd.)
Compression Moulding

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Techniques for Plastic Moulding

Injection Moulding
(Contd.)
 It is associated with processing thermoplastics, however, with the development of the
reciprocating screw type equipment, thermosets can also be injected into the mould.
 The basic process includes plasticizing, injection, cooling and ejection.
 Granules are fed from a hopper into a screw that rotates to feed the material into a
heated chamber to allow the material to change to a molten state.
 The material is then forced through a nozzle into the mould cavity.
 A cooling time is necessary to allow the polymer to become solid, and then is ejected
from the mould by mechanical ejector pins associated with processing thermoplastics.
The dies are the steel/alloy mold to which
you inject the liquid metal. It has two halves:
the fixed half, which is stationary and
attached to the casting machine and the
ejector half which is movable.

Plasticization is the process of changing the

structure of a polymer to make
it easier to bend. The application of heat on
thermoplastic polymers will result
in plasticization.

19 January 2023 <CYC102—Theory Lecture No. 12> 11

Techniques for Plastic Moulding

(Contd.)
Injection Moulding

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Techniques for Plastic Moulding

(Contd.)
Blown Film Moulding

 Used to produce thin film hollow

tubes. Somewhat of a combination of
extrusion, blown moulding and
calendering.
 As material is extruded, air is forced
through the centre of a die, causing the
material to expand to the diameter of
the mould.
 Mould is open at the end, and the
material is continuously taken up on
rollers.
 During the take-up process, the walls
on the tube may be seamed welded
and perforated such as the case with
the garbage bags.

19 January 2023 <CYC102—Theory Lecture No. 12> 13

Techniques for Plastic Moulding

Blown Film Moulding
(Contd.)

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Techniques for Plastic Moulding

(Contd.)
Blown Film Moulding

19 January 2023 <CYC102—Theory Lecture No. 12> 15

Techniques for Plastic Moulding

(Contd.)
Extrusion Moulding
 Continuous flow of molten material is forced through a dies.
 Shape of the final product is determined by the opening of the die opening.
 Thermoplastic material is fed from a hopper, similar to the configuration of the
screw system in injection moulding.
 The screw forces the material through a tapered opening in the die.
 Heat and friction causes plasticizing to occur, softens the material and forces it
through the die opening.
 Material is cooled by either air or water.

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Techniques for Plastic Moulding

(Contd.)
Extrusion Moulding

19 January 2023 <CYC102—Theory Lecture No. 12> 17

Techniques for Plastic Moulding

(Contd.)
Thermoforming

 This process is used to obtain 3D articles from

2D sheets.
 The thermoplastic sheet is heated and
softened and placed between two halves of a
metal die.
 The sheet is compressed between the die to
the desired shape.
 Sometimes, vacuum is also applied so that
the sheet sticks to the shape of the mould.

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Thank You!
19 January 2023 <CYC102—Theory Lecture No. 12> 19

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Elastomers
 Natural Rubber
 Vulcanization
 Synthetic Rubber
 Compounding
 Polymer Composites
 Conducting Polymers

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Elastomers
Elastomers are defined as a long chain polymer which under stress undergoes
elongation by several times and regains its original shape when the stress is fully
released.

Characteristics:
 Should have linear but highly coiled structure
 Inter-chain cohesive forces should be negligible
 Undergoes elongation under stress
 Regain the original size when the stress is fully released.

E.g.,
 Natural rubber,
 synthetic rubber and
 some nylon material

23 January 2023 <CYC102—Theory Lecture No. 13> 3

Natural Rubber

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Natural Rubber (Contd.)

Rubber is a natural elastomeric polymer whose monomer unit is cis-2-methyl-1,3-
butadiene or Isoprene. Raw rubber material is extracted from rubber plant which is milk
like sappy and negatively charged colloid, get polymerized bio chemically. The main
source of natural rubber is rubber tree (scientific name: Hevea Basiliensis.)

Rubber tree is found mainly in tropical countries like southern part of India, Sri lanka,
Malaysia, Thailand, South America.

Solid rubber is white brownish amorphous solid which is soluble in petrol/carbon

disulphide.

The main compositions of latex which is extracted from rubber plant are –
Water - 55-60 %
Rubber (cis isoprene) - 32-35 %
Protein - 02-03 %
Fatty acid - 01 %
Soluble salt - 01 %
Ash - 0.03 %
The approximate molecular weight of rubber polymer is 1,00,000- 1,60,000.

23 January 2023 <CYC102—Theory Lecture No. 13> 5

Natural Rubber (Contd.)

Note: The Isoprene
structure has been
corrected here.

Average Degree of Polymerization is around 5000.

Natural Rubber is the cis isomer while the

trans isomer is called Gutta-Percha.

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Natural Rubber (Contd.)

Drawbacks of Natural Rubber:

 At low temperatures it is hard and brittle but as temperature rises it becomes soft
and sticky.
 It is soluble in many organic solvents
 Gets easily oxidized and produces bad smell even if kept as such for few days.
 Absorbs large quantities of water
 Its chemical resistivity is low and is attacked by acids, alkalis, oxidizing and reducing
agents.
 Its tensile strength, abrasion resistance, wear and tear resistance are low.

23 January 2023 <CYC102—Theory Lecture No. 13> 7

Vulcanization
 Vulcanization is a chemical process in which the
rubber is heated with sulphur or H2S at 100–
140°C.
 Developed by Charles Good Year in 1839.
 The function of Sulphur is breaking of pi electron
in rubber and make three dimensional cross
linking between double bonded carbon atom by
sulpher bridge. This is called vulcanization of
rubber.
 These cross-links between long rubber molecules
helps to achieve improved structural toughness/
stiffness, elasticity, resilience, tensile strength,
viscosity, hardness and weather resistance.
 In tyre industry about 3-4 % S and filler like
Carbon are added.
 If the percentage of S is increased beyond 30 %
full saturation of bonds take place resulting in a
rigid non-flexible rubber called Ebonite.

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Vulcanization (Contd.)

23 January 2023 <CYC102—Theory Lecture No. 13> 9

Synthetic Rubbers
 Buna-S Rubber (SBR)

Buna-S rubber is a copolymer obtained by the addition of butadiene and styrene at a ratio
3:1 in a emulsion system in presence of free radical initiator like benzoyl peroxide or
cumene hydro peroxide with support of dextrose.

The produced rubber is called cold rubber as the polymerization carried at temperature of
-15°C to 5°C. At this temperature the chain length can be controlled. If the reaction
temperature is 50°C then the rubber is called hot rubber and in this case the chain can not
be controlled.

Such types of synthetic rubbers are more efficient than natural rubber. These rubber have
high tensile strength, low abrasion oxidation and resistance to weather oil and acid base.

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Synthetic Rubbers (Contd.)

 Neoprene rubbers (chloroprene rubbers)
Neoprene rubber is also called Polychloroprene or Duprene. Neoprene rubber is a
copolymer obtained by the addition of monomer Chloroprene (2-chloro-1,3-butadiene).
Chloroprene is prepared by dimerization of acetylene by passing through aqueous
solution of ammonium chloride (NH4Cl) and cuprous chloride (Cu2Cl2 )at a temperature
70°C. HCl is added finally. Free radical initiators like benzoyl peroxide or cumene hydro
peroxide or oxygen enhance the polymerization of chloroprene to neoprene.

 Butyl Rubber
Formed by copolymerization of isobutylene with a small amount of isoprene (1-5%) at
90°C.

23 January 2023 <CYC102—Theory Lecture No. 13> 11

Synthetic Rubbers (Contd.)

 Nitrile rubber (Buna- N Rubber)
Buna -N rubber is a copolymer obtained by the addition of butadiene and acrylonitrile
at a ratio 3:1 in a emulsion system in presence of free radical initiator like benzoyl
peroxide or cumene hydro peroxide. Synthetic rubbers can be vulcanized as there is
weak pi bond present in the long back bone polymeric chain.

Such types of synthetic rubbers are more efficient than natural rubber. These rubber
have high tensile strength low abrasion oxidation and resistance to weather oil and
acid base.

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Compounding

The process of including various additives into plastics by mechanical means to get a homogeneous
mixture is called compounding.

23 January 2023 <CYC102—Theory Lecture No. 13> 13

Compounding

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Compounding

23 January 2023 <CYC102—Theory Lecture No. 13> 15

Polymer Composites
The polymer composites have another name called Polymer Matrix Composites (PMC).
A polymer matrix composite (PMC) is a composite material composed of a variety of
short or continuous fibers bound together by an organic polymer matrix. PMCs are
designed to transfer loads between fibers of a matrix.

Advantages:
 Lightweight,
 High stiffness,
 High strength along the direction of their
reinforcements,
 Good abrasion resistance,
 Good corrosion resistance.

A polymer composite is a multi-phase material in which reinforcing fillers are integrated

with a polymer matrix, resulting in synergistic mechanical properties that cannot be
achieved from either component alone.

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Polymer Composites (Contd.)

FIBREGLASS
Fiberglass is simply a composite consisting of glass fibers, either continuous or discontinuous,
contained within a polymer matrix; this type of composite is produced in the largest quantities. Fiber
diameters normally range between 3 and 20 m.

Glass is popular as a fiber reinforcement material for several reasons:

1. It is easily drawn into high-strength fibers from the molten state.
2. It is readily available and may be fabricated into a glass-reinforced plastic economically using a
wide variety of composite-manufacturing techniques.
3. As a fiber it is relatively strong, and when embedded in a plastic matrix, it produces a composite
having a very high specific strength.
4. When coupled with the various plastics, it possesses a chemical inertness that renders the
composite useful in a variety of corrosive environments

Its matrix is made by reacting a polyester with C=C bonds in backbone and styrene. The fiber
trapped inside gives reinforcement and matrix adds toughness to the composite.

23 January 2023 <CYC102—Theory Lecture No. 13> 17

Polymer Composites (Contd.)

CARBON FIBRE

Carbon is a high-performance fiber material that is the most commonly used reinforcement
in advanced (i.e., non-fiberglass) polymer-matrix composites. The reasons for this are as
follows:
 Carbon fibers have the highest specific modulus and specific strength of all reinforcing
fiber materials.
 They retain their high tensile modulus and high strength at elevated temperatures; high-
temperature oxidation, however, may be a problem.
 At room temperature, carbon fibers are not affected by moisture or a wide variety of
solvents, acids, and bases.
 These fibers exhibit a diversity of physical and mechanical characteristics, allowing
composites incorporating these fibers to have specific engineered properties.
 Fiber and composite manufacturing processes have been developed that are relatively
inexpensive and cost effective.

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Polymer Composites (Contd.)

KEVLAR
Aramid (Aromatic Polyamide) fibers are high-
strength, high-modulus materials that were
introduced in the early 1970s. They are
especially desirable for their outstanding
strength-to-weight ratios, which are superior
to metals. Chemically, this group of materials
is known as poly (paraphenylene
terephthalamide). There are a number of
aramid materials; trade names for two of the
most common are Kevlar™ and Nomex™. For
the former, there are several grades (viz.
Schematic representation of repeat unit and
Kevlar 29, 49, and 149) that have different chain structures for aramid (Kevlar) fibers.
mechanical behaviors. During synthesis, the Chain alignment with the fiber direction
rigid molecules are aligned in the direction of and hydrogen bonds that form between
the fiber axis, as liquid crystal domains. adjacent chains are also shown
The aramid fibers are most often used in
composites having polymer matrices;
common matrix materials are the epoxides
and polyesters.
23 January 2023 <CYC102—Theory Lecture No. 13> 19

Conducting Polymers

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Conducting Polymers

23 January 2023 <CYC102—Theory Lecture No. 13> 21

Thank You!
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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Fuels
 Classification
 Comparative Analysis
 Calorific Value
 Numerical

1 February 2023 <CYC102—Theory Lecture No. 14> 2

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Fuels
A fuel is defined as any substance which can be used to produce heat or power by
combustion.

The various types of fuels are categorized as solid, liquid and gaseous fuels
based on their physical state.
Solid fuel: It is characterized by its mass, composition, specific heat,
combustion residue and other thermal properties.
Liquid fuel: It is characterized by its composition, density, viscosity, specific heat
and other thermal properties.
 Density is useful for quantitative calculations and assessing ignition qualities.
The unit of density is kg/m3.
 Viscosity is the most important characteristic in the storage and use of fuel
oil.
 Specific heat is the amount of kilocalories needed to raise the temperature of
1 kg of oil by 1°C.
Gaseous fuel: It is characterized by its composition, volume and pressure, and
thermal properties.

1 February 2023 <CYC102—Theory Lecture No. 14> 3

Classification based on occurrence

Primary or natural fuels: These fuels exist in their natural form.
Secondary or prepared fuels: These fuels are synthesized from naturally occurring
primary fuels.
Examples of primary and secondary fuels based in different physical states.

Physical state Natural or Primary Fuel Prepared or Secondary

Fuel
Solid Wood, Peat, Lignite, Coal Charcoal, Briquettes,
Coke , Petroleum coke
Liquid Crude petroleum, natural Tar, Petroleum distillates:
gasoline, Gasoline, Kerosene, Gas
oils, Petroleum residues,
alcohol
Gas Natural gas Producer gas, water gas
CNG

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Comparative Analysis of Fuels

Property Solid Fuels Liquid Fuels Gaseous Fuels
Due to ash and moisture High calorific value Higher calorific value
content, their calorific and thermal and thermal
Calorific Value value and thermal efficiency than solid efficiency
efficiencies are low. fuels

Control of Controlled by Controlled by varying

Combustion Cannot be controlled regulating the flow temperature and
process of liquid controlling air supply
Cannot be used in
Application internal combustion Can be used Can be used
engines

1 February 2023 <CYC102—Theory Lecture No. 14> 5

Comparative Analysis of Fuels

Property Solid Fuels Liquid Fuels Gaseous Fuels
Merits Moderate ignition Products of combustion Undergoes complete
temperature are relatively clean and combustion in slight
free from dust and soot excess of air and do not
particles release smoke or ash
particles into air
Cost of production is Require less air for Heat of combustion
also low as they are complete combustion could be recovered by
not explosive, easily pre-heating the gases
transportable and using hot waste gases
stored
Easy to fire and can be
extinguished easily

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Comparative Analysis of Fuels

Property Solid Fuels Liquid Fuels Gaseous Fuels
Demerits Require excess of air High cost of High cost of
for combustion and production as they production as they
the process cannot cannot be stored cannot be stored
be controlled easily easily easily
During combustion, Have offensive odour High risk of fire
they block the and require special hazard as they are
circulation of air and burners for highly flammable
corrode the parts of combustion
the furnace
Flue gases released
in combustion
contain dust and
soot particles

1 February 2023 <CYC102—Theory Lecture No. 14> 7

Characteristics of good fuel

A good fuel should possess the following characteristics:
 It should ignite easily. The temperature of the fuel at which ignition starts and continues to
burn without further addition of heat is called ignition temperature. It should be moderate
for a good fuel. Very low ignition temperature leads to fire hazard and very high ignition
temperature disfavors the starting of fire.
 It should give out a lot of heat, that is, its specific heat should be high.
 It should have low smoke and combustible matter such as ash. It should not give out
harmful combustion products. This property depends on the nature of elements present in
the fuel.
 It should be inexpensive and readily available.
 It should be easy to store and transport.
 It should have low ash content. Ash reduces the calorific value of the fuel, causes
hindrance to the how of air and heat, reduces the specific heat and leads to unwanted
disposable problems.

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Calorific Value
The most important property of a fuel is the amount of heat that can be obtained from
it. This amount of heat is expressed in the English system in terms of British Thermal
Units (BTU) and in the metric system in terms of Calories. They are defined as follows:

 British Thermal Unit (BTU): It is 1/180 of the amount of heat necessary to raise 1
lb of water from 32 to 212°F.
 Calorie (cal): It is 1/100 of the amount of heat necessary to raise 1 g of water from
0 to 100°C.

The conversion between the two units can be achieved by the following formula:
1 BTU = 252 cal
Also, the larger unit kilogram-calorie is related to calorie by
1 kg-cal = 1000 cal

1 February 2023 <CYC102—Theory Lecture No. 14> 9

Calorific Value (Contd.)

Higher calorific value (HCV) or gross calorific value: It is defined as the total amount of heat
liberated when one unit of the fuel is burnt completely and the combustion products are cooled
to room temperature.
Hydrogen is found to be present in almost all fuels and when the calorific value of such fuel is
determined, hydrogen is converted into steam. When the products of combustion are
condensed to room temperature, the latent heat of condensation of steam also gets included in
the measured heat. The total value of heat calculated in this way is called higher calorific value.
Thus, gross calorific value is always greater than the net calorific value.

Lower calorific value (ICV) or net calorific value: In actual practice, the water vapor escapes
along with hot combustion gases and thus, it is not condensed. As a result, a lesser amount of
heat is available. The amount of heat, so available, is called as lower calorific value.
Lower calorific value is defined as the amount of heat liberated when one unit of the fuel is
completely burnt and the combustion products are allowed to escape. Thus,

Net calorific value = Gross calorific value - Latent heat of water vapor formed

Therefore, we see that due to the addition of latent heat of the water vapor formed, the gross
calorific value is higher than the net calorific value.
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Determination of Calorific Value

Theoretical Determination
Theoretical calculations of calorific value are worked out by what is known as the Dulong's
formula. The calorific value of a fuel can be approximately calculated by knowing the
percentage of the constituent elements (C, H, O and S). According to Dulong, the calorific value
of a fuel is the sum of the calorific values of its constituent elements. Thus, Dulong's formula for
calculating the calorific value from the chemical composition of the fuel may be written as
follows:
Gross Calorific Value= × 8080 𝐶 + 34500 𝐻 − + 2240 𝑆 𝑘𝑐𝑎𝑙/𝑘𝑔

where C, H and S are the %age of carbon, hydrogen, oxygen and sulphur, respectively and the
calorific values of carbon, hydrogen and sulphur are 8080, 34500 and 2240, respectively.

𝐿𝑜𝑤𝑒𝑟 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 = 𝐻𝑖𝑔ℎ𝑒𝑟 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑣𝑎𝑙𝑢𝑒 − 0.09𝐻 𝑋 587 𝑘𝑐𝑎𝑙/𝑘𝑔

Where 587 kcal/g is the latent heat of steam

1 February 2023 <CYC102—Theory Lecture No. 14> 11

Numerical Problems
Gross Calorific Value= × 8080 𝐶 + 34500 𝐻 − + 2240 𝑆 𝑘𝑐𝑎𝑙/𝑘𝑔

𝐿𝑜𝑤𝑒𝑟 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑉𝑎𝑙𝑢𝑒 = 𝐻𝑖𝑔ℎ𝑒𝑟 𝐶𝑎𝑙𝑜𝑟𝑖𝑓𝑖𝑐 𝑣𝑎𝑙𝑢𝑒 − 0.09𝐻 𝑋 587 𝑘𝑐𝑎𝑙/𝑘𝑔

Calculate LCV of a fuel which has 8% Hydrogen and HCV as 6500 cal/g. Given that
the latent heat of steam= 580 cal/g.

LCV= 6500-(0.09X8X580)= 6500-417.6 = 6082.4 cal/g

Calculate the Gross and net calorific values of a coal sample containing 84% C, 1.5%
S, 6% N, 5.5% H, 8.4% O. The calorific values of C, H and S are 8080 kcal/kg, 34500
kcal/kg, 2240 kcal/kg, respectively, and latent heat of steam is 587 cal/g.
.
Gross Calorific Value= × 8080 × 84 + 34500 5.5 − + 2240 × 1.5 𝑘𝑐𝑎𝑙/𝑘𝑔

= 8356.05 kcal/kg
Lower Calorific Value = Higher Calorific value − 0.09H X 587 kcal/kg
= 8356.05 – 0.09x 5.5 x 587 = 8065.485 kcal/kg

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Thank You!
1 February 2023 <CYC102—Theory Lecture No. 14> 13

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Bomb Calorimeter
 Numericals based on Bomb Calorimeter
 Coal
 Types of coal
 Pulverized coal

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Bomb Calorimeter
Principle:
 The calorific value of solid and liquid fuels is found by burning a known amount of fuel at constant
volume conditions, and the temperature of the surrounding water is increased due to the heat
evolved.
 This quantity of heat is calculated and from this value, the calorific value of the fuel is obtained.

The electrodes are then connected to a battery

Beckmann's thermometer, which is

capable of reading even a small
difference like 1/100th of a degree.
The bomb lid is tightly screwed
and filled with oxygen at about 25
atm pressure.

copper calorimeter

nickel or stainless steel

crucible
8 February 2023 <CYC102—Theory Lecture No. 15> 3

Bomb Calorimeter (Contd.)

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Bomb Calorimeter (Contd.)

Let x= mass of fuel sample taken in crucible (g)
W= mass of water in the calorimeter
w = water equivalent of bomb calorimeter
T1= initial temperature of water in calorimeter
T2= final temperature of water in calorimeter
L = Higher calorific value in fuel in cal/g
Heat liberated by burning of fuel = xL
Heat absorbed by apparatus = (W+w)(T2-T1)

But Heat liberated by fuel = Heat absorbed by apparatus

xL = (W+w)(T2-T1)

( )( )
HCV of fuel (L) = cal/g (or kcal/kg)

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Bomb Calorimeter (Contd.)

( )( )
HCV of fuel (L) =
Combustion of Hydrogen fuel

If H = Percentage of Hydrogen in fuel, then: 2𝐻 + 𝑂 = 2𝐻 𝑂

9𝐻
g = Mass of H2O from 1 gm of fuel = 0.09 H g 4 : 32 : 36
100 1 : 8 : 9

Heat taken by water in forming steam = 0.09 H x 587 cal

(Latent heat of steam = 587 cal/g)

LCV = HCV – Latent heat of water formed

LCV = [L- (0.09 H x 587)] cal/g

LCV of fuel = [L- (0.09 H x 587)]

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Bomb Calorimeter (Contd.)

Corrections: For more accurate calculations, certain corrections are incorporated:
1. Fuse wire correction: The heat liberated as measured above, includes the heat
given out by ignition of the fuse wire used.

2. Acid correction: When fuels containing S and N are oxidized to higher temperatures,
they form H2SO4, and HNO3, respectively. The heat evolved due to these exothermic
reactions is considered.
S + 2H + 2O2 H2SO4 + Heat
2N + 2H + 3O2 2HNO3 + Heat
The correction for 1 mg of S is 2.25 cal and for 1ml of N/10 HNO3 formed is 1.43 cal.

3. Cooling correction: Time taken to cool the water in calorimeter from maximum
temperature to room temperature is noted. From the rate of cooling (dt°/min)
and the actual time taken for cooling (t min), the cooling correction dt x t is added to
rise in temperature.

Incorporating the above corrections, in the expression of HCV, we get

[ ]
HCV of fuel (L) =
( )

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Bomb Calorimeter (Contd.)

Uses of Bomb Calorimeter
Bomb calorimeters are devices which are useful to compute the heat of combustion of a chemical reaction. Such
information collected from a bomb calorimeter during a chemical reaction will tell scientists whether certain food
products are safe for use or not. Some popular uses are as follows:
1.Thermodynamic Studies
Bomb calorimetry is used mainly in the scientific study of thermodynamic processes. It measures the heat of combustion
produced in a chemical reaction. Also, it measures reaction enthalpy and change in enthalpy throughout the reaction.
Obviously Bomb calorimeter is very essential to scientific and theoretical thermodynamic studies.
2.Educational Training
This is another use of bomb calorimeters which is in education training. Calorimetry is being studied in university-level
science courses and also in some high school classes.
3.Fuel Testing
These are used to test the calorific value of solid and liquid fuels, which are traded based on these values. Fuels such as
coal and oil must meet the regulations regarding the total calorific value, quality, and purity of the fuel. Bomb calorimetry
can also test liquid fuels such as gasoline and kerosene.
4.Waste and Refuse Disposal
The cement industry uses hazardous waste as an alternative fuel. But the use of hazardous waste as fuel is regulated by
the government, by Environmental Protection Agency. Using Bomb calorimetry we can determine whether hazardous
waste fuel meets the regulations or not.
5.Metabolic Studies
Bomb calorimetry can also determine the calorie content of a product. Using this process one can examine the effects of
energy content in food on humans and animals. These studies are showing implications that extend into nutritional
considerations and the effects of diet on the body.
6.Propellant and Explosive Testing
We use bomb calorimeter to test propellants and explosives to find the product’s heat of detonation.

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Bomb Calorimeter (Contd.)

Problem: 0.72 g of a fuel containing 80 % Carbon, when burnt in a bomb calorimeter,
increased the temperature of water from 27.3° to 29.1°C. If the Calorimeter contains 250
g of water and its water equivalent is 150 g; Calculate the HCV of the fuel. Give your
answer in kJ/kg.

Solution:
x= 0.72g
W=250g
( )( )
w=150g HCV of fuel (L) =
T1= 27.3°C
T2= 29.1°C = [(250 + 150)(29.1-27.3)]/0.72
=[400*1.8]/0.72
=1000 kcal/kg * 4.2 kJ/kg
=4200 kJ/kg

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Bomb Calorimeter (Contd.)

Problem: On burning 0.83g of a solid fuel in a bomb calorimeter, the temperature of
3500 g of water increased from 26.5°C to 29.2°C. Water equivalent of calorimeter and
latent heat of steam are 385.0 g and 587.0 cal/g respectively. If the fuel contains 0.7%
hydrogen, Calculate its gross and net calorific value.

Solution: ( )( )
x= 0.83g HCV of fuel (L) =
W=3500g = [(3500 + 385)(2.7)]/0.83
w=385g =12638 cal/g
T1= 26.5°C
T2= 29.2°C LCV of fuel = [L- (0.09 H x 587)]
T2-T2 = 2.7°C = [12638 – (0.09*0.7*587)]
H % = 0.7 % = 12601 cal/g
Latent heat of steam = 587 cal/g

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Bomb Calorimeter (Contd.)

Problem: A sample of coal contains: C=93%, H=6% and ash=1%. The following data were
obtained when the above coal was tested in bomb calorimeter:
Weight of coal burnt=0.92g, weight of water taken=550g, water equivalent of bomb and
calorimeter= 2200g, rise in temperature=2.42°C, Fuse wire correction= 10 cal and acid
correction=50 cal. Calculate the gross and net calorific value of the coal, assuming the
latent heat of condensation of steam as 580 cal/g.
Solution: [ ]
HCV =
x= 0.92g ( )
W=550g = [(550 + 2200)(2.42)- (10+50)]/0.92
w=2200g =7168.5 cal/g
T2-T2 = 2.42°C
H%=6% LCV of fuel = [L- (0.09 H x 587)]
Latent heat of steam = 580 cal/g
= [7168.5 – (0.09*6*580)]
Fuse wire correction=10 cal
= 6855.3 cal/g
Acid correction=50 cal

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Coal (Contd.)
 Coal is a complex organic compound derived from the dead plants which had been buried
for several million years. The dead plants due to pressure and temperature, and contact
with silt and water were subjected to various chemical and biochemical reactions resulting
in the formation of coal.
 It is believed that, in the earlier stages, wood was attacked by aerobic and anaerobic
bacteria to bring about its degradation. The bacterial attack led to the formation of acid,
which would otherwise stop further degradation by bacteria.
 However, because of the alkalinity of soil,
the acid was neutralized and the bacterial
action continued to take place bringing
about further degradation of the matter.
 The degraded matter, as the time elapsed,
was converted into various types of coal:
Peat, lignite, bituminous and anthracite, of
varying maturity.
 This process of conversion of degraded
matter into various form of coal is called
coalification.

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Coal (Contd.)

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Coal (Contd.)
Coal is classified or ranked on the basis of its carbon content. The highest ranking coal has the largest carbon
content.
1. Peat: In the process of coalification from wood, the first stage is peat formation. It is the lowest rank of
coal with the lowest carbon content, and hence with the lowest calorific value. It is not economical to obtain
peat lying buried deep under earth. The deposits of peat are found in West Bengal (Sunderbans) and Tamil
Nadu (Nilgiri Hills).
2. Lignite: This brown variety of coal is older than peat and younger than other types of coal. The
transformation of wood into coal has taken place to a greater extent than in peat. Hence, this variety is the
next lowest ranking coal. It contains about 60-71% carbon and 60% moisture content. Hence, it has a low
calorific value. Lignite is mined in Neyveli, Tamil Nadu. Small amounts of lignite are also found in Rajasthan
and Kashmir.
3. Sub-bituminous coal: The next low ranking coal is sub-bituminous coal. It has 71-77% carbon content. It is
black, and contains high moisture and volatile matter content.
4. Bituminous coal: It is a hard black colored variety of coal. It contains 77-87% carbon. It is brittle and burns
with a yellow smoky flame. The moisture content is 6%.
5. Anthracite coal: This is the highest ranking coal. Its carbon content is about 86-97%. It is harder than
bituminous variety and is brittle. It is black and burns without smoke and with a non-luminous flame giving
maximum heat energy.

On comparing the different varieties of coal, the order of ranking followed is:
Anthracite > Bituminous > Sub-bituminous > Lignite > Peat

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Coal (Contd.)
Uses of Coal

1. As a primary fuel: Coal is used to produce steam through heat and combustion,
which is again used for running turbines to generate electricity in power plants.

2. As a secondary fuel: The product of burning coal in the absence of air is of

metallurgical importance. The byproducts are useful in making plastics, tar and
synthetic fibers and also used making steel in industries.

Though uses of coal are aplenty, there are adverse impacts on the environment also.
Coal mining, in general, has an adverse effect on ecosystems and water quality. It
also changes landscapes. The combustion products of coal which cause pollution to
the environment include CO, CO, NO, SO, and particulates. CO, is a primary
greenhouse gas. CO, NO, SO, and particulates are major air pollutants and develop
lung diseases in humans. Sulphur dioxide forms acid rain in the atmosphere. NO, is
responsible for the formation of photochemical smog.

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Pulverized Coal
Pulverized coal generally refers to coal in powdered form obtained by crushing, grinding or
pulverizing coal. As the surface area of pulverized coal is large, the volatile matter present in it
comes quickly in contact with air and is released, enabling the combustion of fixed carbon. This
increases the calorific value of the coal and enhances its quality.

The advantages of pulverized coal are as follows:

1. It provides easy transportation and storage.
2. Even high grade coal having high ash content, such as found in India, could be used
satisfactorily.
3. It can easily undergo combustion in small percentage of excess air with less wastage of heat,
and has high thermal efficiency.
4. It does not form clinkers (incombustible residue) and provides an oxidizing and reducing
atmosphere inside the furnace for metallurgical purposes.

However, it has some disadvantages also:

1. It involves the extra cost of pulverizing and sieving.
2. Special types of burners are required for good mixing of air and fuel.
3. During the process of grinding, crushing and pulverizing, finely divided ash is generated in
form of fly-ash causing air pollution and causing problems associated with its disposal.

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Thank You!
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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Analysis of Coal
 Proximate Analysis
 Ultimate Analysis
 Combustion
 Fuel Gas analysis

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Proximate Analysis

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Significance of Proximate Analysis

1. Moisture in coal evaporates during the burning of coal, and some of the liberated heat is in the form of
latent heat of evaporation. Therefore, moisture lowers the effective calorific value of coal. Moreover,
it quenches the fire in the furnace. Hence, lesser the moisture content, better the quality of coal as a fuel.
However, presence of moisture, up to 10%, produces a more uniform fuel bed and less amount of fly-ash.

2. High volatile matter content means that a high proportion of fuel will distill over as gas or vapor, a large
proportion of which escapes unburnt. The volatile matter present in the coal may be as high as 50%.
The volatile matter present in the coal may be combustible gases or non-combustible matter. The presence
of non- combustible matter is always undesirable as they do not add to heat value, but the increase the
volume of the furnace required. Therefore, higher volatile content in coal is undesirable. A high volatile
matter containing coal burns with a long fame, large amount of smoke and has low calorific value. Hence,
lesser the volatile matter better is the rank of the coal.

3. Ash is a useless non-combustible matter which reduces the calorific value of coal. Moreover, ash causes
the hindrance to the flow of air and heat, thereby lowering the temperature. Also, it often causes trouble
during combustion by forming clinkers (incombustible residue), which causes obstruction to air supply;
thereby the combustion of coal becomes incomplete. It also causes wear of furnace walls. Burning of
apparatus and feeding mechanism. Hence, lower the ash content better is the quality of coal. The
presence of ash also increases the transport, handling, storage and disposal costs.

4. Higher the fixed carbon content, better is the quality of coal as higher is the calorific value of coal. This also
represents the quality of carbon that can be burnt by a primary current of air drawn through the hot bed of
the fuel. Hence, high percentage of fixed carbon is desirable. It is useful for designing the furnace and
firebox.

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Ultimate Analysis

At. Wt. of C

At. Wt. of CO2

At. Wt. of H2

At. Wt. of H2O

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Ultimate Analysis (Contd.)

2N +3H2 + H2SO4 (NH4)2SO4

(NH4)2SO4 + 2NaOH 2NH3 + Na2SO4 +2H2O
NH3 + HCl NH4Cl At. Wt. of N

× ×
Nitrogen (%) = x 100

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Ultimate Analysis (Contd.)

At. Wt. of S

At. Wt. of BaSO4

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Significance of Ultimate Analysis

1. Greater the percentage of carbon and hydrogen, better is the coal in quality and calorific
value. However, hydrogen is mostly associated with the volatile matter and hence, it affects
the use to which the coal is put to.

2. Nitrogen has no calorific value and hence its presence in coal is undesirable. Thus, a good
quality coal has very little nitrogen content.

3. Sulphur is usually present to the extent of 0.5-3.0% and is derived from ores like iron pyrite
and gypsum, etc., mines along with the coal. Sulphur, although contributes to the heating
value of coal, on combustion it produces acids which have harmful effects of corroding the
equipments and also causes atmospheric pollution. Presence of sulphur is highly undesirable
in coal to be used for making coke for iron industry, since it is transferred to the iron metal
and badly affects the quality and properties of steel.

4. Oxygen content decreases the calorific value of coal. High oxygen content coals are
characterized by high inherent moisture content, low calorific value and low coking power.
Moreover, oxygen is in combined form with hydrogen in coal and thus, hydrogen available for
combustion is lesser than actually present. An increase in 1% of oxygen content decreases
the calorific value by about 1.7% and hence, oxygen is undesirable. Thus a good quality
should have low percentage of oxygen.

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Combustion
The use of fuel efficiently relies on the supply of correct amount of air for combustion, heating fuel to reach
its ignition temperature and allowing the combustion to proceed in a properly designed furnace.

1. Ignition temperature: It is the temperature at which a substance ignites and continues to burn without
further addition of heat. It is influenced by the surface area of fuel in the case of solid or liquid fuel while for
gaseous fuels; it depends on pressure, the ratio of combustible gas to air and size and shape of the vessel.
Increase in pressure of gaseous fuel decreases the ignition temperature. The increase in surface-to-
volume ratio of vessel increases. The presence of a catalyst may lower the ignition temperature.

2. Explosive Range: The limiting composition of a gas-air mixture beyond which the mixture will not ignite
and continue to burn is called explosive limit or limit of ignitability. For every combustible gas, there are two
limits:
 Lower limit representing the smallest proportion.
 Upper limit the largest proportion of combustible gas that when mixed with air, will sustain combustion.

3. Flame: When two or more gases interact rapidly, with the evolution of more or less heat and light, the
phenomenon is known as a flame. Although the combustion of liquids and many solids is accompanied by
a flame, this is not due to the combustion of the solids and liquids themselves but due to the gases
produced from these from the heat of the reaction.

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Combustion (Contd.)
4. Surface combustion: When an air-gas mixture is allowed to impinge upon a heated surface, it is
found that combustion proceeds more rapidly on the surface than in the body of the gas. This is
known as surface combustion, and the rate at which it proceeds depends on the temperature, the
extent of the surface and the speed with which reactants can diffuse to the surface and the products
away from the surface.

5. Primary combustion: The primary combustion reaction of solid fuels such as coke or charcoal,
which do not vaporize, takes place on the surface of the solid. Such combustion is similar to the
surface combustion of gases, except that only the oxygen of the air must diffuse to the surface,
since the fuel carbon is already there.

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Flue gas Analysis

 The gaseous products of combustion of fuel constitute flue gas.
 The significance of flue gas analysis is that it is useful for finding the correct quantity of air to be supplied in
a furnace. The combustion products include carbon dioxide, carbon monoxide, sulphur dioxide (if sulphur is
present) and the excess of oxygen, if any, is supplied.
 The flue gas analysis is carried out using Orsat's apparatus

3 Way stopcock

Absorb CO Absorb O2 Absorb CO2

8 February 2023 <CYC102—Theory Lecture No. 16> 11

Flue gas Analysis (Contd.)

Solution of CuCl in NH3 or ammoniacal CuCl absorbs carbon monoxide CO to
form colourless complexes. For example, formation of chloride-bridged dimer
such as [CuCl(CO)]2.

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Thank You!
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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 General Overview
 Numerical Problems

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General Overview
CALORIFIC VALUE ANALYSIS

( )( )
HCV of fuel (L) =
[ ]
HCV of fuel (L) =
( )

LCV = HCV – Latent heat of water formed

LCV = [L- (0.09 H x 587)] cal/g

9 February 2023 <CYC102—Theory Lecture No. 17> 3

General Overview Initial weight = a gm

PROXIMATE ANALYSIS
105° -110°C
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 1 Hour
𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒% = 𝑋 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛
𝑎−𝑏 weight = b gm
𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒% = 𝑋 100
𝑎 250° - 270°C
7 Mins
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡
𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟% = 𝑋 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛
weight = c gm
𝑏−𝑐 700° -750°C
𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟% = 𝑋 100
𝑎 1-2 hours

𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑠ℎ 𝑙𝑒𝑓𝑡

𝐴𝑠ℎ% = 𝑋 100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛
weight = d gm
𝑑
𝐴𝑠ℎ% = 𝑋 100
𝑎
𝐹𝑖𝑥𝑒𝑑 𝐶𝑎𝑟𝑏𝑜𝑛% = 100 − % 𝑜𝑓 (𝑚𝑜𝑖𝑠𝑡𝑢𝑟𝑒 + 𝑣𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑚𝑎𝑡𝑡𝑒𝑟 + 𝑎𝑠ℎ)

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General Overview (Contd.)

ULTIMATE ANALYSIS

𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐾𝑂𝐻 𝑥 12

𝐶𝑎𝑟𝑏𝑜𝑛% = 𝑋 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛 𝑥 44
𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑎𝐶𝑙 𝑥 2
𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛% = 𝑋 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛 𝑥 18
.
Nitrogen% =
Volume of acid is taken after subtracting the value of excess acid

𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐵𝑎𝑆𝑂 𝑥 32
𝑆𝑢𝑙𝑝ℎ𝑢𝑟% = 𝑋 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑖𝑛 𝑏𝑜𝑚𝑏 𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 𝑥 233

𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑠ℎ 𝑙𝑒𝑓𝑡

𝐴𝑠ℎ% = 𝑋 100
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑡𝑎𝑘𝑒𝑛
𝐹𝑖𝑥𝑒𝑑 𝐶𝑎𝑟𝑏𝑜𝑛% = 100 − % 𝑜𝑓 (𝐶 + 𝐻 + 𝑁 + 𝑆 + 𝑎𝑠ℎ)

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General Overview (Contd.)

COMBUSTION OF FUEL
 Write combustion reactions for the elements present in the fuel.
 Calculate weight of oxygen required.
 Subtract oxygen already present in the fuel
 C,H, S and hydrocarbons are the combustible substances present in the
fuel.
 N, Ash, CO2 and water vapours are the incombustible substances present in
the fuel
 Calculate weight and volume of air.
 In case of weight of air multiplication factor is 100/23 and in case of volume
of air multiplication factor is 100/21. [Percentage of oxygen in air by volume
is 21% and 23.2% by weight]

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Practice Problems
Calculate the weight and volume of air required for complete combustion of 4 Kg
of coal with the following composition:
C=85%, H=10% and O=5%.
Solution:
Combustion reactions
Elements Weight of O2 required for
C + O2 CO2 complete combustion in Kg
12 32 44
C=0.85 or 850 gm C=0.85 X = 2.26 kg
H2 + 0.5 O2 H2O H=0.1 or 100 gm H=0.1 X = 0.8 kg
2 16 18
O=0.05 or 50 gm --
Total oxygen (2.26 + 0.8)=3.06 kg
Weight of oxygen required = weight of oxygen needed – weight of oxygen present
Weight of oxygen required = 3.06– 0.05 = 3.01 kg

9 February 2023 <CYC102—Theory Lecture No. 17> 7

Practice Problems
Calculate the weight and volume of air required for complete combustion of 4 Kg
of coal with the following composition:
C=85%, H=10% and O=5%.
Solution:
Weight of oxygen required = 3.01 kg

Therefore, air required for complete combustion

=3.01 𝑥 = 13.08 kg per 1 kg of coal
Therefore for 4 kg of coal= 13.08 x 4 = 52.32 kg

Volume of air
28.94 kg of air = 22.4 L volume of air at NTP

. .
Therefore 52.32 kg of air = = 40.496 L of air
.

9 February 2023 <CYC102—Theory Lecture No. 17> 8

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Practice Problems
A gaseous fuel has the following composition by volume:
CH4 = 25%, CO=10%, H2 = 6%, C3H8 = 10%. Calculate the weight of air required
for complete combustion.
Solution:

Combustion reactions Volume of O2 required

CH4 + 2O2 CO2 + 2H2O 2 x 0.25 = 0.5 m3

1 vol 2 vol
CO + 0.5 O2 CO2 0.5 x 0.1 = 0.05 m3
1 vol 0.5 vol
H2 + 0.5O2 H2O 0.5 x 0.06 = 0.03 m3
1 vol 0.5 vol
C3H8 + 5O2 3CO2 + 4H2O 5 x 0.1 = 0.5 m3
1 vol 5 vol
Total = 1.08 m3

9 February 2023 <CYC102—Theory Lecture No. 17> 9

Practice Problems
A gaseous fuel has the following composition by volume:
CH4 = 25%, CO=10%, H2 = 6%, C2H8 = 10%. Calculate the weight of air required
for complete combustion.
Solution:

Volume of air = volume of O2 x = 1.08 𝑥

= 5.142 m3 of air
= 5.142 L of air

Weight of air
22.4 L volume of air at NTP = 28.94 kg of air

. .
Therefore, for 5.142 L = ( ) 𝑘𝑔 𝑜𝑓 𝑎𝑖𝑟
.

= 6.643 kg of air

9 February 2023 <CYC102—Theory Lecture No. 17> 10

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Practice Problems
The air required for oxidizing a coal sample containing C% of Carbon, H% of
Hydrogen and S% of Sulphur, then weight of air:

32 32 32 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 100

𝐶+ 𝐻+ 𝑆
12 4 32 100 23.2

Nitrogen, ash and moisture are incombustible and hence not included.

9 February 2023 <CYC102—Theory Lecture No. 17> 11

Practice Problems
A sample of coal requires 20% excess air for complete combustion. Calculate
weight of air for 250 gm of the coal, if its composition is, C=81%, H=4%,
N=1.5%, S=1.2%, O=3% and ash=9.3%
Solution:

Combustion reactions Volume of O2 required

Weight of O2 required for
C + O2 CO2 complete combustion in Kg
12 32 44
H2 + 0.5 O2 H2O C=0.81 X = 2.16 kg
2 16 18
S + O2 SO2 H=0.04 X = 0.32 kg
32 32 64
S= 0.012 X = 0.012 kg
(2.16+0.32+0.012)=2.492 kg
O2 present in coal = 0.03kg
Net O2 required = (2.492-0.03)= 2.462 kg

9 February 2023 <CYC102—Theory Lecture No. 17> 12

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Practice Problems
A sample of coal requires 20% excess air for complete combustion. Calculate
weight of air for 250 gm of the coal, if its composition is, C=81%, H=4%,
N=1.5%, S=1.2%, O=3% and ash=9.3%
Solution:
Weight of oxygen required = 2.462 kg

Therefore, air required for complete combustion

=2.462 𝑥 = 10.7 kg
Now 20% excess air is required for complete combustion, the practical weight of
air required:
=10.7 𝑥 = 2.14 kg
Total air required=10.7+2.14= 12.84 kg of air

Now, 1 kg of coal requires 12.84 kg of air

Therefore, for 250 gm of coal = 12.84 x = 3.211 𝑘𝑔 𝑜𝑓 𝑎𝑖𝑟

9 February 2023 <CYC102—Theory Lecture No. 17> 13

Practice Problems
A gaseous fuel has the following composition by volume. CH4= 5%, H=20%,
CO=25%, CO2=6% and rest if N. If 20% excess air is used for combustion, then
calculate volume of air supplied per m3 of fuel and composition of dry flue gases.
Solution:

Combustion reactions Volume of O2 Volume of dry flue gases

required m3 (m3)
CH4 + 2O2 1CO2 + H2O 0.05 X 2= 0.100 CO2= 0.05X1 = 0.05

H2 + 0.5 O2 1H2O 0.2 x 0.5= 0.100 --

CO + 0.5O2 1CO2 0.25x 0.5=0.125 CO2= 0.25X1 = 0.25

Total CO2 =0.06

From Fuel
=(0.1+0.1+0.125) N2=0.44
=0.325 m3 CO2 = (0.05+0.25+0.06)
= 0.36 m3;
N2= 0.44 m3
9 February 2023 <CYC102—Theory Lecture No. 17> 14

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Practice Problems
A gaseous fuel has the following composition by volume. CH4= 5%, H=20%,
CO=25%, CO2=6% and rest if N. If 20% excess air is used for combustion, then
calculate volume of air supplied per m3 of fuel and composition of dry flue gases.
Solution:
Weight of oxygen required = 0.325 m3
Therefore, air required for complete combustion
=0.325 𝑥 = 1.547 m3

Total air required=1.547+0.309= 1.856 m3 of air required

9 February 2023 <CYC102—Theory Lecture No. 17> 15

Practice Problems
A gaseous fuel has the following composition by volume. CH4= 5%, H=20%,
CO=25%, CO2=6% and rest if N. If 20% excess air is used for combustion, then
calculate volume of air supplied per m3 of fuel and composition of dry flue gases.
Solution:
Volume of oxygen required = 0.325 m3 Total air required=1.856 m3

Gases Composition of flue gases

CO2 = 0.36 m3 =
.
= 15.4%
.
Excess O2= 20% of = x 0.325 = 0.065 m3 =
.
=2.79%
.
theoretical O2 required
N2 from fuel = 0.44 m3 =
.
= 81.76%
.
From total air = x 1.856 = 1.466 m3
Total 0.44 +1.466 = 1.906 m3
Overall =(0.36+0.065+1.906)
=2.331 m3

9 February 2023 <CYC102—Theory Lecture No. 17> 16

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Practice Problems
1.56 g of the coal was kjeldahlized and NH3 gas thus evolved was absorbed in
50 ml of 0.1 N H2SO4. After absorption, the excess (residual) acid required 6.25
ml of 0.1 N NaOH for exact neutralization. 2.60 g of the coal sample in
quantitative analysis gave 0.1755 g of BaSO4. Calculate the percentage of N and
S in the coal sample.
Solution:
.
Nitrogen% =

𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐵𝑎𝑆𝑂 𝑥 32
𝑆𝑢𝑙𝑝ℎ𝑢𝑟% = 𝑋 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑐𝑜𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒 𝑖𝑛 𝑏𝑜𝑚𝑏 𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 𝑥 233

N=3.926%
S=0.927%

9 February 2023 <CYC102—Theory Lecture No. 17> 17

Thank You!
9 February 2023 <CYC102—Theory Lecture No. 17> 18

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Coke
 Carbonization of Coke
 Manufacture of Metallurgical Coke
 Petroleum
 Fractional distillation
 Cracking
 Petroleum Processing
 Knocking and Octane number
 Cetane number

21 February 2023 <CYC102—Theory Lecture No. 18> 2

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Coke
Carbonization : It is a process in which coal is heated in the absence of oxygen. After
combustion, carbonization of coal is the most important use of coal to produce coke.
Coke : It is the solid residue that remains when coal is heated out of contact with air.
Principal use : Coke is basically formed, so that it can be used in iron and steel manufacture
( metallurgical purpose ) where it provides heat energy and acts as a reducing agent for iron
ore in blast furnace.
The residue from the carbonization process is a non- porous powder or granular mass, it is
known as char. Char may be used in the form of specially moulded briquettes, in much the
same way as coke.

Coke and Coal:

 Coke possesses much strength and porosity compared to coal. Therefore, it is hard,
porous and of good mechanical strength.
 By coking/carbonization the undesirable sulfur content of coal is removed from coke
and due to lower volatile matter of coke it burns with a short flame.
 All these properties of coke make it suitable for metallurgical processes compared to
coal.

21 February 2023 <CYC102—Theory Lecture No. 18> 3

Carbonization of coal
Depending on the operation temperature there are mainly two types of carbonisation
processes.
Low Temperature High Temperature
Carbonisation Carbonisation
Heating Temperature 500-700°C 900-1200°C
Coke Yield 75-80% 65-75%
Volatile Matter % 5-15% 1-3%
Mechanical strength Soft and Weak Hard and Strong
Use Domestic Purposes Metallurgical purposes
By-product formed 130-150 m3/tonne 300-390 m3/tonne
Calorific Value of gas 6500-9500 kcal/m3 5400-6000 kcal/m3
% aromatic hydrocarbons in gas Lower Higher
% straight chain hydrocarbons in gas Higher Lower
Smoke produced on burning Smokeless Smoky

21 February 2023 <CYC102—Theory Lecture No. 18> 4

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Manufacture of Metallurgical Coke

Beehive Oven Otto Hoffman’s by-product Oven

21 February 2023 <CYC102—Theory Lecture No. 18> 5

Manufacture of Metallurgical Coke

Beehive Oven Otto Hoffman’s by-product Oven

21 February 2023 <CYC102—Theory Lecture No. 18> 6

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By-product oven
Carbonization of a charge of coal takes about between 11 to 18 hours.

When carbonization is completed, a massive ram pushes the red hot coke into a truck. It
is subsequently quenched by a water spray (wet quenching'). In place of wet quenching,
"dry quenching" offers advantages, because the coke produced is more strong, dense,
graphitized and non-reactive. In this method, the red hot coke is placed in a chamber
and cooled by passing inert gases from boilers (like nitrogen). The heated inert gases are
then circulated to boilers, where they generate steam. The coke produced by 'dry
quenching' is cheaper, drier and contains lesser dust than 'wet-quenched' coke.

21 February 2023 <CYC102—Theory Lecture No. 18> 7

Recovery of By-Products

liquor water water at petroleum moist

ammonia very Fe2O3
low
temperature

21 February 2023 <CYC102—Theory Lecture No. 18> 8

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Recovery of By-Products
The gas coming out from the oven is known as "coke oven gas" and is mainly composed of
ammonia, H2S, naphthalene, benzene, tar, moisture, etc.
 Recovery of tar: The gas is first passed through a tower in which liquor ammonia is sprayed.
Here dust and tar get collected in a tank below, which is heated by steam coils to recover
back ammonia sprayed. The ammonia is used again.
 Recovery of ammonia: The gases from the chamber are then passed through a tower in
which water is sprayed. Here ammonia goes into solution as NH4OH.
 Recovery of naphthalene: The gases are then passed through another tower in which water
at very low temperature is sprayed. Here naphthalene gets condensed.
 Recovery of benzene: The gases are then sprayed with petroleum, when benzene and its
homologues are removed.
 Recovery of H2S: The gases are then passed through a purifier, packed with moist Fe2O3. Here
H2S is retained.
Fe2O3 + 3H2S Fe2S3 + 3H2O
After sometime, when all Fe2O3 is changed into Fe2S3, the purifier is exposed to atmosphere,
when Fe2O3 is regenerated.
Fe2S3 +4O2 2FeO + 3SO2
4FeO + O2 2Fe2O3

21 February 2023 <CYC102—Theory Lecture No. 18> 9

Petroleum
Petroleum or crude oil (petra = rock ; oleum = oil), is a dark greenish-brown, viscous oil found
deep in earth's crust. It is composed mainly of various hydrocarbons (like straight-chain
paraffin's, cyclo-paraffins or naphthalene, olefins and aromatics), together with small
amounts of organic compounds containing oxygen, nitrogen and sulphur. The oil is, usually,
found floating upon a layer of brine and has a layer of gas on top of it.

The average composition of crude petroleum is: C = 79.5 to 87.1% ; H = 11.5 to 14.8%; S = 0.1
to 3.5%; N + 0 = 0.1 to 0.5%.
Classification of petroleum
Paraffinic-base type crude Asphaltic-base type crude Mixed-base type crude
Mainly composed of the Contains mainly cyclo-paraffins Contains both paraffinic
saturated hydrocarbons from or naphthalenes with smaller and asphaltic hydrocarbons
CH4 to C35H72 and a little of the amount of paraffins and and are, generally, rich in
naphthalenes and aromatics. aromatic hydrocarbons. semi-solid waxes
The hydrocarbons from C18H38
to C35H72 are semi-solids, called
'waxes'.
(Naphthalene) (Methyl
naphthalene)

21 February 2023 <CYC102—Theory Lecture No. 18> 10

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Refining of Crude oil

The petroleum obtained by mining is viscous and dark colored liquid. Due to the
presence of sulphur has an unpleasant smell. It also contains impurities of sand,
brine or sea water. Hence it is called crude oil has an unpleasant smell.
The process of converting crude oil into several useful fractions is referred as
refining of petroleum

The important steps involved are:

 Fractional distillation to give various fractions.
 Conversion of less desirable fractions to valuable products by processes like
cracking.
 Treatment of fractions to remove undesirable substances.

21 February 2023 <CYC102—Theory Lecture No. 18> 11

Fractional distillation
 Crude oil is a mixture of hydrocarbons, mainly alkanes and it is difficult to separate
the individual compounds. Below 200°C, there may be more than 400 compounds.
When fractional distillation is performed the crude oil is separated into a number of
fractions having different and definite boiling ranges. These fractions find immense
use in industries and in domestic purposes.
 The fractional distillation of petroleum is carried out continuously in a specially
designed fractionating tower or column made of steel.
 The crude oil is preheated in a furnace to about 400°C and introduced in this
tower.
 The tower is hot towards the lower end and comparatively cooler at the upper end.
 As the vapors of the oil rise up the fractionating column, they get cooled and
condensed in the trays. The highest boiling fraction condenses first at the bottom
and the lowest boiling fraction at the top.
 Outlets are provided in the side of the column at suitable heights to withdraw a
number of fractions.

21 February 2023 <CYC102—Theory Lecture No. 18> 12

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Fractional distillation

21 February 2023 <CYC102—Theory Lecture No. 18> 13

Cracking
Cracking is defined as the process of the decomposition of the higher molecular weight hydrocarbons,
having high boiling points, to the lower molecular weight hydrocarbons, having low boiling point.

Thermal Cracking Catalytic Cracking

When the cracking is carried out simply by When the cracking is done in the presence of
the application of heat and pressure. The catalysts, it is known as thermal cracking. Here high
bigger hydrocarbon molecules break down to pressures and temperatures are not necessary. The
give smaller molecules of the paraffins, catalyst is generally a mixture of silica and alumina or
olefins and some hydrogen. aluminium silicate, Fuller's earth, bauxite, etc.

Liquid phase thermal crackings Fixed bed cracking

475-530°C and 7-70 atm pressure. The cracked
products are then separated in a fractionating Fluidized-bed catalytic cracking
column. The yield is approximately 60-65% and
octane rating is in the range of 65-70.
Vapor phase thermal cracking
The cracking oil is first vaporized and then
heated at 600-650°C and subjected to a
pressure of 3.5-10.5 atm pressure for a
short time for cracking. It requires less time
but heavy oil or residual oil is not vaporized
completely.
21 February 2023 <CYC102—Theory Lecture No. 18> 14

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Cracking (Contd.)
Fixed bed cracking
Here the catalyst is used in the form of a fixed bed and the cracking is carried out around 500°C. A number
of cracking furnaces are used, so that if the catalyst spent in one furnace, the other one is used. The spent
catalyst which is deposited by carbon is regenerated by burning the carbon in a current of air
Fluidized-bed catalytic cracking
In this process, the fluidized catalyst is used in order to perform cracking continuously. The catalyst is
suspended in a stream of oil vapors. The spent catalyst continuously flows out of the bottom of the
furnace and can be regenerated, while fresh amount of catalysts are continuously added from the
top. The temperature is maintained between 450°C and 550°C and the pressure between 1 and 2
atm. Cracking takes place on the surface of the turbulent catalyst as it circulates with the oil vapor in
the reactor. The fluidized catalyst is regenerated by removing a part of the catalyst from the reactor
continuously and is burnt off at 590°C in the regenerator to free it from the tarry carbon residue
deposited on the surface of catalytic particles

The fluidized bed cracking has the following advantages over fixed-bed cracking.
 Better contact with the feed and the catalyst, enabling uniform temperature and efficient heat
transfer.
 The catalyst can be regenerated and used again for the cracking process.

21 February 2023 <CYC102—Theory Lecture No. 18> 15

Petroleum Processing
Polymerization, alkylation and isomerization.
The cracker gases in the refinery are rich in olefins. These compounds undergo polymerization
either in presence of catalyst (catalytic polymerization) like phosphoric acid, H2SO4, or by heating
at temperatures of 500°C-600°C and pressure (thermal polymerization) to yield products rich in
branched-chain hydrocarbons. By this process superior quality gasolines are obtained.

Reforming.
This process also helps in preparing high quality gasoline by heating with or without a catalyst, the
naphtha fractions of gasoline. This upgrading is a result of reforming of molecules without
disturbing their average molecular weights, like formation of aromatics from naphthene and
paraffins.

21 February 2023 <CYC102—Theory Lecture No. 18> 16

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Overview of Fractional distillation

21 February 2023 <CYC102—Theory Lecture No. 18> 17

Knocking and Octane number

Octane Number
Maximum power is derived from gasoline when it burns silently and uniformly in an internal combustion
engine. Due to presence of certain constituents in the gasoline, the rate of oxidation sometimes becomes
so great that the unburnt fuel may burn rapidly with the formation of explosive violence. This is known as
knocking. Knocking results in loss of efficiency of the engine and also leads to its short life.

The anti-knock quality of a fuel is expressed as its octane number.

Octane number is equal to the percentage by volume of iso-octane (2,2,4-trimethyl pentane) in a mixture
of n-heptane; iso-octane has the best antiknocking properties and assigned an octane number of 100
whereas n-heptane has poor antiknocking property and assigned an octane number of zero.
The hydrocarbons present influence the knocking properties of gasoline which vary according to the
series:
straight chain paraffin > branched chain paraffin > olefin > cycloparaffin > aromatics
The fuel which has same knocking tendency with the mixture having 80% isooctane has octane number
80.

The most effective antiknock agent added is tetraethyl lead (TEL) along with ethylene dibromide which
prevents the deposition of lead by forming volatile lead halides. Other antiknocking agents are tetramethyl
lead (TML), tertiary butyl acetate, diethyl telluride.TEL functions by being converted to a cloud of finely
divided lead oxide particles, which react with any hydrocarbon peroxide molecules formed in the engine
cylinder thereby solving down the chain oxidation reaction and preventing knocking.

21 February 2023 <CYC102—Theory Lecture No. 18> 18

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Cetane number
Cetane Number
There is a delay period between the injection of diesel fuel and its ignition. This delay period if becomes
large, too much fuel accumulates in the cylinder and burn very rapidly and causes "diesel knock". This
delay period is connected to the type of hydrocarbons present in the diesel.

Increasing delay period occurs in the series:

n-paraffins < olefins < naphthenes < isoparaffins < aromatics.
The order is the reverse for gasoline anti-knock quality.
n-hexadecane is given cetane number 100 and α-methyl naphthalene given cetane number zero. If a
given fuel matches in quality with the blend having 40/60 blend of cetane and a-methyl naphthalene, it
is assigned a cetane number 40. The cetane number of diesel can be improved by adding amyl/butyl
nitrate, carbamates, ditertiary butyl peroxide and metal organic compounds.

21 February 2023 <CYC102—Theory Lecture No. 18> 19

Thank You!
21 February 2023 <CYC102—Theory Lecture No. 18> 20

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Lubricants
 Basic types
 Mechanism of lubrication
 Classification of lubricants
 Lubricant additives
 Application of lubricants

7 March 2023 <CYC102—Theory Lecture No. 19> 2

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Lubricants
In all working machineries, the friction between metal to metal parts arise due to the
moving surfaces rubbing against each other and experience a resistance that retards their
movement. This friction will cause a lot of wear and tear of surfaces of moving parts. Due
to the friction, large amount of energy is dissipated in the form of heat thereby the
efficiency of machine gets reduced.
Lubricants: Any substance introduced between two moving/sliding surfaces with a view to
reduce the frictional resistance between them, is known as lubricant. The main purpose
of lubricant is to keep the sliding/moving surfaces apart and minimize heat generation.

Lubrication: the process of reducing frictional resistance between moving /sliding

surfaces by the introduction of lubricants in-between them.

7 March 2023 <CYC102—Theory Lecture No. 19> 3

Basic Types of Lubricants

Lubricants are usually divided into four basic classes.

 Oils: Liquid lubricants encompass all mineral oils, natural oils, synthetics, emulsions or
even process fluids.
 Greases: Greases are oils, which contain a thickening agent to make them semi-solid. It
is convenient; the semi-fluid greases come under the same heading.
 Dry lubricants: Many bulky solids, paint like coatings or loose powders in the solid form
are used as lubricants.
 Gases: The gas usually used in gas bearings is air, but any gas can be used which will not
attack the bearings, or decompose itself.

7 March 2023 <CYC102—Theory Lecture No. 19> 4

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Lubricants (Contd.)
The important functions of lubricants are as follows:

 It prevents the contact between the moving surfaces and keeps the surfaces separate
under all loads, temperatures and speeds and reduces wear, tear and surface
deformation of the concerned parts.
 It reduces the energy so that the efficiency of the machine is enhanced.
 It reduces the frictional heat and acts as a cooling fluid removing the heat produced by
friction or from external source, prevents the expansion of metals and remains
adequately stable in order to guarantee constant behaviour over the forecasted useful
life.
 Protects surfaces from the attack of aggressive products formed during operation.
 Sometimes, it acts as a seal preventing the entry of dust and leakage of gases at high
pressure.
 It reduces the maintenance and running cost of the machine.
 It minimizes corrosion.
 It also reduces power loss in internal combustion engines

7 March 2023 <CYC102—Theory Lecture No. 19> 5

Lubricants (Contd.)
To accomplish the above functions, a good lubricant should possess the following properties:

 Suitable viscosity
 Oiliness to ensure the adherence of the bearings, for friction loss and wear when the
lubrication is in the boundary region and as a protective covering against corrosion.
 High strength to prevent the metal to metal contact and seizure under heavy load.
 Should not react with the lubricating surface.
 No tendency to form deposits by reacting with air, water, fuel or products of
combustion
 Nonfoaming characteristic
 Nontoxic
 Nonflammable
 Low cost

7 March 2023 <CYC102—Theory Lecture No. 19> 6

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Types of Lubrication Mechanism

There are three mechanisms to illustrate the lubrication process between the
surfaces of two rubbing metals/objects.

 Hydrodynamic or Fluid-Film or Thick Film Lubrication

 Boundary or Thin Film lubrication

 Mixed Film or Elastohydrodynamic lubrication

7 March 2023 <CYC102—Theory Lecture No. 19> 7

Hydrodynamic Lubrication
Hydrodynamic lubrication is a system of lubrication in
which the shape and relative motion of the sliding
surfaces cause the formation of a fluid film having
sufficient pressure to separate the surfaces.

A Hydrodynamic or full fluid film

lubrication

 The moving metal surfaces are actually separated by lubricating oil film eliminating all
metal contacts under hydrodynamic lubrication. This is also known as ‘fluid film
lubrication’.
 The reason for the separation of two surfaces without metal to metal contact is due to
the noncompressible nature of this lubricating film.
 The condition in which surfaces are completely separated by a continuous film of
lubricating fluid is commonly referred to as ‘hydrodynamic lubrication’.
 In this regime, the lubricant immediately adjacent to each surface travels at the same
speed and direction as that of each surface.

7 March 2023 <CYC102—Theory Lecture No. 19> 8

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Hydrodynamic Lubrication (Contd.)

7 March 2023 <CYC102—Theory Lecture No. 19> 9

Boundary Lubrication
 There may be excessive loading, speeds
or a change in the fluid’s characteristics
during the operation of metal parts of
machines; as a result, the lubricating film
may be very thin in between the metal
parts.
 In such a situation, contact between
surface asperities (peaks and valleys)
occurs. Boundary lubrication (thin film
lubrication) is a condition in which the
lubricant film becomes too thin to
provide total separation.
 Friction reduction and wear protection is
then provided via chemical compounds
rather than properties of the lubricating
fluid.

7 March 2023 <CYC102—Theory Lecture No. 19> 10

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Boundary Lubrication
 In order to overcome this effect, an additive is added to basic mineral oil to create an
effective boundary lubricant. Generally, the best additives are active organic compounds
with long chain molecules and active end groups.
 These compounds bind tightly and intricately with each other, forming a film that builds
up on the surface of the metal itself binding strongly to the metal. This results in a thin
film that is very difficult to penetrate.
 The boundary lubricant should also, obviously, be able to maintain a strong attachment to
the surfaces under high temperatures and load pressures. The most common boundary
lubricants are probably greases.
 Greases are so widely used because they have the most desirable properties of a
boundary lubricant. They not only shear easily but flow also. They also dissipate heat
easily form a protective barrier for the surfaces, preventing dust, dirt and corrosive agents
from harming the surfaces.

7 March 2023 <CYC102—Theory Lecture No. 19> 11

Elastohydrodynamic Lubrication
 A mixed film lubrication process is obtained by
a combination of both hydrodynamic and
boundary lubrication. Only occasional asperity
(hills and valleys) contact occurs in mixed film
lubrication process.
 Elastohydrodynamic lubrication occurs as
pressure or load increases to a level where the
viscosity of the lubricant provides a higher
shear strength than the metal surface it
supports.
 As a result, the metal surfaces deform
elastically in preference to the highly
pressurized lubricant, which increases the
contact area.

7 March 2023 <CYC102—Theory Lecture No. 19> 12

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Elastohydrodynamic Lubrication

7 March 2023 <CYC102—Theory Lecture No. 19> 13

Classification of Lubricants
Lubricants are classified on the basis of their physical state as follows:
 Liquid lubricants
 Vegetable oils: palm oil, castor oil, etc.
 Animal oils: whale oil, tallow oil, etc.
 Mineral oils: petroleum fractions.
 Synthetic lubricant: silicones, polyglycol ethers, etc.
 Blended oils or compounded oils: mineral oils with various additives
 Semi-solid lubricants
 Greases, Vaseline, etc.
 Solid lubricants
 Graphite, molybdenum-disulphide, etc.
 Emulsions
 Oil in water type: Cutting emulsions.
 Water in oil type: Cooling liquids.

7 March 2023 <CYC102—Theory Lecture No. 19> 14

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Semi-Solid Lubricants
Semi-solid lubricants or Grease:
 A semi-solid lubricant obtained by combining oil with thickening agents. Grease
comprises mixtures of lubricating oils and thickeners. The thickeners are dispersed in
lubricating oils in order to produce a stable and colloidal structure or gel. Thus, a
grease consists of oil constrained by minute thickener fibres with some additives.
 Lubricating oil is the principal component and it can be either petroleum oil or a
synthetic hydrocarbon of low to high viscosity.
 The thickeners consists primarily of special soaps of Li, Na, Ca, Ba, Al, etc. Non-soap
thickeners include carbon black, silica gel, polyureas and other syntheic polymers,
clays etc.
 Grease can support much heavier load at lower speed. Internal resistance of grease is
much higher than that of lubricating oil; therefore it is better to use oil instead of
grease.
 Compared to lubricating oils grease can not effectively dissipate heat from the
bearings, so work at relatively lower temperature.

7 March 2023 <CYC102—Theory Lecture No. 19> 15

Semi-Solid Lubricants

Classification of grease: Greases are classified after the soap used in their manufacture.
Important greases are
 Calcium based greases or cup greases: are emulsions of petroleum oils with calcium
soaps. They are prepared by adding calcium hydroxide to a hot oil. They are insoluble
in water and are the cheapest
 Soda base grease: are petroleum oils, thickened by mixing sodium soaps. They are not
water resistant, because the sodium soap content is water soluble. However they can
be used upto 175⁰C. They are suitable in ball bearings.
 Lithium based greases : are petroleum oils thickened by mixing lithium soaps. They are
water resistant and suitable for use at low temperatures (<15°C).
 Axle grease: are very cheap resin greases, prepared by adding lime to resin and fatty
oils. The mixture is thoroughly mixed and allowed to stand, when grease floats as stiff
mass. Fillers like talc and mica also added to them. They are water resistant.

7 March 2023 <CYC102—Theory Lecture No. 19> 16

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Solid Lubricants
 Solid lubricants possess lamellar that prevents direct contact between the
sliding surfaces even at high loads.
 Generally, graphite and molybdenum disulphide (MoS2) particles are
commonly used as solid lubricant. Boron nitride, tungsten disulphide and
polytetrafluoroethylene (PTFE) are other solid lubricants.
 Solid lubricants are also used in the form of dry powder or as constituents of
coatings. Solid lubricants are mainly used as additives to oils and greases.
Inorganic Lubricants with Lamellar  Graphite
Structure  Molybdenum Disulphide
 Boron nitride
 Polytetrafluoroethylene
Oxides e.g. B O , MoO , ZnO, Re O , TiO , CuOMoO , NiO-Mo , PbO-B O and CuO-Re O .
2 3 2 2 7 2 2 2 2 3 2 7

Soft Metals They find application as alloys in the form of coatings (lead based engine
bearing overlays), (tin based engine bearing overlays) or the second phase in metal matrix
composites (copper based bearing materials, aluminium based bearing materials).

Self-lubricating Composites Solid lubricants are compounded in plastics to form a ‘

self-lubricating’ or ‘internally lubricated’ thermoplastic composite. MoS2 compounded in nylon
reduces wear, friction and stick-slip.
7 March 2023 <CYC102—Theory Lecture No. 19> 17

Solid Lubricants (Contd.)

MoS2 occurs naturally in the form of thin solid veins within granite. It is purified form of the
mineral molybdenite. It has hexagonal crystalline structure. The total surface resistance is
reduced among interacting surfaces thus reducing surface friction and resistance.
Molybdenum disulfide is thermally stable in vacuum or inert environments, but in air or
oxygen it begins to oxidize to MoO3 at approximately 400oC.

Benefits of molybdenum disulfide include :

 Adhesion is excellent
 Wide temperature range
 It protects against fretting corrosion
 Load carrying capacity is high
 Stick - slip prevention
Limitations of molybdenum disulfide include :
 It is hydroscopic in nature, so it cannot be used in wet conditions as it increases friction
 Oxidation can cause corrosion

Major application with Moly :

Automotive sector, rails, mining, construction, agriculture, military and aerospace.

7 March 2023 <CYC102—Theory Lecture No. 19> 18

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Solid Lubricants (Contd.)

Graphite occurs naturally in rocks such as marble. It has properties of a metal and a non
metal, which makes it opt for many industrial application. It is a layer lattice lamellar
hexagonal structure. Graphite comprises of carbon and water vapour. It has excellent
lubricating properties till the time moisture is available and will work satisfactorily upto
temperature limit of 788°C.
Benefits of graphite includes :
 Excellent lubrication in humidity
 Protects against fretting corrosion
 Good temperature stability
 Low co-efficient of friction under high temperature
Limitations of graphite include :
 It can not provide lubrication in absence of moisture
 The oxidation product is Carbon dioxide which is hazardous to health

Major application with graphite:

Hot and cold forming, wire drawing and billet coatings, mold release for die cast, plastic and
rubber mold, automotive engine and many common industrial applications.

7 March 2023 <CYC102—Theory Lecture No. 19> 19

Solid Lubricants (Contd.)

PTFE constitute of carbon and fluorine atoms and are one of the most slippery materials since
it has a very low surface tension. Unlike other solid lubricant, PTFE does not have layered
structure. The molecules of PTFE slip along each other very easily similar to other lamellar
structure. PTFE can be used upto temperature limit of 260°C.

Benefits of PTFE include :

 Good sliding - friction reduction
 Excellent chemical resistance
 Low load carrying capacity
 lubricating film Chemically inert

Limitations of PTFE include :

 Low melting point
 Low thermal conductivity
 Load carrying properties is poor

Major application with PTFE:

Acts as coating in cookware, stain repellent for fabrics and textile industry, Chemical industry.

7 March 2023 <CYC102—Theory Lecture No. 19> 20

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Emulsions
Water-based lubricants
In metal cutting and grinding, water-based lubricants find extensive uses. The
simplest water-based lubricant is water itself. A more complex, commercial water-
based lubricant usually consists of water mixed with some type of base oil. Water-
based lubricants are also used as personal lubricants.

Soaps
Soaps are alkali metal salts of fatty acids. Soaps are obtained by reacting oils and fats
with strong alkaline solutions. A soap molecule is composed of a long nonpolar
hydrocarbon tail which is hydrophobic (repelled by water) and the salt polar end which
is hydrophilic (water soluble). The soap molecules attached to the substrate surface
provide good adhesion of the soap lubricant and low coefficient of friction.

7 March 2023 <CYC102—Theory Lecture No. 19> 21

Lubricant Additives
The additives for lubricants are chemicals preferably organic or organometallic
that are incorporated into oils in few weight percent to improve the lubricating
capacity and durability of the oil. Additives are present in many liquid lubricants.

Examples of lubricant additives include:

 antifoaming agents
 Antioxidants
 antiwear agents
 corrosion inhibitors
 demulsifying agents
 emulsifying agents
 rust inhibitors
 viscosity improvers

7 March 2023 <CYC102—Theory Lecture No. 19> 22

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Lubricant Additives (Contd.)

Wear and Friction Improvers
Among the additives to lubricant, the one which improve wear and friction properties, are
probably the most important of all the additives used in oil formulations.

Adsorption or Boundary Additives Antiwear Additives Extreme Pressure Additives

The additives added to control the
adsorption type lubrication. They are
‘friction modifiers’ since they are often
used to prevent the slip-stick
phenomena. Generally, these types of
additives are mostly the fatty acids and
the esters and amines of the same
fatty acids. They usually have the polar
group (–OH) at one end of the
molecule and react with the contacting
surfaces through the mechanism of
adsorption. The surface film generated
by this mechanism is effective only at
relatively low temperatures and loads.

7 March 2023 <CYC102—Theory Lecture No. 19> 23

Lubricant Additives (Contd.)

Wear and Friction Improvers
Among the additives to lubricant, the one which improve wear and friction properties, are
probably the most important of all the additives used in oil formulations.

Adsorption or Boundary Additives Antiwear Additives Extreme Pressure Additives

The extreme pressure additives

are introduced to lubricants to
react with metal surfaces under
extreme conditions of load and
velocity, that is slowly moving,
heavily loaded gears. The most
commonly used are dibenzyl
disulphide, chlorinated paraffin
and wax, cetyl chloride, lead
naphthenates, and MoS2.

7 March 2023 <CYC102—Theory Lecture No. 19> 24

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Lubricant Additives (Contd.)

Wear and Friction Improvers
Among the additives to lubricant, the one which improve wear and friction properties, are probably the
most important of all the additives used in oil formulations.

Adsorption or Boundary Additives Antiwear Additives Extreme Pressure Additives

Specifically synthesized antiwear additives

were added in order to protect contacting
surfaces at higher temperatures above the
range of effectiveness of adsorption or
boundary agents. There are several different
types of antiwear additives that are currently
used in oil formulations. For example, in
engine oils the most commonly used antiwear
additive is zinc dialkyl dithiophosphate (ZDDP),
in gas turbine oils tricresyl phosphate or other
phosphate esters are used. Phosphorous
additives are used where antiwear protection
at relatively low loads is required. These
additives react with the surfaces through the
mechanism of chemisorption, and the
protective surface layer produced is much
Zinc Dialkyl Dithiophosphate Tricresyl Phosphate more durable than that generated by the
adsorption or boundary agents.
7 March 2023 <CYC102—Theory Lecture No. 19> 25

Lubricant Additives (Contd.)

Corrosion and Anti-oxidants:
 Oxidation of an oil leads to the oil darkening and thickening as chemical species are
broken down forming insoluble sludge or soot particles. Organic acids are produced which
are extremely corrosive towards non-ferrous metals leading, for example, to bearing
corrosion.
 Inhibitors work as antioxidants by disrupting the chain propagating steps of the oxidative
process by which these insoluble species are formed.
 The oxidative process is a chain reaction which once started, propagates at an exponential
rate producing increasing amounts of free radical and or peroxide species. The inhibitors
themselves function as either peroxide decomposers or as free radical traps.
 ZDDPs are able to act as antioxidants by disrupting the chain propagation steps of
the oxidative reaction, by acting as either peroxide decomposers or free radical
traps. ZDDPs also act as metal deactivators or anticorrosion agents by forming
protective films on metal surfaces.

7 March 2023 <CYC102—Theory Lecture No. 19> 26

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Lubricant Additives
Antifoam Agents:
The presence of additives can slow up the release of gases churned into lubricating oil. This may result
in foaming and/or air entrainment. Air entrainment, especially in modern, high speed, high
temperature engines, may result in diminished engine reliability. Foam is countered by adding tiny
amounts of antifoam additives. Silicon chemicals, such as polydimethylsiloxanes are very commonly
used as antifoam agents.

7 March 2023 <CYC102—Theory Lecture No. 19> 27

Application of Lubricants
The main applications of lubricants are primarily used to reduce friction stress between
surfaces. They have the following uses:
 As antiwear, antioxidants and antifoaming agents.
 As demulsifying and emulsifying agents.
 As rust and corrosion inhibitors.
 In machinery as engine oils, compressor oils, gear oils and piston oils.
 As hydraulic, brake and gear box fluids.
 Used in the soap and paint industries.

Some specific uses of certain variants of lubricants are as follows:

 Synthetic lubricants are used in turbines, vacuum pumps and semiconductor devices.
 Molybdenum is used as a paint pigment and as a catalyst.
 Liquid lubricants are used in medicines.
 Lubricants are also used as cutting fluids in many industries. Oil, water and oil emulsion
are used as cutting fluids. These liquids are used to cool as well as to lubricate surfaces.

7 March 2023 <CYC102—Theory Lecture No. 19> 28

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Thank You!
7 March 2023 <CYC102—Theory Lecture No. 19> 29

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Electromagnetic spectrum
 Absorption and Emission Spectroscopy
 UV-Vis spectroscopy
 Beer Lambert Law
 Woodward Fieser Rules

3 March 2023 <CYC102—Theory Lecture No. 20> 2

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Unit-4
Techniques Principle Instrumentation Application

UV-Visible
Spectroscopy
IR Spectroscopy

NMR

Thermal Analysis
TGA/DTA/DSC
Chromatography

3 March 2023 <CYC102—Theory Lecture No. 20> 3

Electromagnetic Spectrum

3 March 2023 <CYC102—Theory Lecture No. 20> 4

2
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Spectroscopy

3 March 2023 <CYC102—Theory Lecture No. 20> 5

Absorption spectrum

3 March 2023 <CYC102—Theory Lecture No. 20> 6

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UV-Vis spectroscopy
Ultraviolet visible spectroscopy or uv-vis spectroscopy involves the
measurement of absorption or transmittance of energy in the ultraviolet and visible
regions of the electromagnetic spectrum. It is primarily used to measure the
multiple chemical bonding in organic compounds and colour of transition metals.

Electronic changes

3 March 2023 <CYC102—Theory Lecture No. 20> 7

Molecular orbitals

3 March 2023 <CYC102—Theory Lecture No. 20> 8

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Electronic Transitions

𝜎 → 𝜎∗ 𝜋 → 𝜋∗ 𝑛 → 𝜋∗
𝜎 → 𝜋∗ 𝜋 → 𝜎∗ 𝑛 → 𝜎∗

∗
𝜎 → 𝜎∗ > 𝜎 → 𝜋∗ ~ 𝜋 → 𝜎∗ > 𝜋 → 𝜋∗ ~ 𝑛 → 𝜎∗ > 𝑛 → 𝜋

3 March 2023 <CYC102—Theory Lecture No. 20> 9

Electronic Transitions
 Sigma to sigma star transition (σ → σ∗)
A transition of an electron from bonding sigma orbital to higher energy antibonding sigma orbital is
designated σ → σ∗ (sigma to sigma star transition in ultraviolet visible spectroscopy. In alkanes, there
are only sigma bonds are available. Therefore, alkenes are showing this type of transition. In general,
sigma bonds are very strong. Therefore, high energy is required for σ → σ∗ transition.
 n to sigma star transition (n → σ∗)
n to sigma star transition (n → σ∗) involves saturated compounds with one hetero atom
like oxygen, nitrogen, fluorine, chlorine, etc. Normally, saturated halides, alcohols, ethers, aldehyde,
ketones, and amines participate in this type of transition. These transitions require comparatively less
energy than the σ → σ∗ transition.
 pi to pi star transition (π → π∗)
pi to pi star transition (π → π∗) in uv vis spectroscopy is available in compounds with unsaturated
centers like unsaturated hydrocarbons and carbonyl compounds. It requires lesser energy than n to
sigma star transition (n → σ∗).
 n to pi star transition (n → π∗)
In n to pi star transition (n → π∗), an electron in unshared pair on a hetero atom is excited to
π∗ antibonding orbital. It involves the least amount of energy than all types of transition in ultraviolet
visible spectroscopy. Therefore, the n → π∗ transition gives the absorption with a longer wavelength.
n → π∗ is forbidden by symmetry consideration. Thus the intensity of the band due to this transition is
low.

3 March 2023 <CYC102—Theory Lecture No. 20> 10

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Chromophore and Auxochrome

3 March 2023 <CYC102—Theory Lecture No. 20> 11

Chromophore and Auxochrome

3 March 2023 <CYC102—Theory Lecture No. 20> 12

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Spectral shifts

(Conjugation)

3 March 2023 <CYC102—Theory Lecture No. 20> 13

UV source: Hydrogen Discharge Lamp

Instrumentation
Visible light source: Tungsten Filament

3 March 2023 <CYC102—Theory Lecture No. 20> 14

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Beer-Lambert Law
Beer’s-Lambert Law is a combination of Beer’s law and Lambert’s law. This law associates the intensity of absorbed
light with the thickness of the absorbing medium and the concentration of the solution.

Io c
I

(Beer’s law)
(Lambert’s law)

3 March 2023 <CYC102—Theory Lecture No. 20> 15

Beer-Lambert Law

3 March 2023 <CYC102—Theory Lecture No. 20> 16

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Beer-Lambert Law
Characteristics of UV-Vis spectra:
λmax Value: The wavelength at which maximum absorption occurs. It is different for different molecules.
ɛ-value: The extent of absorption for a given concentration (c) of a compound at any given wavelength is
defined by Molar absorptivity (or Molar extinction coefficient.).
These two depends on the concentration and structure of the molecule.

Problem:
Guanosine has a maximum absorbance of 275 nm. Ɛ275 = 8400 M-1cm-1 and the path length is 1 cm.
Using a spectrophotometer, you find the that A275 = 0.70. What is the concentration of guanosine?
Solution:
𝑰𝒐 𝟏
𝑨 = ∈ 𝒄𝒍 = 𝑳𝒐𝒈𝟏𝟎 = 𝑳𝒐𝒈𝟏𝟎 𝒐𝒓 −𝑳𝒐𝒈𝟏𝟎 𝑻
𝑰 𝑻
0.70 = (8400 M-1cm-1) (1 cm)(c) T=Transmittance
C = 8.33x10-5 mol/L

3 March 2023 <CYC102—Theory Lecture No. 20> 17

Woodward-Fieser Rules
(To determine the wavelength of maximum absorption (λmax) of conjugated dienes and polyenes)

λmax = Base value + Σ Substituent Contributions + Σ Other Contributions

Exocyclic
Double bond

Transoid/Heteroannular diene

Endocyclic
Double bond

Cisoid/Homoannular diene
3 March 2023 <CYC102—Theory Lecture No. 20> 18

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Woodward-Fieser Rules
(To determine the wavelength of maximum absorption (λmax) of conjugated dienes and polyenes)

Class Chromophore Influence to λmax (nm)

Core Chromophore Transoid/Heteroannular diene 215
Cisoid/Homoannular diene 253
Substituent effects -R 5
-OR 6
-X (Halogen) 10
-OCOR 0
-SR (Sulphide) 30
-NR2 (Amine) 60
-C=C (extending conjugation) 30
-C6H5 60
Other contributors Exocyclic Double bond 5
Solvent effects Negligible

3 March 2023 <CYC102—Theory Lecture No. 20> 19

Woodward-Fieser Rules
(To determine the wavelength of maximum absorption (λmax) of conjugated dienes and polyenes)

Core: Transoid = 215 nm

Substituents: 3 alkyl groups = 3 x 5= 15 nm
Other effects = 0
Calculated = 215 + 15 = 230 nm
Observed = 234 nm

3 March 2023 <CYC102—Theory Lecture No. 20> 20

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Woodward-Fieser Rules
(To determine the wavelength of maximum absorption (λmax) of conjugated dienes and polyenes)

Core: Heteroannular = 215 nm

Substituents: 5 alkyl groups = 5 x 5= 25 nm
Double bond extending conjugation = 30 nm
Other effects = 3 exocyclic double bonds = 15 nm
Calculated = 215 + 25 + 30 + 15= 285 nm
Observed = 283 nm

3 March 2023 <CYC102—Theory Lecture No. 20> 21

Thank You!
3 March 2023 <CYC102—Theory Lecture No. 20> 22

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Problems and their solutions based on
 Beer Lambert Law
 Woodward Fieser Rules

7 March 2023 <CYC102—Theory Lecture No. 21> 2

1
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Woodward-Fieser Rules
(To determine the wavelength of maximum absorption (λmax) of conjugated dienes and polyenes)

λmax = Base value + Σ Substituent Contributions + Σ Other Contributions

Exocyclic
Double bond

Transoid/Heteroannular diene

Endocyclic
Double bond

Cisoid/Homoannular diene
7 March 2023 <CYC102—Theory Lecture No. 21> 3

Woodward-Fieser Rules
(To determine the wavelength of maximum absorption (λmax) of conjugated dienes and polyenes)

Class Chromophore Influence to λmax (nm)

Core Chromophore Transoid/Heteroannular/linear diene 215
Cisoid/Homoannular/cyclic diene 253
Substituent effects -R or ring residue 5
-OR 6
-X (Halogen) 10
-OCOR 0
-SR (Sulphide) 30
-NR2 (Amine) 60
-C=C (extending conjugation) (DBEC) 30
-C6H5 60
Other contributors Exocyclic Double bond (EDB) 5
Solvent effects Negligible

7 March 2023 <CYC102—Theory Lecture No. 21> 4

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Woodward-Fieser Rules
(To determine the wavelength of maximum absorption (λmax) of conjugated dienes and polyenes)

Core: Heteroannular = 215 nm

Substituents: 5 alkyl groups = 5 x 5= 25 nm
Double bond extending conjugation = 30 nm
Other effects = 3 exocyclic double bonds = 15 nm
Calculated = 215 + 25 + 30 + 15= 285 nm
Observed = 283 nm

7 March 2023 <CYC102—Theory Lecture No. 21> 5

Woodward-Fieser Rules
(To determine the wavelength of maximum absorption (λmax) of enones)
Class Chromophore Influence to λmax (nm)
Core Chromophore 6 membered ring/Acyclic parent enone 215
5 membered ring parent enone 253
Acyclic dienone 245
Substituent effects -R or ring residue α= 10 β= 12 ɣ= 18
-OH α= 35 β= 30 ɣ= 50
-Cl α= 15 β= 12 --
-Br α= 25 β= 30 --
-OCOCH3 6
-OCH3 α= 35 β= 30 ɣ= 17
-NR2 (Amine) -- β= 95 --
-C=C (extending conjugation) (DBEC) 30
Other contributors Exocyclic Double bond (EDB) 5
Homocyclic Diene component 39
7 March 2023 <CYC102—Theory Lecture No. 21> 6

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Woodward-Fieser Rules

C C C C C O
ε δ ɣ β α

α,β unsaturated Ketone or Acyclic enone

O O
α
β
α α
O α

β β β

6 Membered ring 5 Membered ring Acyclic Dienone

7 March 2023 <CYC102—Theory Lecture No. 21> 7

Beer-Lambert Law

𝑰𝒐 𝟏
𝑨 = ∈ 𝒄𝒍 = 𝑳𝒐𝒈𝟏𝟎 = 𝑳𝒐𝒈𝟏𝟎 𝒐𝒓 −𝑳𝒐𝒈𝟏𝟎 𝑻
𝑰 𝑻

7 March 2023 <CYC102—Theory Lecture No. 21> 8

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Thank You!
7 March 2023 <CYC102—Theory Lecture No. 21> 9

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Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 TGA (Thermogravimetric analysis)
 DSC (Differential Scanning Calorimetry)
 DTA (Differential thermal analysis)

9 March 2023 <CYC102—Theory Lecture No. 22> 2

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Thermal Analysis
Thermal Analysis is the term applied to a group of methods and techniques in which chemical
or physical properties of a substance, a mixture of substances or a reaction mixture are measured
as function of temperature or time, while the substances are subjected to a controlled
temperature programme.

Thermal analysis is a branch of material science where the properties of materials are studied as
they change with temperature (under a constant pressure)

When a material is heated, the kinetic energy of that material increases and it's atoms and
molecules move about more. This means that each atom will take up more space due to its
movement so the material will expand. When it is cold the kinetic energy decreases, so the
atoms take up less space and the material contracts.

9 March 2023 <CYC102—Theory Lecture No. 22> 3

Different Techniques For Thermal

Analysis

Technique Symbol Measurement

Thermal Gravimetric Analysis Weight Loss due to decomposition
TGA

Differential Thermal Analysis DTA Differential temperature

Differential Scanning
DSC Heat flow during Transitions
Calorimetry

9 March 2023 <CYC102—Theory Lecture No. 22> 4

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Thermogravimetric Analysis (TGA)

(It is a technique in which a change in the weight of a

substance is recorded as a function of temperature or time)

9 March 2023 <CYC102—Theory Lecture No. 22> 5

Thermogravimetric Analysis
TGA measures the amount and rate of change in the weight of a material as a function
of temperature or time in a controlled atmosphere.

Measurements are used primarily to determine the composition of materials and to

predict their thermal stability at temperatures up to 1000°C.

The technique can characterize materials that exhibit weight loss or gain due to
decomposition, oxidation, or dehydration.

In thermogravimetry, a continuous graph of

mass change against temperature is
obtained when a substance is heated at a
uniform rate or kept at constant
temperature.

9 March 2023 <CYC102—Theory Lecture No. 22> 6

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Mechanisms of weight change in TGA

9 March 2023 <CYC102—Theory Lecture No. 22> 7

Mechanisms of weight change in TGA

Weight Loss:
Decomposition: The breaking apart of chemical bonds
Evaporation: The loss of volatiles with elevated temperature
Reduction: Interaction of sample to a reducing atmosphere (hydrogen,
ammonia, etc.)
Desorption

Weight Gain:
Oxidation: Interaction of the sample with an oxidizing atmosphere
Absorption

9 March 2023 <CYC102—Theory Lecture No. 22> 8

4
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Mechanisms of weight change in TGA

9 March 2023 <CYC102—Theory Lecture No. 22> 9

Example- TGA of Drug A Monohydrate

105 6

4.946%
(0.7505mg) Decomposition

100
4
Deriv. Weight (%/min)

95
Weight (%)

Water weight loss 2

90

0
85
Sample: Drug A Monohydrate
Size: 15.1740mg
Heating Rate: 10°C/min
80 -2
0 50 100 150 200 250 300
Temperature (°C) Universal V3.4C TA Instruments

9 March 2023 <CYC102—Theory Lecture No. 22> 10

5
 3/9/2023

Applications of TGA
 Thermal Stability of Materials

 Oxidative Stability of Materials

 Composition of Multi-component Systems

 Estimated Lifetime of a Product

 Decomposition Kinetics of Materials

 The Effect of Reactive or Corrosive atmospheres on Materials

 Moisture and Volatiles Content of Materials

9 March 2023 <CYC102—Theory Lecture No. 22> 11

Instrumentation
The instrument used in thermogravimetry (TG) is called a thermo- balance.
Thermogravimetric instrumentation should include several basic components to
provide the flexibility necessary for the production of useful analytical data. Basic
components of a typical thermo-balance are listed below:
a) A balance
b) A heating device
c) A unit for temperature measurement and control
d) A means for automatically recording the mass and
temperature changes
e) A system to control the atmosphere around the
sample

9 March 2023 <CYC102—Theory Lecture No. 22> 12

6
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Instrumentation (Contd.)
Balance : Balances are of two types:-
(i) Null point
(ii) Deflection type.

(i) Null type balance : Incorporates a sensing element which detects a deviation of the balance
beam from its null position, A sensor detects the deviation and triggers the restoring force to
bring the balance beam to back to the null position. The restoring force is directly proportional
to the mass change.

(ii) Deflection balance: It involve the conversion of the balance beam deflection about the fulcrum
into a suitable mass-change trace.. Usually of the following types: beam, cantilever, torsion or
spring type.

The different balances used in TG instruments are having measuring range from
0.0001 mg to 1 g depending on sample containers used.

9 March 2023 <CYC102—Theory Lecture No. 22> 13

Instrumentation (Contd.)
Furnace : The furnace and control system must be
designed to produce linear heating at over the whole
working temperature range of the furnace and provision
must be made to maintain any fixed temperature. A wide
temperature range generally -150°C to 2000°C of
furnaces is used in different instruments manufacturers
depending on the models. The range of furnace basically
depends on the types of heating elements are used.

Block diagram of thermobalance

Temperature Measurement and Control : Temperature measurement are commonly done using
thermocouples :-
Chromel-Alumel thermocouple are often used for temperature up to 1100 °C
Pt/(Pt–10%Rh) is employed for temperature up to 1750°C
Temperature may be controlled or varied using a program controller with two thermocouple
arrangement, the signal from one actuates the control system whilst the second thermocouple is used to
record the temperature.

9 March 2023 <CYC102—Theory Lecture No. 22> 14

7
 3/9/2023

Instrumentation (Contd.)
Recorder: Graphic recorders are preferred to meter type recorders. X-Y recorders are commonly used
as they plot weight directly against temperature. The instrument facilitate microprocessor controlled
operation and digital data acquisition and processing using personal computer with different types
recorder and plotter for better presentation of data.

In this diagram you can clearly see that the whole of the
balance system is housed in a glass to protect it from dust
and provide inert atmosphere. There is a control
mechanism to regulate the flow of inert gas to provide
inert atmosphere and water to cool the furnace. The
temperature sensor of furnace is linked to the program to
control heating rates, etc. The balance output and
thermocouple signal may be fed to recorder to record the
TG Curve.

9 March 2023 <CYC102—Theory Lecture No. 22> 15

Overview of instrumentation
 Hence the TGA must accurately:
 control heating rate (furnace)
 measure the change in temperature (thermocouple)
 measure the mass of a sample and the change in mass as it is heated or
held at an isothermal temperature (balance)

9 March 2023 <CYC102—Theory Lecture No. 22> 16

8
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TGA: Sample Pans - Types/Sizes

Deep-walled pans are good for larger mass and low-density materials but
may impact the decomposition profile
9 March 2023 <CYC102—Theory Lecture No. 22> 17

TGA: Sample Preparation

crushed

 Sample mass
 10-20mg for most applications
 50-100mg for measuring volatiles

9 March 2023 <CYC102—Theory Lecture No. 22> 18

9
 3/9/2023

Visual representation of working of TGA

9 March 2023 <CYC102—Theory Lecture No. 22> 19

Example of TGA profiling

Calcium Oxalate Decomposition

9 March 2023 <CYC102—Theory Lecture No. 22> 20

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Example of TGA profiling

Calcium Oxalate Decomposition

9 March 2023 <CYC102—Theory Lecture No. 22> 21

Example of TGA profiling

Copper Sulfate Pentahydrate Decomposition

9 March 2023 <CYC102—Theory Lecture No. 22> 22

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 3/9/2023

Factors affecting TG Curve

There are many factors which influence a TGA curve. These factors may be due to
instrumentation or nature of sample. We have listed the main factors which affects
the shape, precision and accuracy of the experimental results in thermogravimetry.
Mainly two factors (i) Instrumental factors (ii) Sample characteristics

Instrumental factors Sample Characteristics

 Furnace heating rate  Amount of sample
 Recording or chart speed  Solubility of evolved gases in sample
 Furnace atmosphere  Particle size
 Sample holder  Heat of reaction
 Sensitivity of recording mechanism  Sample packing
 Composition of sample container  Nature of sample
 Thermal Conductivity

9 March 2023 <CYC102—Theory Lecture No. 22> 23

Factors affecting TG Curve

Furnace heating rate
Polystyrene 20°C/min
100 Polystyrene 10°C/min
Polystyrene 5°C/min
Polystyrene 1°C/min

80

60
Weight (%)

40

20

0 100 200 300 400 500 600

Temperature (°C) Universal V4.2D TA Instruments

9 March 2023 <CYC102—Theory Lecture No. 22> 24

12
 3/9/2023

Factors affecting TG Curve

Furnace atmosphere

TG Curve of Calcium Oxalate in O2 and N2 atmosphere:[N2 , -------- O2]

9 March 2023 <CYC102—Theory Lecture No. 22> 25

Factors affecting TG Curve

Effect of Sample mass
Polystyrene 17.6 mg
100 Polystyrene 10.2 mg
Polystyrene 5.4 mg
Polystyrene 2.7 mg

80

60
Weight (%)

40

20

0 100 200 300 400 500 600

Temperature (°C) Universal V4.2D TA Instruments

Larger sample mass increases the observed decomposition temperature

9 March 2023 <CYC102—Theory Lecture No. 22> 26

13
 3/9/2023

Overview
We have seen how TGA can be used to understand the chemistry of
decomposition of a particular compound.
TGA also provides information about the temperature range over which a
particular sample appears to be stable or unstable.
We have also interpreted TG curves qualitatively.

Beside these there are many other applications of thermogravimetric analysis.

 Purity and thermal Stability
 Solid state reactions
 Decomposition of inorganic and organic compounds
 Determining composition of the mixture.
 Corrosion of metals in various atmosphere
 Sublimation, vaporizations, sorption and desorption
 Evaluation of gravimetric, precipitates
 Oxidative and reductive stability
 Determining moisture, volatile and ash contents

9 March 2023 <CYC102—Theory Lecture No. 22> 27

Differential Scanning Calorimetry (DSC)

(It is a technique in which the difference of energy inputs into a
substance and a reference material is measured as a function of
temperature; whilst the substance and reference material are subjected
to a controlled temperature programme)

9 March 2023 <CYC102—Theory Lecture No. 22> 28

14
 3/9/2023

DSC
 Calorimetry is a technique for determining the quantity of heat that
is either absorbed or released by a substance undergoing a physical
or chemical change.
 A DSC measures the difference in heat flow rate between a sample
and inert reference as a function of time and temperature.

9 March 2023 <CYC102—Theory Lecture No. 22> 29

DSC (Contd.)

Sample

Reference Sensor Sample Sensor

An empty pan on the Heat absorbed by the

reference sensor should sample gives an endothermic
react similarly to the pan response
on the sample sensor, thus
canceling out any pan Heat released by the sample
contribution gives an exothermic
response

9 March 2023 <CYC102—Theory Lecture No. 22> 30

15
 3/9/2023

DSC Instrument
Temperature Range Dependent On The Cooling System
• Finned Air Cooling System (FACS): Ambient to 725°C
• Quench Cooling Accessory (QCA): -180°C to 400°C
• Liquid Nitrogen Cooling System (LN2P): -180°C to 550°C

Purge Gas Selection

• Nitrogen- inert, inexpensive and readily available with flow rate of 50ml/min
• Helium- a high thermal conductivity gas which improves response time and cooling
capabilities
• Air/Oxygen-
• used when studying oxidative stability of materials

Sample Press and Pan Selection

• Aluminum: max. temperature of 600°C
• Gold
• Copper
• Graphite, Alumina
• Platinum
• Stainless Steel

9 March 2023 <CYC102—Theory Lecture No. 22> 31

Sample holder

9 March 2023 <CYC102—Theory Lecture No. 22> 32

16
 3/9/2023

Characteristics of DSC Peaks

 Melting is the process of converting solid, crystalline structure (lower energy)
to a liquid amorphous structure (higher energy).
 Crystallization – the process of converting either solid amorphous structure
(cold crystallization on heating) or liquid amorphous structure (cooling) to a
more organized solid crystalline structure
 Melting:
 Low energy state → high energy state;
 requires input of energy; endothermic peak
 Crystallization:
 High energy state → low energy state;
 releases energy; exothermic peak
 We integrate these peaks, on a time basis to determine the heat of fusion
(melting) and heat of crystallization

9 March 2023 <CYC102—Theory Lecture No. 22> 33

DSC Profiling

9 March 2023 <CYC102—Theory Lecture No. 22> 34

17
 3/9/2023

DSC Profiling (Contd.)

A modest cooling rate of 10C/min quenches

PLA into its' amorphous phase Crystallization

Glass Transition
Melting

Solid, rigid amorphous

Rubbery, amorphous Solid, crystalline

Liquid, amorphous

Exo
9 March Up
2023 <CYC102—Theory Lecture No. 22> 35

DSC Profiling (Contd.)

Decomposition

9 March 2023 <CYC102—Theory Lecture No. 22> 36

18
 3/9/2023

DSC Profiling (Contd.)

Purity determination

9 March 2023 <CYC102—Theory Lecture No. 22> 37

Applications of DSC
DSC Thermal Analysis Measures:
1.Thermal Phase change
Thermal Glass transition temperature
Crystalline melt temperature
Endothermic effects
Exothermic effects
Thermal Stability
Thermal formulation stability
Oxidative stability studies
Transition phenomena
Solid state structure
Analysis of a diverse range of materials

9 March 2023 <CYC102—Theory Lecture No. 22> 38

19
 3/9/2023

Differential Thermal Analysis (DTA)

(It is a technique in which the temperature difference

between a substance and a reference material is measured as
a function of temperature; whilst the substance and reference
are subjected to a controlled temperature programme)

9 March 2023 <CYC102—Theory Lecture No. 22> 39

Differential Thermal Analysis

(DTA)
TG curves represent the variation in the mass
(m) of the sample with the temperature (T) or
time (t). Normally, we plot mass loss
downward on the ordinate (y) axis and mass
gain upwards as shown in Fig. below.

Sometime we also record derivative

thermogravimetric (DTG) Curves. A DTG
curve presents the rate of mass change
(dm/dt) as a function of temperature, or time
(t) against T on the abscissa (x axis) as
shown in Fig. When substance is heated at Fig. TG Curve. Plateau of constant
weight (region A), the mass loss portion
uniform rate. In this figure, the derivatives of
(region B), and another plateau of
the Curve is shown by dotted lines. constant mass (region C)

9 March 2023 <CYC102—Theory Lecture No. 22> 40

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 3/9/2023

DTA Principle
DTA is a technique in which the
temperature of the substance
under investigation is compared
with the temperature of a
thermally inert material.
This differential temperature is
then plotted against time, or
against temperature (DTA
curve/ thermogram).

9 March 2023 <CYC102—Theory Lecture No. 22> 41

DTA Profiling
Calcium oxalate crystal decomposition

9 March 2023 <CYC102—Theory Lecture No. 22> 42

21
 3/9/2023

Overview

/solid

9 March 2023 <CYC102—Theory Lecture No. 22> 43

Thank You!
9 March 2023 <CYC102—Theory Lecture No. 22> 44

22
 3/13/2023

Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 IR Spectroscopy

13 March 2023 <CYC102—Theory Lecture No. 23> 2

1
 3/13/2023

Overview

13 March 2023 <CYC102—Theory Lecture No. 23> 3

Introduction to IR spectroscopy

There should be net change of dipole moment to undergo IR absorption

13 March 2023 <CYC102—Theory Lecture No. 23> 4

2
 3/13/2023

Applications

13 March 2023 <CYC102—Theory Lecture No. 23> 5

Limitations

13 March 2023 <CYC102—Theory Lecture No. 23> 6

3
 3/13/2023

Nature of IR Spectra

13 March 2023 <CYC102—Theory Lecture No. 23> 7

Absorption vs Transmittance

13 March 2023 <CYC102—Theory Lecture No. 23> 8

4
 3/13/2023

Principle of IR Spectroscopy

13 March 2023 <CYC102—Theory Lecture No. 23> 9

Principle (Contd.)

13 March 2023 <CYC102—Theory Lecture No. 23> 10

5
 3/13/2023

Modes of stretching and bending

13 March 2023 <CYC102—Theory Lecture No. 23> 11

Modes of stretching and bending

(Contd.)

13 March 2023 <CYC102—Theory Lecture No. 23> 12

6
 3/13/2023

Vibrational frequency
To help understand IR, it is
useful to compare a vibrating
bond to the physical model of
a vibrating spring system. The
value of stretching vibrational
frequency of bond can be
calculated by using Hooke’s
Law.

 Consider a bond and the connected atoms to be a spring with two masses attached. Using the
force constant k (which reflects the stiffness of the spring) and the two masses m1 and m2,
then the equation indicates how the frequency, u, of the absorption should change as the
properties of the system change.
 Hooke’s law states that the vibrational frequency of a bond is directly proportional to the
bond strength and inversely proportional to the masses at the ends of the bond.

13 March 2023 <CYC102—Theory Lecture No. 23> 13

Vibrational Frequency (Contd.)

13 March 2023 <CYC102—Theory Lecture No. 23> 14

7
 3/13/2023

Vibrational Frequency (Contd.)

cm-1

13 March 2023 <CYC102—Theory Lecture No. 23> 15

Vibrational Frequency (Contd.)

13 March 2023 <CYC102—Theory Lecture No. 23> 16

8
 3/13/2023

Regions of IR spectra

13 March 2023 <CYC102—Theory Lecture No. 23> 17

Regions of IR spectra (Contd.)

13 March 2023 <CYC102—Theory Lecture No. 23> 18

9
 3/13/2023

Regions of IR spectra (Contd.)

13 March 2023 <CYC102—Theory Lecture No. 23> 19

Regions of IR spectra (Contd.)

13 March 2023 <CYC102—Theory Lecture No. 23> 20

10
 3/13/2023

Regions of IR Spectra (Contd.)

13 March 2023 <CYC102—Theory Lecture No. 23> 21

Elucidation of IR Spectra

13 March 2023 <CYC102—Theory Lecture No. 23> 22

11
 3/13/2023

Thank You!
13 March 2023 <CYC102—Theory Lecture No. 23> 23

12
 3/16/2023

Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 Overview of IR Spectroscopy
 Instrumentation of IR spectroscopy
 Numericals

16 March 2023 <CYC102—Theory Lecture No. 24> 2

1
 3/16/2023

Overview of IR Spectroscopy

16 March 2023 <CYC102—Theory Lecture No. 24> 3

Instrumentation

REFERENCE

IR instruments require the use of a source of energy that emits IR radiation that must be constant and
intense enough to be detected and extend to what is needed in the wavelength.

The various types of IR radiations are listed below.

Nernst glower, Incandescent lamp, Mercury arc, Tungsten lamp, Glober source.

16 March 2023 <CYC102—Theory Lecture No. 24> 4

2
 3/16/2023

Instrumentation (Contd.)

REFERENCE

Sample cells and sampling of substances

IR spectrum has been employed to characterize gas, liquid or solid samples.
Solid – A variety of methods are employed for the preparation of solid samples, including the pressed pellet method
solid run-in-solution mull technique, solid films and so on.
Liquid – Liquid samples can be stored in the liquid sample cell that is composed of alkali halides. Solvents that are
aqueous cannot be used since they dissolve alkali halides. Only organic solvents, such as chloroform can be utilized.
Gas– It is similar to the sampling of liquids.

16 March 2023 <CYC102—Theory Lecture No. 24> 5

Instrumentation (Contd.)

REFERENCE

Monochromators
There are many kinds of monochromators: prisms, gratings, and filters. Prisms are constructed of
Potassium bromide, Sodium chloride, or Caesium Iodide. Filters are comprised of Lithium Fluoride,
and Diffraction gratings comprise alkali Halides.

16 March 2023 <CYC102—Theory Lecture No. 24> 6

3
 3/16/2023

Instrumentation (Contd.)

REFERENCE

Detectors can be used to measure the strength of the infrared radiation. There are several different types of detectors such as:
Thermal detectors: Thermal detectors, also known as bolometers, are devices that measure the change in temperature of a
material as a result of absorbed radiation.
Photovoltaic detectors: Photovoltaic detectors, also known as photodiodes, are devices that convert absorbed radiation into an
electrical current.
Photoconductive detectors: Photoconductive detectors are devices that measure the change in electrical conductivity of a
material as a result of absorbed radiation.
Photoresistive detectors: Photoresistive detectors are devices that measure the change in resistance of a material as a result of
absorbed radiation.
16 March 2023 <CYC102—Theory Lecture No. 24> 7

Instrumentation (Contd.)

REFERENCE

Recorders
In an infrared spectrometer, the detector measures the intensity of the infrared light that is transmitted or
absorbed by the sample, and the recorder is a device that records the measurement data. Data acquisition
system is a type of recorder that collect and store data from multiple sensors or detectors. They are often
used to record and analyze the absorption spectrum of a sample in real-time, and they offer a high
resolution and a wide dynamic range.

16 March 2023 <CYC102—Theory Lecture No. 24> 8

4
 3/16/2023

Analysis of IR Vibration

16 March 2023 <CYC102—Theory Lecture No. 24> 9

Numericals
(These Numericals were solved in the class. Please consult your peers who were present in the
class for their solution)

Calculate the frequency (in Hz and cm-1) of O-H bond, if the force constant and
reduced mass of the atom are 770 N/m and 1.563 x 10-27 Kg respectively.
1H35Cl has a force constant value of 480 N/m. Calculate the fundamental
frequency and its wavenumber.

The value of force constant is same for 1H35Cl and 2D35Cl. If the fundamental
frequency of 1H35Cl is 2890 cm-1. Calculate the fundamental frequency of
2D35Cl.

Compound X exhibits a Molar extinction coefficient of 245 m2/mol at 450 nm.

What concentration of X in a solution will cause 25% decrease in the intensity
of 450 nm radiation, when solution is placed in 0.01 m absorption cell.

In an absorption cell, the transmittance of a 0.1 M solution of a substance X is

80% and that of 0.1 M solution of another substance Y is 60% at a given
wavelength. What is the transmittance of a solution which is 0.1 M in X and 0.1
M in Y? [Given: antilog 0.3188=2.0835]
16 March 2023 <CYC102—Theory Lecture No. 24> 10

5
 3/16/2023

Thank You!
16 March 2023 <CYC102—Theory Lecture No. 24> 11

6
 3/20/2023

Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh

Overview
 NMR Spectroscopy

20 March 2023 <CYC102—Theory Lecture No. 25> 2

1
 3/20/2023

NMR Spectroscopy

20 March 2023 <CYC102—Theory Lecture No. 25> 3

Nuclei spin

20 March 2023 <CYC102—Theory Lecture No. 25> 4

2
 3/20/2023

Nuclei spin (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 5

Nuclei spin (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 6

3
 3/20/2023

Nuclei spin (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 7

NMR Principle

20 March 2023 <CYC102—Theory Lecture No. 25> 8

4
 3/20/2023

NMR Principle (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 9

NMR Principle (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 10

5
 3/20/2023

NMR Principle (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 11

NMR Principle (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 12

6
 3/20/2023

NMR Principle (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 13

NMR Principle (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 14

7
 3/20/2023

NMR Instrumentation

20 March 2023 <CYC102—Theory Lecture No. 25> 15

NMR Working

20 March 2023 <CYC102—Theory Lecture No. 25> 16

8
 3/20/2023

Chemical shift

20 March 2023 <CYC102—Theory Lecture No. 25> 17

Chemical shift (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 18

9
 3/20/2023

Analysis of NMR

20 March 2023 <CYC102—Theory Lecture No. 25> 19

NMR Signals

20 March 2023 <CYC102—Theory Lecture No. 25> 20

10
 3/20/2023

Spin multiplicity

20 March 2023 <CYC102—Theory Lecture No. 25> 21

Spin Multiplicity (Contd.)

20 March 2023 <CYC102—Theory Lecture No. 25> 22

11
 3/20/2023

Applications of NMR

20 March 2023 <CYC102—Theory Lecture No. 25> 23

Thank You!
20 March 2023 <CYC102—Theory Lecture No. 25> 24

12
 Engineering Chemistry
CYC102
Dr. Jaspreet Kaur
School of Basic Sciences
Indian Institute of Information Technology Una
Himachal Pradesh
 Overview
 NMR Spectroscopy Problems
 Overview of exam pattern

29 March 2023 <CYC102—Theory Lecture No. 26> 2

 NMR Problems

29 March 2023 <CYC102—Theory Lecture No. 26> 3

 NMR Problems
O
H2
C
H3C C CH3
H2

O
H2
C
H3C C CH3
H2

29 March 2023 <CYC102—Theory Lecture No. 26> 4

 NMR Problems (Contd.)
CH3
HO CH
C CH3
H2

29 March 2023 <CYC102—Theory Lecture No. 26> 5

 NMR Problems (Contd.)
O
H3C CH3
C O
H2

29 March 2023 <CYC102—Theory Lecture No. 26> 6

 NMR Problems (Contd.)
O
H3C
C OH
H2

29 March 2023 <CYC102—Theory Lecture No. 26> 7

 Thank You!
All the Best for your exams!!
29 March 2023 <CYC102—Theory Lecture No. 26> 8