Engineering Chemistry Semester I Common Branches Water Treatment

SEMESTER I (Common to all Branches) ENGINEERING CHEMISTRY
UNIT I : Water and its treatment

Water: Sources and impurities, Water quality parameters: Definition and significance of
colour, odour, turbidity, pH, hardness, alkalinity, TDS, COD and BOD, flouride and arsenic.
Municipal water treatment: Primary treatment and disinfection (UV, Ozonation, break-point chlorination).
Desalination of brackish water: Reverse Osmosis. Boiler troubles: Scale and sludge, Boiler corrosion, Caustic
embrittlement, Priming & foaming. Treatment of boiler feed water: Internal treatment (phosphate, colloidal,
sodium aluminate and calgon conditioning) and External treatment - Ion exchange demineralisation and zeolite
process.
Unit II: Nanochemistry
Basics: Distinction between molecules, nanomaterials and bulk materials; Size-dependent properties (optical,
electrical, mechanical and magnetic); Types of nanomaterials: Definition, properties and uses of - nanoparticle,
nanocluster, nanorod, nanowire and nanotube. Preparation of nanomaterials: sol-gel, solvothermal, laser
ablation, chemical vapour deposition, electrochemical deposition and electro spinning. Applications of
nanomaterials in medicine, agriculture, energy, electronics and catalysis.
Unit III: Phase Rule and Composites
Phase Rule: Introduction, definition of terms with examples. One component system - water system; Reduced
phase rule; Construction of a simple eutectic phase diagram - Thermal analysis; Two component system: lead-
silver system
- Pattinson process.
Composites: Introduction: Definition & Need for composites; Constitution: Matrix materials (Polymer
matrix, metal matrix and ceramic matrix) and Reinforcement (fiber, particulates, flakes and whiskers).
Properties and applications of: Metal matrix composites (MMC), Ceramic matrix composites and
Polymer matrix composites. Hybrid composites - definition and examples.
Unit IV Fuels and combustion
Fuels: Introduction: Classification of fuels; Coal and coke: Analysis of coal (proximate and ultimate),
Carbonization, Manufacture of metallurgical coke (Otto Hoffmann method). Petroleum and Diesel:
Manufacture of synthetic petrol (Bergius process), Knocking - octane number, diesel oil - cetane
number; Power alcohol and biodiesel.
Combustion of fuels: Introduction: Calorific value - higher and lower calorific values, Theoretical
calculation of calorific value; Ignition temperature: spontaneous ignition temperature, Explosive range;
Flue gas analysis - ORSAT Method. CO2 emission and carbon foot print.
Unit V: Energy sources and storage devices

Stability of nucleus: mass defect (problems), binding energy; Nuclear energy: light water nuclear power
plant, breeder reactor. Solar energy conversion: Principle, working and applications of solar cells;
Recent developments in solar cell materials. Wind energy; Geothermal energy;
Batteries: Types of batteries, Primary battery - dry cell, Secondary battery - lead acid battery and
lithium-ion-battery; Electric vehicles - Working principles; Fuel cells: H2-O2 fuel cell, microbial fuel
cell; Super Capacitors: Storage principle, types and examples.
Total 45 Periods
Unit - I Chapter 1
Water and its Treatment
1.1
INTRODUCTION
Water is the most important compound for the existence

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

purest form of water but it is very difficult to collect whereas
sea water is the most impure form. So, surface and
underground water are normally used for domestic and
industrial purposes. Such water must be free from undesirable
impurities. The process of removing all types of impurities
from water and making it fit for domestic or industrial purposes
is called water treatment. Before treating the water, we should
know the nature as well as the amount of impurities.
1.2
TYPEt OF IMPURITIEt IN WATER
The impurities present in the water may be broadly

classified into three types.
1. Physical impurities
(a) Suspended impurities like sand, oil droplets, vegetable
and animal matter, impart turbidity to water.
(b) Colloidal impurities like finely divided silica, clay and
organic waste products impart colour, odour and taste to water.
2. Chemical impurities
(a) Dissolved salts like bicarbonates, sulphates and chlorides
of Ca and Mg and carbonates, bicarbonates of Na and K.
Dissolved Mg and Ca salts in water cause “hardness”,
whereas alkali salts (bicarbonates, carbonates of K and Na and
bicarbonates of Ca & Mg) make the water “alkaline”.
(b) Dissolved gases like O2, CO2, H2S, SO2 make the water
“acidic”. So they accelerate the rate of corrosion.
3. Bacterial impurities like fungi, bacteria and other
microorganisms cause diseases.
1.3
WATER QUALITY PARAMETERt
The quality of water is a very important parameter to
be determined in order to decide the type of application or
treatment required. The quality of water varies to place to place
and seasons.
The followings are some important parameters of quality
of water.
Water and its Treatment 1.
1.3.1 Colour
Colour is a shade imparted by organic or inorganic
material, which change the appearance of the water.
Colour is found mostly in surface water. The colours of
natural water range from pale straw through yellowish-brown
to dark brown. The colour of natural waters is mainly due to
the presence of dissolved or colloidal organic or inorganic
materials.
Sources
1. Organic sources  Algae, tannins, humic compounds

organic dyes, etc.
2. Inorganic sources  Fe and Mn compounds, chemicals
and inorganic dyes from various industries.
Sanitary Significance
1. The colours and the materials which produce colour are
often objectionable in which the water and the
manufactured product come into contact.
e.g., Dyeing, scouring and laundering
2. Variation in colour of water from the same source with
time serves as index of quality of the water.
e.g.,
(a)
Yellowish tinge  indicates the presence of ‘Cr’
and organic matter.
(b)
Yellowish red  indicates the presence of iron.
(c)
Red-brown  indicates the presence of peaty
matter.
Removal of colour
Colour and colour producing materials are removed by
coagulation, settling, adsorption and filtration.
1.4 Engineering Chemistry
1.3.2 Tastes and Odours
Taste
Taste is the sensation of flavour perceived in the mouth
and throat on contact with a substance.
Odour
Odour is a smell (or) scent caused by one (or) more
volatilized chemical compounds that are generally found in
low concentration.
Sources
Organic sources: Algae and decaying vegetation, etc.
Inorganic sources: Mercaptans, amines and sulphides, etc.
The tastes and odours observed in chlorinated waters are
due to chloro-organic compounds formed by the reaction
between chlorine and organic matter present in the water.
How to Evaluate the Odour?

It is impossible to isolate and identify clearly the odour
causing materials. Evaluation of odour depends on the olfactory
senses of the testing person and on his ability to distinguish
between different types of odours.
Significance
1. Disagreeable odours and tastes are objectionable for
various industrial processes such as food products,
beverages, textiles, paper, pulp. Most of the odours in
natural waters are organic in nature, except H2S.
2. Tast helps us to decide what to eat and influences how
efficiently we digest these foods.
3. Senses of smell and taste are vital in identification of
valuable nutrients in the environment.
4. Taste enables the evaluation of foods for toxicity.
Removal of Tastes and Odours
(i) Organic tastes and odours may be removed by aeration
(or) activated carbon treatment.
(ii) Inorganic tastes due to H2S (or) Iron may be removed
by chemical methods like oxidation, chlorination (or)
precipitation.
1.3.3 Turbidity and sediments

Turbidity is the reduction of clarity of natural water
due to the presence of finely divided, insoluble impurities
suspended in water.
Sources
1. Inorganic sources
Clay, silt, silica, ferric hydroxide, calcium carbonate,
sulphur, etc.,
2. Organic sources
Finely divided vegetable or animal matter, oils, fats,
greases, micro-organisms, etc.,
Problems Caused by Turbidity
(i) Presence of turbidity and sediments in boiler water and
cooling water system cause problems.
(ii) Water-softening processes cannot be carried out.
(iii) Due to deposition of these organic impurities,
disinfection efficiency gets reduced.
Significance
(i) Turbidity affects the taste and odour of drinking water.
(ii) As turbidity affects the disinfection process, it must be
removed.
(iii) Turbidity have many negative effects on aquatic life, it
block light to aquatic plants, aquatic organisms.
(iv) Turbidity affects the growth rate of algae.
(v) It increases water temperature because suspended
particles absorbs more heat.
Removal of Turbidity and Sediments

Turbidity of water may be removed by sedimentation
followed by
(a) Coagulation and filtering
(b) Coagulation and settling
(c) Coagulation, settling and filtering.
Exam
1. Turbidity caused by suspended silt and mud is
objectionable in boilers and in cooling-water
systems.
2. Turbidity caused by colloidal or dissolved organic
matter will interfere with water-softening
processes.
1.3.4 pH
The hydrogen ion concentration is represented by the
pH value, which is defined as

pH   log10[ H ]
pH is defined as negative logarithm of hydrogen ion

concentration. The pH value ranges from 0-14 as
0  7  14
Acidic  Neutr al  Basic

Generally pH of natural waters lies in the neutral range.
For drinking water recommended pH  6.5 to 8.5. For irrigation
recommended pH  6.0 to 9.0. Some surface waters passing
over areas rich in sodium and potassium posses alkaline pH.
[Type text]
The rain water contaminated by the dissolved gases such as

SO2 and NOx will have acidic pH.
Significance of pH
(i) pH determines the solubility (amount that can be
dissolved in water).
(ii) It also determines the biological availability (amount that
can be utilized by aquatic life).
(iii) A rise (or) fall in pH can indicate chemical pollution
(or) acid rain. Many animals cannot live in water at a
pH level below 5 (or) above 9.
1.3.5 Alkalinity
Alkalinity of water is a measure of its acid-neutralising
ability. The natural alkalinity in waters is imparted by the
hydroxides, carbonates and bicarbonates.
Sources
1. Hydroxides,

carbonates and Industries like fertilizer,
bicarbonates of 
detergent, leather and paint.
 alkalimetals, borates,
 silicates, phosphates.

Sanitary significance
1. Very high values of alkalinity are harmful to
aquatic organisms.
2. Alkalinity in boiler feed water causes caustic
embrittlement of pipes.
Removal of Alkalinity
Alkalinity in water, can be removed by adding limited
amount of HCl.
1.3.6 TDS
TDS stands for Total Dissolved Solids. It is defined as

the measure of all inorganic and organic substances present
in water.
Significance
(i) TDS impacts the salinity of water.
(ii) TDS in water may not be ideal for your health and must
be filtered out before intake.
(iii) Water with TDS level higher than 300 ppm may not be
potable as it can taste salty.
(iv) Water with high level of TDS (> 1200) impacts the
color, odour and taste dramatically.
(v) Water with high level of TDS may not be suitable due
to excessive scaling caused by it in water pipes, heaters,
boilers and household appliances.
1.3.7 Fluoride
Fluoride is found in ground water as a result of

dissolution from geologic formulations. Surface waters
generally contain much smaller concentration of fluoride.
Sources
Fluoride containing 
 Fluorapatite Ca F PO  ,
 10 2 46
minerals

cryolite Na3 AlF6 and igneous rocks containing fluosilicates.
Contam inated 
domestic. sewage, 
runoff  Phosphate fertilizers

from agricultural lands 
Water and its Treatment 1.9
Sanitary significance
1. Optimum fluoride concentrations, prescribed in public
water supplies, are in the range of 0.7 to 1.2 mg / lit.
2. Beneficial health effects have been observed where the
fluoride levels are optimum.
3. If the fluoride concentration is low in drinking water it
causes dental caries in children.
4. If the fluoride concentration is high it causes fluorosis.
Removal of fluoride (Defluoridation)

1. Precipitation using aluminium salts in alkaline
media.
2. Using strongly basic anion exchange resin.
3. By adsorption on activated carbon.
1.3.8 Arsenic
Arsenic is a metallic element that forms a number of
poisonous compounds. It is found in nature at low levels,
mostly in compounds, with oxygen, chlorine and sulfur.
Source
Arsenic can get into drinking water from natural deposits
(or) runoff from agriculture, mining and industrial processes.
Significance
(i) Long-term intake of arsenic contaminated water leads to
arsenic poisoning with cancer of skin, bladder, kidney.
(ii) Association of arsenic contaminated water produces
diabetes, hypertension and reproductive disorders.
(iii) Children may have more exposure to arsenic in drinking
water. As a result, children may be at greater risk of
illness when higher levels of arsenic are present.
1.3.9 Chemical Oxygen Demand (COD)

COD is defined as, “the measure of amount of oxygen
required to chemically oxidise all the oxidisable impurities
present in the sewage using an oxidising agent like acidified
K2Cr2O7”.
Significance of COD
(i) Determination of COD is carried out only in 3 hours,

but determination of BOD is carried out after 5 days.
(ii) It measures both the biologically oxidisable and
biologically inert organic matter.
(iii) COD test is used to monitor water treatment plant
efficiency.
(iv) COD is used to measure pollutants in water, waste water
and aqueous hazardous wastes.
(v) It provides an index to assess the effect of discharged
waste water on the environment.
1.3.10 Biological Oxygen Demand (BOD)

BOD is defined as, “the amount of free oxygen required
by bacteria for the biological oxidation of the organic matter
under aerobic conditions at 20C for a period of 5 days”.
Significance of BOD
(i) It indicates the amount of decomposable organic matter

present in the sewage.
(ii) It enables us to determine the degree of pollution at any
time in the sewage stream.
(iii) Lesser the BOD, better is the quality of water. ie. the
water sample with BOD of less than 3 ppm is considered
as pure water, whereas the water more than 4 ppm is
considered as polluted water.
1.3.11 Hardness of Water

Hardness is the property (or) characteristics of water,
which does not produce lather with soap.
Types of hardness
Depending upon the types of dissolved salts present in
water, hardness of water can be classified into two types
1. Temporary hardness.
2. Permanent hardness.
1. Temporary hardness (or) Carbonate hardness (CH) (or)

Alkaline hardness
This is due to the presence of bicarbonates of calcium
and magnesium. It can be removed by (i) boiling the water
(ii) adding lime to the water.
2. Permanent hardness (or) Non-carbonate hardness (NCH)

(or) Non-alkaline hardness
This is due to the presence of chlorides and sulphates
of calcium and magnesium. It cannot be removed by boiling
the water. But, it can be removed by (i) Lime-soda process
(ii) Zeolite process.
Significance of Hardness
1. Hardness affects the amount of soap that is needed to
produce foam (or) lather.
2. Hardness is very important in industrial uses, because it
forms scale in heat exchange equipment boilers and pipe
lines.
2
3. Hardness mitigates metal toxicity because Ca and
2
Mg help keep fish from absorbing metals such as lead,
arsenic and cadmium into their blood stream.
1.4 TREATMENT OF WATER FOR DOMEtTIC

tUPPLY (or) MUNICIPAL WATER TREATMENT
Rivers and lakes are the most common sources of water
used by municipalities. These water should be free from
colloidal impurities, domestic sewages, industrial effluents and
disease producing bacterias. Hence domestic supply of water
involves the following stages in the purification processes.
I. Primary Treatment
1. Screening
It is a process of removing the floating materials like,
leaves, wood pieces, etc. from water. The raw water is allowed
to pass through a screen, having large number of holes, which
retains the floating materials and allows the water to pass.
2. Aeration
The process of mixing water with air is known as
aeration. The main purpose of aeration is
(i) to remove gases like CO2, H2S and other volatile
impurities causing bad taste and odour to water.
(ii) to remove ferrous and manganous salts as
insoluble ferric and manganic salts.
3. Sedimentation
It is a process of removing suspended impurities by
allowing the water to stand undisturbed for 2-6 hours in a big
tank. Most of the suspended particles settle down at the bottom,
due to forces of gravity, and they are removed. Sedimentation
removes only 75% of the suspended impurities.
4. Coagulation
Finely divided clay, silica, etc. do not settle down easily
and hence cannot be removed by sedimentation. Such
impurities are removed by coagulation method.
In this method certain chemicals, called coagulants, like
alum, Al2SO43 etc., are added to water. When the
Al2SO43 is added to water, it gets hydrolysed to form a
gelatinous precipitate of AlOH3. The gelatinous precipitate of
AlOH3 entraps the finely divided and colloidal impurities,
settles to the bottom and can be removed easily.
5. Filtration
It is the process of removing bacteria, colour, taste, odour
and suspended particles, etc., by passing the water through
filter beds containing fine sand, coarse sand and gravel. A
typical sand filter is shown in the figure 1.1.
The sand filter consists of a tank containing a thick top
layer of fine sand followed by coarse sand, fine gravel and
coarse gravel. When the water passes through the filtering
medium, it flows through the various beds slowly. The rate of
filtration decreases slowly due to the clogging of impurities in
the pores of the sand bed. When the rate of filtration becomes
very slow, the filtration is stopped and the thick top layer of
fine sand is scrapped off and replaced with clean sand.
Bacterias are also partly removed by this process.
Fig 1.1 Sand filter
II. Sterilisation (or) Disinfection

The process of destroying the harmful bacterias is known
as sterilisation or disinfection. The chemicals used for this
purpose are called disinfectants. This process can be carried
out by the following methods.
1. By using ozone
Ozone is a powerful disinfectant and is readily absorbed
by water. Ozone is highly unstable and breaks down to give
nascent oxygen.
O3  O2  [O]
The nascent oxygen is a powerful oxidising agent and

kills the bacterias.
Disadvantages
(a) This process is costly and cannot be used in large
scale.
(b) Ozone is unstable and cannot be stored for long
time.
2. By using ultraviolet (UV) radiations

UV rays are produced by passing electric current through
mercury vapour lamp. This is particularly useful for sterilizing
water in swimming pool.
Disadvantages
(i) It is costly.
(ii) Turbid water cannot be treated.
3. By chlorination
The process of adding chlorine to water is called
chlorination. Chlorination can be done by the following methods.
(a) By adding chlorine gas

Chlorine gas can be bubbled in the water as a very good
disinfectant.
(b) By adding chloramine

When chlorine and ammonia are mixed in the ratio 2:1,
a compound chloramine is formed.
Cl2  NH3  ClNH2

Chloramine  HCl
Chloramine compounds decompose slowly to give

chlorine. It is a better disinfectant than chlorine.
(c) By adding bleaching powder

When bleaching powder is added to water, it produces
hypochlorous acid (HOCl). HOCl is a powerful germicide.
CaOCl2  H2O  CaOH2 

Cl2 Bleaching powder
Cl2  H2O  HCl  HOCl

Hypochlorous acid
HOCl  Bacterias  Bacterias are killed

Break point Chlorination

Water contains the following impurities
(i) Bacterias.
(ii) Organic impurities.
2
(iii) Reducing substances Fe , H2S, etc..
(iv) Free ammonia.
Fig 1.2 Break point chlorination
Chlorine may be added to water directly as a gas or in

the form of bleaching powder. When chlorine is applied to
water, the results obtained can be depicted graphically in the
following Fig. 1.2. The graph shows the relationship between
the amount of chlorine added to water and the residual
chlorine.
It is observed from the graph that initially the applied

chlorine is used to kill the bacterias and oxidises all the
reducing substances present in the water and there is no free
residual chlorine.
As the amount of applied chlorine increases, the amount

of combined residual chlorine also increases. This is due to
the formation of chloramine and other chloro compounds.
At one point, on further chlorination, the oxidation of

chloramines and other impurities starts and there is a fall in
the combined chlorine content.
Break point chlorination is the point at which the
combined residual chlorine decreases to a minimum point
where oxidation of chloramines and other impurities complete
and free residual chlorine begins to appear.
Thus, the break point chlorination eliminates bacterias,
reducing substances, organic substances responsible for the bad
taste and odour, from the water.
1.5
DEtALINATION OF BRACHItH WATER
The process of removing common salt (sodium chloride)
from the water is known as desalination. The water containing
dissolved salts with a peculiar salty (or) brackish taste is called
brackish water.
Depending upon the quantity of dissolved solids, water
is graded as
1. Fresh water - Contains < 1000 ppm of dissolved
solids.
2. Brackish water - Contains > 1000 but < 35,000
ppm of dissolved solids.
3. Sea water - Contains > 35,000 ppm of dissolved
solids.
Sea water and brackish water can be made available as
drinking water through desalination process. Desalination is
carried out by reverse osmosis.
1.5.1 Reverse Osmosis (RO)

When two solutions of different concentrations are
separated by a semi-permeable membrane, solvent (water)
flows from a region of lower concentration to higher
concentration. This process is called osmosis. The driving force

in this phenomenon is called osmotic pressure.
If a hydrostatic pressure in excess of osmotic pressure
is applied on the higher concentration side, the solvent flow
is reversed i.e., solvent flows from higher concentration to
lower concentration. This process is called reverse osmosis
(Fig. 1.3). Thus, in the process of reverse osmosis pure water
is separated from salt water. This process is also known as super-
filtration. The membranes used are cellulose acetate, cellulose
butyrate, etc.
Fig. 1.3 Reverse Osmosis
Advantages
(i) The life time of the membrane is high, and it can
be replaced within few minutes.
(ii) It removes ionic as well as non-ionic, colloidal
impurities.
(iii) Due to low capital cost, simplicity, low operating,
this process is used for converting sea water into
drinking water.
1.д BOILER TROUBLEt (OR) BOILER FEED WATER

The water fed into the boiler for the production of steam
is called boiler feed water. Boiler feed water should be free
from turbidity, oil, dissolved gases, alkali and hardness causing
substances. If hard water obtained from natural sources is fed
directly into the boilers, the following troubles may arise.
Boiler troubles (or) disadvantages of using hardwater in boilers
1. Formation of Scales and sludges in boilers.
2. Priming and foaming (carry over).
3. Caustic embrittlement.
4. Boiler corrosion.
1.6.1 Formation of Scales and Sludges in boilers

When water is continuously converted into steam in
boilers (or) heat exchangers, the concentration of dissolved salts
in water increases progressively. When the concentration of the
salts reaches their saturation point, they are thrown out in the
Fig. 1.4 (a) Sludge in boiler (b) Scale in boiler

form of precipitates on the inner walls of the boilers (or) heat

exchangers. The least soluble one gets precipitated first.
1. Sludge (Loose deposit)

If the precipitate is loose and slimy it is called sludge.
Sludges are formed by the substances like MgCl2, MgCO3,
MgSO4 and CaCl2. They have greater solubilities in hot water
than cold water.
2. Scale (Hard deposit)

On the other hand, if the precipitate forms hard and
adherent coating on the inner walls of the boiler, it is called
scale. Scales are formed by substances like CaHCO32,
CaSO4 and MgOH2.
Table 1.1 Comparison of Scales and Sludges
S.No. Sludge Scale

1. Sludge is a loose, slimy Scale is a hard, adherent
and non-adherent coating.
precipitate.
2. The main sludge forming The main scale forming
substances are MgCO3, substances are CaHCO32,
MgCl2 , MgSO4 and CaSO4, MgOH2.
CaCl2 etc,.
3. Disadvantages: Sludges Disadvantages: Scales act
are poor conductors of as thermal insulators. It
heat. Excess of sludge decreases the efficiency of
formation decreases the boiler. Any crack
efficiency of boiler. developed on the scale,
leads to explosion.
S.No. Sludge Scale

4. Prevention Prevention
(i) Sludge formation can (i) Scale formation can
be prevented by be prevented by
using softened water. dissolving using acids
like HCl, H2SO4.
(ii) Sludges can also be (ii) Scale formation can
removed by be removed by
“blow-down (a) External
operation”. treatment.
(b) Internal
treatment.
(iii) Blow-down operation (iii) They can also be
is a process of removed by applying
removing a portion thermal shocks,
of concentrated water scrapers, wire brush,
by fresh water etc.,
frequently from the
boiler during steam
production.
Disadvantages of Scale Formation

1. Wastage of fuels
Scales have low thermal conductivity, so the heat transfer
from boiler to inside water is not efficient. In order to provide
steady supply of heat to water, overheating is done and this
causes wastage of fuel. The wastage of fuel depends on the
thickness and nature of the scale, which is shown in the table.
Thickness of scale (mm) 0.325 0.625 1.25 2.5 12

Wastage of fuel 10% 15% 50% 80% 150%
2. Decrease in efficiency
Scales sometimes deposit in the valves and condensers
of the boiler and choke. This results in decrease efficiency of
the boiler.
3. Boiler explosion
Sometimes due to over heating the thick scales may
crack and causes sudden contact of high heated boiler material
with water. This causes formation of a large amount of steam
and high pressure is developed which may lead to explosion.
Prevention of scale formation

1 At the initial stage, scales can be removed using
scraper, wire brush etc.
2 If scales are brittle, they can be removed by
thermal shocks.
3 By using suitable chemicals like dil. acids (for
CaCO3 scale), EDTA (for CaSO4 scale) with
which they form suitable complexes.
4 If the scales are loosely adhering, they can be
removed by frequent blow down operation.
1.6.2 Priming and Foaming (carry over)

During the production of steam in the boiler, due to rapid
boiling, some droplets of liquid water are carried along with
steam. Steam containing droplets of liquid water is called wet
steam. These droplets of liquid water carry with them some
dissolved salts and suspended impurities. This phenomenon is
called carry over. It occurs due to priming and foaming.
1. Priming
Priming is the process of production of wet steam.
Priming is caused by
(i) High steam velocity.
(ii) Very high water level in the boiler.
(iii) Sudden boiling of water.

(iv) Very poor boiler design.
Prevention
Priming can be controlled by
(i) Controlling the velocity of steam.
(ii) Keeping the water level lower.
(iii) Good boiler design.
(iv) Using treated water.
2. Foaming
The formation of stable bubbles above the surface of
water is called foaming. These bubbles are carried over by
steam leading to excessive priming.
Foaming is caused by the
(i) presence of oil, and grease,
(ii) presence of finely divided particles.
Prevention
Foaming can be prevented by
(i) adding coagulants like sodium aluminate,
aluminium hydroxide,
(ii) adding anti-foaming agents like synthetic
polyamides.
1.6.3 Caustic Embrittlement (Intercrystalline

Cracking)
Caustic embrittlement means intercrystalline cracking of
boiler metal.
Boiler water usually contains a small proportion of
Na2CO3. In high pressure boilers this Na2CO3 undergoes
decomposition to give NaOH.
Na2CO3  H2O  2NaOH  CO2
This NaOH flows into the minute hair cracks and

crevices, usually present on the boiler material, by capillary
action and dissolves the surrounding area of iron as sodium
ferroate.
Fe  2NaOH  Na2FeO2  H2
This causes brittlement of boiler parts, particularly

stressed parts like bends, joints, rivets, etc., causing even failure
of the boiler.
Prevention
Caustic embrittlement can be prevented by
(i) using sodium phosphate as softening agent instead
of sodium carbonate.
(ii) by adding tannin, lignin to the boiler water, which
blocks the hair cracks.
1.6.4 Boiler corrosion

Corrosion in boilers is due to the presence of
1. dissolved oxygen.
2. dissolved carbon dioxide.
3. dissolved salts.
1. Dissolved oxygen
Dissolved oxygen in water is mainly responsible for the
corrosion of boiler. The dissolved oxygen in water attacks the
boiler material at higher temperature.
4Fe  6H2O  3O2  4FeOH3 
Removal of dissolved oxygen

Dissolved oxygen can be removed by chemical (or)
mechanical methods.
(a) Chemical method
Sodium sulphite, hydrazine are some of the chemicals
used for removing dissolved oxygen.
2Na2SO3  O2  2Na2SO4
N2H4  O2  N2  2H2O

Hydrazine is found to be an ideal compound for
removing dissolved oxygen in the water, since the products
are water and inert N2 gas.
(b) Mechanical de-aeration
Dissolved oxygen can also be removed from water by
mechanical deaeration (Fig. 1.5).
In this process, water is allowed to fall slowly on the
perforated plates fitted inside the tower. The sides of the tower
are heated, and a vacuum pump is also attached to it. The
high temperature and low pressure produced inside the tower
reduce the dissolved oxygen content of the water.
Fig. 1.5 Mechanical de-aeration of water

2. Dissolved carbon dioxide
Dissolved carbon dioxide in water produces carbonic
acid, which is acidic and corrosive in nature
CO2  H2O  H2CO3
Carbon dioxide gas is also produced from the

decomposition of bicarbonate salts present in water.

CaHCO32  CaCO3   H2O  CO2 
Removal of dissolved Carbon dioxide

(a) Carbon dioxide can be removed from water by
adding a calculated amount of NH4OH into water.
2NH4OH  CO2  NH42CO3  H2O
(b) Carbon dioxide along with oxygen can also be

removed mechanically by de-aeration method.
3. Dissolved MgCl2
Acids, produced from salts dissolved in water, are also
mainly responsible for the corrosion of boilers. Salts like
MgCl2, CaCl2, etc, undergo hydrolysis at higher temperature
to give HCl, which corrodes the boiler.
MgCl2  2H2O  MgOH2 
2HCl Fe  2HCl  FeCl2  H2
FeCl2  2H2O  FeOH2  2HCl
Removal of acids by neutralisation

Corrosion by acids can be avoided by the addition of
alkali to the boiler water.
HCl  NaOH  NaCl  H2O

1.7
TREATMENT OF BOILER FEED WATER
(tOFTENING OR CONDITIONING METHODt)
Water used for industrial purposes should be free from
hardness producing substances, suspended impurities and
dissolved gases etc. The process of removing hardness
producing salts from water is known as softening (or)
conditioning of water.
Softening of water can be done in two methods
1. Internal treatment.
2. External treatment.
1.7.1 Internal Conditioning (or) Internal

Treatment (or) Boiler Compounds
It involves the removal of scale forming substance, which
were not completely removed in the external treatment, by
adding chemicals directly into the boiler. This chemicals are
also called boiler compounds.
1. Phosphate conditioning
Scale formation can be avoided by adding sodium
phosphate. It is used in high pressure boilers. The phosphate
2  2 
reacts with Ca and Mg salts to give soft sludges of
calcium and magnesium phosphates.
3 CaSO4  2 Na3PO4  Ca3PO42 
3Na2SO4 Generally 3 types of phosphates are
employed.
(a) Trisodium phosphate - Na3PO4 (Too alkaline) - used for
too acidic water.
(b) Disodium hydrogen phosphate - Na2HPO4 (weakly
alkaline) - used for weakly acidic water.
(c) Sodium dihydrogen phosphate - NaH2PO4 (acidic) - used
for alkaline water.
2. Colloidal conditioning
Scale formation can be avoided by adding colloidal
conditioning agents like kerosene, agar-agar, gelatin, etc., It is
used in low pressure boilers. These colloidal substances get
coated over the scale forming particles and convert them into
non-adherent, loose precipitate called sludge, which can be
removed by blow down operation.
3. Sodium aluminate conditioning

Sodium aluminate (NaAlO2 under goes hydrolysis in
boiler water to give gelatinous white precipitate of aluminium
hydroxide and sodium hydroxide.
NaAlO2  2H2O  AlOH3  NaOH
The sodium hydroxide, thus formed, precipitates

magnesium as magnesium hydroxide. The gelatinous
precipitates of aluminium hydroxide and magnesium hydroxide
entrap the colloidal silica and finely divided solids and settled
easily. This can be removed easily by blow down operations.
4. Calgon conditioning
Calgon is sodium hexa meta phosphate
Na2 [Na4PO36]. This substance interacts with calcium ions
forming a highly soluble complex and thus prevents the
precipitation of scale forming salt.
2 CaSO4  Na2[Na4PO36]  Na2[Ca2PO36]  2

Na2SO4.
The complex Na2 [Ca2PO36] is soluble in water and

there is no problem of sludge disposal. So calgon conditioning
is better than phosphate conditioning.
1.7.2 External conditioning (or) External

Treatment
It involves the removal of hardness producing salts from
the water before feeding into the boiler. The external treatment
can be done by two process
1. Demineralisation (or) Ion-exchange process
2. Zeolite process.
1. Ion Exchange (or) Demineralisation process

This process removes almost all the ions (both anions
and cations) present in hard water.
The soft water, produced by zeolite processes, does not
2 2
contain hardness producing Ca and Mg ions, but it
contains
  2 
other ions like Na , K , SO , Cl etc., On the other hand D.M.
4
(Demineralised) water does not contain both anions and
cations.
Thus a soft water is not demineralised water whereas a
demineralised water is soft water.
Demineralisation process is carried out by using ion
exchange resins, which are long chain, cross linked, insoluble
organic polymers with a microporous structure. The functional
groups attached to the chains are responsible for the ion
exchanging properties. The following two types of ion
exchange resins are used.
1. Cation exchange resin (or) cation exchanger
2. Anion exchange resin (or) Anion exchanger
1. Cation exchanger
Resins containing acidic functional groups

COOH, SO3H are capable of exchanging their H ions with
other cations of hard water. Cation exchange resin is
represented as RH2.
Exampl
(i) Sulphonated coals.
(ii) Sulphonated polystyrene.
R  SO3H ; R  COO H  RH2
2. Anion Exchanger
Resins containing basic functional groups NH2, OH
are capable of exchanging their anions with other anions of
hard water. Anion exchange resin is represented as R OH2.
Exampl
(i) Cross-linked quaternary ammonium salts.
(ii) Urea-formaldehyde resin.
R  NR3OH ; ROH ; RNH2  ROH2
Process
Fig. 1.6 Demineralisation process

The hard water first passed through a cation exchange

column, (Fig. 1.6) which absorbs all the cations like
2 2  
Ca , Mg , Na , K , etc., present in the hard water.
RH2  CaCl2  RCa  2HCl
RH2  MgSO4  RMg 
H2SO4 RH  NaCl  RNa 

HCl
The cation free water is then passed through a anion

exchange
 2column,
 which absorbs all the anions like
Cl , SO , HCO , etc., present in the water.
4 3
ROH2  2HCl  R Cl2  2H2O
ROH2  H2SO4  RSO4 
2H2O
The water coming out of the anion exchanger is

completely free from cations and anions. This water is known
as demineralised water (or) deionised water.
Regeneration
When the cation exchange resin is exhausted, it can be
regenerated by passing a solution of dil HCl or dil H2SO4.
RCa  2HCl  RH2 
CaCl2 RNa  HCl  RH 
NaCl
Similarly, when the anion exchange resin is exhausted,
it can be regenerated by passing a solution of dil NaOH.
RCl2  2NaOH  ROH2  2NaCl.
Advantages of ion-exchange process

(i) Highly acidic (or) alkaline water can be treated
by this process.
(ii) The water obtained by this process will have very

low hardness (nearly 2 ppm).
Disadvantages of ion-exchange process

(i) Water containing turbidity, Fe and Mn cannot be
treated, because turbidity reduces the output and
Fe, Mn form stable compound with the resin.
(ii) The equipment is costly and more expensive
chemicals are needed.
2. Zeolite (or) Permutit process

Zeolites are naturally occurring hydrated sodium
aluminosilicate. Its general formula is Na2O . Al2O3 . xSiO2
. yH2O . x  2  10 , y  2  6 . Natural zeolites are green
sand and non-porous. The synthetic form of zeolite is known
as permutit, which is porous and possess gel like structure,
hence it is generally used for water softening.
Synthetic zeolite is represented by Na2Ze. The sodium
2
ions which are loosely held in Na2Ze are replaced by Ca
2
and Mg ions present in the water.
Process
When hard water is passed through a bed of sodium
zeolite Na2Ze, kept in a cylinder (Fig. 1.7), it exchanges its
2 2
sodium ions with Ca and Mg ions present in the hard water
to form calcium and magnesium zeolites. The various reactions
taking place during softening process are
CaHCO32  Na2Ze  CaZe  2NaHCO3
MgHCO32  Na2Ze  MgZe  2NaHCO3
CaSO4  Na2Ze  CaZe  Na2SO4
MgSO4  Na2Ze  MgZe  Na2SO4

Fig. 1.7 Zeolite Process
CaCl2  Na2Ze  CaZe  2NaCl
MgCl2  Na2Ze  MgZe 

2NaCl
The softened water is enriched with large amount of
sodium salts, which do not cause any hardness, but cannot be
used in boilers.
Regeneration
After some time zeolite gets exhausted. The exhausted
zeolite is again regenerated by treating with 10% solution of
NaCl.
CaZe  2NaCl  Na2Ze 
CaCl2 MgZe  2NaCl  Na2Ze
 MgCl2
Advantages of Zeolite process

(i) Water obtained by this process will have only hardness
of 1-2 ppm.
(ii) This method is cheap, because the regenerated zeolite
can be used again.
(iii) No sludge is formed during this process.
(iv) The equipment used is compact and occupies a small space.
(v) Its operation is easy.
Disadvantages of Zeolite process

(i) Turbid water cannot be treated, because it blocks the
pores of the zeolite bed.
(ii) Acidic water cannot be treated, because it decomposes
the structure of zeolite.
(iii) The softened water contains more dissolved sodium salts
like NaHCO3, Na2CO3, etc. When such water is boiled
in boilers, CO2 and NaOH is produced resulting in boiler
corrosion and caustic embrittlement.
(iv) Water containing Fe, Mn cannot be treated, because
regeneration is very difficult.
(v) This process cannot be used for softening brackish water,

because brackish water contains Na ions. So the ion
exchange reaction will not occur.
Table 1.2 Differences between Zeolite and

Demineralisation process
Zeolite Demineralisation
S.No.
Process Process.
1. It exchanges only cations. It exchanges cations as
well as anions.
2. Acidic water cannot be Acidic water can be
treated because acid treated.
decomposes the zeolite.
3. The treated water The treated water does
contains relatively large not contain any dissolved
amount of dissolved salts, salts. Hence there is no
which leads to priming, priming and foaming.
foaming and caustic
embrittlement in boilers.
Zeolite Demineralisation
S.No.
Process Process.
4. Water containing Here also water
turbidity, Fe, Mn cannot containing turbidity, Fe,
be treated. Mn cannot be treated.
1.8 ANNA UNIVERtITY QUEtTIONt

1. Define and explain the significances of the followings.
(i) Clour (ii) Tastes and odours (iii) pH
2. Explain the significances of
(a) TDS (b) COD (c) BOD
3. What is meant by sterilization of water? What are the
chemicals that are normally used for this purpose? Explain
break-point chlorination.
4. Explain how sterilisation of water carried out using
chlorine? Give the mechanism.
5. Explain with a neat sketch the various steps in the
treatment of water for municipal supply.
6. What is desalination? With a neat diagram, describe the
‘reverse osmosis’ method for the desalination of brackish
water. (Chen A.U. Jan 2010)
7. What is desalination? Explain any one method of
desalination. (Coim A.U. Jan 2010) (AU Jan 2013)
8. What is reverse osmosis? How will you purify the sea
water by reverse osmosis? Mention its advantages.
(TNV A.U. Jan 2010)
9. What is meant by reverse osmosis? Explain the
purification of water by reverse osmosis.
(Chen. A.U. Jan 2009, May 2008)
10. Describe the Reverse Osmosis method for desalination of
water.
(Chen A.U. June 2009)(TNV. AU. May 2009, May 2017)
11. Define the term desalination with a neat diagram, describe

desalination by reverse osmosis method.
(Dec 2003; May 2003, May 01)
12. What are boiler troubles? How are they caused? Suggest
steps to minimize the boiler troubles. (A.U. Dec 97)
13. What are boiler troubles? How they are caused? How they
are minimized by colloidal conditioning, phosphate
conditioning and calgon conditioning. (A.U. May 2007)
14. Discuss the disadvantages of using hard water in boilers.
(Chen A.U. Dec 2006)(TNV. AU. Jan 2009)
15. What are scales and sludges. Describe the disadvantages
of scale and sludge formation.
(A.U. June 05 A.U.TNV A.U. Jan 2010)
16. What is caustic embrittlement. How can it be prevented.
(A.U. June 05)
17. Discuss the causes and prevention of priming and
foaming. (A.U. June 06)
18. What are the problems one would face when hard water
is used in boiler industries. (A.U. Dec. 05)
19. Explain the following boiler troubles suggesting the
remedial methods:
(i) Sludge and scale formation
(ii) Caustic embrittlement.
(CBE. A.U. Jan 2009) (AU Jan 2013)
20. How will you protect boiler from corrosion.
(A.U. Dec. 06)
21. Describe de-mineralisation process of water softening.
Explain the reactions involved.
(A.U Dec-2002, May 2007, May 2008)
22. How is the exhausted resin regenerated in an ion-
exchanger? What are the merits and demerits of ion-
exchange method? (A.U. Model Q.P)
23. With a neat diagram describe the ionization process of

water softening. (TNV. AU. May 2009)
24. Explain how demineralization of water is done in water
technology? (CBE. A.U. Jan 2009)
25. Explain the softening of water by deionization process.
(TNV A.U. Jan 2009)(Chen. A.U. Jan 2009)
26. Explain the demineralization of water by ion-exchange
process. How are exhausted cation and anion exchange
resins regenerated? (TNV A.U. Jan 2010, A.U May 2017)
27. How is the softening of water carried out using the zeolite
process? (TCY A.U. Jan 2010)
28. Describe the principle and procedure involved in the
zeolite process for water treatment. (A.U Jan 2013)
29. What are ion exchange resins? How are they useful in
removing hardness of water. (Chen A.U. Jan 2010)
30. How is internal treatment of boiler water carried out using
phosphate and calgon. (A.U. June 06)
31. Explain the Phosphate conditioning. (A.U. Dec. 05)
32. Give an account of internal treatment of boiler water.
(A.U. Dec 2006, Jan 2013)(TNV. AU. Jan 2009)
33. Describe briefly the various methods of internal
conditioning of boiler feed water. (Chen. A.U. June 2009)
34. What is calgon? Why is calgon conditioning better than
phosphate conditioning? (TNV A.U. Jan 2010)
35. Explain the boiler troubles, ‘scales and caustic
embrittlement’ in detail. (AU June 2014, May 2017)
36. How is water softened by Ion exchange method? Explain
in detail with a neat diagram. (AU June 2014)
37. What are zeolites? How do they function in removing the
hardness of water? (AU June 2014)
38. What is meant by internal conditioning of water?

(AU June 2017)
39. What are the factors which causes boiler corrosion? How
can it be minimized? (A.U Dec 2014)
40. With necessary diagram, describe the reverse osmosis
method for the desalination of brackish water.
(A.U Dec 2014)
41. Write a brief note on the following:
1. Caustic embrittlement
2. Calgon conditioning (A.U Dec 2014)
42. Describe the principle and procedure involved in the
zeolite process for water treatment. (A.U Dec 2014)
43. What is reverse osmosis? How is it useful for desalination
of brackish water? Explain with a diagram.
(AU May 2015)
44. What are sludge and scale in boilers? How are they
formed? Suggest any two methods to prevent their
formation. (AU May 2015)
45. What are zeolites? How are they used in softening of
water? Use a diagram for your explanation?
(AU May 2015)
46. Explain the internal conditioning of water? Take two
examples for your explanation. (AU May 2015)
47. Draw a suitable diagram and describe the ion exchange
process for the softening of hard water. (AU Dec 2015)
48. Write a brief note on priming and foaming.
(AU Dec 2015)
49. How can the boiler feed water be purified by calgon and
phosphate conditioning? (AU Dec 2015)
50. With neat diagram, explain the Zeolite process for water
treatment. (AU June 2016)
51. Describe the demineralization process of water softening

and write down the reaction involved in it.
(AU June 2016)
52. Explain with neat diagram, the desalination of brackish
water of reverse osmosis method. (AU June 2016)
Unit - II Chapter 2
Nanochemistry
2.1
INTRODUCTION
The prefix (nano), in the word nanochemistry, means a
9
billionth 1  10 m. Atoms are very small and the diameter
of a single atom can vary from 0.1 to 0.5 nm. It deals with
various structures of matter having dimensions of the order of
a billionth of meter.
2.2
BAtICt OF NANOCHEMItTRY
1. Nanoparticles
Nanoparticles are the particles, the size of which ranges
from 1-50 nm. Generally they are obtained as colloids. The
colloidal particles have a tendency to remain single crystal and
hence are called as nanocrystals. A large percentage of atoms
in nanocrystals are present on the surface.
Nanocrystals possess electronic, magnetic and optical
properties. Since the nanoparticles exhibit an electronic
behavior, governed by the quantum physics, they are also called
as quantum dots.
2. Nanomaterials
Nanomaterials are the materials having components with
size less than 100 nm at least in one dimension.
 Nanomaterials, in one dimension, are layers such as a
thin films or surface coatings.
 Nanomaterials, in two dimension, are tubes such as
nanotubes and nanowires.
 Nanomaterials, in three dimension, are particles like

precipitates, colloids and quantum dots.
3. Nanochemistry (or) Nanoscience
Nanoscience is defined as the study of phenomena and
manipulation of materials at atomic, molecular and
macromolecular scales.
4. Nanotechnology
Nanotechnology is defined as the design,
characterization, production and applications of structures,
systems and devices by controlling size and shape at
9
10 m scale or the single-atomic level.
2.3 DltTlNCTlON BETWEEN NANO PARTlCLEt,

MOLECULEt AND BULH MATERlALt
1. The size of nano particles are less than 100 nm in
diameter, molecules are in the range of picometers, but
bulk materials are larger in micron size.
2. Molecule is a collection of atoms, nano particles are
collection of few molecules that is less than 100 nm but
bulk materials contains thousands of molecules.
3. Surface area of nano particles is more than the bulk
materials.
4. Hardness of nano materials is 5 times more than the bulk
materials.
5. Strength of nano materials is 3 - 10 times higher than
the bulk materials.
6. Nano particles possesses size dependent properties, but
bulk materials possess constant physical properties.
7. Corrosion resistance is more than the bulk materials,
hence localised corrosion in nano materials is stopped.
8. Behavior of bulk materials can be changed, but cannot
enter inside the nano particles.
Nanochemistry 2.3
9. Nano particles, due to its size, possess unexpected optical

(visible) properties.
Exampl
(i) Gold nano particles appear deep red to black
colour in solution compared to yellow colour with
Gold.
(ii) ZnO nano particles possesses superior UV
blocking property compared to bulk material.
(iii) Absorption of solar radiation in photovoltaic cell
containing nano particles are higher than the film
(bulk material).
10. Nano particles possesses lower melting point than the
bulk materials.
Exampl
Gold nanoparticles melt at lower temperature 300C for
2.5 nm, but Gold slab melts at 1064C.
11. Sintering of nano particles takes place at lower
temperature and in short time than the bulk materials.
12. Electr ical pr oper ties, resistivity of nano particles are
incr eased by 3 times.
13. Suspension of nano particles is possible, because nano
particles possess high surface area, but bulk materials
cannot.
14. The wear resistance of nano particles are 170 times
higher than the bulk materials.
Table 2.1 Comparison of atom/molecule, nano

particles/cluster, bulk materials
Nano
S. Atom/ particles/ Bulk
Properties
No. Molecule Nano material
cluster
1. Size of Few Angstrom to Microns to
constituting Angstroms nanometer higher
particles. (Å)  10
10 m to
 10
10 m 9
10 m
2. Number of 1 for atom, 2 to several Infinite
constituting many for thousands.
particles. molecules.
3. Electronic Confined. Confined. Continuous.
structure.
4. Geometric Well-defined Well-defined Crystal
structure. structure and structure and structure
predictable. predictable. decides.
Example NaCl, HCl (NaCl)n Gold bar &
Silver bar
2.4 tlZE DEPENDENT PROPERTlEt

Nearly all the properties as shown in figure 2.1, like
hardness, strength, ductility, melting point and density, change
for nanomaterials. These behaviors vary so significantly by a
mere reduction in grain size. Nanomaterials are composed of
grains and grain boundaries. Nanometre sized grains contains
only a few thousands of atoms with in each grain.
Nanochemistry 2.5
Fig. 2.1 Shows how different properties change in the

nano-materials
A large number of atoms reside at the grain boundaries.

As the grain size decreases, there is a significant increase in
the volume fraction of grain boundaries or interfaces.
The properties of the materials are bound to be governed
to a large extent by defect configurations. Hence the
mechanical and chemical properties of nanomaterials are
significantly altered due to defect dynamics. The elastic
property of nanomaterials are different from that of bulk alloys
due to the presence of increased fraction of defects.
Exampl
1. Nanocrystalline ceramics are tougher and stronger

than those with coarse grains.
2. Nano-sized metals exhibit significant decrease in
toughness and yield strength increases.
2.4.1 Important Properties of Nanomaterials

1. Electrical Properties
(i) Electrical conductivity decreases with a reduced
dimension due to increased surface scattering. However,
it can be increased, due to better ordering in

micro-structure.
Exam Polymeric fibres.

(ii) Nanocrystalline materials are used as very good separator
plates in batteries, because they can hold more energy
than the bulk materials.
Exam
Nickel-metal hydride batteries made of nanocrystalline

nickel and metal hydride, require far less frequent recharging
and last much longer.
2. Optical Properties
Reduction of material dimensions has pronounced effects
on the optical properties. Optical properties of nano-materials
are different from bulk forms.
The change in optical properties is caused by two factors
(i) The quantum confinement of electrons within the nano-
particles increases the energy level spacing.
Exam
The optical absorption peak of a semiconductor nano-

particles shifts to a short wavelength, due to an increased band
gap.
(ii) Surface plasma resonance, which is due to smaller size
of nano-particles than the wavelength of incident
radiation.
Exam
The colour of metallic nano-particles may change with

their sizes due to surface plasma resonance.
Nanochemistry 2.7
3. Mechanical properties
The nano-materials have less defects compared to bulk
materials, which increases the mechanical strength.
(i) Mechanical properties of polymeric materials can

be increased by the addition of nano-fillers.
(ii) As nano-materials are stronger, harder and more
wear resistant and corrosion resistant, they are
used in spark plugs.
Exampl
Nano-crystalline carbides are much stronger, harder and

wear resistant and are used in micro drills.
4. Magnetic properties
Magnetic properties of nano materials are different from
that of bulk materials. Ferro-magnetic behaviour of bulk
materials disappear, when the particle size is reduced and
transfers to super-paramagnetics. This is due to the huge
surface area.
2.5 TYPEt OF NANO MATERlALt
Based on dimensions, nano materials are classified in to

four types.
1. Nanoparticles
2. Nanoclusters
3. Nanowire
4. Nanorods
5. Nanotubes
S.No Co-ordinates Examples

1. 0 - dimension Nanoclusters
2. 1 - dimension Thin Films, surface coatings
3. 2 - dimension Nanotubes, nanowires
4. 3 - dimension Precipitates, colloids
2.5.1 Nanoparticles
from 1 to 100 nm. These are tiny aggregates of atoms but
smaller than their crystals but bigger than molecules. They have
three dimensional structures.
Exampl TiO2, gold, silver, ZnO, etc.,

Applications of Nanoparticles
1. TiO2 is used in cosmetics as they are very good
UV - absorber.
2. Nano silver particles are used as a catalyst in industries.
3. Nanoparticles are used in medicine.
4. Nano silver particles are used in making bone cement,
surgical instruments, etc.,
2.5.2 Nanoclusters
Nanoclusters are fine aggregates of atoms or molecules.
The size of which ranges from 0.1 to 10 nm. Of all the nano
materials, nanoclusters are the smallest sized nano materials
because of their close packing arrangement of atoms.
Exampl CdS, ZnO, etc.,

All the atoms, in nanocluster, are bound by forces like
metallic, covalent, ionic, hydrogen bond or Vander Waals
forces of attraction. Clusters of certain critical size are more
stable than others. Nanoclusters consisting of up to a couple
Nanochemistry 2.9
3
of hundred atoms, but larger aggregates, containing 10 or more
atoms, are called nanoparticles.
Magic number
Magic number is the number of atoms present in the
clusters of criticle sizes with higher stability.
Different types of nanoclusters can be distinguished from
the nature of forces present between atoms. Generally clusters
containing transition metal atom have unique chemical,
electronic and magnetic properties. These properties vary with
the number of constituent atoms, the type of element and the
net charge on the cluster.
Properties of nanoclusters
1. Atomic clusters or molecular clusters are formed by the
nucleation of atoms or molecules respectively.
2. The reactivity of nanoclusters are decreased due to their
decrease in size.
3. The melting point of nanoclusters are lower than the bulk
materials due to high surface to volume ratio.
4. The electronic structure of the nanocluster is more
confined than the bulk materials.
Applications of nanocluster
1. Nanoclusters are used as catalysts in many reactions.
2. It is used in nano based chemical sensors.
3. It is also used as a light emitting diode in quantum
computers.
2.5.3 Nanorods
Nanorod is two dimensional cylindrical solid material
having an aspect ratio i.e., length to width ratio less than 20.
Exampl Zinc oxide, Cadmium sulphide,

Gallium nitride nano rods.
Synthesis of nanorods
Nano-rods are produced by direct chemical synthesis. A
combination of ligands act as shape control agents and bond
to different facets of the nano-rods with different strength.
This allows different nanorods to grow at different rates

producing an elongated objects. Many of the above nanorods
are not manufactured due to lack of commercial demand.
Properties of nanorods
1. Nanorods are two-dimensional materials.
2. It exhibits optical and electrical properties.
Applications of nanorods
1. Nanorods find application in display technologies.
2. It is also used in the manufacturing of micro mechanical
switches.
3. Nanorods are used in an applied electric field, micro
electro mechanical systems, etc.,
4. Nanorods along with noble metal nanoparticles function
as theragnostic agents.
5. They are used in energy harvesting and light emitting
devices.
6. Nanorods have used as cancer therapeutics.
2.5.4 Nanowires
Nanowire is two dimensional cylindrical solid material

having an aspect ratio ie., length to width ratio greater than
20. Diameter of the nanowire ranges from 10 - 100 nm.
Exampl Different types of nanowires

Nanochemistry 2.11
S.No Types of nanowires Examples

1. Metallic nanowires Au, Ni, Pt
2. Nanowires of semiconductors InP, Si, GaN
3. Nanowires of insulators SiO2, TiO2
4. Molecular nanowires DNA
Synthesis of nanowires
1. Template-assisted synthesis
Template assisted synthesis of nanowires is a simple way
to fabricate nanostructures. These templates contain very small
cylindrical pores or voids within the host material and the
empty spaces are filled with the chosen material to form
nanowires.
2. VLS (Vapour - Liquid - Solid) method

It involves the absorption of the source material from
the gas phase into a liquid phase of catalyst. Upon
supersaturation of the liquid alloy, a nucleation event generates
a solid precipitate of the source material. This seed serves as
a preferred site for further deposition of material at the
interface of the liquid droplet, promoting the elongation of the
seed into a nanowire.
Properties of nanowires
1. Nanowires are two-dimensional material.
2. Conductivity of a nanowire is less than that of
the corresponding bulk materials.
3. It exhibits distinct optical, chemical, thermal and
electrical properties due to this large surface area.
4. Silicon nanowires show strong photoluminescence
characteristics.
Uses of nanowires
1. Nanowires are used for enhancing mechanical
properties of composites.
2. It is also used to prepare active electronic
components such as pn junction and logic gates.
3. Semiconductor nanowire crossings are expected to
play a important role in future of digital
computing.
4. Nanowires find applications in high-density data
storage either as magnetic read heads or as
patterned storage media.
5. Nanowires replace conventional copper wires used
in computers, televisions.
6. It is also used to link tiny components into very
small circuits.
2.5.5 Nanotubes
Nanotubes are tube like structures with diameter of 1-
100 nm and a length of few nm to microns. Nanotubes consist
of tiny cylinders of carbon and other materials like boron
nitride. Nanotubes may be organic (or) inorganic.
Exampl
1. Carbon nanotube
2. Silicon nanotube
3. DNA nanotube
4. Boron nitride nanotube
1. Carbon nanotubes (CNTs)

Carbon nanotube is a tubular form of carbon with 1-3
nm diameter and a length of few nm to microns.
Nanochemistry 2.13
Generally carbon in the solid phase exits in different

allotropic forms like graphite, diamond, fullerence and nano
tubes.
Fig. 2.2 Single walled carbon nanotubes
Carbon nanotubes are tubular forms of carbon. When

graphite sheets are rolled into a cylinder, their edges join to
each other form carbon nanotubes. Each carbon atom in the
carbon nanotubes is linked by covalent bonds. But the number
of nanotubes align into ropes and are held together by weak
Vander Walls forces.
Structures (or) types of carbon nanotubes

Depending upon the way in which graphite sheets are
rolled, two types of CNTs are formed.
1. Single - walled nanotubes (SWNTs).
2. Multi - walled nanotubes (MWNTs).
1. Single - walled nanotubes (SWNTs)

SWNTs consist of one tube of graphite. It is one-atom
thick having a diameter of 2 nm and a length of 100 m.
SWNTs are very important, because they exhibit important
electrical properties. It is an excellent conductor.
Fig. 2.3 Types of single walled carbon nanotubes
Three kinds of nanotubes are resulted, based on the

orientation of the hexagon lattice.
(a) Arm-chair structures: The lines of hexagons are parallel
to the axis of the nanotube.
(b) Zig-zag structures: The lines of carbon bonds are down
the centre.
(c) Chiral nanotubes: It exhibits twist or spiral around the
nanotubes.
It has been confirmed that arm-chair carbon nanotubes
are metallic while zig-zag and chiral nanotubes are
semiconducting.
2. Multi - walled nanotubes (MWNTs)

MWNTs (nested nanotubes) consist of multiple layers of
graphite rolled in on themselves to form a tube shape. It
exhibits both metallic and semiconducting properties. It is used
for storing fuels such as hydrogen and methane.
Nanochemistry 2.15
Fig. 2.4 Multiwalled carbon nanotubes
Synthesis of Carbon Nanotubes

Carbon nanotubes can be synthesized by the following
methods.
1. Pyrolysis of hydrocarbons.
2. Laser evaporation.
1. Pyrolysis
Carbon nanotubes are synthesized by the pyrolysis of
hydrocarbons such as acetylene at about 700C in the presence
of Fe-silica or Fe-graphite catalyst under inert conditions.
2. Laser evaporation
It involves vapourization of graphite target, containing
small amount of cobalt and nickel, by exposing it to an intense
pulsed laser beam at higher temperature 1200C in a quartz
tube reactor. An inert gas such as argon (or) helium is
simultaneously allowed to pass into the reactor to sweep the
evaporated carbon atoms from the furnace to the colder copper
collector, on which they condense as carbon nanotubes.
Fig. 2.5 Laser evaporation technique
Properties of CNTs
1. CNTs are very strong, withstand extreme strain
in tension and posses elastic flexibility.
2. The atoms in a nano-tube are continuously
vibrating back and forth.
3. It is highly conducting and behaves like metallic
or semiconducting materials.
4. It has very high thermal conductivity and kinetic
properties.
Uses of CNTs
1. It is used in battery technology and in industries
as catalyst.
2. It is also used as light weight shielding materials
for protecting electronic equipments.
3. CNTs are used effectively inside the body for
drug delivery.
4. It is used in composites, ICs.
5. It also acts as an efficient catalysts for some
chemical reactions.
Nanochemistry 2.17
6. It acts as a very good biosensor. Due to its

chemical inertness carbon nanotubes are used to
detect many molecules present in the blood.
7. It is also used in water softening process as a
filter.
2.д PREPARATlON OF NANOMATERlALt

The following two approaches are used for the synthesis
of nanomaterials.
1. Top-down process (or) Physical (or) Hard methods.
2. Bottom-up process (or) Chemical (or) Soft methods.
2.6.1 Top-down process

Top-down process involves the conversion of bulk
materials into smaller particles of nano-scale structure.
Fig. 2.6 Top-down process
2.6.2 Bottom-up process

Bottom-up process involves building-up of materials
from the bottom by atom by atoms, molecule by molecule or
cluster to the nanomaterials.
Fig. 2.7 Bottom up process
2.6.3 Important Preparations

1. Sol-Cel process
The sol-gel process is a wet chemical technique also
known as chemical solution deposition. It is the method for
producing solid materials from small molecules. This method
is used for the fabrication of metal oxides. It involves
conversion of monomers into a colloidal solution (sol), that
acts as the precursor. This colloidal solution gradually evolves
towards the formation of a gel-like system.
It involves the following steps.
1. Hydrolysis and polycondensation
2. Gelation
3. Aging
4. Drying
5. Densification
6. Crystallization
The volume fraction of particles (particle density) may be
slow that a significant amount of fluid need to be removed for
the gel-like properties to be recognized. It is done by two ways.
(i) Sedimentation
The solution is allowed to keep for some time for
sedimentation to occur and then pour off the remaining liquid.
Nanochemistry 2.19
(ii) Centrifugation
Centrifugation can also be used to accelerate the process
of phase separation.
Drying and densification
Removal of the remaining liquid (solvent) is done by
drying process, which accompanied by shrinkage and
densification.
Firing (or) crystallization
A thermal treatment (firing) is necessary to enhance
mechanical properties and structural stability via sintering,
densification.
Fig. 2.8 Various steps of Sol-Gel process

2. Solvothermal Synthesis
Solvothermal synthesis involves the use of solvent under
high temperature (between 100C to 1000C) and moderate to
high pressure (1 atm to 10,000 atm) that facilitate the
interaction of precursors during synthesis.
Method
A solvent like ethanol, methanol, 2-propanol is mixed
with certain metal precursors and the solution mixture is placed
in an autoclave kept at relatively high temperature and pressure
in an oven to carry out the crystal growth. The pressure
generated in the vessel, due to the solvent vapour, elevates the
boiling point of the solvent.
Exampl Solvothermal synthesis of zinc oxide

Solvothermal synthesis of zinc oxide
Zinc acetate dihydrate is dissolved in 2-propanol at
50C. Subsequently, the solution is cooled to 0C and NaOH
is added to precipitate ZnO. The solution is then heated to
65C to allow ZnO growth for some period of time. Then a
capping agent (1-dodecanethiol) is injected into the suspension
to arrest the growth. The rod shaped ZnO nano-crystal is
obtained.
Fig. 2.9 Solvothermal synthesis

Nanochemistry 2.21
3. Laser ablation
In laser ablation technique, high-power laser pulse is
used to evaporate the material from the target. The
stoichiometry of the material is protected in the interaction.
The total mass ablated from the target per laser pulse
is referred to as the ablation rate.
Fig. 2.10 Laser ablation chamber
This method involves vapourisation of target material

containing small amount of catalyst (nickel or cobalt) by
passing an intense pulsed laser beam at a higher temperature
to about 120C in a quartz tube reactor. Simultaneously, an
inert gas such as argon, helium is allowed to pass into the
reactor to sweep the evaporated particles from the furnace to
the colder collector.
Uses
1. Nanotubes having a diameter of 10 to 20 nm and
100 m can be produced by this method.
2. Ceramic particles and coating can be produced.
3. Other materials like silicon, carbon can also be converted
into nanoparticles by this method.
Advantages of laser ablation.

1. It is very easy to operate.
2. The amount of heat required is less.
3. It is eco-friendly method because no solvent is used.
4. The product, obtained by this method, is stable.
5. This process is economical.
4. Chemical Vapour Deposition (CVD)

This process involves conversion of gaseous molecules
into solid nanomaterials in the form of tubes, wires or thin
films. First the solid materials are converted into gaseous
molecules and then deposited as nanomaterials.
Exampl CNT preparation.

The CVD reactor consists of a higher temperature
vacuum furnace maintained at inert atmosphere. The solid
substrate containing catalyst like nickel, cobalt, iron supported
on a substrate material like, silica, quarts is kept inside the
furnace. The hydrocarbons such as ethylene, acetylene and
nitrogen cylinders are connected to the furnace. Carbon atoms,
Fig. 2.11. Chemical vapour deposition

Nanochemistry 2.23
produced by the decomposition at 1000C, condense on the

cooler surface of the catalyst.
As this process is continuous, CNT is produced
continuously.
Types of CVD Reactor
Generally the CVD reactors are of two types
Fig. 2.12 Types of CVD Reactors
1. Hot-wall CVD
Hot wall CVD reactors are usually tubular in form.
Heating is done by surrounding the reactor with resistance
elements.
2. Cold-wall CVD
In cold-wall CVD reactors, substrates are directly heated
inductively while chamber walls are air (or) water cooled.
Advantages of CVD
1. Nanomaterials, produced by this method, are highly pure.
2. It is economical.
3. Nanomaterials, produced by this method, are defect free.
4. As it is simple experiment, mass production in industry
can be done without major difficulties.
5. Electro-deposition (or) Electrochemical deposition

Electro-deposition is an electrochemical method in which
ions from the solution are deposited at the surface of cathode.
Template assisted electro-deposition is an important technique
for synthesizing metallic nanomaterials with controlled shape
and size. Array of nano-structured materials with specific
arrangements can be prepared by this method using an active
template as a cathode.
Process of electro-deposition
Fig. 2.13 Electrodeposition method

Nanochemistry 2.25
The cell consists of a reference electrode, specially

designed cathode and anode. All these electrodes are connected
with the battery through an voltmeter and dipped in an
electrolytic solution of a soluble metal as shown in figure.
When the current is passed through the electrodes of template,
the metal ions from the solution enter into the pores and gets
reduced at the cathode, resulting in the growth of nanowire
inside the pores of the template.
Exampl Electrodeposition of Gold on Silver

Nanostructured gold can be prepared by the
electrodeposition technique using gold sheets as an anode and
silver plate as a cathode. An array of alumina template is kept
over the cathode as shown in the figure 2.13 and AuCl3 is
used as an electrolyte.
When the current of required strength is applied through

the electrodes, Au ions diffuse into the pores of alumina
templates and gets reduced at the cathode resulting in the
growth of nanowires (or) nanorods inside the pores of the
alumina templates.
Advantages of Electro-deposition
1. This method is relatively cheap and fast.
2. Complex shaped objects can be coated.
3. The film or wire obtained is uniform.
4. Metal nanowires including Ni, Co, Cu and Au can be
fabricated by this method.
6. Electrospinning
Definition
Electrospinning is a method of producing ultrafine (in
nanometers) fibres by charging and ejecting a polymer solution
through a spinneret under a high-voltage electric field and to
solidify (or) coagulate it to form a filament.
Components
1. A high voltage power supply.
2. A polymer reservoir that can maintain a constant flow
rate of solution.
3. A conductive needle, as polymer source, connected to
the high voltage power supply.
4. A conductive collector (plate, drum, etc.)
Fig. 2.14 Electrospinning

Process
A polymer is dissolved in a suitable solvent and is filled
in the capillary reservoir. When sufficiently high voltage is
applied to create an electric field between the needle tip and
the collector, a charge accumulates at the liquid surface. When
the electrostatic repulsion is higher than the surface tension
Nanochemistry 2.27
the liquid meniscus is deformed into conically shaped structure

known as a Taylor cone.
Once the Taylor cone is formed, the charged liquid jet
is ejected towards the collector. Depending upon the viscosity
of the solution, solid fibre will be formed as the solvent
evaporates.
Applications
1. Electrospinning is used in diagnosis and treatment of
diabetes.
2. Electrospun fibres are used in energy storage devices such
as, solar cell, fuel cell, super capacitors.
3. It is also used in textiles for smart clothing, protecting
clothing and fire retardant fibres.
4. It is used in sensors like gas sensors, chemical sensors
and fluorescence sensors.
5. In biomedical, it is used in drug delivery, artificial blood
vessel and wound dressing.
6. e-spun fibres employed in a variety of applications such
as filtration and thermal insulation.
2.6.4 Applications of Nanomaterials

Nano-technology finds significant impact on all most all
the industries and all areas of society. Since nano-materials
possess unique beneficial chemical, physical and mechanical
properties, they can be used for a wide variety of applications.
I. -edicine
1. Nano drugs
Nano materials are used as nano drugs for the cancer
and TB therapy,
2. Laboratories on a chip
Nano technology is used in the production of laboratories
on a chip.
3. Nano-medibots
Nano particles function as nano-medibots that release
anti-cancer drug and treat cancer.
4. Gold-coated nanoshells
It converts light into heat, enabling the destruction of
tumours.
5. Gold nano particles as sensors

Gold nano particles undergo colour change during the
transition of nano particles.
6. Protein analysis
Protein analysis can also be done using nanomaterials.
7. Gold nanoshells for blood immuno assay

Gold nano shells are used for blood immuno assay.
8. Gold nano shells in imaging

Optical properties of the gold nano shells are utilized
for both imaging and therapy.
9. Targeted drug delivery using gold nano particles

It involves slow and selective release of drugs to the
targeted organs.
10. Repairing work

Nano technology is used to partially repair neurological
damage.
II. In Agriculture
1. Nanomaterials prepared by eco-friendly and green
method with plant extracts (Nano formulations) could
increase agriculture potential for improving fertilization
process, plant growth regulators.
2. They also minimize the amount of harmful chemicals
that pollute the environment.
Nanochemistry 2.29
3. Nanosensors are used in crop protection for the

identification of diseases and residues of agrochemicals.
4. Nanodevises are used for the genetic engineering of
plants.
5. Nanomaterials are used in plant disease diagnostics.
6. It is also used in postharvest management.
7. Precision farming techniques might be used to further
improve the crop yields but not damage soil and water.
8. Some nanomaterials are used as antimicrobial agents in
food packing especially silver nanoparticles are in great
interest.
9. Nano particle - based pesticides and herbicides are being
explored for the application of antimicrobial agents to
protect crops from various diseases.
III. In Energy
Nanomaterials are used in several applications to improve
the efficiency of energy generation (or) develop new methods
to generate energy.
1. Power generation
Sun light, concentrated on nanoparticles, can produce
steam with high energy efficiency, which can even be used in
running power plants.
2. Generating hydrogen from sea water
The use of a nanostructured thin film of nickel selenide
as a catalyst for the electrolysis of hydrogen from sea water.
3. Producing high efficiency light bulbs
Nano-engineered polymer matrix is used for the
production of high efficiency light bulbs.
4. Increasing the electricity generated by wind mills
Stronger and lower weight blades, made from nanotubes-
filled epoxy, in wind mills increases the amount of electricity.
5. Generating electricity from waste heat

Sheets of nanotubes have been used to build thermocells
that generates electricity, when the sides of the cell are at
different temperature
6. Storing hydrogen for fuel cell powered cars
Graphene layers are used in fuel tank, resulting in a
higher amount of hydrogen storage and therefore lighter weight
fuel tank.
7. Reducing power loss in electric transmission wires
The wires containing carbon nanotubes lowers resistance
than the wires currently used in the electric transmission grid.
8. Reducing the cost of solar cell
Nanotech solar cells are manufactured at significantly
lower cost than the conventional solar cells.
9. Nano battery and fuel cell
Nanomaterials, used in batteries and fuel cell, increases
their efficiency.
IV. Electronics
1. Quantum wires are found to have high electrical
conductivity.
2. The integrated memory circuits have been found to be
effective devices.
3. A transistor, called NOMFET, (Nanoparticle Organic
Memory Field Effect Transistor) is created by combining
gold nanoparticles with organic molecules.
4. Nano wires are used to build transistors without p  n
junctions.
5. Nano radios are the other important devices, using carbon
nanotubes.
6. MOSFET (Metal Oxide Semi conductor Field Effect
Transistor), performs both as switches and as amplifiers.
Nanochemistry 2.31
V. In Catalysis
Nanoparticle catalysts are highly effective because of the
following two reasons
(i) huge surface area
(ii) enhanced reactivity
1. Water purification
Nanosilver catalyst is highly efficient in controlling
microbes in water.
2. Bio-diesel production
Solid base nanocatalyst KF/CaO can be used for
biodiesel production with yield more than 96%.
3. Fuel cell application

Carbon supported electro-catalysts play an important role
in fuel cell.
4. In drug delivery
Carbon nanomaterials find more applications in
biological fields.
CNTs may be suitable for bio-applications in bio
recognition and drug delivery systems.
5. Gold nanoparticles
It is an important catalyst in co-oxidation, epoxidation
of propylene, hydrogenation of unsaturated hydrocarbons.
6. Nanopowder silica catalyst (or) platinum nanoparticles
exhibit very strong catalytic activity for hydrolysation
reactions.
7. Titania-based nanocatalysts are being increasingly used
in photocatalysis.
8. Nanocrystalline MgO particles act as an effective catalyst
for dehydrogeneration.
2.7
ANNA UNlVERtlTY QUEtTlONt
1. Distinguish molecule, nanoparticles and bulk materials.
2. What are nanoparticles? Write any four methods of
preparation of nanoparticles. (A.U (CEG) Dec 2011)
3. Discuss the applications of nano chemistry in biology and
medicine. (A.U (CEG) Dec 2011)
4. Describe various types of synthesis involved in the
preparation of nanomaterials. (A.U. June 2014)
5. Discuss the CVD and laser ablation techniques for the
synthesis of nanoparticles. (A.U (CEG) June 2013)
6. Explain about size dependent properties of nano materials.
(A.U (CEG) Dec 2012, A.U. May 2014)
7. Explain briefly the applications of nano materials.
(A.U.T (TNV) Jan 2009)
8. Explain any six applications of nanomaterials in various
fields. (A.U. May 2014)
9. Write an informative note on the properties and
applications of nanoparticles. (A.U (CEG) June 2013)
10. Define the terms: nanorods, nanotubes, nanowires and
nanoclusters. (A.U (CEG) June 2013)
11. Explain (1) nanocluster (2) nanowire with examples
(A.U. Jan 2014)
12. What are nano materials? Discuss the types of carbon
nano tubes and their applications. (A.U June 2012)
13. How are carbon nano tubes synthesized? What are its
applications? (A.U (CEG) Dec 2011)
14. Discuss any four salient properties of nanomaterials
(A.U. Jan 2014)
15. Discribe any two methods of synthesisizing nanomaterials.
(A.U. May 2014)
Unit - III Chapter 3
Phase rule
3.1 INTRODUCTION
All the chemical reactions can be broadly classified into
two types.
1. Irreversible reaction:
Zn  H2SO4  ZnSO4  H2
2. Reversible reaction
(a) Homogeneous reversible reaction
N2g  3H2g 2NH3g
(b) Heterogeneous reversible reaction
CaCO3s CaOs  CO2g
The reversible reactions are represented by two arrows
in opposite directions.
The homogeneous reversible reactions can be studied
using the law of mass action. But the heterogeneous systems
require different methods. The phase rule, given by Willard
Gibbs (1874), is used to study the behavior of heterogeneous
reversible reactions.
3.2 PHAtE RULE

If the equilibrium between any number of phases is not
influenced by gravity, or electrical, or magnetic forces but is
influenced only by pressure, temperature and concentration,
then the number of degree of freedom (F) of the system is
related to number of components (C) and number of phases
(P) by the following phase rule equation.
FCP2
3.2.1 Definition of terms with examples

1. Phase (P)
Phase is defined as, “any homogeneous physically
distinct and mechanically separable portion of a system which
is separated from other parts of the system by definite
boundaries”.
Examples
(a) Gaseous phase
All gases are completely miscible and there is no
boundary between one gas and the other.
Example
Air, which is a mixture of O2, H2, N2, CO2 and water
vapour, etc., constitutes a single phase.
(b) Liquid phase
The number of liquid phases depends on the number of
liquids present and their miscibilities.
(i) If two liquids are immiscible, they will form three
separate phases two liquid phase and one vapour phase.
Example
Benzene - Water.
(ii)If two liquids are completely miscible, they will form
one liquid phase and one vapour phase.
Example
Alcohol - Water.
(c) Solid phase
Every solid constitutes a separate phase.
Phase Rule 3.3
Example
Decomposition of CaCO3
It involves three phases, solid CaCO3, solid CaO and

gaseous CO2.
(d) Consider a water system consisting of three phases.
Ices Waterl Vapourg
Each phase is physically distinct and homogeneous and

there are definite boundaries between phases. So this forms
three phases.
(e) A solution of a substance in a solvent consists of one

phase only.
Example
Sugar solution in water.
(f) An emulsion of oil in water forms two phases
(g) MgCO3 s  MgOs  CO2 g
It involves three phases, solid MgCO3, solid MgO and

gaseous CO2.
(h) Rhombic sulphur s  Monoclinic sulphur (s)
It forms two phases.
(i) Consider the following heterogeneous system.
CuSO4  5 H2Ol CuSO4  5 H2Os

s
Number of phase = 3; Number of component = 2

2. Component (C)
Component is defined as, “the smallest number of
independently variable constituents, by means of which the
composition of each phase can be expressed in the form of
a chemical equation”.
Examples
(a) Consider a water system consisting of three phases.

The chemical composition of all the three phases is
H2O, but are in different physical form. Hence the number of
component is one.
(b) Sulphur exists in 4 phases namely rhombic, monoclinic,
liquid and vapour, but the chemical composition is only
sulphur. Hence it is a one component system.
(c) Thermal decomposition of CaCO3
The system consists of three phases namely, solid

CaCO3, solid CaO and gaseous CO2. But it is a two component
system, because the composition of each of the above phases
can be expressed in terms of any two of the three components
present. When CaCO3 and CaO are considered as components.
Phase Components
CaCO3 CaCO3  0CaO
CaO 0CaCO3  CaO
CO2 CaCO3  CaO
(d) PCl5s  PCl3l  Cl2g

Phase Rule 3.5
This system has three phases, but the number of

component is only two.
(e) An aqueous solution of NaCl is a two component system.
The constituents are NaCl and H2O.
(f) CuSO4 . 5H2Os CuSO4 . 3H2Os  2H2Og

It is also a two component system.
(g) In the dissociation of NH4Cl, the following equilibrium
occurs.
NH4Cls NH3g  HClg
The system consists of two phases namely solid

NH4Cl and the gaseous mixture containing NH 3  HCl. When
NH3 and HCl are present in equivalent quantities the
composition of both the phases can be represented by the same
chemical compound NH4Cl and hence the system will be a
one component system.
3. Degree of freedom (F)

Degree of freedom is defined as, “the minimum number
of independent variable factors such as temperature, pressure
and concentration, which must be fixed in order to define
the system completely”.
A system having 1, 2, 3 and 0 degrees of freedom is
called univariant, bivariant, trivariant and nonvariant
respectively.
Examples
(a) Consider the following equilibrium

Ices Waterl
Vapourg
These three phases will be in equilibrium only at a
particular temperature and pressure. Hence, this system does
not have any degree of freedom, so it is non variant or zero
variant.
(b) Consider the following equilibrium

Waterl Water vapourg
Here liquid water is in equilibrium with water vapour.
Hence any one of the degrees of freedom such as temperature
or pressure has to be fixed to define the system. Therefore the
degree of freedom is one.
(c) For a gaseous mixture of N2 and H2, we must state both
the pressure and temperature. Hence, the system is
bivariant.
3.3 PHAtE DIAGRAM

Phase diagram is a graph obtained by plotting one
degree of freedom against another.
3.3.1 Types of Phase Diagrams

1. P-T diagram
If the phase diagram is plotted between temperature
against pressure, the diagram is called P  T diagram. P  T
diagram is used for one component system.
2. T-C diagram
If the phase diagram is drawn between temperature
against composition, the diagram is called T  C diagram.
T  C diagram is used for two component system.
3.3.2 Uses of Phase Diagram

1. It is possible to predict from the phase diagrams whether
an eutectic alloy or a solid solution is formed on cooling
a homogeneous liquid containing mixture of two metals.
2. The phase diagrams are useful in understanding the
properties of materials in the heterogeneous equilibrium
system.
Phase Rule 3.7
3. The study of low melting eutectic alloys, used in

soldering, can be carried out using phase diagrams.
3.4 ONE COMPONENT tYtTEM
3.4.1 The water system

Water exists in three possible phases namely solid, liquid
and vapour. Hence, there can be three forms of equilibria.
Solid Liquid
Liquid Vapour
Solid Vapour
Each of the above equilibrium involves two phases. The
phase diagram for the water system is shown in the Fig. 3.1.
This phase diagram contains curves, areas, and triple

point.
1. Curve OA
The curve OA is called vapourisation curve, it
represents the equilibrium between water and vapour. At any
point on the curve the following equilibrium will exist.
Water Water vapour

The degree of freedom of the system is one, i.e.,
univariant. This is predicted by the phase rule.
F  C  P  2; F  1  2  2; F  1
This equilibrium (i.e. line OA) will extend upto the

critical temperature 374C. Beyond the critical temperature
the equilibrium will disappear only water vapour will exist.
2. Curve OB
The curve OB is called sublimation curve of ice, it
represents the equilibrium between ice and vapour. At any
point on the curve the following equilibrium will exist.
Ice Vapour
The degree of freedom of the system is one, i.e.
univariant. This is predicted by the phase rule.
Fig 3.1 Phase diagram of water system
F  C  P  2; F  1  2  2; F  1
This equilibrium (line OB) will extend upto the absolute
zero  273C, where no vapour can be present and only ice
will exist.
Phase Rule 3.9
3. Curve OC
The curve OC is called melting point curve of ice, it
represents the equilibrium between ice and water. At any point
on the curve the following equilibrium will exist.
Ice water
The curve OC is slightly inclined towards pressure axis.
This, shows that melting point of ice decreases with increase
of pressure.
The degree of freedom of the system is one, i.e.,
univariant.
4. Point ‘O’ (Triple point)
The three curves OA, OB and OC meet at a point ‘O’,
where three phases namely solid, liquid and vapour are
simultaneously at equilibrium.
This point is called triple point, at this point the
following equilibrium will exist.
The degree of freedom of the system is zero i.e.,
nonvariant. This is predicted by the phase rule.
F  C  P  2; F  1  3  2; F  0
Temperature and pressure at the point ‘O’ are
0.0075C and 4.58 mm respectively.
5. Curve OB: (Metastable equilibrium)
The curve OB is called vapour pressure curve of the
super-cool water or metastable equilibrium where the following
equilibrium will exist.
Supercool water Vapour
Sometimes water can be cooled below 0C without the
formation of ice, this water is called super-cooled water. Super
cooled water is unstable and it can be converted into solid by
“seeding” or by slight disturbance.
6. Areas
Area AOC, BOC, AOB represents water, ice and vapour
respectively. In order to define the system at any point in the
areas, it is essential to specify both temperature and pressure.
The degree of freedom of the system is two. i.e., Bivariant.
This is predicted by the phase rule
F  C  P  2; F  1  1  2; F  2
3.5 EXPERIMENTAL METHOD OF

CONtTRUCTION OF A tIMPLE EUTECTIC
PHAtE DIAGRAM
3.5.1 Thermal analysis (or) cooling curves

Thermal analysis is a method involving a study of the
cooling curves of various compositions of a system during
solidification. The shapes of the freezing point curves for any
system (involving metals) can be determined by thermal
analysis. The form of the cooling curve indicates the
composition of the solid.
Example Cooling curve for a pure solid
A pure substance in the fused state is allowed to cool
slowly and the temperature is noted at different time interval.
Then graph is plotted between temperature and time (Fig. 3.2).
Fig. 3.2 Cooling curve of Fig 3.3 Cooling curve of a

pure solid mixture A+B
Phase Rule 3.11
Initially the rate of cooling is continuous. When it

reaches the point ‘b’ solid begins to appear, now the
temperature remains constant until the liquid melt is completely
solidified. Solidification completes at the point ‘c’. The
horizontal line ‘bc’ represents the equilibrium between the solid
and liquid melt. After the point ‘c’, temperature of the solid
begins to decrease along the curve ‘cd’.
Example Cooling curve for a mixture

If a mixture of two substances (say A and B) in the
fused state is allowed to cool slowly, the cooling curve is
obtained in a similar manner (Fig. 3.3).
Initially the rate of cooling is continuous. When it
reaches the point ‘b’ one substance (either A or B) begins to
solidify out of the melt, which is indicated by a break and
the rate of cooling is different. On further cooling at the break
point ‘c’ the second compound also begins to solidify. Now
the temperature remains constant until the liquid melt is
completely solidified, which forms the eutectic mixture (line
cd). After the break point ‘d’ cooling of solid mass begins.
The temperature of horizontal line ‘cd’ gives the eutectic
temperature.
The experiment is repeated for different compositions of
A and B and the various cooling curves are recorded. From
the cooling curves of various compositions, the main phase
Fig. 3.4 Cooling curve of various compositions of two solids

diagram can be drawn by taking composition in X-axis and

the temperature in Y-axis. (Fig. 3.4)
Uses of cooling curves
1. Melting point and eutectic temperature can be noted from
the cooling curve.
2. Percentage purity of the compounds can be noted from
the cooling curve.
3. The behaviour of the compounds can be clearly
understood from the cooling curve.
4. The composition corresponding to its freezing point
yields the composition of the alloy.
5. The procedure of thermal analysis can be used to derive
the phase diagram of any two component system.
3.д
TWO COMPONENT tYtTEMt
3.6.1 Reduced phase rule (or) Condensed

system
The maximum number of degree of freedom in a two
component system will be three, when the system exists as a
single phase.
F  C  P  2; F  2  1  2; F  3
In order to represent the conditions of equilibrium
graphically, it requires three co-ordinates, namely P,T and C.
This requires three dimensional diagram, which cannot be
conveniently represented on paper. Therefore, any two of the
three variables must be chosen for graphical representation.
A solid-liquid equilibrium of an alloy has practically no
gaseous phase and the effect of pressure is negligible.
Therefore, experiments are conducted under atmospheric
pressure. Thus the system in which only the solid and liquid
phases are considered and the gas phase is ignored is called
Phase Rule 3.13
a condensed system. Since the pressure is kept constant, the

phase rule becomes
F  C  P  1
This equation is called reduced phase rule or

condensed phase rule.
3.7 BINARY ALLOY tYtTEM (or) THE

tIMPLE EUTECTIC tYtTEM
3.7.1 The Lead-Silver system

Since the system is studied at constant pressure, the
vapour phase is ignored and the condensed phase rule is used.
F  C  P  1
The phase diagram of lead-silver system is shown in Fig.
3.5. It contains lines, areas and the eutectic point.
1. Curve AO
The curve AO is known as freezing point curve of silver.
Point A is the melting point of pure Ag 961C. The curve
AO shows the melting point depression of Ag by the successive
addition of Pb. Along this curve AO, solid Ag and the melt
are in equilibrium.
Solid Ag Melt
According to reduced phase rule equation.
F  C  P  1; F  2  2  1; F 
1 The system is univariant.
2. Curve BO
The curve BO is known as freezing point curve of lead.
Point B is the melting point of pure lead 327C. The curve
BO shows the melting point depression of ‘Pb’ by the
Fig. 3.5 Phase diagram of Lead - Silver system
successive addition of ‘Ag’. Along this curve ‘BO’, solid ‘Pb’

and the melt are in equilibrium.
Solid Pb Melt
F  C  P  1; F  2  2  1; F 
1 The system is univariant
3. Point ‘O’ (Eutectic point)

The curves AO and BO meet at point ‘O’ at a
temperature of 303C, where three phases (solid Ag, solid Pb
and their liquid melt) are in equilibrium.
Solid Pb + Solid Ag Melt

Phase Rule 3.15
F  C  P  1; F  2  3  1; F 
0 The system is non-variant.
The point ‘O’ is called eutectic point or eutectic
temperature and its corresponding composition, 97.4%Pb +
2.6%Ag, is called eutectic composition. Below this point the
eutectic compound and the metal solidify.
4. Areas
The area above the line AOB has a single phase
molten Pb  Ag. According to reduced phase rule equation.
F  C  P  1; F  2  1  1; F 
2 The system is bivariant.
Both the temperature and composition have to be
specified to define the system completely.
The area below the line AO solid Ag  liquid melt,
below the line BO solid Pb  liquid melt and below the point
‘O’ (Eutectic compound + solid Ag or solid Pb) have two
phases and hence the system is univariant
F  C  P  1; F  2  2  1; F  1.
Application of Pattinson’s process for the desilverisation of

Argentiferous lead
The argentiferous lead, consisting of a very small amount
of silver (say 0.1%), is heated to a temperature above its
melting point, so that the system consisting of only the liquid
phase represented by the point ‘p’ in the Figure 3.5. It is then
allowed to cool. The temperature falls down along the line
‘pq’. As soon as the point ‘q’ is reached, Pb is crystallised
out and the solution will contain relatively increasing amount
of ‘Ag’. On further cooling, more and more ‘Pb’ is separated
along the line ‘BO’ the melt continues to be richer and richer
in silver until the point O is reached, where the percentage of
Ag rises to 2.6%.
Thus, the process of raising the relative proportion of

Ag in the alloy is known as Pattinson’s process.
Uses of Eutectic system

1. Suitable alloy composition can be predicted with the help
of eutectic systems.
2. Eutectic systems are used in preparing solders, used for
joining two metal pieces together.
3.8
UtEt (OR) MERITt OF PHAtE RULE
1. It is applicable to both physical and chemical equilibria.
2. It is a convenient method of classifying the equilibrium
states in terms of phases, components and degree of
freedom.
3. It indicates that the different systems having the same
degrees of freedom behave similarly.
4. It helps in deciding whether the given number of
substances remain in equilibrium or not.
3.9
LIMITATIONt OF PHAtE RULE
1. Phase rule can be applied only for the systems in
equilibrium.
2. Only three variables like P, T & C are considered, but
not electrical, magnetic and gravitational forces.
3. All the phases of the system must be present under the
same conditions of pressure and temperature.
4. Solid and liquid phases must not be in finely divided
state, otherwise deviations occur.
3.10 ANNA UNIVERtITY QUEtTIONt

1. State phase rule and explain the terms involved in it.
(TNV A.U. May 2009)(June 2009)(June-2006)
Phase Rule 3.17
2. Draw a neat one component water system and explain in

detail. (A.U. Jan 2014, May 2017)
3. Explain the various stable and unstable equilibria in ice-
water-water vapour system and state the effect of
decreasing pressure on each of the equilibria.
(TNV A.U. May 2009)(May 2008)
4. What is metastable equilibrium? Explain this state in
H2O system. (A.U. Dec 2008)
5. What is condensed phase rule? what is the number of
degrees of freedom at the eutectic point for a two
component system? [A.U. May 2003, June 2006]
6. Discuss in detail the Lead-Silver system. Give its
applications. [A.U. Jan 2014, A.U (CEG) Dec 2011)
7. Draw a neat phase diagram and explain the lead-silver
system? Briefly write about Pattinson’s process.
[A.T. May 2003], [A.U. (CEG) Apr. 2002, May 2003]
8. Mention the limitations of phase rule. (A.U. Dec 2008)
detail. (A.U. Jan 2014)
10. Draw a neat two component Lead - Silver system and
explain. (A.U. June 2014)
11. State Phase rule and explain the terms involved in it with
examples. (A.U. June 2014)
12. Draw a neat one component water system and explain.
(A.U. Dec 2014)
13. Apply phase rule to water system and explain the
characteristics. (A.U. May 2015)
14. Discuss the phase diagram of silver-lead system and
explain the eutectic mixture, characteristics and uses.
(A.U. May 2015)
15. Draw the phase diagram of lead-silver system and explain.
Briefly write about Pattinson’s process.
(A.U. Dec 2015)
16. Discuss the application of phase rule to water system.

(A.U. Dec 2015)
17. What is thermal analysis. Draw the cooling curves of a
pure substance and a mixture and discuss.
(A.U. June 2006)
detail. (A.U. Dec 2016)
19. Discuss in detail the lead-silver system and explain in
detail. (A.U. Dec 2016)
Unit - III Chapter 4
Composite Materials
4.1 INTRODUCTION
All the engineering materials (high polymers, metals and
ceramics) possess their outstanding characteristics as well as
limitations. None of these can be properly used where very
stringent and specific requirements are required, e.g., high
temperature reactors, supersonic aircrafts, missiles, etc. In order
to meet such a stringent and specific requirements, scientists
and technologists have developed a new class of materials
called “composites”.
4.2 DEFINITION
A composite material may be defined as, “a material
system consisting a mixture of two (or) more micro-
constituents, which are mutually insoluble, differing in form
(or) composition and forming distinct phases”. Such a
combination, possesses properties different from those of any
of its constituents.
4.3
NEED FOR COMPOtITEt
1. As composites never rust and have less fracture
toughness than metals, we need different composites.
2. To reduce maintenance cost and ensure long-term
stability composites are essential.
3. It is essential because according to the needs, using
different fibres and matrix, properties of composites can
be modified.
4. In telecommunication industries, need of power
transmission along with data transmission is increasing,
so composites are highly essential.
5. Composites are highly required because, of its lower

weight reduces fuel consumption and emission.
6. As carbon fibre weighs about 25% as much as steel and
70% as much as aluminium and is much stronger and
stiffer than both materials, we need composites.
4.4 ADVANTAGEt (OR) CHARACTERltTlCt

OF COMPOtlTEt
(i) They possess higher specific strength and lower specific
gravity.
(ii) They possess lower electrical conductivity and thermal
expansion.
(iii) They possess better creep, fatigue strength, corrosion and
oxidation resistance.
(iv) They maintain very good strength, even upto high
temperatures.
4.5 CONtTlTUENTt OF COMPOtlTEt

Composites consist of two important constituents.
(i) Matrix phase (or) Matrix resin
(ii) Dispersed phase (or) Reinforcement.
4.5.1 Matrix Phase (or) Matrix resin

Matrix phase is the continuous body constituent, which
encloses the composite. Matrix phase may be metals, ceramics
(or) polymers (liquid resins), composites using these matrix are
known as
(i) Metal Matrix Composites (MMC)
(ii) Ceramic Matrix Composites (CMC)
(iii) Polymer Matrix Composites (PMC) respectively.
Composite Materials 4.3
Liquid Resins
Polymers used as adhesives, potting compounds, sealants,
etc., in a liquid form are called as liquid resins.
Exampl Epoxy adhesives, polysulphides are typical

commercially available adhesives.
Cure reactions
Formation of cross-linking in certain polymers is known
as cure reaction.
Cure reactions are done by using a curing agent. These
uncross-linked linear polymers contain functional groups (or)
double bonds. They are usually not high molecular weight resin
and are in the form of liquid resins. They are also called as “pre-
polymers”. The liquid resins will be cured in the moulding to get
solid mass of cross linked products.
4.5.2 Dispersed Phase (or) Reinforcement

Dispersed phase is the structural constituent, which
determines the internal structure of composite.
Exampl Fibres, Particulates, Flakes, Whiskers.

Reinforcement
It is a process of improving the characteristics of the
plastic matrix by adding reinforcing agents. The reinforcing
agents may be organic (or) inorganic in nature. They may be
in the form of powder, flakes, fibres. These materials are
characterised by high strength to weight ratio, excellent
resistance to erosion, corrosion, etc., and ease of fabrication.
For effective structural performance, there should be a strong
adhesive bond between the matrix phase (or) matrix resin and
the dispersed phase (or) reinforcing agents.
1. Fibres
Fibres are long and thin filament of any macromolecular
substance such as polymer, metal (or) ceramic having high
length to diameter ratio at least 100:1.
The fibre (reinforcement material) can be used in variety

of forms like continuous rovings, cloth, chopped strands, etc.,
Characteristics of Fibre
(i) Fibre possesses high tensile strength.
(ii) It possesses high stiffness.
(iii) It lowers overall density of composites.
Classification of Fibres
The fibres used in reinforcements are classified as
(i) Natural fibres: These are derived from naturally available
sources.
Exampl Cotton, wool, silk, sisal, jute and coir.

(ii) Semi-synthetic fibres: These are produced by modifying
the naturally occurring materials.
Exampl Rayon, cellulosic.

(iii) Synthetic fibres: These are produced exclusively by the
laboratory processes.
Exampl Polyester fibre, polypropylene and carbon

fibre (poly acrylonitrile), glass fibres, aramid
fibres.
(iv) Aramid fibres: These are aromatic polyamides.
Exampl Kevlar.
(i) Important Natural Fibres

(a) Cotton Fibres: Cotton is a vegetable fibre and is made
of cellulose molecule, which is a linear polymer of -glucose.
Cotton fibres provide a low cost fibrous reinforcements for the
use in dough moulding compounds (DMC). Mostly phenolic
resin based moulding compounds.
The painted fabrics can be used to provide a decorative
finish for applications like wall panels.
(b) Wool Fibre: Wool is an animal protein fibre. Like other

proteins, wool is also made up of -aminoacids. These
aminoacids are joined end-to-end in the form of peptide chains
forming long chain molecules. Many of the physical and
chemical properties of wool are due to the disulphide bonds
formed by the covalent cross-linking of the cystein molecule.
Any chemical that affect the disulphide bonds may cause
structural break down of the fibre. The elastic properties of
the wool fibre is due to the presence of hydrogen bond between
various peptide chain.
(c) Silk: Silk is a natural protein fibre produced by the
insect, silk worm. It possesses all the desirable qualities of fibre
such as softness, strength, elongation, etc. It has a bright lusture
and it is an excellent insulator of heat, hence it is warm in
winter and cool in summer.
(d) Sisal: Sisal is another low-cost fibrous material, which
is also used in phenolic based dough moulding compounds.
(e) Jute and Coir: They are also low-cost fibrous material
for reinforcement for polyester resin. They can be used as
woven cloth (or) in yarn form for filament winding. A variety
of objects like houses, fishing boats have been developed.
(ii) Synthetic Fibres
(a) Polyethylene terephthalate (PET) (or) Terylene (or)
Dacron
PET is produced by the condensation of ethylene glycol
(EG) and terephthalic acid (TPA). This fibre is used as surface
tissues which can be used to provide improved chemical and
abrasion resistance. They may be used in light weight woven
fabrics. They are rarely used as the main reinforcement,
although they give laminates with high impact resistance,
excellent chemical and abrasion resistance. Generally they are
used in combination with glass fibres.
(b) Poly Propylene: It is obtained by polymerisation of
propylene. These fibres possess better hardness, strength,
stiffness. These fibres are used in making ropes, carpets,

blankets, hand bags, apparels, etc.
(c) Carbon fibres: Carbon fibres are obtained as a
continuous filament by the pyrolysis of organic fibres in an
inert atmosphere such as cellulose, polyacrylonitrile (PAN)
Properties
The carbon fibres are widely used because of their
specific strength, stiffness, high modules even at elevated
temperatures. Also they are resistant to moisture, acids, bases
and a number of solvents.
PAN
  CH
 polyacrylonitrile
CH2 
n
|
Uses CN
PAN fibre is used to make surfacing tissues to provide
improved chemical resistance. Tissues may be used in
conventional constructions (or) light weight woven fabrics.
(d) Nylon
O
||
 NH  CH25  C n
Nylon fabrics are used as reinforcements for epoxide

resin systems to give flexible laminates with high impact,
abrasion and chemical resistance. They are sometimes
combined with glass fibre reinforcements for specialized
applications.
(iii) Aramid Fibres

The wholly aromatic polyamides are called as aramids.
They are made by spinning liquid crystal aramid oligomers
(Kevlar).
The meta-linked poly-m-phenylene isophthalimide is

called Nomex, where as para-linked poly-p-phenylene
phthalimide is called Kevlar.
Properties
These are used as high performance fibers because of
their high modules, tensile strength, stability at high
temperatures, wide temperature range   200 to 200C for
retaining mechanical properties, excellent toughness and impact
resistance.
Uses
Aramid fibres are used in reinforcements, widely used
in tyre card reinforcement, bullet proof clothing, race drivers,
astronaut suits, etc.,
2. Particulates
Particulates are small pieces of hard solid materials. They
may be metallic (or) non-metallic. Generally distribution of
particles in a given matrix is random, so the resulting
composites are usually isotropic. Due to the inherent hardness,
the particles in a composite cause constraints on the plastic
deformation on the matrix.
Effect of particulate in particulate composite

(i) Surface hardness gets increased.
(ii) Wear and abrasion resistance are increased.
(iii) Performance at elevated temperature is improved.
(iv) Shrinkage and friction is reduced.

(v) Electrical and thermal conductivities are modified.
3. Flakes
Flakes are very thin solid like materials.
Exampl Mica flakes

(i) They impart equal strength in all directions in a plane
compared to fibres which reinforce unidirectionally only.
(ii) Flakes can be packed more efficiently than fibres (or)
spherical particles.
(iii) Flakes especially mica can be used in electrical and
thermal insulating appliances.
4. Whiskers
Whiskers are thin strong fibre like material made by
growing a crystal.
Exampl Graphite, silicon carbide, silicon nitride

(i) Perfect whiskers possess much higher strength than in
bulk, but irregularities decreases their strength.
(ii) They possess high elastic modulus and high degree of
crystallinity.
(iii) They possess exceptionally high strength.
(iv) As it is costly and difficult to incorporate in matrix they
find limited use in composite.
4.д TYPEt OF COMPOtlTEt
4.6.1 Polymer composites (or) Fibre

Reinforced Polymer Composites
The fibre reinforced polymer composites constitute more
than 90% (by weight) of the total composites used in various
industries. The advantages of using polymer in structural
composites is the ease of fabrication of complex structural

shapes. It can be easily manufactured.
Preparation
Fibre-reinforced plastics are produced by suitably
bonding a fibre material with a resin matrix and curing them
under pressure and heat. The main reinforcing agents used in
FRP composites are, glass, graphite, alumina, carbon, boron,
etc. The reinforcement material can be in different forms such
as short fibres, continuous filaments (or) woven fabrics.
The resin matrix commonly used in FRP are polyesters,
epoxy, phenolic, silicone, and polyamide polymer resins.
Characteristics (or) Properties of FRP

1. It possess superior properties like higher yield strength,
fracture strength and fatigue life.
2. Since fibre prevents slip and crack propagation, the
mechanical properties of FRP gets increased.
3. It possess high corrosion resistance and heat resistance
property.
The properties of FRP mainly depends on nature of the
resin matrix
S.No. Resin Reason

1. Polyester resin To provide very good strength
and mechanical properties.
2. Epoxy resin To impart good mechanical
properties.
3. Silicone resins To impart excellent thermal
and electrical properties
4. Phenolic resins To withstand high
temperatures
5. Thermoplastics Because of its repeatability and
(polyamide, PET, etc) repairability.
Table 4.1: Types of FRP Composites

Name of
S.No. Properties Applications
FRP
1. Glass-FRP (i) lower Automobile parts,
densities, dielectric storage tanks,
constants. plastic pipes,
(ii) Higher tensile flourings,
strengths and transportation
impact resistance. industries, etc.,
(iii) Excellent
corrosion
resistance,
chemical
resistance,
Non-flammability.
2. Boron-FRP (i) Excellent Horizontal and
stiffness and vertical tail in
compressive aeroplane,
strength stiffening spares,
(ii) Manufacturi ribs, etc.,
ng of B-FRP is
difficult.
3. Carbon-FRP (i) Lighter Structural
density. components of air
(ii) Excellent craft and
resistance to helicopters,
corrosion. recreational
(iii) Retention of equipments, sports
desired properties materials, Antenna
even at elevated disc, solar panal
temperatures. etc.,
Name of
S.No. Properties Applications
FRP
4. Aramid-FRP They are metal - Structural
like ductile and component in
respond non- aircraft, helicopter
catastrophically to parts.
compressive
stresses (because,
capable of
absorbing energy).
5. Alumina-FRP Good abrasion Components of
resistance, creep engine parts in
resistance and automobile
dimensional industry, and
stability. components of
turbine engine.
Advantages of polymer composites (FRP)

1. Polymer composite has very high strength to weight ratio
than the metal.
2. The weight of FRP is 75% lower than the weight of
steel, so it improves performance, reduces energy need,
simplifies handling.
3. Using polymer composite devices both capacitance and
leakage current can be reduced.
4. FRP offers better corrosion resistance to a wide range
of chemicals resulting in longer service life, less
maintenance and repair down time.
5. FRP possesses excellent durability and fire resisting
properties.
6. It is ideal for outdoor installation, because it is
impervious to the effect of sunlight, heat, cold and other
weather conditions.
7. Specifying the orientation of reinforcing fibres, can

increase the strength and resistance to deformation of the
polymer.
8. GRP (glass reinforced polymer) are strongest and most
resistive to deforming forces, when the polymer fibres
are parallel to the force being exerted and are weakest
when the fibres are perpendicular.
9. CRP (carbon fibre reinforced polymer) in place of sheet
aluminium in traditional rudded are
(i) 25% reduction in weight.
(ii) 95% reduction in components by combining parts
and forming simpler moulded parts.
4.6.2 Metal Matrix Composites
Properties
(i) Metal matrix composites exhibit extremely good thermal
stability, high strength, good stiffness and low specific
weight.
(ii) MMCs also have other advantages like fracture
toughness, ductility and enhanced elevated temperature
performance at
(iii) They can withstand at elevated temperatures in corrosive
environment than polymer composites.
Uses
(i) Polymer based composites cannot be utilized for engine
parts due to their limitations in their applications at high
temperatures where as MMCs are suitable alternatives
with Al, Ti, Ni alloys as one of the matrix material and
Al2O3, B, C, SiC as one of the reinforcements.
(ii) They are used in engine blades, combustion chambers,
etc.
(iii) Al and Mg MMCs are used in automotive industry.
(iv) They improve fuel efficiency because of the weight

reduction.
(v) Apart from aerospace, defence and automotive
applications, MMCs are also used in biomedical and
sports equipment industry
4.6.3 Ceramic Matrix Composites

Properties
1.
CMCs are used at temperatures above 1500C, because
of their good corrosion resistance, stability at elevated
temperatures and high compressive strength.
2.
Ceramics provide necessary strength at high temperature
with good oxidation resistance.
3.
The matrixes used are glass, ceramics, carbides, nitrides,
oxides and borides, the reinforcements are
Al2O3, B, C, SiC and SiO2
Uses
They are used in re-entry thermal shields in space
vehicles and tiles, pump seal, round rings, brake linings etc.
4.6.4 Hybrid composites

Hybrid composites are new class of materials composed
of a suitable polymer matrix reinforced with two different
fibres (or) fillers.
Types of Hybrid composites
Functionally hybrid composites are of three types
1. Structurally hybridized composites
2. Materials hybridized in chemical bond
3. Functionally hybridized composites.
Properties
Hybrid composites possess very good properties
compared to their single fibre composites.
1. They possess strong, tough and higher impact resistance.

2. When hybrid composites are stressed in tension, failure
does not occur suddenly.
3. They possess balanced strength and stiffness.
4. They also have balanced thermal distortion stability,
reduced weight, improved fatigue resistance.
5. They exhibit superior mechanical and tribological
properties than other composites.
Uses
1. It is used in light-weight transport (land, water (or) oil)
structural components.
2. It is also used in light weight orthopedic components
and sporting goods.
3. It is used to make furniture like chair, table and bath
tubs
4. It is used in railway coach interiors.
5. It is also used in making daily used applications like
plates and spoons.
6. Automobile industry utilizes hybrid composites in many
of the interior and exterior applications.
4.7 ANNA UNlVERtlTY QUEtTlONt

1. What is the need of composites? Mention its advantages
and disadvantages.
2. Explain the constituents of composites.
3. Explain the types and characteristics of FRP.
4. Explain the properties and uses of metal-matrix composite.
5. Write notes on
(i) Ceramic matrix composites
(ii) Hybrid composites.
Unit - IV Chapter 5
Fuels
5.1
INTRODUCTION
A fuel is a combustible substance, containing carbon as
the main constituent, which on burning gives large amount of
heat. During the process of combustion of a fuel, the atoms
of carbon, hydrogen, etc., combine with oxygen with
simultaneous liberation of heat.
C  O2  CO2  94 k cals.
2H2  O2  2H2O  68.5 k

cals.
The main source of fuel is coal and crude petroleum oil.
These are stored fuels available in earth’s crust and are
generally called fossil fuels, because they were formed from
fossilised remains of plants and animals.
5.2
CHARACTERItTICt (OR) REQUIREMENTt
OF A GOOD FUEL
1. It should be cheap and readily available.
2. It should be safe and economical for storage and
transport.
3. It should not undergo spontaneous combustion.
4. It should have higher calorific value.
5. It should have moderate ignition temperature.
6. The combustion should be easily controllable.
7. It should have low moisture content, because the
moisture content reduces the calorific value.
8. The products of combustion should not be harmful.
9. It should have low non-combustible matter or ash

content.
5.3
CLAttlFlCATlON OF FUELt
Fuels are classified based on occurance and physical
state as follows.
I. Classification based on occurrence
Fuels are classified into two types.
1. Primary fuels: It occurs in nature as such.
eg., coal, petroleum, natural gas.
2. Secondary fuels: It is derived from primary fuels.
e.g., coke, gasoline, coal gas.
II. Classification based on their physical state
Both primary and secondary fuels may be further sub-
classified into three types.
1. Solid fuels, eg., coal, coke.
2. Liquid fuels eg., gasoline, diesel.
3. Gaseous fuels eg., coal gas, natural gas
Thus, the classification is summarised as follows.
Fuels 5.3
l. tOLlD FUELt
5.4
COAL
Coal is an important primary solid fuel, that has been
formed as a result of alteration of vegetable matter under some
favourable conditions.
Coalification (or) Metamorphism
The process of conversion (or alteration) of vegetable
matter to anthracite (coal) is called coalification or
metamorphism of coal.
5.4.1 Classification of Coal

Coal is classified on the basis of its rank. The rank of
coal indicates its degree of maturity. Various types of coal are:
The progressive transformation of wood to anthracite results in

1. decrease in moisture content,
2. decrease in volatile content,
3. decrease in hydrogen, oxygen, nitrogen and
sulphur contents,
4. increase in carbon content,
5. increase in hardness,
6. increase in calorific value.
5.5
ANALYtlt OF COAL
In order to assess the quality of coal the following two

types of analysis are made.
5.5.1 Proximate Analysis

It is the analysis involving the determination of physical
constituents like percentage of
(i) Moisture content.
(ii) Volatile matter.
(iii) Ash content.
(iv) Fixed carbon in coal.
1. Moisture content
About 1 gm of powdered air-dried coal sample is taken
in a crusible, and is heated at 100  105C in an electric hot-air
oven for 1 hour. The loss in weight of the sample is found
out and the % of moisture is calculated as
% of moisture in coal  loss in weight of the coal  100

weight of airdried coal
2. Volatile matter
After the analysis of moisture content the crusible with
residual coal sample is covered with a lid, and is heated at
950  20C for 7 minutes in a muffle furnace. The loss in
weight of the sample is found out and the % of volatile matter
is calculated as
% of volatile matter in coal = loss in weight of the coal  100

3. Ash content
After the analysis of volatile matter, the crusible with
residual coal sample is heated without lid at
700  50C for 2 an hour in a muffle furnace. The loss in
1
weight of the sample is found out and the % of ash content

is calculated as
% of ash content in coal  weight of ash formed  100

Fuels 5.5
4. Fixed carbon
It is determined by subtracting the sum total of moisture,
volatile and ash contents from 100.
% of fixed carbon in coal
 100  % of moisture content  volatile matter  ash content
Significance (or) Importance of Proximate Analysis

1. Moisture content
High percentage of moisture is undesirable because
(i) it reduces the calorific value of coal,
(ii) moisture in coal consumes more heat in the form
of latent heat of evaporation and hence more heat
is to be supplied to the coal,
(iii) it increases the transport cost.
2. Volatile matter
High percentage of volatile matter is undesirable because
(ii) large proportion of fuel on heating will distill over
as vapour, which escapes out unburnt,
(iii) coal with high percentage of volatile matter burns
with a long flame with high smoke,
(iv) the coal containing high percentage of volatile
matter do not coke well.
3. Ash content
High percentage of ash content is undesirable because
(ii) ash causes hindrance to heat flow as well as
produces clinkers, which blocks the air supply
through the fuel,
(iii) it increases the transporting, handling and storage

costs,
(iv) it involves additional cost in ash disposal.
4. Fixed carbon
(i) High percentage of fixed carbon is desirable
because higher the percentage of fixed carbon in
a coal, greater is its calorific value,
(ii) the percentage of fixed carbon helps in designing
the furnace and the shape of the fire-box.
5.5.2 Ultimate Analysis

It is the analysis involving the determination of chemical
constituents like percentage of
(i) carbon and hydrogen contents
(ii) nitrogen content
(iii) sulphur content
(iv) ash content
(v) oxygen content
1. Carbon and Hydrogen contents
A known amount of the coal sample is burnt in a current
of O2 in a combustion apparatus. The carbon and hydrogen,
present in the coal sample, are converted into CO2 and H2O
respectively according to the following equations.
C  O2  CO2 
H2  1/2O2  H2O 

The liberated CO2 and H2O vapours are absorbed
respectively in KOH and anhydrous CaCl2 tubes of known
weights. The increase in weight of KOH tube is due to the
formation of CO2 while increase in weight of CaCl2 tube is
due to the formation of H2O. From the weights of
Fuels 5.7
CO2 and H2O formed, the % of carbon and hydrogen present

in the coal can be calculated as follows.
Calculations
2KOH  CO2  K2CO3  H2O
CaCl2  7H2O  CaCl2  7H2O
Let
m = weight of the coal sample taken.
x = increase in weight of KOH tube.
y = increase in weight of CaCl2 tube.
(a) % of carbon
C  O2  CO2
12 44
44 gms of CO2 contains, 12 gms of carbon
12  x
 x gms of CO2 contains  gms of carbon
4
12  x
m gms of coal contains gms of carbon
 44
12  x 100
100 gms of coal contains   gms of carbon
44 m
12  x 100
 % of carbon in coal  
44 m
(or)
Increase in weight
of KOH tube  12  100
% of carbon in coal 
weight of coal 44
sample taken
(b) % of hydrogen
H2  12O2  H2O

2 18
18 gms of water contains 2 gms of hydrogen
2y
 y gms of H2O contains  gms of hydrogen
1
2y
m gms of coal contains gms of hydrogen
 18
2  y 100
100 gms of coal contians   gms of hydrogen
18 m
2  y 100
 % of hydrogen in coal  
18 m
(or)
Increase in weight of CaCl2 tube  2  100
% of hydrogen 
weight of coal sample taken18
2. Nitrogen content
The determination of nitrogen content is carried out by
Kjeldahl’s method. A known amount of powdered coal sample
is heated with con. H2SO4 in presence of K2SO4 (catalyst) in
a long necked flask (called Kjeldahl’s flask). Nitrogen in the
coal is converted into ammonium sulphate and a clear solution
is obtained.
2N  3H2  H2SO4  NH42SO4
The clear solution is then heated with excess of NaOH and

the liberated ammonia is distilled over and is absorbed in a
known volume of standard N/10 HCl.
NH42SO4  2NaOH  2NH3  Na2SO4  2H2O
NH3  HCl  NH4Cl

Fuels 5.9
The volume of unused N/10 HCl is then determined by titrating

it against standard N/10 NaOH. Thus the amount of acid
neutralised by liberated ammonia from coal is determined.
From this the percentage of nitrogen is calculated as follows.
Calculation
Let, the weight of the coal sample taken  m gms
N
Initial volume of HCl V ml
10  1
N
Volume of unused HCl V ml
10  2
 The acid neutralised by ammonia  V1  V2 ml
we know that
1000 ml of 1 N HCl  1 mole of HCl  1 mole of NH3
[ HCl  NH3  NH4Cl]

1 mole 1 mole
 14 gms of N2 [or 17 gms of

NH3]
N 14  V1  V2  N/10
 V  V  ml of HCl  gms of N
1 2 2
10 1000  1N
m gms of coal sample contains
14  V1  V2  N/10

 1000  1 gms of N 2
100 gms of coal sample contains
14  V1  V2  N/10 100

 1000  1  m gms of N2
% of N2 in coal
14  Volume of acid consumed  Normality

 1000  weight of coal sample  100
(or) % of N2 in coal
1.4  Volume of acid consumed Normality weight of coal sample


3. Sulphur content
A known amount of coal sample is burnt completely in
a bomb calorimeter. During this process sulphur is converted
into sulphate, which is extracted with water. The extract is then
treated with BaCl2 solution so that sulphates are precipitated
as BaSO4. The precipitate is filtered, dried and weighed. From
the weight of BaSO4 obtained, the sulphur present in the coal
is calculated as follows.
Calculation
Let, the weight of coal sample  m gms
weight of BaSO4 obtained  x gms
S  2O 2

 SO BaCl2 
BaSO 
2 4  4
32 233
233 gms of BaSO4 contains 32 gms of sulphur

32  x
x gms of BaSO contains gms of S
 4  233
32  x
m gms of coal sample contains gms of S
 233
32  x 100
100 gms of coal sample contains   gms of S
233 m
Fuels 5.11
32  x
 % of sulphur in coal   100
233  m
32  weight
of BaSO4 obtained  100
(or) % of sulphur in coal 
233  weight
of coal sample
4. Ash content
Determination of ash content is carried out as in
proximate analysis
5. Oxygen content
The percentage of oxygen is calculated as follows.
% of oxygen in coal  100  % of C  H  N  S  ash
Significance (or) Importance of Ultimate Analysis

1. Carbon and hydrogen contents
(i) Higher the % of carbon and hydrogen, better is
the quality of coal and higher is its calorific value.
(ii) The % of carbon is helpful in the classification
of coal.
(iii) Higher % of carbon in coal reduces the size of
combustion chamber required.
2. Nitrogen content
(i) Nitrogen does not have any calorific value, and
its presence in coal is undesirable.
(ii) Good quality coal should have very little nitrogen
content.
3. Sulphur content
Though sulphur increases the calorific value, its presence
in coal is undesirable because
(i) The combustion products of sulphur, i.e.,
SO2 and SO3 are harmful and have corrosion
effects on equipments.
(ii) The coal containing sulphur is not suitable for the

preparation of metallurgical coke as it affects the
properties of the metal.
4. Oxygen content
(i) Lower the % of oxygen higher is its calorific
value.
(ii) As the oxygen content increases its moisture
holding capacity increases, and the calorific value
of the fuel is reduced.
Table 5.1 Differences between proximate analysis and
ultimate analysis
S.No. Proximate analysis Ultimate analysis

(i) It involves the It involves the
determinations of physical determination of chemical
constituents like moisture, constituents like carbon,
volatile, ash and fixed hydrogen, nitrogen and
carbon contents in coal. sulphur and oxygen
contents in coal.
(ii) It gives the approximate It gives the exact
composition of the main composition of the
constituents of coal. elementary constituents of
coal.
5.д
CARBONltATlON
When coal is heated strongly in the absence of air (called
destructive distillation) it is converted into lustrous, dense,
porous and coherent mass known as coke. This process of
converting coal into coke is known as Carbonisation.
Caking coals and coking coals
When coals are heated strongly, the mass becomes soft,
plastic and fuses to give a coherent mass. Such type of coals
are called Caking Coals.
Fuels 5.13
But if the mass so produced is hard, porous and strong

then the coals are called Coking Coals. Coking coals possess
lower volatile matter and are used for the manufacture of
metallurgical coke.
Thus all coking coals are caking coals but all caking
coals are not coking coals.
5.6.1 Types of carbonisation

Based on the temperature, used for carbonisation,
carbonisation is classified into two types.
1. Low Temperature carbonisation (LTC)
In LTC, carbonisation is carried out at 500  700C.
2. High Temperature carbonisation (HTC)
In HTC, carbonisation is carried out at 900  1300C.
Table 5.2 Differences between LTC and HTC
S.No. Property LTC HTC

1. Temperature 500  700C 900  1200C
2. Nature of the soft hard
coke formed
3. Yield 75 - 85% 65 - 75%
4. Percentage of 5 - 15% 1 - 3%
volatile matter
5. Yield of gaseous 130 - 150 300 - 390
products
3
(m /tonne)
6. Mechanical less strong
strength of coke
obtained
7. Calorific value Low High
of gaseous
products
S.No. Property LTC HTC

8. Use of the coke Domestic Metallurgical
obtained purposes purposes
5.7 METALLURGlCAL COHE

When bituminous coal is heated strongly in the absence
of air, the volatile matter escapes out and the mass becomes
hard, strong, porous and coherent which is called Metallurgical
Coke.
5.7.1 Requisites (or) characteristics of good

metallurgical coke
1. Purity
The moisture, ash, sulphur and phosphorus contents in
metallurgical coke should be low, because moisture and ash
reduce the calorific value. Sulphur and phosphorus may
contaminate the metal.
2. Porosity
Coke should be highly porous so that oxygen will have
intimate contact with carbon and combustion will be complete
and uniform.
3. Strength
The coke should have very high mechanical strength
inorder to withstand high pressure of the overlying material in
the furnace.
4. Calorific value
The calorific value of coke should be very high.
5. Combustibility
The coke should burn easily.
6. Reactivity
The reactivity of the coke should be low because low
reactive cokes produce high temperature on combustion.
Fuels 5.15
7. Cost
It should be cheap and readily available.
5.8 MANUFACTURE OF METALLURGlCAL COHE

There are so many types of ovens used for the
manufacture of metallurgical coke. But the important one is
Otto-Hoffman’s by product oven.
5.8.1 Otto-Hoffman’s by-product oven

Inorder to
1. increase the thermal efficiency of the carbonisation
process and,
2. recover the valuable by products (like coal gas,
ammonia, benzol oil, etc.) Otto-Hoffman developed
modern by product coke oven.
The oven consists of a number of silica chambers. Each
chamber is about 10  12 m long, 3  4 m height and
0.4  0.45 m wide. Each chamber is provided with a charging
hole at the top. It is also provided with a gas off take valve
and iron door at each end for discharging coke (Fig 5.1).
Coal is introduced into the silica chamber and the
chambers are closed. The chambers are heated to 1200C by
burning the preheated air and the producer gas mixture in the
interspaces between the chambers.
The air and gas are preheated by sending them through
2nd and 3rd hot regenerators. Hot flue gases produced during
combustion are allowed to pass through 1st and 4th
regenerators until the temperature has been raised to 1000C.
While 1st and 4th regenerators are being heated by hot flue
gases, the 2nd and 3rd regenerators are used for heating the
incoming air and gas mixture.
Fig. 5.1 Otto - Hoffmann’s by product oven

Fuels 5.17
For economical heating, the direction of inlet gases and

flue gases are changed frequently. The above system of
recycling the flue gases to produce heat energy is known as
regenerative system of heat economy. When the process is
complete, the coke is removed and quenched with water.
Time taken for complete carbonisation is about 12-20
hours. The yield of coke is about 70%.
The valuable by products like tar, ammonia, H2S and
benzol, etc. can be recovered from coal gas.
Recovery of by-products
1. Tar
The coal gases are first passed through a tower in which
liquor ammonia is sprayed. Tar and dust get dissolved and
collected in a tank below, which is heated by steam coils to
recover back the ammonia sprayed.
2. Ammonia
The gases are then passed through another tower in
which water is sprayed. Here ammonia gets converted to
NH4OH.
3. Naphthalene
The gases are again passed through a tower, in which
cooled water is sprayed. Here naphthalene gets condensed.
4. Benzene
The gases are passed through another tower, where
petroleum is sprayed. Here benzene gets condensed to liquid.
5. Hydrogen Sulphide
The remaining gases are then passed through a purifier
packed with moist Fe2O3. Here H2S is retained.
The final gas left out is pure coal gas, which is used
as a gaseous fuel.
Advantages of Otto Hoffman's process

1. Valuable by products like ammonia, coal gas,
naphthalene etc., are recovered.
2. The carbonisation time is less.
3. Heating is done externally by producer gas.
ll. LlQUlD FUELt

5.9
PETROLEUM
Petroleum or crude oil is naturally occuring liquid fuel.
It is a dark brown or black coloured viscous oil found deep
in earth’s crust. The oil is usually floating over a brine solution
and above the oil, natural gas is present. Crude oil is a mixture
of paraffinic, olefinic and aromatic hydrocarbons with small
amounts of organic compounds like N, O and S.
The average composition of crude oil is as follows
Constituents Percentage (%)

C 80 - 87
H 11 - 15
S 0.1 - 3.5
N + O 0.1 - 0.5
5.9.1 Classification of Petroleum

Petroleum is classified into three types.
1. Paraffinic-Base type crude oil
It contains saturated hydrocarbons from CH4 to
C35 H72 with a smaller amount of naphthenes and aromatics.
2. Naphthenic (or) Asphaltic Base type crude oil

It contains cycloparaffins or naphthenes with a smaller
amount of paraffins and aromatics.
Fuels 5.19
3. Mixed Base type crude oil

It contains both paraffinic and asphaltic hydrocarbons.
5.9.2 Refining of Petroleum or Crude Oil

The crude oil obtained from the earth is a mixture of
oil, water and unwanted impurities. After the removal of water
and other impurities, the crude oil is subjected to fractional
distillation. During fractional distillation, the crude oil is
separated into various fractions.
Thus, the process of removing impurities and separating
the crude oil into various fractions having different boiling
points is called Refining of Petroleum. The process of refining
involves the following steps.
Step
Step 1 Separation of water (Cottrell’s process)
The crude oil from oil well is an extremely stable
emulsion of oil and salt water. The crude oil is allowed to
flow between two highly charged electrodes, where colloidal
water droplets combine to form large drops, which is then
separated out from the oil.
Step
Step 2 Removal of harmful sulphur compounds
Sulphur compounds are removed by treating the crude
oil with copper oxide. The copper sulphide formed is separated
out by filtration.
Step
Step 3 Fractional distillation
The purified crude oil is then heated to about 400C in
an iron retort, where the oil gets vapourised. The hot vapours
are then passed into the bottom of a “fractionating column”
(Fig 5.2). The fractionating column is a tall cylindrical tower
containing a number of horizontal stainless steel trays at short
distances. Each tray is provided with small chimney covered
with a loose cap.
Fig 5.2 Fractional distillation of crude petroleum
When the vapours of the oil go up in the fractionating

column, they become cooler and get condensed at different
trays. The fractions having higher boiling points condense at
lower trays whereas the fractions having lower boiling points
condense at higher trays. The gasoline obtained by this
fractional distillation is called straight-run gasoline. Various
fractions obtained at different trays are given in table 5.3.
Table 5.3 Various fractions, compositions and their uses
S. Name of Boiling Range of

Uses
No the fraction Range C C-Atoms
1. Uncondensed Below 30 C1  C4 As a fuel
gases under the
name of LPG.
2. Petroleum 30-70 C5  C7 As a solvent.
ether
3. Gasoline or 40-120 C5  C9 Fuel for IC
petrol engines.
Fuels 5.21
S. Name of Boiling Range of

Uses
No the fraction Range C C-Atoms
4. Naphtha or 120-180 C9  C10 As a solvent
solvent spirit in paints and
in dry
cleaning.
5. Kerosene oil 180-250 C10  C16 Fuel for
stoves and jet
engines.
6. Diesel oil 250-320 C15  C18 Diesel engine
fuel.
7. Heavy oil 320-400 C17  C30 Fuel for ships
and for
production of
gasoline by
cracking.
Table 5.4 Refractionation of Heavy oils

Heavy oils on refractionation gives
S.No. Name of the Fraction Uses

1. Lubricating oils As lubricants.
2. Petroleum jelly or Used in medicines and
vaseline cosmetics.
3. Grease Used as lubricant.
4. Paraffin wax Used in candles, boot
polishes etc.
5. Pitch at above 400C Used for making roads,
water proof roofing etc.
5.10 tYNTHETlC PETROL

The gasoline, obtained from the fractional distillation of
crude petroleum oil, is called straight run petrol. As the use
of gasoline is increased, the amount of straight run gasoline
is not enough to meet the requirement of the present
community. Hence, we are in need of finding out a method
of synthesizing petrol.
5.10.1 Hydrogenation of coal (or) Manufacture

of synthetic petrol
Coal contains about 4.5% hydrogen compared to about
18% in petroleum. So, coal is a hydrogen deficient compound.
If coal is heated with hydrogen to high temperature under
high pressure, it is converted to gasoline. The preparation of
liquid fuels from solid coal is called hydrogenation of coal
(or) synthetic petrol.
An important method, available for the hydrogenation of
coal is Bergius process (or direct method).
Bergius process (or) (direct method)

In this process, (fig. 5.3) the finely powdered coal is
made into a paste with heavy oil and a catalyst powder (tin
or nickel oleate) is mixed with it. The paste is pumped along
with hydrogen gas into the converter, where the paste is heated
to 400  450C under a pressure of 200  250 atm.
During this process hydrogen combines with coal to form
saturated higher hydrocarbons, which undergo further
decomposition at higher temperature to yield mixture of lower
hydrocarbons. The mixture is led to a condenser, where the
crude oil is obtained.
The crude oil is then fractionated to yield
(i) Gasoline (ii) Middle oil (iii) Heavy oil.
Fuels 5.23
Fig. 5.3 Bergius process

The middle oil is further hydrogenated in vapour phase

to yield more gasoline. The heavy oil is recycled for making
paste with fresh coal dust. The yield of gasoline is about 60%
of the coal used.
5.11 HNOCHlNG
Definition
Knocking is a kind of explosion due to rapid pressure
rise occurring in an IC engine.
5.11.1 Causes of knocking in S.I (Spark

Ignition) Engine [Petrol engines]
In a petrol engine, a mixture of gasoline vapour and air
at 1:17 ratio is used as fuel.
This mixture is compressed and ignited by an electric
spark. The products of oxidation reaction (combustion)
increases the pressure and pushes the piston down the cylinder.
If the combustion proceeds in a regular way, there is no
problem in knocking. But in some cases, the rate of combustion
(oxidation) will not be uniform due to unwanted chemical
constituents of gasoline. The rate of ignition of the fuel
gradually increases and the final portion of the fuel-air mixture
gets ignited instantaneously producing an explosive sound
known as “Knocking”. Knocking property of the fuel reduces
the efficiency of engine. So a good gasoline should resist
knocking.
Chemical structure and knocking
The knocking tendency of fuel hydrocarbons mainly
depends on their chemical structures. The knocking tendency
decreases in the following order.
Straight chain paraffins  Branched chain paraffins 
Cycloparaffins  Olefins  Aromatics.
Thus olefins of the same carbon-chain length possess
better anti-knock properties than the corresponding paraffins.
Fuels 5.25
5.11.2 Improvement of antiknock characteristics

Prevention
The octane number of fuel can be prevented by
1. blending petrol of high octane number with petrol
of low octane number, so that the octane number of the latter
can be improved,
2. the addition of anti-knock agents like Tetra-Ethyl
Lead (TEL),
3. now a days aromatic phosphates are used as
antiknock agent because it avoids lead pollution.
5.12 OCTANE NUMBER (or) OCTANE RATlNG

Octane number is introduced to express the knocking
characteristics of petrol. It has been found that n-heptane
knocks very badly and hence, its anti-knock value has been
given zero. On the other hand, iso-octane gives very little
knocking and so, its anti-knock value has been given 100.
Definition
Thus, octane number is defined as ‘the percentage of
iso-octane present in a mixture of iso-octane and n-heptane.’
CH3
CH3
|
CH  CH2  C  CH3
CH3 |
CH3
Isooctane
Octane number  100
CH3  CH2  CH2  CH2  CH2  CH2  CH3

n  heptane
Octane number  0
5.13 LEADED PETROL (ANTl-HNOCH AGENT)

The anti-knock properties of a gasoline can be improved
by the addition of suitable additives. Tetra Ethyl Lead (TEL)
C2H54 Pb is an important additive added to petrol. Thus the
petrol containing tetra ethyl lead is called leaded petrol.
Mechanism of knocking
TEL reduces the knocking tendency of hydrocarbon.
Knocking follows a free radical mechanism, leading to a chain
growth which results in an explosion. If the chains are
terminated before their growth, knocking will cease. TEL
decomposes thermally to form ethyl free radicals which
combine with the growing free radicals of knocking process
and thus the chain growth is stopped.
Disadvantages of using TEL

When the leaded petrol is used as a fuel, the TEL is
converted to lead oxide and metallic lead. This lead deposits
on the spark plug and on cylinder walls which is harmful to
engine life. To avoid this, small amount of ethylene dibromide
is added along with TEL. This ethylene dibromide reacts with
Pb and PbO to give volatile lead bromide, which goes out
along with exhaust gases.
CH2 Br
Pb  |  PbBr2   CH2  CH2
CH2 Br
But this creates atmospheric pollution. So now a days

aromatic phosphates are used instead of TEL.
5.14
DlEtEL OlL
It is a fraction obtained between 250  320C during

fractional distillation of petroleum. It is a mixture of C15H32
Fuels 5.27
to C18 H38 hydrocarbons. Its calorific value is about

11000 kcal/kg. It is used as a very good diesel engine fuel.
Causes of knocking in CI engines (Diesel engines)
In a diesel engine, first air is alone compressed. This
compression raises the temperature of the cylinder to about
500C. Then the oil is sprayed into the heated air. This further
raises the temperature as well as pressure. The expanding gases
push the piston and power stroke begins.
The combustion of a fuel in a diesel engine is not
instantaneous and the time between injection of the fuel and
its ignition is called Ignition lag or Ignition delay. This delay
is due to the time taken for the vapourisation of oil droplets
and raising the temperature of vapour to its ignition
temperature. Long ignition lags lead to accumulation of more
vapours in the cylinder, which undergo explosion during
ignition. This is responsible for diesel knock. If the ignition
lag is short, diesel knock will not occur.
5.14.1 Diesel index

The quality of a diesel oil is indicated by diesel index
number using the following formula.
Diesel index  Specific gravity API  Aniline point in F 100

number

Aniline point and specific gravity is noted from API
(American Petroleum Institute) Scale.
5.15
CETANE NUMBER OR CETANE RATlNG
Cetane number is introduced to express the knocking
characteristics of diesel. Cetane (hexa decane) C16 H34 has a
very short ignition lag and hence its cetane number is taken
as 100. On the other hand -methyl naphthalene has a long
ignition lag and hence its cetane number is taken as zero.
Definition
Thus, cetane number is defined as "the percentage of
hexa decane present in a mixture of hexa decane and
-methyl naphthalene, which has the same ignition lag as
the fuel under test".
CH3  CH214  CH3

n  cetane hexadecane
cetane number  100
The cetane number decreases in the following order.

Straight chain paraffins  Cycloparaffins  Olefins
 Branched paraffins  Aromatics.
The cetane number of a diesel oil can be increased by
adding additives called dopes.
Important dopes: Ethyl nitrate, Iso-amyl nitrate.
5.15.1 Comparison of gasoline oil and diesel

oil
S.
Gasoline Oil Diesel Oil
No.
1. Low boiling fraction of High boiling fraction of
petroleum contains petroleum contains
C5  C9 hydrocarbons. C15  C18 hydrocarbons.
2. Fuel for SI engine. Fuel for CI engine.
3. Knocking tendency is Knocking tendency is
measured in octane rating. measured in cetane rating.
4. Knocking is due to Knocking is due to ignition
premature ignition. lag.
Fuels 5.29
S.
Gasoline Oil Diesel Oil
No.
5. Anti-knocking is improved Anti-knocking is improved
by the addition of TEL. by doping with ethyl
nitrate.
6. Its exhaust gases contain Its exhaust gases contain
higher amount of lesser amount of pollutants.
pollutants.
7. More consumption, lower Less consumption, higher
thermal efficiency. thermal efficiency.
5.1д POWER ALCOHOL

When ethyl alcohol is blended with petrol at
concentration of 5-10%, it is called power alcohol. In other
words absolute alcohol (100% ethyl alcohol) is also called
power alcohol. Ethyl alcohol is used in an internal combustion
(IC) engine. The addition of ethyl alcohol to petrol increases
its octane number. When ethyl alcohol is blended with diesel
it is called E diesel.
%anufacture
Manufacture of power alcohol involves the following two
steps
Step
Step I Manufacture of Ethyl alcohol
Ethyl alcohol can be synthesised by fermentation of
carbohydrates (sugar material). Fermentation of molasses,
which is the residue left after the crystallization of sugar, with
yeast generates alcohol. This fermentation yields only about
20% alcohol.
yeast
C6H12O6  2 C2H5OH  2 CO2
Glucose (sugar) Ethyl alcohol
Concentration of alcohol can be increased up to 97.6%

by fractional distillation yields rectified spirit. The
concentration of alcohol cannot be increased by distillation
above 97.6%, because it forms a constant boiling mixture with
water. The constant boiling mixture has a lower boiling point
than alcohol.
Step II
Step Conversion of ethyl alcohol into power alcohol
But, for the use in IC engines, 100% alcohol (absolute
alcohol) is prepared by removing last traces of water from
rectified spirit. It can be done by the following two methods.
(i) Alcohol, containing traces of water, is distilled

with benzene. When benzene passes over with a
portion of alcohol and water, it leaves behind
absolute (power) alcohol.
(ii) Alcohol is distilled in the presence of dehydrating
agent, which holds the water.
Finally absolute alcohol is mixed with petrol at
concentration of 5-10% to get power alcohols.
Properties
1. Power alcohol has a lower calorific values (7000
k.cal/kg).
2. It has high octane number (90).
3. Its anti-knocking properties are good.
4. It generates 10% more power than the gasoline
of same quantity.
5. Its compression ratio is also higher.
Uses
It is used, as a very good fuel, in motors.
Fuels 5.31
5.16.1 Advantages and Disadvantages of

power alcohol
Advantages
1. It is cheaper than petrol.
2. If any moisture is present, power alcohol absorbs it.
3. As ethyl alcohol contains oxygen atoms, complete
combustion occurs, so emission of CO, hydrocarbon,
particulates are reduced.
Disadvantages
1. As the calorific value of power alcohol (7000 cal/gm)
is lower than petrol (11,500 cal/gm), specially designed
engine is required.
2. Output power is reduced upto 35%.
3. Due to its high surface tension, atomization of power
alcohol is difficult, so it causes starting trouble.
4. It may under go oxidation to give acetic acid, which
corrodes engine part.
5. As it contains oxygen atoms, the amount of air required
for combustion is less therefore, the engine and
carburetor need to be modified.
5.17
BlO-DlEtEL
Vegetable oils comprise of 90-95% triglycerides with

small amount of diglycerides, free fatty acids, phospholipids,
etc., Triglycerides are esters of long chain fatty acids, like
stearic acid and palmitic acid. The viscosity of vegetable oils
are higher and their molecular weights are in the range of 600
to 900, which are about 3 times higher than those of the diesel
fuels.
Problems in using vegetable oils directly

1. As the viscosity of vegetable oils are high, atomization
is very poor and hence inefficient mixing of oil with air
leads to incomplete combustion.
2. Oxidation and thermal polymerization of vegetable oils
cause deposit formation.
3. Their high viscosity causes misfire and ignition delay.
4. Their high volatility and consequent high flash point lead
to more deposit formation.
5. The use of vegetable oils as direct fuel requires
modification of the conventional diesel engine design.
%anufacture : Trans-esterification (or) alcoholysis
The above problems are overcome by reducing the
viscosity of the vegetable oils by the process known as trans-
esterification or alcoholysis. Alcoholysis is nothing but
displacement of alcohol from an ester by another alcohol.
It involves treatment of vegetable oil (sunflower oil, palm
oil, soyabean oil, mustard oil, etc) with excess of methanol in
presence of catalyst to give mono ethyl esters of long chain
fatty acid and glycerine. It is allowed to stand for some time
and glycerine is separated.
Alcoholysis reaction is represented as
Methyl esters of fatty acids, thus formed, are called “Bio-

diesel”. Bio-diesel is defined as mono-alkyl esters of long
Fuels 5.33
chain fatty acids derived from vegetable oils or fats. It is a

pure fuel before blending with conventional diesel fuel. Bio-
diesel can be blended with petroleum diesel.
5.17.1 Advantages and Disadvantages of

Bio-diesel
Advantages
1. Bio-diesel is bio-degradable.
2. It is prepared from renewable resources.
3. The gaseous pollutants are lesser as compared to the
conventional diesel fuel.
4. Bio-diesel can be produced from different types of
vegetable oils.
5. Best engine performance and less smoke emission are
achieved.
Disadvantages
1. Bio-diesel gels in cold weather.
2. As bio-materials are hygroscopic, bio-diesel can absorb
the water from atmosphere.
3. Bio-diesel decreases the horse power of the engine.
4. Bio-diesel degrades and soften the rubber and plastics,
that are used in some old cars.
5. Bio-diesel has about 10% higher nitrogen-oxide (NOx)
emission than conventional petroleum.
5.18 ANNA UNlVERtlTY QUEtTlONt
1. Explain the proximate analysis of coal.

(TCY A.U. July 2009)(June 05, Dec 05, Dec 06)
2. What is proximate analysis? Write its significance.
(Chen A.U. May 2009)
3. Explain the ultimate analysis of coal.

(TCY A.U. Dec 2009) (A.U. Dec 2009, June 2014,
May 2017)
4. What is the importance of proximate analysis?
(AU Dec 2015)
5. What is meant by Proximate analysis? (AU June 2016)
6. What is meant by proximate analysis of coal? What are
the quantities estimated in this analysis and their
significance? (AU May 2015)
7. What is metallurgical coke. How does it differs from coal.
Describe the process of its manufacture.
(A.U. June 2006)
8. Why is coke preferred to coal in metallurgical process.
(June 06)
9. How is metallurgical coke manufactured by Otto-Hoffman
oven. (TCY A.U. Dec 2009)
(Coim A.U. July 2009)(Dec 2009)(TNV A.U. May 2009)
(May 2008, Dec 2012)
10. What are the characteristics of good metallurgical coke?
(A.U May 2007) (TCY A.U. June, Dec 2009)
11. What is meant by knocking in petrol engines? How is
knocking prevented? (AU May 2015)
12. What is metallurgical coke? How is it superior than coal?
Describe any one method of manufacturing metallurgical
coke. (AU May 2015)
13. Describe the Otto Hoffman process for the manufacture
of metallurgical coke. (AU Dec 2015)
14. Describe the Otto Hoffman’s process for preparing coal.
(A.U Dec 2014)
15. Explain the petroleum refinary process in detail with neat
sketches. What are the properties and applications of its
various fractions. (AU June 2013)
Fuels 5.35
16. Give a brief account of refining of petroleum and the

products obtained and their uses. [Nov. 2003]
(TCY A.U. Dec 2009)
(TNV A.U May 2009)(Chen A.U. May 2009)
17. Describe the different methods by which synthetic petrol
can be obtained. (A.U Dec. 05)
(A.U Dec 2006)
18. What is power alcohol? Explain its manufacture,
properties of power alcohol.
19. What is bio-diesel? Explain trans-esterification and
advantages of bio-diesel. (A.U. May 2017)
20. Describe the manufacture of petrol by Bergius process.
(AU June 2014)
21. Write note on:
1. Power alcohol
2. Bio-diesel (A.U Dec 2014)
22. With neat diagram, explain the manufacturing of
metallurgical coke by Otto-Hoffman method.
(AU June 2016)
Unit - IV Chapter 6
Combustion of Fuels
д.1
INTRODUCTION
Combustion is a process of rapid exothermic oxidation,

in which a fuel burns in the presence of oxygen with the
evolution of heat and light.
Aim of combustion is to get the maximum amount of
heat from a combustible substance in the shortest time. Most
of the combustible substances are enriched with carbon and
hydrogen. During combustion they undergo thermal
decomposition to give simpler products, which are oxidised to
CO2, H2O, etc.,
C  O2  CO2 ; Exother
mic. H2  12O2  H2O ;
Exothermic.
Since the above reactions are exothermic, large quantity
of heat is given out.
д.2
CALORIFIC VALUE
The efficiency of a fuel can be understood by its calorific

value. The calorific value of a fuel is defined as “the total
amount of heat liberated, when a unit mass of fuel is burnt
completely.”
Units of calorific values

The quantity of heat can be measured by the following
units:
1. Calorie.
2. Kilocalorie.
3. British Thermal Unit (B.T.U).
4. Centigrade Heat Unit (C.H.U).
Calorie: It is defined as the amount of heat required
to raise the temperature of 1 gram of water through 1C (15
to 16C).
д.3
HIGHER AND LOWER CALORIFIC VALUEt
6.3.1 Higher (or) Gross calorific value (GCV)

It is defined as the total amount of heat produced, when
a unit quantity of the fuel is completely burnt and the
products of combustion are cooled to room temperature.
When a fuel containing hydrogen is burnt, the hydrogen
is converted into steam. If the combustion products are cooled
to room temperature, the steam gets condensed into water and
latent heat is evolved. Thus, the latent heat of condensation
of steam is also included in gross calorific value.
6.3.2 Lower (or) Net Calorific Value (NCV)

It is defined as the net heat produced, when a unit
quantity of the fuel is completely burnt and the products of
combustion are allowed to escape.
 NCV  GCV – Latent heat of condensation
of water vapour produced.
 GCV – Mass of hydrogen  9  Latent
heat of condensation of water vapour.
1 part by weight of H2 produces 9 parts by weight of
H2O as follows. The latent heat of steam is 587 cal/gm.
Combustion of Fuels 6.3
H2  O  H2O
2 gms 16 gms 18 gms
1 8 9
Thus,
9
NCV GCV H 587
 100 
 GCV  0.09H  587
where
H  % of H2 in the fuel.
д.4
THEORETICAL CALCULATION OF
CALORIFIC VALUEt
Dulong’s formula
Dulong’s formula for the theoretical calculation of
calorific value is
GCV (or) HCV
1  8080 C  34500  H  O   2240 S  kcal/kg
 100  8  
   
where C,H,O and S represent the % of the corresponding

elements in the fuel.
It is based on the assumption that the calorific values
of C, H and S are found to be 8080, 34500 and 2240 kcal,
when 1 kg of the fuel is burnt completely. However, all the
oxygen in the fuel is assumed to be present in combination
with hydrogen in the ratio H : O as 1:8 by weight. So the
O
surplus hydrogen available for combustion is H
8
 N C V (or) L C V   HCV  100H

9 587  kcal/kg

 
6.4.1 Problems based on calorific value

Problem 1
Calculate the gross and net calorific values of coal

having the following compositions, carbon = 85%, hydrogen
= 8%, sulphur = 1%, nitrogen = 2%, ash = 4%, latent heat
of steam  587 cal/gm. (A.U. June 2007)
Solution
Soluti
(i) 1Gross calorific value (GCV) %O

 
 8080  % C  34500 % H 
 
100  8
  
2240  % S  kcal/kg
 
1   0 
 8080  85  34500 8   2240  1 kcal/kg
  
100   8 

1
  6,86,800  2,76,000  2240  kcal/kg
1
1
9,65,040 kcal/kg
100 
 9,650.4 kcal/kg.
(ii) Net Calorific Value (NCV)

9
GCV H 587 kcal/kg
 100 
9
 9650.4   8  587 kcal/kg
1
 9650.4  422.64
 9227.76 kcal/kg.
Problem 2
Calculate the gross and net calorific values of a coal

sample having the following composition C  80% ;
H  7% ; O  3% ; S  3.5% ; N  2.5% and ash 4.4%.
Solution
Soluti
(i) 1 GCV
  %O 
 8080  % C  34500 %H 
 
100 8 
 
2240  % S  k. cal/kg

1   3  
 8080  80  34500 7   2240  3.5 k cal/kg
  
100  8 

 [8080  0.80  3457  0.375  22.40  3.5] k cal/kg
 [6464  2285.6  78.4] k. cal/kg
 8828.0 k. cal/kg .
(ii) NCV
 GCV  [0.09H  587] k. cal/kg
 8828  [0.09  7  587] k. cal/kg
 [8828  369.8] k. cal/kg
 8458.2 k. cal/kg .
Problem 3
On analysis, a coal sample has the following

composition by weight; C = 85%; O = 3%; S = 0.5% and
ash = 3%. Net calorific value was found to be 8,400 kcal/kg.
Calculate the percentage of hydrogen and gross calorific
value of coal.
Solution
Soluti
GCV   NCV  0.09H  587  kcal/kg
  8,400  0.09H  587  kcal/kg
  8,400  52.8 H  kcal/kg............................................ (1)

1   %O 
GCV  8080  % C  34,500 %H 
 
100  8
  
2240  % S  kcal/kg
  
1   3
 8080  85  34,500 H   2240  0.5 kcal/kg
  
100   8  

1
  686800  34500H  12937.5  1120  kcal/kg
1
  6,868  345H  129.4  11.2  kcal/kg
 6,749.8  345 H kcal/kg............................................... (2)

Equation (2) is substituted in equation (1)
6749.8  345 H  8400  52.8 H
345 H  52.8 H  8400  6749.8
292.2 H  1650.2
1650.2
H  292.2
H  5.647
% of H  5.647............................................... (3)
Equation (3) is substituted in equation (1)
 GCV  8400  52.8  5.647
 8698.16 kcal/kg
Problem 4
Calculate the net and gross calorific value of a coal

sample having following composition:
C  82%, H  8%, O  5%, N  1.4% and ash  3.6%.
(APJAKTU, Jan. 2016)
Solution
(i) GCV
1   %O  
 8080  % C  34500 %H  2240  % S kcal/kg
   
100  8  
1   5 
 8080  82  34500 8   0 kcal/kg
100  
8
 
  
1
[662560 254437.5]
100 
 9169.98 kcal/kg
(ii) NCV
9
GCV H 587 kcal/kg
 100 
9
 9169.98   8  587
1
 8747.34 kcal/kg
Problem 5
Calculate the gross and net calorific value of a fuel

having following composition 82% C, 8% H, 5% O, 2.5% S,
1.4% N and 2.1% ash. (APJAKTU, July 2016)
Solution
We know that,
GCV  1/100 [8080C  34500 H  O/8  2240S] kcal/kg
 1/100 [8080  82  34500 8  5/8  2240  2.5]

 9225.97 kcal/kg
NCV  GCV  0.09H  587 kcal/kg
NCV  9225.97  0.09  8  587  8803.3 kcal/kg
Problem 6
A coal sample has 80% of carbon, 9% of hydrogen,

6% of sulphur and remaining is ash. Calculate the HCV and
LCV of the coal sample. (JNTU(H), June 2017)
Solution
(i) Higher Calorific Value (HCV)
1   %O
 8080  % C  34500 % H 
 
100  8 
 
2240  % S  kcal/kg

1   0  
 8080  80  34500 9   2240  6 kcal/kg
100    
  8 
1
  64,6400  3,10,500  13440  kcal/kg
1
1
9,70,340 kcal/kg
100 
 9,703.4 kcal/kg.
(ii) Lower Calorific Value (LCV)
9
GCV H 587 kcal/kg
 100 
9
 9703.4   9  587 kcal/kg
1
 9703.4  475.47
 9227.93 kcal/kg.
д.5
IGNITION TEMPERATURE (IT)
It is defined as, “the lowest temperature to which the
fuel must be heated, so that it starts burning smoothly”.
Ignition temperature of coal is about 300C. In the case
of liquid fuels, the ignition temperature is called the flash point,
which ranges from 200  450C. For gaseous fuels, the ignition
temperature is in the order of 800C.
6.5.1 Spontaneous Ignition Temperature (SIT)

It is defined as “the minimum temperature at which
the fuel catches fire (ignites) spontaneously without external
heating”.
If the ignition temperature of a fuel is low it can catch
fire very quickly. On the other hand if the ignition temperature
is high it is difficult to ignite the fuel. If the heat evolved in
a system is unable to escape, temperature of the system goes
on increasing and when SIT is reached, the system burns on
its own.
д.д
EXPLOtIVE RANGE (or) LIMITt OF
INFLAMMABILITY
All gaseous fuels have two limits called upper limit and
lower limit. These limits represents percentage by volume of
fuel present in fuel-air mixture.
1. Lower limit represents the smallest proportion of
combustible gas (fuel).
2. Upper limit represents the largest proportion of
combustible gas.
The range covered by these limits is termed as explosive
range of the fuels. For continuous burning the amount of fuel
present in the fuel-air mixture should not go below the lower
limit or above the upper limit.
Example
The explosive range of petrol is 2-4.5. This means that
when the concentration of petrol vapour in petrol-air mixture
is between 2 and 4.5 by volume, the mixture will burn on
ignition. When the concentration of petrol vapour in petrol-air
mixture is below 2% (lower limit) or above 4.5% (upper limit)
by volume, the mixture will not burn on ignition. Some of the
limits of inflammability are given in the following table. 6.1.
Table 6.1: The limits of inflammability of hydrogen,

acetylene, natural gas
Lower limit of Upper limit of
Gas
inflammability inflammability
Hydrogen 4 74
Acetylene 3 80
Natural gas 5 14
Thus, explosive range (or) explosive limit is the limiting
composition of a gas-air mixture beyond which the mixture
will not ignite and continue to burn is called explosive range
(or) explosive limit.
д.7
FLUE GAt ANALYtIt (ORtAT METHOD)
The mixture of gases (like CO2, O2, CO, etc) coming out
from the combustion chamber is called flue gases. The analysis
of a flue gas would give an idea about the complete or
incomplete combustion process. The analysis of flue gases is
carried out by using orsat’s apparatus.
Description of orsat’s apparatus
It consists of a horizontal tube. At one end of this tube, U-
tube containing fused CaCl2 is connected through 3-way stop
cock. The other end of this tube is connected with a graduated
burette. The burette is surrounded by a water-jacket to keep
the temperature of gas constant. The lower end of the burette
is connected to a water reservoir by means of a rubber tube.

The level of water in the burette can be raised or lowered by
raising or lowering the reservoir (fig 6.1)
The horizontal tube is also connected with three different
absorption bulbs 1, 2, and 3 for absorbing CO2, O2 and CO.
Bulb Reagent Function

1 Potassium hydroxide Absorbs only CO2
solution.
2 Alkaline pyrogallol Absorbs CO2 and O2
solution.
Ammoniacal cuprous Absorbs CO2, O2 and CO
3
chloride solution.
Working
The 3-way stop-cock is opened to the atmospher e and
the reser voir is raised, till the bur ette is completely filled with
water and air is excluded from the burette. The 3-way stop-
cock is now connected to the flue gas supply and the flue gas is
sucked into the bur ette and the volume of flue gas is adjused to
100 cc by raising and lower ing the reser voir . Then the 3-way
stop cock is closed.
(a) Absorption of CO2

The stopper of the absorption bulb-1, containing KOH
solution, is opened and all the gas is passed into the bulb-1
by raising the level of water in the burette. The gas enters
into the bulb-1, wher e CO2 pr esent in the flue gas is absor bed
by KOH.
The gas is again sent to the burette. This process is

repeated sever al times to ensur e complete absor ption of CO 2.
The decr ease in volume of the flue gas in the bur ette indicates
the volume of CO2 in 100 cc of the flue gas.
Fig. 6.1 Orsat’s apparatus

(b) Absorption of O2
Stop-cock of bulb-1 is closed and stop cock of bulb-2
is opened. The gas is again sent into the absorption bulb-2,
where O2 present in the flue gas is absorbed by alkaline
pyrogallol. The decrease in volume of the flue gas in the
burette indicates the volume of O2.
(c) Absorption of CO
Now stop-cock of bulb-2 is closed and stop-cock of bulb-
3 is opened. The remaining gas is sent into the absorption bulb-3,
where CO present in the flue gas is absorbed by ammoniacal
cuprous chloride. The decrease in volume of the flue gas in
the burette indicates the volume of CO. The remaining gas in
the burette after the absorption of CO2, O2 & CO is taken
as nitrogen.
Significance (or) uses of flue gas analysis

1. Flue gas analysis gives an idea about the complete
or incomplete combustion process.
2. If the flue gases contain considerable amount of
CO, it indicates that incomplete combustion is
occuring and it also indicates that the short supply
of O2.
3. If the flue gases contain considerable amount of
O2, it indicates that complete combustion is
occuring and also it indicates that the excess of
O2 is supplied.
Precautions
1. Care must be taken in such a way that, the reagents in
the absorption bulb 1, 2 and 3 should be brought to the
etched marked level one by one by raising and lowering
reservoir bottle.
2. All the air from the reservoir bottle is expelled to
atmosphere by lifting the reservoir bottle.
3. It is essential that CO2, O2 and CO are absorbed in that

order only.
4. As the CO content in flue gas is very small, it should
be measured quite carefully.
д.8
CARBON EMIttION
Definition
It is defined as the release of carbon into the
atmosphere. Since green house gas emissions are often
calculated as carbon dioxide equivalents, they are often
referred to as “carbon emissions”.
Source
Burning of fossil fuels like coal, oil and natural gas are
the primary sources due to the following activates.
(i) Transportation
(ii) Electricity production
(iii) Industry
(iv) Agriculture
(v) Land use and forestry
(vi) Commercial and residential
6.8.1 Reduction of carbon emission

Carbon emission can be reduced by reducing green house
gas emission. It can be done by the following ways.
1. In industry, green house gases can be reduced by many
ways.
(i) Including energy efficiency
(ii) Fuel switching
(iii) Combined heat and power
(iv) Use of renewable energy
2. Avoid of using HFC’s in refrigeration, air conditioning
and foam blowing.
3. In oil and gas production, the leakage of green house

gases can be controlled by reducing pressure from
pipelines.
д.9
CARBON FOOTPRINT
Definition
It is the total amount of green house gases (including
CO 2 and CH 4 that are generated (emitted) by our direct and
indirect activities.
Individual carbon footprint
It is the sum total of their direct and indirect carbon
emissions over the course of a year.
i.e., Smaller your carbon
: better for the future
footprint
Bigger your carbon
: Have bigger negative
footprint
impact in environment
The average carbon footprint for a person in united state

is 16 tons. Globally, the average is closer to 4 tones. To avoid
2C rise in global temperatures, the average global carbon
footprint per year needs to drop under 2 tons by 2050.
Fig. 6.2 Carbon Footprint

6.9.1 Sources of carbon footprint

(i) Climate change.
(ii) Natural process like volcanos.
(iii) Green house gases emitted from human activities.
(iv) Pollution released by human beings doing human things.
(v) Transportation accounted for about 28% of total country.
(vi) Electricity generation accounted for about 28%
(vii) Industrial activities 22%
(viii) Heating and cooling in homes and businesses contribute
11%
6.9.2 How to lower carbon footprint (or) 15

ways to reduce your carbon footprint
Lowering individual carbon footprint from 16 tons to 2
tons does not happen over night. But, by making small changes
in our action we can reduce carbon footprint.
Once you understand where your emission comes from,
you can take steps to reduce your impact.
1. Calculate your carbon footprint.
2. Drive less.
3. Switch to an electric (or) hybrid car.
4. Travel smart.
5. Switch to renewable energy.
6. Consider solar panels.
7. Make your home more efficient.
8. Turn your thermostat just 2 degrees cooler in winter and
2 degrees warmer in summer.
9. Get energy efficient appliances.
10. Unplug electrical devices when not in use.
11. Buy locally - sourced food.
12. Start a home garden.

13. Eat less meat.
14. Don’t waste water.
15. Reduce, reuse and recycle.
д.10
ANNA UNIVERtITY QUEtTIONt
1. Explain: Gross and Net calorific value. (A.U. Dec 06)
2. Define gross and net calorific values of a fuel. How are
they related. (A.U. June 2006)
3. Calculate the gross and net calorific value of coal having
the following compositions.
Carbon - 85%, hydrogen - 8%, sulphur - 1%,
nitrogen - 2% and ash - 4% (A.U. May 2007)
4. How the flue gas analysis is carried out? Explain with
neat diagram. Mention the significane of such analysis.
(TCY A.U. July, Dec 2009)
(TNV & Chen A.U. May 2009)(A.U Dec 2012)
5. With a neat diagram explain the analysis of flue gas by
Orsat apparatus and mention the precautions to be
followed during the analysis. (Chen A.U. Dec 2009)
6. Explain the flue gas analysis by orsat method with
suitable diagram. (A.U. May 2017)
7. Write detailed notes on
(i) Carbon emission
(ii) Carbon footprint
Unit - V Chapter 7
Energy Sources
7.1 INTRODUCTION
For our energy requirement, we mainly depend on the
conventional sources of energy like coal, petroleum, natural
gas, etc., These sources are limited in quantity and can be
exhausted in near future. This is because of their continuous
and rapid use.
To overcome this energy crises, the scientists have
accelerated the search and use of non-conventional (renewable)
sources of energy like wind energy, solar energy, nuclear
energy, etc.
7.2
tTABILITY OF NUCLEUt
7.2.1 Mass defect

It has been found that the actual mass of an isotope is
always less than the sum of the masses of the protons, neutrons
and electron from which it is formed.
Definition
The difference between the calculated and experimental
masses of nucleus is called mass defect. It is denoted by
 m.
 Total mass of 
 

 m  the protons, neutrons  Experimental mass 
 o f the nucl e us
 
   
and electron 

(or)
It is defined as the loss of mass during the formation
of the nucleus of the isotope.
Calculation of mass defect

Consider an isotope,
let its atomic number  Z
Mass number  A
If its atom contains
Z protons, Z electrons and (A-Z) neutrons
Let,
mp  mass of proton
mn  mass of neutron
me  mass of an electron
 Calculated mass of isotope
M   Zm  Zm  A  Zm
p e n
 Zm  A  Z mn
H
(where, mp  me  mass of H atom 
mH Let,
M  Actual experimental mass of the nucleus,
then, the mass defect  m  M   M
(or)
 m  Zm  A  Z mn  M
H
Energy Sources 7.3
Problems on ass defect

40
1. Calculate the mass defect of 20Ca , which has atomic
mass of 39.975 amu. The mass of proton is 1.0078 amu
and the mass of neutron is 1.0086 amu.
Solution
Soluti
Mass defect  m of Ca-atom  Zmp  A  Z mn  M
Note
Not Calcium atom is composed of 20 protons and 20
neutrons.
Given: Z  20; A  Z  20 ; mH  1.0078 amu ;
mn  1.0086 amu; M  39.975 amu;
 m   20 mp  20 mn  M . .
 [ . me  Neglected]
 
 [20  1.0078  20  1.0086  39.975]
 [20.156  20.172  39.975]
 40.328  39.975
 0.353 amu
4
2. Calculate the mass defect of 2He , if its experimentally
determined mass is 4.00390 amu. The masses of a proton,
an electron and a neutron are 1.007825, 0.0005852 and
1.008668 amu respectively.
Solution
Soluti
Mass defect m of He-atom  [2mp  2me  2mn  M]
4
Note 2He atom is composed of 2 protons, 2 electrons and
Not
2 neutrons.
Given: mp  1.007825 amu; me  0.0005852 amu ;
mn  1.008668 amu
  m  [2  1.007825  2  0.0005852  2  1.008688
 4.00390] amu
 [4.0341964  4.00390] amu
 0.0302964 amu
3. Mass of hydrogen and neutron are 1.008 amu and
1.0072 amu respectively. If experimentally determined
23
mass of sodium atom 11Na  is 23.0092 amu. Calculate
mass defect.
Solution
Soluti
Mass defect of Na-atom
 m   11  mH  12 mn  M 
 
23
Note 11Na
Not is made up of 11-H-atom and 12-neutrons.
Given: mp or mH  1.008 amu; mn  1.0072 amu ;
M  23.0092
 m   11  1.008  12  1.0072  23.0092  amu
 0.1652 amu
4. Calculate the mass defect of -particles. Given that the

mass of proton  1.00758 amu, mass of neutron
 1.00897 amu and mass of helium nucleus
 4.00820 amu.
Solution
Soluti
Mass defect  m of -particle  [2mp  2mn  M]
Note
Not An -particle is composed of 2 protons and 2 neutrons
Given: mp  1.00758 amu ; mn  1.00897 amu ;
Energy Sources 7.5
M  4.00820 amu
 m   2  1.00758  2  1.00897  4.00820  amu
 0.02490 amu
5. Calculate the mass defect of the following fission
reaction.
235 1 95 139 1
92U  0n  36Kr  57Ba  2 0n
235
Given that atomic mass of U  235.124 amu;
95 139 1
Kr  94.945 amu ; Ba  138.954 amu ; 0n  1.0099 amu
Solution
Soluti
  m  Atomic mass of [U  n  Kr  Ba  2n]
 [235.124  1.0099  94.945  138.954  2  1.0099]
 236.1339  233.899  2.0198
 236.1339  235.9188
 0.2151 amu
7.2.2 Binding energy

Loss of mass during the formation of nucleus from
nucleons gets converted into energy. This energy is known as
binding energy. Binding energy is responsible for the stability
of the nucleus. The greater the energy liberated the greater is
the stability of the nucleus. Hence, binding energy (BE) is the
energy equivalent of mass defect.
Definition
Binding energy is defined as the energy released when
a given number of protons and neutrons coalesee to form
nucleus.
(or)
It is the energy required to disrupt the nucleus into its

constituent protons and neutrons.
Binding Energy Vs Nuclear Stability
A plot of Binding energy per nucleon against mass
number for different elements gives the following graph:
Fig. 7.1 A plot of binding energy vs mass number
The graph shows that BE and hence the stability of

nucleus increases upto a mass number of 65 and decreases
thereafter. There are some subsidiary peaks in the plot at
4 12 16
2He , 6C and 8O indicating stable nuclear configurations.
This is probably due to the presence of equal number of
protons and neutrons.
Calculation of binding energy

Binding energy can be calculated from the mass defect
using the relation.
2
Emc
2
E  [ZmH  A  Z mn  M]  c
where, E – Binding energy of the nucleus

m – Mass defect
c – 8
Velocity of light 3  10 m  s
Energy Sources 7.7
7.3
NUCLEAR ENERGY
The enormous amount of energy released during the
235 239
nuclear chain reaction of heavy isotope like U (or) Pu
is called nuclear energy.
7.3.1 Definition
The energy released by the nuclear fission (or) nuclear
fusion, is called nuclear energy.
Illustration
235 239
The fission of U or Pu occurs instantaneously,
producing enormous amount of energy in the form of heat and
radiation.
Fig. 7.2 Nuclear energy
7.3.2 Cause of the release of energy

The enormous amount of energy released during the
nuclear fission is due to the loss in some mass, when the
reaction takes place. It has been observed that during nuclear
fission, the sum of the masses of the products formed is
slightly less than the sum of masses of target species and
bombarding neutron. The loss in mass gets converted into
energy according to Einstein equation
2
E  mc
 m  M  M
where
c  velocity; m  loss in mass and E  energy.
M  Mass of radioactive substance before emitting radiation
M  Mass of radioactive substance after emitting radiation
7.3.3 Hazards of using nuclear energy

The radiation is harmful to the living organisms. The
long and constant exposure of living organisms to these
radiations causes the following disease.
(i) The nuclear radiation can damage the structure of cells
in the human body.
(ii) It causes diseases like cancer and blindness.
(iii) It causes genetic disorder in a human body.
(iv) It causes sterility in young generation.
7.3.4 Applications of nuclear energy

1. Electricity generation
Nuclear energy is an environmental-friendly energy
resource for power generation.
2. Source of pure water
The water discharged from the nuclear reactors is free
from radiation and is clean enough to conserve animals and
aquatic animals.
3. Health care
Radioactive isotopes (nuclear energy) find use in
treatment of cancer by radiotherapy. It is also used for
sterilization to destroy micro-organism.
Energy Sources 7.9
4. Agriculture
It is used to control of agricultural pests. Nuclear
radiation delays ripening of fruits.
7.4 NUCLEAR REACTOR (OR) PILE

Reactors, which are designed to carry out nuclear
reactions for generation of heat, electricity and radioactive
isotopes are called nuclear reactors.
Definition
The arrangement or equipment used to carry out fission
reaction under controlled conditions is called a nuclear
reactor.
7.4.1 Light Water Nuclear-Power Plant
Definition
Light-water nuclear-power plant is the one, in which
235
U fuel rods are submerged in water. Here the water acts
as coolant and moderator.
I. Components of a Light water nuclear power plant

The main components of the light water nuclear power
plant are
1.
Fuel rods
The fissionable materials used in the nuclear reactor is
235
enriched U . The enriched fuel is used in the reactor in the
form of rods or strips.
Exampl
U235; Pu239
Function: It produces heat energy and neutrons, that starts
nuclear chain reaction.
2.
Control rods
To control the fission reaction (rate), movable rods, made
of cadmium (or) boron, are suspended between fuel rods. These
rods can be lowered or raised and control the fission reaction
by absorbing excess neutrons.
If the rods are deeply inserted inside the reactor, they
will absorb more neutrons and the reaction becomes very slow.
On the other hand, if the rods are pushed outwards, they will
absorb less neutrons and the reaction will be very fast.
113 1 114
Cd  n  Cd  ray
43 0 43
10 1 11
B  n   B  ray
5 0 5
Exampl
Cd113 ; B10
Function: It controls the nuclear chain-reaction and avoids
the damage of the reactors.
3.
Moderators
The substances used to slow down the neutrons are called
moderators.
Fig. 7.3 Functions of a moderator
When the fast-moving neutrons collide with moderator,

they lose energy and gets slow down.
Energy Sources 7.11
Exampl
Ordinary water, heavy water, graphite, beryllium.
Function: The kinetic energy of fast moving neutrons

(1 meV) is reduced to slow neutrons (0.25 eV).
4.
Coolants
In order to absorb the heat produced during fission, a
liquid called coolant is circulated in the reactor core. It enters
the base of the reactor and leaves at the top. The heat carried
by out-going liquid is used to produce steam.
Exampl
Water (act as moderator & coolant), heavy water, liquid
metal (Na or K), air (CO2).
Function: It cools the fuel core.
5.
Pressure vessel
It encloses the core and also provides the entrance and
exit passages for coolant.
2
Function: It withstand the pressure as high as 200 kg/cm .
6.
Protective shield
The nuclear reactor is enclosed in a thick massive
concrete shield (more than 10 meters thick).
Function: The environment and operating personnels are

protected from destruction in case of leakage of radiation.
7.
Turbine
The steam generated in the heat exchanger is used to
operate a steam turbine, which drives a generator to produce
electricity.
Fig. 7.4 Light water nuclear power plant
II. Working
The fission reaction is controlled by inserting or
10
removing the control rods of B automatically from the spaces
in between the fuel rods. The heat emitted by fission of
235
U in the fuel core is absorbed by the coolant (light water).
The heated coolant (water at 300C) then goes to the heat
exchanger containing sea water. The coolant here, transfers heat
to sea water, which is converted into steam. The steam then
drives the turbines, generating electricity.
Pollution
Though nuclear power plants are very important for
production of electricity, they will cause a serious danger to
environments.
Problem on disposal of reactor waste

Disposal of reactor waste is another important problem
139 92
because the fission products viz., Ba & Kr are themselves
radioactive. They emit dangerous radiation for several hundred
years. So the waste is packed in concrete barrels, which are
Energy Sources 7.13
buried deep in the sea. Salt water will not allow the radiation
to come out.
7.5 BREEDER REACTOR
Breeder reactor is the one which converts

non-fissionable material U238, Th232 into fissionable
235 239
material U , Pu . Thus the reactor produces or breeds
more fissionable material than it consumes.
Illustration
1 239 
U238  n   Pu  2e
92 0 94
Nonfissionable Fissionable
239 1 1
Pu  n  Fission products  3n
94 0 0
In breeder reactor, of the three neutrons emitted in the

235
fission of U , only one is used in propagating the fission
235
chain with U . The other two are allowed to react with
238 239
U . Thus, two fissionable atoms of Pu are produced for
235
each atom of U consumed. Therefore, the breeder reactor
239
produces more fissionable material than it uses. Hence Pu
Fig. 7.5 Principle of breeder reactor

is a man made nuclear fuel and is known as secondary nuclear

fuel.
Significance
238
1. The non-fissionable nucleides, such as U &
232
Th , called fertile nucleides, are converted into
fissile nucleides.
235 239
2. The fissionable nucleides such as U & Pu
are called fissile nucleides.
3. As regeneration of fissile nucleides takes place,
its efficiency is more.
7.д tOLAR ENERGY CONVERtION

Solar energy conversion is the process of conversion of
direct sunlight into more useful forms. This solar energy
conversion occurs by the following two mechanisms.
1. Thermal conversion.
2. Photoconversion.
7.6.1 Thermal conversion

Thermal conversion involves absorption of thermal
energy in the form of IR radiation. Solar energy is an important
source for low-temperature heat (temperature below 100C,
which is useful for heating buildings, water and refrigeration.
ethods of thermal conversion

1. Solar heat collectors.
2. Solar water heater.
1. Solar heat collectors
Solar heat collectors consist of natural materials like
stones, bricks (or) materials like glass, which can absorb heat
during the day time and release it slowly at night.
Energy Sources 7.15
Uses
It is generally used in cold places, where houses are kept
in hot condition using solar heat collectors.
2. Solar water heater
Fig 7.6 Solar Water Heater

It consists of an insulated box inside of which is painted
with black paint. It is also provided with a glass lid to receive
and store solar heat. Inside the box it has black painted copper
coil, through which cold water is allowed to flow in, which
gets heated up and flows out into a storage tank. From the
storage tank water is then supplied through pipes.
7.6.2 Photoconversion
Photoconversion involves conversion of light energy
directly into electrical energy by the photoelectric effect.
When the energy of solar radiation falls on the surface

of a metal, it is absorbed and used to excite and eject electrons
from the surface. This ejected electrons move in a circuit and

generate electric current.
ethods of photoconversion
Photo conversion can be made by the following method.
Photogalvanic cell (or) Solar cell
7.7 tOLAR CELL (or) PHOTOGALVANIC CELL

Definition
Solar cell (or) Photogalvanic cell is the one, which
converts the solar energy (energy obtained from the sun)
directly into electrical energy.
Principle
The basic principle involved in the solar cells is based
on the photovoltaic (PV) effect. When the solar rays fall on
a two layer of semi-conductor devices, a potential difference
between the two layer is produced. This potential difference
causes flow of electrons and produces electricity.
Construction
Solar cells consist of a p-type semiconductor (such as
Si doped with B) and n-type semiconductor (such as Si doped
with P). They are in close contact with each other.
Fig. 7.7 Solar cell

Energy Sources 7.17
Working
When the solar rays fall on the top layer of p-type
semiconductor, the electrons from the valence band get
promoted to the conduction band and cross the p-n junction
into n-type semiconductor. There by potential difference
between two layers is created, which causes flow of electrons
(ie., an electric current). Thus, when the p and n layers are
connected to an external circuit, electrons flow from n-layer
to p-layer, and hence current is generated.
The potential difference and hence current increases as
more solar rays falls on the surface of the top layer.
7.7.1 Applications of solar cells

1. Lighting purpose
Solar cells can be used for lighting purpose. Now a days
electrical street lights are replaced by solar street lights.
Fig. 7.8 Solar light

2. Solar pumps run by solar battery
When a large number of solar cells are connected in
series it form a solar battery. Solar battery produces more
electricity which is enough to run, water pump, street-light,
Fig. 7.9 Solar pump run by solar cells (Battery)

etc., They are also used in remote areas where conventional
electricity supply is a problem.
3. Solar cells are used in calculators, electronic watches,
radios and TVs.
4. Solar cells are superior to other type of cells, because
these are non-polluting and eco-friendly.
5. Solar energy can be stored in Ni-Cd batteries and
lead-acid batteries.
6. Solar cells can be used to drive vehicles.
7. Solar cells, made of silicon, are used as a source of
electricity in space craft and satellites.
7.7.2 Advantages and Disadvantages of solar

cells
Advantages (or) Merits
1. Solar cells can be used in remote and isolated areas,
forests and hilly regions.
2. Maintenance cost is low.
Energy Sources 7.19
3. Solar cells are noise and pollution free.

4. Their lifetime is long.
5. They operate at ambient temperature.
6. They need not be recharged.
Disadvantages (or) Demerits

1. Capital cost is higher.
2. Storage of solar energy is not possible.
3. It produces only DC voltage.
4. Solar energy is not available throughout day and night.
7.8 RECENT DEVELOPMENTt IN tOLAR CELL

MATERIALt
A typical solar cell consists of semiconducting materials
such as p- and n-type silicon. In order to achieve maximum
solar-to-electricity efficiency, innovative solar energy materials,
at low cost, are being used.
7.8.1 Types of highly investigated solar cell

materials
Some types of highly investigated semiconducting
materials now used are
1. Crystalline Si
2. Thin films
3. Next generation Perovskite Solar Cells (PSCs)
4. Solar paints
5. Transparent solar windows
6. Thermoradiative PV devices
7. Solar distillation
1. Crystalline silicon (c-Si)

Crystalline silicon (c-Si) is the most used (90% of the
global PV market) semiconducting material in solar panels.
But, its efficiency is only 30%. So, solar cells with low-cost
and high-efficiency materials are emerging.
Exampl
(i) III-V multijunction materials: (efficiency > 30%)
(ii) Hybrid tandem III-V/Si solar cells: (efficiency > 30%)
(iii) Sixjunction IIIV solar cells

 efficiency  47.1%

under concentrated light

(iv) Si-based bifacial technology: (efficiency is 11% more
compared to standard panels)
2. Thin films
Due to their narrow design (light weight, flexibility and
ease of installation) second-generation thin-film solar cells are
growing as one of the most promising PV technologies. This
films are 350 times smaller light absorbing layers compared
to standard Si-panels.
Exampl
(i) Cadmium-telluride (CdTe).
(ii) Amorphous silicon.
(iii) Gallium - arsenide (GaAs).
(iv) Copper - Indium - Gallium - Selenide (CIGS).
Of all, CIGS is the more efficient with efficiency upto
21%.
3. Perovskite solar cells

Among the next generation solar cells, hybrid metal
halide perovskite solar cells (PSCs), play an important role due
to their low price, thinner design, low temperature processing
and excellent light absorption properties.
Energy Sources 7.21
Exam
Combined perovskite and Si-PV materials shows a record
efficiency of upto 28%.
4. Solar paints
Solar paint is the another transformative technology.
These can be coated over the polymer films.
Exampl
(i) Solar paint hydrogen generates energy from photovoltaic
water splitting.
(ii) Quantum dots (Photovoltaic paint)
(iii) Perovskite - based paints
5. Transparent solar windows
They possess highly innovative applications. Their solar-
to-electricity conversion efficiency is 10% more.
6. Thermoradiative PV devices (or) Reverse solar panels
They can generate electricity at night by utilizing the
heat irradiated from the panels to the optically coupled deep
space, which serves as a heat sink.
Fig. 7.10 Thermoradiative PV devices
7. Solar distillation
It can harvest solar energy while utilizing the dissipated
heat from panels to purify water, if there is an integrated
membrane distillation attachment.
7.9 WIND ENERGY

Moving air is called wind. Energy recovered from the
force of wind is called wind energy. Energy possessed by the
wind is due to its high speed. Kinetic energy of the wind is
converted into mechanical energy.
7.9.1 Methods of harnessing wind energy

1. Wind mill
It is a device used to convert wind energy into
mechanical energy.
Sequence of energy conversion
Construction and working of a wind mill

It consists of a wheel containing number of blades. The
wheel rotates about an axle mounted on a pole (Fig. 7.11).
The wind energy is used to rotate the wheel. One end of the
axle is connected to the armature of a generator, which rotates
between two poles (north and south poles) of a strong magnet.
Fig. 7.11 Wind Energy

Energy Sources 7.23
Another end of the axle is connected to the shaft of the wind

mill. When wind falls on the wheel of a wind mill, it rotates
and electric current is produced. Thus, the kinetic energy of
the wind is converted into electric energy.
2. Wind farm
The electricity produced by a single wind mill is very
small, which cannot be used for commercial purpose. To
produce electricity on a large scale, a large number of wind
mills are connected.
Thus, the region where large number of wind mills are
erected to produce electricity is called wind energy farm. The
small amount of electricity produced by each generator
connected to each wind mill is combined to get electricity on
a large scale.
3. Other methods
Other methods adopted for harnessing wind energy are
(a) Sky sail.
(b) Ladder mill.
(c) Kite ship (Large free flying sails).
(d) Sky wind power (Flying electric generator).
(e) Briza technologies (Hovering wind turbine).
(f) Sequoia automation (The kite wind generator).
7.9.2 Advantages and Disadvantages of wind

energy
Advantages (or) Merits
(i) It does not cause any pollution.
(ii) It is very cheap and economic.
(iii) It is renewable.
Disadvantages (or) Demerits

1. Public resists for locating the wind farms in populated
areas due to noise generated by the machines and loss
of aesthetic appearance.
2. Wind farms located on the migratory routes of birds will
cause hazards.
3. Wind farms produce unwanted sound.
4. Wind turbines interfere with electromagnetic signals (TV,
Radio signals).
5. Wind energy is not sufficient to operate very heavy
machine.
7.9.3 Uses of wind energy

1. Wind energy is used to move the sail boats in lakes,
rivers and seas.
2. It is used to operate water pumps.
3. It is used to run the flour mill to grind the grains.
4. It is also used to produce electricity.
7.10
GEO-THERMAL ENERGY
Temperature of the earth increases at a rate of

20  75C per km, when we move down the earth surface. High
temperature and high pressure steam fields exist below the
earth’s surface in many places. The energy harnessed from the
high temperature present inside the earth is called geothermal
energy.
1. Natural geysers
In some places, the hot water (or) steam comes out of
the ground through cracks naturally in the form of natural
geysers.
Energy Sources 7.25
Fig. 7.12 Geo-thermal Energy
2. Artificial geysers
In some places, we can artificially drill a hole up to the
hot region and by sending a pipe in it, we can make the hot
water or steam to rush out through the pipe with very high
pressure.
Thus, the hot water (or) steam coming out from the
natural (or) artificial geysers is allowed to rotate the turbine
of a generator to produce electricity.
Significance of geothermal energy
1. The power generation level is higher for geothermal than
for solar and wind energies.
2. Geothermal power plants can be brought on line more
quickly than most other energy sources.
3. GTE is effectively and efficiently used for direct uses
such as hot water bath, resorts, aquaculture, greenhouses.
7.11
1. Define mass defect. How is it calculated?
40
2. Calculate the mass defect of 20Ca , which has atomic
mass of 39.975 amu. The mass of proton is 1.0078 amu
and the mass of neutron is 1.0086 amu.
3. What is binding energy? How is it calculated? How is
binding energy related to nuclear stability?
4. What are the components of a nuclear reactor? Write
briefly about each component. (Chen. A.U. June 2009)
5. Give an account of Light water nuclear reactor with a
neat diagram. (TNV. AU. May 2009)
6. Explain the power generation from light water nuclear
reactor. (CBE. A.U. Jan 2009)
7. Describe using a block diagram the light water nuclear
reactor for power generation.
(Chen AU. Jan 2009)(TNV. AU. Jan 2009)(June 2005)
8. Explain with a neat diagram the parts and functions of
a nuclear reactor.
(Chen A.U. Jan 2010, Jan 2013, May 2017)
9. What is a nuclear reactor? Describe the components of a
light-water nuclear power plant with a suitable block
diagram. (TCY A.U. Jan 2010)
10. Describe the breeder reactor. (Coim A.U. Jan 2010)
11. State the principle and application of solar batteries.
(A.U Jan 2013, May 2008)
12. Describe the conversion of solar energy into electrical
energy. (CBE. A.U. Jan 2009)
13. Give an account of solar cells.
(Chen A.U. Jan 2009)(TNV. AU. Jan 2009)
14. Write a note on photovoltaic cell. (Chen A.U. Jan 2010)
Energy Sources 7.27
15. Write a note on wind energy.

(TNV A.U May 2009)(Chen. A.U. June 2009)
16. Explain the method of conversion of nuclear energy into
electrical energy in a nuclear reactor. (AU June 2014)
17. Write a detailed note on breeder reactors.
(AU June 2014)
18. Write informative note on breeder reactor.
(A.U Dec 2014)
19. Describe the principle behind the functioning of solar
cells. (A.U Dec 2014)
20. What is a photovoltaic cell? Explain the construction and
working of a photovoltaic cell with a diagram.
(AU May 2015)
21. Explain the construction, working and uses of a nuclear
reactor with a neat diagram. (AU May 2015)
22. Describe the functioning of a light water nuclear reactor
using a suitable diagram. (AU Dec 2015)
23. What is a breeder reactor? Describe with a neat diagram
the conversion of U-235 into Pu-239. (AU June 2016)
24. Write notes on recent developments in solar cell materials.
25. How is wind energy harnessed? What are its advantages
and limitations? (AU May 2015)
26. Explain how electric power is generated by using wind
energy. (AU June 2016)
27. What is Geo-thermal energy? Explain their types and
significance.
Unit - V Chapter 8
Batteries
8.1 INTRODUCTION
In electrochemical cells, the chemical energy is converted
into electrical energy. The cell potential is related to free
energy change (G). In an electrochemical cell, the system
does work by transferring electrical energy through an electric
circuit. Thus G for a reaction is a measure of the maximum
useful work, that can be obtained from a chemical reaction.
ie., G = maximum useful work
But we know that
maximum useful work = nFE
When a cell operates, work is done on the surroundings
(flow of electricity).
G   nFE (or) G  0
Decr ease in fr ee ener gy is indicated by (–)ve sign.
One of the main uses of the galvanic cells is the
gener ation of portable electr ical ener gy. These cells are known
asbatteries.
8.1.1 Battery
A battery is an arrangement of several
electrochemical cells connected in series, that can be used
as a source of direct electric current.
A Cell: It contains only one anode and cathode.
A Battery: It contains several anodes and cathodes.
8.1.2 Requirements of a battery
A useful battery should fulfil the following requirements
1. It should be light and compact for easy transport.

2. It should have long life both when it is being
used and when it is not used.
3. The voltage of the battery should not vary
appreciably during its use.
8.2
TYPEt OF BATTERY
1. Primary Battery (or) Primary cells

(or) Non-reversible Battery
In these cells, the electrode and the electrode reactions
cannot be reversed by passing an external electrical energy.
The reactions occur only once and after use they become dead.
Therefore, they are not chargeable.
Exampl
Dry cell, mercury cell.
2. Secondary Battery (or) Secondary cells

(or) Reversible Battery
In these cells, the electrode reactions can be reversed by
passing an external electrical energy. Therefore, they can be
recharged by passing electric current and used again and
again. These are also called Storage cells (or) Accumulators.
Exampl
Lead acid storage cell, Nickel-cadmium cell.
Batteries 8.3
3. Flow battery (or) Fuel cells

In these cells, the reactants, products and electrolytes are
continuously passing through the cell. Here chemical energy
gets converted into electrical energy.
Exampl
Hydrogen-oxygen fuel cell.
8.3
IMPORTANT PRIMARY BATTERY
8.3.1 Dry Cell (or) Leclanche’s Cell

It is a primary cell, which works without fluid component.
Description
A dry cell consists of a zinc cylinder, which acts as
anode. This zinc cylinder is filled with an electrolyte consisting
of NH4Cl, ZnCl2 and MnO2 in the form of paste using starch
and water. A carbon rod (graphite), acts as cathode, is
immersed in the electrolyte in the centre of the cell. The zinc
Fig. 8.1 Leclanche’s Cell

cylinder has an outer insulation of cardboard case. During use,

the zinc cylinder gets consumed and at the end, it will develop
holes which are responsible for leakages.
Working
When the cell is working, zinc loses electrons and
2
Zn ions gets dissolved in the electrolyte. The electrons pass
through the circuit and are consumed at cathode. This causes

discharge of NH 4ions from the electrolyte.
Cell reactions:
2 
At anode: Zn  Zn  2e
At cathode:
  
N 4 aq  MnO2 s2e  MnOOH  NH3
Overall Reaction:
 2 
Zn  NH  MnO  Zn  MnOOH  NH
4 aq 2 s 3
In cathode reaction, Mn is reduced from +4 oxidation

state to +3 oxidation state. The liberation of NH 3 gas, which
disrupts the current flow, is prevented by a reaction of
2
NH3 g with Zn (from ZnCl2.
ZnCl2  2 NH3  [ZnNH32] Cl2s
The voltage of Leclanche’s cell is about 1.5 V.
Disadvantages
1. This dry cell does not have an indefinite life,
because NH4Cl being acidic corrodes the zinc
container, even if it is not used.
2. When current is drawn rapidly from it, products
build up on the electrodes, so voltage drop occurs.
Batteries 8.5
Uses:
It is used in transistor radios, calculators, Flash lights,
torches etc.,
8.4
IMPORTANT tECONDARY BATTERIEt
8.4.1 Lead - Acid Storage Cell
Storage cell
A lead acid storage cell is a secondary battery, which
can operate both as a voltaic cell and as an electrolytic cell.
When it acts as a voltaic cell, it supplies electrical energy and
becomes “run down”. When it is recharged, the cell operates
as an electrolytic cell.
Description
A lead-acid storage battery consists of a number of (3
to 6) voltaic cells connected in series to get 6 to 12 V battery.
In each cell, the anode is made of lead. The cathode is made
of lead dioxide PbO2 or a grid made of lead, packed with
PbO2. A number of lead plates (anodes) are connected in
parallel and a number of PbO2 plates (cathodes) are also
connected in parallel. Various plates are separated from the
adjacent one by insulators like rubber or glass fibre. The entire
combinations is then immersed in dil. H 2SO4 (38% by mass)
having a density of 1.30 gm/ml.
The cell may be represented as;
Pb / PbSO4 // H2SO4 aq / PbO2 / Pb
Working (Discharging)
When the lead-acid storage battery operates, the
following reaction occurs.
Fig. 8.2. Lead storage cell

2
At anode: Lead is oxidized to Pb ions, which further
2
combines with SO4 forms insoluble PbSO 4.
2 discharging 
Pb  SO PbSO  2e
s 4 aq 4 s
charging
2
At cathode: PbO2 is reduced to Pb ions, which further
2
combines with SO4 forms insoluble PbSO 4.
discharging
 2 
PbO  4H  SO  2e  2H O
PbSO
2 s 4 4 s 2
chargin
g
Overall cell reaction during use (discharging):
Pbs  PbO2 s  2H2SO4

discharging
aq
2PbSO4 s
charging
 2H2O  Energy
From the above cell reactions it is clear that, PbSO 4 is

precipitated at both the electrodes and H2SO4 is used up. As
a result, the concentration of H2SO4 decreases and hence the
Batteries 8.7
density of H2SO4 falls below 1.2 gm/ml. So the battery needs

recharging.
Recharging the Battery

The cell can be charged by passing electric current in
the opposite direction. The electrode reaction gets reversed. As
a result, Pb is deposited on anode and PbO2 on the cathode.
The density of H2SO4 also increases.
The net reaction during charging is
2PbSO4s  2H2O  Ener char ging

gy Pbs  PbO2 s
discharging
 2H2SO4 eq
Advantages of lead-acid batteries

(i) It is made easily.
(ii) It produces very high current.
(iii) The self-discharging rate is low when compared to other
rechargeable batteries.
(iv) It also acts effectively at low temperature.
Disadvantages of lead-acid batteries

(i) Recycling of this battery causes environmental hazards.
(ii) Mechanical strain and normal bumping reduces battery
capacity.
Uses
1. Lead storage cell is used to supply current mainly in
automobiles such as cars, buses, trucks, etc.,
2. It is also used in gas engine ignition, telephone
exchanges, hospitals, power stations, etc.,
8.4.2 Lithium-ion battery (LIB) (or) Lithium-ion

cell
Lithium-ion battery is a secondary battery. As in lithium
cell, it does not contain metallic lithium as anode. As the name
suggests, the movement of lithium ions are responsible for
charging and discharging. Lithium-ion cell has the following
three components.
 A positive electrode (Layers of lithium-metal oxide)
(cathode)
 A negative electrode (Layers of porous carbon) (anode)
 An electrolyte (Polymer gel) (separator)
Construction
The positive electrode is typically made from a layers
of chemical compound called lithium-cobalt oxide LiCoO2.
The negative electrode is made from layers of porous

carbon (C) (graphite).
Both the electrodes are dipped in a polymer gel
electrolyte (organic solvent) and separated by a separator,

which is a perforated plastic and allows the Li ions to pass
through.
Working
Charging

During charging, Li ions flow from the positive
electrode LiCoO2 to the negative electrode (graphite) through
the electrolyte. Electrons also flow from the positive electrode
to the negative electrode through the wire. The electrons and

Li ions combine at the negative electrode and deposit there
as Li.
LiCoO2  C  Li1  xCoO2  CLix

Batteries 8.9
Fig. 8.3 Lithium-ion cell during charging

Discharging

During discharging, the Li ions flow back through the
electrolyte from negative electrode to the positive electrode.
Electrons flow from the negative electrode to the positive

electrode through the wire. The Li ions and electrons combine
at the positive electrode and deposit there as Li.
Li1  xCoO2  CLix  LiCoO2  C

Fig. 8.4 Lithium-ion cell during discharging
Advantages (or) Characteristics of Lithium cell

1. Lithium-ion batteries are high voltage and light weight
batteries.
2. It is smaller in size.
3. It produces three time the voltage of Ni-Cd batteries.
4. It has none of the memory effect seen in Ni-Cd batteries.
Uses of Lithium cell
It is used in cell phone, note PC, portable LCD TV,
semiconductor driven audio, etc.,
8.5
ELECTRIC VEHICLEt
Definition
Electric vehicles are the vehicles that are powered on
electric power. These are also referred to as battery electric
vehicles. They have an electric motor instead of an internal
Batteries 8.11
combustion (IC) engine. Running costs are very low as they

have less moving parts for maintaining. As it runs on
electricity, the vehicle emits no exhaust gases.
8.5.1 Working Principle

Electric vehicles work by plugging into a charge point
and taking electricity from the grid. They store electricity in
rechargeable battery that power on electric motor, which rotates
the wheels. Electric vehicles accelerate faster than the
traditional fuel engines. So they feel lighter to drive.
Various steps of working

Step I Controller takes and regulates electrical energy
Step
from battery to inverter.
Step II
Step The inverter then sends a certain amount of
electrical energy to the motor.
Step III
Step The motor converts electrical energy into
mechanical energy (rotation).
Step IV
Step Rotation of the motor rotor rotates the
transmission, so the wheels turn and then the
vehicle moves.
Step V
Step When the brakes are pressed, the motor becomes
an alternator and produces power, which is sent
back to the battery.
8.5.2 Components of EV
The followings are important and essential components
in a electrical vehicles.
1. Battery: It provides electricity to power the vehicles.
2. Charge port: It allows the vehicle to connect to an
external power supply to recharge the battery.
3. DC/DC converter: It converts higher voltage DC power
from battery to lower voltage DC power.
4. Electric motor: It drives the vehicle’s wheels.

5. Onboard charger: It converts AC electricity to DC
power for charging the battery.
6. Power electronics controller: It controls the flow of
electrical energy from battery to motor and controls the speed.
7. Thermal system (cooling): It maintains the proper
operating temperature range of the engine, motor etc.
8. Transmission: It transfers mechanical power from the
motor to drive the wheels.
8.5.3 Plug-in electric vehicles

Any motor vehicle that can be recharged from any
external source of electricity such as wall sockets, rechargeable
battery packs are called plug-in electric vehicles.
Types of plug - in electric vehicles
They can be further divided into two types.
1. Battery Electric Vehicles (BEVs) (or) pure electric
vehicles (or) fully electric vehicles.
2. Hybrid type vehicles
(a) Hybrid Electric Vehicle (HEV)
(b) Plug-in Hybrid Electric Vehicles (PHEVs)
1. Battery Electric Vehicles (BEV)
These are the vehicles powered by a battery. These
batteries can be charged by plugging the vehicle into the
charging equipment. Its typical driving ranges from 150 to 300
miles. This type of vehicles do not have an ICE.
2. Hybrid type vehicles
(a) Hybrid Electric Vehicle (HEV)
It has both an Internal Combusion Engine (ICE) and an
electric motor. In this type of electric cars, ICE gets energy
Batteries 8.13
from fuel while the motor gets electricity from batteries. It

offers a mixture of battery and gasoline powers.
The gasoline engine and electric motor simultaneously
rotate the transmission, which drives the wheels. Batteries in
HEC can only be charged by ICE by the motion of the wheels.
The battery cannot be recharged from outside the system.
(b) Plug-in Hybrid Electric Vehicle (PHEV)
This type of electric cars are powered by a conventional
fuel (gasoline) and by a rechargeable battery pack. This battery
can be charged up with electricity by plugging into an electrical
plug. It can also be recharged by ICE.
It operates on electricity until their battery pack is
depleted. Once the battery is empty, the engine takes over and
the vehicle operates as a conventional non-plug-in hybrid
(gasoline) vehicle.
(c) Fuel cell Electric vehicles
Fuel cell technology is to generate electricity, which is
required to run the vehicle. Here chemical energy of the fuel
is converted directly into electric energy. The main advantage
of this vehicle is, it generates electricity, required to run their
vehicle, on the vehicle itself.
8.5.4 Advantages and disadvantages of

electric vehicles
Advantages
(i) Electric cars are energy efficient
(ii) It reduces emission.
(iii) Its performance is high and has low maintenance.
(iv) It can be fuelled for very low price.
(v) It is more convenient and easy to recharge.
Disadvantages
(i) Electric cars can travel less distance.
(ii) It takes longer time to refuel (recharge)

(iii) These are more expensive and battery packs may need
to be replaced.
(iv) Electric fuelling stations are still in the developing stages.
(v) Initial investment is very high.
8.д
FUEL CELLt
Definition
Fuel cell is a voltaic cell, which converts the chemical
energy of the fuels directly into electricity without
combustion.
Fuel cell converts the energy of the fuel directly into
electricity. In these cells, the reactants, products and
electrolytes pass through the cell.
Fuel  Oxygen  Oxidation products  Electricity .
Exam
Hydrogen-oxygen fuel cell.
Fuel Battery
When a large number of fuel cells are connected in
series, it forms fuel battery.
8.6.1 Hydrogen-Oxygen fuel cell

Hydrogen-oxygen fuel cell is the simplest and most
successful fuel cell, in which the fuel-hydrogen and the oxidiser-
oxygen and the liquid electrolyte are continuously passed
through the cell.
Description
It consists of two porous electrodes anode and cathode.
These porous electrodes are made of compressed carbon
containing a small amount of catalyst (Pt, Pd, Ag). In between
the two electrodes an electrolytic solution such as 25% KOH
Batteries 8.15
or NaOH is filled. The two electrodes are connected through

the volt meter.
Working
Hydrogen (the fuel) is bubbled through the anode
compartment, where it is oxidised. The oxygen (oxidiser) is
bubbled through the cathode compartment, where it is reduced.
Fig 8.5 H2O2 Fuel cell

Various reactions
At Anode
Hydrogen gas, passed through the anode, is oxidised with
the liberation of electrons which then combine with hydroxide
ions to form water.
 
H2  2H  2e
 
2H  2OH  2H2O
 
H2  2OH  2H2O  2e
 
Multiply by 2: 2H2  4OH  4H2O  4e
At cathode
The electrons, produced at the anode, pass through the
external wire to the cathode where it is absorbed by oxygen
and water to produce hydroxide ions.
 2
O2  4e  2 O
 2 
2O  2H2O  4OH

O2  2H2O  4e

 4OH
Overall cell reaction
At anode: 
2H2  4OH  4H2O  4e

At cathode: 
O2  2H2O  4e  4OH

2H2  O2  2H2O
➨ The emf of the cell  0.8 to 1.0 V

Applications of H2  O2 fuel cell
1.
H2O2 fuel cells are used as auxiliary energy source in
space vehicles, submarines or other military-vehicles.
2.
In case of H2O2 fuel cells, the product of water is
proved to be a valuable source of fresh water by the
astronauts.
Advantages of H2  O2 fuel cell

(i) It emits only water vapour and no other harmful
chemicals to the environment.
(ii) Efficiency is more than 75%.
Batteries 8.17
(iii) As hydrogen is the lightest element, it can be transported

easily from one place to another.
(iv) Hydrogen, as a fuel, can replace the use of batteries.
(v) It causes less noise pollution.
Limitations (or) Disadvantages of H2  O2 fuel cell

1. Hydrogen gas is explosive.
2. It is very expensive to be carried out.
3. As hydrogen is a gas, it is difficult to compress into
liquid form.
4. Hydrogen is not present as it is, but always present in
combined form with either oxygen or some other
element, so it must be separated first.
5. While using H2  O2 fuel cell in an automobile, a high
pressure must be created inside the engine, which is
risky.
8.6.2 Advantage and Disadvantages of Fuel

cells
Advantages of Fuel cells

1. Fuel cells are efficient (75%) and take less time for
operation.
2. It is pollution free technique.
3. It produces electric current directly from the reaction of
a fuel and an oxidiser.
4. It produces drinking water.
Disadvantages of Fuel cells

1. Fuel cells can not store electric energy as other cells do.
2. Electrodes are expensive and short lived.
3. Storage and handling of hydrogen gas is dangerous.
8.6.3 Microbial Fuel Cells (MFCs)

Microbial fuel cell is a device that converts chemical
energy to electrical energy by the action of micro-organisms
under anaerobic conditions.
Bioelectricity is generated by the oxidation of organic
waste and renewable biomass using bacteria.
Construction (or) Principle

MFCs are type of electrochemical cells, constructed using
either bioanode and (or) a biocathode. A membrane separates
the compartments of the anode (where oxidation occurs) and
the cathode (where reduction occurs). The electrons produced
during oxidation are transferred directly to the cathode. The
charge balance of the system is maintained by the ionic
movement inside the cell.
Organic electron donors, that is oxidized to produce
CO2, protons and electrons, are used in most MFCs. The
cathode reaction uses a variety of electron acceptors, mostly
oxygen O2.
Components
A typical MFC consists of the following two
compartments.
(i) Anodic compartment (ii) Cathodic compartment
(i) Anodic compartment
It consists of microbes suspended under anaerobic
conditions in the anolyte.
(ii) Cathodic compartment
It consists of electron acceptor (oxygen)
Permeable membrane
Anionic and cationic compartments are separated by a
selectively permeable, cation-specific membrane.
Batteries 8.19
Fig. 8.6 Microbial Fuel cell
Working
When both the electrodes are connected, anode oxidation
occurs on organic waste (biomass) and electrons released from
the process are transferred to the anode. The electrons,
transfered to the anode, can be accomplished by the electron
mediators.
From the anode these electrons are directed to the
cathode across an external circuit. For every electron,
conducted, a proton is transported across the membrane to the
cathode. Finally oxygen present at the cathode recombines with
hydrogen and electron to produce water.
Applications
1. In waste water treatment, MFCs, generate less excess
sludge as compared to the aerobic treatment process.
2. MFCs can be used in river and deep-water environments,
where it is difficult to use batteries.
3. MFCs are used to convert carbon rich wastewater into
methane gas.
4. MFCs are used as convenient biosensor for waste water

streams.
5. MFCs are used in space, especially to operate remotely
operated vehicles.
6. MFCs play an important role in the field of
microbiology, soil chemistry and electrical engineering.
7. Many commercial soil based MFC kits are available for
the purchase on the web and in toy stores.
8.7
tUPER CAPACITOR
Super capacitor is an electronic device that store large
amount of electric charge. They store 10 to 100 times more
energy per unit volume and deliver charge much faster than
batteries.
Unlike ordinary capacitors, super capacitors, do not use
the conventional solid dielectric, but rather they use
electrostatic double-layer capacitance.
Design of super capacitor

Super capacitor (Electro-chemical capacitor) consists of
two electrodes (made from metal coated with a porous substance
like powdery activated carbon) separated by an ion-permeable
membrane (separator) and dipped in an electrolyte, containing
positive and negative ions, connecting both the electrodes.
Working (or) Storage Principle

When the electrodes are connected to the power source,
ions in the electrolyte form electric double layers (Helmholtz
electrical double layer) of opposite polarity to the electrodes
polarity, creating an electric field between them.
For example, positively polarized electrodes will have a
layer of negative ions at the electrode/electrolyte interface.
Similarly negatively polarised electrodes will have a layer of
positive ions at the electrode/electrolyte interface.
Batteries 8.21
Fig. 8.7 Typical construction of a super capacitor
1. Power source 2. Collector

3. Polarized electrode 4. Helmholtz double layer
5. Electrolyte having positive and negative ions
6. Separator
This electric field polarizes the dielectric, so its
molecules lineup in the opposite direction to the field and
reduce its strength. It means that it stores more electrical
energy at an electrode-electrolyte interface.
8.7.1 Type of super capacitors
Supercapacitors are mainly classified into three types
1. Double layer capacitors
2. Pseudo capacitors
3. Hybrid capacitors
1. Double layer capacitors

It consists of two electrodes separator and electrolyte.
The electrolyte is the mixture of positive ions and negative
ions dissolved in water. The two electrodes are separated by
a separator.
2. Pseudo capacitors
It starts electrical energy by electron change transfer
between electrode and electrolyte. This can be done by redox
reaction.
3. Hybrid capacitors
It is developed by using techniques of doubld layer
capacitors and pseudo capacitors. In hybrid capacitor both
double layer capacitance and pseudo capacitance is achieved.
Table 8.1: Differences between battery, capacitor and

super capacitor
S.No. Battery Capacitor Super Capacitor

1. Can store large cannot store large can store large
amount of amount of charge amount of charge
charge
2. Can not deliver can deliver the can deliver the
the charge very charge quickly charge quickly
quickly
Batteries 8.23
8.7.2 Advantages and disadvantages of super

capacitors
Advantages
1. It is highly safe
2. Its life time is very high (10 to 20 years)
3. It can be cycled millions of time
4. It can be charged in seconds
5. It provides high power density and high load currents
6. Its performance is excellent even at low temperature
 40C
Disadvantages
1. Cost per watt is high
2. It cannot be used as source for continuous power supply
3. If higher voltage is required, the cells must be connected
in series.
4. High self-discharge, it is higher than most batteries.
8.7.3 Applications
Super capacitors are used in many power management
applications like,
1. Voltage stabilization in start/stop system
2. Energy harvesting
3. Kitchen appliances
4. Regenerative braking system
5. Consumer electronics
6. Wind energy
7. Utility meters
8. Remote power for sensors, LEDs, switches
9. Energy efficiency and frequency regulation
8.8
1. What is a primary battery. Give an example.

(A.U June 2006)
2. Write a brief note on lead-acid storage cell.
(A.U June 2006)
3. Explain the construction and workings of lead acid
battery. (A.U June 2006)
(Dec. 2005)(Coim AU Jan 2008)
4. What is reversible battery? Describe the construction and
working of lead acid storage battery with reaction
occuring during charging and discharging.
(A.U May 2007)
5. Give the description of lead storage cell and explain its
functioning during discharging and recharging.
(A.U Jan 2013)
6. Explain the construction and working of a lead storage
battery. (Coim A.U Jan 2009) (TNV. AU. May 2009)
(Dec 2008, Jan 2013)
7. Describe the principle and functioning (charging and
discharging) of lead acid battery.(Chen. A.U. June 2009)
8. Explain the construction and working principles of Lead-
acid battery? (TNV A.U. Jan 2010)
9. Explain the construction, working of lead-acid battery,
with relevant sketches. (Coim A.U. Jan 2010)
10. Write notes on Lead acid storage battery.
(TCY A.U. Jan 2010)
11. Explain the construction and working of
Hydrogen-Oxygen fuel cell, giving a neat diagram.
(TNV A.U. Jan 2010)
12. With a neat sketch explain the functioning of H2  O2
fuel cell. (Coim A.U. Jan 2010)
Batteries 8.25
13. Explain the working of hydrogen-oxygen fuel cell.

(Chen A.U. Jan 2010, Jan 2013)
14. Write short notes on:
Hydrogen-oxygen fuel cell. (TCY A.U. Jan 2010)
15. What are lead accumulators? Explain the constructions
and functioning of a lead accumulator. (AU June 2014)
16. What is a fuel cell? Explain the working of any one fuel
cell. (AU June 2014)
17. Describe the construction of lead-acid battery with the
reaction occurring during discharge. (A.U Dec 2014)
18. Explain charging and discharging reactions of lithium-ion
cell.
19. Describe the construction and working of
hydrogen-oxygen fuel cell. (A.U Dec 2014)
20. Write in detail about lead acid battery. (AU Dec 2015)
21. Describe the construction of lead-acid battery with
reaction occurring during discharging. (AU June 2016)
22. With a neat diagram, explain the working principle of
H2  O2 fuel cell with cell reaction.
(AU June 2016, May 2017)
23. Write notes on super capacitors.
24. Explain advantages, disadvantages and applications of
super capacitors.
Anna University TWO MARKS
Questions & Answers
Two Marks Questions and Answers A.1
1. Water and its Treatment
1. Define Taste and Odour.
Taste
Taste is the sensation of flavour perceived in the mouth
and throat on contact with a substance.
Odour
Odour is a smell (or) scent caused by one (or) more
volatilized chemical compounds that are generally found in low
concentration.
2. What is meant by turbidity?
Turbidity is the reduction of clarity of natural water due
to the presence of finely divided, insoluble impurities
suspended in water.
3. What is the significance of pH in water?
(i) pH determines the solubility (amount that can be
dissolved in water).
(ii) It also determines the biological availability (amount that
can be utilized by aquatic life).
(iii) A rise (or) fall in pH can indicate chemical pollution
(or) acid rain. Many animals cannot live in water at a
pH level below 5 (or) above 9.
4. Define hardness.
Hardness is the property (or) characteristics of water,
which does not produce lather with soap.
5. What is BOD.
BOD is defined as, “the amount of free oxygen required
by bacteria for the biological oxidation of the organic matter
under aerobic conditions at 20C for a period of 5 days”.
A.2 Engineering Chemistry
6. What is the significance of BOD.(APJAKTU, Jan 2016)

(i) It indicates the amount of decomposable organic matter
present in the sewage.
(ii) It enables us to determine the degree of pollution at any
time in the sewage stream.
(iii) Lesser the BOD, better is the quality of water. ie. the
water sample with BOD of less than 3 ppm is considered
as pure water, whereas the water more than 4 ppm is
considered as polluted water.
7. Define COD.
COD is defined as, “the measure of amount of oxygen
required to chemically oxidise all the oxidisable impurities
present in the sewage using an oxidising agent like acidified
K2Cr2O7”.
8. What are the advantages of COD.

(i) Determination of COD is carried out only in 3 hours,
but determination of BOD is carried out after 5 days.
(ii) It measures both the biologically oxidisable and
biologically inert organic matter.
9. What is chlorination.
The process of adding chlorine to water is called
chlorination. Chlorination can be done by the following methods.
(a) By adding chlorine gas
(b) By adding chloramine
(c) By adding bleaching powder
10. What is sterilisation.

The process of destroying the harmful bacterias is known
as sterilisation or disinfection. The chemicals used for this
purpose are called disinfectants.
11. What is break-point chlorination? Explain

Break point chlorination is the point at which all the
impurities are removed and free chlorine begins to appear.
12. What is blow-down operation?
Blow-down operation is a process of removing a portion
of concentrated water by fresh water frequently from the boiler
during steam production.
13. Define desalination. (Coim AU June 2008)
The process of removing common salt (sodium chloride)
from the water is known as desalination. The water containing
dissolved salts with a peculiar salty or brackish taste is called
brackish water.
14. Write the principle involved in the desalination of water
by reverse osmosis. (A.U. (Chem-II) Dec 2006)
(or)
What is meant by ‘Reverse osmosis’? How is it applied
in the desalination of water?
(A.U. (Chem-II) June 2007)(CBE AU Jan 2009, Jan. 2018)
If pressure in excess of osmotic pressure is applied on
the higher concentration side, the solvent flow is reversed ie.,
solvent flows from higher concentration to lower concentration.
This process is called reverse osmosis.
Salt water is taken as higher concentration and water is
taken as solvent. If pressure is applied on the salt water, the
water flows from salt water to water side.
15. Name the method which separate both ionic and non-
ionic impurities from water. [A.U. Nov.96]
Reverse osmosis process.
16. Name some of the membranes employed in reverse
osmosis process. State the advantages of this process.
[A.U. Dec.97]
Example: Cellulose acetate, cellulose butrate.
Advantages (i) It removes ionic as well as non-ionic, colloidal

impurities.
(ii) The life time of the membrane is high and it can
17. What are the advantages of reverse osmosis method.
(i) The life time of the membrane is high, and it can
(ii) It removes ionic as well as non-ionic, colloidal
impurities.
(iii)Due to low capital cost, simplicity, low operating,
this process is used for converting sea water into
drinking water.
18. Why is water softened before using in boiler?
(A.U. June 2007, May 2017)
If hard water obtained from natural sources is fed
directly into the boilers, the following troubles may arise.
1. Scale and sludge formation.
2. Priming and foaming (carry over).
3. Caustic embrittlement.
4. Boiler corrosion.
19. What are scales and sludges? (TNV AU May 2009)
1. Sludge
If the precipitate is loose and slimy it is called sludge.
Sludges are formed by substances like MgCl2, MgCO3,
MgSO4 and CaCl2. They have greater solubilities in hot water
than cold water.
2. Scale
On the other hand, if the precipitate forms hard and
adherent coating on the inner walls of the boiler, it is called
scale. Scales are formed by substances like CaHCO32,
CaSO4 and MgCl2.
20. Mention any two disadvantages of formation of deposits

in steam boilers (A.U. Dec 2015)
(or)
What are the disadvantages of scale formation
(Chen. A.U. June 2009)
Scales act as thermal insulators. It decreases the
efficiency of boiler. Any crack developed on the scale, leads
to explosion.
21. What is meant by priming and foaming? How can they
be prevented. (A.U Oct. 98)
Priming can be prevented by controlling the velocity of steam
and keeping the water level lower.
Foaming is the formation of stable bubbles above the
surface of water. Foaming can be prevented by adding
coagulants like sodium aluminate and antifoaming agents like
synthetic polyamides.
22. What is meant by priming and mention its causes.
(AUT, TNU Jan 2011)
Priming is caused by
(i) High steam velocity.
(ii) Very high water level in the boiler.
(iii) Sudden boiling of water.
(iv) Very poor boiler design.
23. List two disadvantages of using hard water in boilers.
(AUT TNV June 2011, May 2015)
1. Scale and sludge formation
2. Priming and foaming (carry over)
3. Caustic embrittlement
4. Boiler corrosion
24. Mention any two compounds that cause caustic
embrittlement in boilers. (AU June 2014)
Alkali metal carbonates and bicarbonates like Na2CO3,
K2CO3 , NaHCO3 , KHCO3
25. What is meant by caustic embrittlement? How is it
prevented.
(A.U.June 2007, AU Dec 2009, Jan 2010, Dec 2015, May 2016)
Caustic embrittlement means intercrystalline cracking of
boiler metal.
Prevention
Caustic embrittlement can be prevented by
(i) using sodium phosphate as softening agent instead
of sodium carbonate.
(ii) by adding tannin, lignin to the boiler water, which
blocks the hair cracks.
26. Indicate the reasons for boiler corrosion
(Coim. A.U. 2008)
Boiler corrosion arises due to the presence of
(i) dissolved oxygen,
(ii) dissolved carbon dioxide,
(iii) dissolved salts.
27. What are the requisites of drinking and boiler feed
water? [A.U. Nov.2001]
(i) Boiler Must have zero hardness and free from

feedwater dissolved gases like O2, CO2.
(ii) Drinking (i) pH of water should be in the range of
water 7.0  8.5.
(ii) Total hardness and dissolved solids of
water should be less than 500 ppm.
28. Define softening of water. How is it caried out.

The process of removing hardness producing salts from
water is known as softening (or) conditioning of water.
Softening of water can be done in two methods
1. External treatment. 2. Internal treatment.
29. Soft water is not DM water whereas DM water is soft
water - Justify. (or)
Distinguish between soft water and demineralised water.
(A.U Jan 2013)
The soft water, produced by lime-soda and zeolite
processes, does not contain hardness producing
2 2
Ca and Mg ions, but it will contain other ions like
  2 
Na , K , SO 4 , Cl etc., On the other hand D.M.
(Demineralised) water does not contain both anions and cations.
30. What are the advantages of ion-exchange process.
(i) Highly acidic or alkaline water can be treated by
this process.
(ii) The water obtained by this process will have very
low hardness (nearly 2 ppm).
31. How is exhausted resin regenerated in ion-exchange
process. (Coim A.U. Feb 2010)
When the cation exchange resin is exhausted, it can be
regenerated by passing a solution of dil HCl or dil H2SO4.
RCa  2HCl  RH2 
CaCl2 RNa  HCl  RH 
NaCl
Similarly, when the anion exchange resin is exhausted,
it can be regenerated by passing a solution of dil NaOH.
RCl2  2NaOH  ROH2  2NaCl.

32. Give some examples for cation exchange resin.

(i) Sulphonated coals.
(ii) Sulphonated polystyrene.
33. Give some examples for anion exchange resin.
(i) Cross - linked quaternary ammonium salts.
(ii) Urea - formaldehyde resin.
34. How is boiler corrosion, due to dissolved oxygen, removed.
Sodium sulphite, hydrazine are some of the chemicals
used for removing dissolved oxygen from water.
2Na2SO3  O2  2Na2SO4
N2H4  O2  N2  2H2O
35. Name the gases dissolved in water that cause corrosion?

(i) Dissolved oxygen (DO)
DO in water attacks the boiler material at higher
temperature.
4Fe  6H2O  3O2  4Fe OH3 
(ii) Dissolved carbon dioxide

Dissolved CO2 in water produces carbonic acid, which
is acidic and corrosive in nature.
CO2  H2O  H2CO3
36. How does carbon dioxide cause boiler corrosion.

Dissolved carbon dioxide in water produces carbonic
acid, which is acidic and corrosive in nature.
CO2  H2O  H2CO3
Carbon dioxide gas is also produced from the

decomposition of bicarbonate salts present in water.

CaHCO32  CaCO3   H2O  CO2 
37. What are ion exchange resins? (AUT TNU June 2010)
Ion exchange resins are long chain, cross linked,
insoluble organic polymers with a microporous structure. The
functional groups attached to the chains are responsible for the
ion exchanging properties.
38. What are the disadvantages of ion-exchange process.

(i) Water containing turbidity, Fe and Mn cannot be
treated, because turbidity reduces the output and
Fe, Mn form stable compound with the resin.
(ii) The equipment is costly and more expensive
chemicals are needed.
39. How is water demineralised in an ion-exchanger?
[A.U Nov.2001]
When the water containing ions (both anion and cation)
are passed through ion exchange columns, it absorbs all the
ions (anions and cations) as shown below.
Cation exchanger: RH2  CaCl2  RCa  2HCl.
Anion exchanger: ROH2  2HCl  RCl2  2H2O.
40. What is meant by internal conditioning of water.

(A.U May 2014)
Internal conditioning is the process which involves the
removal of scale forming substance by adding chemicals
directly into the boiler.
41. Explain the function of a coagulant with example.

When the coagulant is added to water, it gets hydrolysed
to form a gelatinous precipitate of coagulatant AlOH3. The
gelatinous precipitate, AlOH3, entraps the finely divided and
colloidal impurities, settles to the bottom and can be removed
easily.
42. What is phosphate conditioning (Coim A.U. Feb 2010)

(or)
What is the role of phosphates in the internal treatment
of water? (May 2008)
Scale formation can be avoided by adding sodium
phosphate. It is used in high pressure boilers. The phosphate
2  2 
reacts with Ca and Mg salts to give soft sludges of
calcium & magnesium phosphates.
3 CaSO4  2 Na3PO4  Ca3PO42  3Na2SO4
43. What are boiler compounds? Mention two different

boiler compounds and their actions.
[May 2001, May 2015]
Scale forming substances can be removed by adding
chemicals directly to the boiler. These chemicals are called
boiled compounds.
Examples: Sodium carbonate and sodium phosphate.
(i) CaSO4  Na2CO3  CaCO3  Na2SO4.
(ii) 3CaSO4  2Na3PO4  Ca3 PO42  3Na2SO4.
44. What is calgon conditioning? How is it functioning in

water treatment?
(TCY AU July 2008)(Chen A.U. June 2005, Jan 2010)
(or)
Write the chemical reaction involved in calgon
conditioning. (AU June 2014)
Calgon is sodim hexa meta phosphate Na 2 [Na4 PO36].
This substance interacts with calcium ions forming a highly
soluble complex and thus prevents the precipation of scale
forming salt.
2 CaSO4  Na2 [Na4 PO36]  Na2 [Ca2 PO36]  2Na2SO4

45. Distinguish between internal and external conditioning

of water. (A.U. Dec 2014)
S.
External treatment Internal treatment
No
1. It is expensive It is cheap
2. No chemicals are used Chemicals are used
3. It is carried out before It is carried out within the
feeding the water into the boiler.
boiler.
4. It is used for high pressure It is used for low pressure
boilers. boilers.
5. Blow down operation is not It requires blow down
required. operation.
46. Why calgon conditioning is better than phosphate

conditioning? (A.U. June 2016)
In calgon conditioning calgon forms highly soluble
complex, but in phosphate conditioning, it gives sludge. So
periodical disposal of sludge is important in phosphate
conditioning, but in calgon conditioning no problem of disposal.
Two Marks Questions and Answers B.1
2. Nanochemistry
1. What are nonoparticles?

from 1-100 nm.
2. What are nano-materials?
Nanomaterials are the materials having components with
size less than 100 nm at least in one dimension.
3. What is nano-chemistry? (A.U.T. (Coim) May 2011)
Nano-chemistry is the branch of nano-science, which
deals with the chemical applications of nanomaterials. It also
includes the study of synthesis and characterisation of
nanomaterials.
4. Distinguish between bulk particles and nano-particles.
(A.U. (CEG) Dec. 2012 June 2013)
Nano-particles Bulk particles

1. Size is less than 100 nm Size is larger in micron size
2. Collection of few Collection of thousands of
molecules molecules.
3. Surface area is more Surface area is less
4. Strength, hardness are Strength, hardness are less
more
5. Name some important physical methods of synthesising

nano-materials.
1. Laser ablation
2. Chemical Vapour Deposition (CVD)
3. Electro-deposition
B.2 Engineering Chemistry
6. What is CVD?
CVD is Chemical Vapour Deposition. It is a process of
chemically reacting a volatile compound of a material with
other gases, to produce a non-volatile solid that deposits
automatically on a suitably placed substrate.
7. What is the basic principle involved in solvothermal
synthesis of nano-materials.
Solvothermal synthesis involves the use of solvent under
high temperature (between 100C to 1000C) and moderate to
high pressure (1 atm to 10,000 atm) that facilitate the
interaction of precursors during synthesis.
8. Define nano-wires.
Nano-wire is a material having an aspect ratio ie., length
to width ratio greater than 20. Nano-wires are also referred to
as “quantum wires”.
9. What are the characteristics of nano-wires.
1. Nano-wires are two-dimensional material.
2. Conductivity of a nano-wire is less than that of
the corresponding bulk materials.
3. It exhibits distinct optical, chemical, thermal and
electrical properties due to this large surface area.
10. Mention some important applications of nano-wires.
1. Nanowires are used for enhancing mechanical
properties of composites.
2. It is also used to prepare active electronic
components such as pn junction and logic gates.
3. Semiconductor nanowire crossings are expected to
play a important role in future of digital
computing.
11. What is nano-Rod?
Nanorod is two dimensional cylindrical solid material
having an aspect ratio i.e., length to width ratio less than 20.
Two Marks Questions and Answers B.3
12. What are nanoclusters? (A.U. (CEG) Dec 2012)

Nanoclusters are fine aggregates of atoms or molecules.
The size of which ranges from 0.1 to 10 nm. Of all the nano
materials, nanoclusters are the smallest sized nano materials
because of their close packing arrangement of atoms.
13. What is magic number
It is the number of atoms in the clusters of criticle sizes
with higher stability.
14. What are carbon nano-tubes.
Carbon nanotube is a tubular form of carbon with 1-3
nm diameter and a length of few nm to microns.
15. Mentin some uses of CNTs.
1. It is used in battery technology and in industries
as catalyst.
2. It is also used as light weight shielding materials
for protecting electronic equipments.
3. CNTs are used effectively inside the body for
drug delivery.
4. It is used in composites, ICs.
16. Mention some characteristic properties of nanomaterials.
(Chen. A.U Jan 2010)
1. Nanomaterials are very strong and withstand
extreme strain and tension.
2. It possesses very good electrical properties and
thermal conductivity.
17. List any four nano-materials. (Coim. A.U Feb 2010)
1. Carbon nanotubes.
2. Nanowire.
3. Qauntum dots.
4. Dendrimers.
Two Marks Questions and Answers C.1
3. Phase Rule
1. State phase rule and explain the terms involved.

(A.U. Dec 2005)(A.U. June 2007)
If the equilibrium between any number of phases is not
influenced by gravity, or electrical, or magnetic forces but are
influenced only by pressure, temperature and concentration,
then the number of degree of freedom(F) of the system is
related to number of components (C) and number of phases
(P) by the following phase rule equation.
FCP2
2. Define phase (P) with suitable example.
(Chen A.U. Dec 2009)
Phase is defined as, “any homogeneous physically
distinct and mechanically separable portion of a system which
is separated from other parts of the system by definite
boundaries”.
Consider a water system consisting of three phases.
Each phase is physically distinct and homogeneous and

there are definite boundaries between phases. So this forms
three phases.
3. What is degree of freedom (F)?
(Or)
Comment on the degree of freedom.
(A.U. (CEG) Chen A.U. Dec 2011, May 2017, Jan. 2018)
Degree of freedom is defined as, “the minimum number
of independent variable factors such as temperature, pressure
and concentration, which must be fixed in order to define the
system completely”.
C.2 Engineering Chemistry
4. Define component with suitable example.

(Chen A.U. Dec 2009, Dec 2015, Jan. 2018)
Component is defined as, “the smallest number of
independently variable constituents, by means of which the
composition of each phase can be expressed in the form of a
chemical equation”.
Consider a water system consisting of three phases.
The chemical composition of all the three phases is

H2O, but are in different physical form. Hence the number of
component is one.
5. How many phases and components are present in the
following system? (Chen A.U.T. Dec 2012; June 2010)
It consists of two solid phases and one gaseous phase.
P3;C2;
F  C  P  2  2  3  2  1.
6. NH4Cls NH3 g  HClg. Write the values of

P, F and C for this system. (A.U. Dec 2016)
This system consists of two phases and one component
P2;C1;
F  C  P  2  1  2  2  1.
7. Calculate the number of phases present in the following
systems.
(Coim. A.U. July 2009)(A.U. June 2007, Dec 2016)
(a) MgCO3 s MgOs  CO2 g
Three phases.
(b) Rhombic sulphurs Monoclinic
sulphurs Two phases.
(c) Ices waterl water
vapourg Three phases.
(d) An emulsion of oil in water

Two phases
(e) NH4Cls NH3 g 
HClg Two phases.
8. How many components are present in the system.

KCl  Water  KCl  hydrate
(A.U.T(Coim) July 2010)
Number of phases  3 ; Components  2.
9. What is Phase diagram? What is the use of studying such
diagrams?
Phase diagram is a graph obtained by plotting one degree
of freedom against another.
It is possible to predic from the phase diagrams whether
an eutectic alloy or a solid solution is formed on cooling a
homogeneous liquid containing mixture of two metals.
10. What are the types of phase diagrams?
(i) P-T diagram
If the phase diagram is plotted between temperature
against pressure, the diagram is called P  T diagram. P  T
diagram is used for one component system.
(ii) T-C diagram
If the phase diagram is drawn between temperature
against composition, the diagram is called T  C diagram.
T  C diagram is used for two component system.
11. What is triple point? (A.U. June 2014)

It is the point at which three phases namely solid, liquid
and vapour are simultaneously at equilibrium.
12. What is metastable equilibrium?

Sometimes water can be cooled below 0C without the
formation of ice, this water is known as super-cooled water.
The equilibrium between super-cool water and the vapour is
known as metastable equilibrium.
13. What is the effect of pressure on the melting point of

ice?
Melting point of ice decreases with increase of pressure.
14. How many phases and components are existing at triple

point in ice - water - water vapour system?
Phases - 3; Components - 1.
15. State reduced phase rule. (or) Write down the condensed
phase rule. Explain.
(Coim.&TNV A.U. July 2009 & A.U. Jan 2014, May 2015)
A solid-liquid equilibrium of an alloy has practically no
gaseous phase and the effect of pressure is negligible.
Therefore, experiments are conducted under atmospheric
pressure. Thus the system in which only the solid and liquid
phases are considered and the gas phase is ignored is called
a condensed system. Since the pressure is kept constant, the
phase rule becomes
FCP1
This equation is called reduced phase rule or condensed

phase rule.
16. A system consists of benzene and water. What is the

number of phases? (A.U. Dec 2007)
Two liquid phases and one vapour phase.
17. State the number of degrees of freedom for the following

systems:
(a) PCl5 s PCl3 g  Cl2 g at 50C
(b) CaCO3 s CaOs  CO2 g
(A.U. May 2008)

(a) F  C  P  1 ; 2  3  2 ; F 
1 (b) C  P  1 ; 2  3  2 ; F  1
18. State the conditions under which two substances can

form a simple eutectic.
(i) They must be completely miscible in the liquid state
but completely immiscible in the solid state. (ii) They should
not chemically react with each other.
19. What is eutectic point?(A.U. June 2006)

(or)
Define eutectic point.
It is the point at which two solid and one liquid phase
are in equilibrium.
20. Eutectic is a mixture and not a compound explain.

Eutectic is an unique mixture of two solids which has
the lowest melting point. Since it is completely immiscible in
the solid state, it is a mixture and not a compound.
21. What is an eutectic alloy?

It is an unique composition of two solids, which has the
lowest melting point, when compared to the melting point of
two solids,
Since, it has the same composition both in the liquid

and solid states, it behaves like a pure solid substance.
22. What are the uses (or) significance of eutectic mixture?

(A.U. Dec 2008)
1. Suitable alloy composition can be predicted with the help
of eutectic systems.
2. Eutectic systems are used in preparing solders, used for
joining two metal pieces together.
23. Mention the merits of phase rule. (or) Mention the
applications of phase rule.
(i). It is applicable to both physical and chemical
equilibria; (ii). It is convenient method of classifying the
equilibrium states interms of phases, components and degree
of freedom. (iii) It helps in deciding whether the given number
of substances remain in equilibrium or not.
24. Differentiate melting point, eutectic point and triple
point.
Melting point: It is the temperature at which the solid and
liquid phases, having the same composition, are in equilibrium.
Solid A Liquid A
Eutectic point: It is the temperature at which two solids and
a liquid phase are in equilibrium.
Solid A  Solid B Liquid

Triple point: It is the temperature at which three phases are
in equilibrium.
Solid Liquid Vapour

25. Write the number of phases and components in the
following heterogeneous system:
CuSO 4 s  5H2O 1 CuSO4  5H2O s.
(Chen A.U. June 2009)
Number of phases = 3
Number of components = 2
26. What is the degree of freedom at eutectic point in

Lead-Silver system? (A.U. Dec 2014)
Degree of freedom is zero ie., F  0
27. What is thermal analysis.

Thermal analysis is a method involving a study of the
cooling curves of various compositions of a system during
solidification. The shapes of the freezing point curves for any
system (involving metals) can be determined by thermal
analysis. The form of the cooling curve indicates the
composition of the solid.
28. How is cooling curve drawn.

A pure substance in the fused state is allowed to cool
slowly and the temperature is noted at different time interval.
Then graph is plotted between temperature and time
29. What are the important uses of cooling curves.

1. Melting point and eutectic temperature can be noted from
the cooling curve.
2. Percentage purity of the compounds can be noted from
the cooling curve.
3. The behaviour of the compounds can be clearly
understood from the cooling curve.
4. The composition corresponding to its freezing point
yields the composition of the alloy.
5. The procedure of thermal analysis can be used to derive
the phase diagram of any two component system.
30. What are the uses (applications) of phase diagrams.

(A.U. May 2017, Jan. 2018)
1. It is possible to predict from the phase diagrams whether
an eutectic alloy or a solid solution is formed on cooling
a homogeneous liquid containing mixture of two metals.
2. The phase diagrams are useful in understanding the
properties of materials in the heterogeneous equilibrium
system.
3. The study of low melting eutectic alloys, used in
soldering, can be carried out using phase diagrams.
Two Marks Questions and Answers D.1
4. Composite Materials
1. Define a composite.
“A material system consisting a mixture of two (or) more
micro-constituents, which are mutually insoluble, differing in
form (or) composition and forming distinct phases”. Such a
combination, possesses properties different from those of any
of its constituents.
2. What are the constituents of composites?
Composites consist of two important constituents.
(i) Matrix phase (or) Matrix resin
(ii) Dispersed phase (or) Reinforcement.
3. What is matrix phase?
Matrix phase is the continuous body constituent, which
encloses the composite. Matrix phase may be metals, ceramics
(or) polymers (liquid resins), composites using these matrix are
known as
4. What is cure reaction?
Formation of cross-linking in certain polymers is known
as cure reaction.
Cure reactions are done by using a curing agent. These
uncross-linked linear polymers contain functional groups (or)
double bonds.
5. What is meant by reinforcement?
It is a process of improving the characteristics of the
plastic matrix by adding reinforcing agents. The reinforcing
agents may be organic (or) inorganic in nature. They may be
in the form of powder, flakes, fibres.
6. Write some characteristics of fibre.
(i) Fibre possesses high tensile strength.
(ii) It possesses high stiffness.
D.2 Engineering Chemistry
(iii) It lowers overall density of composites.

7. What are whiskers. Give examples.
Whiskers are thin strong fibre like material made by
growing a crystal.
Example: Graphite, silicon carbide, silicon nitride
8. What are the characteristics of FRP?
1. It possess superior properties like higher yield strength,
fracture strength and fatigue life.
2. Since fibre prevents slip and crack propagation, the
mechanical properties of FRP gets increased.
3. It possess high corrosion resistance and heat resistance
property.
9. What are the uses of ceramic matrix composites?
They are used in re-entry thermal shields in space
vehicles and tiles, pump seal, round rings, brake linings etc.
10. What are hybrid composites?
Hybrid composites are new class of materials composed
of a suitable polymer matrix reinforced with two different
fibres (or) fillers.
11. What are the types of hybrid composites?
Functionally hybrid composites are of three types
1. Structurally hybridized composites
2. Materials hybridized in chemical bond
3. Functionally hybridized composites.
12. Write about the uses of hybrid composites.
1. It is used in light-weight transport (land, water (or) oil)
structural components.
2. It is also used in light weight orthopedic components
and sporting goods.
3. It is used to make furniture like chair, table and bath
tubs
Two Marks Questions and Answers D.3
4. It is used in railway coach interiors.

5. It is also used in making daily used applications like
plates and spoons.
6. Automobile industry utilizes hybrid composites in many
of the interior and exterior applications.
Two Marks Questions and Answers E.1
5. Fuels
1. Write the characteristics of a good fuel.
(A.U.T Coim July 2010)
1. It should be cheap and readily available.
2. It should be safe and economical for storage and transport.
3. It should not undergo spontaneous combustion.
4. It should have higher calorific value.
5. It should have moderate ignition temperature.
6. The combustion should be easily controllable.
2. What is coalification (or) metamorphism of coal.
The process of conversion (or alteration) of vegetable
matter to anthracite is called coalification or metamorphism of
coal.
3. What are the different varieties of coal? How do you
rank them in the order of increasing calorific value?
(A.U. (Chem-II) Dec 2006)
(or)
How coals are classified. (A.U. Jan. 2018)
Coal is classified on the basis of its rank. The rank of
coal indicates its degree of maturity. Various types of coal are:
Calorific values increases from left to right.

4. Name the various determinations of proximate analysis.
It involves the determination of percentage of
(i) Moisture content.
(ii) Volatile matter.
(iii) Ash content.
(iv) Fixed carbon in coal.
E.2 Engineering Chemistry
5. What is the significance of volatile matter in coal.

High percentage of volatile matter is undesirable because
(i)it reduces the calorific value of coal,
(ii)large proportion of fuel on heating will distill over
as vapour, which escapes out unburnt,
(iii) coal with high percentage of volatile matter burns
with a long flame with high smoke,
(iv) the coal containing high percentage of volatile
matter do not coke well.
6. What is the importance of kjeldahl’s method.
The determination of nitrogen content is carried out by
Kjeldahl’s method.
7. Mention the significance of nitrogen content in coal.
(i) Nitrogen does not have any calorific value, and
its presence in coal is undesirable.
(ii) Good quality coal should have very little nitrogen
content.
8. What is meant by the term “Fixed carbon”.
(B.D.U. - Nov. 95)
It is the pure non-volatile, carbon content present in the
coal. Higher the percentage of fixed carbon greater is its
calorific value.
9. Distinguish between proximate and ultimate analysis.
(Coim A.U. July 2009, A.U May 2017)

(i) It involves the It involves the
determinations of physical determination of chemical
constituents like moisture, constituents like carbon,
volatile, ash and fixed hydrogen, nitrogen and
carbon contents in coal. sulphur and oxygen
contents in coal.

(ii) It gives the approximate It gives the exact
composition of the main composition of the
constituents of coal. elementary constituents of
coal.
10. What is carbonisation of coal.

(or)
What is metallurgical coke?
When bituminous coal is heated strongly in the absence
of air, the volatile matter escapes out and the mass becomes
hard, strong, porous and coherent which is called Metallurgical
Coke. This process is called carbonisation.
11. What are the desirable characteristics of metallurgical
coke. (A.U. June 2013)(Coim A.U.T July 2010)
(i) Purity: The moisture, ash, sulphur contents in metallurgical
coke should be low.
(ii) Porosity: Coke should be highly porous.
(iii) Strength: It should have high mechanical strength.
(iv) Calorific Value: The calorific value of coke should be high.
12. How is coke superior to coal? (or) Distinguish between
coal and coke.
(Chen A.U.T. June 2010)(Coim A.U.T May 2011)
(i) Percentage of fixed carbon and hence the calorific
value of coke is high.
(ii) Percentage of moisture, volatile and ash contents
are higher in coal, where as they are low in coke.
13. What is the difference between caking coals and coking
coals. (A.U. Dec 2012)
When coals are heated strongly, the mass becomes soft,
plastic and fuses to give a coherent mass. Such type of coals
are called Caking Coals.
But if the mass so produced is hard, porous and strong

then the coals are called Coking Coals. Coking coals possess
lower volatile matter and are used for the manufacture of
metallurgical coke.
14. What is the drawback of presence of sulphur in the
coal? (Chen A.U. June 2009, May 2015)
(i) The combustion products of sulphur, i.e.,
SO2 and SO3 are harmful and have corrosion
effects on equipments.
(ii) The coal containing sulphur is not suitable for the
preparation of metallurgical coke as it affects the
properties of the metal.
15. What are the advantages of Otto-Hoffman’s process.
1. Valuable by products like ammonia, coal gas,
naphthalene etc., are recovered.
2. The carbonisation time is less.
3. Heating is done externally by producer gas.
16. Why is coke used in metallurgical process than coal?
(A.U. Dec 2007)
(or)
Why coke is prefered to coal for metallurgical purpose?
(TCY A.U. July, Dec 2009)(A.U.T Madurai)
(i) Percentage of fixed carbon in coke is more.
(ii) The moisture, ash, sulphur contents are very low.
(iii) The mechanical strength, calorific value is high.
17. What is meant by refining of petroleum?
The process of removing impurities and separating the
crude oil into various fractions having different boiling points
is called refining of petroleum.
18. What is Cottrell’s process in crude oil refining.

(TCY A.U. Dec, July 2009)
The crude oil from oil well is an extremely stable
emulsion of oil and salt water. The crude oil is allowed to
flow between two highly charged electrodes, where colloidal
water droplets combine to form large drops, which is then
separated out from the oil.
19. What do you mean by synthetic petrol? Give the suitable
reaction. (A.U.T Coim Dec 2011)
The conversion of solid coal into liquid fuel by heating
it with hydrogen to higher temperature under high pressure is
called synthetic petrol.
20. What are the important by-products recovered from Otto
- Hoffman’s by product oven.
(i) Tar (ii) Ammonia (iii) Naphthalene (iv) Benzene
(v) H2S.
21. Explain the chemical structure and knocking

The knocking tendency of fuel hydrocarbons mainly
depends on their chemical structures. The knocking tendency
decreases in the following order.
Straight chain paraffins  Branched chain paraffins 
Cycloparaffins  Olefins  Aromatics.
Thus olefins of the same carbon-chain length possess
better anti-knock properties than the corresponding paraffins.
22. How to improve the antiknock properties of gasoline (or)
octane number.
The octane number of fuel can be improved by
(i) blending petrol of high octane number with petrol
of low octane number, so that the octane number
of the latter can be improved.
(ii) the addition of anti-knock agents like Tetra-Ethyl
Lead (TEL).
(iii) now a days aromatic phosphates are used as

antiknock agent because it avoids lead pollution.
23. Select the compound which possesses highest octane
number and highest cetane number out of n-heptane, n-
hexadecane, n-octane and iso octane.
(i) Highest octane number  Iso octane
(ii) Highest cetane number  n-hexadecane.
24. What is the cause of knocking in internal combustion

engine? Name a commonly used antiknock compound.
(A.U. June 2006)
(or)
Explain the term ‘knocking’ of a petrol engine.
(Chen A.U. Dec 2009)(A.U. Dec 2005, June 2013)
Knocking is a kind of explosion due to rapid pressure
rise occuring in petrol engine.
This can be reduced by adding TEL.
Example: Tetra ethyl lead.
25. Define octane number (or) Octane rating of a petrol?

How can it be improved?
(Chen A.U. May 2008, Coim. A.U.T. 2010, May 2011)
Octane number is defined as, “the percentage of iso-
octane present in a mixture of iso-octane and n-heptane.”
Octane number can be improved by adding anti-knock

agents like Tetra Ethyl Lead (TEL).
26. Why should leaded petrol not to be used?

(Mds - Apr. 2001)
(i) Lead deposits on the spark plug and on cylinder
walls, which is harmful to engine life.
(ii) This creates atmospheric pollution.
27. Define cetane number (or) cetane rating of a diesel oil?

How can it be improved?
(Chen A.U. July 2009)(TCY A.U.T. June 2010)
Cetane number is defined as, “the percentage of cetane
present in a mixture of cetane and -methyl naphthalene.”
The cetane number of a diesel oil can be improved by

adding dopes like Ethyl nitrate.
28. Define cetane number. Mention the cetane number of

two hydrocarbons. (A.U.T Chen June 2011)
Thus the cetane number is defined as the percentage of
hexa decane present in a mixture of hexa decane and
-methylnaphthalene, which has the same ignition lag as the
fuel under test.
CH3  CH214  CH3

n  cetane hexadecane
cetane number  100
29. What is leaded petrol? Give its significance in

automobiles. (A.U. (chem - II) Dec 2006)
When the petrol is mixed with Tetra - Ethyl Lead (TEL),
it is called leaded petrol.
Significance: Knocking in petrol engine is minimised.
30. How will you improve the anti-knocking characteristics

of diesel. (A.U. (chem - II) Dec 2006)
Antiknocking characteristics of diesel can be improved
by increasing n-cetane (hexa decane) value of the fuel.
Cetane value can be increased by adding dopes like ethyl

nitrate, iso-amyl nitrate.
31. What is meant by hydrogenation of coal?

(Bharathiar - Apr. 97)
If coal is heated with hydrogen to high temperature under
high pressure, it is converted to gasoline. The preparation of
liquid fuels from solid coal is called hydrogenation of coal.
32. What is power alcohol? Mention the advantage.
(AU. June 2014)
When ethyl alcohol is blended with petrol at a
concentration of 5-10%, it is called power alcohol.
1. It is cheaper than petrol.
2. If any moisture is present, power alcohol absorbs
it.
3. As ethyl alcohol contains oxygen atoms, complete
combustion occurs, so emission of CO,
hydrocarbon, particulates are reduced.
Two Marks Questions and Answers F.1
6. Combustion of Fuels
1. What is meant by combustion of fuels?
Combustion is a process of rapid exothermic oxidation,
in which a fuel burns in the presence of oxygen with the
evolution of heat and light.
2. Mention combustible and non-combustible constituents
present in the fuel.
Combustible constituents : C, H, S and O
Non-combustible constituents : N, CO2
3. Define calorific value of a fuel. (TNV A.U.T. July 2010)
(or)
What is meant by calorific value of fuel.
(A.U Dec 2015, June 2016)
The calorific value of a fuel is defined as “the total amount
of heat liberated, when a unit mass of fuel is burnt completely.”
4. Define GCV and LCV of a fuel. (A.U. Dec 2005, June 2006)
(i) Higher (or) Gross calorific value (G.C.V)
It is defined as the total amount of heat produced, when
a unit quantity of the fuel is completely burnt and the products
of combustion are cooled to room temperature.
(ii) Lower (or) Net Calorific Value (N.C.V)
It is defined as the net heat produced, when a unit
quantity of the fuel is completely burnt and the products of
combustion are allowed to escape.
5. What is Calorie. (A.U. Jan. 2018)
It is defined as the amount of heat required to raise the
temperature of 1 gram of water through 1C (15 to 16C).
6. Name the important units of calorific values. (A.U Jan. 2018)
(i) Calorie
(ii) Kilocalorie
F.2 Engineering Chemistry
(iii) British Thermal Unit (B.T.U)

(iv) Centigrade Heat Unit (C.H.U).
7. What are the factors, which influence the rate of combustion?
The rate of combustion depends on the following factors
1. The nature of the combustible substance (fuel).
2. The temperature.
3. The concentration of the fuel and air.
8. Give the Dulong’s formula for the calculation of GCV

and NCV.
1   O
GCV
  8080 C  34500 H   2240 S k. cal/kg
  
100   8  
  9 
NCV  HCV  H  587 k. cal/kg.
 100 
 
9. What are the reagents used in flue gas analysis? Indicate
their functions?
(or)
Name the reagents used for absorbing
CO2 , CO and O2 during flue gas analysis by orsat
apparatus.
Reagents Absorbent
KOH solution CO2
Alkaline pyrogallic acid O2
Ammoniacal cuprous chloride CO
10. Mention the uses of flue gas analysis.

Flue gas analysis gives an idea about the complete or
incomplete combustion process. If the flue gases contain
considerable amount of CO, it indicates that incomplete
combustion. If the flue gases contain considerable amount of
O2, it indicates that complete combustion.
Two Marks Questions and Answers F.3
11. What is the molecular mass and density of air?

Molecular mass of air is taken as 28.94 g/mol
3
Density of air at NTP  1.29 kg/m
12. The ultimate analysis of a coal sample indicates Carbon
= 85, Sulphur = 1.5%, Nitrogen = 0.6%, Hydrogen =
5.5% and Oxygen = 8.4%. Calculate the GCV.
(A.U. June 2012)
Solution
1   %0  
GC V  8080  %C  34500 %H   2240%S k  cal/kg
100    
  8 
1   8.4  
 8080  84  34500 5.5   2240  1.5 k  cal/kg
  
100   8 

1
 [678720  34500 5.5  1.05  3360] k  cal/kg
1
GCV  8356.05 k  cal/kg
13. What is ignition temperature? (AU June 2014)

It is “the lowest temperature to which the fuel must be
heated, so that it starts burning smoothly”.
14. Define spontaneous ignition temperature.
(AU June 2014)
It is defined as “the minimum temperature at which the
fuel catches fire (ignites) spontaneously without external
heating”.
15. Define explosive range of a fuel. (AU June 2014)
All gaseous fuels have two limits called upper limit and
lower limit. These limits represents percentage by volume of
fuel present in fuel-air mixture.
(i) Lower limit represents the smallest proportion of
combustible gas (fuel).
(ii) Upper limit represents the largest proportion of
combustible gas.
The range covered by these limits is termed as explosive
range of the fuels.
F.4 Engineering Chemistry
16. Define carbon emission?

It is defined as the release of carbon into the atmosphere.
Since green house gas emissions are often calculated as carbon
dioxide equivalents, they are often referred to as “carbon
emissions”.
17. Suggest any two methods of reducing carbon emission.
Carbon emission can be reduced by reducing green house
gas emission. It can be done by the following ways.
1. In industry, green house gases can be reduced by many
ways.
(i) Including energy efficiency
(ii) Fuel switching
(iii) Combined heat and power
(iv) Use of renewable energy
2. Avoid of using HFC’s in refrigeration, air conditioning
and foam blowing.
18. Define carbon footprint.
It is the total amount of green house gases (including
CO2 and CH4 that are generated (emitted) by our direct and
indirect activities.
Two Marks Questions and Answers G.1
7. Energy Sources
1. Define mass defect.

The difference between the calculated and experimental
masses of nucleus is called mass defect. It is denoted by
 m.
Total mass of 
 

 m  the protons, neutrons 
Experimental mass 

 of the nucleus
    
and electron
 
2. What is binding energy?
Binding energy is defined as the energy released when
a given number of protons and neutrons coalesee to form
nucleus.
3. Define nuclear energy.

The energy released by the nuclear fission (or) nuclear
fusion, is called nuclear energy.
4. What are the drawbacks of nuclear energy.

(A.U. June 2014)
(i) The nuclear radiation can damage the structure of cells
in the human body.
(ii) It causes diseases like cancer and blindness.
(iii) It causes genetic disorder in a human body.
(iv) It causes sterility in young generation.
(v) It causes serious pollution problems
(vi) Disposal of nuclear waste is the biggest problem.
5. Which isotope of uranium is used in nuclear reactor?
(A.U.T Coim July 2010)
235
U92
G.2 Engineering Chemistry
6. What are the general components of a nuclear reactor?

(TCY AU Jan 2008)
1. Fuel rods
2. Control rods
3. Coolents
4. Moderaters
5. Pressure vessel
6. Protective shield
7. Turbine
7. What is a nuclear reactor?
The arrangement or equipment used to carry out fission
reaction under controlled conditions is called a nuclear reactor.
8. What is light water nuclear - power plant?
Light-water nuclear-power plant is the one, in which
235
U fuel rods are submerged in water. Here the water acts
as coolant and moderator.
9. What are moderators. Give some examples.
The substances used to slow down the neutrons are called
moderators.
Examples
Ordinary water, Heavy water, Graphite, Beryllium.
10. What are Coolants? Give example.
(A.U.T TNV June 2011)
In order to absorb the heat produced during fission, a
liquid called coolant is circulated in the reactor core. It enters
the base of the reactor and leaves at the top. The heat carried
by out-going liquid is used to produce steam.
Example:
Water (act as moderator & coolant), heavy water, liquid
metal (Na or K), air CO2.
11. What is the major role of pressure vessel in the nuclear

reactor?
2
It withstand the pressure as high as 200 kg/cm .
12. What is fissile nucleides and fertile nucleides?

(A.U Jan 2013)
235 239
(i)
The fissionable nucleides such as U & Pu
are called fissile nucleides.
238
(ii)
The non-fissionable nucleides such as U &
232
Th are called fertile nucleides.
13. What is Breeder reactor?
(Chen & TNV AU Jan 2009) (A.U Jan 2013)
Breeder reactor is the one which converts non-fissionable
238 232 235 239
material U , Th  into fissionable material U , Pu .
14. What is meant by Solar energy conversion. How is it

done?
Solar energy conversion is the process of conversion of
direct sunlight into more useful forms. This solar energy
conversion occurs by the following two mechanisms.
1. Thermal conversion.
2. Photo conversion.
15. What is thermal conversion?
Thermal conversion involves absorption of thermal
energy in the form of IR radiation. Solar energy is an important
source for low-temperature heat (temperature below 100C,
which is useful for heating buildings, water and refrigeration.
16. Define photo conversion.

Photo conversion involves conversion of light energy
directly into electrical energy.
G.4 Engineering Chemistry
17. What is photogalvanic cell (or) Solar cell.

(Coim AU Jan 2008) (A.U Jan 2013)
Photogalvanic cell is the one, which converts the solar
energy (energy obtained from the sun) directly into electrical
energy.
It consists of a p-type semiconductor (such as Si doped
with B) and n-type semiconductor (such as Si doped with P).
They are in close contact with each other.
As the solar energy is available freely and also it is
pollution free, in future its utility is very important.
18. Explain the applications of solar cells.
1. Solar cells are used in calculators, electronic
watches, radios and TVs.
2. Solar cells are superior to other type of cells,
because these are non-polluting and eco-friendly.
3. Solar energy can be stored in Ni-Cd batteries and
lead-acid batteries.
4. Solar cells can be used to drive vehicles.
5. Solar cells, made of silicon, are used as a source
of electricity in space craft and satellites.
19. What is wind energy. How is it obtained?
(or)
Write how wind energy is generated. (A.U. Dec 2015)
Moving air is called wind. Energy recovered from the
force of the wind is called wind energy. The energy possessed
by wind is because of its high speed. The wind energy is
harnessed by making use of wind mills.
20. What are the drawbacks of wind energy.
1. Public resists for locating the wind farms in
populated areas due to noise generated by the
machines and loss of aesthetic appearance.
2. Wind farms located on the migratory routes of

birds will cause hazards.
21. What are the merits of wind energy?
(Coim A.U Feb 2010)
(i) It does not cause any air pollution.
(ii) It is very cheap and economic.
(iii) It is renewable.
(iv) It does not cause any pollution
22. Write any four methods adopted for harnessing wind

energy? (CBE. A.U. Jan 2009)
(a) Sky sail.
(b) Ladder mill.
(c) Kite ship (Large free flying sails).
(d) Sky wind power (Flying electric generator).
(e) Briza technologies (Hovering wind turbine).
(f) Sequoia automation (The kite wind generator).
23. Name any three highly invesigated solar cell materials.

1. Crystalline Si
2. Thin films
3. Next generation Perovskite Solar Cells (PSCs)
24. Define geo-thermal energy.

The energy harnessed from the high temperature present
inside the earth is called geothermal energy.
Two Marks Questions and Answers H.1
8. Batteries
1. What is a battery? How does it differ from a cell?

(A.U June 2014, June 2016)
A battery is an arrangement of several electrochemical
cells, connected in series, that can be used as a source of direct
electric current.
Thus,
A Cell: Contains only one anode and cathode.
A Battery: Contains several anodes and cathodes.
2. What are the important requirement of a battery?

A useful battery should fulfil the following requirements
1. It should be light and compact for easy transport.

2. It should have long life both when it is being
used and when it is not used.
3. The voltage of the battery should not vary
appreciably during its use.
3. What is a primary battery? Give an example
(A.U. June 2006)
(or)
What are primary cells?
Primary cells are cells in which the electrode and the
electrode reactions cannot be reversed by passing an external
electrical energy. The reactions occur only once and after use
they become dead. Therefore, they are not chargeable.
Example: Leclanche’s cell

H.2 Engineering Chemistry
4. What are secondary cells? (A.U Jan 2013)

Secondary cells are cells in which the electrode reactions
can be reversed by passing an external electrical energy.
Therefore, they can be recharged by passing electric current
and used again and again. These are also called Storage cells
(or) Accumulators.
Example: Lead acid storage cell, NiCd cell.
5. Will the emf of battery vary with size? Give reason for
your answer. (A.U. June 2014)
No, emf of a battery will not vary with size.
Reason
Emf of a battery depends only on concentration and

nature of anode and cathode.
6. Write the cell representation of lead storage cell.

The cell may be represented as;
Pb / PbSO4 // H2SO4 aq / PbO2 / Pb
7. State the reaction when a lead storage battery is

recharged. (Chen & TNV. A.U. Jan 2009)
The cell can be recharged by passing electric current in
the opposite direction. The electrode reaction gets reversed. As
a result, Pb is deposited on anode and PbO2 on the cathode.
The density of H2SO4 also increases.
The net reaction during charging is
2PbSO4s  2H2O  char ging

Energy Pbs  PbO2 s
discharging
 2H2SO4 eq
8. Write the charging and discharging reaction of lead

accumulator. (Coim AU Jan 2008)
charging
Pbs  PbO2 s  2H2SO4 2PbSO4 s
discharging
aq
 2H2O  Energy
9. What are the applications of lead acid storage cell?

1. Lead storage cell is used to supply current mainly
in automobiles such as cars, buses, trucks, etc.,
2. It is also used in gas engine ignition, telephone
exchanges, hospitals, power stations, etc.,
10. What are the advantages of storage batteries?
(i) It is made easily.
(ii) It produces very high current.
(iii) The self-discharging rate is low.
(iv) It also acts effectively at low temperature.
11. What are fuel cells?

Fuel cell is a voltaic cell, which converts the chemical
energy of the fuels directly into electricity without combustion.
It converts the energy of the fuel directly into electricity. In
these cells, the reactants, products and electrolytes pass through
the cell.
Fuel  Oxygen  Oxidation products  Electricity .
12. What are the electrodes used in the fuel cells porous?
(CBE. A.U. Jan 2009)
Compressed carbon containing a small amount of catalyst
like Pt, Pd, Ag, are used in the fuel cells porous.
H.4 Engineering Chemistry
13. What are the applications of H2O2 fuel cell?

1. H2O2 fuel cells are used as auxiliary energy
source in space vehicles, submarines or other
military-vehicles.
2. In case of H2O2 fuel cells, the product of water
is proved to be a valuable source of fresh water
by the astronauts.
14. What are the limitations of H2  O2 fuel cell?
(A.U. May 2015)
(a) Hydrogen gas is explosive.
(b) It is very expensive to be carried out.
(c) As hydrogen is a gas, it is expensive to compress
into liquid form.
(d) Hydrogen is not present as it is, but always
present in combined form with either oxygen or
some other element, so it must be separated first.
(e) While using H2  O2 fuel cell in an automobile,
a high pressure must be created inside the engine,
which is risky.
15. What is lithium-ion battery?
Lithium-ion battery is a secondary battery. As in lithium
cell, it does not contain metallic lithium as anode. As the name
suggests, the movement of lithium ions are responsible for
charging and discharging.
16. What are the components of LIB?

 A positive electrode (Layers of lithium-metal oxide)
(cathode)
 A negative electrode (Layers of porous carbon) (anode)
 An electrolyte (Polymer gel) (separator)

17. What are the advantages of lithium cell? (AU. Jan. 2018)
1. Lithium-ion batteries are high voltage and light weight
batteries.
2. It is smaller in size.
3. It produces three time the voltage of Ni-Cd batteries.
4. It has none of the memory effect seen in Ni-Cd batteries.
18. What are the uses of lithium-ion cell?
It is used in cell phone, note PC, portable LCD TV,
semiconductor driven audio, etc.,
19. What are super capacitors?
Super capacitor is a high capacity capacitor with
capacitance value much higher than other capacitor. They store
10 to 100 times more energy per unit volume and deliver
charge much faster than batteries.
20. Mention some important applications of super capacitors.
Super capacitors are used in many power management
applications like,
1. Voltage stabilization in start/stop system
2. Energy harvesting
3. Kitchen appliances
4. Regenerative braking system

Engineering Chemistry Semester I Common Branches Water Treatment

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Engineering Chemistry Semester I Common Branches Water Treatment

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SEMESTER I (Common to all Branches) ENGINEERING CHEMISTRY

UNIT I : Water and its treatment

Unit V: Energy sources and storage devices

Water and its Treatment

Water is the most important compound for the existence

(ii) rivers and lakes (surface water)

(iii) wells and springs (underground water)

(iv) sea water.

Among the above sources of water, rain water is the

The impurities present in the water may be broadly

1. Organic sources  Algae, tannins, humic compounds

1.3.2 Tastes and Odours

How to Evaluate the Odour?

1.3.3 Turbidity and sediments

Removal of Turbidity and Sediments

pH is defined as negative logarithm of hydrogen ion

Acidic  Neutr al  Basic

The rain water contaminated by the dissolved gases such as

TDS stands for Total Dissolved Solids. It is defined as

Fluoride is found in ground water as a result of

Removal of fluoride (Defluoridation)

1.3.9 Chemical Oxygen Demand (COD)

(i) Determination of COD is carried out only in 3 hours,

1.3.10 Biological Oxygen Demand (BOD)

(i) It indicates the amount of decomposable organic matter

1.3.11 Hardness of Water

1. Temporary hardness (or) Carbonate hardness (CH) (or)

2. Permanent hardness (or) Non-carbonate hardness (NCH)

1.4 TREATMENT OF WATER FOR DOMEtTIC

Fig 1.1 Sand filter

II. Sterilisation (or) Disinfection

The nascent oxygen is a powerful oxidising agent and

2. By using ultraviolet (UV) radiations

(a) By adding chlorine gas

(b) By adding chloramine

Cl2  NH3  ClNH2

Chloramine compounds decompose slowly to give

(c) By adding bleaching powder

CaOCl2  H2O  CaOH2 

Cl2  H2O  HCl  HOCl

HOCl  Bacterias  Bacterias are killed

Break point Chlorination

Fig 1.2 Break point chlorination

Chlorine may be added to water directly as a gas or in

It is observed from the graph that initially the applied

As the amount of applied chlorine increases, the amount

At one point, on further chlorination, the oxidation of

1.5.1 Reverse Osmosis (RO)

concentration. This process is called osmosis. The driving force

Fig. 1.3 Reverse Osmosis

1.д BOILER TROUBLEt (OR) BOILER FEED WATER

1.6.1 Formation of Scales and Sludges in boilers

Fig. 1.4 (a) Sludge in boiler (b) Scale in boiler

form of precipitates on the inner walls of the boilers (or) heat

1. Sludge (Loose deposit)

2. Scale (Hard deposit)

Table 1.1 Comparison of Scales and Sludges

S.No. Sludge Scale

S.No. Sludge Scale

Disadvantages of Scale Formation

Thickness of scale (mm) 0.325 0.625 1.25 2.5 12

Prevention of scale formation