CY8151 KSN Notes - by WWW - Easyengineering.net 1

Download From : www.EasyEngineering.
net
ww
w.E
a syE
ngi
nee
rin
g.n
et
**Note: Other Websites/Blogs Owners Please do not Copy (or) Republish

this Materials, Students & Graduates if You Find the Same Materials with
EasyEngineering.net Watermarks or Logo, Kindly report us to
easyengineeringnet@gmail.com
Download From : www.EasyEngineering.net
Unit Number Page Number
Unit 1 03
ww 23
w.E Unit 2
Unit 3
asy 55
Unit 4 En 94
Unit 5
g138
ine
e rin
By www.EasyEngineering.net
g.n
et

ENGINEERING CHEMISTRY (CY8151)
WATER AND ITS TREATMENT
INTRODUCTION
Water is the most essential mineral for the existence of human beings, animals and plants.
Without food human can survive for a number of days, but water is such an essential thing that
without it, one cannot survive. Water occupies a unique role in agriculture and industries also.
ww Water is one of the most abundant commodities in nature, at the same time it is the
w.E
polluted one. Although earth is a blue planet and 80% of its surface is covered by water, about
97% of it is locked in the oceans which is too saline which cannot be used for drinking as well as
for the direct use of agricultural or industrial purpose. About 2.4% is trapped in polar ice caps
asy
and glaciers. Only less than 1% of water is used by man for various developmental, industrial,
agricultural, steam generation and domestic purposes.
En
gin
SOURCES OF WATER
eer
The main sources of water are:

ing
.ne
Surface water: It includes flowing water (streams and rivers) and still
water
(lakes,ponds and reservoirs).
 Underground water: It includes water from wells and
springs. 
t
Rain water
 Estuarine and Sea water
Among the various sources of water, the rain water is the purest form of water but is
difficult to collect whereas the sea water is the most impure form. So, surface and underground
water is normally used for domestic and industrial purpose.
TYPES OF IMPURITIES PRESENT IN WATER
The impurities present in water may be categorized into following categories
1) DissolvedImpurities 1

a. Dissolved gases : O2, CO2, H2S etc.

b. Inorganic salts: (i)Cations: Ca2+, Mg2+, Na+, K+, Fe2+, Al3+ etc.
(ii)Anions: CO32–, Cl–, SO42–, NO3–etc.
c. Organic salts.
2) Suspended Impurities
a. Inorganic: Clay and sand.
b. Organic: Oil globules, vegetables, and animal material.
c. Colloidal impurities: Finely divided clay and silica Al(OH)3, Fe(OH)3,
organic waste products, coloring matter, amino acids etc.
d. Microscopic Matters: Bacteria, algae, fungi etc.
ww The process of removing all types of impurities from water and making it fit for
domestic and industrial purposes is called water technology (or) water treatment.
w.E
Water can be called as hard or soft water based on the type dissolved inorganic impurities.
Hard water
asy
En
Water which does not produce lather with soap solution, but produces white precipitate
(scum) is called hard water. This is due to the presence of dissolved Ca and Mg salts.
2C17H35COONa + MgSO4
gin
Soap (Sodium stearate) (From hard water)
(C17H35COO)2Mg
Magnesium stearate
+ Na2SO4
(Insoluble scum)
Soft water
ee rin
g.n
Water which produces lather readily with soap solution is called soft water.
C17H35COONa + H2O
Soap (Sodium stearate)
C17H35COOH +NaOH
Stearic acid
et
C17H35COONa + C17H35COOH Lather
Soap (Sodium stearate) Stearic acid
How to detect hard water?
Hardness of water can be detected in two ways.

1. By adding soap, if the water doesn’t give lather with soap, then it is hard water.
2. By adding Eriochrome Black-T (EBT) at pH=9-10, if the water gives wine
red colour then it is hard water.
Hardness of water: It is the property of water which prevents lather with soap due to presence
of calcium and magnesium salt impurities.
Types of Hardness
1. Temporary (or) Carbonate hardness: This is caused due to the presence of

bicarbonates of Ca and Mg. Since it is removed by mere boiling it is called as temporary
hardness.
ww Removal of temporary hardness:

a. On boiling the water
w.E Ca(HCO3)2
b. By adding lime to the water

∆ CaCO3 + H2O + CO2
Mg(HCO3)2 + Ca(OH)2 asy Mg(OH)2 + CaCO3 + H2O + CO2
En
2. Permanent (or) Non-carbonate hardness: This is caused due to the presence of
gin
chlorides and sulphates of Ca and Mg. It cannot be removed by boiling. Permanent
hardness can be removed by
a. Lime soda process

b. Zeolite process
ee rin
a. Lime soda (Ca(OH)2 and Na2CO3) process g.n
MgCl2 + Ca(OH)2
CaCl2 + Na2CO3
b. Zeolite process
Mg(OH)2 + CaCl2
CaCO3 + 2 NaCl et
Na2Ze + MgSO4 Na2SO4 + MgZe
EXPRESSION OF HARDNESS
CaCO3 equivalent hardness
Hardness is usually expressed in terms of CaCO3 equivalent. Because
1. CaCO3 is highly insoluble

2. Molecular weight of CaCO3 is 100 (easy for calculation)

Weight of hardness producing substance

CaCO3 equivalent hardness = X 100
Molecular weight of the hardness causing substance
UNITS OF HARDNESS
The units used to represent hardness are as follows
(i) Parts per million (ppm)
The number of parts of CaCO3 equivalent hardness per 106 parts of water. (ie)
ww (ii)
1 ppm = 1 part of CaCO3 equivalent hardness in 10 6 parts of water
Milligrams per litre (mg/l)
w.E The number of milligrams of CaCO3 equivalent hardness per litre of water.
1 mg/l= 1 mg of CaCO3 equivalent hardness in 1 L of water
asy
1 L of water weighs = 1 kg = 1000 g = 1000 x 1000 mg
= 106mg
= 1 mg of CaCO3 equivalent hardness in 106 mg of water.
1 mg/l
En= 1 part of CaCO3 equivalent hardness in 106 parts of water
Thus 1 mg/l = 1 ppm gin

= 1 ppm
(iii) Clarke’s degree : (Cl)

ee
The number of parts of CaCO3 equivalent hardness in 70,000 parts of water.
rin
1Cl = 1 part of CaCO3 equivalenthardness in 70,000 parts of water.
(iv) Degree French:(Fr) g.n

et
The number of parts of CaCO3 equivalent hardness per 105 parts of water.
1Fr = 1 part of CaCO3 equivalent hardness in105 parts of water.
(v) Milliequivalent per litre (meq/l)

The number of milli equivalents of hardness present per liter.
Thus 1 meq/L = 1 meq of CaCO3 per L of water.
= 10-3 x 50 g of CaCO3 equivalent per L

= 50 mg of CaCO3 equivalent per L
= 50 mg/L of CaCO3 equivalent = 50 ppm
RELATION SHIP BETWEEN UNITS OF HARDNESS

ppm mg/l Cl Fr meq/L

ppm 1 1 0.07 0.1 0.02
mg/l 1 1 0.07 0.1 0.02
Cl 10 10 0.7 1 0.2
Fr 14.3 14.3 1 1.43 0.286
meq/L 50 50 0.35 5 1
Problem on Hardness of water
Calculate the temporary and permanent hardness of a water sample, having the following
ww
on analysis.
w.E
Mg(HCO3)2 – 73 mg/l, Ca(HCO3)2 – 204 mg/l, CaSO4 – 130 mg/l, MgCl2 – 81mg/l, CaCl2 –
100 mg/l, NaCl – 100 mg/l
Solution:
asy
CaCO3equivalents for
hardness causing substance En 𝑤𝑒𝑖𝑔ℎ𝑡𝑜𝑓𝑡ℎ𝑒ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠𝑐𝑎𝑢𝑠𝑖𝑛𝑔𝑠𝑢𝑠𝑏𝑠𝑡𝑎𝑛𝑐𝑒× 100
= 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠𝑐𝑎𝑢𝑠𝑖𝑛𝑔𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
gin
Salt
Mg(HCO3)2
ee CaCO3 equivalent
73 × 100 rin
Ca(HCO3)2
146
204 × 100
= 50𝑚𝑔/𝑙
= 126𝑚𝑔/𝑙 g.n
CaSO4
MgCl2
162
130 × 100
136
81 × 100
= 95.5𝑚𝑔/𝑙 et
= 85.3𝑚𝑔/𝑙
95
CaCl2 100 × 100
= 68.5𝑚𝑔/𝑙
146
NaCl does not contribute to hardness
Temporary hardness = Mg(HCO3)2 + Ca(HCO3)2

= 50 + 126= 176 mg/l or ppm
Permanent Hardness = CaSO4 + MgCl2 + CaCl2

= 95.5 + 85.3 + 68.5

= 249.3 mg/l or ppm
∴ Total hardness = Temporary hardness + Permanent hardness

= 176 + 249.3 = 425.3 mg/l or ppm
ESTIMATION OF HARDNESS OF WATER
The estimation of hardness of water is of great importance for the chemical industry in general.
There are various methods available for estimating the hardness of water. Some of them
ww
are
 Soap titration method
 Alkali titration method
w.E  EDTA method
asy
Here, let us discuss the determination of hardness of water by using EDTA method.
EDTA METHOD
En
This is a complexometric titration method. It is more accurate, convenient and fast. Hence, it is
gin
widely used for the estimation of hardness of water.
EDTA is ee
EDTA is the abbreviated form of Ethylene Diamine Tetra Acetic acid. The structure of
rin
g.n
et
Principle
EDTA is insoluble in water but its disodium salt (Na2EDTA) is soluble in water. Hence
its disodium salt is used. It forms complex with metallic ions. Hence used as a complexing agent.
Eriochrome black - T (EBT) is an azo dye of steel blue colour (used as an indicator) and it
forms a wine red colored weak complex with Mg2+ and Ca2+ ions of hard water at pH 9 to 10.
When the sample water is buffered to a pH of 9 to 10 and by the addition of few

drops of EBT, water colour turns into wine red as EBT forms complex with few Ca2+
and Mg2+ ions. Then it is titrated against EDTA taken in the burette. Now EDTA starts

forming complex all the Ca2+ and Mg2+ ions and finally it extracts metallic ions from
unstable EBT complex also. Since EBT is left free in the water, the water colour turns
into steel blue which indicates the end point of the titration.
Metal ions (in water) + EBT Metal ion-EBT complex (wine red) (less stable)
Metal ion-EBT complex + EDTA Metal ion-EDTA complex (more stable) + Free EBT
(colourless) (Steel blue)
Procedure:
ww
(i)
w.E Standardization of EDTA solution using standard hardwater:
Pipette out 50 ml standard hard water in to a clean conical flask. Add 10 ml of buffer
asy
solution and 5 drops of EBT indicator and titrate it against EDTA solution taken in
the burette. The end point is the change of colour from wind red to steel blue. Repeat
En
the titrations for concordant value.
gin
Let the volume of EDTA consumed be V1 ml
(ii)
ee
Estimation of total hardness of water sample using standardized EDTA solution:
rin
Pipette out 50 ml of the hard water sample in to a clean conical flask. Add 10 ml of
g.n
buffer solution and 5 drops of EBT indicator and titrate it against standardized EDTA
solution taken in the burette. The end point is the change of color from wind red to
steel blue. Repeat the titrations for concordant value.

et
(iii) Estimation of permanent hardness of water sample using standardized EDTA
solution:
Take 100 ml of hard water sample in a 250 ml beaker. Boil it to expel temporary
hardness. Cool and filter the solution in to a 100 ml standard flask. Make up the
solution by adding distilled water.
Pipette out 50 ml of this made up solution in to a clean conical flask and add 10 ml of
buffer solution and 5 drops of EBT indicator and titrate it against standardized EDTA

solution taken in the burette. The end point is the change of color from wind red to
steel blue. Repeat the titrations for concordant value.
Calculations
(i) Standardization of EDTA solution using standard hard water:
1 ml of standard hard water = 1 mg of CaCO3

50 ml standard hard water = 50 mg of CaCO3
50 ml standard hard water requires V1 ml of EDTA
ww V1 ml of EDTA
1 ml of EDTA
= 50 mg of CaCO3 equivalent hardness
50
= 𝑉1 mg CaCO3 equivalent hardness
w.E (ii) Estimation of total hardness of water sample using standardized EDTA
solution:
asy 50
50ml of sample hard water = V2 ml of EDTA = V2x𝑉1mg of CaCO3
En
Hardness in 1000ml of sample hard water = V2x𝑉1x
50 1000
mg of CaCO3
gin
50
𝑉2
(i.e) Total hardness =𝑉1 X 1000 mg of CaCO3
(iii)
ee rin
Estimation of permanent hardness of water sample using standardized
EDTA solution:
50 g.n
50ml of boiled hard water = V3 ml of EDTA = V3x𝑉1mg of CaCO3
Hardness in 1000ml of boiled hard water = V3x𝑉1x
𝑉3
(i.e) Permanent hardness = 𝑉1X 1000 mg of CaCO3
50 1000
50
et
mg of CaCO3
(iv) Estimation of Temporary hardness:

𝑉2 𝑉3
Temporary hardness = (Total – Permanent) =𝑉1x 1000 - 𝑉1x 1000
𝑉2−𝑉3
= x 1000 mg of CaCO3
𝑉1
Problems on estimation of hardness of water

1. 100 ml of a water sample requires 20 ml of EDTA solution for titration. 1 ml of

EDTA solution is equivalent to 1.1 mg of CaCO3. Calculate hardness in ppm.
Solution:
1 ml of EDTA solution = 1.1 mg of CaCO3
CaCO3
20 ml of EDTA solution = 20 x 1.1 mg of CaCO3
= 22 mg of CaCO3
100 ml of water sample requires = 20 ml of EDTA = 22 mg of CaCO3
∴ 1000 ml of water sample = 22 x1000 mg of CaCO3
100
Hardness = 220 mg/l or ppm
ww 2. 100 ml of water sample requires 18 ml of EDTA solution for titration. 22 ml of the

same EDTA solution was required for the titration of 100 ml of standard hard water
w.E containing 1 gm CaCO3 per litre. Calculate hardness of water sample in ppm.
Solution:
asy
1 litre of std. hard water contains 1 gm of CaCO3
∴ 1 ml of std. hard water En

i.e. 1000 ml of std. hard water contains 1000 mg of CaCO3
= 1 mg of CaCO3
22 ml of EDTA
gin = 100 ml of std. hard water
= 100 x 1 mg of CaCO3
∴ 1 ml of EDTA
100 ml of water sample ee=
100
22
mg of CaCO3
= 18 ml of EDTA
100
rin
g.n
= 18 x 22 mg of CaCO3
100 1000
∴ 1000 ml of water sample = 18 x 22 x 100
Hardness = 818.18 mg/l (or) ppm
et
3. 0.28 gm of CaCO3 was dissolved in HCl and the solution was made upto 1 litre with
distilled water. 100 ml of the above solution requires 28 ml of EDTA solution on
titration. 100 ml of hard water requires 33 ml of same EDTA solution on titration.
100 ml of this water, after boiling, cooling and filtering requires 10 ml of EDTA
solution on titration. Calculate the temporary and permanent hardness of water.
Solution:
1000 ml of std. hard water = 0.28 g of CaCO3
= 0.28 x 1000 mg of CaCO3
= 280 mg of CaCO3
∴ 1 ml of std. hard water = 0.28 mg of CaCO3
28 ml of EDTA = 100 ml of std. hard water

= 100 x 0.28 mg of CaCO3

100×0.28
1 ml of EDTA = = 1 mg of CaCO3
28
(i) Total hardness
100 ml of hard water = 33 ml of EDTA
= 33 x 1 mg of CaCO3 = 33 mg of CaCO3
33×1000
∴ 1000 ml of hard water = 100
Total hardness = 330 mg/l or ppm
(ii) Permanent hardness
1000 ml of boiled hard water = 10 ml of EDTA
= 10 X 1 mg of CaCO3 = 10 mg of CaCO3
10×1000
ww ∴ 1000 ml of boiled hard water =

Permanent hardness = 100 mg/l or ppm
100
w.E (iii) Temporary hardness

Temporary hardness = Total hardness – Permanent hardness
= 330 – 100
asy
= 230 mg/l or ppm
En
4. 100 ml of water sample requires 20 ml of 0.01 M of EDTA for the titration with EBT
indicator. 100 ml of the same water sample after boiling and filtering requires 10 ml
gin
of 0.01 M EDTA. Calculate the total, carbonate and non-carbonate hardness of the
sample.
Solution:
We know that
1 ml of 1M EDTA ≡ 100 mg of CaCO3
ee rin
1 ml of 0.01 M EDTA ≡ 1 mg of CaCO3
(i) Total Hardness g.n
100 ml of water sample
CaCO3
= 20 ml of 0.01 M EDTA
= 20 X 1 mg of CaCO3 et
= 20 mg of
20×1000
∴ 1000 ml of water sample = 100
Total hardness = 200 mg/l or ppm
(ii) Non-carbonate hardness (PH)

100 ml of boiled water sample = 10 ml of 0.01 M EDTA
= 10 X 1 mg of CaCO3 = 10 mg of CaCO3
10×1000
∴ 1000 ml of boiled water sample = 100
Non-carbonate hardness = 100 mg/l or ppm
(iii) Carbonate hardness
10

Carbonate hardness = Total hardness – Non-carbonate hardness

= 200 – 100
=100 mg/l or ppm
BOILER FEED WATER
Boiler feed water: The water which is fed into the boiler for the production of steam is called
boiler feed water.
Requirements of boiler:
 Boiler feed water must have nearly zero hardness

 It must be free from dissolved gases
ww 

It should be free from suspended impurities
It should be free from dissolved salts and alkalinity.
w.E
 It should be free from oil and turbidity.
asy
Boiler troubles (or) Disadvantages of using hard water in boilers
En
Formation of deposits (scale and sludge) in steam boilers
When water is continuously heated, the concentration of dissolved salts in water
gin
increases. When the concentration of the dissolved salts reaches the saturation point they get
precipitated on the inner walls of the boiler. The least soluble salt gets precipitated first.
(a)
ee (b)
rin
g.n
et
Fig 1.1 (a) Sludge in boiler (b) Scale in boiler
Sludge (Loose deposit):

 It is a soft and non-adherent deposit.
 It can be removed by blow down operation.
 E.g. MgCl2, MgCO3, CaCl2, MgSO4, etc.,
Scale (Hard deposit):
11

 It is hard and adherent deposit.

 It is difficult to remove.
 However it can be removed by external and internal treatment and by applying
thermal shocks etc.,
 E.g. Mg(OH)2, Ca(HCO3)2, CaSO4, Silica etc.,
Disadvantages of scale formation:
1. Wastage of fuels:
 Scales are poor conductors of heat.
 They act as insulators and reduces the rate of heating.
ww  Hence, in order to produce steam, excessive or over heating is done.

 This causes increase in fuel consumption.
w.E Thickness of scale (mm)

Wastage of fuel (%)
0.325
10
0.625
15
1.25
50
2.5
80
12
150
2. Decrease in efficiency: asy

En
Scales may sometimes deposit in the valves and condensers. This results in decrease in
efficiency of the boilers.
3. Boiler explosion:
gin
ee
When thick scales are formed in the boiler, minute cracks may be formed in the boilers
due to overheating. This may lead to sudden contact of water with overheated iron plates.
rin
This lead to sudden formation of large amount of steam. Hence, sudden high pressure is
developed which may even cause boiler explosion.
Prevention of scale formation: g.n

1. By using soft water
2. By internal and external conditioning methods
3. By using scraper, wire brush etc.,
et
4. By applying thermal shocks.
5. By using suitable chemicals (like dilute acids, EDTA etc.,)
6. If it is sludge, it can be removed by blow down operation.
Table 1.1 Comparison of Scales and Sludges
S.No Sludge Scale

1. Sludge is a loose, slimy and non-adherent Scale is a thick, hard, adherent coating.
precipitate.
2. The main sludge forming substances are The main scale forming substances are
MgCO3,MgCl2 etc., Ca(HCO3)2,CaSO4 etc.,
12

3. Disadvantages: Sludges are poor conductors Disadvantages: Scales act as thermal

of heat. It decreases the efficiency of boiler. insulators. Sometimes it even ends in
explosion.
4. Prevention: Prevention:
(i) By using softened water. (i) By using acids like HCl, H2SO4.
(ii) By “blowdown operation” (ii)Scale formation can be prevented
(iii) Blow-down operation is a process of by
replacing concentrated water by fresh water. (a) External treatment
(b) Internal treatment
(iii) They can also be removed by
applying thermal shocks, using wire
brushes etc.,
ww
w.E
asy
Softening or conditioning methods:
En
The process of removal of hardness producing salts from water is known as softening or
conditioning of hard water. This can be done by two methods
1. Internal conditioning gin

2. External conditioning
1. Internal conditioning
ee rin
g.n
It is the process of treating the water inside the boilers by adding suitable chemicals. It is used to
et
remove the traces of hardness causing substances (which were not removed in external
treatment) either by converting it into sludge or as into soluble complex.
(i) Phosphate conditioning: In this method, scale formation can be prevented by

adding phosphate salts to the boiler water.
Example: 2Na3PO4 + 3CaSO4 (scale) Ca3(PO4)2 (sludge) + 3Na2SO4
The sludge Ca3(PO4)2 can be removed by blow-down operation.
The commonly used phosphates are
a) Trisodium phosphate (Na3PO4)

b) Disodium hydrogen phosphate (Na2HPO4)
c) Sodiumdihydrogen phosphate (NaH2PO4)
13

(ii) Colloidal conditioning
In this method organic substances like kerosene, tannin, agar-agar (a gel) , etc. are
added. It is suitable for low pressure boilers. These substances get coated over the scale
forming precipitates. They get converted into sludge which is removed by blow down
operation.
(iii) Sodium aluminate conditioning

Sodium aluminate added to the boiler water gets hydrolysed, yielding sodium hydroxide
and a gelatinous precipitate of aluminium hydroxide as in the reaction.
NaAlO2 + 2 H2O NaOH + Al(OH)3↓
ww The sodium hydroxide so formed, precipitates some of the magnesium ion of hard water
w.E as magnesium hydroxide.
MgCl2 + 2 NaOH2 NaCl + Mg(OH)2↓
asy
The flocculent precipitates of Al(OH)3 and Mg(OH)2 produced inside the boiler, entrap
En
finely suspended and colloidal impurities including oil drops and silica.
gin
The loose precipitate can be removed by pre-determined blow down operation.
(iv)
ee
Calgon conditioning: In this method, hardness causing salts are converted into
rin
highly soluble complexes by adding calgon. Calgon is sodium hexa meta phosphate
(NaPO3)6 or Na2[Na4(PO3)6].
2CaSO4 (scale) + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 2Na2SO4g.n

Hence scale formation is avoided.
( highly soluble complex)
et
External conditioning
It involves the removal of hardness producing salts from the water before feeding into the
boiler. It can be done by the following ways.
1. Lime soda process
2. Ion – exchange process
(a) Demineralization process
(b) Zeolite process
(a) Demineralisation process
14

This process removes almost all the ions (both anions and cations) present in the water.
Deminerelized water does not contain both anions and cations.
Thus soft water is not a demineralized water where as a demineralized water is a
soft water.
Ion exchange Resins

These are long chain, cross linked, insoluble organic polymers with micro porous structure
and having replaceable functional group. They are of two types.
1. Cation Exchanger: They contain acidic functional groups (-COOH, -SO3H) and are
capable of exchanging their H+ ions with cations of hard water. They are represented by
RH+. E.g. sulphonated coals, sulphonated polystyrene etc.,
ww2. Anion Exchanger: They contain basic functional groups (-OH) are capable of
exchanging their OH- ions with anions of hard water. They are represented by R’OH -.
E.g. cross linked quaternary ammonium salts, Urea formaldehyde resins etc.,
w.E
Diagram:
asy
En
gin
ee rin
g.n
Process
et
a. Hard water is first passed through a cation exchange column. All the cations like Ca2+,
Mg2+, Na+, K+ etc., exchange with H+ ions.
2RH+ + Ca2+ R2Ca2+ + 2H+
2RH+ + Mg2+ R2Mg2+ + 2H+
b. The cation free water is then passed through anion exchange column. These exchange
all the anions like SO42-, Cl-, CO32-, HCO3- etc., present in the water with OH- ions.
2R’OH- + SO42- R’2 SO42- + 2OH-

R’OH- + Cl- R’Cl- + OH-
15

Now the water coming out of the anion exchanger is completely free from both anions
and cations. Therefore it is called as demineralised water or deionized water.
Regeneration
a) The cation exchanger resin can be regenerated with dilute acid.

R2Ca2+ + 2H+ 2RH+ + Ca2+
R2Mg2+ + 2H+ 2RH+ + Mg2+
b) The anion exchanger resin can be regenerated with dilute NaOH.

R’2 SO42- + 2OH- 2R’OH- + SO42-
ww R’Cl- + OH- R’OH- + Cl-
w.E
Advantages
(i) Highly alkaline and acidic water can be treated.
Produces water with very low hardness (0 – 2 ppm)
(ii)
Disadvantages asy
(i)
(ii)
Equipment is costly.
Chemicals are expensive. En
(iii)
gin
Fe, Mn containing water cannot be treated ( because the regeneration is very
difficult)
(b) Zeolite (permutit) process

ee rin
g.n
Zeolites are naturally occurring hydrated sodium aluminosilicates. Its general formula is
Na2O.Al2O3.xSiO2.yH2O. Natural zeolites are green sands which are non-porous. Synthetic
zeolites is known as permutit. It is porous and has gel like structure.
et
Synthetic zeolite is represented by Na2Ze. The sodium ions which are loosely held in
Na2Ze are replaced by Ca2+ and Mg2+ ions present in the water.
Process
When hard water is passed through sodium zeolite (Na2Ze), kept in a cylinder, it exchanges
its sodium ions with Ca2+ and Mg2+ ions present in the hard water to form calcium and
magnesium zeolites.
CaSO4 + Na2Ze ----------> CaZe + Na2SO4

MgSO4 + Na2Ze ----------> MgZe + Na2SO4
Zeolite Process diagram refer page no. 1.37
16

CaCl2 + Na2Ze ---------> CaZe + 2NaCl

MgCl2 + Na2Ze ---------->MgZe + 2NaCl
The softened water contains a large amount of sodium salts, which do not cause any
hardness, but cannot be used in boilers.
Regeneration
After some time the zeolite gets exhausted. Regeneration is done by using 10% solution of
NaCl.
CaZe + 2NaCl ---------->Na2Ze + CaCl2
MgZe + 2NaCl --------->Na2Ze + MgCl2
ww
Diagram
w.E
asy
En
gin
ee rin
g.n


hardness.
et
The softened water will contain large amount of sodium salts. But they do not cause any
Soft water obtained by this process is mostly used for laundry purposes.
 Water softened by this method cannot be used in boilers, because it contains large
amount of dissolved salts (sodium salts).
Regeneration
Zeolite is regenerated by treatment with 10% solution of sodium chloride.
CaZe + 2 NaCl Na2Ze + CaCl2
MgZe + 2 NaCl Na2Ze + MgCl2
Advantages
1. Water obtained by this process will have hardness of 1 to 10 ppm only
17

2. The equipment used is compact.

3. No sludge is formed.
4. Its operation is easy
5. The process is cheap.
Disadvantages
1. Turbid water cannot be treated ( because it blocks the pores of zeolite bed)
2. Water softened by this method cannot be used in boilers, because it contains large
amount of dissolved salts (sodium salts).
3. Acidic water cannot be treated (because it affects zeolite bed)
4. Fe, Mn containing water cannot be treated ( because the regeneration is very difficult)
5. This process cannot be used for softening brackish water.
ww
w.E
Comparison of zeolite process with demineralization process:
S.No
1
Zeolite process
asy
It removes only cations
Demineralization process
It removes both cations and anions
2 En
Soft water is produced by this process
completely
Demineralized water is produced by this
3 gin process
This method cannot be used to treat This method can be used to treat highly
4
acidic water
ee acidic or alkaline water
rin
Water obtained from this treatment Water obtained from this treatment can be
cannot be used in boilers. It contains used in high pressure boilers
large amount of sodium salts
g.n
Desalination of brackish water
et
The process used for the removal of total dissolved salts from the brackish or saline
water is called desalination.
Differenttechniques of desalination are

 Distillation
 Electro dialysis
 Reverse osmosis
Let us discuss the reverse osmosis.
18

Osmosis: It is the spontaneous flow of solvent i.e. water (due to osmotic pressure) from a dilute
solution to the more concentrated solution, when these are separated by a semi-permeable
membrane. The driving force is called osmotic pressure.
Reverse osmosis: It is defined as flow of solvent i.e. water from a more concentrated solution
(salt water) to a dilute solution (fresh water), when these are separated by a semi permeable
membrane and high pressure (greater than osmotic pressure) is applied on the salt water side.
This process is also known as super filtration or hyper filtration.
The commonly used semi permeable membrane is cellulose acetate, cellulose butyrate,
aromatic polyamide and a thin film of polymer composites etc.,
ww
w.E
asy
En
gin
Advantages: ee rin
g.n
1. The lifetime of the membrane is high (2 years).
2. Water obtained by this process can be used in high pressure boilers.
3.
4.
5.
Low capital and operating cost.
Low energy consumption.
et
Removes all types of impurities like ionic, non-ionic and colloidal impurities.
Disadvantages:
1. The membrane is costly.
2. The membrane must be capable of withstanding pressure of the order of 20-100 atm.
19

ww
w.E
asy
En
gin
ee rin
g.n
et
20

R.M.D ENGINEERING COLLEGE

R.S.M.NAGAR, KAVARAIPETTAI - 601 206
ENGINEERING CHEMISTRY
UNIT-2
SURFACE CHEMISTRY
INTRODUCTION
The surfaces of solids or liquids do not have all its forces satisfied by union with other molecules
ww
or ions. This is due to the imbalance or unsaturation of molecular forces on the surface.
Therefore, molecules on the surface of a solid or liquid experience a strong inward pull due to
w.E
which the solid or liquid surface has a tendency to contact and exhibit the property of surface
tension. Adsorption is a surface phenomenon but absorption is a bulk phenomenon.E.g.
asy
hydrogen gas is absorbed by metallic palladium, whereas acetic acid is adsorbed from its
solution by activated charcoal. The word sorption is used to include both adsorption and
absorption.
En
Adsorption: The process of accumulation of a substance on the surface of a solid or liquid is
called adsorption.
gin
When adsorption is accumulation of liquid, gas or solute on the surface, absorption is the
Examples: ee
uniform distribution of the solute, liquid or gas throughout the body of solid or liquid.
rin
1. Decolourization of drinking water by activated charcoal in domestic aqua guard.
2. Decolourization of sugar solution by activated charcoal.
3. Refining of vegetable oils by fuller’s earth. g.n
4. Softening of water by ion-exchangers.
Adsorbate: The adsorbed substance on the surface is called adsorbate.

et
Example: Gases like He, Ne, O2, NH3, solutes like NaCl, CaCl2, KCl etc.
Adsorbent: The substance to which adsorbate is attached is called adsorbent.

Example: Activated charcoal, fuller’s earth, silica gel, metals like Ni, Cu, Pt, Ag etc.
Molar heat of adsorption: Adsorption is an exothermic process and the amount of heat
evolved when one mole of an adsorbate is adsorbed on an adsorbent is known as molar heat
of adsorption and it is based on the nature of adsorbent.

DIFFERENCE BETWEEN ADSORPTION AND ABSORPTION:
Adsorption Absorption
1. It is a surface phenomenon 1. It is a bulk phenomenon
2. Concentration of the substance is more 2. Substance distributed uniformly
on the surface throughout the body of the solid.
3. A fast process 3. A slow process
4. Rate of reaction increases steadily and 4. Occurs at uniform rate
reaches equilibrium 5. Endothermic process
5. Exothermic process 6. Temperature has no effect
6. Influenced by temperature 7. E.g. Absorption of carbon dioxide by
7. E.g. Adsorption of toxic gases by sodium hydroxide
activated charcoal in gas masks
ww
w.E
MECHANISM OF ADSORPTION
The process of adsorption arises due to the fact that the forces acting on the surface
asy
particles of a substance are not the same as that acting on the bulk of the material. Unlike the
particles inside the bulk, on the exposed surface, the particles are not surrounded by atoms on all
En
sides. Consequently, the forces on the inside balance each other, whereas those on the surface are
unbalanced. The unbalanced residual forces on the surface have the tendency to attract the
gin
adsorbate particles. This leads to the process of adsorption. It is to be noted here that at a given
temperature and pressure, the greater the surface area of adsorbent, higher is the extent of
adsorption.
ADSORPTION OF GASES ON SOLIDS

ee rin
Types of adsorption
g.n
The studies of adsorption of gases show that there are two main types of adsorption
depending upon the kind of forces involved.
et
1. When the intermolecular forces of attraction is weak between adsorbent and
adsorbate and the phenomenon is only physical, then it is termed as physical
adsorption or physisorption.
Ex.adsorption of H2 or O2 on charcoal
2. When adsorption involved chemical interaction between the surface atoms of
adsorbent and the atoms of the adsorbate, then it is called chemisorption.
Example:
(a) N2 is chemisorbed on nickel.
(b) H2 is chemisorbed on Ni under suitable conditions forming a surface
complex.

Comparison of chemisorption and physisorption
S.No. Physical Adsorption Chemical Adsorption

1. Occurs at very low temperature (below Occurs at all temperatures.
the boiling point of adsorbate).
2. Physisorption decreases with rise in Chemisorption increases with rise in
temperature. temperature.
3. Heat evolved is very low (4-40KJ) Heat evolved is very high (40-400KJ)
4. Reversible as the gas adsorbed can be Irreversible as the adsorbate cannot
recovered by loweringthe pressure of the recovered by lowering pressure of the
system. system
5. Multilayered adsorption is possible. Chemical forces operate withinshort
ww distances
monolayer.
only,hence chemisorptionis
w.E
6. Weak Vander Waals force. Strong covalent forces.
7. Does not show any specificity i.e. all Highly specific (occurs only whenthere is
extent
asy
gases are adsorbed on all solids to some some possibility of chemical interaction
between adsorbent solidand gas adsorbate).
En
8. No compound formation takes place in Surface compounds are formed
these cases
gin
9. Equilibrium is established rapidly. It requires time.
10. It does not require any activation energy It requires any activation energy
FACTORS AFFECTING ADSORPTION OF GASES ee rin

1. Temperature of gas:
g.n
temperatue. et
Physical adsorption: It occurs rapidly at lower temperature and decreases with increase in
Chemical adsorption: It increases with increase in temperature and then decreases.

2. Pressure of gas:
Since dynamic equilibrium exists between the absorbed gas and the gas in contact with
the solid, increase of pressure increases adsorption and decrease of pressure causes desorption
(decrease of adsorption)
3. Heat or Enthalpy of adsorption
Adsorption is always accompanied by the evolution of heat i.e. it is an exothermic. Heat

of adsorption is defined as "the energy liberated when 1 gm. of a gas is adsorbed on the solid
surface". In physical adsorption, the attraction between gas molecules and solid surfaces are due
to relatively weak VanderWaal’s forces. Hence the heat of adsorption is small (about 5
ww
k.cal/mol). In chemical adsorption, the attractive forces are due to the formation of chemical
bonds. The heat of adsorption is large. (about 100 k.cal/mol)
w.E
4. Nature of the gas
Gases which are more readily soluble and easily liquefiable such as ammonia, chlorine,
asy
hydrochloric acid and sulphur dioxide etc., are adsorbed more than the permanent gases like
hydrogen, nitrogen, oxygen etc. The reason is that Vander Waals forces which are involved in
En
adsorption are more predominant in the former, than in the latter type of gases.
5. Nature of adsorbent
gin
Since adsorption is a surface phenomenon, it is evident that greater the surface area per
temperature and pressure. ee

unit mass of the adsorbent, greater is its capacity for adsorption under the given conditions of
rin
6. Effect of activation of adsorbent
g.n
As the surface area of the adsorbent increases adsorption also increases. The surface area
et
of adsorbent can be increased by activation i.e., by creating rough surface (by mechanical or
chemical methods) and increasing effective area of the surface (by subdividing adsorbent
particles), adsorption can be increased.
ADSORPTION ISOTHERMS
The process of adsorption is usually studied through graphs known as
adsorption isotherm. It is the graph between the amounts of adsorbate (x) adsorbed on the
surface of adsorbent (m) and pressure at constant temperature.
Some basic adsorption isotherms are
1. Freundlich adsorption isotherm

2. Langmuir adsorption isotherm
3. BET (Brunauer, Emmett and Teller) adsorption isotherm

Types of adsorption isotherms

A large number of adsorption isotherms of gases on a variety of adsorbents at different
temperatures have been studied. Their results are given in to five different types of adsorption
isotherms. In each type, the saturation pressure, where the maximum adsorption occurs, is
indicated by Ps.
ww
w.E
asy
TYPE 1 corresponds to monomolecular adsorption of Langmuir. The volume of gas
adsorbed approaches a limiting value Ps which is just enough to complete a monomolecular
En
layer, even when the gas pressure is low. Further increase in pressure will not increase the
gin
amount of adsorption. Ex. Adsorption of H2 or N2 on charcoal at -180oC.
ee
TYPE 2 and TYPE 3 show deviations from Langmuir model. The amount of gas
rin
adsorbed increases with increase in pressure. This explains the formation of multilayers on the
surface of the adsorbent due to the Vander wallsforces of attraction.
Example: Type 2: Adsorption of N2on Fe or Pt catalyst at 195oC.
Type 3: Adsorption of Br2 on silica or Alumina gel at 80oC. g.n
et
TYPE 4 and TYPE 5 indicate that there is a possibility of condensation of gases in the minute
capillary pores of the adsorbent at pressures even below the saturation pressure Ps of the gas. In
these cases not only multilayers are formed but also condensations of gases in the capillary pores
of adsorbent molecule take place. This is known as capillary condensation of the gas.
Examples:
Type- 4:Adsorption of benzene vapours on ferric oxide gel at 50 ºC
Type -5: Adsorption of water vapour on charcoal at 100ºC .
THEORIES OF ADSORPTION ISOTHERMS
1. Freundlich adsorption isotherm

A plot of the amount of gas adsorbed on a solid adsorbent surface versus pressure of the
gas at constant temperature is called adsorption isotherm. Freundlich proposed an empirical
relationship (Freundlich adsorption isotherm) between the quantity of gas adsorbed by a given
amount of solid adsorbent surface and pressure at a particular temperature as
a = x/m = kp1/n (1)
Where
a = amount of gas adsorbed per unit mass of the adsorbent
x = weight of gas absorbed
m = mass of the adsorbent in g.
p = pressure of the gas
ww k and n are constants at a particular temperature and for a particular adsorbent and gas.
w.E
This equation for freundlich's adsorption isotherm may derived from the result observed from the
graph. Thus
asy
En
gin
ee rin
g.n
(i)At low pressure: Adsorption increases with pressure. et
(ii)At high pressure: Adsorption is almost constant.
(iii)At intermediate pressure:
Where n = whole number.

The equation (1) is called Freundlich's adsorption isotherm.

Taking log on both sides the equation (1) becomes

log x/m = log k + 1/n log p. ------------ (2)
This is an equation of a straight line with a slope equal to 1/n and the intercept equal to log k.
Limitations
1. Valid over a certain range of pressure only.
2. The constants k and n vary with temperature.
3. Purely empirical.
2. The Langmuir’s theory of adsorption or Langmuir’s adsorption isotherm

In 1916, Irving Langmuir proposed a theory of adsorption on the solid surface. It is
ww
considered that the adsorbent surface has sites which adsorbs one molecule of gas.
Assumptions
1. All adsorption sites are equivalent, that is, have the same affinity towards gas molecules.
w.E
2. A dynamic equilibrium exists between the adsorbed molecules and free molecules.
3. The adsorbed gas behaves ideally in the gas phase.
asy
4. Only a monolayer is formed.
5. There is no interaction between the adsorbate molecules.
En
6. The adsorbed molecules are localized, that is, they do not move around on the surface.
Derivation:
gin
ee
According to Langmuir's assumptions, when the gas molecules strike the solid surface, some of
rin
the molecules are adsorbed and some of these are desorbed. Thereby dynamic equilibrium is
established between adsorption and desorption. If A is gas molecule and M is surface then,
g.n
et

Let us consider,
Surface area = 1 cm2& pressure = P
Fraction of the total surface covered by the adsorbed molecules surface area = θ
Fraction of uncovered area (vacant area) = (1 – θ)
Where kd= Rateconstant for desorption
ww
w.E Where ka = Rate constant for adsorption.
asy
At equilibrium, rate of desorption = rate of adsorption
En
gin
ee
But θ α a, where a is the amount of gas molecules adsorbed.
rin
g.n
Equation (2) is called as Langmuir’s adsorption isotherm.
Interpretation of Langmuir’s adsorption isotherm:

et
Case 1 - At low pressure:
If, kaP <<kd The equation (4) becomes,
θ = a = kaP / kd (or) a = const x P1
This behavior corresponds to first order reaction.
Case 2 - At high pressure:
kaP>>Kd. The equation (4) becomes,

θ = a = kaP / kaP = 1 i.e. θ = a = 1 (or) const x P0
i.e., the reaction follows the zero order reaction.
Case 3 - At moderate pressure:

At low pressure a = const x P1
At high pressure a = const x P0
At moderate pressure a = const x P1-0
i.e, a = kP1/n where n is a whole number. This is Freundlich isotherm.
Graph:
ww
w.E
asy
En
ADSORPTION FROM SOLUTIONS gin
ee
Only monolayer adsorption is possible in case of solutions. Because the formation of
rin
multilayer is inhibited by the solvating power of the solvent. Freundlisch isotherm is applicable
to adsorption of solute from solutions.
a= kC1/n (or) x/m = kC1/n

g.n
Where, a = amount of solute adsorbed
x = mass of solute adsorbed
m= mass of adsorbent
et
C= concentration of the solution
Types of adsorption of solute from solution:
1. Positive adsorption: It involves the adsorption of solute particles on the adsorbent

which leads to decrease in concentration of solution. Example: charcoal in acetic acid
solution
2. Negative adsorption: It involves the adsorption of solvent molecules on the adsorbent
which leads to increase in concentration of solution. Example: charcoal in dilute KCl.
3. Electrostatic adsorption: sometimes electrostatic charges may acquire on the surface of
the adsorbent when it comes in contact with polar solvents like H2O, HCl etc., which
attracts the oppositely charged ions from the solution.

ROLE OF ADSORBENT IN CATALYTIC REACTION (SURFACE REACTIONS) (OR)

CONTACT THEORY:
Theory of heterogeneous catalysts:

1. The surface of a solid catalyst has active spots.
2. Concentration of liquid or gas will be more on the surface than in the bulk.
3. Since the rate of the reaction is proportional to concentration, the rate will be faster at the
surface.
4. Products leaves the surface after some time, leaving free surface for further reaction.
ww
Mechanism: Ni-cat
CH3 – CH3
w.E
Example : CH2 = CH2 + H2
1. Diffusion of reactant to the surface: The reactants undergo diffusion on the surface of
catalysts.
asy
2. Adsorption of reactant: The surface of the solid catalyst possesses some isolated active
En
centres, which adsorbs gaseous reactants either by physisorption (or) chemisorption.
Heat of adsorption evolved during chemisorption provide necessary activation energy for
the adsorption reaction.
gin
ee rin
g.n
et
3. Formation of activated complex: The adsorbed molecules interact with the surface and
form an activated complex.

4. Decomposition of activated complex: Activated complex breaks to give the products.

The seperated particles of the products bound to the catalysts surface by partial chemical
bonds.
ww 5. Diffusion of products: Products get desorbed and diffused away from the surface.
w.E
asy
En
Factors affecting surface reactions: gin
surface area.
ee
1. Particle size of the catalyst: Finely divided catalyst is more effective due to its larger
rin
g.n
et
2. Rough surfaced catalyst: Rough surface have larger no. of active centers which
increases the rate of reaction.
3. Promoters: These are catalysts of catalyst. They produce more active centers.
4. Poisons: These are anti catalysts of catalysts. It reduces the adsorption of reactants.
5. Specificity: catalysts are highly specific.

KINETICS OF SURFACE CATALYZED REACTIONS
UNIMOLECULAR REACTIONS:
Examples of unimolecular reactions
a) Decomposition of NH3 to N2 and H2 metal surfaces.

b) Decomposition of phosphine on glass
c) Decomposition of formic acid on glass, Pt, Ag, Au or TiO 2.
d) Decomposition of N2O on gold.
e) Decomposition of HI on platinum.
Mechanism:
ww
w.E Rate = K2A
asy
Where A = Surface coverage of A and K2<<<K1 (ie) the rate of reaction of adsorbed A
En
molecules ie., much greater than the rate of desorption of unreacted A.
gin
Langmuir adsorption isotherm can be used to determine Aas
ee rin
g.n
This type of reaction shows two limiting rate laws, corresponding to the two extreme behaviours
of the Langmuir isotherm.
(a) At low pressure (PA 0)
Ais very small and 1 + KAPA in the denominator can be neglected. Now
et
At low P, rate = K2KAPA (or)
rate  PA
Thus, it is a first orer with respect to A(g).
(b) At high pressure
 is approximately equal to unity as

as KAPA>>>1
Thus, the reaction is zeroth order.
These discussions are shown graphically as
ww
w.E
asy
En
gin
ee
ACTIVATED CARBON IN POLLUTION ABATEMENT OF AIR AND WATER:
rin
Among the various adsorbents, in pollution abatement of air and waste water, activated carbon is
the most commonly used adsorbent because it has a large surface area per unit volume of the
solid.
g.n
1. Granular Activated Carbon (GAC)
2. Powdered Activated Carbon (PAC)
et
Polluted water and air can be treated by using the following two types of activated carbon.
1. Using Granular Activated Carbon (GAC):
Several types of fixed bed activated-carbon column with GAC are used in the treatment of
polluted water (or) air, of which the following are important.
a) Down flow fixed bed activated carbon column:

It usually consists of 2 or 3 columns operated in series (o) in parallel as shown in the
figure.

The water (or) air is applied to the top of the column and withdrawn at the bottom. The
activated carbon is held at the bottom of the column.
ww Advantages: Absorption of organic materials and filtration of suspended solids are

accompanied in a single step.
w.E Disadvantages: Requires more back washing because of the accumulation of suspended
materials on the surface of the column.
asy
b) Up-flow fixed bed activated carbon column:
En
Here the polluted water (or) air moves upward from the base of the column as
shown in the figure.
gin
ee rin
g.n
et
Advantages: As the carbon adsorbs organic material, its apparent density increases and
encourages the migration of heavier carbon downward.
Disadvantages: It may have more carbon fines in the effluent than down flow columns.
Because upflow tends to expand the carbon which allows the fines to escape through
passage ways.
2. Using Powdered Activated Carbon (PAC):
Here PAC is directly added into the effluent coming out from the various biological
treatment processes. The effluent is mixed with PAC and a coagulant. The water is allowed to
store in a clarification tank, where the carbon particles settled at the bottom. Since the carbon

particles are very fine a coagulant such as polyelectrolyte is added to remove the carbon
particles. The spent carbon is regenerated and is used again for the process. Finally the water is
filtered by passing it through the filtration column.
ww
w.E
asy
En
Applications of Activated Carbon in pollution abatement:
gin
1. Odour control: Activated carbon adsorbents are commonly used for odour control.
ee
2. Removes colour: Activated carbon with its great surface area and pore volume,
removes colour from the solution
rin
3. Used in water purifier: Activated carbon is also used in cleaning sugar solution
and for the removal of bad tastes from water.
g.n
4. Used ingas masks: Activated carbon is used in gas masks, because of its ability to
adsorb poisonous gases. It is now employed in both military and industrial gas
masks.
et
5. Used inair conditioning: Activated carbon is used in air conditioning systems to
control odours in large restaurants, auditoriums etc.,
6. Used incigarette filters: Specially impregnated grades of activated carbon are used
in cigarette filters.
7. Removal of the organic and inorganic compounds: Activated carbon is generally
used for the removal of the organic compounds as well as residual amounts of
inorganic compounds such as nitrogen, sulfides and heavy metals.
8. Removal of impurities: Used as adsorbent to remove impurities from gases such as
H2, N2, He, NH3 etc.,
9. Removal of Sulphur: Activated carbon impregnated with Fe/Cu salts is used in the
removal of organic sulfur compounds, H2S and other impurities.

10. Used in nuclear reactor: Radioactive emanations can be adsorbed from nuclear
reactor.
CATALYSIS
INTRODUCTION
Berzelius in 1836 realized that there are substances which increase the rate of a reaction
without themselves being consumed. He believed that the function of such a substance was to
loosen the bonds which hold the atoms in the reaction molecules together. Thus, he coined the
term catalysis (Greek, kata = wholly, lein = to loosen).
There is no doubt that usually a catalyst accelerates a reaction. But a number of cases are
ww
now known where the catalyst definitely slows down the rate of the reaction.
w.E
DEFINITION
CATALYST
asy
A catalyst is defined as a substance which alters the rate of a chemical reaction, itself remaining
chemically unchanged at the end of the reaction.
CATALYSIS En
gin
The process of altering (increasing or decreasing) the rate of a chemical reaction with the help of
catalyst is known as catalysis.
TYPES OF CATALYSTS ee rin

1. Positive catalyst:
g.n
A catalyst, which enhances (increases) the rate of the chemical reaction is called a positive
catalyst.
Example:
et
2. Negative catalyst:
A catalyst, which retards (decreases) the rate of the chemical reaction is called a negative catalyst
(or) Inhibitors.
EFFECT OF A CATALYST:
A catalyst increases the rate of a reaction by lowering the energy barrier between the reactant and
products. Otherwise we may say that, the catalyst provide another path for the reaction, that has
lower energy of activation (Ea). The below figure shows the new path, in presence of the
catalyst.

ww
TYPES OF CATALYSIS
w.E
There are two main type of catalysis
a) Homogeneous catalysis
b) Heterogeneous catalysis
asy
En
Also, there is a third type of catalysis known as Enzyme catalysis which is largely of biological
interest.
a) Homogeneous catalysis gin

distributed throughout.
ee
In homogeneous catalysis, the catalyst is in the same phase as the reactants and is evenly
rin
g.n
This type of catalysis can occur in gas phase or the liquid (solution) phase.
1) Examples (Gas phase)

(i) et
Oxidation of sulphur dioxide (SO2) to sulphur trioxide (SO3) with nitric oxide
(NO) as catalyst
(ii) Decomposition of acetaldehyde with iodine as catalyst.
2) Examples (Solution)
(i) Hydrolysis of cane sugar in aqueous solution in presence of mineral acid as
catalyst.
(ii) Hydrolysis of an ester in the presence of acid or alkali.

(iii) Decomposition of H2O2 in the presence of catalyst I- as catalyst.
Heterogeneous catalysis
The catalysis in which the catalyst is in a different physical phase from the reactants is
termed heterogeneous catalysis.
The most important of such reactions are those in which the reactants are in the gas phase,
ww while the catalyst is a solid the process is called contact catalysis since the reaction occurs by
contact of reactants, with the catalyst surface. Usually the catalyst is a finely divided metal or
a gauze .This form of catalysis has great industrial importance.
w.E
Examples (Gaseous reactants)
(i)
asy
Combination of sulphur dioxide (SO2) and oxygen in the presence of finely divided
platinum or vanadium pentoxide. This is called contact process of sulphric acid
manufacture.
En
(ii) gin
Combination of nitrogen and hydrogen to form ammonia in the presence of finely
divided iron.(Haber process )
ee rin
(iii)
g.n
Oxidation of ammonia to nitric oxide in the presence of platinum gauze.
(iv) et
Hydrogenation reactions of unsaturated organic compounds are catalyzed by finely
divided nickel.
Examples (Liquid reactants)
(i) The decomposition of aqueous solution of hydrogen peroxide is catalyzed by MnO2

orcolloidal platinum.

(ii) Benzene and acetyl chloride react in the presence of anhydrous aluminium chloride
to form acetophenone (Friedrel Crafts aceylation)
Examples (Solid reactants)
The decomposition of potassium chlorate is catalyzed by manganese dioxide.
ww Differences between homogeneous catalysis and heterogeneous catalysis
w.E S.No
1
Homogeneous catalysis
Reactants, products and catalyst
Heterogeneous catalysis
Reactants, products and catalyst are
asy
are present in only one phase. present in different phase.
2 Catalyst is not generated. Catalyst is regenerated.
3 Thermal stability of the catalyst Thermal stability of the catalyst is high.
4
is low.
En
Reactions are carried out at low Reactions are carried out at high
5 gin
temperature and pressure.
Selectivity of the catalyst does
temperature and pressure.
Selectivity of the catalyst depends on
not depend on the physical
nature.
ee the physical nature.
rin
Criteria of catalysis
g.n
et
The following characteristics are generally common to most of the catalytic reactions.
1) A catalyst remains unchanged in mass and chemical composition.
Qualitative and quantitative analyses show that a catalyst undergoes no change in mass or
chemical nature. However, it may undergo some physical change.
2) Only a small quantity of the catalyst is generally needed.
In many reactions only a small amount of the catalyst is required .For instance, such a
low concentration as one gram atom of colloidal platinum in 10 8 litres can catalyze the
decomposition of H2O2 .
As low concentration of one gram of ion of Cu (II) in 10 6 litres can catalyze the oxidation
of sodium sulphite by atmospheric oxygen.

On the other hand there are catalysts which need to be present in relatively large amount
to be effective.
The rate of the above reaction is proportional to the concentration of the catalyst (H + or
OH- ).
3) The catalyst does not alter the position of equilibrium in a reversible reaction.
Bodenstein was able to show that although the use of a catalyst hastened the approach of
equilibrium in the hydrogen iodide decomposition.
ww
w.E It did not alter the concentration of the reactants or the products. This has been found to
be true in the case of several other reversible reactions as well.
asy
4) The catalyst does not initiate the reaction
En
The reaction is already occurring, though extremely slowly, in the absence of the catalyst.
The function of the catalyst seems to be only to speed up the reaction considerably. The
gin
reaction in the presence of a catalyst takes place through some alternative path which
required much lower energy of activation. Hence, it is speeded up.
ee
5) The catalyst is generally specific in its action
rin
Manganese dioxide, for example, can catalyze the decomposition of potassium chlorate
g.n
but not that of potassium perchlorate or potassium nitrate. Thus, manganese dioxide is
specific in its action.
Enzymes also have specific catalytic actions.
6) The catalyst cannot alter the nature of the products of the reaction.
et
The combination of nitrogen and hydrogen under suitable conditions forms ammonia
whether a catalyst is added or not.
Potassium chlorate on decomposition gives potassium chloride and oxygen whether

manganese dioxide is added or not.
There are however a few exceptions. CO and H2 combine to form CH4, CH3OH or
HCHO depending upon the nature of the catalyst used.
Ni
CO + 3H2 CH4 + H2O

ZnO+Cr2O3
CO + 2H2 CH3OH
O+
Cu
CO + H2 HCHO
7) A catalyst is more effective when finely divided
In heterogeneous catalyst the solid catalyst is more effective when it is in a state of fine
division than it is used in bulk.
Thus a lump of platinum will have much less catalytic activity than colloidal or platinized
asbestos
Finely divided Nickel is a better catalyst than lumps of solid nickel.
ww 8) A catalyst is poisoned by certain substances or catalytic poison.
w.E It has been found that impurities of any type, even if it is present in small amounts,
inhibit or retard the rate of catalyzed reactions to a large extent. These impurities are
therefore called catalytic poisons.
asy
For example, the rate of combination of sulphur dioxide and oxygen (in contact process)
En
is slowed down considerably if some arsenic compounds are present even in traces.
AUTOCATALYSIS
gin
When one of the products of a reaction acts as a catalyst for that reaction the phenomenon
is called autocatalysis.
Examples:
ee rin
1. Hydrolysis of an ester
g.n
The hydrolysis of ethyl acetate forms acetic acid and ethyl alcohol. Of these products
acetic acid acts as a catalyst for the reaction.
et
2. Decomposition of arsine
The free arsenic produced by the decomposition of arsine autocatalyses the reaction
3. Oxidation of oxalic acid

When oxalic acid is oxidized by acidified potassium permanganate, manganese sulphate
produce during the reaction acts as a catalyst for the reaction

CATALYTIC PROMOTERS
A substance which promotes the activity of the catalyst to which it is added in small
amounts is known as catalytic promoters. This process is called as activation.
Examples:
1. In Haber’s process of ammonia manufacture – iron acts as a catalyst while molybdenum
or a mixture of Al2O3 and K2O acts as a promoter.
2. In the manufacture of CH3OH from CO and H2, ZnO is the catalyst while chromium is
the promoter.
Promoters improve one or more of the following properties of the catalyst.
ww i)
ii)
Activity enhancement
Selectivity enhancement
w.E
iii)
Function
Increased catalyst lifetime
1. Promoters increase the spaces between the catalyst particles
asy
Hence the adsorbed gas molecules like H2 are weakened and finally broken. This
enhances the rate of the reaction.
En
2. Promoters increases the number of peaks and cracks on the surface of the
catalyst.
CATALYTIC POISON
gin
A substance which reduces or destroys the catalytic activity of a catalyst is known as
Examples:
ee
catalytic poison. The process is called as a catalytic poisoning. This is observed in solid
catalyst.
rin
1. In the contact process of H2SO4 manufacture-platinum is the catalyst, traces of
arsenic compounds are catalytic poison.
2. Iron catalyst is poisoned by H2S. g.n
Catalytic poisoning is of the following two types
Function:
(i)
(ii)
Temporary poisoning
Permanent poisoning
et
(i) By preferential adsorption of catalytic poisons on the surface of solid catalyst, the
number of active centres or free valencies of the catalysts are reduced.
(ii) The catalyst may combine chemically with the catalytic poison.
Example:
The poisoning of iron catalyst by H2S
ACID BASE CATALYSIS

A large number of homogeneous catalytic reactions are brought about by acids or bases
or both. These reactions are called acid-base catalysis.The acid is the proton donor and the base
is the proton acceptor, known as Bronsted-Lowry acid and base respectively

ACID CATALYSIS
This is of the following two types.
1. Specific H+ ion catalysis
2. General acid catalysis
Examples for type I - Specific H+ ion catalysis
i) Inversion of cane sugar H+

C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose glucose fructose
ii) Hydrolysis of an ester H+
CH3COOC2H5 CH3COOH + C2H5OH
iii) Keto-enol tautomerism in acetone
ww
w.E
asy
Examples for type II - General acid catalysis
i)
En
Iodination of acetone into iodo acetone catalysed by H2O
ii) gin
Conversion of N-chloroacetanide to p-chloroacetanilide
BASE CATALYSIS
This is of the following two types
1. Specific OH- ion catalysis
ee rin
2. General base catalysis
g.n
Example for type I - Specific OH- ion catalysis
i.) Hydrolysis of an ester

et
CH3COOC2H5 OH- CH3COO- + C2H5OH
ii.) Conversion of acetone into diacetone alcohol

OH-
2CH3COCH3 CH3COCH2C(OH)(CH3)2
Example for type II - General base catalysis
CH3coo-
i) NH2NO3 N2O + H2O

REACTION CATALYSED BOTH BY ACIDS AND BASES

1. Ester hydrolysis
H+& OH-
CH3COOC2H5 CH3COOH + C2H5OH
2. Hydrolysis of an alkyl nitrile

H+& OH-
RCN + 2H2O RCOONH4
3. Mutarotation of glucose
H+
α-glucose β-glucose
OH-
APPLICATION OF CATALYSIS
ww
w.E
S.No Process Catalyst used
1. Haber process of ammonia Iron
2. Syn gas (CO+H2) production Nickel
3
4
5. asy
Cracking of petroleum
Contact process of H2SO4 production
Ostwald process of HNO3 production
Zeolite
V2O5 on silica
Pt and Rh
6.
7 En
Hydrogenation of oil
Methanol production
Nickel
ZnO/Cr2O3
CATALYTIC CONVERTER gin

ee
A catalytic converter is an emission control device. This converts toxic gases and
rin
pollutants in exhaust gas to less toxic pollutants by catalyzing a redox (both reduction and
oxidation) reaction.
g.n
These are used in internal combustion engines fueled by either petrol or diesel including
lean burn engines as well as kerosene heaters and stoves.
Types:
There are two types of catalytic converters
(i)
(ii)
Two way / stage converter
Three way / stage converter
et
Two stage converter:
It has two converters ie I converter and II converter
In the first converter (reducing stage), the oxides of nitrogen are reduced to N2 and small
amount of NH3 in the presence of reducing catalyst and reducing agents (Pt and Rh) CO
and hydrocarbons (HC)

In the second converter (oxidizing stage) air is introduced to provide an oxidizing

atmosphere to complete the oxidation of CO and HCs in to CO2 and water vapours in the
presence of finely divided oxidizing catalyst (Pt and Pd).
The flow diagram of two stage converter is shown in the figure.
ww
w.E
Three stage converter:
This system operates at high temperature, > 800oC as ceramic honey comb is used.
asy
This catalyst is composed of platinum and rhodium.
En
This system is capable of eliminates all air contaminents.
gin
This unit oxidises HCs and CO simultaneously to CO2 and water. At the same time, it
reduces NOx to N2.
ee
Here, the HCs and CO react with the oxygen of NOx to form CO2, water, N2 and O2.
rin
g.n
et
Advantages of three stage converter
(i) This is more efficient than two stage converter system

(ii) This is quite effective in reducing the exhaust emissions to negligible levels.
Disadvantages
Three stage converters require either rich or stoichiometric combustion to successfully

reduce NOx.
Applications
Catalytic converters are used in (i) electrical generators (ii) forklifts (iii) mining
equipments (iv) trucks (v) buses (vi) locomotives (vii) motorcycles (viii) wood
stoves.
ww Reaction which occur in 2 way converter is
CxH2x+2 +
3𝑥+1
O2 x CO2 + (x+1) H2O
w.E 2
Reaction which occur in 3 way converter is
(i) Reduction of NOx to N2

asy
(ii) Oxidation of CO to CO2
En
gin
(iii) Oxidation of HCs to CO2 and H2O
3𝑥+1
ENZYME CATALYSIS
CxH2x+2 + 2
O2
ee x CO2 + (x+1) H2O
rin
g.n
Numerous organic reactions are taking place in the body of animals and plants to
maintain the life process. These reactions are remarkably catalyzed by the organic
et
compounds known as enzymes. All enzymes have been found to be complex protein
molecules with relatively high molar mass of the order of 10,000 or even more.
DEFINITION:
Enzymes are protein molecules which act as catalysts to speed up organic reactions to
living cells. The catalyst brought about by enzymes is known as enzyme catalysis.
Some common examples of the biochemical reactions catalyzed by enzymes are
(i) The enzyme diastase converts starch in to maltose

(ii) Maltase converts maltose in to glucose
(iii) Zymase produced by living yeast cells converts glucose in to ethyl alcohol.
ww (iv) Invertase present in yeast converts sucrose in to glucose and fructose. This is
called inversion of cane sugar.
w.E
(v)
asy
The enzyme urease present in soya beans brings about quantitative hydrolytic
decomposition of urea in to ammonia and carbon dioxide,
En
gin
CHARACTERISTICS OF ENZYME CATALYSIS ee rin
Some important features of enzyme catalysis are listed below –
g.n
(i)
(ii)
Enzymes are the most efficient catalyst known. et
Enzyme catalysis is noted for its absolute specificity.
(iii) The rate of enzyme catalyzed reactions is maximum at the optimum
temperature.
(iv) The rate of enzyme catalyzed reactions is maximum at the optimum
pH.
(v) Enzymes are markedly inhibited or poisoned.
(vi) Catalytic activity of enzymes is greatly enhanced by the presence of
activators or coenzymes.

MECHANISM OF ENZYME CATALYSIS
The long chains of the enzyme (proteins) molecule are coiled on each other to make a
rigid colloidal particle with cavities on its surface. These cavities which are of
characteristic shape and around in active groups like OH, COOH, SH, NH2 are termed
active centres.
The molecule of substrate (reactants) which have complementary shape, fit into these
cavities just as key fits into a lock ( lock and key theory).
By the virtue of the presence of active groups , the enzyme forms an activated
complex with the substance which at once decompose to yield the products. Thus, the
ww substrate molecule enters the cavities , forms complex, reacts and at once the product get
out of the cavities.
w.E
asy
En
gin
ee rin
Kinetics of Enzyme Catalyzed Reaction (Or) Michaelis-MentenEquation:
g.n
BiochemistL.Michaelis and M.Menten in 1913 proposed a mechanism for the kinetics of
enzyme catalyzed reactions which involves the following steps.
et
Let the enzyme E react with the substrate (reactant) S. The first reaction, which is fast
reaction, is the formation of the intermediate complex X.
This Intermediate complex may dissociate back into E and S.
Or it may form the product P slowly.

Here, k1,k2 and k3 are the rate constants for the respective reactions.
The rate of formation of the intermediate complex X is given by
Here, [E], [S] and [X] are the molar concentration of the enzyme, substrate and
intermediate complex respectively.
ww The rate of formation of the product, P is given by
w.E
asy
As [Eo] = [E] + [X] or [E] = [Eo] – [X] the equation (4) can be written as
En
gin
ee
Here [E0] = total concentration of the enzyme
[E] = molar concentration of the unreacted enzyme

rin
[X] = concentration of the enzyme present in the complex
g.n
The intermediate complex is unstable, it decomposes instantaneously.
et
This state is called stationary state. At this state, we can write equation (6) as

𝑘1 [𝐸𝑜][𝑆]
(or),[𝑋 ] = − − − −(12)
k1[S] + (k2 + k3)
Dividing by k1[S] we have
[𝐸𝑜]
[𝑋 ] = − − − − − (13)
𝑘2 + 𝑘3
1 +
𝑘1[𝑆]
ww Substituting the value of [X] in the equation (5) we get,
w.E 𝑑[𝑃]
𝑑𝑡
=
𝑘1[𝐸𝑜]
1 +
𝑘2 + 𝑘3
𝑘1[𝑆]
− − − − − (14)
asy
𝑘2 + 𝑘3
En
𝑘1[𝑆]
= 𝑘𝑚 = 𝑀𝑖𝑐ℎ𝑎𝑒𝑙𝑖𝑠𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑑[𝑃]
𝑑𝑡 gin
=
𝑘1[𝐸𝑜]
1 +
𝑘𝑚
− − − − − (15)
Multiplying both Nr and Dr by [S]

ee[𝑆]
rin
𝑟𝑎𝑡𝑒 =
𝑘1[𝐸𝑜][𝑆]
[S] + km
− − − − − (16) g.n
Equation 16 is known as Michaelis – Menten equation et
Case 1:- At lower concentration:
When the concentration of the substrate is less than km, [S] may be neglected in the
denominator, i.e., [S] << km
𝑑[𝑃] 𝑘1[𝐸𝑜][𝑆]
= − − − − − (17)
𝑑𝑡 km
This is the first order reaction, i.e., first order with respect to substrate.
Case 2:- At higher concentration:

When the concentration of the substrate is higher than km, i.e., [S] >>km, then
𝑑[𝑃] 𝑘1[𝐸𝑜][𝑆]
= = 𝑘1[𝐸𝑜] − − − − − (18)
𝑑𝑡 [S]
This is the zero order reaction, i.e., zero order with respect to substrate.
Effect of substrate concentration on the rate:
From the above 2 cases, it is clear that the reaction rate of an enzyme catalyzed reaction
changes from first order to zero order to increasing the substrate concentration. This is due
to the presence of one or more active sites in the enzyme molecules.
ww (i) When the substrate concentration is low, most of these active sites remain unoccupied
w.E at any time. When we increase the substrate concentration, the number of active sites
which are occupied also increase. This increases the reaction rate.
(ii)
asy
When the substrate concentration is very high, almost all the active sites get occupied
En
at any time. At this stage further increase of concentration of the substrate will not
increase in the formation of enzyme-substrate complex. Thus, the reaction becomes a
zero order reaction.
gin
ee
Importance of Michaelis-Menten Equation:
rin
g.n
1) When all the enzyme has reacted with the substrate at high concentration, the reaction
will be going at maximum rate. No free enzyme will remain. Hence, [Eo] = [X],
From equation (5) we have, et

Here, Vmax = Maximum rate
The Michaelis - Menten Equation (16) can now be written as
Vmax[𝑆]
𝑟𝑎𝑡𝑒 = − − − − − (20)
[S] + km

( BecauseVmax = k3[Eo] if km = [S], then)
Vmax[𝑆] Vmax[𝑆] Vmax

𝑟𝑎𝑡𝑒 = = = − − − − − (21)
[S] + [S] 2 [ S] 2
Definition of Km:
Michaelis-Menten constant Km is equal to that concentration of S at which the rate

of formation of product is half the maximum rate obtained at high concentration of S.
Determination of Km:
Reciprocal pf Michaelis-Menten equation (20) is known as Lineweaver-Burk
ww equation and is written as
w.E 1
𝑟
=
1
+
𝑘𝑚
𝑉𝑚𝑎𝑥 𝑉𝑚𝑎𝑥[𝑆]
− − − − − (22)
asy
Equation (22) is an equation for a straight line of the form Y = mx + C.
1 1 1
𝑘𝑚
A plot of
𝑟
En
Vs
[𝑆]
gives a straight line with intercept =
𝑉𝑚𝑎𝑥
and slope =
𝑉𝑚𝑎𝑥
gin
(or) km = slope x Vmax
ee
Thus Michaelis – Menten constant is obtained.
rin
g.n
Definition for Turn over number (k3):
et
The constant k3 is known as turn over number. It is the number of molecules
converted into products in unit time by one molecule of enzyme.

3 PHASE RULE AND ALLOYS
3.1 Introduction
The phase rule is the most important principle and a versatile
tool for the study of heterogeneous phase equilibrium. In
ww
1875-1878, the famous physicist J. Willard Gibbs established
w.E
the phase rule. He showed that for equilibrium to exist in a
multicomponent, multi phase closed system, that the changes
a
in entropy, volume, number of moles are zero making the
syE
change in internal energy to be zero. For phase equilibria to
ngi
exist in a multicomponent, multi phase closed system, it is
required that the variables such as temperature, pressure and
nee
composition to be equal in all phases. These variables are not
rin
all independent. Thus for any system at equilibrium, the
number of independent variables that must be arbitrarily fixed
g.n
to establish its state of equilibrium as formulated by Gibbs’s
Phase rule.
et
3.2 Phase Rule
Gibbs predicted qualitatively the effect of pressure,
temperature, concentration and explained the equilibrium
existing in heterogeneous system. It stated as “provided the
equilibrium between any number of phases is not influenced by
gravity / electrical / magnetic forces/ surface action and only by
temperature, pressure and concentration, then the number of
degrees of freedom (F) of the system is related to the number of

119
components (C) and of phases (P) by the phase rule equation,
F =C−P+2
for any system at equilibrium at a definite temperature and

pressure. To understand phase rule better it is necessary to
know about the terms involved in it.
3.2.1 Phase
It may be defined as “any particular portion of a system, which
is physically distinct, homogeneous, mechanically separable
ww
from any other phase in the system and has a specific
composition and a definite boundary”. A system may consist of
w.E
one phase or more than one phase. It is illustrated clearly in
the following examples:
a syE
1. Air a mixture of N 2 , O2 , CO2 etc forms a single gaseous
phase.
ngi
nee
2. A system containing only liquid water is one-phase
system.
rin
3. A system containing liquid water and water vapour is two-
phase system. g.n
H2 O(l) ⇋ H2 O(g)
4. A system containing liquid water, water vapour and solid

et
ice is three -phase system.
H2 O(s) ⇋ H2 O(l) ⇋ H2 O(g)
5. Immiscible liquids constitute separate phases. Example:

Water and chloroform P = 2.
6. Miscible liquids constitute one single liquid phase.

Example: Water and alcohol P = 1.

ENGINEERING CHEMISTRY 121
7. The mixture : CaCO3(s) ⇋ CaO(s) + CO2(g) consists of 3 -
phases (two solid and one gas phase; each and every solid
constitute a separate phase).
8. A solution constitute a single phase. Example: Sugar

solution P=1.
9. A saturated solution constitutes two phase one solid and

other liquid (solution) phase. Example: Sat. KCl solution.
3.2.2 Component
ww
A component is the ‘smallest number of independently variable
chemical constituents, taking part in the state of equilibrium,
w.E
by means which the composition of each phase can be expressed
a
in the form of chemical equation’. Components may be oxides,
syE
elements or minerals, dependent on the system being
examined. For example,
ngi
1. Experiments carried out in the H2 O system, shows that
nee
the phases which appear over a wide temperature and
rin
pressure range are ice, liquid water and water vapour.
g.n
The composition of each phase is H2 O and thus C=1 only
one chemical parameter or component is required to
describe the composition of each phase.
et
ice(s) ⇋ water(l) ⇋ water vapour(g)
H2 O(s) ⇋ H2 O(l) ⇋ H2 O(g)
2. A saturated solution of NaCl consists of the solid NaCl,

NaCl solution and water vapour. The chemical
composition of all the three phases are NaCl and water.
Hence it is two component system.
NaCl(s) ⇋ NaCl(aq) ⇋ H2 O(g) ; C = 2

3. Thermal decomposition of CaCO3
CaCO3(s) ⇋ CaO(s) + CO2(g)
There are three components namely CaCO3 , CaO, CO2 but

the composition of each phase can be expressed in the
form of a chemical equation using any two constituents
(C=2). Consider CaCO3 and CO2 as components to define
the system is as follows,
CaCO3 = CaCO3 +0 CO2

CaO = CaCO3 - CO2
ww CO2 = 0CaCO3 + CO2
w.E
Thus it is a two component system.
If we take CaO and CO2 , it can be written as follows
a syE CaCO3 = CaO +CO2
ngi
CaO = CaO + 0CO2
CO2 = 0CaO + CO2
nee
Thus it is a two component system.
rin
g.n
4. PCl3(l) + Cl2(g) ⇋ PCl5(s) is a two component system.
5. When NH4 Cl dissociates, the following equilibrium exists.

et
NH4Cl(s) ⇋ NH3(g) + HCl(g)
In closed system, if C=1, the system has two phases

namely solid and gas. Each can be expressed using one
chemical constituent namely NH4Cl as long as NH3 and
HCl exists in 1:1 ratio.
In open system, If the composition of NH3 > HCl or
HCl > NH3 , then it exists as two component system
(C=2).

3.2.3 Degree of freedom or variance
It is ‘the minimum number of independent variables such as
concentration, pressure and temperature which must be
arbitrarily specified in order to represent perfectly the condition
of a system’.
1. For system Water(l) ⇋ Water vapour(g)
Either the temperature or the pressure need to be stated
for defining the system completely (on a line). Hence, the
degrees of freedom is one or system is univariant (or)
mono variant.
ww i.e. F = C − P + 2 ; where C=1, P=2
w.E ∴ F =1−2+2=1
a syE
2. For a system consisting of water vapour only, both
temperature and pressure should be stated in order to
ngi
define the system (in an area). Hence, the degrees of
freedom is two or system is bivariant.
nee
rin
i.e. F = C − P + 2 ; where C=1, P=1
∴ F =1−1+2=2
g.n
Note: One can explain degrees of freedom with respect to a
graph. At the origin F = 0 (invariant) ie., no need to define x
et
and y axis value. To define a point on the x or y axis only one
variable is required, other variable is 0. Thus F = 1
(monovariant). To define a point in any quadrant, both x and y
axis value is required to define a point. It is bivariant (F=2).
3.3 Phase Diagram

Phase diagrams provide a graphical means of presenting the
results of experimental studies of complex natural processes at

equilibrium. The chemical or physical variation of system with
temperature, pressure and composition is represented in the
graph. Phase diagram is a graph obtained by plotting one
degrees of freedom against another.It is of two types.
• P-T phase diagram: A plot of temperature (T) against

pressure (P) it is called P-T diagram. It is used to explain
one component system.
• T-C phase diagram: A plot of temperature against

composition known as T-C diagram. From the diagram
ww we can understand the behavior of system stability and

equilibrium between phases with respect to temperature
w.E
and composition. It is used for more than one component
system.
a syE
3.3.1 Uses of Phase Diagram
ngi
nee
• We can understand the properties of materials in a
heterogeneous equilibrium system.
rin
g.n
• It is graphical representation of phase changes with
concentration, pressure and temperature
• It helps in studying and controlling the various processes et

such as phase separation, solidification of metals and
change of structure during heat treatment processes like
annealing, quenching, etc.
3.4 Application Of Phase Rule

3.4.1 One-Component System - Water System
ice(s) ⇋ water(l) ⇋ water vapour(g)

It is a one-component system. The phase diagram explains the
behaviour of three different phases of water in equilibrium,
with temperature and pressure. The salient features of the
phase diagram:
(a) The curves OA, OB, OC.

(b) the Triple Point O, Critical Point A.
(c) The areas AOC, AOB, BOC.
ww
w.E
a syE
nogi
, nee
rin
g.n
et
Figure 3.1 Phase diagram of one component water system
Explanation for the curves OA, OB, OC:
Curve OA: Vapour pressure curve of water.
H2 O(l) ⇋ H2 O(g)

It represents the vapour pressure of liquid water at different
temperatures. The two phases water and water vapour coexist
in equilibrium along this curve. The curve OA terminates at
A, the critical point (218 atm, temp 374◦ C) when the liquid and
vapour are indistinguishable from each other and there is only
one phase.
Curve OB: Sublimation curve of ice.
H2 O(s) ⇋ H2 O(g)
It shows the vapour pressure of solid ice at different

ww
temperatures. The two phases solid ice and vapour coexist in
w.E
equilibrium along this curve. At the lower limit, the curve OB
terminates at absolute zero where no vapour exists.
a syE
Curve OC : Fusion curve of ice.
ngi
H2 O(s) ⇋ H2 O(l)
nee
It depicts the effect of pressure on the melting point of ice. The
fact that OC slopes to the left indicates that the melting point
rin
of ice decreases with increase of pressure. Since ice melts with
g.n
decrease in volume, by Le Chatelier’s principle the melting
point is lowered by an increase of pressure. It may be noted
that the 1 atmosphere line meets the fusion curve at 0◦ C which et
is the normal melting point of ice.
Along the curves OA, OB, OC there are two phases in
equilibrium and one component. Apply the phase rule;
F = C - P + 2 ; 1 - 2 + 2 = 1 (monovariant)
The curves are monovariant because, for a given value of

pressure, the temperature is automatically fixed on a curve
and vice verse.

The Triple point ‘O’
H2 O(s) ⇋ H2 O(l) ⇋ H2 O(g)

The curves OA, OB, and OC meet at the triple point ‘O’ where
all the three phases liquid water, ice, vapour are in equilibrium.
This occurs at 0.0075◦ C and vapour pressure 4.58 mm Hg (or
0.00603 atm). Since there are three phases and one component,
F = C - P + 2 = 1 - 3 + 2 = 0 ( non variant)
The triple point is non variant because, variation of any one of

ww
the variables, temperature or pressure, causes the
w.E
disappearance of one of the three phases.
a
Areas AOC, AOB, BOC:
syE
Area AOC represents conditions for the one-phase system
ngi
water. Area BOC represents conditions for the one-phase
nee
system ice. In all the three areas, there being one-phase and
one-component,
rin
F = C - P + 2 = 1 - 1 + 2 = 2 ( Bi variant)
g.n
The system is bivariant because to locate any point in any
area, the variables, pressure as well as the temperature need et
to be specified.
Metastable system:
The vapour pressure curve of water AO is continued as dashed

line OA’. That is, water can be super-cooled by carefully below
its freezing temperature without the separation of ice. The
super-cooled water/vapour system is metastable (unstable),
because as soon as small particle of ice dust comes in contact
with the super-cooled liquid, the entire liquid solidifies. But

the phase change from ice to supercooled liquid phase is not
possible.
H2 O(l) → super cooled liquid 8 H2 O(s)
3.5 Two component system

The classification of two component system or solid -liquid
equlibria is done according to the miscibility, solubility and
reactive ability of the liquid phases
ww1. Simple eutectic formation
w.E
2. Eutectic with compound formation
• Formation of compound with congruent melting
a
point.
syE
• Formation of compound with incongruent melting
point. ngi
3. Formation of solid solution. nee
(i) Simple Eutectic Formation rin
g.n
It is a binary system containing two substances, which are
completely miscible in the liquid state, but completely
immiscible in the solid state. This is known as eutectic (easy
et
melt) system. They do not react chemically. Of the different
mixtures, the mixture having the lowest melting point is
known as the eutectic mixture.
(ii) (a) Formation of compound with congruent melting

point
The binary alloy system with two substances form one or more
compounds with definite proportions. The compound is said to
have congruent melting point, if it melts exactly at a constant

temperature into liquid, having the same composition as that
of the solid.
(ii) (b) Formation of compound with incongruent melting

point
Of the above compounds, a compound is said to have
incongruent melting point, if it decomposes completely at a
temperature below its melting point forming a new solid phase
with a different composition from that of the original.
(iii) Formation of solid solution
ww
A binary system in which two substances, more particularly in
w.E
two metals, are completely miscible in both solid and liquid
states form solid solutions and their mixing takes place in the
a
atomic levels. This happens only when the atomic radius of the
syE
two metals not differ by more than 15%.
3.6 Condensed Phase Rule ngi

nee
rin
In a two component system, When P = 1, degrees of freedom
(F) has the highest value:
g.n
F =C−P+2
=2−1+2=3
et
Since the maximum degrees of freedom in a two component
system is three, so the phase behaviour of a binary system may
be represented by a three dimensional diagram of pressure,
temperature and composition requiring three axes, which
cannot be conveniently shown on paper.
Hence, the two component system of solid ⇋ liquid equilibrium
is generally characterized by the absence of the vapour phase.
The process is conducted at 1 atmospheric pressure i.e.

keeping the pressure constant. In other words, the effect of
pressure is negligible on this solid-liquid equilibrium alloy
system. If we keep one of the variables viz. pressure as
constant for the system, then it will constitute a condensed
system. The degrees of freedom get reduced by one and for
such a system the phase rule becomes
F’ = C - P + 1
known as condensed (reduced) phase rule. Two variables to be

considered viz temperature and composition. Solid-liquid
ww
equilibrium are represented on T-C diagrams.
Definition: In two component systems, the study of solid -
w.E
liquid equilibrium at 1 atm and ignoring the gaseous phase
a
(pressure is neglected) is called condensed system and phase
syE
rule applied to such systems is as follows:
F’ = C - P + 1 - known as condensed phase rule.
ngi
3.7 Cooling curves / Thermal Analysis nee
rin
The shape of the freezing point curves for any system,
especially those involving metals, can be determined by g.n
thermal analysis - a method involving a study of the cooling
curves of various compositions of a system during et
solidification.
Construction of phase diagram

When a graph is plotted between temperature and time it is
called as cooling curve. The thermal analysis involves the
study of cooling curve of various compositions of a two
component system during solidification with time.
(1) Consider a pure solid substance which is in its fused state

is cooled slowly. The fall in temperature is noted at periodic

time intervals. Initially the rate of cooling is continuous. At
the point ‘B’ freezing starts. The temperature remains
constant until the liquid melt is completely solidified and this
temperature is called freezing point of substance. This is
because the liquid melt and solid crystals are of the same
composition. At the horizontal section ‘BC’ the solid crystals
and liquid melt are in equilibrium. After the point ’C’ the
temperature of solid again falls with time along the curve ‘CD’
as shown in figure 1.2.
ww
w.E
a syE
ngi
nee
Figure 3.2 Cooling curve of pure substance
rin
(2) Considering a mixture of two solids A and B is in fused state.
g.n
It is allowed to cool slowly. Initially the rate of cooling will be
continuous (ab), when the
et
Figure 3.3 Cooling curve of two substances

crystals of either solid A or B is formed from the liquid melt,
which is indicated by break in continuity of the cooling curve.
Now the temperature again decreases with time but at a
different rate, because the solid-crystal and liquid melt are not
of the same composition. The slope ‘bc’ of the curve represents
a continuous and progressive change in composition of liquid
melt as shown in figure 1.3.
Finally the liquid melt reaches the point ‘c’ at which it
separates as solid A and solid B. Now the temperature will
remain constant until the liquid melt is completely solidified.
Point ‘c’ is called eutectic point, the minimum freezing point
ww
for the given eutectic system. Thereafter temperature remain
w.E
constant till solidification upto ‘d’. Experiment is repeated for
different compositions of A and B and the various cooling
a
curves are recorded. From the cooling curves of various
syE
compositions, the main phase diagram can be drawn by taking
ngi
composition in the X-axis and the temperature in Y-axis as
shown in the figure.
nee
rin
g.n
et
Figure 3.4 Phase diagram from cooling curve
Uses of cooling curves

1. From cooling curves, melting points and eutectic points

are obtained.
2. Behavior of compounds is understood.
3. Percentage purity of compounds is determined.
4. Phase diagram can be obtained.
5. The composition corresponding to the freezing point gives

the composition of an alloy.
ww
w.E
3.7.1 Application of cooling curves
Eutectic system:
a syE
A binary system consists of two
components, which are completely miscible with one another
ngi
in liquid state but they do not form any compound and on
solidification they give rise merely to an intimate mixture
nee
known as eutectic (easy melting) mixture. Example: Pb-Ag
system, Pb-Sb system, etc.
rin
Eutectic point g.n
In a simple eutectic system, the minimum freezing point
where all the three phases are in equilibrium and degree of
et
freedom is zero is called eutectic point.
Solid A + Solid B ⇋ Liquid melt AB
Eutectic mixture
It is a solid solution of two or more substances having the lowest
freezing point of all the possible mixture of components. This
mixture cannot be separated by physical methods.

3.8 Simple eutectic systems: Lead-Silver
system
Lead-Silver system is a two component system with the

formation of a simple eutectic mixture. This system has two
components and four phases. The phases are (a) solid Ag (b)
solid Pb (c) solution of molten Ag and Pb and (d) vapour. The
boiling points of silver and lead being considerably high, the
vapour phase is practically absent.
The salient features of the diagram are:
ww (a) Two curves, AO and BO

(b) Eutectic point O
w.E
(c) Three areas (i) above AOB (ii) below AO (iii) below
BO
a syE
ngi
nee
rin
g.n
et
%
%
Figure 3.5 Phase diagram of simple eutectic Pb-Ag system
Explanation for the curves AO, BO:

Curve AO : Freezing point curve of Ag

It shows the effect on freezing point of Ag on addition of lead in
small quantities. The point A (961◦ C)is the melting point of pure
Ag, where pure Ag co-exists as solid and liquid (one component).
This curve indicates that the melting point of Ag falls gradually
as the addition of Pb increases,along AO, till the lowest point O
(303◦ C) is reached. At point O,the solution gets saturated with
respect to lead. Along the curve AO, solid Ag and liquid melt
co-exist (P = 2, C = 2) and hence, according to reduced phase
rule equation:
Ag(s) ⇋ AgPb(l)
ww F’ = C - P + 1 ; 2 - 2 + 1 = 1 (monovariant)
w.E
Thus, either composition or temperature is needed to define
the system along the curve AO.
a syE
Curve BO: Freezing point curve of Pb
ngi
It represents the effect on freezing point of Pb on gradual
addition of small amounts of Ag to it. Point B is the melting
nee
point of pure lead (327◦ C). At this point the system is one
rin
component. Along BO, the melting point gradually falls on the
addition of Ag, till lowest point O is reached. At C, where the
solution gets saturated with respect to Ag. g.n
Pb(s) ⇋ AgPb(l)
et
F’ = C - P + 1 ; 2 - 2 + 1 = 1 (monovariant)
Thus, either composition or temperature is needed to define

the system along the curve BO.
Eutectic point O:
The curve AO and BO intersect at O, which is called the
eutectic point. Here three phases solid Ag, solid Pb, and liquid
melt are in equilibrium. Applying the reduced phase rule; (

P=3; C=2, then the degrees of freedom is
F’ = C - P + 1 = 2 - 3 + 1 = 0 (nonvariant)
Both variables temperature (303◦ C) and composition (97.4 %

Pb, 2.6% Ag: eutectic composition) are fixed. If the
temperature is raised above the eutectic temperature, the solid
phases Ag and Pb disappear. No mixture of lead and silver has
a melting point lower than the eutectic temperature.
Area ACB: This region represents the single phase system,
ww
the solution of molten Ag and Pb (P = 1; C = 2). Applying the
reduced phase rule;
w.E
F’ = C - P + 1 = 2 - 1 + 1 = 2 (Bivariant)
a syE
Thus, to define a system in this area, both temperature and
composition are required.
ngi
Pattinson’s Process for the nee
Desilverisation of
Argentiferrous lead
rin
g.n
The argentiferrous lead contains small amount of silver (0.1%
of Ag). It is melted well above the melting temperature of pure
lead (327◦ C). Let the point M represent the system ‘molten
lead’ on the diagram. It is then allowed to cool when the
et
temperature of the melt falls along the dashed line MN. As the
temperature corresponding to N on the curve BO is reached,
solid pure lead begins to separate. On further cooling, more of
pure lead separates along the curve NO until the eutectic point
O is reached. Lead is continuously removed by means of ladles
and so it is free of Ag and the percentage of silver in the melt
goes on increasing upto 2.6%. This process is called
desilverisation of lead.

Uses of eutectic systems
1. Study of eutectic system helps to predict suitable alloy

composition.
2. Eutectic system is useful to prepare solders, used to join

two metal pieces.
3.8.1 Differences between melting point, eutectic point

and triple point
Melting point: It is the temperature at which a solid and its
ww
liquid phase of a pure compound is at equilibrium.
w.E
Eutectic point: It is the lowest temperature at which two
solids A and B and a liquid melt of A and B are at equilibrium.
a syE
Triple point: It is the temperature at which three phases
namely, solid, liquid and vapour are in equilibrium in one
ngi
component system. Eutectic point is a melting point. But
melting point need not be eutectic point.
nee
3.8.2 Merits of phase rule rin
1. The rule is applied to physical as well as chemical g.n
equilibrium. et
2. It takes no account of the nature and amount of the
substances.
3. It explains the behaviour of the system when they are

subjected to changes in variables. It shows that different
systems with the same degrees of freedom have similar
behavior.
4. We can decide whether the given number of substances

can remain in equilibrium or not.

5. Phase rule is applicable to macroscopic systems.
Therefore, it is not necessary to have information about
molecular structure.
3.8.3 Limitations of phase rule

1. The rule is applied to only heterogeneous systems in
equilibrium.
2. It takes into account only the pressure , temperature and

composition variables.
ww3. The influences of the external forces like electrical,

magnetic and gravitational forces are ignored.
w.E
4. In phase rule, time is not a variable because it applies to
a syE
system under equilibrium. The equilibrium state is
independent of time factor.
ngi
3.9 Summary
nee
1. Water system rin
g.n
BO Sublimation curve
H2 O(s) ⇋ H2 O(g)
P=2,C=1,
F=1
Monovariant, to
define a system
et
either T or P is
required.
OA Vaporization curve P=2,C=1, Monovariant, to

H2 O(l) ⇋ H2 O(g) F=1 define a system
either T or P is
required.

OC Fusion curve P=2,C=1, Monovariant, to

H2 O(s) ⇋ H2 O(l) F=1 define a system
either T or P is
required.
Area Solid phase P=1,C=1, Bivariant, to

BOC H2 O(s) F=2 define a system
both T and P are
required.
Area Liquid phase P=1,C=1, Bivariant, to

ww
AOC H2 O(l) F=2 define a system
w.E both T and P are

required.
AOB H2 O(g)
a
Area Vapour phase
syE P=1,C=1,
F=2
Bivariant, to
define a system
ngi both T and P are
nee required.
Point Triple point

O H2 O(s) ⇋ H2 O(l) ⇋
P=3,C=1,
F=0 rin
Invariant, Fixed
T=0.0075◦ C and
H2 O(g) P=4.6 mmHg) g.n
Point Critical point (Critical
A temperature, critical
F=0 Invariant, Fixed
Tc =374◦ C, Pc =
et
pressure) 217.5 atm
OA’ Meta stable P=2,C=1, Super cooled

equilibrium F=1 liquid state
H2 O(l) → super cooled below 0◦ C
liquid 8 H2 O(s)

2. Pb-Ag system
B Freezing point of C=1, Invariant, Fixed T

lead P=2, F=0 (327◦ C)
A Freezing point of C=1, Invariant,Fixed T

silver P=2, F=0 (961◦ C)
O Eutectic point C=2, Invariant, Fixed T

P=3, F=0 and Composition
◦
(303 C, 97.4 mass
% Pb; 2.6 mass %
ww Ag)
BO w.E
Freezing curve
curve of Pb w.r.to Ag,
C=2,
P=2, F=1
Univariant, either
T or composition
a
lead begins
syE
Crystallization of are required to
define the system.
AO Freezing curve ngi

C=2, Univariant, either
of Pb w.r.to Ag, P=2, F=1nee T or composition
Crystallization of
silver begins rin
are required to
define the system.
Area Liquid melt C=2, g.n

Bivariant, both T
above
AOB
P=1, F=2 and composition are
required to define
et
the system.
COD Solidus line C=2, Below 303◦ C

line P=3, F=0 both lead and
silver separate
as solid from
liquid of eutectic
composition O.

3.10 Alloys
An alloy is a metallic, intimately mixed solid solution of two or
more different elements, one of which at least is essentially a
metal. Addition of small amounts of one or more metals (such
as Ni, Cr, Co, etc.,) imparts special properties.
High malleability, ductility,corrosion resistance, hardness,
luster and good electrical conductivity are the certain
properties possessed by metal. But for most of the
applications, their tensile strength, are not sufficient.
ww
Need for alloying:
w.E
Main purpose of alloying is to improve the properties of
materials like tensile strength, ductility, toughness, hardness,
a
elasticity, improve heat-resistance, corrosion resistance,
abrasion resistance etc. syE
Significance / Advantages of alloys ngi
nee
(a) To enhance the hardness of metal: Pure metal are in
rin
general soft. An alloy is harder than its component
elements.Example: Gold and silver are alloyed with
Copper to increase its hardness. g.n
i. Gold and silver are alloyed with Copper to increase
its hardness.
et
ii. Addition of 0.5 % arsenic to lead makes it so hard
that it can be used for making bullets.
iii. Addition of 0.15 - 1.5% carbon to pure iron which is
very soft will result in the formation of steel alloy,
which is hard.
(b) Lowering of melting point: The melting point of an alloy is

lower than of its constituents elements - alloying can
enhance the fusibility of metals. Example:

Wood’s metal, an alloy (lead, bismuth, tin and cadmium)
used for soldering melts at 60o C which is far below the
melting points of constituent metals.
(c) Enhancement of tensile strength: Tensile strength of a

metal can be increased. Example: Tensile strength of pure
iron is increased upto ten times by adding one percent
carbon.
(d) Enhancement of corrosion resistance: Alloys are more

resistant to corrosion than metal. Example: Pure iron
ww gets rusted, but when it is alloyed with carbon and

chromium, resists corrosion.
w.E
(e) Color modification: Alloying can alter the color and
a
brightness. Brass is yellow obtained from Copper (pink)
and Zinc (grey). syE
(f) Enhancement of castability:
ngi Alloys expand on
nee
solidification. This expansion is one of the essential
requirement to good castings. Example: 5% tin and 3%
rin
antimony when alloyed to lead, the alloy shows
exceptionally good casting properties.
g.n
(g) To modify the chemical activity of the metal: Chemical
activity of the metal is altered by alloying with elements.
et
Examples:
• Sodium amalgam is less active than sodium.
• Aluminium amalgam is more active than aluminium.
3.10.1 Specific effects of alloying elements:

The properties of alloys are greatly enhanced by the presence
of alloying elements. A brief account of the effect of different
alloying elements on alloys is given in the following table 1.

Table 1. Effect of alloying elements
S.No Alloying Effects

elements
1. Nickel Improves tensile strength,

toughness, corrosion resistance
and elasticity.
2. Chromium Improves hardness and toughness

simultaneously. 1.5% addition
ww imparts tensile strength; and

12% addition imparts corrosion
w.E resistance.
3.
a
Manganese
syE
1.5% addition increases strength,
toughness and brittleness; 14%
ngi
addition provides a high degrees of
hardness.
4. Molybdenum nee
Increases strength at elevated
rin
temperatures, corrosion resistance
and abrasion. resistance and
eliminate temper brittleness.
g.n
5. Tungsten Increases hardness, toughness,
et
abrasion resistance and shock
resistance.
6. Vanadium Improves tensile strength, ductility

and shock resistance.

3.11 Classification of alloys
1. Based on position in lattice of atom
1. Substitutional alloys: These alloys are formed by the

substitution or exchange of the alloying atoms in the
lattice site of main metal. This is based on both the size
(similar) and amount of the elements in the mixture. For
example bronze and brass are substitutional alloys
because some of the copper atoms are substituted with
either tin or zinc atoms.
ww2. Interstitial Alloys: These are alloys formed in which one
w.E
atom is smaller than the other hence the smaller atoms
are held firmly in the interstitial space in the crystal
a
lattice is called interstitial alloys. For example steel is an
syE
interstitial alloy, carbon atoms fit into interstices of the
iron matrix.
ngi
nee
3. Combined Alloys: These are alloys that combine the
mode of formation of substitutional alloys and interstitial
rin
alloys because while the carbon atoms fit into the
g.n
interstices however some of the iron atoms are replaced
with nickel and chromium atoms as seen in stainless
steel. et
Figure 3.6 Types of alloy
1. Ferrous alloys or alloy steels

Steel is an alloy of iron and carbon. Plain carbon steel

finds only limited use. Addition of small amount Cr, Ni,
Mo etc. imparts properties to steel. Such steels are called
alloy steels or special steels.
2. Non-Ferrous alloys
Non-ferrous alloys do not contain iron as the major
element. Some of the important non-ferrous alloys have
the major element Cu, Al, Ni, Zn, Sn and Pb. They find
wide applications because of their properties like
a) Attractive colours, Good formability and Easy
ww castability.
b) Special electrical and magnetic properties.
w.E
c) Low coefficient of friction, Softness and Low density.
a
d) Atmospheric corrosion resistance.
syE
3.11.1 Important Ferrous Alloys
ngi
3.11.1.1 Nichrome
nee
rin
Nichrome is an alloy of Ni, Cr and iron. Its composition is given
below
g.n
Constituent
Ni
Percentage
60
et
Cr 12
Fe 26
Mn 2
Properties:
1. Nichrome is silver-grey in colour.
2. It shows good resistance to oxidation and heat.

3. It shows high resistant to corrosion and wear.
4. It possesses high melting point.
5. It can withstand heat upto 1000 to 1100◦ C.
6. It possesses high electrical resistance.
Uses:
1. It is widely used for making resistance coils, heating

elements in stoves.
ww2. It is used in aircraft engine turbines, aero-engine valves.
w.E
3. It is used in household electrical appliances.
a
4. It is used in making parts of boilers, gas-turbines, retorts,
annealing boxes.
syE
ngi
5. It is used in making motorcycle silencers.
3.11.1.2 Stainless steels nee

rin
Stainless steels are iron alloys with a minimum of 10-16%
g.n
chromium. Other alloying elements like Ni, Mo,Ti,Cu etc. are
added to enhance its properties such as formability, strength
and cryogenic toughness. The carbon content in stainless steel et
ranges from 0.3 to 1.5%.
Stainless steel is a corrosion resistant alloy steels. This
resistance to attack is due to the chromium oxide film formed
on the surface of the steel. Although extremely thin, this inert
film is tightly adherent to the metal and extremely protective
to corrosive media. The film self repairs in the presence of
oxygen hence damage by abrasion, cutting or machining is
quickly repaired.

Types of stainless steel:
1. Heat treatable stainless steels
2. Non heat treatable stainless steels.
1. Heat treatable stainless steels:(Martensitic)

Composition: Its contain high carbn content (upto 1.2%) and
less than 12-16% of Chromium.
Properties:
1. They are magnetic in nature.

ww
2. They can be hardened by heat treatment.
w.E
3. They can be worked in cold condition.
a syE
4. They can be used upto 800◦ C.
ngi
5. They posses moderate corrosion resistance.
6. weldabilityand formability is poor. nee

Uses: rin
g.n
1. They are used in making surgical instruments, scissors,
blades, etc.,
et
2. In making shafts,spindles and pins.
2. Non- Heat treatable stainless steels

These steels possess less strength at high temperature. They
are more resistant to corrosion.
Types:
1. Magnetic type: (Ferritic)
2. Non- Magnetic type (Austenitic)

1. Magnetic type: (Ferritic) Composition: It contains 12-
22% of Cr and 0.10-0.35% of C.
Properties:
1. They are magnetic and posses good ductility.
2. Resistance to corrosion and oxidation.
3. It can be forged, rolled and machined by the use of

specially designed tools.
4. It resists corrosion better than heat-treatable stainless

ww steel.
w.E
5. Weldability and Formability is poor.
Uses: a syE
ngi
1. They are used for cold-working treatments.
nee
2. It is used in water tanks, exhaust systems and outdoor
applications.
rin
g.n
3. It can be used in aggressive conditions such as sea water.
2. Non- Magnetic type (Austenitic): et

Composition: It contains 18-26% of chromium, 8-21% of
nickel and 0.15% of carbon. Total percentage of Cr and Ni in
such steel should be more than 23%.
Austenitic grades are the most commonly used stainless steels
accounting for more than 70% of production. They exhibit
maximum resistance to corrosion. They are referred as 18/8
stainless steel.
18/8 Stainless steel: Steel containing 18% of Cr and 8% Ni,
is referred to as 18/8 stainless steel. It is the most widely used

stainless steel and flexible form of stainless steel. It is highly
durable and can be fabricated with ease. Cleaning the metal is
easy and it is available in various appearances and finishes.
The percentage of nickel and chromium that is present in this
grade of stainless steel provides this metal with good corrosion
resistance properties, particularly to moderately caustic and
acidic solutions.
Properties:
1. It exhibits maximum resistance to corrosion.
ww
2. Corrosion resistance of which can be further increased by
adding a little quantity of Mo.
w.E
3. They are non-magnetic in nature.
a syE
4. It posses good formability and weldability.
ngi
5. They cannot be hardened by heat treatment
nee
6. They can be hardened by cold working the material
Uses: rin
It is used in making g.n
1. Household utensils and sinks. et
2. Dental and surgical instruments.
3. Wheel covers and Truck bodies.
3.12 Heat treatment of Steels

Heat treatment is the process of heating and cooling of solid
steel articles under carefully controlled conditions, thereby
developing in it certain physical properties without altering its

chemical composition. Heat treatment results in refining of
grain structure, improved ductility, hardness, tensile strength,
removal of imprisoned gases, to relieve internal stresses.
Theory
It is observed that on heating changes takes place in the
internal structure of the steel at specific temperatures. Below
725◦ C, the steel of pure iron does not fully combine with C to
form iron carbide. On gradually increasing the temperature
above 725◦ C ( lower critical temperature), the metal does not
get heated up further. Instead, it brings about changes in the
ww
internal structure thereby combining with carbon to form solid
w.E
solution. The temperature at which this structural changes
occur is called critical temperature. At lower critical
a
temperature iron and carbon starts binding with each other.
syE
At upper critical temperature above process gets completed
(925◦ C). Due to this changes in chemical composition takes
ngi
place which forms different crystalline structures to stell such
nee
as Pearlite, martinsite, ferrite, austinite and cementite.
rin
The various heat treatment processes differ in temperatures in
g.n
the way in which the metal is heated and the rate at which it
is cooled. Heat treatment can be done by the following ways:
1. Annealing 4. Normalizing et
2. Hardening (or) quenching
3. Tempering 5. Case hardening
1. Annealing:
Annealing is a softening of iron which improves ductility and
reduces brittleness. The metal is heated to a certain high
temperature, followed by cooling in a furnace. It increases
machinability, ductility and removes the imprisoned gases and
internal stresses. There are two types of annealing:

a. Full annealing
b. Process annealing
a. Full annealing:
To perform a full anneal the steel is heated to 50◦ C above
the austenic temperature and held for sufficient time to
allow the material to fully form austenite-cementite grain
structure. The material is then allowed to cool slowly so
that the equilibrium microstructure is obtained. In some
cases the material is allowed to air cool. In other cases the
ww
material is allowed to furnace cool.
machinability, ductility and shock resistance.
It increases
w.E
b. Process annealing:
a syE
The piece is heated to a temperature typically below the
austenizing temperature, and held there long enough to
ngi
relieve stresses in the metal. The piece is then furnace
nee
cooled. It can also be subjected to additional cold working.
It is applied for the steel which undergoes processes such
rin
as rolling, drawing, forging, spinning, extruding and
heading.
g.n
2. Hardening or Quenching: et
Steel is heated beyond the critical point then quenched
suddenly either in oil or brine solution. It contains mostly
martensite structure. Steel of great hardness and strength can
be produced. But it makes it less ductile. It increases abrasion
resistance and used for producing cutting tools. It is used for
hardening medium and high carbon steels. Low carbon steels
cannot be hardened by this method.

3. Tempering:
The already hardened steel is brittle and internally stressed.
Before use, it is usually necessary to reduce these stresses and
increase toughness by ’tempering’. Tempering is heating to a
temperature lower than its own hardening temperature and
then slowly cooled. The process increases toughness and
ductility, reduce brittleness.
4. Normalising:
It involves heating of steel to a definite temperature above its
ww
higher critical temperature and allowing it to cool gradually in
air. It produces ferrite-pearlite structure. It results in increase
w.E
toughness, removal of internal stresses and refined grains.
Homogeneity of steel is recovered. Softness is less compared to
annealing.
a syE
5. Case hardening:
ngi
The process of obtaining a hard and wear resistant surfaces
nee
over a strong and tough ductile core is known as case
rin
hardening. The principle forms of case hardening are as
follows:
5.1 Carburising: g.n
The process in which very hard surface is produced on steel et
which has a soft core inside. The mild steel article is enclosed
in a cast iron box containing material rich in carbon such as
wood, charcoal etc., This is heated to 900-950◦ C and the
temperature is maintained for sufficient time to enable the
carbon to be absorbed to the required depth. Now the surface
is converted to high carbon steel containing 0.8 to 1.2% carbon.
The article in the box is subjected to slow cooling. The
carburized steel is heated to 900◦ C and quenched in oil for
making tough and soft.

5.2 Nitriding:
The metal alloy is heated with NH3 at 550◦ C results in
super-hard surface. Nitrogen from ammonia reacting with
surface constituents to form extremely hard nitrides. This
process is time consuming. Nitrided steel have much better
properties than any of hardening processes. It has higher case
hardness, improved fatigue strength and better corrosion
resistance. This process is used to case harden gears, cylinder
sleeves, camshafts, etc.
5.3 Cyaniding:
ww
A layer of hard surface is produced on low or medium carbon
w.E
steel. This is done by immersing the metal in a solution
containing KCN or NaCN at a temperature of about 870◦C
a syE
followed by quenching in oil or water. It is fast and efficient
than carburising and can be completed in 20-30 minutes. The
ngi
major drawback is that cyanide bath is a deadly poison.
nee
rin
g.n
et
Figure 3.7 Heat treatment curve

154
ww
Summary of heat treatment of steel
w.E
Types of Heating Rate of Properties Application
heat
treatment
temperature
asy cooling
Annealing
a. Full
Annealing
50◦ C above
the
critical
higher
Very
E slow
cooling inside
the furnace
Improves
ngi
i.
softness
Machinability and
It is carried on hot
worked machining,
forging, rolling and
nee
PHASE RULE AND ALLOYS

temperature ii.Ductility and toughness welding materials.
(<900◦ C) iii. Expels trapped gases.
b. Process below the Very slow

rin
i. Improves ductility. It is carried on cold
annealing critical
temperature
cooling inside
the furnace
ii. Releases stresses in the
metal.
g.n
rolled steel like wire
drawn steel, etc.
(<725◦ C) iii. It has reduced risk of
distortion.
et
ww
w.E
a syE
ngi
nee
rin
g.n
et

i. It provides greater
ww
Hardening
above the
upper critical
Rapid cooling
in oil or brine
hardness and strength.
ii. High resistance to
For the production of
or
w.E
quenching
temperature solution wear
iii. Excess brittleness.
cutting tools.
Heated below
its own asy i. Strength and hardness
is retained.
i. For cutting and
Tempering
hardening
temperature
(400 to 600◦
E
Gradual
cooling in air.
ii. Ductility and
ngi
toughness is improved.
iii. Stress is released.
measuring tools.
ii. For connecting rod,
shaft and gears.
C)
nee
i. Provides homogeneity Materials produced by
above the
Gradual ii. rin
of the steel structure
Removes internal
machining, forging, or
welding. Normalized
Normalising upper critical
temperature
cooling in air stresses
iii. Refines grains g.n
steels are
and stronger than
harder
iv. Increase of toughness.

et
annealed steels.
155
156
ww The mild steel
Hard-wearing
surface is produced
Transmission gears
Case
w.E
Hardening
is heated to 900
- 950◦ C along
with charcoal in
Slow cooling
inside the box
on low carbon steel
having a soft core
and shafts
automotive,
for
wind
turbine and pump
asy
inside. Steel contains
1.Carburising a cast iron box components
0.8 - 1.2% C.
2. Nitriding
Metal alloy is
heated in the
presence of
E ngi
Rapid cooling
Super-hard surface is
obtained. Improved
fatigue strength
Used for camshafts,
cylinder sleeves and
nee
PHASE RULE AND ALLOYS

ammonia at a in oil
and better corrosion gears.
temperature of
resistance.
about 550◦ C.
Metal is rin Used on small parts
3. Cyaniding
immersed into a
molten KCN or
Rapid cooling Super-hard surface is
g.n
such as bolts, nuts,
screws, self drilling
NaCN solution
at 870◦ C
in oil obtained.
et
screws and small
gears.

4 FUELS AND COMBUSTION
4.1 Introduction
Fuel is a combustible substance containing carbon as main
constituent which on proper burning gives large amount of
ww
heat which can be used economically for domestic and
w.E
industrial purposes. Fuels in the broad sense include the
stored fuels that is available in the earth crust as fossil fuels
a
which have been derived from fossil remains of plants and
syE
animals. In this chapter the sources and characteristics of
ngi
solid, liquid and gaseous fuels are described along with the
principles involved in their combustion reactions.
nee
4.2 Classification of fuels
rin
Fuels are classified according to their occurence as : g.n
1. Natural or Primary fuels are those which are found in
nature. Example: Wood, peat, coal, petroleum, natural
et
gas etc.
2. Artificial or Secondary fuels are those which are

prepared from the primary fuels to give high calorific
value. Example: Charcoal, coke, kerosene, diesel, petrol,
coal gas, oil gas, producer gas, blast furnace gas, etc.
Fuels are classified according to their state of aggregation as
i. Solid fuels: Exist in nature as solid. Example: Coal

ii. Liquid fuels: Exist in nature as liquid. Example: Crude oil
iii. Gaseous fuels: Exist in nature as gas. Example: Natural

gas.
ww
w.E
a
Calorie: It is defined as the amount of energy required to
syE
raise temperature of one liter of water through 1◦ C. It is the
unit measure of energy.
ngi
nee
Calorific value: Calorific value of a fuel may be defined as
“the total quantity of heat liberated, when a unit mass (or
rin
volume) of a fuel is burnt completely and is usually expressed
as cal g−1 or kcal kg− .1
Fuels mainly contain carbon and hydrogen. Carbon reacts g.n
with oxygen and forms carbon dioxide and hydrogen reacts
with oxygen and forms water vapour.
et
C + O2 −→ CO2 + Heat/Energy
2H2 + O2 −→ 2H2 O + Energy

The vapour formed carries some amount of heat with it. If this
vapour formed is cooled, it gives away its latent heat. Thus
fuels containing hydrogen has low calorific values. Based on
the amount of hydrogen present in a fuel, it is classified as
higher calorific value and lower calorific value.

Higher calorific value (HCV) or Gross calorific
value(GCV)
‘Gross calorific value is the heat liberated when a unit quantity
of fuel is completely burnt and the products of combustion are
cooled to room temperature’. The latent heat of condensation
of steam is included in the gross calorific value.
Lower calorific value (LCV) or Net calorific value (NCV)

‘Net calorific value is the quantity of heat liberated, when a
unit mass (or volume) of a fuel is burnt completely and the
ww
products (water vapours) are allowed to escape’.
H2 + 12 O2 −→ H2 O + Energy
w.E 2 18
a 1
syE 9
ngi
Note: The weight of water formed is nine times the weight of
hydrogen in the fuel. Therefore,
Net calorific value = nee
Gross calorific value - (Mass of
rin
hydrogen per weight of fuel burnt) × 9
g.n
× latent heat of vaporization of water)
NCV = GCV −
H
100
× 9 × 587 et
Latent heat of steam is 587 kcal/g.
Dulong’s formula for calorific value from the chemical

composition of fuel
The calorific value may be theoretically calculated from the

chemical composition of the fuel.
X
Calorific value = weight of an element per g of
a fuel × its calorific value.

If both hydrogen and oxygen are present, it may be assumed
that all the oxygen is already combined with 1/8 of its weight of
hydrogen to form water thus making hydrogen unavailable for
combustion. This fraction is then deducted from the hydrogen
content of the fuel in the calculation. Thus for a fuel containing
carbon, hydrogen, oxygen and sulphur, the calorific value of the
fuel is given by
1 O
Calorific value = [8080 C + 34500 (H − ) + 2240 S] cal/g
100 8
where C, H, O, S refer to % of carbon, hydrogen, oxygen and

ww
sulphur respectively.
w.E NCV = GCV −

9
× H × 587 cal/g
a syE
100
4.2.1 Requirements of a good fuel

Quality of a good fuels are ngi
nee
1. It should have moderate ignition temperature.
rin
2. It should have high calorific value.
g.n
3. It should freely burn with high combustion efficiency.
4. It should not produce harmful gases or smoke.

et
5. It must produce less ash.
6. It should be cheaper and easily available.
7. Its storage must be easy.
8. Its transportation and handling should be easy.
9. The flue gas should not react with the material of the
furnace.

4.3 Solid Fuels
Natural solid fuels are of following types
(a) Wood (b) Peat (c) Lignite (d) Bituminous Coal
(e) Anthracite
Wood
Mainly consists of carbon, hydrogen and water. Freshly cut

wood contains 25 to 50% moisture. It is not used as commercial
fuel. It is raw material for other solid fuels. Its calorific value
ww
varies according to the kind of wood and water content in it. It
burns with a long and non-smoky flame. Its calorific value is
w.E
about 3,500- 4,500 kcal/kg. Wood when burried under the
earth crust for long period with high temperature and pressure
a
gets converted into coal.
syE
4.3.1 Classification of Coal by Rank
ngi
nee
Coal is classified on the basis of its ranking. The rank of coal
denotes its degree of maturity and purity. Peat is the most
rin
immature coal with the lowest rank and athracite s the most
mature coal with the highest rank. The process of conversion g.n
of lignite to anthracite is called coalification of wood. During
the process of coalification, the percentage of moisture, oxygen, et
nitrogen, hydrogen, volatile matter content decreases and
carbon content increases.
Wood Peat Lignite Bituminous Anthracite
Carbon content, Calorific value and hardness
Moisture content, H, O, N, S and Volatile matter

Peat
It is a brown fibrous jelly like mass. It is first stage of coal
derived from wood and vegetable matters from earth. It
contains 80% to 90% of water. It burns without smoke or soot
formation. Its calorific value is approx. 5,400 kcal/kg. It is
available at Nilgiris.
Lignite
It is soft, brown coloured containing 20 - 60% moisture. Air
dried lignite contains C = 70%; O = 20%. It burns with long
ww
and smoky flame. Its calorific value is about 6,500- 7,500
w.E
kcal/kg. It is available at Neyveli.
a
Bituminous coal
syE
It is pitch black to dark grey, which show a laminated
ngi
structure of alternate very bright and dull layers. It is sub
nee
classified on the basis of carbon content. Bituminous coal
shows a banded appearance and carbon content ranges from
rin
78-90% and volatile matter 20-45%. Its calorific value is about
g.n
8,000-8,500 kcal/kg. Coal of this class is used for making coke,
coal gas and domestic heating. It is available at Madhya
Pradesh and Orissa. et
Anthracite
It is a class of highest rank coal containing highest percentage
of carbon (92-98%) and has lowest moisture and volatile
matter. They are hardest, quite dense, and lustrous in
appearance. They possess no caking power. Their calorific
value is about 8,650- 8,700 kcal/kg. They are used for steam
raising and metallurgical purposes. It is available at Eastern
Himalayas.

4.4 Analysis of Coal
In order to access the quality of coal, the following two types of
analysis are made.
4.4.1 Proximate Analysis

Proximate analysis involves in the following determinations
1. Moisture: Finely powdered air-dried coal sample is

weighed in a crucible (Wg). The crucible is placed inside
an electric hot air-oven, maintained at 105 to 110◦ C. The
wwcrucible is allowed to remain in oven for 1 hour and then
w.E
taken out, cooled in a desiccator and weighed (w1 g). Loss
in weight is reported as mass of moisture.
a syE
Percentage of moisture =
Loss in weight
Weight of coal taken
× 100
ngi
% moisture =
W
nee
W − w1
× 100
rin
2. Volatile Matter: The dried sample of coal left in the
crucible is then covered with a lid and placed in an g.n
electric furnace or muffle furnace, maintained at 925 ±
20◦ C. The crucible is taken out of the oven after 7
et
minutes of heating. The crucible is cooled first in air, then
inside desiccators and weighed again (w2 g). Loss in
weight is reported as volatile matter on percentage-basis.
Wt. loss due to volatile matter

% Volatile matter = × 100
w1 − w2
% Volatile matter = × 100
W

3. Ash: The left out residual coal in the crucible is then
heated without lid in a muffle furnace at 700 ± 50◦ C for
1
2 an hour. The crucible is then taken out, cooled first in
air, then in desiccators and weighed. Heating, cooling
and weighing is repeated, till a constant weight (w3 g) is
obtained. The residue is reported as ash on
percentage-basis.
Weight of ash
% Ash = × 100
ww %Ash =
w3
W
× 100
w.E
4. Fixed carbon It is the pure carbon present in the coal.
a syE
It is determined indirectly by deducing the sum total of
moisture content, volatile matter and ash percentage from
100.
ngi
nee
100 − % of (Moisture + Volatile matter + Ash)
rin
Significance of proximate analysis
g.n
Proximate analysis provides following valuable informations in
assessing the quality of coal. et
1. Moisture
# Moisture lowers the effective calorific value of coal.
# It quenches the fire in the furnace, hence lesser the

moisture content, better the quality of coal.
# Presence of moisture, up to 10% is advisable since it

produces a more uniform fuel-bed and less of “fly-ash”.

2. Volatile matter
# A high volatile matter content means that a high

proportion of fuel distills over as vapour and a large
proportion of which escapes not burnt.
# A high volatile matter containing coal burns with a long

sooty flame, high smoke and has low calorific value and
interferes in furnace design.
# A coal sample having
ww – high volatile matter does not cake well.

– medium volatile matter yield strong coke and
w.E
– low volatile matter do not cake at all.
a syE
# Hence moderate the volatile matter, better the rank of the
coal.
3. Ash ngi
nee
# Ash is a non-combustible matter, which reduces the
calorific value of coal. rin
g.n
# The presence of ash also increases transporting, handling
and storage costs.
et
# It also involves additional cost in ash disposal.
# It leads to the formation of clinkers which puts off the air

supply and hence incomplete combustion occurs.
# Lower the ash content, better the quality of coal.
4. Fixed carbon
# Higher the percentage of fixed carbon, greater is its calorific

value and better the quality coal.

# The percentage of fixed carbon helps in designing the
furnace and the shape of the fire-box, because it is the
fixed carbon that burns in the solid state.
4.4.2 Ultimate Analysis

Ultimate analysis is elemental analysis of fuel. The methods of
determinations of each element is as follows:
1. Carbon and Hydrogen
About 1 gram of accurately weighed coal sample is burnt

ww in a current of oxygen in a combustion apparatus. C and
w.E
H of the coal are converted into CO2 and H 2 O respectively.
The gaseous products of combustion are absorbed
a
respectively in KOH and CaCl2 tubes of known weights.
syE
From the increase in weights of these tubes % of C and H
ngi
is calculated respectively as follows
C + O2 −→ nee
CO2
12 44 rin
H2 + 21 O2 −→ H2 O g.n
2 18 et
2KOH + CO2 −→ K2CO3 + H2 O
CaCl2 + 7H2 O −→ CaCl2 .7H2 O
Increase in weight of KOH tube × 12 × 100

% of C =
Weight of coal sample taken × 44
Increase in weight of CaCl2 tube × 2 × 100

% of H =
Weight of coal sample taken × 18

2. Nitrogen (Kjeldahl’s Method)
About 1 gram of accurately weighed powdered coal is
heated with concentrated H2 S O4 along with K2 S O4
(catalyst) in a long-necked Kjeldahl’s flask. After the
solution becomes clear, it is treated with excess of KOH
and the liberated ammonia is distilled over and absorbed
in a known volume of standard acid solution. The unused
acid is then determined by back titration with standard
NaOH solution. From the volume of acid used by
ammonia liberated, the percentage of N in coal is
wwcalculated as
Volume of acid used × Normality of the acid × 1.4
w.E
% of N =
3. Sulphur
a syE
Sulphur is determined from the washings obtained from
ngi
the burning of known mass of coal in a bomb calorimeter
nee
for determination of a calorific value. During this
determination, the washings are treated with barium
rin
chloride solution, where barium sulphate is precipitated
g.n
(S is converted into sulphate). This precipitate is filtered,
washed, dried and weighed.
% of S =
Weight of BaS O4 obtained × 32 × 100
Weight of Coal taken × 233
et
4. Ash
Ash determination is carried out as given in proximate
analysis.
5. Oxygen
It is determined indirectly as follows:
% of Oxygen = 100 − % of ( C + H + S + N + Ash)

Significance of ultimate analysis
1. Carbon and Hydrogen
# Greater the percentage of carbon and hydrogen better is

the coal in quality and has high calorific value.
# Since hydrogen is mostly associated with the volatile

matter, it affects the use of coal.
2. Nitrogen
# Nitrogen is non combustible and has no calorific value and
ww hence, its presence in coal is undesirable.
w.E
# Thus, a good quality coal should have very little nitrogen
content.
3. Sulphur a syE
# Greater the percentage of sulphur, higher is the calorific
value. ngi
nee
# Sulphur on combustion produces acidic gases such as SO2 ,
rin
SO3 which have harmful effects of corroding the
equipments and also cause atmospheric pollution.
g.n
# Presence of sulphur is highly undesirable in coal to be used
for making coke for iron industry, since it badly affects theet
quality and properties of steel.
4. Oxygen
# High oxygen-content coals are characterized by high

moisture content, low calorific value, and low coking
power.
# Moreover, oxygen is in the combined form with hydrogen in

coal and thus, hydrogen available for combustion is lesser
than actual one.

# An increase in 1% oxygen content decreases the calorific
value of about 1.7% and hence the oxygen is undesirable.
# Thus a good quality of coal should have a low percentage of

oxygen.
4.5 Carbonisation of Coal - Metallurgical

Coke
Coke is an important secondary fuel of industrial importance.
ww
It is produced by strongly heating the coal in the absence of air.
This process is known as carbonization.
w.E
1. Coal that soften on heating producing a ‘pasty’ or ‘plastic
a
mass’ impervious to air are called caking coal.
syE
2. The coal which produces hard, porous and strong coke on
heating is called coking coal.ngi
∆
nee
Coal −→ Coke + Volatile gases
rin
g.n
Obviously all coking coals are caking coals but all caking
coals are not coking coals.
4.5.1 Requisites of a metallurgical coke

et
Good coke for metallurgy should possess the following
characteristics:
1. Purity: It should have moisture, ash, sulphur and

phosphorous contents as low as possible.
2. Porosity: Coke should be moderately porous so that

oxygen can easily come in contact with carbon of coke,
there by helping in complete combustion at a high rate.

3. Strength: The coke should be quite compact, hard, strong
to with stand dropping abrasion as well as the pressure of
the over burden in the furnace.
4. Size: The size of metallurgical coke should be neither too

big nor too small.
5. Calorific value: The calorific value of coke should be

high.
6. Volatile Content: It should have moderate volatile

content.
ww7. Coke should be cheap and easily available.
w.E
8. Coke should burn easily.
a syE
4.5.2 Types of Carbonization
ngi
The process of carbonization can be classified into two types
depending on the temperature as
nee
a. Low temperature carbonization
rin
b. High temperature carbonization
g.n
S.No Characteristics Low High
et
temperature temperature
carbonization carbonization
1 Heating 500 - 7000 C 900 - 1200◦ C

temperature
2 Yield of coke 75 - 80% 65 - 75%
3 Volatile matter 5 - 15% 1 - 3%

4 Mechanical Poor Good

strength
5 Calorific value 6500-9500 5400-6000

kcal/m3 kcal/m3
6 Quantity of by- 130-150 300-390

product gases m3 /tone m3 /tone
7 Coke produced Soft Hard
8 Smoke produced Smokeless Smoky
9
ww In gas, % of Lower Higher
w.E
(a) Aromatic
hydrocarbons
a
(b) Aliphatic
hydrocarbons
syE
Higher Lower
10 Uses ngi
Domestic Metallurgy
nee
4.6 rin
Manufacture of Metallurgical Coke
g.n
Otto Hoffman’s by-product oven Method
Otto Hoffman developed a modern by-product coke oven on the

et
basis of "regenerative system of heat economy". The advantages
of this method over other methods are
• Recovery of valuable by-products (like coal gas, ammonia,

benzol oil, tar, etc.)
• Increased thermal efficiency of the carbonization process.

The by-product coke oven consists of number of narrow
silica chambers (each about 10 to 12m long, 3 to 4m high

Fe2O3
H2O Petroleum
Cool
ww
H 2O
w.E
a syE
NH3
ngi
nee
rin
g.n
et
Figure 4.1 Otto Hoffman method

and 0.40 to 0.45m wide) erected side-by-side with vertical flues
in-between them to form a sort of battery. Each chamber is
provided with a charging hole at the top, a gas off- take and a
refractory-lined cast iron door at each ends for discharging
coke.
The finely crushed coal is introduced through the charging
holes at the top of chambers, which are then closed tightly at
both ends to prevent any access of air. The coke ovens are
heated to 1,200◦ C by burning gaseous fuel (like producer gas).
The flue gases produced during combustion, pass on their
ww
sensible heat to one of the two sets of checker brick-work (2&3)
and raised the temperature to 1,000◦ C. The heating is actually
w.E
continued, till the evolution of volatile matter in coal ceases
completely. Carbonization of a charge of coal takes about
a
between 11 to 18 hours.
syE
When carbonization is completed, a massive ram pushes the
ngi
red hot coke into a truck. It is subsequently quenched by ’dry
nee
quenching’ or ’wet quenching’. "Dry quenching" produces more
strong, dense, graphitized and non- reactive coke. In "‘Wet
rin
quenching" method the red hot coke is cooled by sprinkling
water. The coke produced by dry quenching process is much
g.n
cheaper, drier and contains lesser dust than ’wet-quenched’
coke. et
Recovery of by-products: The gas coming out from the oven
is known as "coke oven gas" and is mainly composed of
ammonia, H2 S, naphthalene, benzene, tar, moisture, etc.
1. Recovery of tar: The gas is first passed through a tower

in which liquor ammonia is sprayed. Here dust and tar
get collected in a tank below, which is heated by steam
coils to recover back ammonia sprayed. The ammonia is
used again.

2. Recovery of ammonia: The gases from the chamber are
then passed through a tower in which water is sprayed.
Here ammonia goes into solution as NH4 OH.
3. Recovery of naphthalene: The gases are then passed

through another tower in which cool water is sprayed.
Here naphthalene gets condensed.
4. Recovery of benzene: The gases are then sprayed with

petroleum, when benzene and its homologues are
removed.
ww5. Recovery of H2 S : The gases are then passed through a
w.E
purifier, packed with moist Fe2 O3 . Here H2 S is retained.
a Fe2 O3 + 3H2 S −→ Fe2 S 3 + 3H2 O
syE
After some time, when all Fe2 O3 is changed into Fe2 S3 ,
ngi
the purifier is exposed to atmosphere, where Fe2 O3 is
regenerated.
nee
rin
2Fe2 S 3 + 7O2 −→ 2Fe2 O3 + 6S O2
4.7 Liquid Fuels g.n

The important liquid fuels are petroleum, petroleum products,
et
tar, alcohols. Petroleum or crude oil is a dark greenish 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 containing mixture of
paraffinic, olefinic and aromatic hydrocarbons with minor
amounts of organic compounds like N, O and S. The average
composition of crude oil is C=80 - 87 %, H =11 - 15%, S = 0.1 -
3.5%, (N +O) =0.1 - 0.5%.

4.7.1 Hydrogenation of Coal - Manufacture of
Synthetic Petrol
The gasoline obtained from the fractional distillation of crude
petroleum oil is not enough to meet the requirement of the
present community due to vast increase of automobiles. Hence
to meet this demand synthetic petrol is manufactured by the
process of hydrogenation of coal. The preparation of liquid
fuels from solid coal by the addition of hydrogen is called
hydrogenation of coal. Gasoline is synthesised by the following
methods
ww
1. Fischer- Tropsch process
w.E
2. Bergius process.
a
4.7.2 Bergius process syE
ngi
nee
rin
g.n
et
Figure 4.2 Bergius process
This method was developed by Bergius in Germany during the

First World War. The low ash coal is finely powdered and made

into a paste with heavy oil and then a catalyst (nickel oleate) is
incorporated. The whole is heated with hydrogen at 450◦ C and
under a pressure 200-250 atm for about 1.5 hours. During
which hydrogen combines with coal to form saturated
hydrocarbons, which decompose at prevailing high
temperature and pressure to yield low-boiling liquid
hydrocarbons. The coal gases (from the reaction vessel) are led
to condenser, where a liquid resembling crude oil is obtained,
which is then fractionated to get: (i) gasoline, (ii) middle oil,
and (iii) heavy oil. The heavy oil fraction is recycled to make a
paste with fresh batch of coal dust. The middle oil is
ww
hydrogenated in vapour-phase in presence of a solid catalyst to
w.E
yields more gasoline. The yield of gasoline is about 60% of the
coal dust used.
a syE
4.8 Knocking
ngi
nee
Knocking is a kind of explosion due to rapid pressure rise
occurring in an IC engine and leads to incomplete combustion
and decreases the efficiency of engine. rin
g.n
Knocking in S.I. Engine [Petrol engines]
In a petrol engine, a mixture of gasoline vapour and air at 1:

et
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 work is done by
pushing the piston down the cylinder. If the combustion
proceeds in this way, there is no knocking. But in some cases,
even before the mixture is fully compressd, the fuel - air
mixsture may get heated to a temperature greater than its
temperature and spontaneous combustion occurs before
sparking. This is called pre-ignition. Further, the spark is

also emitted which makes the combustion of the whole of the
mixture faster and explosive. Due to this sudden and
uncontrolled burning and explosion, a characteristic metallic
or rattling sound is heard from the engine. This is known as
"Knocking" or "detonation" or "pinking". The knocking
property of the fuel reduces the efficiency and life of engine. So
a good fuel is required to resist knocking.
The pre-ignition and knocking tendency of fuel (hydrocarbons)
mainly depends on their chemical structures. The knocking
tendency decreases in the following order.
ww
n-alkane > Branched alkane > Cycloalkane> Olefins > Aromatics
w.E
Measurement of knocking in petrol engines
a syE
Octane number (or) Octane rating of a fuel
Octane number is introduced to express the pre ignition
ngi
characteristics of petrol. It has been found that n-heptane
nee
knocks very badly and hence, its anti-knock value has been
given zero. On the other hand, iso-octane gives very little
rin
knocking and so, its anti-knock value has been given 100.
Higher the octane rating, better is the fuel. Thus octane
g.n
number is defined as ’the percentage of iso-octane present in a
mixture of iso- octane and n-heptane which has the same
knocking characteristics as the fuel under test’.
et

Improvement of antiknock characteristics
The antiknock characteristics can be improved by

(i) blending petrol of high octane number
(ii) the addition of anti-knock agents like Tetra-Ethyl Lead
(TEL).
ww
Leaded petrol
The anti-knock properties of a gasoline can be improved by the
w.E
addition of suitable additives. Tetra ethyl lead (TEL) or
(C2 H5 )4 Pb is an important additive added to petrol. Thus the
a syE
petrol containing tetra ethyl lead is called leaded petrol.
TEL reduces the knocking tendency of hydrocarbon. Knocking
ngi
follows a free radical mechanism, leading to a chain growth
nee
which results in an explosion. If the chains are terminated
before their growth, knocking will cease. TEL decomposes
rin
thermally to form ethyl free radicals which combine with the
g.n
growing free radicals of knocking process and thus the chain
growth is stopped.
Disadvantages of using TEL

et
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 reduces engine life. To
improve 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. But this creates atmospheric pollution. So
nowadays aromatic phosphates (example: Cresyl diphenyl
phosphate) are used as antiknock agent.

Knocking in C.I. Engine [Diesel engines]
In C.I. engine air alone is compressed. This raises the cylinder
temperature as high as 300◦ C. When the oil is sprayed as tiny
droplets, ignites spontaneously. Some times, even after the
diesel oil is sprayed, burning may not start. Also more and
more fuel is injected automatically and sudden ignition may
occur and burn the whole of the oil. This is called ignition lag
or delayed ignition. This delayed ignition results in
uncontrolled, excessive combustion known as diesel knock.
The diesel knock mainly depends on the chemical structure of
ww
the fuel (hydrocarbons). The knocking tendency increases in
the following order.
w.E
n-alkane < Cycloalkane < alkene < branched alkane < aromatics
a syE
ngi
Measurement of knocking in diesel engines
Cetane number (or) Cetane rating
nee
Cetane number is introduced to express the ignition lag
rin
characteristics of diesel. Cetane has a very short ignition lag
and hence its cetane number is taken as 100. On the other
g.n
hand 2-methyl naphthalene has a long ignition lag and hence
its cetane number is taken as zero. Higher the octane rating,
better is the fuel.
et
Thus the cetane number is defined as "the percentage of hexa
decane present in a mixture of hexa decane and 2- methyl
napthalene, which has the same ignition lag as the fuel under
test".
Improvement of antiknock characteristics
The cetane number of the oil is improved by adding substances
like ethyl nitrite, ethyl nitrate, isoamyl nitrate and acetone
peroxide.

ww
4.9 Gaseous Fuels
w.E
Gas fuels are the most convenient because they are easy to
handle and are used in the simplest and most
a syE
maintenance-free burner systems. Gas is delivered "on tap" via
a distribution network and so is suited for areas with a high
population or industrial density.
ngi
4.9.1 Natural Gas nee
rin
1. Methane is the main constituent of natural gas and
accounting for about 85% of the total volume. g.n
Hydrocarbon % Composition
et
Methane 85
Ethane 8
Propane 4
Butane 1.5
Other hydrocarbons 11.5
N2 , CO2 , other gases traces

2. Natural gas is a high calorific value fuel (1200-1400
kcal/m3 ) requiring no storage facilities.
3. It mixes with air readily and does not produce smoke or

soot.
4. About 14 % of the gas produced is used for making C black.

It is used as industrial and domestic fuel.
4.9.2 Compressed Natural Gas (CNG)
ww
When the natural gas is compressed, it is called Compressed
Natural Gas (CNG). The primary component present in CNG is
w.E
methane. The composition of CNG is
a
Hydrocarbon
CH4
syE Composition %
85
C2 H6
ngi 1.5
Other hydrocarbons
nee
2
rin
Advantages
g.n
1. The natural gas can either be stored in a tank of a vehicle
as compressed natural gas (CNG) at 3,000 or 3,600 psi.
et
2. CNG requires a much larger volume to store the same
mass of natural gas and the use of very high pressures
(205 to 275 bar).
3. CNG has been made mandatory for all public transport in

New Delhi.
4. CNG is the cheapest, cleanest and least environmentally

impacting alternative fuel.

5. Vehicles powered by CNG emits 40% less NO, 90% less
hydrocarbons, 80% less CO and 25% less CO2 .
6. It is less expensive than petrol and diesel.
7. One kg of CNG is equivalent to 1.39 litres of petrol and

1.18 litres of diesel.
8. The octane number of CNG is 130 which correspondingly

higher than that of 93 octane petrol and hence it is more
energy efficient.
ww9. The noise level CNG engine is much lower than that of
diesel.
w.E
10. The ignition temperature of CNG is about 550◦ C.
Drawbacks
a syE
ngi
• It requires large space for storage.
nee
rin
• Refrigerating can increase the density by 50%.
Advantages of LPG over other gaseous fuels

g.n
• LPG assures complete combustion without any smoke.
et
• It contains no CO.
• Its calorific value is 3 times higher than natural gas and

7 times higher than coal gas.
• It requires little maintenance.
• It has very high thermal efficiency.
• It can be controlled very easily.

Advantages of CNG over LPG
• CNG produces less pollutants than LPG.
• CNG is safer fuel fuel since it ignites at higher

temperature.
• CNG mixes better with air.
• CNG vehicle does not produces S O2 ,S O3 , smoke etc.
• Operating cost is very much low.
ww
• Conversion of CNG operated vehicle is easier.
LPG w.E
a
LPG may be defined as those hydrocarbons, which are gaseous
syE
at normal atmospheric pressure, but may be condensed to the
ngi
liquid state at normal temperature, by the application of
moderate pressures. The composition of LPG is
S.No. Hydrocarbon
nee
% Composition
rin
1. Propane 57
g.n
2.
3.
Butane
ethane, pentane
41
2
et
Properties
• Although they are normally used as gases, they are stored

and transported as liquids under pressure for convenience
and ease of handling.
• Liquid LPG evaporates to produce about 250 times volume

of gas.

• Its calorific value is 27,000 kcal/m3 .
• Escape of even small quantities of the liquefied gas can

give rise to large volumes of vapour / air mixture and thus
cause considerable hazard.
• To aid in the detection of atmospheric leaks, all LPG’s are

required to be odourized with mercaptan. There should be
adequate ground level ventilation where LPG is stored.
4.10 Power alcohol

ww
Ethanol (ethyl alcohol) and methanol (methyl alcohol) used as
w.E
fuels are used as fuel in internal combustion engines as an
alternative to gasoline is called power alcohol. Ethanol is used
a syE
widely, since methanol is toxic. When ethanol is used as an
additive to motor fuels to act as a fuel for internal combustion
ngi
of engines, its called "power alcohol"
nee
Production of ethylalcohol: Ethyl alcohol can be produced
from sugar crops (sugarcane, wheat, maize etc), starch,
rin
cornstalks, vegetable leftover and fruits. The molasses from
sugar cane is diluted to 10%. Temperature is maintained at
30◦ and pH is maintained around 4-5. the enzyme invertase is
g.n
added to convert sucrose to glucose and fructose. et
Invertase
C12 H22 O11 +H2 O −−−−−−−→ C6 H12 O6 + C6 H12 O6
Sucrose Glucose Fructose
Zymase enzyme is added to the mixture of glucose and fructose

to ferment and produce 20% ethylalcohol. It is fractionally
distilled to get rectified spirit.
Zymase
C6 H12 O6 −−−−−→ C2 H5 OH +2CO2 ↑
Glucose or ethylalcohol
Fructose

It has very good performance as a motor fuel with less
emission of pollutants. It is a substitute to gasoline. It can be
combined with gasoline in any concentration up to pure
ethanol. E85 is an abbreviation for an ethanol fuel blend of
85% denatured ethanol fuel and 15% gasoline or other
hydrocarbon by volume. E85 has higher octane rating, which
improves engine performance and reduces engine heat and
wear. It can be produced in large quantity from the
agricultural waste.
ww
Advantages of power alcohol
1. Power alcohol is cheaper and eco-friendly than petrol.
w.E
2. A renewable source of energy extracted from plant.
a syE
3. Ethyl alcohol has good antiknocking property and its
octane number is high (90) when compared to petrol (65).
ngi
nee
4. Alcohol absorbs traces of water, if present in petrol.
5. Specially designed engine with higher compression ratio

is used. rin
6. The presence of oxygen reduces emission of CO by 25%. g.n
7. It emits very less pollutants of S O2 , hydrocarbon, et
particulates etc,.
Disadvantages of power alcohol

1. Power alcohol due to its low calorific value reduces power
output upto 35%.
2. Ethyl alcohol has high surface tension and its

atomisation, at lower temperature, is difficult causing
starting trouble.

3. Ethyl alcohol undergoes oxidation reaction to form acetic
acid, which corrodes engine parts.
4. Special type of carburettor and engine is needed, when

only ethyl alcohol is used as fuel.
4.11 Biodiesel
Biodiesel is a clean burning, eco-friendly, natural and better

ww
alternative for fossil fuel. It is made from renewable sources
w.E
like new and used vegetable oils and animal fats such as,
soybean, sunflowers, corn, olive, peanut, palm, coconut,
a
sesame, cottonseed, etc. It is produced by a process called
syE
transesterfication. and then combined with alcohol like
methanol, biodiesel and glycerine, soaps etc., is formed.
ngi
Preparation:
nee
The fats or vegetable oils are filtered from their hydrocarbons
rin
and taken in a large jar to which glycerol is added and mixed
well. Carefully NaOH is dissolved in the methanol to form
g.n
sodium methoxide. It is poured on top of the vegetable oil in a
large jar. The jar is closed and sealed tightly. Then Shaked
vigorously for 15 minutes. The jar is left undisturbed for
et
atleast 8 hours for the separation of biodiesel (top layer) &
glycerin (bottom layer).
CH2 - OH HOOCH35C17 CH2 - O OCH35C17
CH - OH + HOOCH35C17 CH - OOCH35C17
CH2 - OH HOOCH35C17 CH2 - OOCH35C17

Glycerol Fatty acid Triglyceride

CH2 - O OCH35C17 CH3OH CH2 - OH
NaOH
CH - OOCH35C17 + CH3OH 3C17H35COOCH3 + CH - OH
CH2 - OOCH35C17 CH3OH CH2 - OH

Triglyceride Methanol Biodiesel Glycerol
Vegetable oils
or Esterification Methanol
Animal oils NaOH
ww Wash water Washing

Biodiesel + Glycerol
w.E
(soap water)
a syE Pure Biodiesel
ngi
Advantages: nee
1. Biodiesel is renewable energy sources. rin
2. Biodiesel reduces smoke due to soot free and complete g.n
combustion. et
3. Biodiesel reduces hydrocarbon emission.
4. Biodiesel reduces carbon monoxide emission.
5. Biodiesel is safe for transport due to high flash point.
6. Biodiesel is safe to handle as it is bio-degradable and non-

toxic.
7. Biodiesel emissions show decreased levels of polycyclic

aromatic hydrocarbons (PAH) and nitrated polycyclic

aromatic hydrocarbons(nPAH), which have been
identified as potential cancer causing compounds.
Disadvantages:
1. Biodiesel gels in cold weather.
2. Biodiesel contains higher percentage of water.
3. Biodiesel has low horsepower.
4. Biodiesel has higher nitrogen oxide emissions.
ww
Applications:
w.E
1. On-Road Vehicles: Car, bus etc
a
2. Off-Road Vehicles: In construction, mining, and farm
machinery.
syE
ngi
3. Marine Vessels: It can be used in marine engines safely.
nee
4. It is used in stationary power generation.
rin
5. It is used as boiler fuel and in hybrid vehicles.
6. It is also used as lubricity agent/additives. g.n

4.12 Ignition temperature and explosive range
et
Ignition temperature of a fuel is the minimum temperature
at which fuel ignites and burns smoothly, in the presence of
external source like spark or flame.
Auto ignition temperature or kindling point of a
substance is the lowest temperature at which it will
spontaneously ignite without an external source of ignition,
such as a flame or spark. The temperature at which a fuel will
ignite decreases as the pressure or oxygen concentration

increases.
Condition for ignition:
• A fuel and oxygen (air) must exist in certain proportions.
• Ignition source such as a spark or flame.
• The ratio of fuel and oxygen that is required varies with

each combustible gas or vapour.
Lower Explosive Limit (LEL): The minimum concentration

of a particular combustible gas or vapor necessary to support
ww
its combustion in air is defined as the Lower Explosive Limit
w.E
(LEL) for that gas. Below this level, the mixture is too lean to
burn.
a syE
Lower Explosive Limit (LEL): The maximum concentration
of a gas or vapor that will burn in air is defined as the Upper
ngi
Explosive Limit (UEL). Above this level, the mixture is too rich
to burn. The range between the LEL and UEL is known as the
flammable range for that gas or vapour. nee
Flammable range rin
g.n
It refer to the range of compositions, for fixed temperature and
pressure, within which an explosive reaction is possible when
an external ignition source is introduced. This can happen
et
even when the mixture is cold. Flammability limits are given
in terms of fuel concentration (by volume) at a specified
pressure and temperature.
Explosive range
It refers to the range of pressure and temperature for which an
explosive reaction at a fixed composition mixture is possible.
The composition has to be within the flammable range. The
reaction is usually initiated by autocatalytic (sometimes called

self-heating) reaction at those conditions, without any external
ignition source. In practical terms, this means that the
mixture needs to be sufficiently hot. Explosion limits are given
in terms of a minimum autoignition temperature (AIT) for
ignition of fuel injected into hot air.
Gas UFL LFL Ignition temp◦
Propane 9.6 2.15 466
Butane 8.5 1.9 405
ww Natural gas 15 4.7 482-632
w.E
Diesel
Ethanol
0.6
3.3
7.5
19.0
210
365
a
Gasoline syE
1.2 7.1 280
Hydrogen 75 ngi 4 400
4.13 Combustion
nee
rin
Combustion is an exothermic chemical reaction which is
g.n
accompanied by the development of heat and light rapidly with
the rise in temperature. For proper combustion, the substance et
must be brought to its kindling or ignition temperature which
may be defined as ‘the minimum temperature at which the
substance ignites and burns without further addition of heat
from outside’.
Calculation of air qualities:
To find the amount of oxygen and hence, the amount of air

required for the combustion of unit quantity of a fuel, it is
necessary to apply the following elementary principles.

1. Substances always combine in definite proportions and
these proportions are determined by the molecular
masses of the substances involved and the products
formed. For example when carbon combines with oxygen
to form carbondioxide, the equation
C(s) + O2(g) −→ CO2(g)
Mass Proportions 12 32 44
indicates that mass proportions of carbon, oxygen and

wwcarbon dioxide formed are 12 : 32 : 44 respectively. In the
w.E
same way, when hydrogen combines with oxygen to form
steam the involved equation
a syE H2(s) + 1
O2(g) −→ H2 O(g)
Mass Proportions 2 ngi 2
16 18
nee
rin
indicates that mass proportions of hydrogen, oxygen and
steam formed are 2:16:18 respectively.
g.n
2. 22.4 liters of any gas at STP = 1 mole of that gas.
3. Air contains 21% of oxygen by volume and 23% of oxygen

et
by weight.
4. Molecular mass of air is taken as 28.94.
5. Minimum oxygen required = oxygen required - oxygen

present in the fuel.
6. In the total amount of hydrogen present in the fuel, some

of it is in the combined form (H2 O). It is non combustible
and it does not take part in combustion.

7. The theoretical amount of oxygen for the complete
combustion of 1 kg of solid and liquid fuel.
( )
32 O
= × C + 8(H − ) + S kg
12 8
8. The theoretical amount of air required for the complete

combustion of 1kg of fuel
( )
100 32 O
= × × C + 8(H − ) + S kg
23 12 8
ww
w.E
4.14 Solved Problems
a
Problem 4.1. Calculate the gross and net calorific value of coal
syE
having the following composition C = 85%, H2 = 8%, S = 1%, N2
ngi
= 2%, ash = 4%. Laten heat of steam = 587 kcal /kg.
Solution
nee
Gross calorific value
rin
GCV =
1
100
O
[8080C + 34500(H − ) + 2240S ] kcal/g
8 g.n
=
1 0
[8080 × 85 + 34500(8 − ) + 2240 × 1] kcal/g
et
100 8
1
= [6, 86, 800 + 2, 76, 000 + 2, 240]kcal/g
100
= 1/100[9, 65, 040] kcal/g
= 9, 650.4 kcal/kg.

Net calorific value
NCV = GCV − 0.09H × 587 kcal/kg
= 9, 650.4 − 0.09 × 8 × 587 kcal/kg
= 9, 227.8 kcal/kg.
Problem 4.2. A sample of coal was found to contain: C = 80%,

H2 = 5%, O2 = 1%, N2 = 2%, and the remaining ash. Calculate
the amount of minimum air required for complete combustion of
1 Kg of coal sample.
ww
Solution
Constituent w.E Combustion reaction Wt. of O2
a C(s) + syE
O2(g) → CO2(g)
required kg
=
32
× 0.80
C = 0.80
12 32 ngi 12
= 2.133
H2(g) + 1
2
nee
O2(g) → H2 O(g)
16
= × 0.05
H2 = 0.05
2 16 rin 2
= 0.4
Total = 2.533 g.n

Less Oxygen in fuel = 0.010 kg
et
Net oxygen required = 2.523 kg
100
Therefore, weight of air required = 2.523 × = 10.97 kg
23
Problem 4.3. A sample of coal was found to contain: C =
66.2%, H2 = 4.2%, O2 = 6.1%, N2 = 1.4%, S= 2.9% and the
remaining ash. Calculate the amount of minimum air required
for complete combustion of 5 Kg of coal sample with 25% excess
air.

Solution:
Constituents Combustion reactions Wt. of oxygen

required kg
32
C(s) + O2(g) → CO2 (g) = × 0.662
C = 0.662 12
12 32 = 1.765
1 16
H2(g) + O2(g) → H2 O(g) = × 0.042
H2 = 0.042 2 2
2 16 = 0.336
ww
S = 0.029
S (s) + O2(g) → SO2(g)
32
= × 0.029
32
w.E 2 16 = 0.029
a Total
syE
Less Oxygen in fuel
= 2.130
= 0.061 kg
ngi
Net oxygen required = 2.069 kg
Therefore nee
i) Weight of air required = 2.069 ×
100
23 rin
= 8.995 kg
ii) Wt. of air required with 25% excess air g.n

= 8.995 ×
125
= 11.244 kg
et
100
iii) Wt. of air required for the combustion of 5 kg of coal

= 11.244 × 5 = 56.222 kg
Problem 4.4. A gas used in an internal combustion engine had
the following composition by volume: H2 = 45%, CH4 = 36%, CO
= 15%, N2 = 4%. Find the minimum volume of air required for
the combustion of 1 m3 of the gas.
Solution:

Constituent Combustion reaction Wt. of O2

required m3
1
H2(g) + 2 O2(g) → H2 O(g)
H2 = 0.45 =0.45 × 0.5
1 vol 0.5 vol = 0.225
CH4(g) + 2O2(g) → CO2(g) +H2 O(g)

CH4 = 0.36 =0.36 × 2
1 vol 2 vol = 0.720
ww CO(g) + 1
O2(g) → CO2(g)
CO = 0.15
w.E 1 vol
2
0.5 vol
= 0.15 × 0.5
= 0.075
aTotal
syE =1.020
Less Oxygen in fuel

ngi =0
Net oxygen required

nee = 1.020 m3
rin
Therefore volume of air required per m3 of gas = 1.020 ×
100
= 4.857m3
g.n
21
Problem 4.5. A gaseous fuel has the following composition: H2

et
= 25%, C2 H6 = 11%, CH4 = 30%, C2 H4 = 4.5%, C4 H8 = 2.5%, CO
= 6.0%, CO2 = 8%, O2 = 2%, N2 = 12%. Find the volume of air
required for the combustion of 1 m3 of the gas using 40% excess
air.

Solution
vol. of O2
Consti-
Combustion reactions required
tuent
m3
1
H2(g) + 2 O2(g) → H2 O(g) =0.25 × 0.5
H2 = 0.25
1 vol 0.5 vol = 0.125
7
C2 H6(g) + → 2CO2(g) +3H2 O(g) =0.11 × 3.5
2 O2(g)
C2 H6 =0.11
= 0.385
ww 1 vol
CH4(g) +
3.5 vol
2O2(g) → CO2(g) +2H2 O(g)

CH4 =0.30
w.E 1 vol 2 vol
=0.30 × 2
= 0.600
C2 H4 =0.045
a C2 H4(g) +
syE 3O2(g) → 2CO2(g) +2H2 O(g) =0.045 × 3
1 vol 3 vol
ngi = 0.135
C4 H8 =0.025
C4 H8(g) +
nee
6O2(g) → 4CO2(g) +4H2 O(g) =0.025 × 6
1 vol 6 vol
rin = 0.150
CO = 0.06
CO( g) + 1
2 O2(g) → CO2(g)
g.n
= 0.06 × 0.5
1 vol
Total
0.5 vol = 0.030
=1.425m3
et
Less Oxygen in fuel = 0.020 m3
Net oxygen required = 1.405 m3
Therefore
i) volume of air required per m3 of gas
100
= 1.405 × = 6.690m3
21

140
ii) volume of air required with 40% excess air = 6.690 ×
100
= 9.366m3
Problem 4.6. Calculate the weight and volume of air required

for the combustion of 3 kg of carbon.
Solution
Step 1: Weight of air required for combustion of 3 kg of C
= Wt. of C x (32/12) x 100/23
ww = 3 kg x (32/12) x 100/23
w.E = 34.783 kg or 34783 g
a syE
Step 2: Volume of air required for combustion of 3 kg of C
We know that , Molecular mass of air = 28.94g/mol = 22.4 l/mol
Therefore, volume of air required is
ngi
= nee
wt. of air in g × (22.4 l/mol)
(mol/mol.wt)
rin
=
34783 × (22.4)
(28.94) g.n
= 26.92 × 103 l or 26.92 m3 et
4.15 Flue Gas Analysis (Orsat’s method)
The mixture of gases such as CO2 , O2 , CO, etc., coming out
from the combustion chamber is called flue gases. The analysis
of a flue gas gives an idea about the complete or incomplete
combustion process. If the flue gases contains CO, it indicates
that incomplete combustion and if it contains excess amount of
oxygen, it indicates, complete combustion. The analysis of flue

gas is carried out by using orsat’s apparatus.
Description
It consists of a horizontal tube, having 3 way stopcock. At one

end of this tube, U-tube containing fused CaCl2 is connected.
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
ww
raising or lowering the reservoir. The horizontal tube is also
connected with three different absorption bulbs I, II and III for
w.E
absorbing CO2 , O2 and CO.
a
Bulb-I: It contains ’potassium hydroxide’ solution, and it
absorbs only CO2
syE
Bulb-II: It contains ’alkaline pyrogallol’ solution, and it
absorbs only CO2 and O2 ngi
nee
Bulb-III : It contains ’ammoniacal cuprous chloride’ solution,
and it absorbs only CO2 , O2 and CO.
rin
Working g.n
The 3-way stopcock is opened to the atmosphere and the
reservoir is raised, till the burette is completely filled with
et
water and air is excluded from the burette. The 3-way stopcock
is opened to suck the flue gas into the burette, and the volume
of flue gas is adjusted to 100 cc and the 3-way stop cock is
closed.
a) Absorption of CO2
The stopper of the bulb-1 containing KOH solution is opened

and all the gas is passed into the bulb-I by raising the level of

water in the burette. The CO2 present in the flue gas is
absorbed by KOH. The gas is again resent to the burette. This
process is repeated several times to ensure complete
absorption of CO2 .
The decrease in volume of the flue gas in the burette indicates
the volume of CO2 in 100 cc of the flue gas.
CO2 O2 CO
ww
Alkaline pyrogallol
Ammoniacal CuCl2
w.E
caustic potash
a syE
ngi
nee
Figure 4.3 Orsat Apparatus rin
g.n
b) Absorption of O2
Stopcock of bulb-II is opened and the flue gas passes into the
et
absorption bulb-II, where O2 present in the flue gas is
absorbed by alkaline pyrogallol (925 g of pyrogallol + 200g of
KOH in 500 ml distilled water).
the volume of O2 .
c) Absorption of CO
Stopcock of bulb-III is opened and the remaining gas is sent

into bulb-III. The CO present in the flue gas is absorbed by
ammoniacal cuprous chloride (100g CuCl2 + 125 ml liquor
ammonia + 375 ml distilled water).
the volume of CO.
The remaining gas in the burette after the absorption of CO2 ,
O2 and CO is taken as nitrogen.
Significance
ww1. Gives an idea about the complete or incomplete

combustion process.
w.E
2. Flue gas with more CO shows incomplete combustion and
a
demand of oxygen.
syE
3. Flue gas with more O2 shows complete combustion and
excess of oxygen.
ngi
ANNA UNIVERSITY QUESTIONS AND ANSWERSnee
PART A
rin
1. Define calorific value. g.n
Calorific value of a fuel may be defined as “the total
quantity of heat liberated, when a unit mass (or volume)
et
of a fuel is burnt completely and is usually expressed as
cal g−1 or kcal kg−1 .
2. Define gross and net calorific value.

‘Gross calorific value is the heat liberated when a unit
quantity of fuel is completely burnt and the products of
combustion are cooled to room temperature’. Thus the
latent heat of condensation of steam is included in the
gross calorific value.

5 ENERGY SOURCES
5.1 Introduction
Man is always in search of abundance of energy, because it is
the mark of standard of living, technical growth, industrial
ww
growth etc. A source of energy is one that can provide
w.E
adequate amount of energy in a usable form over long period of
time. These sources can be of two types:
a syE
Renewable source or non-conventional energy resource
which can be generated continuously in nature and are
ngi
inexhaustible. Example: Solar, wind, tidal energy, etc.
nee
Non Renewable source or conventional energy resource
which have accumulated in nature over a long span of time
rin
and cannot be quickly replenished when exhausted. Example:
Coal, petroleum, nuclear energy, etc.
g.n
Nuclear energy is the energy that is trapped inside each atom.
Nuclear reaction gives energy which is million times greater
et
than energy given by a chemical reaction. One kg of uranium
on fission provides 2 x 107 KWh. An equivalent amount energy
is provided by 3000 tonnes of high grade coal.
5.2 Terms and terminology

Radioactivity: The phenomenon of spontaneous and
continuous emission of powerful invisible radiation by the
disintegration of an element is called radioactivity. It affects

226 ENERGY SOURCES
the photographic plate. The most common types of radiation
are called alpha, beta, and gamma radiations.
Mass defect: The difference in mass of an isotope of an

element to the sum of masses of protons, neutrons and
electrons present in it is called mass defect. It is the loss of
mass during the formation of the nucleus of the isotope.

Theoretical mass 



= M ′ = Zm p + Zme + (A − Z)mn



of an isotope is 


ww
where
w.E
Z = Atomic number; A = Mass number; m p , me , mn are the
a
respective masses of protons, electrons and neutrons.
syE
ngi
Mass defect ∆m = M ′ − M
= Zm p + Zme + (A − Z)mn − M
nee
where M = Experimental atomic mass
rin
g.n
Binding Energy: The energy release during the formation of
nucleus with the constituent nucleons. In other words the
minimum energy required to break the nucleus into its
et
constituent nucleons. Greater the binding energy greater is
the stability. It is expressed in MeV/nucleon.
5.2.1 Nuclear reaction
The reaction which brings about the changes in the nucleus of

an atom is called nuclear reaction. There are two types of
nuclear reaction namely Nuclear fission and nuclear fusion.

5.2.2 Nuclear Fission Reaction
When a heavy nucleus is bombarded with fast moving
neutrons, it splits to two approx. equal nucleus with liberation
of enormous amount of heat energy. Example fission of U 235 .

93
Ba140 + 3n10 + Energy

+ K36





 56










235 236
+ n10 −→ U92

90
U92 −→  Cs144 1

55 + Rb37 + 2n0 + Energy





ww









 Xe144
 90 1
54 + S r38 + 2n0 + Energy
w.E


Newtron
Generation
a syE
First Second Third Fourth
ngi
nee
rin
g.n
et
235
U
Fission fragment
Neutron leading
to additional fissions
Neutron not leading
addition fissions available
for plutonium production
Figure 5.1 Nuclear fission reaction

228 ENERGY SOURCES
Characteristics of nuclear fission reaction
* 235 U tends to absorb only slow neutrons.
* Every fission is accompanied by emission of two or more

neutrons.
* In all cases, very large disintegrating energies are released.
* Fission fragments are all radioactive which then decay to

stabilize nuclei by a series of β-emissions.
ww
w.E
* The atomic masses of fission products ranges from about 70
to 160.
a syE
* Fission reaction is a self propagating chain reaction
releasing neutrons which cause further fission reaction in
ngi
other nuclei producing more secondary neutrons.
nee
* The chain reaction can be controlled and maintained steady
rin
by absorbing a desired number of neutrons so that on an
average only one neutron remains available for exciting
g.n
further fission. Such a reaction is called controlled chain
reaction. A device in which a nuclear chain reaction is
initiated, maintained and controlled is called a nuclear
et
reactor.
Critical mass: Every released secondary neutron in nuclear

fission does not strike a nucleus and cause further fission. Some
neutrons miss their targets and some escape into air. To avoid
this, a minimum size of the fuel is required to undergo chain
reaction. This is called critical size. The corresponding mass of
the fuel is called critical mass.

Super critical size: The size of the fuel material greater than
the critical size is called super critical size. This maintains the
nuclear chain reaction and relatively fewer neutron escapes and
as a result a chain reaction is set up.
Sub Critical mass: The size of the fuel material less than the
critical size is called sub critical size. This does not maintain
the chain reaction due to escaping of neutrons which is not
explosive.
ww
w.E
a syE
(a) (b) ngi (c)
nee
Figure 5.2 (a) Subcritical mass (b) Critical mass (c) Supercritical
mass
rin
Multiplication factor: The number of neutron released from g.n
a single fission is known as multiplication factor (K). When
this is less than one (K < 1) no chain reaction takes place. If it
et
is carefully controlled to one (K = 1), controlled chain reaction
takes place. Example: Nuclear reactor. If it is greater than
one (K > 1 ), uncontrolled chain reaction takes place. Example:
Atom bomb.
5.2.3 Nuclear Fusion Reaction
Nuclear fusion is the process of combination of lighter nuclei

into heavier nucleus with simultaneous release of huge amount

230 ENERGY SOURCES
of energy.
2
1H + 1 H 3 −→2 He4 +0 n1 + 17.6 MeV Energy
H21 He42
ww H1
3
w.E n
a
Figure 5.3 syE
Schematic diagram of Nuclear fusion reaction
Nuclear fusion in sun: ngi

1H
1 nee
+ 1 H 1 −→1 H 2 +01 e+ + ν(neutrino)
1H
2 rin
+ 1 H 1 −→2 He3 + γ
1H
1
+ 2 He3 −→2 He4 +01 e+ + ν g.n
1 He
3
+ 2 He3 −→2 He4 +1 H 1 +1 H 1 + γ et
Characteristics of nuclear fusion reaction
# Fusion of nuclei with lower mass than iron releases energy

while fusion of nuclei heavier than iron generally absorbs
energy. This phenomenon is known as iron peak.
# The sun uses nuclear fusion of hydrogen atoms into helium

atoms. This gives off heat and light and other radiation. In
this reaction 0.026 amu mass is lost which is converted into
energy.

# To combine two positively charged nuclei, we have to
overcome nucleus - nucleus electrostatic strong repulsive
forces.
# A temperature of 106 Kelvin is required to create a plasma

for the reaction to take place.
# In the hydrogen to helium fusion reaction in the Sun takes

place at about 100 million degrees centigrade.
# Thus a temperature of high order would have to be reached.

Hence fusion reactions are also called thermo nuclear
ww
reactions.
w.E
# The strength of nuclear fusion is that it creates less
radioactive material than fission, and its supply of fuel can
a syE
last longer than the sun.
ngi
# Nuclear fusion is also applied in nuclear weapons like
hydrogen bomb.
nee
rin
5.2.3.1 Differences between nuclear fission and nuclear
fusion g.n
S.No Nuclear fission Nuclear fusion
et
1. It is the process of It is the process of
breaking a heavier combining two lighter
nucleus into lighter nuclei into a heavier
nuclei with the release nucleus with the release
of enormous amount of of enormous amount of
energy. energy

232 ENERGY SOURCES
2. It does not occur in It occurs in nature like

nature. stars.
3. It emits neutrons. It emits positrons.
4. Fission requires large High density, high

critical mass and temperature environment
a slow neutron to is required.
initiate the process.
5. It occurs at ordinary It occurs at very high

ww temperature. temperature (>106 K).
6. w.E
Takes little energy to Extremely high energy
a
split two atoms in a
syE
fission reaction.
is required to bring two
or more protons close
enough that nuclear
ngi forces overcome their
nee
electrostatic repulsion.
7. Fission produces many

highly radioactive rin
Few radioactive particles
are produced by fusion
particles. reaction. g.n
8. It produces compara- It produces 3 or 4 time et
tively low energy. more energy.
9. It can be controlled to It cannot be controlled.

produce power.
10. Example: Atom Example: Hydrogen

bomb. bomb, which uses a fission
reaction to "trigger" a
fusion reaction..

5.2.4 Classification of Nuclear reactor
They are classified on the basis of utilization of heat and

generation of electricity.
1. Light Water Reactors: In it pure water (light water) is

used to produce steam and in turn electricity. They are of
two types
# Boiling Water Reactors (BWR): In a BWR, the water

that cools the nuclear reactor is boiled, turns into steam
and drives a steam turbine.
ww# Pressurized Water Reactors(PWR): The high
w.E
pressure water that cools reactor, does not turn into
steam and a secondary water supply is converted into
a syE
steam and from there to the steam turbine.
ngi
2. Heavy Water Reactors (HWR): The heavy water (D2 O)
is used to cool the reactor.
nee
rin
3. Gas-cooled Reactors (GCR): Reactors that use gas as a
coolant (and to drive a gas turbine) are called high
temperature gas-cooled reactors (HTGR). Gas such as g.n
helium or carbon dioxide is used. et
4. Fast Reactors or Breeder reactor (FBR): Liquid
sodium metal is used as the coolant, at or near
atmospheric pressure, thereby obviating the need for
pressure vessels. The boiling point of sodium is high, it
can operate at a considerably higher temperature.
5. Thorium Reactors: It is a breeder reactor which use

thorium as fuel material and liquid fluoride (a moten
salt) as coolant. It is also called (LFTR).

234 ENERGY SOURCES
5.3 Nuclear reactor
Nuclear reactor is one where nuclear fission chain reaction is
made to occur at controlled conditions having a multiplication
factor of slightly greater than one.
5.3.1 Light water nuclear power plant

A nuclear power plant is a plant where a controlled chain
nuclear fission reaction is carried out, and the liberated
enormous amount of energy is utilised for power generation.
ww
The following are the parts of a nuclear reactor.
w.E
1. Reactor core: It is the core part of nuclear power plant,
where controlled chain reaction occurs. The reactor core
a
consists of following components.
syE
a) Fuel: The nuclear fuel generally used are
ngi
* Natural uranium- It contains 99.3% U − 239 and
0.7%U − 235
nee
rin
* Enriched uranium- It has greater % of U − 235.
* Pu − 239.
g.n
The U 239 doesnot undergo fission only U 235 undergoes
fission. The fuel materials are mixed homogeneously
with moderator to form fuel element or fuel materials
et
may be surrounded by moderators.
b) Moderator: The moderator is used to slow down

the fast moving neutron in a fraction of second. The
kinetic energy is reduced from 1MeV to 0.25eV. The
materials used as moderators are graphite,
beryllium and heavy water. The heavy water is most
effective costly moderator and graphite is cheap but
reactive with O2 and CO2 .

Figure 5.4
ww Containment
building
Secondary loop
w.E Turbine
Generator
asy
Schematic diagram of Nuclear reactor
Control rod EPrimary

ngi
loop Hot water
Reactor vessel
Fuel rod
Heat
nee Heat
Exchanger
Cool water
Pump
rin
Water
g.n
Pump Condenser
et
235
236 ENERGY SOURCES
c) Coolant: The coolants are used to reduce the heat
energy produced in the reactor due to fission
reaction and to make use of it for electricity
generation. The material used as coolants are water,
heavy water, liquid sodium, gases etc. Water and
heavy water act as both coolant and moderator. They
are corrosive at high temperature. Liquid sodium is
a good coolant for high temperature. Air is used as
coolant in low power reactor. It is highly reactive at
high temperature.
ww d) Control rods: The functions of control rod is

i. To start the reaction
w.E
ii. To control the nuclear reaction for continuous
a generation of energy.
syE
iii. To stop the reaction. Cadmium and boron rods
ngi
are commonly used. They do all the functions by
absorbing neutrons.
nee
They are moved up and down from the core top. To
rin
start the reaction they are pulled up such that the
g.n
multiplication factor is greater than one. To maintain
the reaction they are pushed down slightly such that
the multiplication factor is equal to one. To stop theet
process they pushed still deeper and to reduce the
multiplication factor to less than one.
2. Pressure vessel: It is placed around the reflector. It has

the entrance and exit passage for coolant. It withstands a
high pressure of 200 kg/m2 . It has holes for control rods
to be pulled up and down at the top.
3. Shield: Its purpose is to shield the hazardous radiation.

There are two types of shields in high power plant.

a) Thermal shield: The thermal shield is made up of
steel or iron sheet of 50- 60 cm thickness. It is next to
the pressure vessel. It absorbs most of the gama rays
and get heated up and cooled with a coolant.
b) Biological shield: It is a layer of thick concrete
surrounding the thermal shield. It absorbs the
remaining gamma rays and neutrons to ensure
safety for the operating personnel.
4. Heat exchanger: Here heat from coolant is exchanged

with water and steam at about 400 kg/cm2 pressure is
wwproduced.
w.E
5. Turbine: The pressured steam rotates the turbine to
generate electricity. The exhaust steam is condensed and
a syE
sent back to the heat exchangers.
5.3.2 Breeder reactor ngi

nee
It is a reactor where fast moving neutrons are bombarded with
rin
fertile material (non-fissionable material) to convert into fissile
material (fissionable material). A breeder reactor is a nuclear
reactor capable of generating more fissile material than it g.n
consumes. They are used as fuel in nuclear power plants. The
fissile materials are those that undergo fission by slow moving
et
neutrons. Example: U − 235, Pu − 239. The fertile materials are
those materials which undergo fission only with fast moving
neutrons. Example: U − 238, T h − 239.
Reaction mechanism
A primary fertile material like U-238 is bombarded with fast
moving neutrons and it absorbs a neutron to become U − 239.
This undergoes β - decay and forms Np - 239 (Neptunium)
which undergoes further β-decay to give Pu - 239 (Plutonium).

238 ENERGY SOURCES
Pu is a secondary fissile material used as fuel in nuclear
reactor. The burning up of primary fuels may be compensated
by the production of new or secondary fissile fuels. The extent
of compensation is measured by factor called conversion factor.
n U 238 U 239 Np 239 Pu 239
decay ß decay ß decay
Figure 5.5 Breeder reaction mechanism
ww
Conversion factor or Breeding ratio
w.E
It is defined as the ratio of the number of secondary fuel
(Pu − 239) produced to the number of primary fuel atoms
a syE
(U − 238) consumed. It is generally expected is 1.4 and
achieved is 1.2. The time required for a breeder reactor to
ngi
produce enough material to fuel a second reactor is called its
nee
doubling time. It is targeted as 10 years In breeder reactor
there is no moderator and the coolant in breeder reactor used
rin
is liquid sodium. Water cannot act as coolant since it act even
as moderators.
g.n
Draw backs et
1. It involves high risk.
2. It is very difficult to control.
3. Pu-239 has long life; it is very toxic and produces

hazardous radiation.
4. It leads to lungs cancer.
5. It is very easily used to make nuclear weapons.

5.3.2.1 Differences between Nuclear reactor and Breeder
reactor
S.No Nuclear reactor Breeder reactor
1. Fissile material like U − Fertile materials like U −

235, Pu − 239 are used as 238, T h − 239 are used as
fuel. fuel.
2. Fuel is bombarded with Fuel is bombarded with

slow moving neutrons. fast moving neutrons.
3 ww Moderators like heavy No moderators are needed.
w.E
water, graphite are
used to slow down the
4.
a
neutrons.
syE
Ordinary water and Water cannot be used as
heavy water are used as
ngi coolant since it can even
coolants
nee
act as moderator. Liquid
sodium is used as coolant
rin
in fast reactor.
5. The conversion factor is g.n

The conversion factor is
equal to 0.9 unity or even higher than 1
(i.e.) it produces more fuel et
than what is used.
6. It is used to produce It is used to produce fissile

electricity. fuels.
5.3.3 Nuclear Waste Disposal Methods
Radioactive wastes are the leftovers from the use of nuclear

materials for the production of electricity, diagnosis and

240 ENERGY SOURCES
treatment of disease, and other purposes.
In nuclear fission process, radioactive waste is produced that
needs to be safely dealt with in order to avoid permanent
damage to the surrounding environment. Nuclear waste can
be temporarily treated on-site at the production facility using a
number of methods, such as vitrification, ion exchange or
synroc. Although this initial treatment prepares the waste for
transport and inhibits damage in the short-term, long-term
management solutions.
Vitrification is the process of turning radioactive waste into

ww
glass. Radioactive waste is mixed with a substance that will
w.E
crystallize when heated (e.g., sugar, sand) and then calcined.
In a hardened state, the radioactive material is encased,
a
preventing it from leaking.
syE Vitrification allows the
immobilization of the waste for thousands of years.
ngi
Geological Disposal is the process of burrowing nuclear
nee
waste into the ground to the point where it is out of human
reach. The waste needs to be properly protected to stop any
rin
material from leaking out. Seepage from the waste could
g.n
contaminate the water table if the burial location is above or
below the water level.
Reprocessing involves taking waste and separating the

et
useful components from those that are not as useful.
Specifically, it involves taking the fissionable material out from
the irradiated nuclear fuel.
Transmutation involves converting a chemical element into

another less harmful one. Common conversions include going
from Chlorine to Argon or from Potassium to Argon. The
driving force behind transmutation is chemical reactions that
are caused from an outside stimulus, such as a proton hitting

the reaction materials.It is a solution for long term disposal.
Space Disposal is putting nuclear waste on a space shuttle

and launching the shuttle into space. It is low rated and is a
poor method.
5.4 Solar Energy and Solar Cells

The radiation from sun is the primary form of energy. It is
abundant in nature. As we know the conventional non
renewable resources are limited, the world is researching
ww
about harnessing solar energy effectively and efficiently.
w.E
Harnessing solar energy is the process of conversion of
direct sunlight into useful forms of energy like electricity, heat
etc. a syE
ngi
5.4.1 Solar Cell or Photovoltaic cell
nee
A solar cell is a device (P-N junction) that converts the energy
rin
of light directly into electricity (DC) using the photovoltaic
effect. To induce the electric field within a PV cell, two
separate semiconductors (P-type and N-type) are sandwiched g.n
together. A typical silicon PV cell is composed of a thin wafer
consisting of an ultra-thin layer of phosphorus-doped (N-type)
et
silicon on top of a thicker layer of boron-doped (P-type) silicon.
An electrical field is created near the top surface of the cell
where these two materials are in contact, called the P-N
junction. When sunlight strikes the surface of a PV cell (at the
P-N junction) the electricity is generated.
Principle and Working

The principle of solar cell is based on photo voltaic effect. In
absence of sunlight, the positively charged holes are confined

242 ENERGY SOURCES
to p-type region and negatively charged electrons are confined
to N-type region by the depletion region P-N junction. When
P-N junction is exposed to radiation, electron absorbs energy
and moves from valence band to conduction band and the
dissociation electron hole pair occurs. Thus increasing the
concentration hole and electrons in P region and N-region
respectively. When the concentration exceeds equilibrium
concentration, a drift of electron and hole occurs away from the
P-N junction.
ww
w.E
a syE
ngi
nee
rin
g.n
et
Figure 5.6 Solar cell
The electron flows through external circuit causing

illumination of bulb to p-type semiconductor. This electricity is
stored in the storage device (battery) and used whenever
required.

A 4 cm2 area solar cell produces 0.4 - 0.5V and produces a
current of 60 mA. A large number of solar cells are connected
in series and or in parallel to form a solar panel which can
harness a large amount of solar energy. Solar panel produces
electricity enough to run street light, irrigation water pump,
traffic signals etc.
Application of Solar Cell

1. Lighting of street light and running of irrigation water
pumps.
ww
2. In solar cars.
w.E
3. Solar cells are used in calculators, electronic watches,
radios etc.
a syE
4. In TV transmission and radio wireless tranmission.
5. They are used in artificial satellite, space craft for

electricity generation. ngi
Advantages of Solar cells nee
rin
1. Solar cells are used in remote and isolated areas, forests
and hilly regions.
g.n
2. Maintenance cost is low.
3. Solar cells are pollution free.

et
4. They have long life.
Limitations
1. Solar cells installation cost is high.
2. Sunny day is required for solar cells to produce electricity.

On cloudy days it fails.
3. If the angle of the solar cell is slightly changed the

efficiency drops to even 50%.

244 ENERGY SOURCES
5.5 Wind Energy
The high speed wind possess lot of kinetic energy due to their
motion. Wind energy is a source of renewable power which
comes from air current flowing across the earth’s surface.
Wind turbines harvest this kinetic energy and convert it into
usable power which can provide electricity for home, farm,
school or business applications on small residential or large
utility scales. The blades of wind mill keep on rotating
continuously due to force of the wind. The rotational motion of
blades drives machines like water pump, flour mill and electric
ww
generators. Thus the force of wind is harnessed to produce
useful forms of energy. The energy recovered from the forces of
w.E
wind is called wind energy.
a syE
Generation of electricity from wind mill
Wind energy is used to generate electricity with the help of
ngi
wind mills. The crank of the wind mill is connected to a
nee
dynamo. When the blades of wind mill rotate, they turn the
coil of the dynamo and produce electricity. A large number of
rin
wind mills are installed in a cluster called wind farms to
produce reasonable electricity for applications.
g.n
Propellor blade
et
Wind Gear box
direction & Generator
Wind mill
Figure 5.7 Wind mill

The minimum speed of wind to harness energy is 15 km/h. A
large area of open space with good wind speed is required to
install wind farm. These may be ideally installed in coastal
region, hilly areas etc. The wind farm in Tamil Nadu is situated
near Kanyakumari in Arulvaimozhi village, which harness a
energy of 380 MW electricity.
Advantages of wind energy
1. Green Power: The electricity produced from wind power

is said to be "clean" because its production produces no
pollution or green house gases.
ww
2. Sustainable: Wind is a renewable energy resource, it is
w.E
inexhaustible and requires no "fuel".
a syE
3. Investment: This infinite energy supply is secured and
also a stable investment in our energy economy.
ngi
4. Affordable: Wind power is a cost-competitive source of
nee
electricity, largely due to technological advancements.
Disadvantages rin
1. Installation cost of wind mill is very high. g.n
2. Wind turbines interfere with electromagnetic signals. et
3. It creates negative visual impacts on landscape.
4. Wind farms located on the migratory routes of birds create

problems.
Limitations
1. It requires large landscape area.
2. The speed of the wind is not uniform throughout.

246 ENERGY SOURCES
5.6 Fuel Cells
Definition
Fuel cell is a voltaic cell. It converts chemical energy of the fuels
directly into electricity without combustion. The reactants flow
into the cell, and the reaction products flow out of it, while the
electrolyte remains within it. Fuel cells can operate virtually
continuously as long as the fuels are fed.
Examples: Hydrogen - oxygen fuel cell.
ww
5.6.1 Hydrogen - oxygen fuel cell Or Alkaline fuel cell
(AFC)
w.E
Anode
Cathode
a syE
H2 gas in porous electrode
O2 gas in porous electrode
Electrolyte ngi
25% KOH
OCV (open nee

circuit potential)
1.2 V
rin
CCV (closed g.n
circuit potential)
Cell representation
1.0 V
H2 / H2 O // KOH // O2 / OH−
et
Hydrogen - oxygen fuel cell is the simplest and most successful
fuel cell. The fuel hydrogen and the oxidiser-oxygen with the
electrolyte. Other fuels include hydrocarbons and alcohols.
Other oxidants include chlorine and chlorine dioxide.
Description/ Construction
The cell has two porous electrodes, anode and cathode. The
electrodes are made of compressed carbon containing a small

amount of catalyst (Pt, Pd, Ag) impregnated in it. Between the
two electrodes an electrolytic solution, 25% KOH is filled.
V
Anode - + Cathode
H₂ O₂
KOH
ww H₂ O O₂
w.E
a syE
Porous carbon electrode
Porous carbon electrodes
Figure 5.8
ngi
Hydrogen Oxygen fuel cell
Cell reactions nee
At anode: rin
2H 2(g) + 4OH −(aq) −→ 4H 2 O(l) + 4e−
O2(g) + 2H 2 O(l) + 4e− −→ 4OH −

g.n
At cathode:
Net reaction: 2H 2(g) + O2(g) −→ 2H 2 O(l)

et
Working
Hydrogen is passed through the anode compartment, where it is
oxidised. Oxygen is passed through the cathode compartment,
where it is reduced.
Advantages of Fuel Cells

1. They are highly efficient in energy conversion and instant
in operation.

248 ENERGY SOURCES
2. They are pollution free and noise free.
3. Modular and hence parts are exchangeable.
4. Low maintenance cost.
5. Fuel cell holds promises in the energy scenario, replacing

to some extend fossil fuel.
6. Continuous discharge takes place.
Disadvantages
1. High initial cost.

ww2. Large weight and volume of H 2 and O2 gas storage.
w.E
3. Porous electrodes are affected by CO2 hence gases should
a
be free from CO2.
syE
4. H2 should be pure.
ngi
Applications nee
rin
1. H 2 - O2 fuel cells are used as energy source in space
vehicles, submarines.
g.n
et
2. In H 2 - O2 fuel cell, the product water is a valuable source
of fresh water for astronauts.
5.7 Cells
A cell is a device in which a redox reaction is utilized to get
electrical energy. It consists of two electrodes and an
electrolyte. The electrode where oxidation reaction occurs is
called anode, while the electrode where reduction reaction
occurs, is called cathode. Cells are classified based on the
electrical energy utilization or production into two kinds:

1. Electrochemical cell: Here a spontaneous chemical
reaction takes place and produces electrical energy.
2. Electrolytic cell: Here a electrical energy is supplied for

a chemical reaction to take place.
Further electrochemical cell is classified on the basis of their

nature of chemical reaction taking place at electrodes as
primary or irreversible cell or secondary or reversible cells.
1. Primary Cell (or) Irreversible cell In this cell, the
ww
electrode reactions cannot be reversed by passing an external
electrical energy. The reactions occur only once. It is a use and
w.E
throw type of battery. Examples: Lachlanche cell (Dry cell),
Alkaline battery.
a syE
2. Secondary Cells (or) Reversible Cells
ngi
In these cells, the electrode reactions are reversed by passing
nee
an external electrical energy. They are recharged by passing
electric current and used again and again. They are also called
Storage cells (or) Accumulators.
rin
Examples: Lead acid storage cell, Nickel-cadmium cell.
g.n
Battery is the arrangement of number of cells in series or
parallel. Cells connected in series leads to increase in
et
potential. Cells connected in parallel, leads to addition of
energy density.
5.7.1 Alkaline Battery
Anode Zn
Cathode MnO2 / Carbon rod

250 ENERGY SOURCES
Electrolyte 40% KOH
OCV (open
1.6 V
circuit voltage)
CCV (closed
1.5 V
circuit voltage)
Cell
Zn/Zn(OH)2 // KOH(aq) // MnO2 /Mn2 O3
representation
ww
Construction and Working
w.E
Alkaline battery is an improved form of the dry cell, in which
a
the electrolyte NH 4Cl is replaced by KOH. Alkaline battery
syE
consists of a zinc cylinder filled with an electrolyte consist of
powdered KOH and MnO2 (active cathodic material) in the
ngi
form of paste using starch and water. A carbon rod (cathode) is
nee
immersed in the electrolyte in the centre of the cell for
electrical contact for the flow of electrons. The outer cylindrical
zinc body acts as anode. rin
Cell Reactions g.n
At anode:
Zn −→ Zn2+ + 2e−
et
Zn + 2OH − (aq) −→ Zn(OH)2
At cathode :
2MnO2(s) + H 2 O(l) + 2e− −→ Mn2 O3(s) + 2OH −
Net Reaction:
Zn(s) + 2MnO2(s) + H2 O(l) −→ Zn(OH)2(s) + Mn2 O3(s)

Metal cap "+ ve"
Insulating washer
Zinc cup
Carbon rod
Mixture of MnO ₂
graphite, KOH
ww Metal cap "- ve"
w.E
Alkaline Zn/MnO ₂ cell
Figure 5.9 Alkaline Zn/MnO2 dry cell
a syE
In cathode reaction, Mn is reduced from +4 oxidation state to
+3 oxidation state. Manganese dioxide is reduced to manganic
oxide. ngi
Advantages of alkaline cell
nee
rin
The main advantages of alkaline cell over dry cell are
g.n
1. There is no leakage of cell, since Zn does not dissolve
readily in a basic medium. et
2. The life of alkaline battery is longer than the dry battery,
because there is no corrosion of Zn.
3. Alkaline battery maintains its voltage, as the current is

drawn from it.
Uses
It is used in calculators, watches, torch light, transistors, toys
etc.

252 ENERGY SOURCES
5.7.2 Lead Storage battery or Lead Accumulator or
Acid Storage battery
A lead acid storage cell is a secondary cell. It can operate both
as a voltaic cell and an electrolytic cell. When it acts as a voltaic
cell, it supplies electrical energy. When it is recharged, the cell
operates as an electrolytic cell.
Anode Pb
Cathode PbO2 / Pb
wwElectrolyte H2 SO4 (1.2 g/cc)

OCV
w.E
(open
circuit voltage)
2.1 V
CCV a
(closed
circuit voltage) syE
2.0 V
Cell ngi
representation
nee
Pb/PbSO4 // H2 SO4(aq) // PbO2 / PbSO4
Cycle life 250-300

rin
Construction and Working
g.n
12 V
et
Connected in series
+ - + - + - + - + - + -
Anode
Cathode
Electrolyte
Lead acid storage batteries

Figure 5.10 Lead acid storage battery

A lead storage battery consists of six voltaic cells connected in
series to get a 12V battery. The anode is made of lead. The
cathode is made of lead dioxide PbO2 packed on a grid of lead.
Various plates are separated from the adjacent ones by
insulators like rubber or glass fibre. The entire combination is
then immersed in dilute H 2 S O4 (38% by mass) having a
density of 1.2 g/cc.
Electrode reaction while discharging
When the lead - acid storage battery operates, the following
reaction occurs during discharge.
ww
At anode: (+ve plate)
w.E Pb(s) ⇋ Pb2+

(aq) + 2e
−
a Pb2+
syE 2−
(aq) + S O4(aq) ⇋ PbS O4(s)
Pb(s) + S O2−
ngi
4 ⇋ PbS O4(s) + 2e
−
At cathode: (-ve plate) nee

+ ⇋ Pb2+ + 2H O
PbO2(s) + 2e− + 4H(aq) rin
Pb2+ 2−
(aq)
(aq) + S O4(aq) ⇋ PbS O4(s)

2 (l)
g.n
+ + S O2− ⇋ PbS O
PbO2(s) + 2e− + 4H(aq) 4(aq) 4(s) + 2H2 O(l)
et
Overall cell reaction during discharge
Pb(s) + PbO2(s) + 2H2 S O4(aq) ⇋ 2PbS O4(s) + 2H2 O(l)
From the cell reaction it is clear that, PbS O4 is precipitated at

both the electrodes and H 2 S O4 is used up. As a result, the
concentration of H 2 S O4 decreases. Hence the specific gravity of
H 2 S O4 falls below 1.2 g/cc. So the battery needs recharging.

254 ENERGY SOURCES
Recharging of the Battery
The cell is charged by passing electric current in the opposite
direction. The electrode reaction gets reversed and density of
acid increases to 1.2g/cc.
At anode (-ve plate):
+
2PbS O4(s) + 2H2 O ⇋ PbO2(s) + 4H(aq) + S O2−
4(aq) + 2e
−
At cathode (+ve plate):
PbS O4(s) + 2e − ⇋ Pb(s) + S O42−

ww
w.E
Overall cell reaction during Charge:
a
2PbS O4(s) + 2H2 O(l) ⇋ Pb(s) + PbO2(s) + 2H2 S O4(aq)
syE
Disadvantages of lead-acid batteries
ngi
nee
1. Recycling of this battery produces environmental hazards.
rin
2. Mechanical strain and normal bumping reduces battery
capacity.
g.n
3. It is too heavy for handling.
4. It also leaks at times.

et
Application
1. The cell is used for automobile starting, lighting and

ignition batteries.
2. It is used in large backup power supplies for telephone

and computer centers, grid energy and off-grid household
electric power systems.

3. They are used in back-up power supplies for computer
systems.
4. They are used as fuel in electric scooters, electric wheel

chairs, electrified bicycles, marine applications, battery
electric vehicles or micro hybrid vehicles, and
motorcycles.
Applications
1. It is used in calculators, electronic flash units, transistors

and cordless appliances.
ww
2. It is used in toys like remote-controlled electric model
w.E
airplanes, boats, and cars.
a syE
3. Larger flooded cells are used for aircraft starting
batteries, electric vehicles, and standby power.
ngi
5.7.3 Lithium Battery
nee
rin
Lithium battery is a solid state battery. Instead of liquid or a
paste electrolyte, solid electrolyte is used which avoids leakage
g.n
in batteries. It is also called cell of future due to the following
advantages.
1. Its cell voltage is very high, 3.7 V.

et
2. It has very high energy density. 7g Li metal produces 1
Faraday of current.
3. It is light in weight.
4. It has longer shelf life compare to lead acid and nicad.
5. All the constituents of the battery are solids. There is no

risk of leakage from the battery.

256 ENERGY SOURCES
6. It can be made in a variety of sizes and shapes.
There are two types of lithium-based batteries available.
1. Lithium batteries: A pure lithium metallic element is

used as anode and a reductive material as cathode
functions like all conventional batteries.
2. Lithium-ion batteries: Lithium compounds are used as

anode. Lithium ions move from the negative electrode to
the positive electrode during discharge and back when
charging. Because of this reason, the lithium ion
ww batteries are called Rocking chair, Swing cells.
w.E
5.7.3.1 Li-ion (LIB) Battery
a syEC ( intercalated with )Li+
Anode
ngi
Cathode
Electrolyte
LiCoO2
nee
LiPF6 in alkyl carbonate
rin
OCV 3.7V
g.n
CCV
Cell
3.5 V
Li xC6 / C //LiPF6 //Li(1−x)CoO2 /LiCoO2

et
representation
Cycle life 500-1000
Construction
Lithium ion secondary battery depends on an "intercalation"
mechanism. This involves the insertion of lithium ions into the
crystalline lattice of the host electrode without changing its

crystal structure. Lithium ion batteries consist of a Lithium
Metal Oxide positive electrode (cathode) with thin aluminum
foil as current collector, graphite negative electrode (anode)
and electrolyte of a lithium salt in alkyl carbonate solution.
The cathode is made of transition metals oxides or phosphates
as active material such as
• Lithium Cobalt Oxide - LiCoO2
• Lithium Iron Phosphate - LiFePO4
ww
• Lithium Manganese Oxide - LiMnO2
w.E
• Lithium Nickel Manganese Cobalt Oxide - LiCo1/3
Mn1/3 Ni1/3 O2
a syE
Li-ion cell has a four-layer structure. Cathode and anode are
ngi
separated by a membrane made of polypropylene or
nee
polyethylene filled with electrolyte which contains lithium
salts (i.e. LiPF6 ) in ethylene or propylene carbonate at
rin
different ratio. The separator prevents the electrical contact
between the electrodes and at the same time, it allows the
g.n
diffusion of Li-ions from cathode to anode during the charging
and the reverse discharging process.
Working
et
During discharge Li ions are dissociated from the anode
(negative plate) and migrate across the electrolyte and are
inserted into the crystal structure of the host compound of
cathode. For example in Lithium Cobalt Oxide (LiCoO2 ) the
discharge mechanism is as follows:
At anode (negative plate)
Li xC ⇋ xC + xLi+ + xe−

258 ENERGY SOURCES
Figure 5.11 Li-ion cell
At Cathode (positive plate)

ww Li(1−x)CoO2 + xLi+ + xe− ⇋ LiCoO2
w.E
Overall reaction
a syE Discharging
Li xC + Li(1−x)CoO2 −
−−
↽ −−
−−
−−
−−
−−
−−−⇀
−−−− LiCoO2 + C
ngi
Charging
Advantages
nee
1. They have high energy density than other rechargeable
batteries. rin
2. Available in various shapes and sizes and lighter in g.n
weight. et
3. There is no requirement for priming like in nickel
batteries.
4. Do not suffer from memory effect.
5. They possess low self discharge rate (5-10% per month).
6. They are lighter than other battery types.
7. They produce high voltage out about 4 V as compared with

other batteries.

8. No liquid electrolyte means they are immune from
leaking.
9. Low maintenance cost.
Disadvantage
1. They are expensive.
2. The capacity diminishes with charging and ageing.
3. Internal resistance increases with charging and ageing.
ww
4. They are not available in standard cell types.
Applications
w.E
1. The Li-ion batteries are used in cameras, calculators.
a syE
2. They are used in cardiac pacemakers and other
implantable device.
ngi
3. They are used in telecommunication
instruments, portable radios and TVs. nee equipment,
rin
4. They are used to operate laptop computers and mobile
phones and aerospace application g.n
5.8 Supercapasitors (SC’s)
et
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.
A conventional capacitor consist of two conducting electrodes

separated by an insulating dielectric material. When a voltage
is applied to a capacitor, opposite charges accumulate on the

260 ENERGY SOURCES
surfaces of each electrode. The charges are kept separate by
the dielectric, thus producing an electric field that allows the
capacitor to store energy. There are three types of capacitors
and the most basic is the electrostatic capacitor, which has
very low capacitance(pF).
The second type is electrolytic capacitor provides higher

capacitance(µF) than the electrostatic capacitor.
The third type is the supercapacitor, capacitance (F) is
ww
thousands of times higher than the electrolytic capacitor.
w.E
Super capacitor is a high capacity capacitor with capacitance
value much higher than other capacitor. They store 10 to 100
a syE
times more energy per unit volume and deliver charge much
faster than batteries.
ngi
nee
Definition: It is defined as a energy storage device that stores
energy electrostatically by polarising an electrolytic solution.
rin
SC’s store electrical energy, but not chemical energy.
g.n
Supercapacitors, utilizes higher surface area electrodes and
thinner dielectrics to achieve greater capacitances. Unlike
capacitors SC’s contain moving ions. Two very high surface
et
area porous electrodes are soaked in electrolyte. The charge is
stored in electrochemical double layers. Supercapacitors are
also called as electrochemical capacitor (EC Capacitor),
Electric double-layer capacitor (EDLC), ultracapacitor, etc.
Supercapacitor posses a potential of 2.5-2.7V.
Description and working:

Super capacitor consists of an anode, cathode and a liquid

electrolyte assembly with a plastic or paper porous separator.
The electrolytes generally used are KOH or H2 S O4 . The
electrode is made up of thin aluminium foil pasted with
activated conductive carbon. Like conventional capacitors,
they store charge electrostatically or non-Faradaically and
there is no transfer of charge between electrode and
electrolyte. Thus there is no chemical change associated with
non-Faradaic processes. For this reason, charge storage in
EDLCs is highly reversible, and has high cycle life(106 ) .
When the voltage is applied to positive plate attracts
negative ions and negative plate attracts positive ions from
ww
electrolyte. Therefore, there is a formation of a layer of ions on
w.E
the both side of plate. This is called "Double layer" formation.
For this reason, the ultracapacitor can also be called Double
carbon. a
layer capacitor. The ions are then stored near the surface of
syE
Dielectric constant of medium X area of the plate
Capacitance =
ngi
Distance between the plates
nee
rin
g.n
et
Figure 5.12 Schematic diagram of Supercapacitor
Important characteristics of a Supercapacitor:
• It can be fully charged and discharged in seconds.

262 ENERGY SOURCES
• It can be charged and discharged even up to a million
times.
• It has very low energy densities when compared to

batteries.
• It has very high self-discharge than conventional

batteries.
• It has rough electrode surfaces and a liquid dielectric.
Limitations
ww • Low energy densities than batteries.
w.E
• High self-discharge.
a syE
• Linear discharge voltage prevents using the full energy
spectrum.
• High cost per watt. ngi

Applications: nee
Super capacitors are used in rin
• To start backup generators. g.n
• Starting power in start-stop action in any system. et
• They used in industrial lasers, medical equipment.
• They are used in wireless communication system for

uninterrupted service.
• They are used in electric vehicle and for load leveling to

extend the life of batteries.
• There are used in security systems, computers, scanners,

smoke detectors, microwaves and coffee makers etc.

ww
w.E
a syE
ngi
nee
rin
g.n
et


CY8151 KSN Notes - by WWW - Easyengineering.net 1

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

CY8151 KSN Notes - by WWW - Easyengineering.net 1

Uploaded by

Copyright:

Available Formats

Download From : www.EasyEngineering.

**Note: Other Websites/Blogs Owners Please do not Copy (or) Republish

Unit Number Page Number

Download From : www.EasyEngineering.net

ENGINEERING CHEMISTRY (CY8151)

WATER AND ITS TREATMENT

TYPES OF IMPURITIES PRESENT IN WATER

The impurities present in water may be categorized into following categories

Download From : www.EasyEngineering.net

a. Dissolved gases : O2, CO2, H2S etc.

How to detect hard water?

Hardness of water can be detected in two ways.

Download From : www.EasyEngineering.net

1. Temporary (or) Carbonate hardness: This is caused due to the presence of

ww Removal of temporary hardness:

b. By adding lime to the water

Mg(HCO3)2 + Ca(OH)2 asy Mg(OH)2 + CaCO3 + H2O + CO2

a. Lime soda process

CaCO3 equivalent hardness

Hardness is usually expressed in terms of CaCO3 equivalent. Because

1. CaCO3 is highly insoluble

Download From : www.EasyEngineering.net

Weight of hardness producing substance

The units used to represent hardness are as follows

(i) Parts per million (ppm)

Milligrams per litre (mg/l)

En= 1 part of CaCO3 equivalent hardness in 106 parts of water

Thus 1 mg/l = 1 ppm gin

(iii) Clarke’s degree : (Cl)

(iv) Degree French:(Fr) g.n

1Fr = 1 part of CaCO3 equivalent hardness in105 parts of water.

(v) Milliequivalent per litre (meq/l)

Thus 1 meq/L = 1 meq of CaCO3 per L of water.

= 10-3 x 50 g of CaCO3 equivalent per L

RELATION SHIP BETWEEN UNITS OF HARDNESS

Download From : www.EasyEngineering.net

ppm mg/l Cl Fr meq/L

Problem on Hardness of water

NaCl does not contribute to hardness

Temporary hardness = Mg(HCO3)2 + Ca(HCO3)2

Permanent Hardness = CaSO4 + MgCl2 + CaCl2

Download From : www.EasyEngineering.net

= 95.5 + 85.3 + 68.5

∴ Total hardness = Temporary hardness + Permanent hardness

ESTIMATION OF HARDNESS OF WATER

When the sample water is buffered to a pH of 9 to 10 and by the addition of few

Download From : www.EasyEngineering.net

Let the volume of EDTA consumed be V2 ml

Download From : www.EasyEngineering.net

Let the volume of EDTA consumed be V3 ml

1 ml of standard hard water = 1 mg of CaCO3

(iv) Estimation of Temporary hardness:

Problems on estimation of hardness of water

Download From : www.EasyEngineering.net

1. 100 ml of a water sample requires 20 ml of EDTA solution for titration. 1 ml of

ww 2. 100 ml of water sample requires 18 ml of EDTA solution for titration. 22 ml of the

∴ 1 ml of std. hard water En

Download From : www.EasyEngineering.net

= 100 x 0.28 mg of CaCO3

ww ∴ 1000 ml of boiled hard water =

w.E (iii) Temporary hardness

Total hardness = 200 mg/l or ppm

(ii) Non-carbonate hardness (PH)