CHAPTER – 1

FUELS AND COMBUSTION

Introduction

Fuel is a combustible substance, containing carbon as a

main constituent, which on proper burning gives large amount
of heat, which can be used economically for domestic and
industrial purpose.
Example :
Wood, charcoal, coal, kerosene, petrol, diesel, producer gas, oil
gas etc.

During the process of combustion, carbon, hydrogen, etc.,

combine with oxygen with a liberation of heat.
The combustion reaction can be explained as
C + O2 CO2 + 94 kcals
2H2 + O2 2H2O + 68.5 kcals

The calorific value of a fuel depends mainly on the amount of

Carbon and Hydrogen.

Requirements of a Good Fuel

A good fuel should have the following characteristics:

o High calorific value.
o Moderate ignition temperature.
 o Low contents of non-combustible matters.
o Low moisture content.
o Free from objectionable and harmful gases like CO, SOx,
H2S.
o Moderate velocity of combustion.
o Combustion should be controllable.
o Easy to transport and readily available at low cost.

Classification of Fuels
Fuels are classified into
(i) Primary or Natural fuels - These are found in nature.
(ii) Secondary or Artificial fuels - These are derived from
primary fuels.
Primary and secondary fuels may also be divided into 3
classes namely solid, liquid and gaseous fuels.

Fuels

Primary or Secondary or
Natural Fuels Artificial Fuels

Solid Fuels Liquid Fuels Gaseous Fuels

Ex.: Wood Ex.: Oil. Ex.: Natural gas

Solid Fuels Liquid Fuels Gaseous Fuels

Ex.: Charcoal Ex.: Petrol Ex.: LPG
Fossil fuels
Fossil fuels are those, which have been derived from
fossil remains of plant and animal life.
They are found in the earth’s crust.
All conventional fossil fuels whether solid, liquid or
gaseous (coal, petroleum or Natural gas) contain basically carbon
and / or hydrogen. The fuels on combustion in presence of oxygen
in the air release heat energy.
This heat energy can be utilized for domestic and industrial
purposes.
Advantages of Solid fuels
1. Handling and transportation of solid fuels are easy.
2. Solid fuels are cheap and easily available.
3. They have a moderate ignition temperature
4. This type of fuel can be stored conveniently without any
risk.
Disadvantage of solid fuels:
1. During burning, solid fuels produce a large amount of
ash and disposal of ash is a big problem.
2. The calorific value of solid fuel is comparatively low.
3. Since a lot of air is required for complete combustion, its
thermal efficiency is not so high.
4. A large space is required for storage.
5. Combustion is a slow process and it cannot be easily
controlled.

Advantages of Liquid fuels

1. Liquid fuels do not yield any ash after burning.
2. They require comparatively less storage space.
 3. Calorific value of liquid fuel is higher than that of solid
fuels.
4. Their combustion is uniform and easily controllable.
Disadvantages of liquid fuels:
1. Liquid fuels are comparatively costlier than the solid
fuels.
2. They give unpleasant odour during incomplete
combustion.
3. Some amount of liquid fuels will escape due to
evaporation during storage.
4. Special type of burners are for effective combustion.

Advantages of gaseous fuels:

1. Gaseous fuels can be easily transported through the
pipes.
2. They do not produce any ash or smoke during burning.
3. They have high calorific value than the solid fuels.
4. They have high thermal efficiency.
Disadvantages of gaseous fuels
1. They are highly inflammable and hence the chances for
fire hazards are high.
2. Since gases occupy a large volume, they require large
storage tanks.

Combustion
Combustion is an exothermic chemical reaction, which is
accompanied by development of heat and light at a rapid rate,
temperature rises considerably. For example, combustion of
carbon in oxygen:

C(s) +O2(s) CO2 (g) + 97 kcal

For proper combustion, the substance 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.
Factors affecting the rate of combustion
The rate of combustion depends on the following factors:
1. The concentration of the fuel and air.
2. The nature of the combustable substance
3. The temperature
4. With increase in pressure or surface area of the fuel the
rate of combustion can be increased.
5. It increases with in increase in pressure of air.
6. It Increases with preheating of fuel and air.

Calorific Value
It is the most important characteristic property of any fuel.
Calorific value may be defined as “the amount of heat liberated
by the complete combustion of a unit mass of a fuel”.
Unit of heat
i) Calorie: it is the amount of heat required to raise the temperature
of 1 gram of water through one degree centigrade.
i) Kilo Calorie: it is the amount of heat required to raise the
temperature of 1 kilogram of water through one degree centigrade.
iii) British Thermal Unit (BTU): it is the amount of heat required
to raise the temperature of 1 pond of water to one degree
Fahrenheit. 1 B.T.U. = 252 cal = 0.252 kcal 1 kcal = 3.968 B.T.U.
iv) Centigrade Heat Unit (CHU): it is define as the amount of heat
required to raise the temperature of 1 pond of water to one degree
centigrade. 1 kcal = 3.968 B.T.U. = 2.2 C.H.U.
Calorific value Calorific value of fuel can be define as the amount
of heat evolved when one unit mass or volume of the fuel
undergoes completely combustion in presence of oxygen.
i) High or gross calorific value (HCV or GCV): it is defined as
amount of heat evolve when one unit mass or volume of the fuel is
completely burnt and combustible products are cooled to room
temperature (25oC or 77oF).
ii) Low or net calorific value (LCV or NCV): it is defined as amount
of heat evolve when one unit mass or volume of the fuel is
completely burnt and combustible products are permitted to escape.
Therefore net calorific value is lower than gross calorific value.
LCV = HCV – latent heat of water vapour
LCV = HCV – mass of hydrogen × 9 × latent heat of steam (587
kcal/kg)
One part by mass of hydrogen produced nine parts by mass of water
molecule.
Therefore, LCV = HCV – H/100 × 𝟗 × 587 kcal/kg H = percentage
of hydrogen in fuel.

Dulong’s formula (Theoretical calculation)

Dulong’s formula for the theoretical calculation of calorific
value is
1 O
GCV (or) HCV = (8080 C + 34500 [H ] + 2240 S ) kcal/kg
100 8

where, C, H, O & S represent the % of the corresponding

elements in the fuel.

It is based on the assumption that the calorific values of C,

H & S are found to be 8080, 34500 and 2240 kcal, when 1 kg of
the fuel is burnt completely. However, all the oxygen in the fuel is
assumed to be present in combination with hydrogen in the ratio H
: O as 1 : 8 by weight. So the surplus hydrogen available
O
for combustion is H .
8
ii) Net (or) Lower Calorific Value (NCV or LCV)
The net heat produced when a unit quantity of fuel is
completely burnt and the products of combustion are allowed to
escape.
NCV = GCV – Latent heat of condensation of steam produced 1
part by weight of H2 produces 9 parts by weight of H2O as follows.
The latent heat of steam is 587 cal/gm.
 H2 + ½ O2 H2O
2gms 16gms 18gms
1 8 9
Thus,

9
NCV = GCV – H ×587 kcal/kg
100

NCV = GCV – 0.09H ×587 kcal/kg

where , H = % of H2 in the fuel.

Determination of Calorific value using

Bomb Calorimeter

The calorific value of a solid or liquid fuel can be

determined by using bomb calorimeter ( Fig 4.11 ).
Fig 4.11 Bomb Calorimeter
ii) Acid correction
Solid Fuels
1.Coal and its varieties (or) Ranking of Coal
Coal is an important primary solid fuel that has been
formed as a result of alteration of vegetable matter under some
favourable conditions.

The process of conversion of lignite to anthracite is called

coalification (or) metamorphism of coal.
Coal is classified on the basis of its rank. The rank of coal
denotes its degree of maturity. Vegetable matter, under the action
of pressure, heat and anaerobic conditions, gets converted into
different stages of coal namely,

Wood → Peat → lignite → sub-bituminous → bituminous

coal coal
↓
anthracite

With the progress of coal forming reaction, moisture content and

oxygen content reduces and % of carbon increases. Also calorific
value increases from peat to bituminous. (Table 1.1).

Classification of coal
a) Peat
1. Peat is the first stage in the formation of coal.
2. Its calorific value is about 4000-5400 k cal/kg.
3. It is an uneconomical fuel due to its high proportion of
(80 -90%) moisture and lower calorific value.
4. It is a brown fibrous mass.

b) Lignite
1. Lignite is an intermediate stage in the process of coal
formation.
2. Its calorific value is about 6500-7100 k cal/kg
3. Due to the presence of high volatile content, it burns with
long smoky flame.
 Table
Table 4.1
4.1 Classification of solid fuels & its calorific values

Calorific Compo
Fuel Nature value sition Uses
k.cals/kg %
Peat Highly 4000 - C = 57 Domestic
fibrous light 5400 H = 06 fuel, power
brown in O = 35 generation
colour
Lignite Fibrous, 6500 - C = 67 Manufacture
brown 7100 H = 05 of producer
coloured coal O = 26 gas & steam
Sub- Black 7000 - C = 77 Manufacture
bituminous coloured, 7500 H = 05 of gaseous
coal homogenious O = 16 fuels
smooth mass,
Bituminous Black, brittle, 8000 - C = 83 Power
coal burns with 8500 H = 05 generation,
yellow O = 10 coke making,
smoky flame domestic fuel
Anthracite Hard & most 8500 - C = 93 Boiler
matured coal, 8700 H = 03 heating,
burns without O = 03 metallurgical
smoke furnace

Here peat is the most immatured coal, hence it is lowest in

rank where as anthracite is the most matured coal, and hence it is
highest in rank
c) Bituminous coal
Bituminous coal is further sub-classified on the basis of its
carbon content into three types as: i) Sub- bituminous coal, ii)
Bituminous coal and iii) semi-bituminous coal.

d) Anthracite
1. Anthracite is the superior grade of coal.
2. Its volatile, moisture and ash contents are very less.
3. Its calorific value is about 8650 k cal/kg.
 Analysis of Coal
In order to assess the quality of coal, the following two
types of analysis are made.

I. Proximate Analysis
o It means finding out weight percentage of moisture, volatile
matter, fixed carbon and ash in coal

o This analysis gives the approximate composition of the main

constituents of coal.

o It is useful in deciding its utilization for a particular industrial

use.
Determination of moisture content in coal
About 1 gm of powdered, air dried coal sample is heated in
silica crucible at 100 to 105 °C for one hour. Percentage of
moisture can be calculated from the loss in weight of the coal
sample as
Loss in weight of coal
∴ % of moisture in coal = ×100
Weight of coalinitially taken

Determination of Volatile Matter (V.M.) in coal

After the analysis of moisture content the crucible with
residual coal sample is covered with a lid, and it is heated at 950
± 20 °C for 7.0 minutes in a muffle furnace. Percentage of volatile
matter can be calculated from the loss in weight of the coal sample
as

∴ % of volatile matter in coal

Loss in weight of moisture free coal
= ×100
Weight of coalinitially taken
Determination of ash in coal
After the analysis of volatile matter the crucible with
residual coal sample is heated without lid at 700 ± 50 °C for 30
minutes in a muffle furnace.

Percentage of ash content can be calculated from the loss

in weight of the coal sample as

Weight of ash formed

∴ % of ash in coal = ×100
Weight of coal taken

Determination of fixed carbon

It is determined by subtracting the sum of total moisture,
volatile and ash contents from 100.

% of fixed carbon = 100 - % of [moisture + V.M + ash]

Significance (or) Importance of Proximate Analysis

Moisture
High moisture content in coal is undesirable because it,
i) Reduces Calorific Value of coal
ii) Increases the consumption of coal for heating purpose
iii) Lengthens the time of heating.
Hence, lesser the moisture content, better is the quality of coal.

Volatile Matter
During burning of coal, certain gases like CO, CO2, CH4,
H2, N2, O2, hydrocarbons etc. that come out are called volatile
matter of the coal.
The coal with higher volatile content,
o Ignites easily (i.e : it has lower ignition temperature)
o Burns with long yellow smoky flame
o Has lower Calorific Value
o Will give more quantity of coal gas when it is heated in
absence of air.

Ash
o Ash is the combustion product of mineral matters present in
the coal. It consists mainly of SiO2, Al2O3 and Fe2O3 with
varying amounts of other oxides such as Na2O, CaO, MgO
etc.
o Ash containing oxides of Na, Ca and Mg melt early. (Low
melting ash). During coke manufacture, the low melting ash
forms a fused lumpy - expanded mass which block the
interspaces of the ‘grate’ and thereby obstructing the supply
of air leading to irregular burning of coal and loss of fuel.
o High ash content in coal is undesirable because it (a)
increases transporting, handling, storage costs, (b) is harder
and stronger, (c) has lower Caloific Value.

Fixed Carbon
It is the pure carbon present in coal. Higher the fixed
carbon content of the coal, higher will be its Caorific Value.

II. Ultimate Analysis

o It means finding out the weight percentage of carbon,
hydrogen, nitrogen, oxygen and sulphur of the pure coal
free from moisture and inorganic constituents.
o This analysis gives the elementary constituents of coal.
o It is useful to the designer of coal burning equipments and
auxiliaries.
Determination of carbon and hydrogen in coal
A known amount of coal is burnt in presence of oxygen
there by converting carbon and hydrogen of coal into CO2 (C
+ O2 → CO2) and H2O (H2 + ½ O2 → H2O) respectively. The
products of combustion (CO2 and H2O) are made to pass over
weighed tubes of anhydrous CaCl2 and KOH, which absorb H2O
and CO2 respectively.
The increase in the weight of CaCl2 tube represents the
weight of water formed while increase in the weight of KOH tube
represents the weight of CO2 formed. % of carbon and hydrogen in
coal can be calculated as follows.

Let X - the weight of coal sample taken

Y - the increase in the weight of KOH tube
Z - the increase in the weight of CaCl2 tube

a) Carbon
C + O2 → CO2
12 32 44

44 gms of CO2 contain 12 gms of carbon.

12
1 gm of CO2 contains gms of carbon
44
12
Y gm of CO2 contains = × Y gms of carbon
44

12 Y
% of C in coal = × × 100
44 X
b) Hydrogen

H2 + ½ O2 → H2O
2 16 18

18 gms of water contains 2 gms of hydrogen.

1 gm of water contains 2 / 18 gms of hydrogen.
2
∴ Z gms of water contains = × Z gms of Hydrogen.
18

2 Z
% of hydrogen in coal = × × 100
18 X

Determination of Nitrogen in coal

Nitrogen estimation is done by Kjeldahl’s method. A
known amount of powdered coal is heated with con. H2SO4 and
K2SO4in a long necked flask (called Kjeldahl’s flask), there by
converting nitrogen of coal to ammonium sulphate.
When the clear solution is obtained (i.e. the whole nitrogen
is converted into ammonium sulphate), it is heated with 50%
NaOH solution.
(NH4)2 SO4 + 2NaOH Na2SO4 + 2NH3
The ammonia thus formed is distilled over and is absorbed
in a known quantity of standard 0.1N HCl solution. The volume of
unused 0.1 N HCl is then determined by titrating against standard
NaOH solution.

Thus, the amount of acid neutralized by liberated

ammonia from coal is determined.
Let,
Volume of 0.1N HCl = A ml
Volume of unused HCl = B ml
Acid neutralised by ammonia = (A - B ) ml
We know that 1000 ml of 1 N HCl = 1 mole of HCl
= 1 mole of NH3
= 14 gms of N2
14 ×( A B)×0.1
(A - B) ml of 0.1N HCl = gms of N
2
1000 ×1N
 B) x 0.1
gms of N 2
14 x ( A x 1N
X gms of coal sample contains =
1000

% of Nitrogen
14 x Volume of Acid consumed x Normality x 100%
=
1000 x Weight of coalsample(X)
1.4 x Volume of Acid consumed x Normality
= %
Weight of coalsample(X)

Determination of Sulphur in coal

A known amount of coal is burnt completely in bomb
calorimeter in presence of oxygen. Ash thus obtained contains
sulphur of coal as sulphate, which is extracted with dil HCl. The
acid extract is then treated with BaCl2 solution to precipitate
sulphate as BaSO4.
The precipitate is filtered, washed, dried, and weighed,
from which the sulphur in coal can be computed as follows.
Let,
X = weight of coal sample taken
M = weight of BaSO4 precipitate formed.

S + 2O2 SO4 BaSO4

32 233
233 gms of BaSO4 contains 32 gms of sulphur
1 gm of BaSO4 contains 32 / 233 gms of sulphur
∴ M gms of BaSO4 contains (32 / 233) x M gms of sulphur
32 M
% of sulphur in coal = x x 100
233 X
Significance (or) Importance of Ultimate Analysis
i) Carbon and Hydrogen
1. Higher the % of carbon and hydrogen, better the quality
of coal and higher is its calorific value.
2. The % of carbon is helpful in the classification of coal.
3. Higher the % of carbon in coal reduces the size of
combustion chamber required.

ii) Nitrogen
1. Nitrogen does not have any calorific value, and its
presence in coal is undesirable.
2. Good quality coal should have very little nitrogen content.

iii) Sulphur
Though sulphur increases the calorific value, its presence in coal
is undesirable because
1. The combustion products of sulphur, i.e, SO2 and SO3 are
harmful and have corrosion effects on equipments.
2. The coal containing sulphur is not suitable for the
preparation of metallurgical coke as it affects the properties
of the metal.

iv) Oxygen
1. Lower the % of oxygen higher is its calorific value.
2. As the oxygen content increases its moisture holding
capacity increases and the calorific value of the fuel is
required.
Carbonisation of coal
Heating of coal in absence of air at high temperature to
produce a residue coke, tar and coal gas is called as
carbonisation.

i. Caking of coal
When coal is heated strongly, the mass becomes soft and
coherent, then it is called caking of coal.

ii. Coking of coal

Otherwise if the mass produced is hard, porous and strong
then it is called coking of coal.

All the caking coals do not form strong, hard and coherent
residue coke. Hence all the caking coals are not necessarily coking
coal but all the coking coals have to be necessarily caking in
nature.

Metallurgical Coke

When bituminous coal is heated strongly in absence of air,

the volatile matter escapes out and a lustrous, dense, strong,
porous and coherent mass is left, which is called metallurgical
coke.

Properties or Characteristics of Metallurgical Coke

The most important industrial use of coke is in the
metallurgical industry, especially in the blast furnace. Good coke
for metallurgy should possess the following requirements.
i) Purity
Low moisture and ash content are desirable in
metallurgical coke. It must contain minimum % of P and S.
ii) Porosity
High porosity is desirable in furnace cokes to obtain high
rates of combustion.
iii) Strength
The coke should be hard and strong to withstand pressure
of ore, flux etc in the furnace.

iv) Size
Metallurgical coke must be uniform and medium size.
v) Calorific value
The Calorific Value of coke should be high.

vi) Combustibility
It should burn easily.

vii) Reactivity
It refers to its ability to react with O2, CO2, steam and air.
The metallurgical coke must have low reactivity.

viii) Cost
It must be cheap and readily available.

Why is Coke superior as a Metallurgical fuel?

i) Coke is stronger and more porous than coal.
ii) Coke contains lesser amount of sulphur than coal.
iii) Coke does not contain much volatile matter.
Manufacture of Metallurgical Coke
Mainly two types of ovens are used for metallurgical coke
production. They are

i. Beehive Coke Oven Process.

ii. Otto Hoffman’s by-product method.

i) Otto Hoffman’s by-product Coke Oven

In order to increase the thermal efficiency of the
carbonization process and recover the valuable by products (like
coal gas, ammonia, benzene, etc.) Otto Hoffman developed
modern by-product coke oven.

The oven consists of a number of silica chambers. Each

chamber is about 10 - 12 m long, 3 - 4 m height and 0.4 - 0.45 m
wide. Each chamber is provided with a charging hole at the top, it
is also provided with a gas off take valve and iron door at each end
for discharging coke.

A, B, C, D - Coke Ovens Coal gas

1,2,3,4 - Heat re-generators

To Chimney To Chimney
Air Producer gas

4.3 Otto Hoffman’s by-product coke oven

Fig 4.2

Coal is introduced in to the silica chamber and the

chambers are closed. The chambers are heated upto 1200°C by
burning pre heated air and the producer gas mixture in the
interspaces between the chambers.
 The air and gas are preheated by sending them through 2nd
rd
and 3 hot regenerators. Hot flue gases produced during
carbonization are allowed to pass through 1st and 4th regenerators
are heated by hot flue gases, the 2nd and 3rd regenerators are used
for heating the incoming air and gas mixture.

For economical heating, the direction of inlet and flue

gases are changed frequently. The above system of recycling the
flue gases to produce heat energy is known as the regenerative
system of heat economy. When the process is complete, the coke
is removed and quenched with water.

Time taken for complete carbonisation is about 12 - 20

hours. The yield of coke is about 70 %.

The valuable by products like coal gas, tar, ammonia, H2S

and benzene, etc are removed from the flue gas.

Recovery of by products

i) Tar
The coke oven gas is first passed through a tower in
which liquor ammonia is sprayed. Tar and dust get collected in a
tank below, which is heated by a steam coil to recover back the
ammonia sprayed.
ii) Ammonia
The gas is then passed through the other tower where water
is sprayed. Ammonia gets converted to NH4OH.
iii) Benzene and other aromatic compounds
The gas is then passed through the next tower in which
creosite oil is sprayed. Benzene and other aromatic compounds are
dissolved in the oil and recovered.
iv) Hydrogen sulphide
The gas then enters into a purifying chamber packed with
Fe2O3, which removes any sulphur compound present in coal gas.

Advantages of Otto Hoffman’s process

o High thermal efficiency and carbonization time is less.
o Valuable by products (like coal gas, ammonia, benzene,
etc. are recovered as by products.
o Heating done externally by producer gas.

Liquid Fuels
Petroleum

Petroleum or crude oil is a naturally occurring brown to

black coloured viscous oil formed under the crust of earth, on shore
or off shore. Chemically it is a mixture of various hydrocarbons
with small amounts of N, O, S compounds.

The approximate composition of petroleum is

C = 80 - 84%
H = 10 - 14 %
S = 0.1 - 0.5 %
N+ O = Negligible

Classification
Petroleum is classified on the basis of various types of
hydrocarbons.

i) Paraffin based oil - Contains mainly n - alkanes

(Ex : Pennsylvanian and gulf coast oil)
ii) Asphalt base oil - Contains aromatic and alicyclic
hydrocarbons.
(Ex: Californian oil)
iii) Mixed base oil - Contains higher proportion of aromatics
and naphthenes (cyclo alkanes).
(Ex : Mexican oil)

Refining of Petroleum (or) Crude Oil

Definition

The process of removing impurities and separating out

the oil into various fractions having different boiling points is
known as refining of petroleum.

Uncondensed gases

Loose cap
Petroleum ether

Gasoline
Chimney
Naptha
Tray
Kerosene
Crude oil
Diesel oil

Lubricating oil
Heavy oil
Furnace at 400° C Fractionating Column

Fig 1.3
Fig. 4. Fractional distillation of crude oil
i) Removal of Impurities
The impurities present in the oil are the fine water droplets,
NaCl, MgCl2, Sulphur etc. The crude oil is an extremely stable
emulsion of oil and salt water. Water is separated from the oil by
Cottrell’s process using ring electrodes. In this method, the crude
oil is allowed to flow between two highly charged electrodes. The
colloidal water droplets combine to form large drops, which are
then separated from oil.

Modern techniques like electrical desalting are used to

remove NaCl and MgCl2 from oil.

Sulphur is removed by treating the oil with copper oxide

and separated by filtration.

ii) Fractional Distillation

The purified crude oil is heated in a furnace called oil heater
where the temperature will be around 400o C. Here the oil gets
vapourised. The hot vapours are then sent to the fractionating
column (Fig. 1.3 ).

It is a tall cylindrical tower consisting of a number of

horizontal stainless steel tray at short distances. Each tray is
provided with a small chimney, which is covered with a loose cap.
The tower will be hot at the lower end and comparatively cooler at
the upper end.

When the oil vapours go up in the tower, they become cool

and condense. The heavier compounds having higher boiling
points get cooled first and condensed in the trays whereas the
fractions having lower boiling points condense near the top of the
tower.
 Lower fractions are used after purification while the high
boiling point fractions are subjected to cracking operation to get
more useful lower fractions.

The gasoline obtained by this fractional distillation is called

straight-run gasoline. Various fractions obtained at different trays
are given in Table 1.2.

Table 1.2 Various fractions, Compositions and their

uses
Sl.No Name of the Boiling Range of Uses
fraction Range oC C-Atoms
1. Uncondensed Below 30 C1-C4 As a fuel
gases under the
name of
LPG
2. Petroleum ether 30-70 C5-C7 As a solvent
3. Gasoline or 40-120 C5-C9 Fuel for IC
petrol engines
4. Naphtha or 120-180 C9-C10 As a solvent
solvent spirit in paints
and in dry
cleaning
5. Kerosene oil 180-250 C10-C16 Fuel for
stoves and
jet engines
6. Diesel oil 250-320 C15-C18 Diesel
engine fuel
7. Heavy oil 320-400 C17-C30 Fuel for
ships and
for
production
of gasoline
by cracking.
Knocking

Fractions like petrol and diesel oil are used as engine fuels.
Piston engines can be divided into spark ignition (SI) and
compression ignition (CI) engines. The former consumes petrol
and the latter operates on diesel oil.

SI Engines
In a four stroke SI engine, petrol vapour is mixed with air
in the carburetor. It is sucked into the cylinder during the suction
stroke. The mixture is compressed by the piston in the compression
part of the cycle. Then the compressed mixture is ignited by an
electric spark. The product of combustion increases pressure and
pushes the piston out, providing an output of power.

In the last part of the cycle, the piston ascends and expels the
exhaust gases from the cylinder.

Knocking in SI Engines (Petrol Engines)

Normally the fuel - air mixture should burn smoothly and
rapidly by sparking. In some cases, as a result of compression, the
fuel-air mixture may get heated to a temperature greater than its
ignition temperature and spontaneous combustion occurs even
before sparking. This is called pre-ignition.
Further, the spark also is emitted which makes the
combustion of the rest of the mixture faster and explosive. So, we
have a sudden, badly controlled burning and explosion results a
characteristic metallic or rattling sound from the engine. This is
called knocking or detonation or pinking. Knocking lowers the
efficiency of engine which results in loss of energy.

Chemical Structure and Knocking

The knocking tendency decreases as follows :

n-alkanes isoparaffins olefins naphthenes aromatics

n-alkanes have lowest antiknock value. So the presence of
maximum quantity of aromatics and minimum quantity of n-
alkanes is desirable in petrol.

Octane number (Measurement of knocking in SI engines)

Octane number expresses the knocking characteristics of
petrol. n - heptane (a constituent of petrol) knocks very badly, so
its anti-knock value has been given zero. On the other hand, iso-
octane (also a constituent of petrol) gives very little knocking, so
its anti-knock value has been given 100.
 Percentage of iso-octane present in iso octane & n-
heptane mixture, which matches the same knocking
characteristics of gasoline mixture test sample.
If a petrol sample behaves like a mixture of 60% iso-octane
and 40% n-heptane, its octane number is taken as 60.

Leaded Petrol (or) Improvement of Anti-knock Value

Adding some additives in it increases octane number of
petrol. In motor fuel about 1.0 to 1.5 ml tetra ethyl lead (TEL) is
added per litre of petrol. Petrol to which TEL is added is called
leaded petrol.

Mechanism of knocking
Knocking follows free radical mechanism, leading to a
chain growth. If the chains are terminated before their growth,
knocking will cease. TEL decomposes thermally to form ethyl free
radicals, which combines with the free radicals of knocking
process and thus the chain growth is stopped.

Disadvantage of using TEL

TEL forms lead oxide, which deposits on spark plug and
creates problems. So, to remove it, ethylene dibromide is added.
During burning lead bromide is formed which evaporates away in
the heat engines and goes out together with exhaust gases. This
creates atmospheric pollution for human beings. Hence, at present
aromatic phosphates are used instead of TEL.

CH2 - Br
Pb + PbBr2 + CH2 = CH2
CH2 - Br
 Diesel
o It is relatively a high boiling point fraction of petroleum
obtained between 250 - 320o C.
o It is a mixture of hydrocarbons in terms of carbon atoms
C15 - C18
o Its calorific value is about 11,000 kcals/kg. It is used as fuel
for compression ignition engine.
o Its antiknock value can be improved by doping with isoamyl
nitrate.
CI Engines
In a CI engine, air is alone compressed. This raises the
cylinder temperature as high as 300o C. Then the oil is injected or
sprayed, which must ignite spontaneously. Now combustion
products expand and power stroke begins.

Knocking in CI Engines
Some times, even after the compression stroke is over and
even after the diesel oil is sprayed, burning may not start. So, more
and more fuel is injected automatically and sudden ignition may
occur and burn the whole of the oil. This delayed ignition results
an uncontrolled, excessive combustion produces ‘diesel knock’.

So in SI - engine, knocking is due to premature or too early

ignition in CI - engines, knocking is due to delayed ignition or
ignition lag.

Cetane number (or) Cetane Rating

Cetane number expresses the knocking characteristics of
diesel.
Cetane (C16 H 34) has a very short ignition delay and hence
its cetane number is taken as 100. On the other hand, methyl
napthalene has very large ignition delay and hence its cetane
number is taken as zero.
Cetane number is defined as “the percentage of cetane
present in a mixture of α –methyl naphthalene and cetane”.

CH3

CH3 - (CH2)14 - CH3

n-cetane
(cetane number = 100)
n-Hexadecane

Chemical Structure and Knocking

The knocking tendency in CI - engines increases as follows,
n-alkane iso paraffins Olefins naphthenes aromatics

Octane numbers decreases in this order. Therefore an oil

of high octane number has a low cetane number and vice-versa.
Consequently, petroleum crude gives petrol of high octane
number and diesel of low cetane number.

Natural Gas
Natural gas is always found above the oil in the oil wells.
It is also called Marsh gas. It conssists of methane and other
saturated hydrocarbons. The average composition of natural gas is
as follows :

Its calorific value varies from 12,000 to 14,000 kcal/m3.

Constituents Percentage(%)
Methane 88.5
Ethane 5.5
Propane 4
Butane 1.5
Pentane 0.5

If natural gas contains lower hydrocarbons like methane

and ethane it is called lean or dry gas. In the natural gas contains
higher hydrocarbons like propane, butane along with methane it is
called rich or wet gas.

Uses
1. It is used as a domestic and industrial fuel.
2. It is used as a raw material for the manufacture of carbon
black and hydrogen.
3. It is also used for the generation of electricity by using it in
fuel cells.
Liquified Petroleum Gas (LPG)
It is a mixture of propane and butane.
It is obtained as one of the top fractions in the fractional
distillation of petroleum. It is easily liquified and so can be
economically stored and transported in cylinders.

Composition
Its approximate composition is
n-Butane = 70 %
Isobutane = 17 %
n-Propane = 11 %
Butylene and Ethane = rest.

Calorific Value

Its Calorific Value is 27,000 kcals/m3.

Uses
i. It is used as a fuel for domestic cooking.
ii. Used for heating industrial furnaces.
iii. Used as an alternate for Gasoline in automobiles.

Review Questions:

1. What is coal ? how is it formed ? what are its types ?

2. Describe proximate analysis.Bring out its importance
3. What is metallurgical coke ?
4. Describe Otto Hoffmann by product coke oven method
5. What is knocking ? Explain
6. How will you improve octane number of a fuel
7. What is water gas ? How is it manufactured ?
8. Write a brief note on CNG
9. What is calorific value ? mention it’s units
10. Discuss the calculation of minimum air requirement for the
complete combustion.
11. What is flue gas ?. Discuss Dulong’s formula
12. Define i) Gross calorific value ii) Net calorific value