CHEMISTRY

Module – III
FUELS
Govt. College of Engineering Kalahandi, Bhawanipatna

Dr. P K Panigrahi
Module- III FUELS

What is Fuel?
A fuel is a substance that produces useful energy either through combustion or through
nuclear reaction. Energy should be released in a controlled manner and can be harnessed
economically for domestic and industrial purposes. Fuels that produce heat energy by
combustion are called as chemical fuels. Examples: wood, oil, natural gases, producer gas
etc.

Classification of Fuels
On the basis of occurrence, fuels are of two types:

1. Primary or natural fuels- These are found in nature and are used as such, generally
without processing. These are also known as fossil fuels. Examples include wood,
peat, lignite, petroleum, natural gas etc.
2. Secondary or synthetic fuels- These are derived from the natural fuels by further
chemical processing. Examples of this type are coke, charcoal, kerosene, producer
gas, water gas etc.

Classification of the fuels can also be done on the basis of their physical states.

1. Solid fuels: wood, coal, charcoal, coke etc. are coming under this category.
2. Liquid fuels: petroleum, petrol, diesel, kerosene etc. are the examples of this
category.
3. Gaseous fuels: Natural gas, coal gas, water gas, producer gas, bio gas etc. are the
examples of this class of fuels.

Characteristics of a good fuel

(i) High calorific value: The amount of heat energy released when a unity quantity of fuel
is burnt completely is known as calorific value. Higher is the calorific value, the greater
is the heat liberated per unit mass or volume of the fuel and the better is the fuel quality.
(ii) Ignition temperature: It is the lowest temperature to which the fuel must be preheated
so that it starts burning smoothly. An ideal fuel should have moderate ignition
temperature. Fuels with low ignition temperature can burn spontaneously and cause
explosion. High ignition temperature makes the fuel difficult to ignite.
(iii) Moisture content: It should be low because the presence of moisture lowers the calorific
value of the fuel.
(iv) Non-combustible matter (Ash): Non-combustible matter reduces the calorific value of
the fuel. It also needs additional investment for its storage, handling and disposal.

GCEK, Bpatna, Dr. PK Panigrahi Page 2

(v) Velocity of combustion: Fuel must burn with a moderate rate. If the velocity is low,
then a part of heat may get radiated instead of raising the temperature. If it is very high,
then combustion may be uncontrollable.
(vi) Combustion products should be harmless and non-polluting.
(vii) Cost of the fuel: A good fuel should be readily available at low cost.
(viii) Storage & transportation: A good fuel should be easy to handle, store & transport at
low cost.

Net Calorific Value (NCV) or Lower Calorific Value (LCV)

It is defined as the heat produced, when a unit quantity (mass or volume) of fuel is burnt
completely and the hot combustion products are allowed to escape. In actual practice, when
a fuel is burnt, the water vapour is allowed to escape along with the hot combustion gases.

Gross Calorific Value (GCV) or Higher Calorific Value (HCV)

It is defined as the total amount of heat produced, when a unit quantity (mass or volume) of
fuel is burnt completely and the products of combustion are cooled to room temperature.

Relationship between GCV and NCV: Usually, all fuels contain hydrogen. During the
combustion, the hydrogen in the fuel is converted into steam. When the combustion products
are cooled to room temperature, the steam gets condensed and heat equals to the latent heat
of steam is evolved. This heat gets added in the measured heat and so GCV value is higher
than NCV.

The combustion of hydrogen gives water as per the following chemical equation:

H2 (2g) + ½ O2 (16g) H2O (18g)

From the balanced chemical equation, it is indicated that 2 part by weight of hydrogen reacts
with 16 parts by weight of oxygen to give 18 parts by weight of water

That means, 1 part by weight of hydrogen reacts with 8 parts by weight of oxygen to give 9
parts by weight of water.

If the amount of hydrogen in a given fuel is ‘H’,

Amount of heat produced will be 1/9 H x ΔHv

LCV or NCV = (HCV or GCV) – (Latent heat of water vapour formed)

or, LCV or NCV = (HCV or GCV) – (1/9 H x ΔHv)

where, ΔHv = latent heat of steam, which is approximately 587 kcal/kg or cal/g

Problem 1: 2 kg of a coal was burnt in a bomb calorimeter. The heat liberated was found to
be 14114 kcal. Calculate the calorific value of the coal sample. (Ans: 7057 kcal/kg )

GCEK, Bpatna, Dr. PK Panigrahi Page 3

Problem 2: GCV of a fuel containing 8% hydrogen was found to be 9226 Kcal/Kg. Find out
NCV if the ΔHv = 587 kcal/kg. (Ans: NCV= 8803.26 kcal/kg)

Problem 3: Calculate GCV of a coal sample if its NCV is 6767cal. Find the NCV if ΔHv =
587 cal/g. (Ans: NCV= 7031.6 cal/g).

Problem 4: Calculate NCV of a fuel containing 6% hydrogen if its GCV is found to be

9804.6 kcal/kg. ΔHv = 587 kcal/kg. (Ans: NCV= 9487.6 kcal/kg)

Theoretical calculation of calorific value of a fuel

If the composition of a fuel is known, the theoretical calculation of its calorific value can be
done by using Dulong’s formula. Dulong assumed that the heat evolved comes from the
combustion of C, H, & S present in the fuel and the calorific value of a fuel is the sum of the
calorific values of these constituents. The higher calorific value of C, H & S are found to be
8080, 34500, & 2240 kcal/kg respectively.

Dulong’s formula can be written as:

1
=( 8080 + 34500 − + 2240 / … … (3.1)
100 8
Where, C, H, S & O are the percentage of carbon, hydrogen, oxygen & sulphur respectively.

Why the 2nd factor in equation 3.1 is ( − ) not H?

Since some part of the hydrogen is fixed as water in the fuel and it is not available for
combustion, it is required to subtract from the total amount of hydrogen available to calculate
the amount of hydrogen available for combustion.

Thus, amount of hydrogen available for combustion = (Total mass of hydrogen) – (hydrogen
combined with oxygen)

From the balanced chemical equation, H2 (2g) + ½ O2 (16g) H2O (18g)

it is indicated that 1 part by weight of hydrogen reacts with 8 parts by weight of oxygen to
give 9 parts by weight of water.

If the amount of oxygen in the fuel is ‘O’, then

Fixed mass of hydrogen = (1/8) O = (mass of oxygen in the fuel) / 8

So amount of hydrogen available for combustion = −

= −9 × × 587 /
100
, =( − 0.09 × 587) / ........... (3.2)

GCEK, Bpatna, Dr. PK Panigrahi Page 4

However, experimentally, HCV and LCV can be determined by using Bomb calorimeter. For
solid and liquid fuels, Junker’s calorimeter and for gaseous fuels, Boy’s calorimeters are
used.

Bomb Calorimeter
Principle: In this method, a known amount of solid and liquid fuel is burnt in excess oxygen.
The liberated heat is absorbed in a known quantity of surrounding water raising its
temperature. The calorific value is then calculated from the relationship:

Heat produced by the fuel = heat absorbed by the water and calorimeter

Construction: It consists of a cylindrical bomb made of stainless steel. The bomb is provided
with a lid to close it and make itt air
air-tight.
tight. The combustion of the fuel is allowed to take place
inside the bomb with the help of electricity. The electrodes are attached with a small ring
which supports a crucible made of nickel or stainless steel. Supply of oxygen is carried out
through an inlet. The bomb is placed in a copper calorimeter, which is surrounded by an air air-
jacket and water-jacket
jacket in order to prevent loss of heat owing to radiation. The calorimeter is
also provided with a motor-driven
driven stirrer and thermometer.

Figure 3.1: Diagram of Bomb calorimeter

Working: A known amount of the fuel is placed in the crucible supported over the ring. A
fine magnesium wire touching the sample of the fuel is then stretched across the electrodes.
The bomb lid is tightly screwed and filled wi
with
th oxygen at about 25 atm pressure. The bomb is

GCEK, Bpatna, Dr. PK Panigrahi Page 5

then placed in the copper calorimeter containing a known amount of water. The stirrer is
driven and the initial temperature of water is noted. The combustion of the fuel is then started
by connecting the electrodes to a battery. Heat is liberated due to exothermic combustion of
the fuel. The stirring of water is continued and the final temperature of water is recorded.

Calculation: Suppose,

Weight of the fuel sample taken = x g

Weight of the water in the calorimeter = W g

Water equivalent of calorimeter = w g

Initial temperature of water in the calorimeter = T1 oC

Final temperature of water in the calorimeter = T2 oC

If higher calorific value of the fuel is HCV,

Heat liberated by the combustion of the fuel = x (HCV)

Heat absorbed by the water and the calorimeter = (W + w ) S ( T2 -T1)

Where S is the specific heat of water.

But, heat liberated by the fuel = heat absorbed by the water and the calorimeter

Thus, x (HCV) = (W + w ) S ( T2 -T1)

Therefore, HCV = (W + w ) S ( T2 -T1) / x

And , =( − 0.09 × 587) /

Corrections: For more accurate calculations, certain corrections are incorporated.

a. Fuse wire correction- The heat liberated from burning of the magnesium fuse wire is
taken into account
b. Acid correction: when fuels containing S and N are oxidised at higher temperature,
they form acids through exothermic reactions. The heat evolved is considered.
c. Cooling correction: It is the product of t and dt, where t is the time taken to cool the
temperature of water from high temperature to room temperature and dt is the rate of
cooling per minute.

Incorporating all the corrections, we get

HCV = [{(W + w ) S ( T2 -T1+ t dt)}- acid correction – fuse wire correction] / x

Problem 5: Calculate the gross and net calorific values of a coal sample having 85 % C, 8 %
H, 1 % S, 2% N and 4% ash. Latent heat of steam = 587 kcal/kg.

GCEK, Bpatna, Dr. PK Panigrahi Page 6

(Ans: GCV=9650.4 kcal/kg and NCV= 9227.76 kcal/kg)

Problem 6: A sample of coal has the following composition: C = 82 %, H= 7.5 %, S = 1.5 %,

N = 0.6 %, O = 8.4 %. Find GCV using Dulong’s Formula. (Ans: GCV=8965.25 kcal/kg)

Problem 7: Calculate GCV and NCV of coal sample having the following composition:

C = 80%, H = 7%, S= 3.5 %, N = 2.1%, ash = 4.4%.

(Ans: GCV=8828.02 kcal/kg and NCV= 8458.2 kcal/kg)

Calculation of theoretical air for the combustion of a fuel

The volume and weight of the amount of air required for the complete combustion of certain
amount of a fuel can be calculated theoretically using its composition data and the balanced
combustion equation for each of the combustible composition of the fuel.

The stoichimetric equation involved in the combustion of carbon is:

C (12 g) + O2 (32 g)  CO2 (44 g)

Here, 12 parts by weight of carbon requires 32 parts by weight of oxygen to produce 44 parts
by weight of CO2.

Similarly, for hydrogen and sulphur, we can write

2 H2 (4g) + O2 (32g)  2H2O (36g)

S (32g) + O2 (32g)  SO2 (64g)

Here, 4 parts by weight of hydrogen requires 32 parts by weight of oxygen to produce 36

parts by weight of H2O.

32 parts by weight of carbon requires 32 parts by weight of oxygen to produce 64 parts by

weight of SO2.

So the weight of oxygen required to burn (oxidise) W kg of a fuel sample containing C % of

carbon, H % of hydrogen, and S % of sulphur is

+ + × .................................. (3.3)

Nitrogen is incombustible and hence is not included in the equation. However, if the fuel
sample contains O % of oxygen, then that amount must be subtracted from the equation (3.3)
and the equation takes the following form (equation (3.4)).

+8 + − × ......................................(3.4)

GCEK, Bpatna, Dr. PK Panigrahi Page 7

Since the percentage of oxygen in air by volume is 21 % and 23.2 % by weight, the weight of
air required for the complete combustion of the above fuel sample is

+8 + − × × .
..........................(3.5)

Again, the average molecular weight of air is 28.94 g.

Thus, we can write, 28.94 g of air occupies 22.4 L.

This relationship can be used in order to calculate the volume of air required for the complete
combustion of the above fuel sample.

Problem 8: Calculate the weight and volume of air required in combustion of 4 kg of carbon.
(Ans. 69.56 kg, 48695.6 L)

Problem 9: The percentage composition of a coal sample is: C = 85 %, H = 5 %, O = 6 %,

N = 4 %, S = 2 %, ash = 5 % and moisture = 3 %. (i) Calculate the minimum amount of air
needed in combustion of 1 kg of coal. (ii) Calculate the weight and volume of air required in
combustion of 1 kg of coal if it is supplied 40 % in excess. (Ans. (i) 11.68 kg, (ii) 16.35 kg,
11447.6 L )

Problem 10: Calculate the volume of air required for the complete combustion of 1 m3 of the
gaseous fuel having the following composition by volume: H2 = 50 %, CH4 = 36 %, CO = 6
%, C2H4 = 4 %, H2O vapour = 2.5 %, N2 = 1.5 %. (Ans. 5.33 m3)

Solid Fuels - Coal:

Coal is a complex organic compound derived from the dead plants buried under the ground
for several years. The degraded matter was converted into various types of coal: Peat, lignite,
bituminous and anthracite. This classification is made based on the carbon content. The
highest ranking of coal, which has largest carbon content, is anthracite. The lowest rank of
the coal is peat, which is formed at the first stage of the coalification. The next rank is lignite
(also called as brown coal) and then bituminous coal. Thus the order of ranking of coals is:
Anthracite > Bituminous > Sub-bituminous > Lignite > Peat

In order to know the calorific values of the varieties of coal with varying composition of
carbon, moisture, volatile matters, analysis of coal is very much important. There are two
types of analyses for determination of the quality of the coal.

Proximate Analysis

It includes the determination of moisture content, volatile matter, ash and fixed carbon
content. In this analysis, the data varies with the procedure adopted for study.

GCEK, Bpatna, Dr. PK Panigrahi Page 8

Moisture content: About 1g of finely divided powder of air-dried coal sample is weighed in a
crucible and placed inside an electric hot air oven, maintained at 105 – 110 oC. The crucible
is allowed to remain in the oven for an hour and then taken out, cooled in
desiccators and weighed. The loss of weight is reported as moisture percentage.

Moisture % = × 100

Volatile matter: The dried sample of coal left in the crucible after analysis of moisture
content is then covered with a lid and placed in an electric furnace maintained at 925 oC. The
crucible taken out after 7 min of heating and then cooled in air and then in desiccators. After
taking weight, the loss in weight is reported as volatile matter in percentage terms.

Volatile matter % = × 100

Ash content: The residual coal in the crucible after analysis of volatile matter is then heated
without lid in muffle furnace at 700 ±5 oC. After 0.5h, the crucible is taken out, cooled first in
air, then in a desiccators and weighed. Heating, cooling, weighed is repeated till a constant
weight is obtained. The residue is reported as ash in percentage term.

Ash % = × 100

Fixed carbon: this refers to the amount of carbon present in the coal sample. This is
calculated by deducting the percentage amount of moisture, volatile matter and ash from 100.

Fixed carbon % = 100 (Moisture % + Volatile matter % + Ash%)

Significance of Proximate Analysis:

1. Moisture lowers the calorific value of coal and it quenches the fire in the furnce. So
lesser is the moisture content, better is the quality of coal as fuel.
2. High volatile matter content means that a large proportion of the matter escapes
unburnt. This matter may be combustible gasses or non-combustible matter. The
presence of non-combustible matters do not add calorific value, but it increases the
volume of the furnace required. Hence, higher volatile content in coal is undesirable.
3. Ash is a useless non-combustible matter, which reduces the calorific value of coal.
Ash causes the hindrance of flow of air and heat, thereby, lowering the temperature. It
also causes wear of furnace walls, burning of apparatus and feeding mechanism.
Hence, lower is the ash content; better is the quality of coal. The presence of ash also
increases the transport, handling, storage and disposal cost.
4. Higher is the fixed carbon content, better is the quality of coal. It is useful for
designing the furnace and firebox.

Ultimate Analysis

This analysis involves the determination of content of carbon, hydrogen, nitrogen, sulphur,
oxygen and ash present in a coal sample. The content of carbon, hydrogen, nitrogen, sulphur

GCEK, Bpatna, Dr. PK Panigrahi Page 9

and ash are determined experimentally, whereas that of oxygen is determined theoretically.
Greater is the percentage of carbon and hydrogen, better is the quality of the coal and
calorific value. Nitogen has no calorific value, hence its presence is undesirable. Sulphur is
present to the extent of 0.5- 3.0 % and its burning has harmful effects in terms of corrosion of
equipments and the atmospheric pollution. So presence of sulphur is undesirable even though
it contributes to the heating value of coal on combustion. Oxygen content decreases the
calorific value of coal.High oxygen content coals are characterized by high inherent moisture
content, low calorific value and low cooking power. Thus, a good quality coal should have
low percentage of oxygen.

Liquid Fuel:
Petroleum:

Petroleum is a fossil fuel and can be classified into three categories based on the composition.

(a) Paraffinic base petroleum: straight chain paraffin main compound.

(b) Asphaltic or Naphthalic base petroleum: cycloparaffin is the main compound.
(c) Mixed base petroleum: Both straight chain and cycloparaffin are present.

Petroleum is buried underground in tiny pockets in rocks, which is pumped to the surface and
it is sent to refinery to refining for separation into different types of product and fuels. The
petroleum obtained by mining in-viscous and dark colour liquid contains hydrocarbons
(straight and cycloparaffins, olefins, aromatics and some organic compounds containing S, N,
O). In addition it also contains, sand, brine, and sulphur. After removal of the above
impurities, the oil is subjected to fractional distillation in a refinery. The process of
converting crude oil into several useful fractions is referred on refining of petroleum. The
important steps involved are:

(i) Fractional distillation to give various factors

(ii) Conversion of less desirable fraction to valuable products by processes like cracking.
(iii) Treatment of fraction to remove undesirable substances.

Fractional distillation of crude oil in performs to separate into a number of fractions having
different and definite boiling ranges. The crude oil is preheated in a furnace to about 4000C
and introduced in the fractionating tower. The tower is not towards the lower end and
comparatively cooler at the upper end. As the vapour of oil rise up the column, they get
cooled and condensed in the tragus. The highest boiling fraction condenses first at the bottom
and the lowest boiling fraction at the top. Outlets are provided in the side of the column at
suitable height to withdraw the fraction. The uncondensed grazes are liquefied to give the
LPG, which consist of a mix of methane, ethane, propane and butane. The black, tarry residue
left in the retort is called asphalt.

GCEK, Bpatna, Dr. PK Panigrahi Page 10

 Figure 3.2: Diagram of Fractional distillation column.

Table3.1: Major fractions

actions of distillation of crude oil and their uses.
uses

S. Fraction’s name Boiling Approximate Uses

No Temperature
Temperatur Composition
. range
1 Uncondensed gas Bellow 300 C1-C4 Used as domestic fuel and
o
C synthesis of organic compounds
2 Petroleum Ether 70 oC
30-70 C5-C7 Solvents for fats and oils, used in
dry cleaning
3 Gasoline or petrol 120 oC
70-120 C5-C9 Fuels for IC engines of
automobiles and dry cleaning
4 180 oC
Naphtha or solvent 120-180 C9-C10 Solvent for paints and varnishes
spirit and in dry cleaning
5 Kerosene oil 250 oC
180-250 C10-C16 Illuminants, Fuels for stoves, for
making oil gas
6 Diesel 320 oC
250-320 C15-C18 Diesel engine fuel,, synthesis of
gasoline by cracking
7 Heavy oil 400 oC
320-400 C17-C40 Fuel for ships,, synthesis of
On vacuum gasoline by cracking
distillation gives
(i)Lubricating oil (i)As Lubricants
(ii)Petroleum jelly (ii)In
In cosmetics and medicines
(iii)Greases (iii)As lubricant
(iv)Paraffin wax (iv)In
In candles, boot polishes, wax
paper

GCEK, Bpatna, Dr. PK Panigrahi Page 11

7 Residue: (i)Pitch >400 oC Above C40 Road making, water proofing of
roofs
(ii)Petroleum As solid fuel in moulding
cokes electrodes rods for cells

Cracking:
Of all the hydrocarbons obtained in different fraction, gasoline fraction has the highest
demand due to its use in automobiles. The gasoline obtained straight from fractionation tower
is not of good quality and is obtained in poor yield (20%). Hence, a process of thermal
decomposition of high boiling fraction is converted into more valuable lower boiling
fractions. This process is called as cracking.
∆
C12H26 → (C1H6 + C5H10) or (C6H14 + C6H12) + (C5H12 + C7H14)

BP = 216 oC BP range 30 oC-150 oC

Two methods of cracking are:

(1) Thermal cracking:

In this method, heavier oils are subjected to high temperature and pressure, so that bigger
hydrocarbons break into smaller molecules of paraffin, and some hydrogen. This process is
carried out either in liquid or vapour phase.
In liquid phase thermal cracking, the cracking heavy oils is done at a temperature 475-530 oC
or ‘P’ of 7-70atm to keep the product in liquid phase. The yield is approx 60-65%.
In vapour phase thermal cracking, the oil is first vaporized and then heated at 600-650 oC and
subjected to a ‘P’ of 3.5-10.5atm for a short time for cracking.

(2) Catalytic cracking:

Here high temperature and pressures are not necessary and cracking takes place in presence
of a catalyst, which is generally a mixture of silica and alumina and aluminium silicate,
bauxite etc. It may of two types:
(i) Fixed bed cracking:
Cracking is carried out around 5000C over the catalyst, which is used in the form of a fixed
bed. A number of cracking furnaces are used, so that if the catalyst is sent in one furnace, the
other one is used. The spent catalyst which is deposited by carbon can be regenerated by
burning the carbon in a current of air.

GCEK, Bpatna, Dr. PK Panigrahi Page 12

Figure 3.3: Fixed bed catalytic cracking

(ii) Fluidized (moving) bed catalytic cracking:

Fluidized catalyst is used to perform cracking continuously. The catalyst is suspended in a
stream of oil vapour. The spent catalyst continuously flows out of the bottom of the furnace
and can be regenerated, while fresh catalyst is added from the top. The temperature is
maintained at 450-550 oC and pressure at 11-2 atm.
The cracked pooch rise up to the top of the reactor and en
enter
ter the fractionating column and
passed through a cooler, where some grazes condensed.

Figure 3.4: Fluidised bed catalytic cracking

GCEK, Bpatna, Dr. PK Panigrahi Page 13

Knocking:

It is defined as metallic sound similar to rattling of hammer produced in internal combustion

(IC) engine due to immature ignition of fuel oil-air mixture.
An IC engine uses either gasoline or diesel as fuel and a mixture of fuel-air is ignited inside
the IC. The ignition is brought about by means of an electric spark (in petrol engines) or by
compressing the air (in diesel engine).

In petrol engine, the whole process comprises of four strokes:

(i) Suction stroke: The downward moving piston sucks a mixture of air and fuel (petrol)
vapours in the carburettor into the cylinder.
(ii) Compression stroke: The piston moves up, compressing the gas mixture. The ratio of
initial volume (at the end of suction stroke) to the final volume (at the end of compression
stroke) is known as compression ratio (CR).
(iii) Power stoke: Just before the piston reaches the top centre of the cylinder, a spark
from the spark plug ignite the gas mixture. The hot gases produced due to combustion
increase the pressure and push the piston down.
(iv) Exhaust stroke: This is the last stroke, in which the piston rises up and expels the
exhausts gases from the cylinder.
The cycle then repeats itself. After the initiated by a spark, the fuel air mixture should burn
smoothly and rapidly so that the expanding gas drives the piston down the cylinder smoothly.

The efficiency of IC engine depends on compression ratio (CR). Higher is the CR, greater is
the efficiency of the engine. To achieve maximum efficiency a CR of 7-8 is required.
However, if the compression ratio exceeds certain limit, the fuel air-mixture may get heated
to a temperature, greater than its ignition temperature leading to spontaneous ignition and
explosive combustion of fuel, even before sparking. This result in the thermal shock wave,
which hit the cylinder and piston, causing a characteristic metallic or rattling sound, called as
knocking.
Knocking increases the fuel consumption, decreases the efficiency of engine, causes
mechanical damages to piston and cylinder due to overheating. Knocking depends on the
chemical composition of the fuel, engine design, and shape of piston, location of plug etc.
and also on running condition.

Relationship between chemical structure and knocking:

Knocking tendency decreases with increases in compactness of the molecule.

Knocking tendency decreases with increases in double bonds, rings (cyclic structure).
Knocking tendency is higher, when straight chain hydrocarbons are used in IC engine,
whereas branched chain hydrocarbons, aromatics (benzene, toluene), cycloalkane have lesser
tendency to knock. The knocking tendency follows the order:

GCEK, Bpatna, Dr. PK Panigrahi Page 14

Aromatic < Cycloalkane < Olefins < Branched chain alkane < Straight chain alkane
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
For straight chain alkane:
n-butane < n-pentane < n-hexane < n-heptane
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯

Octane Number:

In order to express the knocking (anti-knocking) property of fuel, an arbitrary scale, octane
rating or octane number is provided by G. Edger in 1926. It is determined by matching the
knocking characteristic of the fuel being tested with those of the mixtures of n-heptane and
iso-octane (2, 2, 4- tri-methyl pentane) in a standard cylinder engine of variable CR and
under the same set of conditions.
It is observed that n-heptanes have the poorest anti-knock properties of all pure compounds
suitable as fuels for IC engines. On the other hand, iso-octane has very good antiknock
properties (high resistance to knocking). So octane number of n-heptane and iso-octane are
arbitrary assigned as zero and 100 respectively.

(n-heptane) (Octane no. Zero) iso-octane) (octane no. 100)

Thus, the octane number of a fuel can be defined as the percentage (by volume) of iso-octane
in the iso-octane and n-heptanes mixture that has same knocking characteristics as the fuel
under examination, under same set of conditions.
Thus, a fuel with octane number 80 is one which has the same combustion characteristics to
that of 80:20 mixture of iso-octane and n-heptane.

Anti-knocking agents:

The petrol from fractional distillation has low octane number and is called as unleaded petrol.
The octane number of gasoline (petrol) can be increased by adding addictives like benzol and
alcohol. This process is called blending. Benzol is a mixture of 70% benzene, 18% toluene
and 6% xylene and rest other hydrocarbons and it is obtained during fractional distillation of
light oil in the temperature range 80-170 oC.
The generally used anti-knocking agent, tetraethyl lead (Pb(C2H5)4) (TEL). The process of
addition of TEL to gasoline to increase its octane number is known as doping. TEL is a
colourless liquid with a sweet odour but it is highly poisonous. About 0.5ml TEL per litre is
added for motor fuels and about 1mL of TEL per litres is added for aviation fuels. Gasoline

GCEK, Bpatna, Dr. PK Panigrahi Page 15

containing TEL is coloured with 2% red dye to indicate its poisonous nature and this variety
of petrol is called leaded petrol. It is believed that during combustion of gasoline, TEL forms
Pb and PbO particles, which acts as free radicals chain inhibitors and thus curtail the
propagation of explosive chain reaction and thereby, minimises the knocking (It is believed
that knocking is a free radical mechanism). However lead and PbO vapours so formed
contaminate the atmosphere. PbO is rapidly reduced to Pb which deposited on the spark plug,
cylinder walls and piston heads. Hence, it is harmful to engine. To overcome these
disadvantages of leaded petrol and to improve the octane number of fuels, ethylene di-
bromide (C2H4Br2) is also added, so that lead formed is converted into lead bromide, which is
volatile and escapes into the atmosphere.

Pb + C2H4Br2 → Pb Br2 + CH2= CH2

Unleaded petrol:

Owing to the harmful effect of lead, unleaded petrol is being used. It is the one, where octane
number is increased without the addition of lead compounds. In this case, high octane number
compounds such as isopentane, iso octane, ethyl benzene, isopropyl benzene, methyl tertiary
butyl ether (MTBE) are used. Out of these, MTBE is preferred because it contains oxygen in
the form of ether group and supplies oxygen for the combustion of petrol in internal
combustion engines, thereby reducing peroxy compound formation.
Use of unleaded petrol requires use of catalytic converter. A catalytic converter contains a
catalyst (Rhodium), which converts toxic gases (CO and NO) into harmless gases (CO2 and
N2). Moreover it oxidised un-burnt hydrocarbons to CO2 and H2O.

Knocking in Compression Ignition (diesel) engine:

In diesel engine, the fuel is ignited with help of heat generated by the compression of air
inside the combustion chamber and not by spark, as in case of petrol engine. The injected
diesel droplet gets ignited by absorption of heat in the cylinder. However, the combustion of
fuel in diesel engine is not spontaneous of that of petrol engine. There is a time lag between
fuel injection and its ignition. It is called as ignition delay or ignition lag. For the efficient
functioning of the diesel engine, this induction lag should be as brief as possible.

When a fuel has long induction lag, a portion of the injected fuel gets accumulated in the
cylinder before ignition and when ignition takes place, the accumulated fuel burns violently
leading to sudden increase in temperature and pressure. This non-uniform burning of the fuel
is known as diesel knocking. The greater is the induction lag, higher in the diesel knock.
Chemically, the diesel engine fuel consists of straight long chain hydrocarbons with
minimum amount of branched chain and aromatic hydrocarbons. Thus, in contrast to
gasoline, the diesel engine fuel should have low spontaneous ignition temperature so as to
minimize the induction lag.

GCEK, Bpatna, Dr. PK Panigrahi Page 16

Cetane Number or Cetane Rating:

It is used for rating diesel oil. Cetane number is a measure of fuel’s ignition delay. It
represents the spontaneous ignition temperature of a particular diesel fuel. It is the measure of
the ease, with which the fuel will ignite under compression. The hydrocarbon, cetane (n-
hexadecane) has a very short ignition delay (ignite rapidly) than any other diesel fuel and is
assigned arbitrarily cetane no. 100. On the other hand, -methylnapthalene has a long
ignition delay (ignites slowly) compared to any other diesel fuel and hence, is assigned cetane
no. of zero.

CH3 (CH2)14CH3 (Cetane) (cetane no.100)

CH3

( α-methyl naphthalene) (Cetane No. Zero)

Thus, cetane number of a diesel fuel can be defined as the percentage of cetane and -
methylnapthalene, which has the same ignition properties as that of the fuel under
examination at the same set of conditions. For example, a diesel fuel will have a cetane
number of 60, if it has the same ignition characteristics as that of a mixture of 60% cetane
and 40% -methylnapthalene.
The cetane number of a fuel depends on the nature and composition of hydrocarbons. The
straight chain hydrocarbons ignite quite readily and have higher cetane number compared to
aromatics, which have lower cetane number. The decreasing order of cetane number is as
follows.

n-alkanes > napthalene > alkenes > branched alkanes > aromatics

Thus, hydrocarbons which are poor gasoline fuels are quite good diesel fuels.
The cetane rating of a diesel fuel can be raised by addition of small quality of certain pre-
ignition drops, such as ethyl nitrite, isoamyl nitrite, acetone peroxide, nitronapthaline etc.

Power alcohols (non-petrol fuels):

Power alcohol is a mixture of 5-25% ethyl alcohol with petrol and is used as a fuel in IC
engines.

Advantages of power alcohol:

 Ethyl alcohol has an octane number 90 and has good anti-knocking properties, where
as that of petrol is 60-70. Thus, blending petrol with ethyl alcohol improves the anti-knocking
properties and octane number of the petrol,
 Use of power alcohol reduces the carbon monoxide emission from the engine.

GCEK, Bpatna, Dr. PK Panigrahi Page 17

 Ethyl alcohol absorbs traces of moisture. The petrol power alcohol is cheaper than
alcohol.

Disadvantages of power alcohol:

 Ethyl alcohol lap calorific value is (7000 kcal/kg) is much lesser than that of petrol
(11,500kcal/kg). Hence addition of ethyl alcohol to petrol reduces its calorific value by 35%.
 Its surface tension is high and its atomization is difficult at lower temperature. This
leads to starting trouble in a vehicle and the vehicle remain sluggish for quite some time after
starting.
 It may undergo oxidation reaction to form acetic acid which corrodes engine parts.
 The output power generated is reduced to 35%.
 As it contains oxygen atom, the amount of air required for complete combustion is
less. Therefore, the carburettor and engine need to be modified.

Synthetic petrol:
Synthetic petrol is a mixture of alkanes with composition resembling that of petrol, obtained
artificially from coal. The important methods for preparation are: Bergius process and
Fischer-Tropsch Process.
Bergius process:
This process, developed by Bergius of Germany involves the conversion of low grade coals,
such as bituminous or brown coals into liquid and gaseous fuels by hydrogenating them in the
presence of catalyst. In process, low ash coal is powdered and mixture with heavy oil and
catalyst (tin or Ni) to make a paste. This paste is heated in a converter with hydrogen at 450
o
C and 200-250 atm pressure for 2h.
The coal undergoes hydrogenation to form saturated hydrocarbons that decompose at
prevailing high temperature and pressure to yield low boiling liquid hydrocarbons. The
vapour leaving the chamber is condensed to get a liquid resembling crude oil. This is
subjected to fractional distillation to give gasoline, middle oil and heavy oil. Middle oil is
again hydrogenated to obtained gasoline. The gasoline so obtained contains 74% power
alcohol, 22% aromatics and 4% olefins. Yield is 60%.
/
(Paste of coal dust, + H2 → Mixture of hydrocarbons ⎯⎯⎯⎯⎯⎯⎯⎯ crude oil
Heavy oil and catalyst)

GCEK, Bpatna, Dr. PK Panigrahi Page 18

Fischer-Tropsch method:

In this method, coke is converted into water gas (CO + H2) by passing steam over red hot
coke.

C + H2O ⎯⎯⎯ CO + H2
A mixture of water gas and hydrogen is purified by passing through Fe2O3 (to remove H2S)
and then through a mixture of Fe2O3 + Na2CO3 to remove organic Sulphur compound.
The purified gas is compressed to 5.25 atm and then passed through a catalytic converter
maintained at about 200-300 oC. The catalyst consists of a mixture of cobalt (100 parts)
Thorium (5parts), Magnesia (8 parts) and Keiselghur earth (is a soft, porous, silicious
sedimentary rock, that easily crumbled to powder). A mixture of saturated and unsaturated
hydrocarbons is formed. All the reactions are exothermic.
The vapours formed are passed through a cooler, where liquid resembling crude oil is
obtained. This is then subjected to fractional distillation to yield gasoline, diesel and heavy
oil. The heavy oil is reused for cracking to obtained more gasoline.

Gaseous Fuels
Natural gas:
It is associated with petroleum in nature and occurs near coal mines and oil fields. It is a
mixture of methane and higher hydrocarbons such as n-propane, n-butane, isobutene, iso-
pentane etc. Natural gas associated with crude oil, is termed as dry gas. Wet gas has higher
calorific value than dry gas.
Composition of Natural gas:
CH4= 70-90%, C2H6= 5-10%, H2= 3%, Remaining CO and CO2
3
Calorific value = 12000-14000 kcal / m
Application: As fuel in domestic and industrial sector as well as in motor vehicles.
As important ingredient in manufacture of various fertilizers, plastics, pharmaceuticals,
fabrics and antifreeze agents.

Compressed Natural Gas (CNG):

It is obtained by compressing natural gas to a high pressure of about 1000 atm. It is used as
substitute for petrol and diesel. It is a very clean and economical fuel. It is better than LPG
because it is safer than gasoline and has high ignition temperature than gasoline and diesel.

GCEK, Bpatna, Dr. PK Panigrahi Page 19

Lighter than air and disperses easily in air and minimize the risk of ignition. LPG is heavier
than air and settle at the ground and hence, risky.
CNG produces lesser CO on combustion and do not emit forbidden pollutants such as SO2,
SO3, HCHO etc.

LPG (Liquefied Petroleum Gas):

LPG is used as fuel in domestic, industrial vehicles. It is obtained as a by-product during
cracking of heavy oils or from natural gas. It is bottled in cylinders under high pressure and
ethyl mercaptan is added to detect leakage.

Composition: n-butane, i-butane, butylenes and propane

Properties: Colourless, 1.5-2 times heavier than air, Non toxic and non poisonous gas
High calorific value of about 27800 kcal / m3
It is nearly three times the calorific value of natural gas and 7 times greater than that of coal
gas.

Coal gas:
It is obtained when coal is heated in absence of air at about 1300 oC in coke. The fuel used
for the purpose is a mixture of producer gas and air.
13000C
Coal ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ Coke + coal gas

Tar, NH3, naphthalene and benzene are removed by passing through water, cold water,
petroleum respectively. H2S is removed by passing it over moist ferric oxide.
Fe2O3 + H2S → Fe2S3 + 3H2O
Fe2S3 + 9O2 → Fe2O3 + 6SO2
Coal gas is a colourless gas having characteristic odour is lighter than air and burns with long
smoky flame.
Composition: H2=40%, CH4=32%, CO=7%, C2H2=2%, C2H4=3%, N2=4%, CO2=1%
Calorific value: 4900 kcal / m3
Uses: As illuminants in citis and towns. As Fuel. As raw material for NH3 production.

GCEK, Bpatna, Dr. PK Panigrahi Page 20

Producer gas:
Composition: CO = 22-30%, H2 = 8-12%, N2 = 52-55%, CO2 = 3%
1300 kcal / m3
Calorific value: 900-1300
It is insoluble in water and poisonous in nature.
Uses: As reducing agent in metallurgical operations.
operat used as fuel in the muffle ffurnace and
retorts.
Production:
It is resulted from the incomplete combustion of coal or coke in a partly closed generator
generator,
called gar producer.. It is made by admitting a mixture of air and steam to the bottom of the
gas producer. Upon
pon reaching the combustion zone, the reaction occurs as:

C + O2 ⎯⎯ CO2 (exothermic reaction)

The hot gases from the combustion zone heat the fuel in the
th reduction zone and the following
reaction takes place:
C + O2 → 2CO (endothermic reaction)
C + H2 O → CO + H2 (endothermic reaction)

Figure 3.5: Gas producer for manufacture of producer gas

gas.

GCEK, Bpatna, Dr. PK Panigrahi Page 21

Water gas:
Production:: The principle involved
involve is same as in making producer gas, except in water gas,
the air and steam are blown in an alternate intervals over a red hot coke at about 10000C.
C + H2 O → CO + H2 (endothermic reaction)
(Water gas)

Figure 3.6: Water gas plant.

Composition: H2 = 51%, CO = 41%

41%, N2 = 4%, CO2 = 4%
Calorific value: 2800 kcal / m3
Water gas burns with blue flame, hence it is termed as blue gas.
Uses: As fuel is Fischer-Tropsch
Tropsch process for manufacture of synthetic petrol.
Also used for the manufacture of methanol.

Kerosene gas:
It is obtained by cracking kerosene oil.
Composition: CH4 = 25-30%, H2 = 50-55%, CO = 10-15%, CO2 = 3%
Calorific value: 4500 kcal / m3
Uses: As laboratory gas, used
sed to improve calorific value of water gas and these two gases are
called carburetted water gas.

GCEK, Bpatna, Dr. PK Panigrahi Page 22

Production: A stream of kerosene oil is continuously allowed to fall in a red hot bottom of
the retort resulting in cracking of the oil into a number of lower gaseous hydrocarbons.
C12H26 → (CH4+C2H6+C2H4+C2H2+C3H8+C3H6) + CTar
(Kerosene oil) (mixture of hydrocarbons)
Tar is removed by passing through water tank.

References:

1. Wiley Engineering Chemistry, second edition, Wiley India Pvt. Ltd.

2. Engineering Chemistry- Fundamentals and applications, by Shikha Agarwal,
Cambridge University Press

GCEK, Bpatna, Dr. PK Panigrahi Page 23