4.

CHEMICAL FUELS
INTRODUCTION : Fuel is a combustible substance, containing carbon as main
contitnent, which on proper burning gives large amount of heat, which can be
used economically for domestic and industrial purposes. Wood, Charcoal, Coal,
Kerosene, Petrol, Diesel,, Producer gas, Oil gas, etc. are some of such fuels.
CLASSIFICATION OF FUELS
Chemical Fuels

Solid Liquid Gaseous Fuel

Primary / Natural Secondary / Prepared Primary Secondary Primary Secondary

i) Solid Fuels
(a) Natural Wood, Peat, Lignite, Bituminous and Anthracite
coal.
(b) Secondary / Prepared Wood, Charcoal, Coke.
ii) Liquid Fuels
(a) Natural Petroleum
(b) Secondary Tar, Kerosene, Diesel, Petrol, Fuel oil,
Gasoline, etc.
iii) Gaseous Fuel
(a) Natural Natural Gas
(b) Prepared Producer gas, Water gas, Coal gas and Blast
furnace gas, Bio gas
CHARACTERISTICS OF A GOOD FUEL
i) High Calorific Value : A fuel should posses high calorific value, since the
amount of heat liberated and temperature attained thereby depends upon
the calorific value of fuel.
ii) Moderate Ignition Temperature : Ignition temperature is the lowest
temperature to which the fuel must be preheated so that it starts burning
smoothly. Low ignition temperature is dangerous for storage and transport
of fuel, since it can cause fire hazards on the other hand, high ignition
temperature causes difficulty in igniting the fuel but the fuel is safe during
storage, handling and transport. Hence, an ideal fuel should have
moderate ignition temperature.

1
iii) Low Moisture Content : The moisture content of the fuel reduces the
heating value and involves in a loss of money. Hence, fuel should have
low moisture content.
iv) Low Non-combustible Matter Content : After combustion, the
non-combustible matter remains generally in the form of ash or clinker.
Hence, a fuel should have low content of non-combustible matter.
v) Products of Combustion Should Not be Harmful : Fuel, on burning
should not give out objectionable and harmful gases. In other words, the
gaseous products of a combustion should not pollute the atmosphere.
CO2, SO2, H2S, PH3, etc are some of the harmful gases.

vi) Low Cost : A good fuel should be readily available in bulk at a cheap rate.
vii) Easy Transportation : Fuel must be easy to handle, store and transport
at a low cost. Solid and liquid fuels can easily be transported from one
place to another. On the other hand, transportation of gaseous fuels is
costly and can even cause fire hazards.
viii) Combustion Should be Easily Controlled : i.e. combustion of the fuel
should be easy to start, or stop, when required.
ix) Storage cost in bulk should be low.
x) Should burn in air with efficiency without much smoke.
xi) In case of solid fuel, the size should be uniform so that combustion is
regular.
SOLID FUELS
ADVANTAGES :
(i) They are easy to transport.
(ii) They are convenient to store without any risk of spontaneous
explosion.
(iii) Their cost of production is low.
(iv) They possess moderate ignition temperature.
DISADVANTAGES :
(i) Their ash content is high.
(ii) Their large proportion of heat is wasted during combustion or their
thermal efficiency is low.
(iii) Their cost of handling is high.
(iv) Their calorific value is lower as compared to that of liquid fuels.
(v) They require large excess of air for complete combustion.

2
COAL
Coal is highly carbonaceous matter that has been formed as a result of
alteration of vegetable matter (eg. plants) under certain favourable conditions. It
is chiefly composed of C, H, N and O, besides non-combustible inorganic matter.
ORIGIN OF COAL
The origin of coal in nature is considered due to the gradual
decomposition of vast deposits of wood and other vegetable matter burried under
the earth long ago, under the influence of heat and pressure in the limited supply
of air. The nature of coal depends largely on the type of original deposits and on
the conditions which prevailed at the different stages during the transformation. In
the successive changes that occur hydrogen and oxygen are eliminated and the
product becomes richer in carbon with the result that calorific value is increased.
CLASSIFICATION OF COAL
Wood Peat Lignite Bituminous Anthracite
moisture content, H, O, N & S content, volatile matter
carbon content, calorific value & hardness
(1) PEAT
Peat is brown fibrous jelly like mass. It is regarded as the first stage in the
coalification of wood. Peat is mostly dug by manual labour. It is
uneconomical fuel, since it may contain as much as 80 - 90 % water but
on air drying (after 1 to 2 months drying) it burns freely. The average
composition of air dried peat is
C = 57 %
H = 6%
O = 35 %
ash content = 2.5 to 6 %
Its calorific value is about 5400 Kcal / kg. In India, peat deposits occur in
Nilgiri Hills (South India)
(2) LIGNITE
(brown coals) are soft, brown coloured variety of lowest rank coals, which
consist of vegetable matter decomposed more than that in peat. Lignite is
compact in texture, containing 20 to 60 % moisture and an air drying, it
breaks up into small pieces. Air dryed lignite contains

3
 C = 60 to 70 % ash 8%
O = 20 %
H = 5%
Lignite burn with long smoky flame. The calorific value is about 6500-7100
Kcal / kg.
In India lignite deposits occurs in Assam, Kashmir, Rajasthan and Madras.
(3) BITUMINOUS COAL : (COMMON COALS)
Black to dark grey coal. It is the most important variety of coal. It is soft
and is widely used as a fuel. It contains higher percentage of volatile
matter and thus when distilled, it gives off large quantity of gases and tar
that are used in many chemical industries. So commercially bituminous
coal is very important. Bituminous coal burns with a long bright smoky
flames. It has a higher carbon content than peat and lignite. Its
approximate composition is
C = 83.5 %
H = 5%
O = 5%
ash = 6.5 % calorific value is about 8300 Kcal / kg.
(4) ANTHRACITE
The last stage in coal formation is anthracite. It is very hard, dense, black
and brittle usually having a bright lustre. It contains the least amount of
volatile matter of all coals. It has the highest percentage of carbon and
leaves very little ash after it is burned. It burns with short blue flame.
C = 90 %
H = 3%
O = 2%
ash = 5% calorific value 8750 Kcal / kg.
ANALYSIS OF COAL
Analysis of coal is of two kinds ultimate and proximate. This is carried out
to assess the quality of coal.
Proximate Analysis : Proximate analysis involves in the following determination
(i) Moisture : About 1 gram of finely powdered air dried coal sample is
weighed in a crucible. The crucible is placed inside an electric hot air-oven
0 0
maintained at 105 C - 110 C. The crucible is allowed to remain in oven

4
 for 1 hour and then taken out, cooled in a desiccator and weighed. Loss in
weight is reported as moisture
L o s s in w t .
P e r c e n ta g e o f m o is tu r e x 100
w t . o f c o a l ta k e n
(ii) Volatile Matter : The dried sample of coal left in the crucible in (i) is then
covered with a lid and placed in an electric furnace maintained at 925
0
20 C. The crucible in taken out of the oven after 7 minutes of heating. The
crucible is cooled first in air, then inside a desiccator and weighed again.
Loss in wt. is reported as volatile matter on percentage basis.

L o s s in w t . d u e t o r e m o v a l o f v o la tile m a t te r
P e r c e n t a g e o f v o la tile m a t te r x 100
w t . o f c o a l s a m p le ta k e n

(iii) Ash : The residual coal in the crucible in (ii) is then heated without lid in a
0
muffle furnace at 700 50 C for hour. The crucible is them taken out,
cooled first in air, then in desiccator and weighed. Heating, cooling and
weighing is repeated till a constant weight is obtained. The residual is
reported as ash on percentage basis thus % of ash.
w t . o f a s h le f t
x 100
w t. o f c o a l ta k e n

(iv) Fixed Carbon : Percentage of fixed carbon = 100 % of (moisture +

volatile matter + ash)
ULTIMATE ANALYSIS
The ultimate analysis consists of the determination of percentage of
carbon, hydrogen, nitrogen, sulphur and ash by direct analytical method as
applied in organic compounds.
(i) Carbon and Hydrogen : About 1 - 2 gram of accurately weighed coal
sample is burnt in a current of oxygen in a combustion affartas. C and H of
the coal are converted into CO 2 and H2O respectively. The gaseous
products of combustion are absorbed respectively in KOH and CaCl 2
tubes of known weights. The increase in weights of there are then
determined
C + O2 CO2

12 44
H2 + O 2 H2O

2 16 18

5
 2 KOH + CO2 K2CO3 + H2O

CaCl2 + 7 H2O CaCl2 + 7 H2O

I n c r e a s e in w t . o f O H t u b e x 12 x 100
P e rc e n ta g e o f C
w t . o f c o a l s a m p le ta k e n x 44
I n c r e a s e in w t . o f C a C l 2 tu b e x 2 x 100
% ofH
w t . o f c o a l s a m p le ta k e n x 18

(ii) Nitrogen : Kjeldahls Method. About 1 gram of accurately weighed

powdered coal is heated with conc. H 2SO4 along with K2SO4 (catalyst) in
a long necked flask (called kjeldahls 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.
From the volume of acid used by NH 3 liberated, the % of N in coal is
calculated as follows.
V o lu m e o f a c id u s e d x N o r m a lit y x 1. 4
P e rc e n ta g e o f N
w t. o f c o a l ta k e n

(iii) Sulphur : (Eachka Method)

Sulphur is determined from the washing obtained from the known mass of
coal, used in a Bomb calorimeter for determination of a calorific value.
During this determination, S is converted into sulphate. The washings are
treated with BaCl2 solution, when BaSO4 is precipitated. This ppt. is
filtered, washed and heated to constant weight.
w t . o f B a S O 4 o b ta in e d x 32 x 100
P e rc e n ta g e o f S
233 x w t . o f c o a l t a k e n in b o m b c a lo r im e t e r

(iv) Ash : Ash determination is carried out as in proximate analysis.

(v) Oxygen : Oxygen is obtained by difference
percentage of O = 100 % of (C + H + N + S + Ash)
SIGNIFICANCE OF CONSTITUENTS
(i) Moisture : Moisture in coal evaporates during the burning of coal and it
takes some of the liberated heat in the form of latent heat of evaporation.
Therefore, moisture lowers the effective calorific value of coal. Moreover, it
quenches the fire in the furnace. Hence, lesser the moisture content,
better the quality of coal as a fuel.
(ii) Volatile Matter : A high volatile matter content means that a high
proportion of fuel will distill over as gas or vapour a large proportion of

6
 which escape unburnt. So, higher volatile content is undesirable. A high
volatile matter containing coal burns with a long flame, high smoke and
has low calorific value. Hence lesser the volatile matter, better the rank of
coal.
(iii) Ash : Ash is useless, non-combustible matter and it reduces the calorific
value of coal. Moreover, ash causes the hindrance to the flow of air and
heat, thereby lowering the temperature.
Hence lower the ash content, better the quality of coal. The presence of
ash also increases transporting, handling and storage costs. It also
involves additional cost in ash disposal.
(iv) Fixed Carbon : Higher the percentage of fixed carbon, greater is its
calorific value and better the quality of coal. Greater the % of fixed carbon
smaller is the % of volatile matter. This also represents the quality of coal.
Hence, high % of fixed carbon is desirable.
(v) Carbon and Hydrogen : Greater the % of carbon and hydrogen, better is
the coal in quality and calorific value. However, hydrogen is mostly
associated with the volatile matter and hence, it affects the use to which
the coal is put.
(vi) Nitrogen : Nitrogen has no calorific value and hence its presence in coal
is undesirable. Thus a good quality of coal should have very little nitrogen
content.
(vii) Sulphur : Sulphur although contributes to the heating value of coal, yet
on combustion produces acids (SO 2 & SO3) which have harmful effects of
corroding the equipments and also causes atmosphere pollution sulphur is
usually, present to the extent of 0.5 to 3.0 % and derived from ores like
iron, pyrites, gypsum, etc. mines along with the coal.
(viii) Oxygen : Oxygen content decreases the calorific value of coal. High
oxygen content coals are characterized by high inherent moisture, low
calorific value, and low coking power. Moreover, oxygen is in combined
form with hydrogen in coal and thus, hydrogen available for combustion is
lesser than actual one. An increase in 1 % oxygen content decreases the
calorific value by about 1.7% and hence oxygen is undesirable. Thus, a
good quality coal should have low % of oxygen.
CALORIFIC VALUE
The most important property of a fuel is its calorific value. When a fuel is
burnt, heat is produced. The calorific value of any fuel is a measure of heat that
can be defined as the number of units of heat produced by the complete
combustion of unit quantity of fuel when the products of the combustion are
coded to the initial temperature of the combustible mixture.

7
 Units Cal / gram
KCal / kg
In case of gasous fuel Cal / litre
It is defined as the no. of calories of heat evolved by the complete
combustion of one litre of the gasous fuel saturated with water at a pressure of
76 cm of mercury.
In MKS system c.v. of a gasous fuel is the no. of kilo calories of heat
evolved by the complete combustion of 1 cubic meter of the gasous fuel at 760
0
mm. pressure when the products of combustion are cooled down to 15 C.
GROSS AND NET CALORIFIC VALUE
Calorific value of a fuel can be quoated in two ways
(i) Gross or Higher calorific value and
(ii) Net or Lower calorific value
Gross C. V. : After the complete burning of unit amount of fuel, if the products of
combustion are cooled back to the initial temperature of the combustible mixture
and water formed during the combustion is condensed giving up its latent heat of
vaporization the calorific value is then quoated as gross or higher calorific value.
Net : On the other hand, if the products of combustion are cooled to initial
temperature of the combustible mixture, but water is considered to remain as a
vapour, then the calorific value is known as net or lower calorific value.
CALCULATION OF LOWER CALORIFIC VALUE
Net calorific value = Gross C. V. Latent heat of condensation of the
water vapour produced.
= Gross C. V. (Mass of hydrogen per unit weight of the fuel burnt x 9 x
Latent heat of vaporization of water.
1 part by weight of hydrogen gives 9 part by weight of water as follows
H2 + O2 H2O

2 gram 16 g 18 g
1 gram 8 gram 9 gram
The latent heat of steam is 587 Cal / gram (or KCal / kg)
Thus,
H
N e t C . V . G ro s s C . V . 9 x x 587
100

8
 = Gross C.V. 0.09 x H x 587
where H = % of hydrogen in the fuel.
CALCULATION OF C.V. BY DULONGS FORMULA
Sometimes, experimental determination of calorific value of a fuel is not
possible. Then the calorific value can be obtained by calculation. The calorific
value can be theoritically determined from the ultimate analysis by Dulongs
Formula, according to which it is assumed that heat evolved comes from the
combustion of carbon, hydrogen and sulphur present in the fuel and the total
heat evolved is equal to the sum of the quantity of heat evolved by the
combustion of individual constituent elements present. The calorific value of
these constitent elements is given as under
Calorific value of carbon = 8080 Cal / gram
Calorific value of hydrogen = 34,500 Cal / gram
Calorific value of sulphur = 2250 Cal / gram
Since calorific value of a fuel is assumed as the sum of the calorific values
of each constitiment element, let Q be the C.V. of fuel in Cal / gram
Then,
0
Q Cal / gram = 8080 C + 34,500 H + 2250 S
8

Where C, H, O and S are expressed as the fractional weight of carbon,

hydrogen, oxygen and sulphur respectively obtained by the analysis of 1 gram of
the fuel. In the above equation the expression represent the available hydrogen.
It is assumed that any oxygen present in the fuel unites with hydrogen to form
water and so some of the heating effect of hydrogen is diminished. Since 8 parts
by weight of oxygen combine with 1 part by weight of hydrogen so the actual
heating value of hydrogen is obtained by the above expression.
Though above equation is established on the approximate assumption but
the results obtained are quite appreciable when compared with the results
obtained by experimental determinations.
AMOUNT OF AIR REQUIRED FOR COMPLETE COMBUSTION
(i) Combustion of Carbon :
C + O2 CO2

12 g 32 g 44 g
12 gram carbon require 32 gram oxygen.

9
 32
1 g r a m c a r b o n r e q u ir e s
12
32 8
C g r a m c r a b o n r e q u ir e s x C C
12 3
(ii) Hydrogen
H 2 + O2 H2O

2g 16 g 18 g
16
For H gram hydrogen oxygen required = H 8 H
2
(iii) Sulphur
S + O2 SO2

32 32 64

For S gram sulphur S gram oxygen

8
total oxygen required = C 8 H S
3

if 0 gram oxygen is present in fuel itself then

8
C 8H S O g ra m o x y g e n
3

23 % or 21 %
100 8
C 8 H O g r a m a ir
23 3

LIQUID FUELS
Advantages :
(i) Can easily be transported through pipes but care must be taken to store
them in closed containers only.
(ii) Quick combustion takes place, and it can be controlled or stopped when
needed.
(iii) Lesser handling cost is required.
(iv) No ash problem and burning is clean but high carbon and aromatic liquid
fuels may produce smoke.

10
(v) They can be used in internal combustion engine.
(vi) Calorific value is higher.
(vii) Their thermal efficiency is higher than that of solid fuels.
PETROLEUM or Crude Oil : (Petra = rock; oleum = oil)
Petroleum is a dark greenish brown, viscous oil found deep in earths
crust. It is composed mainly of various hydrocarbons (like straight chain paraffins,
cycloparaffins or naphthalenes, olefins and aromatics) together with small
amounts of organic compounds containing oxygen, nitrogen and sulphur. The
average composition of crude petroleum is
C = 79.5 % to 87.1 %
H = 11.5 to 14.8 %
S = 0.1 to 3.5 %
N+O= 0.1 to 0.5 %
ORIGIN
According to modern theory, petroleum has resulted from the partial
decomposition of marine animals, and vegetable organisms of pre-historic
forests. Changes in earth (like Volcanos) had burried these materials
underground, where they have been subjected to intense pressure and heat,
during the ages of time. The conversion of these materials into various
hydrocarbons has been going on either under the influence of radioactive
substances like uranium or by the bacterial decomposition, under anaerobic and
strongly reducing conditions and temperature under high pressure.

CLASSIFICATION

The chemical nature of the crude petroleum varies with the part of the
world in which it is found. There appears however to be three principle varieties :

(1) Paraffinic base type crude is mainly :

Composed of saturated hydrocarbons from CH 4 to C35 H72 and a little of
the naphthalenes and aromatics. The hydrocarbons from C 18 H38 to C35
H72 are semi solids; called waxes.

(2) Asphaltic : Asphaltic base type crude contains mainly cycloparaffins or

naphthalenes with smaller amount of paraffins and aromatic
hydrocarbons.

11
 (Naphthalene) (methyl naphthalene)
(3) Mixed base type crude contains both paraffinic and asphaltic
hydrocarbons and are generally rich in semi solid waxes.

REFINING OF PETROLEUM

Petroleum as comes from the ground is a

viscous, dark coloured liquid containing a lot of
impurities (eg. sand, brine, etc.). It has
unpleasant smell because of the presence of
sulphur compounds. The technically it is called
as crude oil.

Crude oil is a mixture of hydrocarbons

(aliphatic, alicyclic, and aromatic) along with
small amount of nitrogen, sulphur and oxygen
compounds. Crude oil as such is of little importance. However it can be
separated into a number of useful fractions by fractional distillation. This process
of dividing petroleum into different useful fractions with different boiling ranges is
called refining of petroleum.
0
The crude oil is heated to about 400 C in an iron retort, whereby all
volatile constituents, except the residue are evaporated. The hot vapours are
then passed up a fractionating column, which is a tall cyclindrical tower
containing a no. of horizontal stainless steel trays at short distances. Each tray is
provided with a small chimney, covered with a loose cap. As the vapours go up,
they become gradually cooler and fractional condensation takes place at different
heights of column. Higher boiling fraction condenses first while the lower boiling
fractions turn by turn.

12
 Various principal fractional products thus obtained are given in table

Name of Boiling Approx. composition in Uses

fraction range term of h/c contents
1 Petroleum ether 0 C5 - C7 As a solvent
30 - 70 C
2 Gasoline or 0 C5 - C9 As motor fuel solvent
40 - 120 C
Petrol C.V. - 11,250 KCal/kg and in drycleaning

3 Naphtha or 0 C9 - C10 As solvent and in

120 - 180 C
solvent spirit drycleaning
4 Kerosene oil 0 C10 - C16 As an illuminant, jet
180 - 250 C
C.V. - 11,000 KCal/kg engine fuel

5 Diesel oil 0 C10 - C18 Diesel engine fuel

250 - 320 C
C.V. - 11,000 KCal/kg
6 Heavy oil this on 0 C17 - C30 For getting by
320 - 400 C
refracionation cracking process
gives - petroleum
jelly, grease,
lubricating, wax
7 Residue oil 0 C30 and above Water proofing of
Above 400 C
roofs, and road
making

0
(1) Gasoline or Petrol : Gasoline or petrol is obtained between 40 - 120 C
and is a mixture of hydrocarbon such as C 5 H12 (pentane) to C8 H18
(octane). Its approximate composition is
C = 84 %; H = 15 %; N + S + O = 1 %
Its calorific value is about 11,200 Kcal / kg. It is highly volatile inflammable
and used as fuel for internal combustion engines of automobiles and
aeroplanes.
0
(2) Kerosene Oil : is a fraction obtained between 180 - 250 C and is a
mixture of hydrocarbons such as C 10H22 (decane) to C16H34
(hexadecane). Its approximate composition is C = 84%, H = 16%. With
less than 0.1% S. Its specific gravity is 0.75 - 0.85. Its calorific value is
11,000 KCal/kg. Due to high boiling point range, kerosene does not
vaporise easily. It is used as domestic fuel in stove, as jet engine fuel and
for making oil gas.

13
 0
(3) Diesel Oil : is a fraction obtained between 250 - 320 C and is a mixture
of C15H32 to C18H38 hydrocarbons. Its density is 0.86 to 0.95. Its
calorific value is about 11,000 KCal/kg. It is used as a diesel engine fuel.
LIQUEFIED PETROLEUM GAS (LPG)
When light consensable hydrocarbons gases such as propane (C 3H8)
and butane (C4H10) obtained as a by-product of the refining of petroleum, are
stored under pressure in containers, they are liquefied and then known as LPG.
LPG consist of hydrocarbons of such volatility that they can exist as gases
under atmospheric pressure but are readily liquefied under pressure. The
composition of LPG varies slightly according to its use
A typical composition of LPG is below :
Ethane (C2H6) 1.8 %

Propane (C3H8) 94.1 %

Propene (C3H6) 2.8 %

Butane (C4H10) 1.3 %

Mercptans, sulphides, disulphides or other organic compounds of sulphur

are added in small amount as a warning agent so that the smell will indicate the
presence of some leakage in the system.
LPG is an important fuel for domestic use. It is also used for certain
industrial purposes such as heat treatment and oxy flame cutting of metals, metal
spraying and as a fuel for portable equipment.
CHEMICAL STRUCTURE AND KNOCKING
When gasoline or any other fuel is used to operate an engine, it burns with
air inside the cylinder in a very rapid and haphazard way with the result that the
pressure inside the chamber is at once increased. The rapid rise in pressure sets
up vibration of gases, the cylinder walls and other metallic surfaces giving a
distinct knock or noise. The tendency of a fuel, to knock depends upon the
engine, engine speed, nature of the fuel, and air fuel ratio, etc. The knocking in
the engine causes a loss in power with the result the efficiency of the engine
decreased and hence it is harmful.
Under high compression it was observed that certain types of straight run
gasoline caused knocking while under the same conditions cracked gasoline
showed less tendency to knock. Thus the cracking process also increases the
resistance of gasoline to knock in addition to its main aim of increasing the yield
of gasoline for which purpose it was originally devised.

14
 The phenomenon of knocking is not yet fully understood. However, it has
been found that the tendency of a gasoline to knocking depends upon the nature
and structure of hydrocarbons present in the gasoline, in general the tendency to
knockfall off with change in the nature of the fuel as follows :
Straight chain paraffins > Branched chain paraffins > Olefins >
Naphthalenes > Aromatic hydrocarbons
n-paraffins have poor resistance to knocking and resistance decreases
with increasing length of the hydrocarbon chain. Branched chain paraffins have
better resistance to knocking than n-paraffins and resistance increases with
increasing no. of branches. In olefines, the resistance to knock increases as the
double bond approaches the middle of the carbon chain. In cracked gasoline it is
the presence of olefines isoparaffins and aromatic hydrocarbons that increase its
resistance to knocking. Knocking may also be prevented or minimized by adding
small amount of carbon compounds (anti knock compounds) viz tetraethyl lead
(TEL) to gasoline.
OCTANE NUMBER
The knocking quality of an automobile fuel is measured in terms of the so
called octane number. The hydrocarbon isooctane (2, 2, 4 -trimethyl pentane)
which has good resistance to knocking in highest compression motors, is
arbitrarily given the octane number of 100, and n-neptane with poor resistance to
knocking is given the arbitrary value of 0; the higher the octane number, the
better the fuel. All other fuels are compared with their mixture in suitable
proportions.
CH3 CH3
I I
H3C C CH2 CH CH3 CH3 CH2 CH2 CH2 CH2 CH2 CH3
I n - heptane
CH3 (octane no. = 0)
2, 2, 4 -trimethyl pentane (octane no. = 100)

Thus the octane no. of a gasoline is defined as the percentage of

isooctane present in a mixture of isooctane and n-heptane which matches the
fuel is in knocking. For example, a motor fuel is said to have an octane no. of 70,
when it matches in knocking property to a mixture of 30% n-heptane and 70%
isooctane. Modern good grade of gasoline has an octane no. of 80 which is
obtained by blending straight run gasoline with cracked gasoline and
hydrocarbons synthesis from refinery gases and adding a small amount of
tetraethyl lead.
In addition to tetraethyl lead (60%), small amounts of ethylene bromide
(26%), ethylene chloride (9%) and a red dye (2%) are also added. About 1 -3 ml
of this mixture named as ethyl fluid is added to a gallon of patrol to increase

15
antiknock properties. This type of gasoline is commonly known as leaded
gasoline.
ANTI KNOCK AGENTS
The mode of action of TEL in increasing the octane no. of gasoline may be
any one of the following :
(i) Tetraethyl lead decomposes to metallic lead. The cloud of so formed fine
lead particles acts as a shield between the unburnt charge and the
burning portions.
(ii) The finely divided lead particles act as the oxidation centres, thereby
making the combustion homogeneous and uniform.
(iii) The metal particles may act as deoxidisers and thus may inhibit the
formation of easily detonated peroxides.
(iv) The ethyl free radical, formed by the dissociation of TEL convert some of
the straight chain hydrocarbon to branched chain hydrocarbons, thus
lowering the knocking property of petrol.
The function of ethylene bromide is to remove the deposits of lead, formed
by the decomposition of TEL. Ethylene bromide reacts with lead to form lead
bromide which is volatile at engine temperature.
Br Br
I I
Pb + CH2 CH2 Pb Br2 + CH2 = CH2
ethylene bromide lead bromide

16