Energy Sources

[Link] Bhange
[Link] F.Y
Applied Chemistry-II
R4CH1011T

[Link]
 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
[Link]
 Classification of fuels:-
Classification based on the basis of occurrence:-

(i) Primary or Natural fuels - These are found in nature.

Ex. Wood, coal, peat, petroleum, natural gas etc.

(ii) Secondary or Artificial fuels - These are derived from primary fuels.
Ex. Kerosene, liquid petroleum gas (LPG), Coke, coal gas etc.

Classification on basis of physical basis:-

Primary and secondary fuels may also be divided into 3 classes namely
solid, liquid and gaseous fuels

[Link]
[Link]
 Characteristics of a Good fuels

(1) High calorific value:-

The calorific value of a fuel is the direct measure of its efficiency
of a fuel. If the calorific value of the fuel is high, the fuel is said to
be more efficient. Therefore, a good fuel must have high calorific
value.

(2) Moderate ignition temperature:-

Ignition temperature is the minimum temperature to which the
fuel is to be heated to start combustion. The fuel having very
low ignition temperature causes fire hazards during handling,
applications, storage and transportation. It is very difficult to
ignite the fuel with high ignition temperature. Hence moderate
ignition temperature is the most desired property of the fuel.

[Link]
(3) Low moisture content:-

The presence of high percentage of moisture in the fuel reduces

the efficiency of a fuel. It also increases the ignition temperature
and fuel cost. It decreases the calorific value since some of the
heat produced is utilized to vaporize the moisture. Hence the
moisture content in a good must be at negligible level.

(4) Low ash content:-

Formation of ash during combustion is due to the presence of

inorganic matter in the fuel. High ash content in the fuel causes the
following problems.
(a) lowering the calorific value.
(b) problems in disposal.
Hence, a good fuel must be free from ash content.

[Link]
(5) Combustion control:-

A large wastage of valuable fuel can be avoided by

(a) regulating the combustion rate properly and
(b) stopping the process immediately as when desired.

(6) Ease of availability:-

Fuel must be readily available in abundant and its cost must be

minimum.

(7) Harmless combustion products:-

A good fuel must not produce harmful combustion products like CO,
SO2, NO, H2S, smoke and clinkers during combustion. Therefore, a
good fuel must burn with clean flame without producing undesirable
by products.

[Link]
(8) Low cost.

(9) Easy to transport.

(10) Low storage cost.

(11) Uniform size:-

In the case of a solid fuel, the size should be uniform so that the
combustion is regular.

(12) A fuel must burn in air with efficiency without much smoke.

[Link]
[Link]
 CALORIFIC VALUE OF A FUEL
Defination:- It is defined as amount of heat liberated when unit
mass (solid) or unit volume(liquid) of a fuel is burnt in excess of air
or oxygen.
 In case of gaseous fuel it is necessary to specify both
temperature & pressure in order to define calorific value.
 This is because volume of gas changes with temperature &
pressure.

 Calorific value is expressed in SI units as

 Jkg-1 for solid fuel

 Jm-3 (joules per cubic meter) for liquid fuel

 Jm-3 at given temperature & pressure for gaseous fuel

[Link]
BRITISH THERMAL UNIT OF CALORIFIC VALUE:-

 It is the heat required to raise the temperature of 1lb of water

by 1 F at 65 F.

 It is also expressed in calories per gram (cal g-1 ), which is equal

to 4.187 Jg-1 or 1.8 BTU lb-1

[Link]
[Link]
Higher (Gross) calorific value (Q GROSS)/HCV
Defination:-
The total amount of heat liberated when unit mass or unit volume of
fuel is burnt in excess of air or oxygen & the combustion products
are cooled to room temperature.

Explanation:-
The fuel contains carbon & hydrogen. During combustion carbon gets
oxidized to CO2 and hydrogen to steam. When the products are
cooled to room temperature, the steam undergo condensation by
releasing its latent heat of condensation
HCV / Q GROSS = Heat of combustion + Latent heat of condensation

[Link]
Lower (Net) calorific value (Q NET)/LCV:-
Defination:-
The amount of heat liberated when unit mass of or unit volume of
fuel is burnt in excess of air or oxygen & the combustion products
are allowed to escape.
Explanation:-
When combustion products like steam & CO2 is allowed to escape
The calorific value does not include the latent heat of
condensation.

LCV / Q NET = HCV / Q GROSS – (latent heat of vapour formed)

[Link]
Sine 1 mole of H2 (2 g) produces 1 mole of H2O (18 g).
The mass of water formed is nine times the mass of hydrogen in
the fuel.

LCV / Q NET = HCV / Q GROSS – (latent heat of vapour formed)

= HCV / Q GROSS – (mass of H2× 9×latent heat of

steam)

LCV / Q NET = HCV / Q GROSS – (mass of H2 (in percent) ×

0.09×latent heat of steam)
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 )

[Link]
[Link]
[Link]
[Link]
[Link]
[Link]
[Link]
• Dulong's formula for calorific value from the chemical
composition of fuel is :

• HCV = 1/100 [8,080 C + 34,500 (H – O/8)+ 2,240 S] kcal/kg

• where C, H, O, and S are the percentages of carbon, hydrogen,

oxygen and sulphur in the fuel respectively.

• In this formula, oxygen is assumed to be present in combination

with hydrogen as water, and

• LCV = [ HCV - 9H/100 x 587] kcal/kg = [HCV - 0.09 H x 587]

kcal/kg

• This is based on the fact that 1 part of H by mass gives 9 parts of

H2O, and latent heat of steam is 587 kcal/kg.

[Link]
1) Find the N.C.V. of a fuel which contains: C = 80.5%, H = 4.9%, O =
12.8% S = 0.6%, N = 1.0%. (latent heat of steam = 600 cal/g)

[Link]
2) C=90%, H = 4%, O=3%, S = 0.8 %, and ash=2.2%. If latent heat of
vapourization is 540 Cal/g then calculate HCV and LCV of the fuel.
Answer HCV = 8540.55 Kcal/kg, LCV = 8346.15 Kcal/kg

[Link]
3) An anthracite coal sample has the following composition by
weight: C=90%, O=4%, N=1%, S = 0.5 %, and ash=5%. The NCV of the
fuel was found to be 8480 cal/g. Calculate HCV of the fuel in SI unit.
Answer: HCV=8727.56 cal/g, 3.65 X 10 7 J/Kg, H% =4.686]

[Link]
[Link] the gross and net calorific values of coal in SI units
having the following compositions, carbon = 85%, hydrogen = 8%,
sulphur = 1%, nitrogen = 2%, ash = 4%,latent heat of steam = 587
cal/gm.

[Link] the gross and net calorific values of coal having the
following compositions, carbon = 80%, hydrogen = 7%, sulphur =
3.5 %, nitrogen = 2.1 %, oxygen= 3% ash = 4.4 %

[Link]
DETERMINATION OF CALORIFIC VALUE OF SOLID/LQUID FUEL BY
BOMB CALORIMETER

Bomb

Calorimeter
Platinum Crucible

BOMB CALORIMETER
[Link]
 DETERMINATION OF CALORIFIC VALUE OF SOLID/LQUID FUEL BY
BOMB CALORIMETER

CONSTRUCTION:-

1) It consists of steel vessel (bomb) with air tight lid.

2) Inside the bomb a platinum crucible & ignition coil is placed.

The coil is connected to current source through wires.

3) The bomb has an inlet to introduce oxygen.

4) The bomb is kept in large insulated vessel called calorimeter.

5) The calorimeter has a Beckman’s thermometer & a mechanical

stirrer

[Link]
WORKING:-

1) A known amount of solid or liquid fuel is taken in air tight

bomb (vessel).

2) The bomb is now placed in the calorimeter containing known

amount of water.

3) The initial temperature (t1 oC) is noted. Oxygen is introduced

at 25 to 30 atmospheric pressure & fuel is ignited by passing
current.

4) The liberated heat is absorbed by water present in

calorimeter.

5) The water is stirred well & final temperature (t2 oC) is noted

[Link]
CALCULATION
1) Mass of fuel= x kg

2) Initial temperature of water = t1˚C

3) Final temperature of water = t2˚C

4) Rise in temperature of water = ( t2 – t1 ) = Δt˚C

5) Mass of water in calorimeter = W kg

6) Water equivalent of calorimeter = w kg = mass X Specific heat

7) Specific Heat of water = S Jkg-1 ˚C -1

8) Heat released by the fuel = heat absorbed by water & apparatus

Q GROSS = (W+w) ×S× Δt Jkg-1

x
[Link]
What is the significance of water equivalent in Bomb calorimeter
experiment? How this is measured?
Construction of Bomb Calorimeter involves metallic parts such as
stirrer, bomb, walls of calorimeter and also require a thermometer.
For calibration purpose, we consider a term “water equivalent”
instead of these heat absorbing materials.
Usually, Naphthalene and Benzoic acids are used as standards, using
the following formula to determine water equivalent.
W+w) ×Δt
HCV = x cal/g

[Link]
Calculation for correction:-
weight of the fuel sample taken = x g
Weight of water in the calorimeter = W g
Water equivalent of the Calorimeter, stirrer, bomb, thermometer = w g
Initial temperature of water = t10C
Final temperature of water = t20C
Higher or gross calorific value = L cal/g or Kcal/Kg
Heat gained by Calorimeter = (W+w) (t2-t1) cal
Heat liberated by the fuel = H cal
Heat liberated by the fuel = Heat gained by water and calorimeter
(W+w) (t2-t1) cal/g or Kcal/kg
H (GCV)=
x
[Link]
 Corrections:-

1) Fuse wire correction:-

The heat liberated as measured above includes the heat given out by
ignition of fuse wire used.
2) Acid Correction:-
Fuels containing S and N under high temperature and pressure of
ignition forms H2SO4 and HNO3 respectively
S + 2H + 2O2 H2SO4 + Heat

2N +2H+ 3O2 2HNO3 + Heat

So the measured heat also includes the heat given out during acid
formation.
The heat given out by acids is analyzed by washings or by titration
[Link]
The H2SO4 is determined by precipitation with BaSO4.
Correction for 1 mg of S is 2.25 cal; while for 1 ml of N/10 HNO3 is
1.43 cal
3) Cooling Correction:-
The time taken to cool the water in calorimeter from maximum
temperature to room temperature is noted. From the rate of cooling
(dt/minute) and the actual time taken for cooling (t minute),the
cooling correction dt x t is added to the rise in temperature.

(W + w) (t2 - t1 + cooling correction) – ( Acid + fuse wire correction)

H =
Mass of Fuel (x)

Limitation :- Only Solid and Liquid fuels can be measured

[Link]
1) Following is the data obtained in the determination of calorific
value of a bituminous coal sample using Bomb Calorimeter:

1) Mass of the coal sample fired = 0.945 g

2) Mass of water taken in the calorimeter = 2560 g
3) Water equivalent of the calorimeter = 450 g
4) Initial temperature of the water taken in the calorimeter = 18.32 °C
5) Final temperature of the water taken in the calorimeter = 20.77 °C
6) Fuse wire correction = 10 calories
7) Cooling correction = 0.05 °C
8) Acids correction = 60 calories
If the coal sample contains 5% hydrogen and the latent heat of
condensation of steam is 540cal/g, find out the gross and net calorific
values of this fuel sample.

[Link]
H.W) Following data is obtained in calorific value determination
using Bomb calorimeter:
1) Weight of fuel = 1.084 g
2) Weight of water taken in the calorimeter = 2000 g
3) Water equivalent of the calorimeter = 550 g
4) Rise in temperature = 3.1 °C
5) Cooling correction = 0.051 °C
6) Acid correction = 52.6 cal
7) Fuse wire correction = 2.8 cal
8) Cotton thread correction = 1.5 cal
Calculate the gross calorific value of the fuel

[Link]
H.W) The temperature of 950 g of water was increased from 25.5 °C
to 28.5 °C on burning 0.75 g coal in a Bomb Calorimeter. Water
equivalent of the calorimeter and latent heat of steam are 400 gm
and 587 cal /g respectively. If the fuel contains 5% H2, calculate the
net calorific value of the coal.

[Link]
2)In an experiment of Bomb calorimeter apparatus the following
data were obtained
i) Weight of coal burnt = 0.95g
ii) Weight of water = 2000g.
iii) Rise in temperature = 2.48ºC
iv) Cooling correction = 0.02ºC
v) Fuse wire correction = 10 calories
vi) Acid correction = 60 calories
vii) Calculate G.C.V. and N.C.V. of the coal in calories per gram.
( Specific heat of water = 0.35 cal/g/0c

[Link]
3) 0.87 g of a fuel sample was burnt in a bomb calorimeter and
analyzed. The weight of water taken in bomb is 2540 g and weight
of the bomb calorimeter is 4100 g, Specific heat (S) of the bomb
calorimeter apparatus is 0.095 cals/g/˚C. The rise in temperature of
water was observed to be 2.5˚C. The washings of the bomb on
analysis indicated the presence of 3.5 ml of N/10 HNO3, 6%
Hydrogen is present in this coal sample. Find the HCV and LCV of
the fuel sample.

[Link]
Bomb calorimeter analysis gave the following data in an experiment:
I. Wt. of fuel = 2 g
II. Wt. of calorimeter = 1030 g
III. Wt. of calorimeter + water = 3030 g
IV. water equivalent = 1000 g
V. Initial temp. of water = 11.635 0C
VI. Final temp. of water = 13.635 0C
VII. Cooling correction = 0.050 0C
VIII. Heat from fuse wire = 5 Cal.
Washing of the bomb on analysis indicated the presence of 2.0 mg of
BaSO4.
Calculate the HCV of the fuel.
[Link]
 COAL
 Coal is formed from fossilized remains of animals and plants hence
it is called as fossil fuel.

Coal is an important primary solid fuel that has been formed as a

result of alteration of vegetable matter under some favorable
conditions.

 The process of conversion of lignite to anthracite is called

coalification (or) metamorphism of coal.

Coal and its varieties (or) Ranking 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,
[Link]
(Moisture, volatile, H, O, N, S contents decreases)

Wood → Peat → Lignite → Bituminous coal → Anthracite

(Hardness, calorific value, carbon content increases)

[Link]
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.

C = 57%, H= 6%, O=35%, ash= 2.5-6%

[Link]
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. .

4. C = 60-70%, H= 5%, O=20

c) Bituminous coal:-

Bituminous coal is further sub-classified on the basis of its carbon

content into three types as:-

i) Sub- bituminous coal:-Black and smooth in appearance have 75 to

83% carbon content and its calorific value is about 7000kcal/kg.

[Link]
ii) Bituminous coal:- Carbon content is from 78 to 90% and calorific
value is from 8000 to 8500 kcal/kg

iii) semi-bituminous coal:- Carbon content is 90 to 95% and has

calorific value of about 8500 to 8600 kcal/kg

The Bituminous coal is heated strongly in the absence of air the dense
strong porous mass is metallurgical coke.
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.

[Link]
Classification of solid fuels & its calorific values

[Link]
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

Analysis of Coal

In order to asses the quality of coal, the following two types of

analysis are made.

I. Proximate Analysis

II. Ultimate Analysis

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

 This analysis gives the approximate composition of the main

constituents of coal.

 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. In an electrical ovan.
Percentage of moisture can be calculated from the loss in weight
of the coal sample as

[Link]
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,

[Link]
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

Determination of fixed carbon

It is determined by subtracting the sum of total moisture, volatile

and ash contents from 100.

[Link]
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. <
10%

[Link]
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.
Typical range of volatile matter is 20-35%

The coal with higher volatile content,

 Ignites easily (i.e : it has lower ignition temperature)
 Burns with long yellow smoky flame
 Has lower Calorific Value
Will give more quantity of coal gas when it is heated in absence
of air.
Hence, lesser the volatile matter, better is the quality of coal.

[Link]
Ash:-
 Ash is the combustion product of mineral matters present in the
[Link] consists mainly of SiO2 , Al2O3 and Fe2O3 with varying
amounts of other oxides such as Na2O, CaO, MgO etc.

 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.

[Link]
Typical range is 5 to 40%.
 High ash content in coal is undesirable because it
a) Increases transporting, handling, storage costs,
b) Is harder and stronger,
c) Reduces Calorific Value.
d) Hinder uniform air flow and heat flow, efficiency decreases.

g) The presence of ash also causes early wear of furnace walls,

burning of apparatus. The ash content is important in the
design of the furnace grate, combustion volume, pollution
control equipment and ash handling systems of a furnace.
sulfur : Sulphur corrodes chimney and other equipment such
as air heaters and economizers.
[Link]
Fixed Carbon:-

It is the pure carbon present in coal. Higher the fixed carbon

content of the coal, higher will be its Caorific Value.

[Link]
1) A sample of coal was analyzed as follows: Exactly 2.500g was
weighed into a silica crucible. After heating for one hour at 110°C, the
residue weighed 2.410g. The crucible next was covered with a vented
lid and strongly heated for exactly seven minutes at 950 ±20°C. The
residue weighed 1.78g. The crucible was then heated without the
cover, until a constant weight was obtained. The last residue was
found to weight 0.245g. Calculate the percentage results of the above
analysis.

[Link]
Numericals:-
A sample of coal was analyzed for content of moisture, volatile
matter, ash & fixed carbon content. From the following data,
calculate the percentage of the above quantities.
Weight of coal taken =2.5 g
Weight of coal after heating at 110∘C=2.368 g
Weight of coal after heating in covered crucible at 950∘C=1.75
∘ g
Constant weight obtained at the end of the experiment =0.95 g

[Link]
Selection of Coal:
For the selection of coal for different uses following properties
should be considered:

a) Calorific value: must be high, so that small quantity coal can

produce large quantity of heat. This will also reduce cost of
storage and handling.

b) Moisture content: must be low, as it reduces heating value/

calorific value of coal. Loss of money.

c) Ash content: must be low, non-combustible matter, reduces

heating value (1% ash means 1.5% heat loss). It increases cost of
storage, handling and disposal.

Composition and m.p. of ash are imp.

[Link]
Composition:
Important in metallurgical operations, affects metal and slag
composition, selection of proper flux etc.

Fusion temp. of ash: imp for coal used in boiler

 If constituents fuse at working temp. it form lumps (clinkers) on

‘fire grates’ which will restrict the air supply for combustion.

 coal particles can be embedded on the lumps thus causes loss of

fuel.

lumps can stick to the tube of boiler, reducing the heat transfer.

 low melting ashes (due to Na2O, MgO) form molten slag, which
penetrates the pores of refractory lining of boilers
[Link]
 Ashes spoil and reduce the lifetime of boilers

for common boilers, ashes present must be of high fusion temp.

d) Coal size: must be uniform, eases handling and combustion

process. Small particles with large chunks interfere the free
movement of air and gases.

e) Sulfur and phosphorous quantity: must be low, for

metallurgical purposes. Coke comes in contact with metal directly,
so its impurity may transfer directly to metal. Besides, gases
produced are not environment friendly and corrosive

[Link]
f) Coking quality : Coal on heating in absence of air (carbonization
of coal) if become soft, plastic and fused together to large mass----
called caking coals. Difficult to oxidise.
If coke become strong hard porous suitable for metallurgical
purpose --- -coking coal
No fusing effect --- free burning coal (non-coking coal)

g) Calorific intensity : “‘the maximum temp. reached, when the

coal is completely burnt in the theoretical amount of air.”
Depends on : (1) quantity, (2) nature, (3) specific heat of gaseous
products of coal combustion.
Heat liberated during combustion, preheats air and affect cal.
Intensity.

Theoretically, Flame temp. =

[Link]
 Liquid Fuels:- Petroleum
 Petroleum is the principle source of aliphatic organic compounds.

 It is a dark greenish brown highly viscous oil found in deep in the

earth’s crust.

 Usually oil is floating upon a layer of brine and has a layer of gas
on the top of it.

 It contains various hydrocarbons together with small amounts of

organic compounds having oxygen, nitrogen and sulfur.

 The average composition of petroleum is,

Carbon : 79.5 - 87.1%
Hydrogen: 11.5 - 14.8%;
Sulfur: 0.1 - 3.5%;
Nitrogen and Oxygen: 0.1-0.5%.
[Link]
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 (gasoline) 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.
[Link]
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.

[Link]
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.

[Link]
[Link]
The ratio of the gaseous volume in the cylinder at the end of the
suction stroke to the volume at the end of compression stroke of
the piston is known as the compression ratio.

The efficiency of an internal combustion engine increases with

the compression ratio.

“Knocking is a kind of explosion due to rapid pressure rise occurring

in an IC engine”.

[Link]
 However, successful high compression ratio is dependent on the
nature of the constituents present in the gasoline used.

In certain circumstances, due to the presence of some constituents

in the gasoline used, the rate of oxidation becomes so great that the
last portion of the fuel air mixture gets ignited instantaneously
producing an explosive violence known as knocking.

[Link]
 The knocking results in loss of efficiency, since this ultimately
decreases the compression ratio.
The phenomenon of knocking is not yet fully understood. However,
it is noted that the tendency of fuel constituents to knock is in the
following order:
Straight chain paraffins (n-paraffins) > branched chain paraffins (iso
paraffins) >olefins> cycloparaffins (naphthalenes) > aromatics.
Thus, olefins of the same carbon chain length possess better
antiknock properties than the corresponding paraffins and so on.

[Link]
Octane Number:-(Measurement of knocking in SI engines)

 The most common way of expressing the knocking characteristics of

a combustion engine fuel is by octane number introduced by Edger in
1972.

It has been found that n-heptane,

CH3−CH2−CH2−CH2−CH2−CH2−CH3, knocks very badly and hence, its
antiknock value has been arbitrarily given zero.

On the other hand, iso-octane (2,2,4 –trimethylpentane) gives very

little knocking, so its antiknock value has been given as 100.

“Thus, octane number (or rating) of a gasoline (or any other internal
combustion engine fuel) is the percentage of iso-octane in a mixture
of iso-octane and n-heptane”, which matches the fuel under test in
knocking characteristics.

[Link]
 Thus, if a sample of petrol gives as much of knocking as a mixture
of 75 parts of isooctane and 25 parts of n-heptane, then its octane
number is taken as 75. The octane ratings of some common
hydrocarbons are given in the table.

[Link]
 Fuels with octane rating greater than 100 are quite common
nowadays and they are rated by comparison with a blend of iso-
octane with tetra ethyl lead (TEL) which greatly diminishes the
knocking tendency of any hydrocarbon with which it is mixed. The
value of octane number in such cases is determined by extrapolation.

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.

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

[Link]
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.

[Link]
Diesel
It is relatively a high boiling point fraction of petroleum obtained
between 250 – 320 oC.

It is a mixture of hydrocarbons in terms of carbon atoms C15 - C18

Its calorific value is about 11,000 kcals/kg. It is used as fuel for

compression ignition engine.

Its antiknock value can be improved by doping with isoamylnitrate.

CI Engines:-
 In a CI engine, air is alone compressed. This raises the cylinder
temperature as high as 300 oC.

 Then the oil is injected or sprayed, which must ignite

spontaneously. Now combustion products expand and power stroke
begins
[Link]
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

[Link]
Cetane number (or) Cetane Rating:-

 Cetane number expresses the knocking characteristics of diesel.

Cetane (C16H34) has a very short ignition delay and hence its
cetane number is taken as 100. On the other hand, α- 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”.

[Link]
Chemical Structure and Knocking

 The knocking tendency in CI - engines increases as follows,

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.

Improvement of cetane number

 Centane number can be increased by adding additives called

dopes.

E.g.: ethyl nitrate, isoamyl nitrate

[Link]
[Link]
Comparison between Petrol and Diesel in Internal Combustion
Engines (ICE)

[Link]