Contents

1. Introduction
2. Classification of Fuels
i) Liquid fuel
ii) Solid fuel
iii) Gaseous fuel
3. Characteristics of good fuel
4. Unit of Heat
5. Calorific value
i) Gross calorific value
ii) Net calorific value
6. Determination of calorific value
i) Bomb calorimeter
ii) Dulong’s Method
7. Analysis of Coal
i) Ultimate analysis
ii) Proximate analysis
8. Biogas
 Introduction
A fuel is a substance that contains carbon and hydrogen undergoes combustion in presence of
oxygen to gives large amount of energy.
Fuel + O2 CO2 + H2O + Energy

Classification of Fuel
On the basis of occurrence fuel is classified into two categories; natural or primary fuels and
artificial or secondary fuels.
i) Natural/primary fuels: These fuels are naturally present.
ii) Artificial/ secondary fuels: They are synthesized by primary fuels.

Characteristics of Good Fuel

i) Fuel should have high calorific value.
ii) Must have moderate ignition temperature.
iii) Fuel should have low moisture content.
iv) Available in bulk at low cost.
v) Should not burn spontaneously.
vi) Fuel should burn efficiently, without releasing hazardous pollutants.
vii) Handling, storage and transportation should be easy.

Unit of heat

i) Calorie: it is the amount of heat required to raise the temperature of 1 gram of water
through one degree centigrade.
ii) British Thermal Unit (BTU): it is the amount of heat required to raise the
temperature of 1 pond of water to one degree Fahrenheit.
1 B.T.U. = 252 cal = 0.252 kcal
1 kcal = 3.968 B.T.U.
iii) Centigrade Heat Unit (CHU): it is define as the amount of heat required to raise
the temperature of 1 pond of water to one degree centigrade.
 1 kcal = 3.968 B.T.U. = 2.2 C.H.U.

Calorific value

Calorific value of fuel can be define as the amount of heat evolved when one unit mass or
volume of the fuel undergoes completely combustion in presence of oxygen.

i) High or gross calorific value (HCV or GCV): it is defined as amount of heat evolve
when one unit mass or volume of the fuel is completely burnt and combustible products
are cooled to room temperature (25oC or 77oF).
ii) Low or net calorific value (LCV or NCV): it is defined as amount of heat evolve when
one unit mass or volume of the fuel is completely bu rnt and combustible products are
permitted to escape. Therefore, net calorific value is lower than gross calorific value.

LCV = HCV – mass of hydrogen × 9 × latent heat of steam (587 kcal/kg)

LCV = HCV – latent heat of water vapour

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

Determination of calorific value

i) Bomb calorimeter

Bomb calorimeter is used to determine calorific value of solid and liquid fuels experimentally. A
bomb calorimeter contains a cylindrical bomb made by stainless steel. Combustion takes place in
this cylinder. The lid contains two stainless steel electrodes. Oxygen is supplied through oxygen
valve for combustion. The electrode is attached with a small ring which supports nickel or
stainless steel made crucible. The bomb is taken in a copper calorimeter which is surrounded by
air and water jacket in order to prevent heat loss by radiation. The copper calorimeter also
contains electrically operated stirrer and Beckmann’s thermometer (take reading with
temperature difference up to 0.01oC.
Working: In a crucible, a known amount of the fuel is placed in the nickel or stainless steel
crucible which is supported by a ring. A fine magnesium wire touches the fuel sample, which is
already connected to the electrodes. The bomb lid is lightly screwed and filled with oxygen at
about 25 atm pressure, is placed in copper calorimeter containing a known amount of water. The
electrically operated stirrer is driven and notes the initial temperature of water (T 1). After that
both the electrodes are connected to a battery to complete the circuit. The fuel sample is burn and
heat is liberated. To maintain the uniform temperature, water is continuously stirred and the final
temperature (T2) of water is noted.

Calculation:

Mass of fuel (solid or liquid)= x g

Mass of water taken = W g

Water equivalent of calorimeter = w g

Initial temperature of water in calorimeter = T1 K Final

(𝑾+𝒘)(𝐓𝟐−𝐓𝟏)
temperature of water in calorimeter = T2 K

𝒙
High or gross calorific value = cal/g

LCV = HCV – H/100 × 𝟗 × 587 kcal/kg

H = percentage of hydrogen in fuel

Corrections:
 (𝐖+𝐰)(𝐓𝟐−𝐓𝟏−𝐓𝐜)− (𝐂𝐬+𝐂𝐧+𝐂𝐟+𝐂𝐜)
HCV or GCV = 𝐱

Where

Tc = cooling corrections

Cs = Corrections for sulphuric acid (H2SO4) Cn =

Corrections for nitric acid (HNO3)

Cf = Corrections f or fuse wire

Cc = Corrections for cotton thread

ii) Theoretical calculation by Dulong’s formula:

The theoretical calculation of calorific value of a fuel can be approximately calculated by

Dulong’s formula, based on the percentage of the constituents (C, H, O and S) present in the
fuel.

As per Dulong’s formula

𝟏𝟎𝟎 [𝟖𝟎𝟖𝟎 𝑪 + 𝟑𝟒𝟓𝟎𝟎 (𝑯 ) + 𝟐𝟐𝟒𝟎

HCV = 𝑶

− 𝑺]
kcal/kg
𝟖

Where, C, H, O and S are percentage of carbon, hydrogen, oxygen and sulphur present in fuel. In
above formula the oxygen is assumed to be present in combined form with hydrogen or in form of
water (H2O).

H2 + 1/2O2 H2O

2g 16g 18g

1g 8g 9g

Total mass of hydrogen in fuel – fixed hydrogen

Total mass of hydrogen in fuel – (1/8) mass of oxygen in the fuel

∴ 8 part of oxygen combine with 1 part of hydrogen to form H2O.

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛 𝑖𝑛 𝑡ℎ𝑒 𝑓𝑢𝑒𝑙

Fixed hydrogen

8
=

Then the amount of hydrogen available for combustion

= total mass of hydrogen in fuel – fixed hydrogen

= [H-O/8]
LCV = HCV – H/100 × 𝟗 × 587 kcal/kg

Analysis of Coal

The quality of coal can be analyzed by two analysis: proximate and ultimate analysis.

Proximate analysis:

In this analysis moisture, volatile matter, ash and fixed carbon can be determined.

Moisture: A known amount of finely powdered air-dried coal sample is taken in crucible. The
crucible is placed inside an electric hot air-oven, at 105o to 110oC for
1 hour. The crucible is then taken out, cooled in desiccators and weighed. Difference in the
weight of sample gives the information about the weight loss due to removal of moisture.

𝐥𝐨𝐬𝐬 𝐨𝐟
𝐰𝐞𝐢𝐠𝐡𝐭 × 𝟏𝟎𝟎
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟
% of moisture =
𝐜𝐨𝐚𝐥 𝐭𝐚𝐤𝐞𝐧

Lesser the amount of moisture content, better the quality of fuel.

Volatile matter: The moisture free coal sample is taken in a crucible, covered with a lid and
placed in muffle furnace (electric furnace) at 950oC for 7 minutes and then remove the crucible
from the oven and cooled first in air, then cooled in a desiccator and weighed again. Loss in
weight is due to presence of volatile matter in coal sample.

𝐥𝐨𝐬𝐬 𝐨𝐟 𝐰𝐞𝐢𝐠𝐡𝐭

𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥 𝐭𝐚𝐤𝐞𝐧 × 𝟏𝟎𝟎

% of volatile matter =

Low quantity of volatile matter, better the quality of a coal.

Ash: The residual coal sample taken in a crucible and then heated without lid in a muffle furnace
at 700-750oC for an hour. The crucible is then taken out, cooled first in air, then in desiccators
and weighed again. The process of heating, cooling and weighing are repeated until a constant

𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟
weight is not obtained. The residue is reported as ash on percentage-basis.
× 𝟏𝟎𝟎
𝐫𝐞𝐬𝐢𝐝𝐮𝐞
of ash = 𝐥𝐞𝐟𝐭
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐝𝐫𝐲
%
𝐜𝐨𝐚𝐥 𝐭𝐚𝐤𝐞𝐧

Ash is non-combustible substance which reduces the calorific value of a coal. Therefore, low
quantity of ash contents, better the quality of a coal.

Fixed carbon: The fixed carbon percentage is determined by following equation

% of fixed carbon = 100 – (% of moisture + % of volatile matter + % of ash)

Greater the calorific value, higher the % of fixed carbon.

Ultimate analysis:

Ultimate analysis is involving the measurement of C, H, N, S, and O.

Carbon and hydrogen: In a combustion apparatus, about 1-2 gram of coal sample is burnt in a
current of oxygen to convert C and H into CO 2 and H2O respectively. The gaseous products CO2
and H2O are absorbed in KOH and CaCl 2 tubes of known weights, respectively. The increase in
weights of these (KOH and CaCl2) are then determined.

Calculation:

C + O2 CO2
12 32 44

2KOH + CO2 K2CO3 + H2O

H2 + 1/2O2 H2O
2 16 18

CaCl2 + 7H2O CaCl2.7H2O

𝐈𝐧𝐜𝐫𝐞𝐚𝐬𝐞 𝐢𝐧 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 × 𝟏𝟎𝟎

𝐊𝐎𝐇 ×𝟏𝟐 =
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥
% of carbon
𝐬𝐚𝐦𝐩𝐥𝐞 𝐭𝐚𝐤𝐞𝐧 ×𝟒𝟒

𝐈𝐧𝐜𝐫𝐞𝐚𝐬𝐞 𝐢𝐧 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟
𝐂𝐚𝐂𝐥𝟐 ×𝟐 = × 𝟏𝟎𝟎
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥
% of hydrogen
𝐬𝐚𝐦𝐩𝐥𝐞 𝐭𝐚𝐤𝐞𝐧 ×𝟏𝟖

Nitrogen: In Kjeldahl’s flask add accurately weighed powdered coal and heated with
concentrated H2SO4 and K2SO4 as a catalyst. The solution becomes clear when all the nitrogen is
converted into ammonium sulphate then it is treated with excess of NaOH which convert
ammonium sulphate into ammonia; the liberated ammonia is distilled over and absorbed in a
known volume of standard (N/10) H2SO4 solution. From the volume of H2SO4 used by liberated
ammonia, the percentage of Nitrogen in coal, calculated as follows:
NaOH
N2 + H2SO4 (NH4)2SO4 2Na2SO4 + 2NH3 + 2H2O

2NH3 + H2SO4 (NH4)2SO4

The volume of unused H2SO4 is then determined by titrating against standard NaOH solution
(N/10)
Calculation:

The amount of H2SO4 required to neutralize ammonia evolve from coal is calculated as
follows:

Amount of acid = N/10 V1 – N/10 V2

= 0.1 (V1 – V2) mili equivalents
= 𝟎.𝟏 (𝐕𝟏 –𝐕𝟐) equivalents
𝟏𝟎𝟎𝟎
Thus,
𝟎.𝟏 (𝐕𝟏 –𝐕𝟐)
× 𝟏𝟒
𝟏𝟎𝟎𝟎
Weight of N =

V1 = Volume of standard H2SO4 (N/10) solution V2 =

𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟
Volume of standard NaOH (N/10) solution Thus,
× 𝟏𝟎𝟎
𝐧𝐢𝐭𝐫𝐨𝐠𝐞𝐧
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟
% of nitrogen =
𝐜𝐨𝐚𝐥 𝐬𝐚𝐦𝐩𝐥𝐞

(V1 –V2)
0.1
10 × 14 × 100
00
=

% of nitrogen = 0.1 (V1 – V2) × 𝟏. 𝟒

Sulphur: A known amount of coal sample is burnt in bomb calorimeter in presence of oxygen.
After that, sulphur present in coal is converted into SO 2 and SO3. The ash obtained from the
bomb calorimeter, is extracted with dil. HCl. The washings (acid extracts) are treated with
Barium chloride solution and the sulphates are precipitate as Barium sulphate. This precipitate is
filtered, washed, dried and heated to obtain constant weight.

Calculation:

S 𝐒𝐎𝟐−
� BaSO4
32 � 233

𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐬𝐮𝐥𝐩𝐡𝐮𝐫 𝐚𝐭𝐨𝐦𝐢𝐜 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐬𝐮𝐥𝐩𝐡𝐮𝐫

𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐁𝐚𝐒𝐎𝟒 = 𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐚𝐫 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐁𝐚𝐒𝐎𝟒

𝟑𝟐
𝟐𝟑𝟑 × weight of BaSO4
Weight of sulphur =

𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐁𝐚𝐒𝐎𝟒
Thus,

% of sulphur =×𝟑𝟐
𝐨𝐛𝐭𝐚𝐢𝐧𝐞𝐝 × 𝟏𝟎𝟎
𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐨𝐚𝐥 𝐭𝐚𝐤𝐞𝐧 𝐢𝐧
𝐛𝐨𝐦𝐛 𝐜𝐚𝐥𝐨𝐫𝐢𝐦𝐞𝐭𝐞𝐫 ×𝟐𝟑𝟑
Ash: Percentage of ash calculated by method given in proximate analysis.
 Oxygen: It is calculated by subtracting the sum of total % of carbon, hydrogen, nitrogen,
sulphur and ash from 100.

Calculation:

% of oxygen = 100 – [% carbon + % hydrogen + % nitrogen + % sulphur +

% ash]
KNOCKING
In an internal combustion engine, a mixture of gasoline (petroleum) vapour and air is used as
a fuel. After the initiation of the combustion reaction by spark in the cylinder, the flame should spread
rapidly and smoothly through the gaseous mixture; thereby the expanding gas drives the piston down
the cylinder. 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”.
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. 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.
OCTANE NUMBER
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,
3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.
DIESEL OIL
 It is a relatively high boiling point fraction of petroleum obtained between 250 - 320oC.
 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 isoamyl nitrate.
CETANE NUMBER
In a diesel engine, the fuel is exploded not by a spark but by the application of heat and
pressure. Diesel engine fuels consist of longer chain hydrocarbons than internal combustion engine fuels.
In other words, hydrocarbon molecules in a diesel fuel should be as far as possible the straight chain
ones, with a minimum a mixture of aromatics and side chain hydrocarbon molecules.

Thus, cetane number is defined as “the percentage of hexa decane present in a mixture of hexa
decane and methyl naphthalene, which has the same ignition lag as the fuel under test”.
The cetane number of diesel fuel can be raised by the addition of small quantity of certain pre-
ignition dopes like ethyl nitrite, isoamyl nitrite, and acetone peroxide. 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.
The cetane number decreases in the following order:
straight chain paraffins > cycloparaffins > olefins > branched paraffins > aromatics.