3/1/2024

Fuels and Combustion

Sub Topics
 Fuels –Introduction, definition, classification, calorific value, Gross and
Net, theoretical calculation.
 Solid fuel- Coal- classification ,Analysis- Proximate and ultimate
 Carbonisation process-Metallurgical coke-Manufacture of coke by Otto
Hoffmann process.
 Liquid fuel-Petroleum processing and fractions-manufacture of synthetic
petrol by Bergius process. Knocking in SI and CI engines. Octane and
cetane number
 Gaseous fuels - CNG, LPG, Water gas and a producer gas.
 Power alcohol and Biodiesel
 Combustion- Introduction and theoretical calculation of air.- Problems
 Ignition Temperature and explosive range. Flue gas analysis by Orsat
method.

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INTRODUCTION
 Fuels –Introduction, definition, classification, calorific value, Gross and
Net, theoretical calculation.

 A fuel is a combustible substance containing carbon as the main
constituent which on proper burning gives large amount of heat that can
be used economically for domestic and industrial purposes. During the
process of combustion of a fuel, the atoms of carbon, hydrogen, etc
combine with oxygen with simultaneous liberation of heat. The
calorific value of a fuel depends mainly on the two elements.
 C + O2 CO2 + 94 kcals.
 2H2 + O2 2H2 O + 68.5 kcals.

 So, carbon compounds have been used for many centuries as the source
of heat and energy.
 The main source of fuel is coal and petroleum. These are stored fuels
available in earth's crust and are generally called fossil fuels because
they were formed from the fossilised remains of plants and animals.

Classification of Fuels
 1. Primary fuels which occur in nature as such, e.g. coal, petroleum and
natural gas.
 2. Secondary fuels which are derived from the primary fuels, e.g. coke,
gasoline, coal gas, etc.
 Both primary and secondary fuels may be further classified based upon their
physical state as
 (i) solid fuels (ii) liquid fuels and (iii) gaseous fuels.

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Solid fuel (e.g., wood,

coal)

Liquid fuel (e.g.,

Based on Physical
crude petroleum,
State
natural gasoline)

Gaseous fuel (e.g.,

Classifications natural gas)
of Fuels
Primary or natural
fuels (e.g., wood,
crude petroleum oil,
Based on coal)
occurrence Secondary or
prepared fuels (e.g.,
charcoal, gasoline,
water gas).
Engineering Chemistry (revised edition)
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Characteristics of a Good Fuel

1. It should ignite easily. The temperature of the fuel at which ignition starts
and continues to burn without further addition of heat is called ignition
temperature. It should be moderate for a good fuel. Very low ignition
temperature leads to fi re hazard and very high ignition temperature
disfavors the starting of fi re.
2. It should give out a lot of heat, that is, its specific heat should be high.
3. It should have low smoke and combustible matter such as ash. It should not
give out harmful combustion products. This property depends on the nature
of elements present in the fuel.
4. It should be inexpensive and readily available.
5. It should be easy to store and transport.
6. It should have low ash content. Ash reduces the calorific value of the fuel,
causes hindrance to the flow of air and heat, reduces the specific heat and
leads to unwanted disposable problems.
Engineering Chemistry (revised edition)
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Copyright©2014 Wiley India Pvt. Ltd. All Rights Reserved

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Calorific Value

Units

1. Mean British Thermal Unit (BTU)

2. Calorie (cal)

Gross and Net Calorific Values

1. Higher calorific value (HCV) or gross calorific value

2. Lower calorific value (LCV) or net calorific value

Engineering Chemistry (revised edition)

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CALORIFIC VALUE
Calorific value of a fuel is "the total quantity of heat liberated,
when a unit mass (or volume) of the fuel is burnt
completely."
Units of heat :
(1) 'Calorie' is the amount of heat required to raise the
temperature of one gram of water through one degree
Centigrade (15-16°C).
(2) "Kilocalorie" is equal to 1,000 calories. It may be defined as
'the quantity of heat required to raise the temperature of one
kilogram of water through one degree Centigrade. Thus: 1
kcal = 1,000 cal
(3) "British Thermal unit" (B.T.U.) is defined as "the quantity
of heat required to raise the temperature of one pound of water
through one degree Fahrenheit (60-61°F). This is the English
system unit.
1 B.T.U. = 252 cal = 0.252 kcal 1 kcal = 3.968 B.T.U.
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Calorific value Calorific value of a fuel is the total

quantity of heat liberated when one unit of fuel is burnt
completely. ‘
Gross or Higher calorific value (G.C.V or H.C. V): It is the
total quantity of heat liberated when one unit of fuel is
burnt completely and products of combustion has been
cooled to room temperature.
Net or Lower calorific value (N.C. V or L.C. V) ): It is the
total quantity of heat liberated when one unit of fuel is
burnt completely and products of combustion has been
permitted to escape.
L.C.V= H.C.V — Latent heat of water vapour formed Latent
heat of steam= 587 cal/gm

Theoretical calculation of calorific value

using Dulongs formula
H.C.V= [8080C + 34500(H-O/8)+ 2240 S]/100
kcal/kg
Where,
C= % of carbon in the fuel
H= % of hydrogen in the fuel
0= % of oxygen in the fuel
S= % of sulphur in the fuel
And
Calorific value of carbon= 8080 kcal/kg
Calorific value of hydrogen= 34500 kcal/kg
Calorific value of sulphur= 2240 kcal/kg

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L.C.V= H.C. V — Latent heat of water vapour

formed
=[H.C.V- 9H x 587/100] kcal/kg
=[H.C.V- 0.09H x 587] kcal/kg

This is based on the fact that 1 part of H by mass

gives 9 parts of H20 and latent heat of steam is 587
Kcal/Kg.

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Numerical problems based on calorific value

Problem 1: In a sample of coal containing carbon
60%, hydrogen 6%, sulphur 0.5%, nitrogen 0.2%
and ash 0.3%. Calculate the gross calorific value
(G.C.V) or Higher calorific value (H.C.V).

Problem 2: Calculate the gross calorific value

(G.C.V) and net calorific value (N.C. V) of a sample
of fuel containing carbon 85%, hydrogen 8%,
sulphur 1%, nitrogen 2% and ash 4%. Latent heat
of steam = 587 cal/g

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Experimentally Determination of
calorific value

Bomb calorimeter

1. For calorific values of solid and

liquid fuels
2. Known amount of fuel is burnt at
constant volume
3. Temperature of surrounding water
increases as heat is produced.
4. Quantity of heat and calorific values
are calculated.

Engineering Chemistry (revised edition)

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13

Solid Fuels – Coal

Formed from dead plants buried for several million years.

Peat The lowest carbon content

Brown variety containing 25-

Lignite 30% carbon and 60% moisture
content.
Types of Sub-bituminous
Black variety, 35-45% carbon
Coal coal

Hard black variety, 45-86%

Bituminous coal carbon.

The highest ranking coal,

Anthracite coal carbon content 86-97%.

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Pulverized Coal

Pulverized coal generally refers to coal in powdered form obtained by crushing,

grinding or pulverizing coal. As the surface area of pulverized coal is large, the
volatile matter present in it comes quickly in contact with air and is released,
enabling the combustion of fixed carbon. This increases the calorific value of the
coal and enhances its quality.

Engineering Chemistry (revised edition)

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15

Semi-Solid Fuels – Some Recent Advances

The term semi-solid fuel in modern context refers to non-volatile substances that
are environmentally safe and produce no hazardous waste on burning. These
have long shelf-life and their ignition can be easily started and stopped. The
conventional solid and liquid fuels are now being used as formulations in semi-
solid form to circumvent the problems associated with their use in the regular
form.

The use of coal is associated with many environmental problems, starting from
its excavation from mines to gaseous and fly ash emissions. To overcome these
problems, developing countries are transforming coal into gaseous or liquid fuel
formulations or converting it into low ash and low sulphur varieties. For example,
a solvent-refined, semi-solid form of coal has been prepared by suspending
pulverized coal in a solvent and treating it with hydrogen gas at high temperature
and pressure. The product compares well with high grade anthracite in
combustion properties, is free from ash and has high calorific value of 16000
BTU per pound.
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Liquid fuels – Petroleum

1. Petroleum is made from the remains of plants and animals buried millions
of years ago.
2. It is a non-renewable resource.
3. It contains straight or cycloparaffins.
4. Olefins
5. Aromatics
6. Other organic compounds containing N, O, S.

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Composition

Petroleum is a dark, greenish brown, viscous liquid that is found underground. It

comprises hydrocarbons such as:

1. Straight paraffins such as methane, ethane, propane, butane, isobutane,

pentane, hexane c or cycloparaffins cyclohexane, methyl cyclopentane
2. Olefins such as ethylene, butene, isobutene and acetylene, butadienes.
3. Aromatics such as benzene, naphthalene
4. Some organic compounds containing nitrogen, oxygen and sulphur.

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Production from Refining of Crude Oil

The petroleum obtained by mining is viscous and dark colored liquid. Due to the
presence of sulphur, it has an unpleasant smell. It also contains impurities of
sand, brine or sea water. Hence it is called crude oil.

The important steps involved are:

1. Fractional distillation to give various fractions.

2. Conversion of less desirable fractions to valuable products by processes like
cracking.
3. Treatment of fractions to remove undesirable substances.

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Fractional Distillation

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Fractions of petroleum

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21

Cracking

Cracking is decomposition of high molecular weight compounds (with high

boiling points) to low molecular weigh compounds (with low boiling points).

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Thermal
Cracking
Methods of
Cracking
Catalytic
Cracking

Engineering Chemistry (revised edition)

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23

Knocking

Knocking in Spark Ignition Engines and Octane Number

Petrol is used in spark ignition engines. The rapid compression of the fuel-air
mixture heats the engine, and it detonates without the spark being passed. This
causes a violent jerk to the piston giving a metallic sound called knocking.

Octane number is the percentage volume of isooctane in the isooctane-heptane

mixture that matches the knocking characteristics of the fuel being tested is
called the octane number.

Molecular structure affects the octane number.

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Knocking in Compression Ignition Engines and Cetane Number

Diesel is used in compression ignition engines.

Cetane number represents the spontaneous ignition temperature of a particular
diesel fuel. It is the percentage of cetane present in a mixture of cetane and
alpha-methylnaphthalene which matches the fuel under test in ignition property.

Engineering Chemistry (revised edition)

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25

OCTANE NUMBER (or) OCTANE RATING

 Octane number is introduced to express the knocking characteristics

of petrol. It has been found that n-heptane knocks very badly and
hence, its anti-knock value has been given zero. On the other hand,
iso-octane gives very little knocking and so, its anti-knock value has
been given 100.

 Thus octane number is defined as 'the percentage of iso-octane

present in a mixture of iso-octane and n-heptane.‘

 Iso-octane (Octane number = 100)

 CH3 – CH2 – CH2 – CH2 – CH2 – CH2 - CH3
 n - heptane (Octane number = 0)

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CETANE NUMBER (or) CETANE RATING

 Cetane number is introduced to express the knocking characteristics of

diesel. Cetane has a very short ignition lag and hence its cetane number is
taken as 100. On the other hand 2-methyl naphthalene has a long ignition
lag and hence its cetane number is taken as zero.
 CH3 – (CH2)14 – CH3
 n-cetane (hexa decane) CH 3

 cetane number = 100

 2-methyl naphthalene (cetane number = 0)

 Thus the cetane number is defined as "the percentage of hexa decane
present in a mixture of hexa decane and 2-methyl napthalene, which has
the same ignition lag as the fuel under test".
 The cetane number decreases in the following order.
 n-alkanes > Cycloalkanes > alkenes >branched alkanes >aromatics
 The cetane number of a diesel oil can be increased by adding additives
called dopes.
 Important dopes: Ethyl nitrate, Iso-amyl nitrate.


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COMPRESSED NATURAL GAS

 Natural Gas is obtained from wells dug in the oil bearing regions. When
natural gas occurs along with petroleum in oil wells, it is called as ‘wet gas’
and contains gaseous hydro carbons from C1 to C4. The wet gas is then
suitably treated to remove propane, propene, butane and butane, which is
used as LPG.When the natural gas is compressed, it is called Compressed
Natural Gas (CNG). The primary component present in CNG is methane. It
is mainly derived from natural gas.
 The natural gas can either be stored in a tank of a vehicle as compressed
natural gas (CNG) at 3,000 or 3,600 psi or as liquified natural gas (LNG) at
typically 20-150 psi. A suitably designed natural gas engine may have a
higher output compared with a petrol engine because the octane number of
natural gas is higher than that of petrol.
 Compressed natural gas vehicles require a greater amount of space for fuel
storage than convention gasoline power vehicles. Since it is a compressed
gas, rather than a liquid like gasoline, CNG takes up more space for each
GGE (Gallon of Gas Equivalent). This makes it difficult to design smaller
vehicles that look and operate like the vehicles that people are accustomed
to.

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 CNG is often confused with liquefied natural gas (LNG). While both are
stored forms of natural gas, the key difference is that CNG is in
compressed form, while LNG is in liquefied form. CNG has a lower cost of
production and storage compared to LNG as it does not require an
expensive cooling process and cryogenic tanks. CNG requires a much
larger volume to store the same mass of natural gas and the use of very
high pressures (3000 to 4000 lbf/in², or 205 to 275 bar).
 CNG has been made mandatory for all public transport in the Indian capital
city of New Delhi.

 Properties
 l. CNG is; the cheapest, cleanest and least environmentally impacting
alternative fuel.
 2. Vehicles powered by CNG produce less carbon monoxide and
hydrocarbon (HC) emission.
 3. It is less expensive than petrol and diesel.
 4. The ignition temperature of CNG is about 550°C. CNG requires more air
for ignition.

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Theoretical calculation of calorific value

 1. Elements always combine in definite proportions to give. the products.

For example 12 gm of carbon combines with 32 gm of oxygen to give 44
gm of CO2
 C + O2 CO2
 12 32 44
 Similarly, 4gm of hydrogen combines with 32gm of oxygen to give 36gm
of H2O.
 2 H2(g) + O(g) 2H2O(g)
 4 32 36
2. At STP (273 K, l atm) one mole of all gases occupy a volume of
22.4litres. Hence at S.T.P. 22.4 liters of CO2 will have a weight of 44gm,
its molecular weight.
 3. Air contains 21 % of oxygen by volume and 23 % of oxygen by weight,
Hence 1 m3 of oxygen will be supplied by
 1 x l00 = 4.76m3 of air
 21

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 Similarly 1 kg of oxygen will be supplied by lxl00 = 4.3 5 kg of air.

 23
 4. Molecular weight of air is 28.94mol-1.
 5. Minimum oxygen required = (Theoretical O2 required) - (O2
present in fuels).
 6. The mass of flue gas is calculated by balancing the carbon in the
fuel and the carbon in the flue gas.
 7. Minimum O2 required is calculated on the basis of complete
combustion of fuel. If as a result incomplete combustion or CO is
formed then O2 is calculated for the conversion of CO to CO2.
 8. If the fuel contains both O2 and H2, the amount of hydrogen and
oxygen may be present in the form of as H2O, which is a non-
combustible substance. The remaining available hydrogen takes part
in the combustion reaction.
 2 H2(g) + O(g) 2H20

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 32 gm of oxygen combines with 4gm of hydrogen, Hence 1 part of

hydrogen combines with 8 parts of oxygen.

 Hence, theoretical amount of oxygen required for complete combustion of

1 kg of fuel is given by the equation,
 {32/12 x C + 8[H – O/8] + S} kg

C, Hand S are masses of carbon. Hydrogen and sulphur respectively

per kg of the fuel. Since 1 kg of air-contains 23%of oxygen by weight, the
amount of air required theoretically to burn 1 kg of fuel completely is given
by equation.
 100/23 {32/12 x C + 8[H – O/8] + S} Kg

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 According to Dulong's formula for the theoretical calculation of calorific

value is,
 1/100 [8080C + 34500 (H – O/8) + 2240S] Kcal/kg
 Where C, H, O and S represent the % of the corresponding elements in the
fuel. It is based on the assumption that the calorific value orc, Hand S are
found to be 8080, 34500 and 2240 kcal, when 1 kg of the fuel is burnt
completely.
 However, all the oxygen in the fuel is assumed to be present in combination
with hydrogen in the ratio H:O as 1:8 by weight. So the surplus hydrogen
available for combustion is' H - 0 .
8
 NCV (or) LCV = [HCV – 9/100H x 587] kcal.kg

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Theoretical calculation of minimum air requirement for combustion of

a fuel

 Combustion is the process of burning any combustible substance in

the presence of oxygen, which liberates energy in the form of heat
and light. For efficient combustion, it is essential that the fuel must
be brought into intimate contact with sufficient quantity of air or
oxygen.
 The combustible substance usually present in fuels, which enter into
the combustion, are mainly C, H, S and O. But N, CO2 and ash are
incombustible matters present in the fuel, .do not take any oxygen
during combustion.
 For the complete combustion of a given quantity of fuel can be
calculated by considering the following point. Substances always
combine in definite proportions, which are determined by the
molecular weights of the substances.

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 i) Combustion of carbon
 C + O2 CO2
12 32 44 (by weight)
 12 parts by weight-of carbon requires 32 parts by weight of oxygen for
complete combustion. 'C' parts by weight of carbon requires == 32 C /12
== 2.67 C
 (H- 0/8) parts by weight of hydrogen requires = (H - O/8) X 32
 4
 = 8 (H- O/8)
 ii) Combustion of hydrogen
 . When oxygen is present in the fuel, it always combines with hydrogen.
The combined hydrogen does not take part in combustion reaction.
Therefore, the quantity of combined hydrogen must be deduced from the
total hydrogen in the fuel.
 2H2 + O2 2H2O
 2 2 36 (by weight)

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 4 parts by weight of H2 requires 32 parts by weight O2 (or) 2 parts by

volume of H2 require 1 part by volume of O2
 There fore ‘H’ parts by weight of hydrogen require 32x H parts by weight
of O2. 4


 iii) Combustion of carbon monoxide

 CO + ½ O CO2

 28 16 (by weight)

 1 0.5 (by volume)
 1 volume of CO requires 0.5 volume of oxygen.

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 iv) Combustion of sulphur

 S + O2 SO2
 32 32 (by weight)
 1 1 (by volume)
 1 volume of 'S' requires 1 volume of oxygen.
 v) Combustion of methane
 CH4 + 2O2 CO2 + 2 H20
 16 64 (by weight)
 1 2 (by volume)

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 Problems For the calculation of Calorific value

 Calculate the gross and net calorific values of a coal sample having the
following composition C = 80%; H = 7%;O = 3%; S = 3.5%; N =
2.5% and ash 4.4%
 Solution
 (I) G.C.V = 1/100[8080*%C+34500(%H - %O/8)+2240*%S] kcal/kg
 = 1/100[8080*80+34500(7 - 3/8)+2240*3.5] kcal/kg
 = 8828.0 kcal/kg
 ,,
 (II) N.C.V = G.C.V – [0.09H*587] kcal/kg

 = 8828 – [0.09*7*587] kcal/kg
 = 8458.2 k cal/kg

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LUBRICANTS

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Lubricants and lubrication

 Lubricant is a substance which when
introduced between two moving parts reduces
friction by forming a slippery film between the
two surfaces and thus improving efficiency and
decreasing wear
 So, lubrication is the process of reducing
friction and wear between two moving surfaces
by applying lubricating substances between the
parts.

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Lubricant
 Lubricant may be defined as a
substance which reduces the friction
between the two moving surfaces or
parts of a machine

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Need of Lubricants
 Whenever a machine works, its moving, sliding, or rolling parts rub
against each other because of that, friction is developed. This
friction causes a lot of wear and tear of the concerned surfaces.
 Further due to friction, large amount of energy is dissipated in the
form of heat and thus causes loss in the efficiency of a machine.
 Moreover, the heat produced due to friction causes damage to the
moving parts.

The above ill effects can be minimized

 by applying a thin layer of certain substances known as lubricant in
between the moving parts.
 The process of applying the lubricant in between the two moving or
sliding surfaces is called as lubrication.

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Purpose of lubrication
 To keep moving parts apart: by forming thin layer
between the surfaces
 To reduce friction: lubricant to surface friction is
lesser than surface to surface friction
 To protect against wear: lubricant prevent wear by
keeping moving part apart
 To transfer heat: liquid lubricants are effective in heat
circulation due to high specific capacity
 To prevent corrosion: as surface of metal do not
come in contact with air (Oxygen)
 To seal gapes: lubricant seal the space between
moving parts through capillary force
 To carry away contaminants and debris

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Characteristics of a lubricant
 It should have enough viscosity and oiliness.
 It should have flash and fire points higher than the operating temperature of
the machine.
 It should be chemically inert.
 It should not come out of the surface under pressure.
 It should not evaporate easily.
 It should stick on the surface.
 It should leave low carbon residue.
 It should not form emulsion with water.
 It should have cloud and pour points lower than the operating temperature
of the machine.
 The volatility of the lubricating oil should be low.
 It should possess a higher resistance towards oxidation and corrosion.

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Classification of lubricants

Lubricants may be broadly classified as follows.

 Solid lubricants
 Semi-solid lubricants
 Liquid lubricants

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TEXT BOOKS AND REFERENCES

 Vairam S, Kalyani P and SubaRamesh.,“Engineering Chemistry”.,

Wiley India PvtLtd.,NewDelhi., 2011
 DaraS.S,UmareS.S.“Engineering Chemistry”, S. Chand &
Company Ltd., New Delhi , 2010
 Kannan P. and Ravikrishnan A., “Engineering Chemistry”, Sri
Krishna Hi-tech Publishing Company Pvt. Ltd. Chennai, 2009
 Ashima Srivastava and Janhavi N N., “Concepts of Engineering
Chemistry”, ACME Learning Private Limited., New Delhi., 2010.
 RenuBapna and Renu Gupta., “Engineering Chemistry”, Macmillan
India Publisher Ltd., 2010.
 Pahari A and Chauhan B., “Engineering Chemistry”., Firewall
Media., New Delhi., 2010
 P.C.Jain and Monica Jain, “Engineering Chemistry”, Dhanpat Rai
Pub. Co., New Delhi

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