Fuel and Combustion

Fuels
Fuels are combustible substances in different Physical Forms and different Chemical
Compositions, containing carbon as a main constituent, which on proper burning gives large
amount of heat, which can be used economically for transportation, industrial and domestic
purposes.
Example:
Wood, charcoal, coal, kerosene, petrol, diesel, producer gas, oil gas, CNG, LPG etc.
Types of Fuels
The most common modern fuels are made up of hydrocarbons and are derived mostly
from fossil fuels (petroleum). Fossil fuels include diesel fuel, gasoline and petroleum gas, and
the rarer use of propane. Except for the fuel delivery components, most internal combustion
engines that are designed for gasoline use can run on natural gas or liquefied petroleum gases
without major modifications. Large diesels can run with air mixed with gases and a pilot
diesel fuel ignition injection. Liquid and gaseous biofuels, such as ethanol and biodiesel (a
form of diesel fuel that is produced from crops that yield triglycerides such as soybean oil),
can also be used. Engines with appropriate modifications can also run on hydrogen gas, wood
gas, or charcoal gas, as well as from so-called producer gas made from other convenient
biomass. Experiments have also been conducted using powdered solid fuels, such as
the magnesium injection cycle.
Presently, fuels used include:
Petroleum: Petroleum spirit (North American term: gasoline, British term: petrol) and
Petroleum diesel.
 Autogas (liquified petroleum gas).
 Compressed natural gas.
 Jet fuel (aviation fuel)
 Residual fuel
Coal:
 Gasoline can be made from carbon (coal) using the Fischer-Tropsch process
 Diesel fuel can be made from carbon using the Fischer-Tropsch process
Biofuels and vegetable oils:
 Peanut oil and other vegetable oils.
 Wood-gas, from an on-board wood gasifier using solid wood as a fuel
 Biofuels:
 Bio-butanol (replaces gasoline).
 Biodiesel (replaces petro-diesel).
 Dimethyl Ether (replaces petro-diesel).
 Bioethanol and Biomethanol (wood alcohol) and other biofuels).
 Biogas
 Hydrogen (mainly spacecraft rocket engines)
Even fluidized metal powders and explosives have seen some use. Engines that use gases for
fuel are called gas engines and those that use liquid hydrocarbons are called oil engines;
however, gasoline engines are also often colloquially referred to as, "gas engines" ("petrol
engines" outside North America).
The main limitations on fuels are that it must be easily transportable through the fuel
system to the combustion chamber, and that the fuel releases sufficient energy in the form
of heat upon combustion to make practical use of the engine.
Diesel engines are generally heavier, noisier, and more powerful at lower speeds
than gasoline engines. They are also more fuel-efficient in most circumstances and are used
in heavy road vehicles, some automobiles (increasingly so for their increased fuel
efficiency over gasoline engines), ships, railway locomotives, and light aircraft. Gasoline
engines are used in most other road vehicles including most cars, motorcycles, and mopeds.
Note that in Europe, sophisticated diesel-engined cars have taken over about 45% of the
market since the 1990s.
There are also engines that run on hydrogen, methanol, ethanol, liquefied petroleum
gas (LPG), biodiesel, paraffin and tractor vaporizing oil (TVO).
Hydrogen
Hydrogen could eventually replace conventional fossil fuels in traditional internal
combustion engines. Alternatively fuel cell technology may come to deliver its promise and
the use of the internal combustion engines could even be phased out.
Fuel characteristics
A good fuel should have the following characteristics:
 High calorific value.
 Moderate ignition temperature.
 Low contents of non-combustible matters.
 Low moisture content.
 Free from objectionable and harmful gases like CO, SOx, H2S.
 Moderate velocity of combustion.
 Combustion should be controllable.
 Easy to transport and readily available at low cost.
Combustion
By combustion/ burning of fuel, for Automobiles/ Transportation or industrial use, the
chemical energy is converted to heat energy and then to mechanical energy and produces a
useful work.
Combustion, also known as burning, is the basic chemical process of releasing energy from a
fuel and air mixture. During the process of combustion, carbon, hydrogen, etc., combine with
oxygen (oxidation of fuel occurs) 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.
In an internal combustion engine (ICE), the ignition and combustion of the fuel occurs within
the engine itself. The engine then partially converts the energy from the combustion to work.
The engine consists of a fixed cylinder and a moving piston. The expanding combustion
gases push the piston, which in turn rotates the crankshaft. Ultimately, through a system of
gears in the powertrain, this motion drives the vehicle’s wheels.
There are two kinds of internal combustion engines currently in production: the spark ignition
gasoline engine and the compression ignition diesel engine. Most of these are four-stroke
cycle engines, meaning four piston strokes are needed to complete a cycle. The cycle includes
four distinct processes: intake, compression, combustion and power stroke, and exhaust.
Spark ignition gasoline and compression ignition diesel engines differ in how they supply and
ignite the fuel.  In a spark ignition engine, the fuel is mixed with air and then inducted into
the cylinder during the intake process. After the piston compresses the fuel-air mixture, the
spark ignites it, causing combustion. The expansion of the combustion gases pushes the
piston during the power stroke. In a diesel engine, only air is inducted into the engine and
then compressed. Diesel engines then spray the fuel into the hot compressed air at a suitable,
measured rate, causing it to ignite.
Petroleum
Petroleum or crude oil is a naturally occurring brown to black coloured viscous oil formed
under the crust of earth, on shore or off shore. Chemically it is a mixture of various
hydrocarbons with small amounts of N, O, S compounds.
The approximate composition of petroleum is
C = 80 - 84%
H = 10 - 14 %
S = 0.1 - 0.5 %
N+ O = Negligible
Classification
Petroleum is classified on the basis of various types of hydrocarbons.
Refining of Petroleum (or) Crude Oil
Definition: The process of removing impurities and separating out the oil into various
fractions having different boiling points is known as refining of petroleum.
Fractional Distillation
The purified crude oil is heated in a furnace called oil heater where the temperature will be
around 400 oC. Here the oil gets vapourised. The hot vapours are then sent to the
fractionating column.
When the oil vapours go up in the tower, they become cool and condense. The heavier
compounds having higher boiling points get cooled first and condensed in the trays whereas
the fractions having lower boiling points condense near the top of the tower.
Lower fractions are used after purification while the high boiling point fractions are subjected
to cracking operation to get more useful lower fractions.
The gasoline obtained by this fractional distillation is called straight-run gasoline. Various
fractions obtained at different trays are given in Table.
Table 1, Various fractions, Compositions and their uses
Sl. Name of the Boiling Range of Uses
No. fraction Range C o
C-Atoms
 1. Uncondensed Below 30 C1-C4 As a fuel under the name of LPG
gases
2. Petroleum ether 30-70 C5-C7 As a solvent
3. Gasoline or petrol 40-120 C5-C9 Fuel for IC engines
4. Naphtha or 120-180 C9-C10 As a solvent in paints and in dry
solvent spirit cleaning
5. Kerosene oil 180-250 C10-C16 Fuel for stoves and jet engines
6. Diesel oil 250-320 C15-C18 Diesel engine fuel
7. Heavy oil 320-400 C17-C30 Fuel for ships and for production of
gasoline by cracking.

Table 2, Heavy oils on refraction gives

Cracking
Cracking is defined as “the decomposition of high boiling hydrocarbons of high molecular
weight into smaller, low boiling hydrocarbons of low molecular weight”.
The crude oil on fractional distillation yields only about 15 - 20 % gasoline. This is known as
Straight Run Gasoline.
The quality of straight run gasoline is not so good. It contains mainly straight chain
paraffin’s, which ignite readily and more rapidly than any other hydrocarbons and hence it
produces knocking (unwanted sound) in IC engines.
In order to overcome these difficulties and also to improve the quality of gasoline, high
boiling fractions are cracked into more valuable low boiling fractions suitable for SI engines.
The gasoline obtained by cracking is called Cracked Gasoline.
During cracking
 Straight chain alkanes are converted into branched chain hydrocarbons.
 Saturated hydrocarbons are converted into mixture of Saturated and Unsaturated
hydrocarbons.
 Aliphatic alkanes are converted into cyclic alkanes.
 All hydrocarbons obtained by cracking have lower boiling point than the parent
hydrocarbons.
Types of cracking: There are two kinds of cracking
1. Thermal cracking
2. Catalytic cracking
Purification of Petrol (or) Gasoline
Gasoline or petrol obtained either from crude oil or synthetic process may contain some
undesirable impurities. They are mainly unsaturated olefins, colouring matters, Sulphur
compounds etc.
The unsaturated olefins get oxidised and polymerized there by causing gum and sludge
formation on storing.
On the other hand, sulphur compounds lead to corrosion of ICE and also affect tetra ethyl
lead (TEL) which is added to gasoline to obtain good petrol. So these undesirable contents
must be removed from gasoline. Unsaturated olefins and colouring matter are removed by
using adsorbent like Kieselguhr, fuller’s earth.
Sulphur containing petrol is known as sour spirit. The process of desulphurisation of
petrol is called sweetening of petrol.
Fractions of petroleum commonly used in IC Engines
Petrol (or) Gasoline (C5-C9):
It is a low boiling fraction of petroleum obtained between 40 – 120 oC.
It is a mixture of hydrocarbons pentane to nonane (in terms of carbon atoms C5 - C9).
Its calorific value is about 11,250 kcals/kg.
It is used as fuel in ICE of automobiles and aero planes.
Its antiknock value can be improved by the addition of Tetra Ethyl Lead (TEL).
Uses: It is used as a fuel in IC engine and also used in dry cleaning and as a solvent.
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 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.
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.
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.
Chemical Structure and Knocking
The knocking tendency decreases as follows :
 n-alkanes → isoparaffins → olefins → naphthenes → aromatics
n-alkanes have lowest antiknock value. So the presence of maximum quantity of aromatics
and minimum quantity of n-alkanes is desirable in petrol.
Octane number (Measurement of knocking in SI engines)
Octane number expresses the knocking characteristics of petrol. n - heptane (a constituent of
petrol) knocks very badly, so its anti-knock value has been given zero. On the other hand,
isooctane (also a constituent of petrol) gives very little knocking, so its anti-knock value has
been given 100.
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.
Mechanism of knocking
Knocking follows free radical mechanism, leading to a chain growth. If the chains are
terminated before their growth, knocking will cease. TEL decomposes thermally to form
ethyl
free radicals, which combines with the free radicals of knocking process and thus the chain
growth is stopped.
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.
Diesel Fuel:
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 isoamyl nitrate.
CI Engines
In a CI engine, air is alone compressed. This raises the cylinder temperature as high as 300
o
C. Then the oil is injected or sprayed, which must ignite spontaneously. Now combustion
products expand and power stroke begins.
Knocking in CI Engines
Sometimes, 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.
Cetane number (or) Cetane Rating
Cetane number expresses the knocking characteristics of diesel.
Cetane (C16 H 34) has a very short ignition delay and hence its cetane number is taken as
100. On the other hand, - 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”.
Chemical Structure and Knocking
The knocking tendency in CI - engines increases as follows,
n-alkane → iso paraffins → Olefins → naphthenes → aromatics
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.
Diesel Index
The quality of a diesel oil is indicated by diesel index number using the following formula
Diesel index number = (Specific gravity (API) x Aniline point in oF)/100
Aniline point and specific gravity is noted from API (American Petroleum Institute) Scale.