Fuels and Combustion

(Including Chemical Thermodynamics)

INTRODUCTION
Fuel may be chemical or nuclear. Here we shall consider briefly chemical fuels only.
A chemical fuel is a substance which releases heat energy on combustion. The principal
combustible elements of each fuel are carbon and hydrogen. Though sulphur is a combustible
element too but its presence in the fuel is considered to be undesirable.
In chemical thermodynamics the study of systems involving chemical reactions is an important
topic. A chemical reaction may be defined as the rearrangement of atoms due to redistribution of
electrons. In a chemical reaction the terms, reactants and the products are frequently used.
‘Reactants’ comprise of initial constituents which start the reaction while ‘products’ comprise of
final constituents which are formed by the chemical reaction. Although the basic principles
which will be discussed in this chapter apply to any chemical reaction, here main attention will
be focused on an important type of chemical reaction—combustion.
CLASSIFICATION OF FUELS
Fuels can be classified according to whether :
1. They occur in nature called primary fuels or are prepared called secondary fuels ;
2. They are in solid, liquid or gaseous state. The detailed classification of fuels can be given.
SOLID FUELS
Coal. Its main constituents are carbon, hydrogen, oxygen, nitrogen, sulphur, moisture and ash.
Coal passes through different stages during its formation from vegetation. These stages are
enumerated and discussed below:
Plant debris—Peat—Lignite—Brown coal—sub-bituminous coal—Bituminous coal—Semi
bituminous coal—Semi-anthracite coal—Anthracite coal—Graphite.
Peat. It is the first stage in the formation of coal from wood. It contains huge amount of moisture
and therefore it is dried for about 1 to 2 months before it is put to use. It is used as a domestic
fuel in Europe and for power generation in Russia. In India it does not come in the categories of
good fuels.
Lignite and brown coals. These are intermediate stages between peat and coal. They have a
woody or often a clay like appearance associated with high moisture, high ash and low heat
contents. Lignites are usually amorphous in character and impose transport difficulties as they
break easily. They burn with a smoky flame. Some of this type are suitable for local use only.
Bituminous coal. It burns with long yellow and smoky flames and has high percentages of
volatile matter. The average calorific value of bituminous coal is about 31350 kJ/kg. It may be of
two types, namely caking or noncaking.
Semi-bituminous coal. It is softer than the anthracite. It burns with a very small amount of
smoke. It contains 15 to 20 per cent volatile matter and has a tendency to break into small sizes
during storage or transportation.
Semi-anthracite. It has less fixed carbon and less lustre as compared to true anthracite and gives
out longer and more luminous flames when burnt.
Anthracite. It is very hard coal and has a shining black lustre. It ignites slowly unless the
furnace temperature is high. It is non-caking and has high percentage of fixed carbon. It burns
either with very short blue flames or without flames. The calorific value of this fuel is high to the
tune of 35500 kJ/kg and as such is very suitable for steam generation.
Wood charcoal. It is obtained by destructive distillation of wood. During the process the volatile
matter and water are expelled. The physical properties of the residue (charcoal), however
depends upon the rate of heating and temperature.
Coke. It consists of carbon, mineral matter with about 2% sulphur and small quantities of
hydrogen, nitrogen and phosphorus. It is solid residue left after the destructive distillation of
certain kinds of coals. It is smokeless and clear fuel and can be produced by several processes. It
is mainly used in blast furnace to produce heat and at the same time to reduce the iron ore.
Briquettes. These are prepared from fine coal or coke by compressing the material under high
pressure.
LIQUID FUELS
The chief source of liquid fuels is petroleum which is obtained from wells under the earth’s crust.
These fuels have proved more advantageous in comparison to sold fuels in the following
respects.
Advantages :
1. Require less space for storage.
2. Higher calorific value.
3. Easy control of consumption.
4. Staff economy.
5. Absence of danger from spontaneous combustion.
6. Easy handling and transportation.
7. Cleanliness.
8. No ash problem.
9. Non-deterioration of the oil in storage.
Petroleum. There are different opinions regarding the origin of petroleum. However, now it is
accepted that petroleum has originated probably from organic matter like fish and plant life etc.,
by bacterial action or by their distillation under pressure and heat. It consists of a mixture of
gases, liquids and solid hydrocarbons with small amounts of nitrogen and sulphur compounds.
The refining of crude oil supplies the most important product called petrol. Petrol can also be
made by polymerization of refinery gases.
Other liquid fuels are kerosene, fuels oils, colloidal fuels and alcohol.
GASEOUS FUELS
Natural gas. The main constituents of natural gas are methane (CH4) and ethane (C2H6). It has
calorific value nearly 21000 kJ/m3. Natural gas is used alternately or simultaneously with oil for
internal combustion engines.
Coal gas. Mainly consists of hydrogen, carbon monoxide and hydrocarbons. It is prepared by
carbonisation of coal. It finds its use in boilers and sometimes used for commercial purposes.
Coke-oven gas. It is obtained during the production of coke by heating the bituminous coal. The
volatile content of coal is driven off by heating and major portion of this gas is utilised in heating
the ovens. This gas must be thoroughly filtered before using in gas engines.
Blast furnace gas. It is obtained from smelting operation in which air is forced through layers of
coke and iron ore, the example being that of pig iron manufacture where this gas is produced as
by product and contains about 20% carbon monoxide (CO). After filtering it may be blended
with richer gas or used in gas engines directly. The heating value of this gas is very low.
Producer gas. It results from the partial oxidation of coal, coke or peat when they are burnt with
an insufficient quantity of air. It is produced in specially designed retorts. It has low heating
value and in general is suitable for large installations. It is also used in steel industry for firing
open hearth furnaces.
Sewer gas. It is obtained from sewage disposal vats in which fermentation and decay occur. It
consists of mainly marsh gas (CH4) and is collected at large disposal plants. It works as a fuel for
gas engines which in turn drive the plant pumps and agitators.
Gaseous fuels are becoming popular because of following advantages they possess.
Advantages:
1. Better control of combustion.
2. Much less excess air is needed for complete combustion.
3. Economy in fuel and more efficiency of furnace operation.
4. Easy maintenance of oxidizing or reducing atmosphere.
5. Cleanliness.
6. No problem of storage if the supply is available from public supply line.
7. The distribution of gaseous fuels even over a wide area is easy through the pipe lines and
as such handling of the fuel is altogether eliminated.
8. Gaseous fuels give economy of heat and produce higher temperatures (as they can be
preheated in regenerative furnaces and thus heat from hot flue gases can be recovered).
BASIC CHEMISTRY
Before considering combustion problems it is necessary to understand the construction and use
of chemical formulae. This involves elementary concepts which are discussed below briefly.
Atoms. It is not possible to divide the chemical elements indefinitely, and the smallest particle
which can take part in a chemical change is called an ‘atom’. If an atom is split as in nuclear
reaction, the divided atom does not retain the original chemical properties.
Molecules. It is rare to find elements to exist naturally as single atom. Some elements have
atoms which exist in pairs, each pair forming a molecule (e.g. oxygen), and the atoms of each
molecule are held together by stronger inter-atomic forces. The isolation of a molecule of oxygen
would be tedious, but possible; the isolation of an atom of oxygen would be a different prospect.
The molecules of some substances are formed by the mating up of atoms of different elements.
For example, water has a molecule which consists of two atoms of hydrogen and one atom of
oxygen. The atoms of different elements have different masses and these values are important
when a quantitative analysis is required. The actual masses are infinitesimally small, and the
ratios of the masses of atoms are used. These ratios are indicated by atomic weight quoted on a
scale which defines the atomic weight of oxygen as 16.
The symbols and molecular weights of some important elements, compounds and gases are given
in Table 11.1.
COMBUSTION EQUATIONS
In a combustion chamber proportionate masses of air and fuel enter where the chemical reaction
takes place, and then the combustion products pass to the exhaust. By the conservation of mass
the mass flow remains constant (i.e., total mass of products = total mass of reactants), but the
reactants are chemically different from the products, and the products leave at a higher
temperature. The total number of atoms of each element concerned in the combustion remains
constant, but the atoms are rearranged into groups having different chemical properties. This
information is expressed in the chemical equation which shows (i) the reactants and the products
of combustion, (ii) the relative quantities of the reactants and products. The two sides of the
equation must be consistent, each having the same number of atoms of each element involved.
The oxygen supplied for combustion is usually provided by atmospheric air, and it is necessary
to use accurate and consistent analysis of air by mass and by volume. It is usual in combustion
calculations to take air as 23.3% O2, 76.7% N2 by mass, and 21% O2, 79% N2 by volume. The
small traces of other gases in dry air are included in nitrogen, which is sometimes called
‘atmospheric nitrogen’. Some important combustion equations are given below:
THEORETICAL AIR AND EXCESS AIR
The minimum amount of air that supplies sufficient oxygen for the complete combustion of all
the carbon, hydrogen, and any other elements in the fuel that may oxidise is called the
“theoretical air”. When complete combustion is achieved with theoretical air, the products
contain no oxygen.
In practice, it is found that complete combustion is not likely to be achieved unless the amount of
air supplied is somewhat greater than the theoretical amount. Thus 150 per cent theoretical air
means that air actually supplied is 1.5 times the theoretical air.
The complete combustion of methane with minimum amount of theoretical air and 150 per cent
theoretical air respectively is written as:

The amount of air actually supplied may also be expressed in terms of per cent excess air. The
excess air is the amount of air supplied over and above the theoretical air. Thus 150 per cent
theoretical air is equivalent to 50 per cent excess air.
Note. For complete combustion of fuel, we need air. As per theoretical basis there is a minimum
amount of air which is required by the fuel to burn completely, but always, air in excess is used
because whole of air supplied for combustion purposes does not come in contact with the fuel
completely and as such portion of fuel may be left unburnt. But if a large quantity of excess air is
used it exercises a cooling effect on combustion process which however can be avoided by
preheating the air. The weight of excess air supplied can be determined from the weight of
oxygen which is left unused. The amount of excess air supplied varies with the type of fuel and
the firing conditions. It may approach a value of 100% but modern practice is to use 25% to 50%
excess air.
STOICHIOMETRIC AIR FUEL (A/F) RATIO
Stoichiometric (or chemically correct) mixture of air and fuel is one that contains just sufficient
oxygen for complete combustion of the fuel.
A weak mixture is one which has an excess of air.
A rich mixture is one which has a deficiency of air.
The percentage of excess air is given as:

The ratios are expressed as follows:

For gaseous fuels By volume
For solid and liquid fuels By mass
For boiler plant the mixture is usually greater than 20% weak; for gas turbines it can be as much
as 300% weak. Petrol engines have to meet various conditions of load and speed, and operate
over a wide range of mixture strength. The following definition is used:

AIR-FUEL RATIO FROM ANALYSIS OF PRODUCTS

When analysis of combustion products is known air-fuel ratio can be calculated by the following
methods:
1. Fuel composition known
(i) Carbon balance method (ii) Hydrogen balance method
(iii) Carbon-hydrogen balance method.
2. Fuel composition unknown
(i) Carbon-hydrogen balance method.
1. Fuel composition known
(i) Carbon balance method. When the fuel composition is known, the carbon balance method is
quite accurate if combustion takes place with excess air and when free (solid) carbon is not
present in the products. It may be noted that the Orsat analysis will not determine the quantity of
solid carbon in the products.
(ii) Hydrogen balance method. This method is used when solid carbon is suspected to be present.
(iii) Carbon-hydrogen balance method. This method may be employed when there is some
uncertainty about the nitrogen percentage reported by the Orsat analysis.
2. Fuel composition unknown
When the fuel composition is not known the carbon-hydrogen balance method has to be
employed.
HOW TO CONVERT VOLUMETRIC ANALYSIS TO WEIGHT ANALYSIS?
The conversion of volumetric analysis to weight analysis involves the following steps:
1. Multiply the volume of each constituent by its molecular weight.
2. Add all these weights and then divide each weight by the total of all and express it as
percentage.
HOW TO CONVERT WEIGHT ANALYSIS TO VOLUMETRIC ANALYSIS?
1. Divide the weight of each constituent by its molecular weight.
2. Add up these volumes and divide each volume by the total of all and express it as a
percentage.
WEIGHT OF CARBON IN FLUE GASES
The weight of carbon contained in one kg of flue or exhaust gas can be calculated from the
amounts of CO2 and CO contained in it.

WEIGHT OF FLUE GASES PER KG OF FUEL BURNT

Due to supply of air, the weight of flue gas or exhaust gas is always more than that of fuel burnt.
The actual weight of dry flue gases can be obtained by comparing the weight of carbon present
in the flue gases with the weight of carbon in the fuel, since there is no loss of carbon during the
combustion process. As the analysis of the exhaust gases is volumetric, so this must first be
reduced to weight analysis.

INTERNAL ENERGY AND ENTHALPY OF FORMATION

The first law of thermodynamics can be applied to any system. Non-flow and steady-flow energy
equations deducted from this law must be applicable to systems undergoing combustion
processes.
It has been proved experimentally that the energy released, when a unit mass of a fuel undergoes
complete combustion, depends on the temperature at which the process is carried out.
Thus, such quantities quoted are related to temperature. Now it will be shown that if the energy
released by a fuel at one temperature is known then it can be calculated at other temperatures.
The process of combustion is defined as taking place from reactants at a state identified by the
reference temperature T0 and another property, either pressure or volume, to products at the same
state.

Analysis for a non-flow process involving combustion at ‘constant volume’:

When the combustion process is carried out at constant volume then the non-flow energy
equation, Q = (U2 – U1) + W, can be applied to give

CALORIFIC OR HEATING VALUES OF FUELS

The “calorific value or heating value” of the fuel is defined as the energy liberated by the
complete oxidation of a unit mass or volume of a fuel. It is expressed in kJ/kg for solid and liquid
fuels and kJ/m3 for gases.
If a fuel contains hydrogen water will be formed as one of the products of combustion. If this
water is condensed, a large amount of heat will be released than if the water exists in the vapour
phase. For this reason, two heating values are defined; the higher or gross heating value and the
lower or net heating value.
The higher heating value, HHV, is obtained when the water formed by combustion is completely
condensed.
The lower heating value, LHV, is obtained when the water formed by combustion exists
completely in the vapour phase.

Example 1. A coal sample gave the following analysis by weight, Carbon 85 per cent, Hydrogen
6 per cent, Oxygen 6 per cent, the remainder being incombustible. Determine minimum weight of
air required per kg of coal for chemically correct composition.

Example 2. The percentage composition of sample of liquid fuel by weight is, C = 84.8 per cent,
and H2 = 15.2 per cent. Calculate (i) the weight of air needed for the combustion of 1 kg of fuel;
(ii) the volumetric composition of the products of combustion if 15 per cent excess air is
supplied.
Example 3. Percentage volumetric analysis of a sample of flue gases of a coal fired
boiler gave CO2 = 10.4; CO = 0.2; O2 = 7.8 and N 2 = 81.6 (by difference). Gravemetric
percentage analysis of coal was C = 78, H2 = 6, O2 = 3 and incombustible = 13. Estimate:
(i) Weight of dry flue gases per kg of fuel.
(ii) Weight of excess air per kg of fuel.
Example 4. A single cylinder was supplied with a gas having the following percentage
volumetric analysis; CO = 5, CO2 = 10, H2 = 50, CH4 = 25, N2 = 10. The percentage
volumetric analysis of dry gases was CO2 = 8, O2 = 6 and N2 = 86. Determine the air-fuel ratio
by volume.
Example 5. The following is the ultimate analysis of a sample of petrol by weight:
Carbon = 85 per cent; Hydrogen = 15 per cent.
Calculate the ratio of air to petrol consumption by weight if the volumetric analysis of the
dry exhaust gas is:
CO2 = 11.5 per cent; CO = 1.2 per cent; O2 = 0.9 per cent; N2 = 86 per cent.
Also find percentage excess air.