Combustion

Thermodynamics II__________________________________________________________________ _ AAiT
Chapter 3
Combustion
3.1 Introduction
In the preceding chapters we limited our consideration to non reacting systems (systems whose
chemical composition remains unchanged during a process). In this chapter, we specifically deal
with systems whose chemical composition changes during a process, that is, systems that involve
chemical reactions.
When a chemical reaction occurs, the bonds within molecules of the reactants are broken, and
atoms and electrons rearrange to form products. In combustion reactions, rapid oxidation of
combustible elements of the fuel results in energy release as combustion products are formed.
The three major combustible chemical elements in most common fuels are carbon, hydrogen,
and sulfur. Sulfur is usually a relatively unimportant contributor to the energy released, but it can
be a significant cause of pollution and corrosion problems.
A chemical reaction during which a fuel is oxidized and a large quantity of energy is released is
called combustion. The oxidizer most often used in combustion processes is air, for obvious
reasons it is free and readily available. Pure oxygen O 2 is used as an oxidizer only in some
specialized applications, such as cutting and welding, where air cannot be used.
During combustion, nitrogen behaves as an inert gas and does not react with other elements,
other than forming a very small amount of nitric oxides. However, even then the presence of
nitrogen greatly affects the outcome of a combustion process since nitrogen usually enters a
combustion chamber in large quantities at low temperatures and exits at considerably higher
temperatures, absorbing a large proportion of the chemical energy released during combustion.
Throughout this chapter, nitrogen is assumed to remain perfectly inert. Keep in mind, however,
that at very high temperatures, such as those encountered in internal combustion engines, a small
fraction of nitrogen reacts with oxygen, forming hazardous gases such as nitric oxide.
Combustion is complete when all the carbon present in the fuel is burned to carbon dioxide, all
the hydrogen is burned to water, all the sulfur is burned to sulfur dioxide, and all other
combustible elements are fully oxidized. When these conditions are not fulfilled, combustion is
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incomplete, if the combustion products contain any unburned fuel or components such as C, H 2 ,
CO, or OH.
Insufficient oxygen is an obvious reason for incomplete combustion, but it is not the only one.
Incomplete combustion occurs even when more oxygen is present in the combustion chamber
than is needed for complete combustion. This may be attributed to insufficient mixing in the
combustion chamber during the limited time that the fuel and the oxygen are in contact. Another
cause of incomplete combustion is dissociation, which becomes important at high temperatures.
We should also mention that bringing a fuel into intimate contact with oxygen is not sufficient to
start a combustion process. (Thank goodness it is not. Otherwise, the whole world would be on
fire now.) The fuel must be brought above its ignition temperature to start the combustion. The
minimum ignition temperatures of various substances in atmospheric air are approximately
260°C for gasoline, 400°C for carbon, 580°C for hydrogen, 610°C for carbon monoxide, and
630°C for methane. Moreover, the proportions of the fuel and air must be in the proper range for
combustion to begin. For example, natural gas does not burn in air in concentrations less than 5
percent or greater than about 15 percent.
3.2 Fuels
Any substance that reacts chemically with an oxidizing agent s called a fuel. Most familiar fuels
consist primarily of hydrogen and carbon. They are called hydrocarbon fuels and are denoted by
the general formula C n H m . Hydrocarbon fuels exist in all phases, solid fuels (eg. coal), liquid
fuels (eg. petroleum) and gaseous fuels (eg. coal gas, natural gas).
The main constituent of coal is carbon. Coal also contains varying amounts of oxygen, hydrogen,
nitrogen, sulfur, moisture, and ash.
Most liquid hydrocarbon fuels are a mixture of numerous hydrocarbons and are obtained from
crude oil by distillation. The most volatile hydrocarbons vaporize first, forming what we know as
gasoline. The less volatile fuels obtained during distillation are kerosene, diesel fuel, and fuel oil.
The composition of a particular fuel depends on the source of the crude oil as well as on the
refinery.
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Figure 3.1 Most liquid hydrocarbon fuels are obtained from crude oil by distillation.
Natural gas is produced from gas wells or oil wells rich in natural gas. It is composed mainly of
methane, but it also contains small amounts of ethane, propane, hydrogen, helium, carbon
dioxide, nitrogen, hydrogen sulfate, and water vapor.
Source of thermal energy is an essential requirement of all heat engines. In steam power plants,
for instance, thermal energy is provided by the combustion of suitable fuels like coal or oil in the
boiler furnace. In internal combustion engines, the combustion of fuels which are grouped as
petrol or gas oil provides the required high temperature. In gas turbines, kerosene or natural
gases are used in providing high temperature.
3.3 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
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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 3.1.
Table 3.1 Symbols and molecular weights of some important elements, compounds and gases
3.4 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 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
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calculations to take air as 23.3% O 2 , 76.7% N 2 by mass, and 21% O 2 , 79% N 2 by volume. The
small traces of other gases in dry air are included in nitrogen.
Reactants Products
Fuel + Oxidizer Products
Some important combustion equations are given below :
Combustion of hydrogen
2 H 2 + O2 → 2 H 2O (3.1)
The above equation of combustion of hydrogen tell us that :
(i) Hydrogen reacts with water to form steam or water.

(ii) Two molecules of hydrogen react with one molecule of oxygen to give two molecules
of steam or water,
i.e 2 volumes H 2 + 1 volume O 2 → 2 volumes H 2 O
The H 2 O may be liquid or a vapor depending on whether the product has been cooled
sufficiently to cause condensation.
The proportions by mass are obtained by using atomic weights as follows
2 H 2 + O2 → 2 H 2O
2(2x1)+2x16 → 2(2x1+16)
4kgH 2 + 32kgO2 → 36kgH 2O
1kgH 2 + 8kgO2 → 9kgH 2O
That the total volume of the reactants and product

2 volumes H 2 + 1 volume O 2 → 2 volumes H 2 O
2 volumes H 2 + 1 volume O 2 = 3 volumes
The total volume of the product is only 2 volumes. There is therefore a volumetric contraction
on combustion.
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Since the oxygen is accompanied by nitrogen if air is supplied for the combustion, then this
nitrogen should be included in the equation. As nitrogen is inert as far as chemical reaction is
concerned, it will appear on both sides of the equation.
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% O 2 , 76.7% N 2 by mass, and 21% O 2 , 79% N 2 by volume and it
leads to the conclusion that for each mole of oxygen, 79.0/21.0 = 3.76 moles of nitrogen are
involved.
Hence equation (3.1) becomes,
79 79
2H 2 +O 2 + N 2 → 2H 2 O + N2 (3.2)
21 21
Combustion of carbon
(i) Complete combustion of carbon to carbon dioxide
C + O 2 → CO 2
and including the nitrogen,

C + O 2 + 3.76N 2 → CO 2 + 3.76N 2
By volume :
0 volume C + 1 volume O 2 + 3.76 volumes N 2 → 1 volume CO 2 + 3.76 volumes N 2
The volume of carbon is written as zero since the volume of solid is negligible in comparison
with that of a gas.
By mass :
12kgC+(2 × 16)kgO 2 +3.76(2 × 14)kgN 2 → (12 + 2 × 16)kgCO 2 + 3.76(2 × 14)N 2
12kgC+32k O 2 +105.3kgN 2 → 44kgCO 2 +105.3kgN 2
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8 105.3 11 105.3
1 kg C+ kgO 2 + kgN 2 → kgCO 2 + kgN 2
3 12 3 12
(ii) The incomplete combustion of carbon.
The incomplete combustion of carbon occurs when there is an insufficient supply of oxygen to
burn the carbon completely to carbon dioxide.
2C+O 2 → 2CO
and including the nitrogen,
2C+O 2 +3.76N 2 → 2CO+3.76N 2
By mass :
(2×12)kgC+(2×16)kgO 2 +3.76(2×14)kgN 2 → 2(12+16)kgCO+3.76(2×14)kgN 2
24kgC +32 kgO 2 +105.3kgN 2 → 56kgCO+105.3kgN 2
4 105.3 7 105.3
1kgC+ kgO 2 + kgN 2 → kgCO+ kgN 2
3 24 3 24
If a further supply of oxygen is available then the combustion can continue to completion,
2CO+O 2 +3.76N 2 → 2CO 2 + 3.76N 2
3.5 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 oxidize 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.
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The complete combustion of methane with minimum amount of theoretical air and 150 per cent
theoretical air respectively is written as:
 79   79 
CH 4 +2O 2 +2   N 2 → CO 2 +2H 2 O+2   N 2 (3.3)
 21   21 
With 150 per cent theoretical air
 79   79 
CH 4 +2 (1.5 ) O 2 +2   (1.5 ) N 2 → CO 2 +2H 2 O+O 2 + 3   N 2 (3.4)
 21   21 
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.
3.6 Stoichiometric Air Fuel (AF) Ratio

Stoichiometric (or chemically correct) mixture of air and fuel is one that contains just sufficient
oxygen for complete combustion of the fuel.
A frequently used quantity in the analysis of combustion processes to quantify the amounts of
fuel and air is the air–fuel ratio AF. It is usually expressed on a mass basis and is defined as the
ratio of the mass of air to the mass of fuel for a combustion process.
mair
AF = (3.5)
m fuel
The mass m of a substance is related to the number of moles N through the relation m=NM,
where M is the molar mass. The air–fuel ratio can also be expressed on a mole basis as the ratio
of the mole numbers of air to the mole numbers of fuel. But we will use the former definition.
The reciprocal of air–fuel ratio is called the fuel–air ratio.
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:
Actural AF ratio Stoichiometric AF ratio

% excess air = (3.6)
Stoichiometric AF ratio
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To determine whether a fuel is being burnt completely or not, analysis on the exhaust (flue) gas
is performed. If O 2 appears in a dry flue gas (exhaust free of water vapor) then it means excess
air has been supplied to the fuel over that required for complete combustion. The mass of excess
air supplied can be determined from the dry-flue gas analysis following the procedure indicated
below.
• If the volumetric analysis is given, then, first the mass of dry flue gas per kg of fuel burnt
.
is determined by converting the volumetric analysis of the flue gas into a mass analysis.
• The mass of carbon per kg of flue gas is then determined from the mass analysis and
comparison is made with the mass of carbon per kg of fuel supplied. The C in the fuel
ultimately appears in the flue gas combined with O 2 forming either CO 2 or CO or both
and must be the same quantity.
• Relative molecular mass or CO 2 = 44, made up of 12 parts of carbon and 32 parts of
oxygen. Therefore, in 1 kg of CO 2 there is 12/44 = 3/11 kg C.
• Relative molecular mass of CO = 28, made up of 12 parts of carbon and 16 parts of
oxygen. In 1 kg of CO there is 12/28 = 3/7 kg C.
Thus, in every kg dry flue gas, if CO 2 and CO are the masses of carbon dioxide and carbon
monoxide, (if present), respectively, then;
 3 3 
mass of C / kg flue gas=  CO2 + CO  (3.7)
 11 7 
If m = mass of carbon per kg fuel supplied, then:
m
mass of dry flue gas / kg fuel = (3.8)
 3 3 
 CO2 + CO 
 11 7 
The amount of oxygen per kg dry flue gas is also determined from the mass analysis of the dry
flue gas. Hence,
mass of excess O2 / kg fuel = (mass of O2 / kg dry flue gas) x (mass of dry flue gas / kg fue)
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mass of execss O2 / kg fuel

Mass of excess air / kg fuel = (3.9)
0.232
If the stoichiometric air is calculated for the fuel in the usual manner, then:
total mass of air / kg fuel = stoichiometric air + excess mass of air (3.10)
Molar Analysis of Combustion Problems

When using the mole method, the reaction and product equations of combustion are written .in
terms of the numbers of moles. The analysis is done by equating the number of moles of each
constituent before combustion to the number of moles of products of combustion.
3.7 Analysis of Exhaust and Flue Gas

In each of the illustrations given above, complete combustion is assumed. For a hydrocarbon
fuel, this means that the only allowed products are CO 2 , H 2 O, and N 2 , with O 2 also present
when excess air is supplied. If the fuel is specified and combustion is complete, the respective
amounts of the products can be determined by applying the conservation of mass principle to the
chemical equation. The procedure for obtaining the balanced reaction equation of an actual
reaction where combustion is incomplete is not always so straightforward.
Combustion is the result of a series of very complicated and rapid chemical reactions, and the
products formed depend on many factors. When fuel is burned in the cylinder of an internal
combustion engine, the products of the reaction vary with the temperature and pressure in the
cylinder. In combustion equipment of all kinds, the degree of mixing of the fuel and air is a
controlling factor in the reactions that occur once the fuel and air mixture is ignited. Although
the amount of air supplied in an actual combustion process may exceed the theoretical amount, it
is not uncommon for some carbon monoxide and unburned oxygen to appear in the products.
This can be due to incomplete mixing, insufficient time for complete combustion, and other
factors. When the amount of air supplied is less than the theoretical amount of air, the products
may include both CO 2 and CO, and there also may be unburned fuel in the products. Unlike the
complete combustion cases considered above, the products of combustion of an actual
combustion process and their relative amounts can be determined only by measurement.
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Among several devices for measuring the composition of products of combustion are the Orsat
analyzer, gas chromatograph, infrared analyzer, and flame ionization detector. Data from these
devices can be used to determine the mole fractions of the gaseous products of combustion.
The analyses are often reported on a “dry” basis. In a dry product analysis, the mole fractions
are given for all gaseous products except the water vapor. Since water is formed when
hydrocarbon fuels are burned, the mole fraction of water vapor in the gaseous products of
combustion can be significant. If the gaseous products of combustion are cooled at constant
mixture pressure, the dew point temperature is reached when water vapor begins to condense.
Since water deposited on duct work, mufflers, and other metal parts can cause corrosion, knowledge of
the dew point temperature is important.
The orsat analyser is employed in the analysis of products of combustion. The apparatus in its
simplest form, consists of a measuring tube – the burrete surrounded by a water jacket to
maintain constant temperature, three vessels A, B and C containing the chemicals: Caustic soda
for the absorption of CO 2 , pyrogallic acid for the absorption of O 2 and a solution of cuprous
chloride for the absorption of CO, respectively, the leveling bottle, the sampling vessel, the three
way valve and stop valves or taps. The products of combustion are absorbed in the order indicated
above.
As the sample is collected over water in the sampling vessel, the water vapor in the flue gas is
condensed. Thus, using this method analysis of only dry products of combustion are given by the
method. The three way valve connects the apparatus either to the dry products of combustion
from the sampling vessel or to the atmosphere while in the third position it disconnects the
apparatus from the sampling vessel and the atmosphere. In the analysis of the products of
combustion the following procedure is followed.
The air tapped in the apparatus is removed by opening the three way valve to the atmosphere.
The valve is then closed and the leveling bottle lowered to produce a pressure below the
Atmospheric pressure in the apparatus. The taps on the vessels are opened and each of the levels
is brought to the mark on the stem of the respective vessel. The leveling bottle is then raised to
remove the air from the burrette. The three way valve is then connected to the sampling vessel
and the sample of the products of combustion induced in to the apparatus by slowly lowering the
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leveling vessel. The three way valve is then closed and the pressure in the burrette is brought to
the atmospheric pressure by equalizing the liquid levels in the burrette and the leveling bottle.
The volume of the dry products of combustion is read on the scale of the burrette. The tap of the
vessel A is opened and the whole of the dry products of combustion is let enter the vessel. The
leveling vessel is lowered until the level of the chemical in vessel A rises to the original level.
The volume of CO 2 absorbed in this vessel is read to the scale of the burrette. To ensure that this
reading is taken at atmospheric pressure, the liquid levels in the burrette and leveling vessel are
held at the same level. The remaining sample is forced into the vessel B by opening its tap. The
O 2 present in the dry products of combustion is absorbed by the pyrogallic acid in vessel B. The
same procedure is followed as above to determine the volume of O 2 in the sample. The volume reading
indicated on the burrette is now the sum of the volume of CO 2 and O 2 in the sample. The difference of
this reading and the reading obtained above for the volume of CO 2 gives the volume of O 2 in the sample.
Finally the sample is forced into vessel C by opening its tap where CO is absorbed by the
cuprous chloride solution. The volume of CO in the sample is obtained from the difference of the
final reading on the burrette and the sum of the volumes of the CO 2 and O 2 obtained above. The
volume of N 2 in the sample is determined by subtracting the total volume of CO 2 , O 2 and CO
from the total of 100.
This experimental analysis of the dry products of combustion indicates whether or not a chemical
reaction is complete. The presence of CO in the analysis indicates that the combustion process is
incomplete while the presence of O 2 indicates that excess air has been supplied.
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Figure 3.2 Orsat Analayser
3.8 Enthalpy of Formation

A combustion reaction is a particular kind of chemical reaction in which products are formed
from reactants with the release or absorption of energy as heat is transferred to as from the
surroundings. In some substances like hydrocarbon fuels which are many in number and
complex in structure the heat of reaction or combustion may be calculated on the basis of
known values of the enthalpy of formation, ΔH f of the constituent of the reactants and products
at the temperature T 0 (reference temperature). The enthalpy of formation (ΔH f ) is the increase in
enthalpy when a compound is formed from its constituent elements in their natural form and in a
standard state. The standard state is 25°C, and 1 atm pressure, but it must be borne in mind that
not all substances can exist in natural form, e.g. H 2 O cannot be a vapor at 1 atm and 25°C.
Neglecting changes in kinetic energy, potential energy and the external work terms, the
conservation of energy principle reduces to:
Q12 = ∆H (3.11)
For a system undergoing chemical reactions, the term ∆H is given by:
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∆H = ∆H prod − ∆H react (3.12)
∆H
= ∑ (n ∆h ) − ∑ (n ∆h )
prod
i i
react
i i (3.13)
Were ∆hi = specific enthalpy of any product or reactant and
ni = number of moles of the respective product or reactant of the

chemical reaction
Thermodynamic properties such as enthalpy and entropy are normally given relative to some
arbitrary reference state point where these values are set to zero. Evaluations of properties
involving differences in properties values can be satisfactorily worked out using this approach.
However, when chemical reactions occur and properties of reactants and products are at
completely different states, the approach of differences cannot be applied.
Unless a specific and known reference state is used in the determination of the specific enthalpy
∆h of any product or reactant, the result obtained for ∆H differs from one table to another. To
avoid this, the term enthalpy of formation, ∆h fo is introduced. The enthalpy of formation is
defined as the specific enthalpy change that occurs when a chemical compound is formed
isothermally from its constituents. In a steady-flow process, the enthalpy of formation is equal to
the quantity of heat absorbed or released during a chemical reaction. Some important expressions
related to the enthalpy of formation are stated below.
• The specific enthalpy of any compound at pressure and temperature of 1atm and 298 K
(the standard reference state) is the same as the enthalpy of formation at the same
temperature.
Δh
hcompound (at 1 atm and 298 K)= fo,298k
• The specific enthalpy of any stable element is zero.

• The difference between the enthalpy of formation of the gas phase and the liquid phase is
equal to the specific enthalpy of vaporization h fg the given temperature. That is:
h fg = (∆h fo ,298 k ) gas − (∆h fo ,298 k )liquid
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• The enthalpy of the products of combustion or reactants at a specified temperature T and

pressure, different from the standard temperature and pressure, is evaluated from the
relation:
∆hi ,T =(∆h fo ,298 ) + (hT − h298 ) (3.14)
Where ∆hi ,T = the specific enthalpy of product or reactant at a specified
temperature T,
hT = specific enthalpy at the temperature T,
h298 = specific enthalpy at the reference temperature of 298K.
In the absence of tables of the enthalpy change or the sensible enthalpy change of substance,
( hT - h 298 ) is evaluated from the integral of c p dT. Equation (3.15) indicates that the specific
enthalpy of a reactant or product of combustion is the sum of the enthalpy of formation at the
standard pressure and temperature and the sensible enthalpy change of the substance. The
quantity of heat absorbed or released in a chemical reaction may, therefore, be obtained from the
relation:
∆H=
O ∑ {n (∆h
prod
i fo ,298 + hT − h298 )} − ∑ {ni (∆h fo ,298 + hT − h298 )}
react
(3.15)
Table 3.2 Enthalpy of Formation of Enthalpy of Evaporation for Some Common Elements and
Compounds
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Values of enthalpy of formation and enthalpy of evaporation for some common elements and
compounds are given in Table 3.2, with the subscripts s, g and l. indicating the solid, the gas and
liquid phases; respectively.
3.9 Adiabatic-Flame Temperature

The determination of the maximum attainable combustion temperature is an important aspect in
the selection and design of combustion equipment. The maximum temperature in a chemical
reaction can be obtained when the process occurs in the limit adiabatic operation. This maximum
temperature is known as the adiabatic flame temperature.
For an adiabatic process, Equation (3.15) reduces to:
∑ {n (∆h
prod
i fo ,298 + hT − h298=
)} ∑ {n (∆h
react
i fo ,298 + hT − h298 )} (3.16)
Normally in Equation (3.16):
• The composition and the initial temperature of the reactants are known.
• The number of moles of the reactants and the products of combustion can also be
determined from the chemical reaction.
• The values of the enthalpy of formation ∆h fo,298 and h 298 for the reactants as well as
'
products of combustion can be obtained from tables.

• The h T values of the reactants can also be obtained from tables at the respective reactant
temperature.
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The only unknown in Equation (3.16) is the enthalpy h T of the products of combustion at the
flame temperature. The h T values can be determined from the flame temperature T f . This implies
that the evaluation of the adiabatic flame temperature T f requires an iterative procedure. That is,
an adiabatic flame temperature T f is assumed and the enthalpy h T for the various components of
product of combustion at this assumed temperature are read from tables. These values of h T are
then substituted in Equation (3.16) for the respective components of the products of combustion
and the left hand side of the equation evaluated and compared with the results of the right hand
side of the equation. The procedure of assuming a temperature T f , reading h T values for the
products of combustion from tables at the assumed temperature and evaluation of the left hand
side of the Equation (3.16) is continued until for a specific assumed temperature T f both the left-
hand side and right-hand side of Equation (3.16) are equal. The temperature for which both sides
of Equation (3.16) are the same is the adiabatic-flame or combustion temperature for the
particular chemical reaction process.
3.10 Heating Value of Fuels

Heating value is the amount of heat liberated by the complete combustion of a unit mass of a unit
mass of fuel. There are two cases to consider under the investigation of heating values of fuels
the higher heating value HHV and the lower heating value LHV of fuels.
Higher Heating Value of Fuels

The higher heating value of a fuel is the energy liberated when the products of combustion are
cooled to the original fuel temperature and the water vapor formed as a result of the
combustion process is in liquid phase. All fuels containing hydrogen combine with oxygen
forming water vapor during a chemical reaction. When the products of combustion are cooled to
the initial fuel temperature, the water vapor formed condenses liberating thermal energy. This
heat quantity is the higher heating value. The higher heating value (HHV) of fuels at standard
temperature and pressure may be determined from the relation:
O2
HHV =
34000 C + 144000 ( H - ) + 9290 S kJ / kg (3.17)
8
Where: C, H 2 , O 2 and S are the masses of the components per kg of the fuel.
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Lower Heating Value of Fuels

When hydrogen present in a fuel is burnt, it forms water vapor and this, together with any
moisture in the fuel, appears as water vapor in the products of combustion. Lower heating value
of a fuel is the difference between the higher heating value of fuel and the heat absorbed by
water, due to the combustion of hydrogen and the moisture in the fuel, in having its phase
changed into vapor. The mass of steam products of combustion per kg of fuel burnt is (m + 9 H 2 )
kg where m and H 2 are the mass of moisture and hydrogen per kg of the fuel. The specific
enthalpy of evaporation per kg of vapor which is produced with the products of combustion at
standard temperature of 25 °C is 2442.3kJ/kg.
LHV =
HHV − 2442.3(m + 9 H 2 )kJ / kg (3.18)
Table 3.3 Heating Values of Some Common Fuels
3.11 Experimental Determination of Heating Values of Fuels

Depending on the type of fuel, the heating value of which is to be determined, either bomb
calorimetet or Boys' calorimeter can be utilized for solid & liquid fuels or gaseous fuels,
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respectively. Here, the working principle and the determination of the heating value of solid fuel
using the bomb calorimeter is discussed, Fig. 3.3.
The water formed from the burning of the hydrogen of the fuel in the bomb calorimeter remains
in liquid form in as much as the temperature of the products at the end of the test is always below
the dew point of the mixture. The heating value as determined by the bomb calorimeter is,
therefore, the higher heating value.
The following procedure is followed in the determination of the higher heating value of solid
fuels using the bomb calorimeter.
• The fuel sample, that is formed into a pellet by pressing it, is weighed.
• The calorimeter is filled with a known weight of distilled water.
• The fuel sample is placed inside the bomb and the electrical connections are set.
• The bomb is filled with oxygen to a pressure of approximately 20 - 25 bar.
• The differential thermometer is set to a convenient scale.
• The stirrer is started and the differential thermometer reading is observed until steady
reading is observed. The pre-test is conducted by recording the temperature reading
every minute during stirring.
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• The main-test is then started by igniting the fuel during which period the temperature
reading is recorded until it reaches the maximum value.
• The after-test readings are recorded until the temperature reaches steady state again.
The higher heating value (HHV) of the fuel is determined from the following expression
1
HHV = {∆To (mw + Weq )C pw }kJ / kg
mf (3.19)
∆To =∆Tu + f
Where: m f = mass of fuel (g).

∆To = corrected temperature rise (K) ( ∆To =∆Tu + f ).
∆Tu = uncorrected temperature rise (K) ( ∆Tu = Tn − To ).
Tn = the first temperature reading of the after-test (K).
To = the last temperature reading of the pre-test (K).
f = correction factor (K).
mw = mass of water (g).
Weq = water equivalent of apparatus determined from a known fuel of pre-
determined heating value (g).
C pw = specific heat capacity of water (kJ/kg K).
The correction factor f is defined by:
 ∆v − ∆v   1 
f = n∆v +  1  ∑ tm + (to + tn ) − n∆t  (3.20)
 ∆t1 − ∆t   2 
Where:
n = the number of minutes between the last pre-test reading and the first after-test
reading [min],
∆v = the rate of temperature fall per minute during the pre-test period [K/min]
∆v1 = the rate of temperature fall per minute during the after-test period[K/min]
∆t1 = average temperature during the after-test period [°C]

∆t = average temperature during the pre-test period [°C],
∑t m = sum of temperature readings during the main test period [oC],
1/ 2(to + tn ) = the mean temperature of the last pre-test temperature and the first
after-test temperature [°C].
_____________________________________________________________________________________
3.12 Dissociation
All reaction equations discussed in the preceding sections are ideal reactions. In practice
products of combustion may break up in to the original reactants. The rate of breaking-up of the
products of combustion into the original reactants reduces the rate of formation of the products
of combustion from the reactants. Breaking up of products of combustion to their original
reactants is called Dissociation. Dissociation limits the maximum temperature reached in an
adiabatic combustion process. Consider the following reaction:
1
H2 + O2 → H 2 O (3.21)
2
When the process proceeds in the direction indicated energy is released. If sufficient energy is supplied to
the H 2 O molecules, the above exothermic process-Process accompanied by energy release can be made to
proceed in the reverse direction. At high temperature, then:
1
H 2O → H 2 + O2 (3.22)
2
More generally, from equation (3.20) and (3.21)
1 
H 2 + O2  H 2O
2
A stable chemical equilibrium state is said to exist when the rate of break-up of product molecules is
equal to their rate of formation. The reverse reaction which is accompanied by an absorption of energy is
termed as an endothermic reaction.
The preceding remarks apply equally to CO 2 molecules which dissociate to CO and O 2 .In these reactions,
the products of combustion contain an equilibrium mixture of H 2 O, H 2 and O 2 and an equilibrium
mixture of CO 2 , CO and O 2 .The presence of H 2 and CO in the products indicates that not all the chemical
energy in the fuel is released. Therefore, the maximum possible adiabatic combustion temperature
predicted on the basis of simple chemical equations would be lower with the presence of H 2 and CO.
The combustion reaction of carbon monoxide to carbon dioxide may be written as:
1   2CO2

CO + O2  CO2 or 2CO + O2  (3.23)
2
With mole proportions for CO, O 2 and CO 2 of 1, 0.5,1 and 2, 1, 2, respectively
_____________________________________________________________________________________
The forward reaction in equation (3.22)
1
CO + O2 → CO2
2
If ε is the mole of CO 2 dissociated to CO, then the backward reaction becomes:
ε
ε CO → ε CO + O2 (3.24)
2
The number of moles ε in the reaction varies during the course of the reaction. Equilibrium is established
when ε is constant. The chemical reaction involving the dissociation process is given by chemical
equation:
ε
O2 → (1 − ε )CO2 + ε CO + O2
1
CO + (3.25)
2 2
When equilibrium is established between the rate of breaking up of the products of combustion and the
rate of its formation, that is when ε is constant, the partial pressures of CO 2 ,CO and O 2 are related by the
equilibrium or dissociation constant K P. Given for the above combustion process by:
1
PCO2 − P 2 CO2
KP = 1
atm 2
or K ' P = 2
atm −1 (3.26)
PCO PO2 2
P CO PO2
Where the partial pressures are given in atm, from equation (3.25) it can be seen that
K 'P = KP
2
The equilibrium equation of the combustion reaction of H 2 may be written as:
1   2 H 2O
H 2 + O2  H 2O Or 2 H 2 + O2  (3.27)
2
With mole proportions for H 2 , O 2 and H 2 O of 1, 0.5, 1 and 2, 1, 2, respectively, the equilibrium constant
K P for the above combustion processes are:
1 2
PH 2O − P H 2O
KP = 1
atm 2
Or K '
P = 2
atm −1 (3.28)
PH 2 PO2 2
PH 2 PO2
Again K P = K P
' 2
_____________________________________________________________________________________
In the combustion reaction of hydrocarbon fuels, both the above equations (3.23) and (3.27) may occur
simultaneously. For this reaction:
 CO + H 2O
CO2 + H 2  (3.29)
And the equilibrium constant K P for the above combustion reaction is:
PCO PH 2O
KP = (3.30)
PH 2 PCO2
_____________________________________________________________________________________

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Thermodynamics II__________________________________________________________________ _ AAiT

3.3 Basic Chemistry

3.4 Combustion Equations

Fuel + Oxidizer Products

Some important combustion equations are given below :

The above equation of combustion of hydrogen tell us that :

(i) Hydrogen reacts with water to form steam or water.

The proportions by mass are obtained by using atomic weights as follows

1kgH 2 + 8kgO2 → 9kgH 2O

That the total volume of the reactants and product

2 volumes H 2 + 1 volume O 2 = 3 volumes

(i) Complete combustion of carbon to carbon dioxide

and including the nitrogen,

0 volume C + 1 volume O 2 + 3.76 volumes N 2 → 1 volume CO 2 + 3.76 volumes N 2

12kgC+(2 × 16)kgO 2 +3.76(2 × 14)kgN 2 → (12 + 2 × 16)kgCO 2 + 3.76(2 × 14)N 2

12kgC+32k O 2 +105.3kgN 2 → 44kgCO 2 +105.3kgN 2

(ii) The incomplete combustion of carbon.

2C+O 2 +3.76N 2 → 2CO+3.76N 2

(2×12)kgC+(2×16)kgO 2 +3.76(2×14)kgN 2 → 2(12+16)kgCO+3.76(2×14)kgN 2

24kgC +32 kgO 2 +105.3kgN 2 → 56kgCO+105.3kgN 2

2CO+O 2 +3.76N 2 → 2CO 2 + 3.76N 2

3.5 Theoretical Air and Excess Air

With 150 per cent theoretical air

3.6 Stoichiometric Air Fuel (AF) Ratio

The percentage of excess air is given as:

Actural AF ratio Stoichiometric AF ratio

If m = mass of carbon per kg fuel supplied, then:

mass of execss O2 / kg fuel

Molar Analysis of Combustion Problems

3.7 Analysis of Exhaust and Flue Gas

Figure 3.2 Orsat Analayser

3.8 Enthalpy of Formation

For a system undergoing chemical reactions, the term ∆H is given by:

∆H = ∆H prod − ∆H react (3.12)

Were ∆hi = specific enthalpy of any product or reactant and

ni = number of moles of the respective product or reactant of the

• The specific enthalpy of any stable element is zero.

• The enthalpy of the products of combustion or reactants at a specified temperature T and

Where ∆hi ,T = the specific enthalpy of product or reactant at a specified

h298 = specific enthalpy at the reference temperature of 298K.

3.9 Adiabatic-Flame Temperature

Normally in Equation (3.16):

products of combustion can be obtained from tables.

3.10 Heating Value of Fuels

Higher Heating Value of Fuels

Lower Heating Value of Fuels

Table 3.3 Heating Values of Some Common Fuels

3.11 Experimental Determination of Heating Values of Fuels

Where: m f = mass of fuel (g).

∆t1 = average temperature during the after-test period [°C]

∑t m = sum of temperature readings during the main test period [oC],

More generally, from equation (3.20) and (3.21)

1   2CO2

With mole proportions for CO, O 2 and CO 2 of 1, 0.5,1 and 2, 1, 2, respectively

The forward reaction in equation (3.22)

If ε is the mole of CO 2 dissociated to CO, then the backward reaction becomes:

The equilibrium equation of the combustion reaction of H 2 may be written as: