I84

Thermodynamics of combustion

10.1 Simple chemistry

Combustion is a chemical reaction and hence a knowledge of basic chemistry is required
before it can be analysed. An extremely simple reaction can be written as
2 c o + 0, (j2 c 0 ,

(10.1)

This basically means that two molecules of carbon monoxide (CO) will combine with
one molecule of oxygen (0,)to create two molecules of carbon dioxide (CO,). Both CO
and 0, are diatomic gases, whereas CO, is a triatomic gas. Equation (10.1) also indicates
that two molecules of CO, will always break down into two molecules of CO and one
molecule of 0,; this is signified by the symbol e which indicates that the processes can
go in both directions. It is conventional to refer to the mixture to the left of the arrows as
the reactants and that to the right as the products; this is because exothermic combustion
(i.e. in which energy is released by the process) would require CO and 0, to combine to
give CO,. Not all reactions are exothermic and the formation of NO during dissociation
occurring in an internal combustion (i.c.) engine is actually endothermic.
It should be noted from the combustion eqn (10.1) that three molecules of reactants
combine to produce two molecules of products, hence there is not necessarily a balance in
the number of molecules on either side of a chemical reaction. However, there is a balance
in the number of atoms of each constituent in the equation and so mass is conserved.
10.1.1 FUELS

Hydrocarbon fuels are rarely single-component in nature due to the methods of formation
of the raw material and its extraction from the ground. A typical barrel of crude oil
contains a range of hydrocarbons, and these are separated at a refinery; the oil might
produce the constituents defined in Fig 10.1. None of the products of the refinery is a
single chemical compound, but each is a mixture of compounds, the constituents of which
depend on the source of the fuel.
Light distillates (chemical
feedstock)

Fuel to run
refinery

Heavy fuel, or

Kerosene (paraffin,
aviation fuel)

Middle distillates (gas oil.

diesel, heating oil)
Gases (butane,
propane)

Fig. 10.1 Typical constituents of a barrel of crude oil

Combustion of simple hydrocarbons fuels

185

One fuel which approaches single-component composition is natural gas, which

consists largely of methane (CH,). Methane is the simplest member of a family of
hydrocarbons referred to as paraffins or, more recently, alkanes which have a general
The lower alkanes are methane (CH,), ethane (C,H,), propane (C,H,)
formula C,,HZn+,.
and butane (C,H,,) etc. Two other alkanes that occur in discussion of liquid fuels are
heptane (C,H,,) and octane (CEHIE). The alkanes are referred to as saturated
hydrocarbons because it is not physically possible to add more hydrogen atoms to them.
However, it is possible to find hydrocarbons with less than 2n + 2 hydrogen atoms and
these are referred to as unsaturated hydrocarbons. A simple unsaturated hydrocarbon is
acetylene (C,H,), which belongs to a chemical family called alkenes. Some fuels
contain other constituents in addition to carbon and hydrogen. For example, the alcohols
contain oxygen in the form of an OH radical. The chemical symbol for methanol is
CH,OH, and that for ethanol is C,H,OH; these are the alcohol equivalents of methane
and ethane.
Often fuels are described by a mass analysis which defines the proportion by mass of
the carbon and hydrogen, e.g. a typical hydrocarbon fuel might be defined as 87% C and
13% H without specifying the actual components of the liquid. Solid fuels, such as various
coals, have a much higher carbon/hydrogen ratio but contain other constituents including
oxygen and ash.
The molecular weights (or relative molecular masses) of fuels can be evaluated by
adding together the molecular (or atomic) weights of their constituents. Three examples
are given below:

(m,),,

Methane (CH,)

12 + 4 x 1 = 16

(mw)CsH,s
= 8 x 12 + 18 x 1 = 114

Octane (CEH18)
Methanol (CH,OH)

(mw)CH30H
= 12 + 3 x 1 + 16 + 1 = 32

10.2 Combustion of simple hydrocarbon fuels

The combustion of a hydrocarbon fuel takes place according to the constraints of
chemistry. The combustion of methane with oxygen is defined by
CH,
1 kmol
12+4
16kg

2Q
2 kmol
2x32
64kg

CQ
1 kmol
12x32
44 kg

2H,O
2 kmol
2x(2+16)
36 kg

(10.2)

In this particular case there is both a molar balance and a mass balance: the latter is
essential but the former is not. Usually combustion takes place between a fuel and air (a
mixture of oxygen and nitrogen). It is normal to assume, at this level, that the nitrogen is
an inert gas and takes no part in the process. Combustion of methane with air is given by

a
1 kmol
12+4
16 kg

9.52 kmol
2x(32+105.2)
274.4 kg

CO,
1 kmol
12+32
44 kg

2H2O

2 kmol
2x(2+16)
36 kg

79

+2~-,

21
7.52 kmol
7.52~28
210.67 kg

(10.3)

186 Thermodynamics of combustion

10.2.1

STOICHIOMETRY

There is a clearly defined, and fixed, ratio of the masses of air and fuel that will result
in complete combustion of the fuel. This mixture is known as a stoichiometric one and
the ratio is referred to as the stoichiometric air- fuel ratio. The stoichiometric air-fuel
ratio,
for methane can be evaluated from the chemical equation (eqn 10.3). This
gives
& StOlC
. =

2 x (32 + 105.33)
mass of air
mass of fuel
16

17.17

This means that to obtain complete combustion of 1 kg CH, it is necessary to provide

17.17 kg of air. If the quantity of air is less than 17.17 kg then complete combustion will
not occur and the mixture is known as rich. If the quantity of air is greater than that
required by the stoichiometric ratio then the mixture is weak.
10.2.2

COMBUSTION WITH WEAK MIXTURES

A weak mixture occurs when the quantity of air available for combustion is greater than
the chemically correct quantity for complete oxidation of the fuel; this means that there is
excess air available. In this simple analysis, neglecting reaction rates and dissociation etc,
this excess air passes through the process without taking part in it. However, even though
it does not react chemically, it has an effect on the combustion process simply because it
lowers the temperatures achieved due to its capacity to absorb energy. The equation for
combustion of a weak mixture is
2

7.52

+ - (0,+ 3.76Nz)

CH,

( 10.4)

NZ

$J

where @ is called the equivalence ratio, and

@=

actual fuel-air ratio

stoichiometric air-fuel ratio

stoichiometric fuel-air ratio

actual air-fuel ratio

For a weak mixture q5 is less than unity. Consider a weak mixture with

CH,
10.2.3

+ 2.5(0, + 3.76N2)3CO, + 2H,O + 0.50, + 9.4Nz

(10.5)
c$ = 0.8;

then
(10.6)

COMBUSTION WITH RICH MIXTURES

A rich mixture occurs when the quantity of air available is less than the stoichiometric
quantity; this means that there is not sufficient air to bum the fuel. In this simplified
approach it is assumed that the hydrogen combines preferentially with the oxygen and the
carbon does not have sufficient oxygen to be completely burned to carbon dioxide; this
results in partial oxidation of part of the carbon to carbon monoxide. It will be shown in
Chapter 12 that the equilibrium equations, which control the way in which the hydrocarbon fuel oxidizes, govern the proportions of oxygen taken by the carbon and hydrogen
of the fuel and that the approximation of preferential combination of oxygen and

Heats of formation and heats of reaction

187

hydrogen is a reasonable one. In this case, to define a rich mixture, @ is greater than
unity. Then
2
CH4 + - ( 0 2

+ 3.76N2) *

( :@)co2 +
___

2 H 2 0 + 4(@ - 1)

7.52

co+-

N2

(10.7)

If the equivalence ratio is 1.2, then eqn (10.7) is

CH, + 1.667(0, + 3.76N2)3 0.333C0,

+ 2H,O + 0.667CO + 6.267N2

(10.8)

It is quite obvious that operating the combustion on rich mixtures results in the
production of carbon monoxide (CO), an extremely toxic gas. For this reason it is now not
acceptable to operate combustion systems with rich mixtures. Note that eqn (10.7) cannot
be used with values of @ >4/3, otherwise the amount of CO, becomes negative. At this
stage it must be assumed that the carbon is converted to carbon monoxide and carbon. The
resulting equation is
2
CH4+-(02+3.76N2)*2H20+

Equation (10.9) is a very hypothetical one because during combustion extensive dissociation
occurs and h s liberates oxygen by breaking down the water molecules; this oxygen is then
available to create carbon monoxide and carbon dioxide rather than carbon molecules.
In reality it is also possible to produce pollutants even when the mixture is weaker than
stoichiometric, simply due to poor mixing of fuel and air, quenching of flames on cold
cylinder or boiler walls, trapping of the mixture in crevices (fluid mechanics effects) and
also due to thermodynamic limitations in the process.

10.3 Heats of formation and heats of reaction

Combustion of fuels takes place in either a closed system or an open system. The relevant
property of the fuel to be considered is the internal energy or enthalpy, respectively, of
formation or reaction. In a naive manner it is often considered that combustion is a process
of energy addition to the system. This is not true because the energy released during a
combustion process is already contained in the reactants, in the form of the chemical
energy of the fuel (see Chapter 11). Hence it is possible to talk of adiabatic combustion as
a process in which no energy (heat) is transferred to, or from, the system - the
temperature of the system increases because of a rearrangement of the chemical bonds in
the fuel and oxidant.
Mechanical engineers are usually concerned with the combustion of hydrocarbon fuels,
such as petrol, diesel oil or methane. These fuels are commonly used because of their
ready availability (at present) and high energy density in terms of both mass and volume.
The combustion normally takes place in the presence of air. In some other applications,
e.g. space craft, rockets, etc, fuels which are not hydrocarbons are burned in the presence
of other oxidants; these will not be considered here.
Hydrocarbon fuels are stable compounds of carbon and hydrogen which have been
formed through the decomposition of animal and vegetable matter over many millennia. It
is also possible to synthesise hydrocarbons by a number of processes in which hydrogen is

188 Thermodynamics of combustion

added to a carbon-rich fuel. The South African Sasol plant uses the Lurgi and
Fischer-Tropsch processes to convert coal from a solid fuel to a liquid one. The chemistry
of fuels is considered in Chapter 11.

10.4 Application of the energy equation to the combustion process - a

macroscopic approach
Equations (10.3) to (10.6) show that combustion can take place at various air-fuel ratios,
and it is necessary to be able to account for the effect of mixture strength on the
combustior. process, especially the temperature rise that will be achieved. It is also
necessary to be able to account for the different fuel composition: not all fuels will release
the same quantity of energy per unit mass and hence it is required to characterise fuels by
some capacity to release chemical energy in a thermal form. Both of these effects obey the
First Law of Thermodynamics, i.e. the energy equation.

10.4.1 INTERNAL ENERGIES AND ENTHALPIES OF IDEAL GASES

It was shown previously that the internal energies and enthalpies of ideal gases are
functions of temperature alone ( c pand c, might still be functions of temperature). This
means that the internal energy and enthalpy can be represented on U - T and H-T diagrams.
It is then possible to draw a U-T or H-T line for both reactants and products (Fig 10.2).
The reactants will be basically diatomic gases (neglecting the effect of the fuel) whereas
the products will be a mixture of diatomic and triatomic gases - see eqn (10.3).

Temperature, T

Fig. 10.2 Enthalpy (or internal energy) of reactants and products

The next question which arises is: what is the spacing between the reactants and
products lines? This spacing represents the energy that can be released by the fuel.

10.4.2 HE.4TS OF REACTION AND FORMATION

The energy contained in the fuel can also be assessed by burning it under a specified
condition; this energy is referred to as the heat of reaction of the fuel. The heat of reaction

Application of the energy equation to the combustion process

189

for a fuel is dependent on the process by which it is measured. If it is measured by a

constant volume process in a combustion bomb then the internal energy of reaction is
obtained. If it is measured in a constant pressure device then the enthalpy of reaction is
obtained. It is more normal to measure the enthalpy of reaction because it is much easier to
achieve a constant pressure process. The enthalpy of reaction of a fuel can be evaluated by
burning the fuel in a stream of air, and measuring the quantity of energy that must be
removed to achieve equal reactant and product temperatures (see Fig 10.3).
Control surface

T,= T,

eQP

Fig. 10.3 Constant pressure measurement of enthalpy reaction

Applying the steady flow energy equation

( : ) ( : +)

Q - W s= liz, he + - + gz,

- ri2;

hi

+ gz,

(10.10)

and neglecting the kinetic and potential energy terms, then

(QPh

- ( H R ) T = nP(hP)T - n R ( h d ~

(1G.11)

where n denotes the amount of substance in either the products or reactants; this is
identical to the term n which was used for the amount of substance in Chapter 9. The
suffix T defines the temperature at which the enthalpy of reaction was measured.
is
a function of this temperature and normally it is evaluated at a standard temperature of
25C (298 K). When
is evaluated at a standardised temperature it will be denoted by
the symbol
Most values of Qpthat are used in combustion calculations are the
ones. (In a similar way, (Q,), will be used for internal energy of reaction at the standard
temperature.) The sign of Qp is negative for fuels because heat must be transferred from
the calorimeter to achieve equal temperatures for the reactants and products (it is positive
for some reactions, meaning that heat has to be transferred to the calorimeter to maintain
constant temperatures). The value of the constant volume heat of reaction, the internal
energy of reaction,
can be calculated from
as shown below, or measured
using a constant volume combustion bomb; again (Q,), has a negative value.
and
(Q,), are shown in Figs 10.4(a) and (b) respectively. The term calorific value of the fuel
was used in the past to define the heating value of the fuel: this is actually the negative
value of the heat of reaction, and is usually a positive number. It is usually associated with
analyses in which heat is added to a system during the combustion process, e.g. the air
standard cycles.
Applying the first law for a closed system to constant volume combustion gives

(ep),.

(e,),,

(ep),

(ep),

(ep),

(10.12)

190 Thermodynamics of combustion

If both the products and reactants are ideal gases then h = J c ~dT,, and
~ u = J cy,,, dT,
which can be evaluated from the polynomial expressions derived in Chapter 9. Thus
(QpIs

(QvIs

=~ P ( ~ P) T~ R ( ~ R ) T( ~ P ( ~ P ) Tn R ( u R ) T l
= np( (hP)T-

(up)TJ - nRI (hR)T- (uR)T}

= % T ( n p- n R )

(10.13)

(e,),

This result is quite logical because the definitions of (Qp)sand

require that Tp and
TR are equal. Hence the constant pressure and constant volume processes are identical if
the amounts of substance in the products and the reactants are equal. If the amounts of
substance change during the reaction then the processes cease to be identical and, in the
case of a combustion bomb, a piston would have to move to maintain the conditions. The
movement of the piston is work equal to % T ( n p- nR).
It is also possible to relate the quantity of energy that is chemically bound up in the fuel
to a value at absolute zero of temperature. These values are denoted as -AHo and -AUo
and will be returned to later.
10.4.3 HEAT OF FORMATION - HESS' LAW

The heat of formation of a compound is the quantity of energy absorbed (or released)
during its formation from its elements (the end pressures and temperatures being
maintained equal).
For example, if CO, is formed from carbon and oxygen by the reaction

c + 0, -+ co,

(10.14)

then in a constant pressure steady flow process with equal temperature end states the
reaction results in heat transfer of (
given by

<ep)HP T=

(10.15)

H R

(10.16)

-394 MJ/kmol
x

Reactants

Reactants
/*

,'Products

T,

Temperature, T

Temperature, T

(b)

Fig. 10.4 Internal energy and enthalpy of reaction depicted on (a) internal energy-temperature and
(b) enthalpy -temperature diagrams

Application of the energy equation to the combustion process

191

If a slightly different reaction is performed giving the same end product, e.g.

co + -1

0 2

- co,

(10.17)

then it is not possible to use the same simple approach because the reactants are a mixture
of elements and compounds. However, Hess law can be used to resolve this problem. This
states that:
(a)

if a reaction at constant pressure or constant volume is carried out in stages, the

algebraic sum of the amounts of heat evolved in the separate stages is equal to the
total evolution of heat when the reaction occurs directly;

or
(b) the heat liberated by a reaction is independent of the path of the reaction between the
initial and final states.
Both of these are simply statements of the law of energy conservation and the definition
of properties. However, this allows complex reactions to be built up from elemental ones.
For example, the reaction
1

co + - 0,
2

CO,

(10.18)

can be sub-divided into two different reactions:

1
c + - 0,
2

co + -1 0,
2

co

CO,

(10.19a)
(10.19b)

The heat of formation of CO may be evaluated by reaction (10.19a) and then used in
reaction (10.19b) to give the heat of reaction of that process. From experiment the heat of
formation of carbon monoxide (CO) is - 112 MJ/kmol and hence, for reaction (10.19b),
the energy released is

(Q,),

= Hp-

H R =-394- (-110.5)= -283 MJ/kmol

(10.20)

Hence the heat of reaction for CO + io2-.+ CO, is - 283 MJ/kmol.

The heats of formation of any compounds can be evaluated by building up simple
reactions, having first designated the heats of formation of elements as zero. This enables
the enthalpy of formation of various compounds to be built up from component reactions.
Enthalpies of formation are shown in Table 10.2.
These enthalpies of formation can be used to evaluate heats of reaction of more complex
molecules, e.g. for methane (CH,) the equation is
CH,

+ 20, = CO, + 2H,O (g)

giving
(12,125

=
=

(AH,)co,,g) + 2(AHfh2o(g)- (AHf)c,,g,

-802 279 k.J/kmol

This gives an enthalpy of reaction per kg of CH, of -50 142 kJ/kg.