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Simple chemistry
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.
Fuel to run
refinery
ferostock)
Petrol
Kerosene (parnffin,
aviation fuel)
Methane (CH4 )
Octane (C 8 H 18 )
(mw)c 8 tt 18 = 8
Methanol (CH30H)
10.2
1 = 16
12 + 18
(mw)rn 3ott = 12 + 3
1=114
1 + 16 + 1 = 32
COz
1 kmol
12 x 32
44 kg
2H 2 0
2kmol
2 x (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
CH 4
1 kmol
12+4
16 kg
+ 2(0 2 +
~: N
2)
9.52 kmol
2 x (32 + 105.2)
274.4 kg
C0 2
1 kmol
12+ 32
44 kg
79
+ 2 x - N2
21
7.52 kmol
2 kmol
7.52 x 28
2 x (2 + 16)
210.67 kg
36 kg
2H 20
(10.3)
10.2.l
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, E,, ;c for methane can be evaluated from the chemical equation (eqn 10.3). This
gives
0
fstoic
mass of air
mass of fuel
2 x (32 + 105.33)
16
= 17.17
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
(10.4)
where
</>
(10.5)
</> = - - - - - - - - - - - - - - - - - - - - - -
</>
</> =
0.8; then
(10.6)
10.2.3
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 burn 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
</>
is greater than
(4 - 3</>)
4(</>- 1)
7.52
2
CH 4 + - (0 2 + 3.76N 2 ) => - - C0 2 + 2H 2 0 +
CO+ - - N 2
</>
</>
</>
<P
(10.7)
If the equivalence ratio is 1.2, then eqn (10.7) is
(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 <P >4/3, otherwise the amount of C0 2 becomes negative. At this
stage it must be assumed that the carbon is converted to carbon monoxide and carbon. The
resulting equation is
2 (0 2 + 3.76N 2 ) => 2H 20 + (
4
CH 4 +
- 2) CO+ (3 -
7 .52 N 2
4) C + -;;:
(10.9)
Equation (10.9) is a very hypothetical one because during combustion extensive dissociation
occurs and this 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
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
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 .
It was shown previously that the internal energies and enthalpies of ideal gases are
functions of temperature alone (cp and cv 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).
Reactants
/
/
/
/
Temperature, T
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
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
,- - -
-----
-.
I
___.....L. .----.---n~- - _J
- Qp
Fig. 10.3 Constant pressure measurement of enthalpy reaction
w,
(10.10)
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. (Qph is
a function of this temperature and normally it is evaluated at a standard temperature of
25C (298 K). When (Qph is evaluated at a standardised temperature it will be denoted by
the symbol (Qp),. Most values of QP that are used in combustion calculations are the (Qp) s
ones. (In a similar way, (Qv)s 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, (Qv),, can be calculated from (Qp)s as shown below, or measured
using a constant volume combustion 'bomb'; again (QJ , has a negative value. (Qp) s and
(Qv), 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
(10.12)
If both the products and reactants are ideal gases then h = J cp,m dT, and u = J cv,m dT,
which can be evaluated from the polynomial expressions derived in Chapter 9. Thus
(Qp)s - (Qv)s = np(hph - nR (hRh - {np(uph - nR (uRh}
=
= 9\T(np - nR)
(10.13)
This result is quite logical because the definitions of (Qp)s and (Qv)s 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 9\T(np - 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 -AH0 and -/l.U0
and will be returned to later.
10.4.3
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 C0 2 is formed from carbon and oxygen by the reaction
(10.14)
then in a constant pressure steady flow process with equal temperature end states the
reaction results in heat transfer of (QPh given by
(10.15)
(Qph= Hp- HR
= -
(10.16)
394 MJ /kmol
Reactants
/
,,.
,,. "'Products
-(QJ,
. !-.Uo
,;
~
~
Temperature, T
T,
(a)
Temperature, T
T,
(b)
Fig. 10.4 Internal energy and enthalpy of reaction depicted on (a) internal energy-temperature and
(b) enthalpy-temperature diagrams
If a slightly different reaction is performed giving the same end product, e.g.
1
CO + - 0 2
2
--+
(10.17)
C0 2
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)
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
2 --+
(10.18)
C0 2
c+-
02-+
1
CO + - 0
2
co
2 --+
(10.19a)
C0 2
(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
(QPh =Hp - HR= -394 - (-110.5) = -283 MJ/kmol
(10.20)
= (LiHr)co 2 cg)
= -
+ 2(LiHr)tt2o(g) - (LiHr)c14(g)