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Chemistry of Combustion
The thermodynamics of combustion were considered in Chapter 10, and it was stated that
adiabatic combustion could be achieved. The concept of adiabatic combustion runs counter
to the experience of many engineers, who tend to relate combustion to heat addition or
heat release processes. This approach is encouraged in mechanical engineers by the
application of the air standard cycle to engines to enable them to be treated as heat engines.
In reality combustion is not a process of energy transfer but one of energy transformation.
The energy released by combustion in a spark ignition (petrol) engine is all contained in
the mixture prior to combustion, and it is released by the spark. It will be shown that the
energy which causes the temperature rise in a combustion process is obtained by breaking
the bonds which hold the fuel atoms together.
c m CAH(X-Y),
CAH(X-Y),
Elemental n n n
molecules
m3,
- Wfh
Reactant . V V V
molecules
energy
Distance
Table 11.1 Some atomisation, dissociation and resonance energies (based on 25OC)*
Bond
Bond Energy dissociation Energy Energy
atomisation (AH,) (MJ/kmol) ( A H ( X - Y ) ) (MJ/kmol) Resonance (MJ/kmol)
*note: these values have been taken from different sources and may not be exactly compatible.
2 10 Chemistry of combustion
In addition to the energy associated with particular bonds there are also energies caused
by the possibility of resonance or strain in a particular molecule. For example, the ring
structure of benzene, which is normally considered to be three simple double bonds
between carbon atoms, together with three single ones, plus six carbon-hydrogen bonds,
can reform to give bonding across the cyclic structure (see Fig 11.3).
This results in a substantially higher energy than would be estimated from the simple
bond structure, and some typical values are shown in Table 11.1.
H H H H H
Fig. 11.3 Bonding arrangements of benzene, showing bond resonance through delocalised electrons
In reality the enthalpy of formation is more complex than given above because energy
can be stored in molecules in a number of ways, including resonance energies (in the
benzene ring structure) and changes of phase (latent heats). A more general representation
of the enthalpy of formation is
Example
Evaluate the enthalpy of formation of CO, and H,O from the atomisation and dissociation
energies listed in Table 11.1.
Energy of formation 21 1
Solution
Carbon dioxide (CO,)
Carbon dioxide is formed from carbon and oxygen in the reaction.
cmli, + O,(g)-+CO,(g) (11.3)
where the (g) indicates that the element or compound is in the gaseous (vapour) phase,
and (1) will be used to indicate that the element or compound is in the liquid phase.
The reaction in eqn (1 1.3)is achieved by atomisation of the individual carbon (graphite)
molecules and the oxygen molecules, with subsequent recombination to form carbon
dioxide. Effectively the reactant molecules, which are in a metastable state, are activated
above a certain energy to produce atoms which will then combine to form the stable CO,
molecule (see Fig 1 1.4).
reactants
stable
Progress of reaction
Fig. 11.4 Gibbs energy variation during a reaction
Hence, from Fig 11.1,
(AHf)coz= C AHa -CAH(X - Y ) - C AHRs- C AHIaent (11.4)
In this case there is a resonance energy but the latent energy (i.e. latent heat) is zero.
Then
(AfZf)coz= C AHa[Cgraphie1
+ AHa[O= 01- 2(C = 0)- AH,,[CO,]
= 717.2+ 435.4- 2 x 698.1- 137.9 (11.5)
= -381.5 MJ/km01
The tabulated value is -393.5 MJ/kmoi.
Water (H,O)
This is formed from the hydrogen and oxygen molecules in the reaction
+ ;O,(g)--H,o(g) (11.6)
Thus
(AHf)Hzo= C AHa -C AH(X - Y ) - C AH,, - C AH,,,, (11.7)
212 Chemistry of combustion
In this case AHEs= 0 but AH,,,,, depends upon the phase of the water. First, consider the
water is in vapour phase, when AH,,,,, = 0. Then
(AHf)H20= X AH, - C AH(X - Y )
=AH,[H - HI + iX AH,[O = 01 - [H - OH] - [0- HI (11.8)
= 435.4 + $ (498.2) - 497.5 - 428.7
= -241.7 MJ/kmol
Example
Evaluate the enthalpy of formation of methane, C&.
Solution
The structure of methane is tetrahedral, and of the form shown in Fig 11.5 (a). Methane is
often depicted in planar form as shown in Fig 11.5 (b).
H
H
H- C- H
(4 (b)
Fig. 11.5 Atomic arrangement of methane molecule
Hence
Example
Evaluate the enthalpy of formation of ethanol, C,H,OH.
Solution
The planar representation of the structure of ethanol is shown in Fig 11.6.
H H
I I
H-C-C-0-H
I I
H H
Fig. 11.6 Structure of ethanol molecule
-2C(g) + 2 x 717.2, + 6H +
atomisaoun
energy fur C
-
3 x 435.4
energy for H
+ 0 + 0.5 x 498 2
atomlsation
energy fur 0
Example
Evaluate the enthalpy ofreaction of methane.
Solution
This can be obtained either by using atomisation and dissociation energies, in a similar
manner to that used to find the enthalpies of formation of compounds, or from the
enthalpies of formation of the compounds in the reactants and products. Both methods will
be used in this case. The reaction describing the combustion of methane is
CH4(g) + 20z(g)-~Oz(g) + 2HzO(g) (11.14)
The chemical structure of methane was given above. Hence the enthalpy of formation of
the reactants
(AHf)R = C AHa- C AH(X - Y ) - C AHms- C AH,,,,,
= AH,[C,,,i,] + 2 AHa[H - HI + 2 AHa[O= 01 - 4[H - C ]- 2 [ 0 = 01
(11.15)
Note that the atomisation and dissociation energies of oxygen are equal
(2 AHa[O= 01 = 2 [ 0 = 01) and cancel out, i.e. the enthalpy of formation of oxygen is
zero. This value of zero is assumed as a base level for all elements. Thus
(AHf)R= (AHf)CH4
= 70 MJ/kmOl (11.16)
Similarly for the products
( 11.17)
The heat of reaction is given by
AHR = (AHf)P- (AHf)R
= -381.7 - 2 x 241.7 - (-70)
= -794.9 MJ/kmol (11.18)
This is close to the value of -802.9 MJ/kmol quoted as the lower enthalpy of reaction of
methane in Table 11.2. If the higher heat of reaction of methane is required then eqn
(11.14) becomes
CH4W + 2o~(g)--coz(g) + 2Hz0(1) (11.19)
Energy offormation 215
Example
Evaluate the lower enthalpy of reaction of benzoic acid (C,H&OOH). The planar diagram
of its structure is shown in Fig 11.7.
0
C- 0- H
HC
(I
HC fCH
H
Fig. 11.7 Structure of benzoic acid molecule
Solution
The reaction of benzoic acid with oxygen is
C,H,COOH(g) + 7.5O2(g)-7C0,(g) + 3H20(g) (1 1.20)
The easiest way to evaluate the enthalpy of reaction is from eqn (1 1.18):
AHR = (AHf)P - (AHf)R
The values of Hf were calculated above for CO, and H,O, and hence the only unknown
quantity in eqn (1 1.18) is the enthalpy of formation of the benzoic acid:
= C AH, - C AH(X - Y ) - C AH,, - C AH,,,,
(AHf)C6H5CmH (11.21)
The acid is in gaseous form before the reaction, see eqn (1 1.20), and thus AH,,,,, = 0.
Substituting values into eqn (1 1.21) gives
= C AH, - C AH(X - Y ) - C AH,,
(AHf)C6H5COOH
= 7 AH,[C,,,,ite] + 3 AH,[H - HI + AH,[O = 01
-5[H - C] -4[C - C] - 3 [ C = C ] - [ C = O ]
- LC - O1 - Lo - - [AHreslC6& - [AHmslCOOH (1 1.22)
Hence
= 7 x 717.2 + 3 x 435.4 + 498.2 - 5 x 414.5
(AHf)C6HsCOOH
- 4 x 347.5 - 3 x 615.5 - 698.1 - 351.7 - 428.7 - 150.4 - 117.0
= - 230.1 M J / k m ~ l (11.23)
216 Chemistry of combustion
= 7 x ( - 3 8 1 . 5 ) + 3 ~ (-241.7) (11.24)
= -3395.5 MJ/kmol
Thus the enthalpy of reaction of benzoic acid is
(AHR)c,H,c,H = -3395.6 - (-230.1) = 3165.5 MJ/kmol (11.25)
The tabulated value is 3223.2 MJ/kmol, giving an inaccuracy of about 2%.