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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.
nR,
Gaseous atoms
c m
Elemental molecules
n
CAH(X-Y),
CAH(X-Y),
Reactant molecules
.
m 3 ,
Wfh
V
energy
Distance
Table 11.1 Some atomisation, dissociation and resonance energies (based on 25OC)*
Bond atomisation (AH,) H-H C (graphite) Energy (MJ/kmol) 435.4 717.2 498.2 946.2 Bond dissociation Energy ( A H ( X - Y ) ) (MJ/kmol) C-H N--H 0-H H-OH 414.5 359.5 428.7 497.5 35 1.7 698.1 347.5 615.5 812.2 Energy (MJ/kmol) 150.4 255.4 137.9 117.0
Resonance Benzene: C,H, Naphthalene: C,J& Carbon dioxide: CO, -COOH group
(O=O)o, N=N
*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.
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 A H , = C AH, A H ( X - Y ) - C AHms- C AH,,,,
(11.2)
Example Evaluate the enthalpy of formation of CO, and H,O from the atomisation and dissociation energies listed in Table 11.1.
2 11
Carbon dioxide (CO,) Carbon dioxide is formed from carbon and oxygen in the reaction.
c m l i , + 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, . 4 ) . molecule (see Fig 1 1
reactants
stable
I
Progress of reaction
Fig. 11.4 Gibbs energy variation during a reaction
(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= 0 1- 2(C = 0) - AH,,[CO,]
= 717.2+ 435.4- 2 x
=
698.1- 137.9
(11.5)
-381.5 MJ/km01
Water (H,O) This is formed from the hydrogen and oxygen molecules in the reaction
+ ;O,(g)--H,o(g)
(11.6) (11.7)
Thus
(AHf)Hzo = C AHa -C AH(X - Y ) - C AH,, - C AH,,,,
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 + i X AH,[O = 01 - [H - OH] - [0- HI = 435.4 + $ (498.2) - 497.5 - 428.7 = -241.7 MJ/kmol This compares well with the tabulated values of -241.6 MJ/kmol. If the water was in liquid phase then eqn (1 1.6) becomes H*(g) +$02(g)-HH,0(1) (AHf)H20(1) = (AHf)HiO(g) + (mw)HzOhfg = -241.7 - 18 x 2441.8/1000 = -285.65 MJ/kmol The tabulated value is -285.6 MJ/kmol. (11.9) (11.10) (11.8)
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-
(4
Methane can be formed by the following reaction: Cgraphire + 2H2(g)-C%(g)
(b)
(11.11)
(11.12)
+ 2 x 425.4 -4 x 414.5
-70 MJ/kmol
The tabulated value is -74.78 MJ/kmol, and the difference occurs because the energy of the bonds in methane is affected by the structure of the methane molecule, which results in attraction forces between molecules.
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-C-C-0-H H H
I I
I I
-2C(g)
+ 2 x 717.2, + 6H +
atomisaoun energy fur C
3 x 435.4
energy for H
-
+ 0 + 0.5 x 498 2
energy fur 0
atomlsation
(11.13)
- 5[C-H] -
[C-C]
[C-01 - [O-HI
-C,H,OH(g) -C*H,OH(g)
- 210.7 MJ/kmol
214 Chemistry of combustion Hence the enthalpy of formation of gaseous ethanol is -210.7 MJ/kmol. This is equivalent to -5.853 MJ/kg of ethanol. The value obtained from tables is about -222.8 MJ/kmol, and the difference is attributable to the slight variations in bond energy that occur due to the three-dimensional nature of the chemical structure.
Example
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= 0 1 = 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 Similarly for the products
(11.16)
( 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)
215
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 HC
(I
f
H
CH
Solution
+ 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):
A H R = (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:
(AHf)C6H5CmH = C AH, - C AH(X - Y ) - C AH,, - C AH,,,,
(11.21)
= 0.
The acid is in gaseous form before the reaction, see eqn (1 1.20), and thus AH,,,,, Substituting values into eqn (1 1.21) gives
(AHf)C6H5COOH = C AH, - C AH(X - Y ) - C AH,, = 7 AH,[C,,,,ite] + 3 AH,[H - HI + AH,[O = 0 1 -5[H - C] -4[C - C] - 3 [ C = C ] - [ C = O ] - LC - O1 - Lo - - [AHreslC6& - [AHmslCOOH
(1 1.22)
Hence
(AHf)C6HsCOOH = 7 x 717.2 + 3 x 435.4 + 498.2 - 5 x 414.5 - 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)
(AHf)COz
(AHf)HzO
= 7 x ( - 3 8 1 . 5 ) + 3 ~ (-241.7)
=
(11.24)
-3395.5 MJ/kmol
-3395.6 - (-230.1)
= 3165.5
MJ/kmol
(11.25)
0 0
the enthalpies of reaction of many of the hydrocarbon fuels on a basis of mass are very similar, at around 44000 kJ/kg; the stoichiometric air-fuel ratios of many basic hydrocarbon fuels lie in the range 13:1-17:1; some of the fuels have positive enthalpies of formation; all of the fuels have negative enthalpies of reaction; the enthalpies of reaction of the alcohols are less than those of the non-oxygenated fuels, simply because the oxygen cannot provide any energy of reaction; the commonly used hydrocarbon fuels are usually mixtures of hydrocarbon compounds.
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