11

Chemistry of Combustion

The thermodynamics of combustion were considered in Chapter 10, and it was stateA 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.

11.1 Bond energies and heats of formation

Heats (enthalpies and internal energies) of formation can be evaluated empirically by 'burning' the fuel. They can also be evaluated by consideration of the chemical structure of the compound. Each compound consists of a number of elements held together by certain types of bond. The bond energy is the amount of energy required to separate a molecule into atoms; the energy of a particular type of bond is similar irrespective of the actual structure of the molecule. This concept was introduced in Chapter 10, and heats of formation were used to evaluate heats of reaction (Hess' law). The process of breaking the chemical bonds during the combustion process can be depicted by a diagram such as Fig 11.1. It is assumed that element molecules can be atomised (in a constant pressure process) by the addition of energy equal to AH,. If these atoms are then brought together they would combine, releasing dissociation energy of ]~ A H ( X - Y)R, to form the reactants. The sum of the dissociation and atomisation energies (taking account of the signs) results in the enthalpy of formation of the reactants. In a similar way the enthalpy of formation of the products can be evaluated. Using Hess' law, the enthalpy of reaction of the fuel can be evaluated as the difference between the enthalpies of formation of the products and the reactants These energies are essentially the bond energies of the various molecules, and some of these energies are listed in Table 11.1. Figure 11.2 shows how the energy required to separate two atoms varies with distance: the bond energy is defined as the minimum potential energy relative to that at infinity. The point of minimum energy indicates that the molecule is in equilibrium.

Gaseous atoms

x~qCx-Y)~
ii i ii

XAH(X-Y),

Elemental molecules
i

()

Reactant molecules

(~-i~

AIFI: (~a-O,-(~q&
Product molecules Fig. 11.1 Relationship between enthalpies of formation and reaction

BondI

-'~--

ii

Distance Fig. 11.2 Variation of bond energy with distance between atoms Table 11.1 Some atomisation, dissociation and resonance energies (based on 25"C)* Bond dissociation (AH(X--Y)) C--H N--H O--H H---OH C--O C--O C--C

Bond atomisation (AH,) H--H

Energy (MJ/krnol) 435.4 717.2 498.2 946.2

Energy (MJ/kmol) 414.5 359.5 428.7 497.5 351.7 698.1 347.5 615.5 812.2

Energy Resonance

(MJ/kmol)

c (graphite)

(o--O)o~
N-,,,,N

Benzene: C6I-I~ 150.4 Naphthalene: C~0I~ 255.4 Carbon dioxide: CO2 137.9 -COOH group 117.0

C--C
CEC

note: these values have been taken from different sources and may not be exactly compatible.

210 Chemistryof 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.

// \
HC

H C

/
CH HC HC

H C

%
CH CH

/
HC HC

H C

\
CH

//\
CH

H C

/%

H C

[ II
Clt

HC

II I
\ //
12 H

II II
\
/
C H

%c /
H

\//
C H

%/
C H

Fig. 11.3 Bonding arrangements of benzene, showing bond resonance through delocalised electrons

11.2 Energyof formation

It will be considered in this section that the processes take place at constant pressure and the property enthalpy (h or H) will be used; if the processes were constant volume ones then internal energies (u or U) would be the appropriate properties. A hydrocarbon fuel consists of carbon and hydrogen (and possibly another element) atoms held together by chemical bonds. These atoms can be considered to have been brought together by heating carbon and hydrogen (in molecular form) under conditions that encourage the resulting atoms to bond. There are two processes involved in this: first, the carbon has to be changed from solid graphite into gaseous carbon atoms and the hydrogen also has to be atomised; then, second, the atoms must be cooled to form the hydrocarbon fuel. These two processes have two energies associated with them: the first is atomisation energy (AH,) and the second is dissociation energy (]~ AH(X- Y)R) required to dissociate the chemical bond in the compound C~I-Ir Figure 11.1 shows these terms, and also indicates that the energy of formation of the fuel (AHf) is the net energy required for the process, i.e.

, ~ f = Z AH.- Z A B ( x - DR

(11.1)

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 offormation is

An, = Z An.- Z all(X- Y)- Z a n . . - Z An,...,

(11.2)

Example
Evaluate the enthalpy of formation of CO2 and H2O from the atomisation and dissociation energies listed in Table 11.1.

Energy of formation Solution

Carbon dioxide (C02) Carbon dioxide is formed from carbon and oxygen in the reaction. C~,p~m + O2(g)--" CO2(g)

211

(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 (11.3) 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 CO2 molecule (see Fig 11.4).

~ atomisation metastable reactants ~ ,

..... +

stable

. . . . . . . .

Progress of reaction

Fig. 11.4 Gibbs energy variation during a reaction Hence, from Fig 11.1, (AHf)co2 = ~ A H , - ~ , A H ( X - Y) - ~, AHm- ~, aHLm.t In this case there is a resonance energy but the latent energy (i.e. latent heat) is zero. Then
(AHf)co 2 ffi )". AH,[Cs,~,h~t,] + AH,[O = O] - 2(C = O) - AH,,[CO2]

(11.4)

ffi 717.2 + 4 3 5 . 4 - 2 x 698.1 - 137.9

= - 381.5 M J / k m o l

(11.5)

The tabulated value is -393.5 MJ/kmol. Water (H20) This is formed from the hydrogen and oxygen molecules in the reaction
S2(g) + 89 O2(g) -'+ H 2 0 ( g )

(11.6)

Thus
(AHf)H2 o - ~

AHa --,~_.AH(X- ]I)- ~, AH~,- ~, AH~mm

(11.7)

212 Chemistryof combustion

In this case AH,, = 0 but AH~,~,t depends upon the phase of the water. First, consider the water is in vapour phase, when AH~mt = 0. Then (AHf),2o = X A H , - ~,AH(X- 10 = AH,[H - H] + 89 AH,[O - O] - [H - OH] - [O - H] = 435.4 + 89 (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 (11.6) becomes H2(g) + -~O2(g)--" tt20(1)

(11.8)

(11.9)
(11.10)

(AHf)H2O0) ffi (AHf)n2otg)+ (mw)n2ohfg

ffi - 2 4 1 . 7 - 18 x 2441.8/1000 = -285.65 MJ/kmol The tabulated value is -285.6 MJ/kmol.

Example
Evaluate the enthalpy of formation of methane, CtL.

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

...-

..""..-.

'....'-..in
H

c
H

(a)
Methane can be formed by the following reaction: Cgr~ph~e+ 2H2(g)--' CH4(g)

(b)
(11.11)

Fig. 11.5 Atomic arrangement of methane molecule

Energy offormation
Hence

213

(AHt)cm = Y~ A l l . - Y~ AH(X- I0 - X A H = , - X AH~.,~.,

= A H . [ C ~ , . ] + 2 AH.[H - H] - 4[H - C] = 717.2 + 2 x 425.4 - 4 x 414.5
=-70
MJ/kmol

(11.12)

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,

C2I-IsOH.

Solution
The planar representation of the structure of ethanol is shown in Fig 11.6.
H H

I
H--C---

I
C --- 0--H

I
H

I
H

Fig. 11.6 Structure of ethanol molecule Ethanol can be considered to be made up of the following processes: 2 C m # e + 3H2(g) + 0.502(g)--" C2HsOH(g) giving the enthalpy of formation of ethanol as (eqn (11.12))

(AHf)c2HsOH----" Z

A H . - X A H ( X - Y) - Z AH=,- Z aHlatent

This gives the following equation: 2C~whit~ + 3H2(g) + 0.502(g) ---'2C(g) + 2 x 717.2 + 6H + 3 x 435.4 + O + 0.5 x 498.2
w ~ . e i, , , ,

ii

atomisation energy for C

atomisation energy for H

atomisation energy for O

- 5[C-H] - [C-C] - [C-O] - [O-H]

-"C2HsOH(g) + 2 x 717.2 + 3 x 435.4 + 0.5 x 498.2 - 5 x 414.5 - 347.5 - 3 5 1 . 7 - 428.7 "'*C21-IsOn(g)- 210.7 MJ/kmol

(11.13)

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 attributableto the sfightvariations in bond energy that occur due to the three-dimensional nature of the chemical structure.

Example
Evaluate the enthalpy of reaction 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) + 202(g)--" CO2(g) + 2I~O(g)
(11.14)

The chemical structure of methane was given above. Hence the enthalpy of formation of the reactants

(anfh = Z AH.- Z AH(X- Y)- Z AH.- Z AH,,

= A H , [ C ~ , , ] + 2 AH,[I-I- H] + 2 AH,[O = O ] - 4 [ H - C ] - 2[O = O]

(11. 5) Note that the atomisation and dissociation energies of oxygen arc equal (2 AH,[OffiO] ffi 2[OffiO]) 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)c~ = 70 MJ/kmol Similarly for the products (AHf)p= AH, - Z AH ( X - Y) - Z AH,~ - Z A H ~ t = AH,[Cg,,p~I + 2 AH,[O = Ol + 2 AH,[H - HI
-

(11.16)

2[C = O ] - 2 [ H - O H ] - 2 [ 0 - H] - AH,~ [CO21

= (aH,)co + 2 (aHf)H O = - 381.5 - 2 x 241.7 MJ/kmol The heat of reaction is given by AHR = (AHf)p- (AHf)R
= - 381.7 2 x 241.7 (-

(11.17)

70) (11.18)

=-794.9 MJ/kmol

This is close to the value of -802.9 MJ/kmol quoted as the lower cnthalpy of reaction of methane in Table 11.2. If the higher heat of reaction of methane is required then eqn (11.14) becomes CI-14(g) + 202(g)--'CO2(g) + 2H20(1) (11.19)

Energy offornmtion 215 Example

Evaluate the lower enthalpy of reaction of benzoic acid (C6I-IsCOOH). The planar diagram of its structure is shown in Fig 11.7.

I
C-- 0--- H 12

/
HC

%
CH

HC

CH C H

Fig. 11.7 Structure of benzoic acid molecule

Solution
The reaction of benzoic acid with oxygen is CJ-IsCOOH(g) + 7.502(g)--'7CO2(g) + 3 ~ O ( g ) The easiest way to evaluate the enthalpy of reaction is from eqn (11.18):
AH R = (AHf)p - (AHf)lt

(11.20)

The values of Hf were calculated above for CO2 and 1-120, and hence the only unknown quantity in eqn (11.18) is the enthalpy of formation of the benzoic acid: (AHf)c6HjCX~H----"E AH, - ~ AH (X - Y) - ]~ AH=, - 5'. ~ l a t e n t (11.21)

The acid is in gaseous form before the reaction, see eqn (11.20), and thus AHl,ffi,t= 0. Substituting values into eqn (11.21) gives
(AHf)C6HsLX)OH----Z A U a - X A H ( X - D "- Z Antes
= 7 AH,[Cmph~ + 3 A H , [ H - HI + AH,[O = O] ~]

-5[a-c]-4[C-C]-3[CffiC]- [C-O]
-[C-O]Hence (AHf)c6Hscoon- 7 717.2 + 3 x 435.4 + 498.2 - 5 x 414.5 - 4 347.5- 3 = - 230.1 MJ/kmol - 3 5 1 . 7 - 4 2 8 . 7 - 150.4- 117.0 (11.23) [O-H][aH=]c6n6 - [AH=,]coo. (11.22)

216 Chemistryof combustion

The enthalpy of formation of the products is (AHf)l, = 7 (AHf)coz + 3 (AHf)H2o
= 7 x ( - 381.5) + 3 x ( - 2 4 1 . 7 )

(11.24)

= - 3 3 9 5 . 5 MJ/kmol Thus the enthalpy of reaction of benzoic acid is (AHR)c6.scoo. = -3395.6 - (-230.1) = 3165.5 MJ/kmol The tabulated value is 3223.2 MJ/kmol, giving an inaccuracy of about 2%. (11.25)

11.3 Enthalpy of reaction

The enthalpies of reaction of some commonly encountered fuels are given in Table 11.2. These have been taken from a number of sources and converted to units consistent with this text where necessary. There are a number of interesting observations that can be made from this table: 9 the enthalpies of reaction of many of the hydrocarbon fuels on a basis of mass are very similar, at around 4400010/kg; 9 the stoichiometric air-fuel ratios of many basic hydrocarbon fuels lie in the range 13:1-17:1; 9 some of the fuels have positive enthalpies of formation; 9 all of the fuels have negative enthalpies of reaction; 9 the enthalpies of reaction of the alcohols are less than those of the non-oxygenate~ fuels, simply because the oxygen cannot provide any energy of reaction; 9 the commonly used hydrocarbon fuels are usually mixtures of hydrocarbon compounds.

11.4 Concluding remarks

It has been shown that the energy released by a fuel is contained in it by virtue of its structure, i.e. the bonds between the atoms. It is possible to assess the enthalpies of formation or reaction of a wide range of fuels by considering the chemical structure and the bonds in the compound. A table of enthalpies of formation and reaction for common fuels has been given.

~ii

Ii.l ~ii,4 ~.il

lii4

I ~

',,

I~F~'

I ,.?i I

I ~i~ ~ I I

~'~ I~ I I

,N

9 ~~~,
I I I I I I

~~~=
+ + +

~
I I I

o
o,ii

Ii.l

II II

Iil l, ii
i

[-

~~#.~~~

~o ~, ~7~~~~~#.