CHAPTER 13

Combustion

13.1 COMBUSTION EQUATIONS

Let us begin our review of this particular variety of chemical-reaction equations by considering the
combustion of propane in a pure oxygen environment. The chemical reaction is represented by
C3 H8 + 5O2 ! 3CO2 + 4H2 O ð13:1Þ
Note that the number of moles of the elements on the left-hand side may not equal the number of moles
on the right-hand side. However, the number of atoms of an element must remain the same before, after,
and during a chemical reaction; this demands that the mass of each element be conserved during
combustion.
In writing the equation we have demonstrated some knowledge of the products of the reaction.
Unless otherwise stated we will assume complete combustion: the products of the combustion of a
hydrocarbon fuel will be H2 O and CO2 . Incomplete combustion results in products that contain H2 ,
CO, C, and=or OH.
For a simple chemical reaction, such as (13.1), we can immediately write down a balanced chemical
equation. For more complex reactions the following systematic method proves useful:

1. Set the number of moles of fuel equal to 1.

2. Balance CO2 with number of C from the fuel.
3. Balance H2 O with H from the fuel.
4. Balance O2 from CO2 and H2 O.

For the combustion of propane we assumed that the process occurred in a pure oxygen environment.
Actually, such a combustion process would normally occur in air. For our purposes we assume that air
consists of 21% O2 and 79% N2 by volume so that for each mole of O2 in a reaction we will have
79 mol N2
= 3:76 ð13:2Þ
21 mol O2
Thus, on the (simplistic) assumption that N2 will not undergo any chemical reaction, (13.1) is replaced by
C3 H8 + 5ðO2 + 3:76N2 Þ ! 3CO2 + 4H2 O + 18:8N2 ð13:3Þ

308
CHAP. 13] COMBUSTION 309

The minimum amount of air that supplies sufficient O2 for the complete combustion of the fuel is
called theoretical air or stoichiometric air. When complete combustion is achieved with theoretical air,
the products contain no O2 , as in the reaction of (13.3). In practice, it is found that if complete
combustion is to occur, air must be supplied in an amount greater than theoretical air. This is due to
the chemical kinetics and molecular activity of the reactants and products. Thus we often speak in terms
of percent theoretical air or percent excess air, where
% theoretical air = 100% + % excess air ð13:4Þ
Slightly insufficient air results in CO being formed; some hydrocarbons may result from larger deficiencies.
The parameter that relates the amount of air used in a combustion process is the air-fuel ratio (AF ),
which is the ratio of the mass of air to the mass of fuel. The reciprocal is the fuel-air ratio (FA). Thus
m m
AF = air FA = fuel ð13:5Þ
mfuel mair
Again, considering propane combustion with theoretical air as in (13.3), the air-fuel ratio is
mair ð5Þð4:76Þð29Þ kg air
AF = = = 15:69 ð13:6Þ
mfuel ð1Þð44Þ kg fuel
where we have used the molecular weight of air as 29 kg=kmol and that of propane as 44 kg=kmol. If, for
the combustion of propane, AF > 15:69, a lean mixture occurs; if AF < 15.69, a rich mixture results.
The combustion of hydrocarbon fuels involves H2 O in the products of combustion. The calculation
of the dew point of the products is often of interest; it is the saturation temperature at the partial
pressure of the water vapor. If the temperature drops below the dew point, the water vapor begins to
condense. The condensate usually contains corrosive elements, and thus it is often important to ensure
that the temperature of the products does not fall below the dew point.

EXAMPLE 13.1 Butane is burned with dry air at an air-fuel ratio of 20. Calculate (a) the percent excess air, (b) the
volume percentage of CO2 in the products, and (c) the dew-point temperature of the products.
Solution: The reaction equation for theoretical air is
C4 H10 + 6:5ðO2 + 3:76N2 Þ ! 4CO2 + 5H2 O + 24:44N2
(a) The air-fuel ratio for theoretical air is
mair ð6:5Þð4:76Þð29Þ kg air
AFth = = = 15:47
mfuel ð1Þð58Þ kg fuel
This represents 100% theoretical air. The actual air-fuel ratio is 20. The excess air is then
 
AFact − AFth 20 − 15:47
% excess air = ð100%Þ = ð100%Þ = 29:28%
AFth 15:47
(b) The reaction equation with 129.28% theoretical air is
C4 H10 + ð6:5Þð1:2928ÞðO2 + 3:76N2 Þ ! 4CO2 + 5H2 O + 1:903O2 + 31:6N2
The volume percentage is obtained using the total moles in the products of combustion. For CO2 we have
 
4
% CO2 = ð100%Þ = 9:41%
42:5
(c) To find the dew-point temperature of the products we need the partial pressure of the water vapor. It is
found using the mole fraction to be
 
5
Pv = yH2 O Patm = ð100Þ = 11:76 kPa
42:5
where we have assumed an atmospheric pressure of 100 kPa. Using Table C-2 we find the dew-point
temperature to be Td:p: = 49  C.
310 COMBUSTION [CHAP. 13

EXAMPLE 13.2 Butane is burned with 90% theoretical air. Calculate the volume percentage of CO in the
products and the air-fuel ratio. Assume no hydrocarbons in the products.
Solution: For incomplete combustion we add CO to the products of combustion. Using the reaction
equation from Example 13.1,
C4 H10 + ð0:9Þð6:5ÞðO2 + 3:76N2 Þ ! aCO2 + 5H2 O + 22N2 + bCO
With atomic balances on the carbon and oxygen we find:
)
C: 4=a+b
∴ a = 2:7, b = 1:3
O: 11:7 = 2a + 5 + b

The volume percentage of CO is then

 
1:3
% CO = ð100%Þ = 4:19%
31
The air-fuel ratio is
mair ð0:9Þð6:5Þð4:76Þð29Þ lbm air
AF = = = 13:92
mfuel ð1Þð58Þ lbm fuel

EXAMPLE 13.3 Butane is burned with dry air, and volumetric analysis of the products on a dry basis (the
water vapor is not measured) gives 11.0% CO2 , 1.0% CO, 3.5% O2 , and 84.5% N2 . Determine the percent
theoretical air.
Solution: The problem is solved assuming that there is 100 moles of dry products. The chemical equation is
aC4 H10 + bðO2 + 3:76N2 Þ ! CO2 + 1CO + 3:5O2 + 84:5N2 + cH2 O
We perform the following balances:
C: 4a = 11 + 1 ∴a=3
H: 10a = 2c ∴ c = 15
O: 2b = 22 + 1 + 7 + c ∴ b = 22:5
A balance on the nitrogen allows a check: 3.76b = 84.5, or b = 22.47. This is quite close, so the above values are
acceptable. Dividing through the chemical equation by the value of a so that we have 1 mol fuel,

C4 H10 + 7:5ðO2 + 3:76N2 Þ ! 3:67CO2 + 0:33CO + 1:17O2 + 28:17N2 + 5H2 O

Comparing this with the combustion equation of Example 13.1 using theoretical air, we find
 
7:5
% theoretical air = ð100%Þ = 107:7%
6:5

EXAMPLE 13.4 Volumetric analysis of the products of combustion of an unknown hydrocarbon, measured on
a dry basis, gives 10.4% CO2 , 1.2% CO, 2.8% O2 , and 85.6% N2 . Determine the composition of the hydrocarbon
and the percent theoretical air.
Solution: The chemical equation for 100 mol dry products is
Ca Hb + cðO2 + 3:76N2 Þ ! 10:4CO2 + 1:2CO + 2:8O2 + 85:6N2 + dH2 O
CHAP. 13] COMBUSTION 311

Balancing each element,

C: a = 10:4 + 1:2 ∴ a = 11:6
N: 3:76c = 85:6 ∴ c = 22:8
O: 2c = 20:8 + 1:2 + 5:6 + d ∴ d = 18:9
H: b = 2d ∴ b = 37:9
The chemical formula for the fuel is C11:6 H37:9 . This could represent a mixture of hydrocarbons, but it is not any
species listed in Appendix B, since the ratio of hydrogen atoms to carbon atoms is 3:27 ’ 13=4.
To find the percent theoretical air we must have the chemical equation using 100% theoretical air:
C11:6 H37:9 + 21:08ðO2 + 3:76N2 Þ ! 11:6CO2 + 18:95H2 O + 79:26N2
Using the number of moles of air from the actual chemical equation, we find
 
22:8
% theoretical air = ð100%Þ = 108%
21:08

13.2 ENTHALPY OF FORMATION, ENTHALPY

OF COMBUSTION, AND THE FIRST LAW
When a chemical reaction occurs, there may be considerable change in the chemical composition of
a system. The problem this creates is that for a control volume the mixture that exits is different from the
mixture that enters. Since various tables use different zeros for the enthalpy, it is necessary to establish a
standard reference state, which we shall choose as 25  C (77  F) and 1 atm and which shall be denoted by
the superscript ‘‘ ’’, for example, h .
Consider the combustion of H2 with O2 , resulting in H2 O:
H2 + 1
2 O2 ! H2 OðlÞ ð13:7Þ
If H2 and O2 enter a combustion chamber at 25  C (77  F) and 1 atm and H2 O(l) leaves the chamber at
25  C (77  F) and 1 atm, the measured heat transfer will be − 285 830 kJ for each kmol of H2 O(l) formed.
[The symbol (l) after a chemical compound implies the liquid phase and (g) implies the gaseous phase. If
no symbol is given, a gas is implied.] The negative sign on the heat transfer means energy has left the
control volume, as shown schematically in Fig. 13-1.
The first law applied to a combustion process in a control volume is
Q = HP − HR ð13:8Þ
where HP is the enthalpy of the products of combustion that leave the combustion chamber and HR is the
enthalpy of the reactants that enter. If the reactants are stable elements, as in our example in Fig. 13-1,
and the process is at constant temperature and constant pressure, then the enthalpy change is called the

Fig. 13-1 The control volume used during combustion.

312 COMBUSTION [CHAP. 13

enthalpy of formation, denoted by hf . The enthalpies of formation of numerous compounds are listed in
Table B-6. Note that some compounds have a positive hf , indicating that they require energy to form (an
endothermic reaction); others have a negative hf , indicating that they give off energy when they are
formed (an exothermic reaction).
The enthalpy of formation is the enthalpy change when a compound is formed. The enthalpy change
when a compound undergoes complete combustion at constant temperature and pressure is called the
enthalpy of combustion. For example, the enthalpy of formation of H2 is zero, yet when 1 mol H2 under-
goes complete combustion to H2 O(l), it gives off 285 830 kJ heat; the enthalpy of combustion of H2 is
285 830 kJ/kmol. Values are listed for several compounds in Table B-7. If the products contain liquid
water, the enthalpy of combustion is the higher heating value (HHV); if the products contain water vapor,
the enthalpy of combustion is the lower heating value. The difference between the higher heating value and
the lower heating value is the heat of vaporization hfg at standard conditions.
For any reaction the first law, represented by (13.8), can be applied to a control volume. If the
reactants and products consist of several components, the first law is, neglecting kinetic and potential
energy changes,
X X
Q − WS = Ni ðhf + h − h Þi − Ni ðhf + h − h Þi ð13:9Þ
prod react

where Ni represents the number of moles of substance i. The work is often zero, but not in, for example,
a combustion turbine.
If combustion occurs in a rigid chamber, for example, a bomb calorimeter, the first law is
X X
Q = Up − UR = Ni ðhf + h − h − PvÞi − Ni ðhf + h − h − PvÞi ð13:10Þ
prod react

where we have used enthalpy since the hf

values are tabulated. Since the volume of any liquid or solid is
negligible compared to the volume of the gases, we write (13.10) as
X X
Q= Ni ðhf + h − h − Ru T Þi − Ni ðhf + h − h − Ru T Þi ð13:11Þ
prod react

If Nprod = Nreact , the Q for the rigid volume is equal to Q for the control volume for the isothermal
process.
In the above relations we employ one of the following methods to find (h − h ):
For a solid or liquid
Use Cp T .
For gases
Method 1: Assume an ideal gas with constant specific heat so that h − h = Cp T .

Method 2: Assume an ideal gas and use tabulated values for h.
Method 3: Assume nonideal-gas behavior and use the generalized charts.
Method 4: Use tables for vapors, such as the superheated steam tables.

Which method to use (especially for gases) is left to the judgment of the engineer. In our examples we’ll
usually use method 2 for gases since temperature changes for combustion processes are often quite large
and method 1 introduces substantial error.

EXAMPLE 13.5 Calculate the enthalpy of combustion of gaseous propane and of liquid propane assuming the
reactants and products to be at 25  C and 1 atm. Assume liquid water in the products exiting the steady-flow
combustion chamber.