College of Engineering and Computer Science

Mechanical Engineering Department

Mechanical Engineering 483
Alternative Energy Engineering II
Spring 2010 Number: 17724 Instructor: Larry Caretto
Introduction to Combustion Analysis
INTRODUCTION

These notes introduce simple combustion models. Such models can be used to
analyze many industrial combustion processes and determine such factors as
energy release and combustion efficiency. They can also be used to relate
measured pollutant concentrations to other measures of emissions such as mole
fractions, mass fractions, mass of pollutant per unit mass of fuel, mass of
pollutant per unit fuel heat input, etc. These notes provide the derivation of all
the equations that are used for these relations.

BASIS OF THE ANALYSIS

The simple combustion model assumes complete combustion in which all fuel
carbon forms CO2, all fuel hydrogen forms H2O, all fuel sulfur forms SO2, and all
fuel nitrogen forms N2. This provides results that are accurate to about 0.1% to
0.2% for well operating combustion processes in stationary combustion devices.
It is not valid when the combustion process is fuel rich.

Complete combustion of model fuel formula with oxygen The typical fuel can be
represented by the fuel formula CxHySzOwNv. With this fuel formula we can
analyze a variety of fuels including pure chemical compounds, mixtures of
compounds, and complex fuels such as petroleum and coals where the
elemental composition of the fuel is measured. This type of measurement is said
to provide an ultimate analysis.

Regardless of the source of data for x, y, z, w and v, the mass of fuel

represented by this formula1 can be found from the atomic weights of the various
elements:

M fuel = x M C + y M H + z M S + w M O + v M N [1]

The oxygen required for an assumed complete combustion of this fuel formula
can is determined from the oxygen requirements for complete combustion of the
individual elements. The Cx part of the fuel would require x moles of O2 for
1
We will later consider the inert mineral matter that is present in some petroleum fuels and coal.
In this case the value of Mfuel will represent the mass of the combustible part of the fuel.

Jacaranda (Engineering) 3333 Mail Code Phone: 818.677.6448

Email: lcaretto@csun.edu 8348 Fax: 818.677.7062
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 2

complete combustion of all fuel carbon to CO2. Similarly, y/4 moles would be
required to convert the hydrogen to H2O and z moles for conversion of sulfur to
SO2. The oxygen in the fuel will supply a portion of the oxygen required for
combustion; w/2 moles of O2 need not be provided by the combustion air. Using
these values we can find the minimum moles of O2 required for complete
combustion of one fuel mole. This amount of oxygen is called the stoichiometric
O2 requirement. It is given the symbol A and is found from the equation:

y w
A= x + +z- [2]
4 2

In the real combustion process, the actual oxygen used will be greater than this
stoichiometric amount. The actual amount is defined in terms of the
stoichiometric amount by the oxidizer-fuel equivalence ratio, , i.e.

Actual Moles O 2 = A [3]

With this definition, we can immediately write an expression for the moles of O2
that will appear in the exhaust if the combustion is complete. This will simply be
the initial moles, A, minus the moles required for complete combustion, i.e.,

Moles O 2 in Exhaust = A - A = ( - 1)A [4]

With these expressions for the moles of oxygen in the combustion air and in the
exhaust the equation for the combustion of the fuel, (ignoring the other
components of the combustion air, which are discussed below) can be written as
follows:2

y v
C x H y S z O w N v + A O 2 x CO 2 + H 2 O + z SO2 + ( - 1)A O 2 + N 2 [5]
2 2

Combustion in air In industrial combustion processes and engine combustion,

air is the oxidizer. Here, the other components of air must be considered in the
process. For the simple analysis presented here, these other components are
considered inert. For combustion in air, the oxidizer-fuel equivalence ratio is
called the air-fuel equivalence ratio; this is also called the percent theoretical air;
the quantity ( - 1), expressed as a percentage, is the percent excess air.

The following analysis for dry air can be used to determine the additional
components that enter the combustion equation through the combustion air.

2
The correctness of this equation can be checked by substituting the definition for A and showing
that each chemical element is balanced.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 3

Species: N2 O2 Ar CO2 Trace

Mole Fraction: 0.78084 0.20946 0.00934 0.00033 0.00003

The trace gases and the argon may be lumped together giving a modified argon
mole fraction of 0.00937. The main components of the trace gases are Neon
and Helium; so the molecular weight of air will be a bit low by lumping the trace
gases with Argon, but the error will be less than that caused by the assumption of
complete combustion.

In addition, the humidity of normal air means that some H2O will be present in the
combustion air. If the absolute humidity (mass of water per unit mass of dry air)
of the air is denoted as the moles of water in the air will be given by Mda / Mw
where Mda is the molecular weight of dry air (which is 28.965 for the composition
shown above) and Mw is the molecular weight of water.3

Providing A moles of combustion air then provides a certain number of moles of

CO2, H2O, N2, and Argon; the moles of each of these species can be expressed
as rkA, where rk is the ratio of the moles of species k in combustion air to the
moles of O2 in the air. For the standard analysis of air these ratios are found as

0.78084
r N2 = = 3.72787
0.20946

0.00937
r Ar = = 0.044734
0.20946
[6]
0.00033
r CO2 = = .0015755
0.20946

M da 28.965
rH 2O = M w = 18.0152 = 7.67597
0.20946 .20946

Various other assumptions for the composition of atmospheric air can be used in
this analysis by selecting the appropriate values of r. For example, most

3
The humidity is sometimes expressed in alternative units (e.g., grains of water per pound of dry
air or grams of water per kilogram of dry air.) In these cases, it is necessary to use a unit
conversion so that the mass of both the water and the dry air are in the same units. If the relative
humidity, , and barometric pressure, Pbaro, are given, it is necessary to determine the vapor
pressure of water, Pw, at the air inlet temperature. Then the humidity is given by the equation
Pw
= Mw
M da Pbaro - P w
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 4

introductory analyses assume that the only other constituent of combustion air is
nitrogen. This is equivalent to setting rAr = rCO2 = rH2O = 0 and rN2 = 3.77.

ANALYSIS OF COMPLETE COMBUSTION

This section of the notes considers the case of complete combustion. Here the
exhaust composition is uniquely specified by the fuel formula and the relative
amounts of fuel and oxygen. The analyses done in this section are independent
of the amount of fuel in an actual process. We will do all the analyses here for
one mole of fuel. Results for processes which use other amounts of fuel can be
simply found by scaling by the ratio of the actual fuel used to one mole of fuel.
This concept is known as the basis of the calculation. Here we say that we are
using one mole of fuel as the basis of the calculation. In subsequent analyses of
incomplete combustion we will choose an alternative basis for the calculation.

Relating exhaust composition to initial air/fuel composition If the full set of

species in the combustion air is included in the reactants for the combustion
reaction the following equation is obtained:4

C x H y S z O w N v + A [ O 2 + r CO2 CO 2 + r H 2O H 2 O + r A A + r N 2 N 2 ]
y
(x + A r CO2 ) CO 2 + ( + A r H 2O ) H 2 O + z SO 2 [7]
2
v
+ ( - 1)A O 2 + ( + A r N 2 ) N 2 + A r Ar Ar
2

This equation can be used to find various relations among the fuel, air, and
combustion products. For this equation, the mass of fuel is simply the molecular
weight of the fuel. The mass of air is A times the molecular weight of the
various species in air weighted by their ratio to oxygen. Thus, the air/fuel ratio,
on a mass basis, is given by the following equation:

A rk M k
Air A [ M O + r CO M CO + r H O M H O + r Ar M Ar + r N M N ]
= air
= 2 2 2 2 2 2 2
[8]
Fuel M Fuel xM C + yM H + zM S + wM O + zM N

If we consider the humidity in the air separately, we can compute a numerical

value for the other components as shown below.

4
Although this equation is stated without proof, the reader can show that the equation is
balanced for each chemical element. For example, the moles of carbon on the left side of the
equation are n + ArCO2. The moles of carbon atom on the right side are seen to be the same.
Similar calculations can be done for all atoms appearing in the equation. The analysis for O
atoms is more complex, requiring the use of the definition of A in the analysis.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 5

M O 2 + rCO 2 M CO 2 + r Ar M Ar + r N 2 M N 2 = 31.9988 + 0.0015755( 44.0095)

+ 0.044734(39.948) + 3.72787( 28.0134) = 138.27

Thus, we can write the air/fuel ratio on a mass basis as follows:

Air (138.27 + 0.767597M H 2O )A (138.27 + 13.828 )A

== = [8a]
Fuel M Fuel xM C + yM H + zM S + wM O + vM N

This represents only the combustible portion of the fuel. For fuels with
noncombustible mineral matter known as ash, the actual fuel mass, mfuel, will be
given as

Fuel M Fuel
Actual Fuel Mass = m Fuel = [9]
1 - Ash Fraction 1 - Ash Fraction

The exhaust composition can be determined from the product components in

equation [7]. To get mole fractions, we have to determine the total moles. If we
add the coefficients for all components in the products in equation [7], we get the
total number of product moles, including water. This is called the total wet moles,
W.

y v
W = x + A r CO2 + + A r H 2O + z + ( - 1)A + + A r N 2 + A r Ar [10]
2 2

This may be simplified as follows

y v
W = x+ + z + + A Bw - A [11]
2 2

where Bw is defined as

B w = r CO2 + r H 2O + 1 + r N 2 + r Ar [12]

For many combustion product analyses, the water is removed before the analysis
and the total moles are the dry moles, D. This is the total wet moles minus the
moles of water, which is given by the equation

v
D = x + z + + A Bd - A [13]
2

where Bd is defined as

B d = r CO 2 + 1 + r N 2 + r Ar [14]

From the values of the ri given in equation [6] the value of Bd is seen to be a
constant and the value of Bw depends on the humidity, .
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 6

Bd = 4.7742 and Bw = 4.7742 + 7.67597 [15]

The value of Bd is simply the reciprocal of the mole fraction of oxygen in air. It
represents the sum of the moles of all components in air divided by the moles of
oxygen.

The values of the total product moles in the equations used here refer to the
combustion equation for one mole of the typical fuel. The actual number of
product moles in any real process can be found by multiplying the total moles
computed here by the number of fuel moles in a particular combustion process.

The mass of combustion products is the same as the mass of air plus the
combustible mass of fuel into the process. Thus, the mean molecular weight of
the wet combustion products may be found as

Fuel + Air
M ex,wet = [16]
W

A consistency check on the computations is obtained by using the combustion

product composition may be used to compute the mean molecular weight of the
wet exhaust

y
(x + A r CO2 ) M CO2 + ( 2 + A r H 2O ) M H 2O + z M SO2


v
+ ( - 1)A M O2 + ( + A r N 2 ) M N 2 + A r Ar M Ar
2 [17]
M ex,w =
W

In a similar manner the molecular weight of the dry combustion products may be
found from an overall mass balance,

x
Fuel + Air - ( + A r H 2O ) M H 2O
2 [18]
M ex,d =
D

and verified by a direct calculation from the composition of the dry exhaust
products,

(x + A r CO2 ) M CO2 + z M SO2


v
+ ( - 1)A M O2 + ( + A r N 2 ) M N 2 + A r Ar M Ar
2 [19]
M ex,d =
D
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 7

RELATION BETWEEN , EXHAUST OXYGEN AND OTHER EXHAUST CALCULATIONS

The amounts of each product species allow the development of a relation

between the air-fuel equivalence ratio, , and the exhaust oxygen concentration,
%O2. For dry exhaust the oxygen mole fraction is the moles of oxygen divided by
the number of dry moles. From equations [7] and [13] we can write this mole
fraction as

100( - 1)A 100 ( - 1)A

% O2 = = [20]
D v
x + A Bd - A + z +
2

If the air-fuel equivalence ratio is given, this equation may be used to solve for
the resulting exhaust O2 concentration. The equation can be rearranged to solve
for the air-fuel equivalence ratio when the exhaust O2 concentration is given:

% O2 v
A+ x - A + z +
100 2
= [21]
%
A - A Bd O2
100

Equations [20] and [21] provide the essential relation between a measured
exhaust oxygen concentration and a specified air/fuel ratio. Either of these
variables can be used to characterize a combustion process and it is important to
be able to relate one to the other.

Correction to standard concentrations Many regulatory standards for

combustion gases require that the measured exhaust concentrations, Cmeas, at
the actual exhaust O2 concentration, (%O2)meas, be converted to the equivalent
concentration, Cstd, at a standard oxygen concentration, (%O2)std. The basis for
this conversion is the assumption that the mole number of pollutant species is
small compared to the total moles and will not change the total number of moles.
In this case the measured and standard concentrations are given in terms of the
total number of moles under measured and standard conditions (Nmeas and Nstd).
For the pollutant moles of Npol, the concentration (really mole fraction) equations
are

N pol N pol
C std = and C meas = [22]
N std N meas

Eliminating Npol from these equations gives

N meas
C std = C meas [23]
N std
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 8

Because the standards are usually based on dry moles, the equation for total dry
moles can be used to replace Nmeas and Nstd. Before doing this equation [21] for
can be substituted into equation [13] for the total dry moles, D, giving

% O2 v
A+ x - A+ z +
v 100 2
D= x+ z+ A + AB d [24]
%
2 A - A Bd O2
100

Rearranging this equation gives

v 1 % O2 % O2 v
x + z + 2 A 100 + A + 100 x - A + z + 2
D= Bd [25]
1 % O2

B d 100

The oxygen concentration terms in the numerator cancel leaving

v
x+ z+ A
A+ 2
D= Bd [26]
1 % O2

Bd 100

When this equation is used for Nmeas and Nstd in equation [23] the oxygen
concentration is subscripted to denote the different measured oxygen
concentrations in the measured and standard case. This gives

v
x+ z+ A
A+ 2
Bd
1 [% O 2 ] meas

Bd 100
C std = C meas [27]
v
x+ z+ A
A+ 2
Bd
1 [% O 2 ] std

Bd 100

The constant term, A + (x + z + v/2 - A)/Bd can be cancelled giving the final form
for the correction equation (after multiplying top and bottom by 100),
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 9

100
- [% O 2 ] std
Bd [28]
C std = C meas
100
- [% O 2 ] meas
Bd

Using the value of Bd = 4.7742 from equation [15] the value of 100/Bd is 20.946,5
which is usually rounded to 21, 20.9 or 20.95 in regulatory conversion equations.
(If the oxygen is represented as a mole fraction rather than a mole percent, the
correct value of the constant is 0.20946.)

Alternative approach using CO2 An alternative dilution correction is based on

the measured dry CO2 concentration. From the balanced chemical equation [7],
the number of CO2 moles is x+ArCO2. Using equation [13] for the number of dry
moles, D, gives the mole percentage of CO2 in the dry exhaust, %CO2, by the
following equation.

% CO 2 x + Ar CO 2 x + Ar CO 2
= = [29]
100 D v
x + z + + AB d A
2

Solving this equation for gives

v % CO 2
x x + z + A
= 2 100 [30]
% CO 2
AB d Ar CO 2
100

Substituting this equation into equation [13] for D gives the total dry moles in
terms of the CO2 concentration

v % CO 2
x x + z + A
v
D = x + z + A + AB d 2 100 [31]
2 % CO 2
AB d Ar CO 2
100

Rearranging this equation gives

5
As noted above 1/Bd is simply the mole fraction of oxygen in air so 100/Bd is the mole
percentage of oxygen in air.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 10

v % CO 2 r CO 2 v % CO 2
x + z + 2 A 100 + x x + z + 2 A 100
Bd
D= [32]
% CO 2 r CO 2

100 Bd

Canceling the CO2 terms in the numerator gives the following result, which may
be simplified by ignoring the small terms from CO2 in the inlet air.

v r
x x + z + A CO 2
D= 2 Bd x
[33]
% CO 2 r CO 2 % CO 2

100 Bd 100

Substituting the simplified equation for Nmeas and Nstd in equation [23] (with
appropriate subscripts to denote the measured and standard CO2
concentrations) gives the result that

[% CO 2 ] std
C std = C meas [34]
[% CO 2 ] meas

COMPUTING EMISSIONS PER UNIT OF FUEL ENERGY

Pollutant ratio equations The various relationships outlined above can be used
to compute the pollutant flow rate from the measured concentration and the
measured fuel flow rate. This is based on the knowledge of the ratio of total
exhaust moles to the fuel mass. Since most pollutant concentrations are
reported on the basis of dry exhaust gases the relevant ratio is D/mfuel. From
equations [9] and [26] this ratio is given by the following equation

v
x+ z+ A
A+ 2
D Bd 1 Ash Fraction
= [35]
m fuel 1 % O2 M
fuel
Bd 100

A slight rearrangement of this equation gives an explicit representation of fuel

properties and the air/fuel ratio (as measured by the exhaust oxygen
concentration).

v
A(Bd 1) + x + z + [1 Ash Fraction]
100

=
D 2 Bd [36]
m fuel M fuel 100
% O2
Bd
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 11

The molecular weight of the fuel is found from equation [1]. Using the molecular
weight of the exhaust from equation [19] gives the mass flow rate of dry exhaust,
m& ex ,d , in terms of the fuel flow rate, m& fuel , as follows.

D
m& ex,d = m& fuel M ex,d [37]
m fuel

The relation between mass flow rate and volume flow rate can be found using the
standard density of the exhaust gases. This is usually given for a standard
pressure and temperature, Pstd and Tstd, and can be found from the ideal gas law
for either a wet or a dry basis. These densities are

wet = M ex,w P std or dry = M ex,d P std [38]

R T std R T std

where R is the universal gas constant (R = 0.7302 ft3-atm/lbmole-R). The

volume flow rate of dry exhaust gases, V&ex ,d , can be found as

& ex,d
m D R T std D R T std
V& ex,d = = m& fuel M ex,d = m& fuel [39]
dry m fuel M ex,d P std m fuel P std

The U. S. Environmental Protection Agency (EPA) Method 19 uses the ratio of

dry exhaust gas volume flow rate divided by the heat input rate. The input heat
rate of the fuel, Q& fuel , is simply the product of the fuel flow rate and the heat of
combustion of the fuel, Qc. Dividing equation the left side of equation [39] by
Q& fuel , and the right side of the equation by the equivalent product, m& fuel Qc, gives
the desired Method 19 ratio.

V& ex,d 1 D RT std

= [40]
&
Q fuel Q c m fuel P std

Using equation [36] to eliminate the D/mfuel ratio gives

v
A( B d 1) + x + z + [1 Ash Fraction]
100
&
V ex,d R T std 2 Bd
= [41]
&
Q fuel P std Q c M fuel 100
% O2
Bd

The F factor The right hand side of the equation has three distinct components.
The first is the variables used to compute the density (R, Pstd, and Tstd); the
middle term depends on the fuel properties. The final term, using the measured
exhaust oxygen concentration, is a measure of the excess air. The first two
terms are defined as the dry F-factor, Fd, in EPA method 19, i.e.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 12

v
RT std A( B d 1) + x + z + 2 [1 Ash Fraction]
Fd = [42]
P std Q c M fuel

A typical standard for boiler and furnace operation is 3% exhaust oxygen

concentration. For methane combustion, x = 1, y = 4, and v = w = z = Ash
Fraction = 0. From equation [2], A = 2. The heat of combustion and molecular
weight of methane are 23,861 Btu/lb and 16.04 lb/lb-mol, respectively. The
standard temperature and pressure are typically 527.69oR (= 68oF = 20oC) and
atmospheric pressure,6 and the gas constant with consistent units is 0.7302 ft3-
atm/lbmole-R. With these substitutions the value of Fd for pure methane,
computed from equation [42] is 8604.8 ft3/MMBtu.

The equation for Fd can be rearranged to express the coefficients in terms of the
ultimate analysis of the fuel. The term containing A(Bd - 1) can be rearranged,
using the definition of A from equation [2].

v y w v
A( B d 1) + x + z + = x + + z ( B d 1) + x + z +
2 4 2 2

v y w v
A( B d 1) + x + z + = B d (x + z) + ( B d 1) + [43]
2 4 2 2

The total fuel mass, mfuel, is related to the molecular weight of the combustible
portion of the fuel and the ash fraction by equation [9]

M fuel
m fuel = [44]
1 Ash Fraction

The individual stoichiometric coefficients in the fuel formula, CxHyOwNvSz, are

related to their ultimate analysis (in elemental weight percents) by the following
formulae

wt%C m fuel wt%H m fuel wt%S m fuel

x= y= z=
100 M C 100 M H 100 M S

[45]

wt%N m fuel wt%O m fuel

v= w=
100 M N 100 M O

6
Sometimes a temperature of 15oC = 59oF or 60oF = 15.56oC is used. A standard pressure of
14.73 psia = 30 in Hg is sometimes used as the standard pressure instead of the standard
atmosphere = 14.696 psia = 29.92 in Hg.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 13

In equations [45], MC, MH, MS, MN, and MO represent the atomic weights of
elemental carbon, hydrogen, sulfur, nitrogen and oxygen, respectively.
Substituting equations [45] into equation [43] gives

wt%C wt%S 1 wt%N

Bd + + 2

v m fuel
M C M S MN

A( B d 1) + x + z + = [46]
2 100
+ B d 1 wt%H 2 wt%O

4 MH MO

Substituting this result and equation [44] into equation [42] gives the basic
equation for Fd in terms of the ultimate analysis of the fuel,

wt%C wt%S 1 wt%N

Bd + +
MC MS 2 MN
RTstd
Fd = [47]
100 P std Qc
+ B d 1 wt%H 2 wt%O

4 MH MO

This can be expressed in the following form

K species [wt %]species

1
Fd =
Qc

species = C,H,O,N,S
[48]

where

RT std B d R T std B d RTstd

KC= KS= KN=
100 P std M C 100 P std M S 200 P std M N

[49]

RT std ( B d 1) RT std ( 1 B d )
KH= KO=
400 P std M H 200 P std M O

Substituting the appropriate values for these coefficients gives the results in
Table 1. This table also contains, for comparison, the values for these
coefficients given in Method 19. The coefficients computed here agree with
those in Method 19 to the two significant figures reported in Method 19 except for
the oxygen and hydrogen coefficients. The reason for this difference is not
known.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 14

Alternative F factors based on CO2 Equation [33] which gives the total dry
moles as a function of the CO2 concentration can be used to obtain an alternative
expression for the ratio of dry moles per unit mass of fuel.

D x 1 Ash Fraction
= [50]
m fuel % CO 2 M fuel
100

If this expression for D/mfuel is substituted into equation [40], the following result
is obtained.

V& ex,d R T std x [1 Ash Fraction ] 100

= [51]
Q& fuel P std Qc M fuel % CO 2

Table 1
Computed Coefficients for Ultimate Analysis Factors in EPA Method 19
and Comparison with Published Factors
Coefficient KC KH KS KN KO
This calculation 1.5316 3.6072 0.5738 0.1375 -0.4545
Method 19 1.53 3.64 0.57 0.14 -0.46

The group of terms on the left-hand side of equation [51] is used to define the F
factor for CO2, Fc.

RT std x [1 Ash Fraction] [52]

Fc=
P std Q c M fuel

Substituting the expression for x in terms of the weight percent of fuel carbon
from equations [45] into [52] gives the following expression for Fc.

RT std wt%C = K cc wt%C [53]

Fc=
P std 100 Q c M C Q c

where the constant, Kcc, is defined as follows.

RT std [54]
K cc =
100 P std M C

The value of Kcc found here is 0.32081 ft3/lb-% which matches the value of 0.321
given in Method 19.

ANALYSES OF INCOMPLETE COMBUSTION

When exhaust measurements are available, an alternative approach to the

determination of the various flow rate ratios can be done. This alternative
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 15

method uses measured values for the various exhaust species in place of the
computed ones. The specific approach depends on the actual measurements.
The analysis below assumes that measurements are available for CO, CO2, HC
(representing unburned fuel), O2, NO and NO2. Alternative approaches are then
used if fewer measurements are available.

In the case where exhaust measurements are available, the usual approach is to
determine the amount of fuel required to produce 100 dry moles. This is the
basis used for the calculation here. Results for any process that produces a
different amount of exhaust products can be simply scaled from the results
obtained here. For the basis of 100 dry moles, the combustion equation is
written as follows:

F C x H y S z O w N v + AF [ O 2 + r CO2 CO 2 + r H 2O H 2 O + r A A + r N 2 N 2 ]

a CO 2 + b CO + c C x H y + d H 2 O + e H 2 + F z SO 2 [55]

+ g O 2 + h N 2 + i NO + j NO 2 + F A r Ar Ar

The terms for the product moles of sulfur and argon in this equation provides the
correct balances for these elements. Additional element balance equations are
available for carbon, hydrogen, oxygen and nitrogen. These are, respectively,

F(x + A r CO2 ) = a + b + c x [56]

F(y + 2 A r H 2O ) = c y + 2 d + 2 e [57]

F[w + A (2 + 2 r CO2 + r H 2O )] = 2 a + b + d + 2 F z + 2 g + i + 2 j [58]

F(v + 2 A r N 2 ) = 2 h + i + j [59]

The use of 100 dry moles as the basis for the calculation gives the following
equation

a + b + c + d + e + F z + g + h + i + j + F A rAr = 100 [60]

For convenience the actual moles of oxygen in the fuel-air mixture, AF, is
written as . Making this substitution and rearranging equations [56] to [58]
gives the following set of equations. In constructing these equations we assume
that measurements will be available for CO, CO2, HC, NO, NO2, and O2. Thus,
the values of a, b, c, g, i, and j will be known quantities in this calculation. We
can rewrite equations [56] to [60] denoting the sums of known quantities as
constants K1 to K5.

x F + r CO2 = a + b + c x = K 1 [61]
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 16

- 2 d 2 e + y F + 2 r H 2O = c y = K 2 [62]

d + (w 2 z)F + (2 + 2 r CO 2 + r H 2O )
[63]
= 2 a+b+ 2 g +i+ 2 j = K3

2 h + v F + 2 r N2 = i + j = K 4 [64]

e + h + z F + r Ar = 100 a b c g i j = K 5 [65]

Because of the assumption of 100 dry moles, the values of a, b, c, g, i, and j are
simply the measured values for CO2, CO, HC, O2, NO, and NO2 in mole percent
(dry). E.g., if the measured dry exhaust CO concentration is 100 ppm (a mole
fraction of 10-4 or 0.01%) the value of b is 0.01. Thus, the right hand sides of the
five equations listed above are known. This system of five equations in five
unknowns (d, e, F, h, and ) can be solved by algebraic manipulation to obtain
the following results. These results use the defined constants K6, K7, and K8,
which are given by the following equations.

y v
K6 = w+ 3 z + [66]
2 2

K 7 = r N 2 + r Ar 2 2 r CO2 [67]

K2+ K4
K8= K5 K3+ [68]
2

The moles of oxygen in the fuel-air mixture are found from the following equation:

K1 K6
K8
= x [69]
K 6 r CO 2
K7
x

The value of (combustible) fuel moles is found next by rearranging equation [61].

K 1 r CO 2
F= [70]
x

The relative air/fuel ratio, , can be found from the definition of .

= [71]
FA

The exhaust moles of the remaining constituents, nitrogen, water and hydrogen,
can be found as follows
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 17

v F + 2 rN2 K4
h= [72]
2

d = (w 2 z) F + (2 + 2 r CO 2 + r H 2O ) K 3 [73]

yF
e= + r H 2O K 2 d [74]
2 2

The amount of hydrogen is usually small. If there are analysis errors the value
for hydrogen can become negative or unusually large. As a check the typical
values for hydrogen are governed by the water-gas shift reaction,

CO 2 + H 2 CO + H 2 O Equilibriu m Constant : K wg [75]

The equilibrium constant provides a relationship among the concentrations of the

species in the reaction. The symbols used above, which represent the number of
moles of the species, can be used directly in the equilibrium equation for this
reaction because the numbers of reactant and product moles are the same. This
gives

[CO][ H 2 O] b d
K wg = = [76]
[ CO 2 ][ H 2 ] a e

This equation can be solved for the hydrogen moles in terms of the other species
moles and the value of Kwg. The equilibrium constant depends on temperature.
In most combustion analyses, a value of 3.5 is assumed for this constant.7

bd
e= [77]
a K wg

The value of e found from the element balance equations above should not be
significantly greater than the value found from the water-gas equilibrium
equation.

7
Although this equation has the same form as the equilibrium equation for the water-gas shift
reaction, the value of 3.5 used for the equilibrium constant is not the true value of the constant at
the measurement temperature. Instead it is an empirical value which has been found to provide a
reasonable correlation of actual data for combustion analyses. Fortunately, the H2 concentration
is usually low and the inaccuracies in this equation will not have a significant effect on the overall
result.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 18

Correction of F-factor Approach for Incomplete Combustion An approximate

analysis is available using only measurements of CO, CO2, and exhaust HC. (If
exhaust HC measurements are not available, the HC concentration, c, can be
assumed zero in the analysis below.) This analysis starts with carbon balance in
equation [56], which is repeated below.

F(x + A r CO2 ) = a + b + c x [56]

If the small concentration of CO2 in the combustion air is ignored, the moles of
fuel, F, is simply found as (a + b + cx)/x. The fuel mass is simply this number of
moles divided by the molecular weight of the fuel (with a correction for any fuel
ash content):

M fuel a+b+c x
m fuel = [78]
1 - Ash Fraction x

This equation can be used to find the ratio of the mass of any pollutant species to
the mass of fuel. The species mass is simply the species mole fraction
measured in the analysis times its molecular weight. The mspecies/mfuel ratio can
be divided by the heat of combustion to get the emission factor in units of
pollutant mass per unit heat input, e.g., lb/MMBtu. In the above equation the
moles of NOx is the sum of the NO plus NO2 moles, i+j. The mass of NOx per
unit heat input of fuel is then given by

m& NOx 1 - Ash Fraction x

= M NOx ( i + j ) [79]
&
Q fuel Qc M fuel a+b+c x

In general, the emission factor for any species with molecular weight, Mi, and
mole fraction, yi, is given in terms of the atoms of carbon in one mole of fuel, x,
and the exhaust mole fractions of CO2, CO, and HC (denoted as yCO2, yCO, and
yHC, respectively) as follows.

m& i 1 - Ash Fraction x

= M i yi [80]
&
Q fuel Qc M fuel yCO 2 + y CO + x y HC

This can be compared to the usual equation using the F factor based on CO2.
The first step is using that equation is the conversion of the species mole fraction
(or ppm) into a mass concentration. The values typically used are a mole
fraction in ppm (ppmi) and a (standard) mass concentration (mi/Vstd), typically in
lb/ft3. The conversion between the two is found as follows. The species mass is
simply the species moles, ni, multiplied by the species molecular weight, Mi. The
parts per million, multiplied by 10-6 gives the mole fraction, ni/n. The ideal gas
equation is used to define the standard volume. These steps are all combined in
the following equation.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 19

mi = M i ni = ni n = P std [81]
Mi M i 10 -6 ppmi
V std V std n V std RT std

The mass rate of a pollutant species per unit heat input rate is then found by
multiplying this species mass concentration times the ratio of exhaust volume
flow rate to input heat rate.

m& i m V& ex ,dry P V& ex ,dry

= i = M i 10 -6 ppmi std [82]
& &
Q fuel V Q fuel R T std Q& fuel

Using equation [51] for V

_ ex,d / Q
_ fuel gives the following result for the mass of the
pollutant species per unit heat input:

m& i x [1 Ash Fraction] 100

= M i 10-6 ppmi [83]
&
Q fuel Qc M fuel % CO 2

Replacing 10-6 ppmi by the equivalent mole fraction yi and 100/%CO2 by its
equivalent mole fraction, yCO2, allows equation [83] to be rewritten as

m& i x [1 Ash Fraction] 1

= M i yi [84]
&
Q fuel Qc M fuel y CO 2

This is the value that would be computed from the conventional (CO2 based) F-
factor approach. By comparison with equation with equation [80], which
accounts for partial combustion, we can get a corrected emission factor in terms
of the emission factor computed by the F-factor approach. This is given by

m& i m& y CO 2
& = i [85]
&
Q fuel corrected Q fuel F factor yCO 2 + y CO + x y HC

The correction factor involves the ratio of carbon in incomplete combustion

products to the carbon in CO2. If this ratio is small, then the use of the F-factor
approach should give reasonable results.

m& i m& 1
& = i [86]
& + x y HC
Q fuel corrected Q fuel F factor 1 + y CO
y CO 2

For example, if the mole fraction of CO2 is 0.05 and the yCO + x yHC term is
1000 ppm = 0.001, then the correction factor is 1/[1+.001/.05] = 1/1.02 = 0.98. In
a very rich combustion example the ratio of CO + xHC to CO2 might be 1:1; in
this case the correction factor would be 0.5. Note that the correction factor
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 20

always gives a smaller emission factor than the one computed by the standard F-
factor approach.

CHEMICAL ENERGY TERMS

The usual calculation of thermodynamic property changes uses an arbitrary

reference point at a given temperature and pressure. For example, we can start
with the usual differential equation for the enthalpy as a function of temperature
and pressure.

1 v 1
dh = c p dT + v(1 T p )dP where p = = [87]
v T P T P

In this equation, h, cp, and v represent the per-unit-mole values of enthalpy,

isobaric heat capacity, and specific volume, respectively. If we integrate the dh
equation between an arbitrary reference temperature and pressure, Tref and Pref,
to some other temperature, T, and pressure, P, we can write the result formally
as follows.
h T P
h href = h(T , P) h(Tref , Pref ) = dh' =
href
c p dT ' +
Tref
v(1 T
Pref
p )dP' [88]

In the absence of chemical reactions, the reference enthalpy is arbitrary.

However, in order to account for the energy of chemical reactions we have to
have to include this energy in the reference term. This is done by the following
process.

The enthalpy of formation of chemical elements in their natural state is set

to zero.

The enthalpy of formation of a compound from its elements, in a process in

which the products are at the same temperature and pressure as the
elements, which form it, is taken as the reference enthalpy for a
compound.

The enthalpy of formation is typically measured at a reference temperature of

25 C = 298.15 K = 77 F and a reference pressure of one atmosphere. For
combustion analyses the effect of pressure on enthalpy is negligible and
equation [88] may be written for one chemical species as follows:
T
hi (T ) = hi (Tref ) + c
Tref
pi dT ' [89]
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 21

Values of hi(Tref) may be found in various thermodynamic tables.8

We have previously discussed the heat of combustion or heat content of fuels.

The heat of combustion is defined in terms of the enthalpy change for complete
stoichiometric combustion. The reaction of our typical fuel formula with oxygen in
shown in equation [5]; we can use the coefficients from that equation, setting
equal to one, and recognizing that the heat of formation of oxygen and nitrogen
are zero, to write the following enthalpy change equation.

y
H R (Tref ) = xhCOs (Tref ) + hH O (Tref ) + zhSO2 (Tref ) hFuel (Tref ) [90]
2 2

This will be a negative enthalpy change (indicating that heat is liberated by the
reaction).9 The heat of combustion of the fuel is defined as the negative of this
enthalpy change divided by the molecular weight of the fuel to get units on a
mass basis.

y
H R (Tref ) xhCOs (Tref ) + hH O (Tref ) + zhSO2 (Tref ) hFuel (Tref )
Qc = = 2 2 [91]
m fuel m fuel

For example, the enthalpy change for formation of methane, liquid water, and
CO2 are 74.87 kJ/mol, -285.83 kJ/mol, and 393.52 kJ/mol, respectively. We
can compute the enthalpy change for the reaction CH4 + 2O2 CO2 + 2H2O
from equation [90] as 1(-393.52) + 2(-285.83) (-74.87) = -830.31 kJ/mol. Using
the molecular weight of methane, we can compute the heat of combustion as
follows: Qc = -( -830.31 kJ/mol) / (16.04262 g/mol) = 55.497 kJ/g = 55,497 kJ/kg
= 23,859 Btu/lbm.10

The analysis of a real combustion process, using typical applications of the first
law of thermodynamics, must use these chemical enthalpies as the reference
enthalpy. The usual first law for open systems uses specific enthalpies based on

8
Chase, M. W., Jr., NIST-JANAF Thermochemical Tables, Fourth Edition, J. Phys. Chem.
Ref. Data, Monograph 9, 1998, 1-1951. Note that the usual symbol for this reference
enthalpy, called the enthalpy of formation, is Hfo. This is based on the convention that the
reference enthalpy for the elements in their natural state is zero and the reference enthalpy
for compounds is the enthalpy difference between, measured as the energy input, when a
compound is formed from its elements. The superscript o denotes that the enthalpy of
formation is determined at atmospheric pressure.
9
Reactions in which heat is liberated are called exothermic reactions; reactions which have a
positive enthalpy change, indicated that heat input is required, are called endothermic.
10
The density of methane at 68oF (= 20oC) and atmospheric pressure is 0.41634 lbm/ft3.
Multiplying this by the heat of combustion of 23,859 Btu/lbm gives a heat of combustion per unit
volume of 993.4 Btu/ft3, close to the rule-of-thumb value of 1,000 ft3/lbm for natural gas.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 22

mass units, not molar units. However, it is possible to use molar units, so long as
there is dimensional consistency with the heat and work terms.

For an open system, in steady-state, with one inlet and one outlet, the first law
reduces to the following form, when changes in kinetic and potential energy
terms are negligible.

Q& = W& + H& out H& in [92]

The terms H& out and H& in represent the enthalpy changes from mass flows in the
inlet and outlet streams.

Energy balance for complete combustion If we regard the molar quantities in

equation [7] for complete combustion of a hydrocarbon fuel in air as moles per
unit time, we can write terms like H& out and H& in as the product of a molar flow rate
times a molar enthalpy, such as the one in equation [89]. If the inlet is a fuel-air
mixture at a temperature Tin, and the outlet contains exhaust products (as given
by the molar quantities in equation [7]) at a temperature Tout, we can write the
first law balance of equation [92] as follows.

y
Q& = W& + (x + A rCO 2 ) hCO2 (Tout ) + ( + ArH 2O ) hH 2O (Tout ) + z hSO2 (Tout )
2
v [93]
+ ( - 1)AhO2 (Tout ) + ( + A r N 2 )hN 2 (Tout ) + A r Ar h Ar (Tout )
2
[
hFuel (Tin ) A hO2 (Tin ) + rCO 2 hCO2 (Tin ) + rH 2O hH 2O (Tin ) + r Ar h Ar (Tin ) + rN 2 hN 2 (Tout ) ]
x

In this case we are taking the combustion process as the control volume with
reactants at the inlet and products at the outlet. The heat transfer term is then
the heat transfer to the combustion gases and the work term is the work output
from any device that has reactants as an inlet and products as an outlet.
Substituting equation [89] for the chemical enthalpy term into this equation gives
the following result.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 23

Tout y Tout
Q = W + (x + A r CO 2 ) hCO2 (Tref ) + c pCO2 dT ' + ( + ArH 2O ) hH 2 O (Tref ) + c p H 2O dT '
& &
Tref 2 Tref
Tout Tout
+ z hSO2 (Tref ) + c p SO2 dT ' + ( - 1)AhO2 (Tref ) + c pO2 dT '
Tref Tref

v Tout Tout
+ ( + A r N 2 )hN 2 (Tout ) + c p N 2 dT ' + A r Ar hAr (Tref ) + c p Ar dT '
2 Tref Tref
Tin Tin Tin
hFuel (Tref ) + c p Fuel dT ' AhO2 (Tref ) + c pO2 dT ' A r CO 2 hCO2 (Tin ) + c pCO2 dT '
Tref Tref Tref
Tin Tin
ArH 2O hH 2 O (Tref ) + c p H 2O dT ' A r Ar hAr (Tref ) + c p Ar dT '
Tref Tref
Tin
A rN 2 hN 2 (Tref ) + c p N 2 dT '
Tref [94]

We can simplify this equation by defining reactant and product heat capacities by
the equations below.11

[
C p Re act = c p Fuel + A c pO + r CO 2 c pCO + rH 2O c p H O + r Ar c p Ar + rN 2 c p N
2 2 2 2
] [95]

y
C pPr od = (x + A r CO 2 )c pCO + ( + ArH 2O )c p H O + zc pSO + ( - 1)Ac pO
2 2 2 2 2
[96]
v
+ ( + A r N 2 )c p N + A r Ar c p Ar
2 2

The reference enthalpies of the elements nitrogen, oxygen, and argon are zero,
so we can drop these terms from equation [94]. In addition, we see that the
terms involving CO2 and H2O in the inlet air have the same coefficient multiplying
the reference enthalpies for these terms on both sides of equation [94]. Hence
these terms can be cancelled. If we then collect the remaining reference
enthalpy terms in equation [94] and introduce the heat capacity definitions in
equations [95] and [96], we can rewrite equation [94] as follows.

11
Here we use a capital C for the heat capacity because there are no longer the specific heat
capacities. Instead, these heat capacities are extensive properties that depend on the amount of
mass in the system. They will have units of energy/temperature.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 24

Tout Tin
Q& = W& + Cp Pr od
dT ' Cp Re act
dT '
Tref Tref [97]
y
+ xhCOs (Tref ) + hH O (Tref ) + zhSO2 (Tref ) hFuel (Tref )
2 2

However, we see that the reference enthalpy terms in equation [97] are just the
negative of the heat of combustion defined in equation [89] times the molecular
weight of the fuel. We thus have the following result.

Tout Tin
Q& = W& + Cp Pr od
dT ' Cp Re act
dT ' Qc mFuel [98]
Tref Tref

We wrote the process using the combustion of one mole of fuel as the basis.
The total mass of reactants (which is also the total mass of products) in this basis
is the fuel mass plus the air mass. This can be written in terms of the air/fuel
mass ratio as follows.

Air
m = mPr od = mRe act = mFuel + m Air = mFuel 1 + [99]
Fuel

If we divide by the total mass and use the definition that q and w are the heat
transfer and work per unit mass, we can write equation [98] as follows.
T T
1 out 1 in Qc
q = w+
m Tref
C pPr od dT '
m Tref
C pRe act dT '
Air [100]
1 + Fuel

Up to this point, we have not made any assumptions about the properties (other
than the assumption of complete combustion). If we now assume that the per
unit mass heat capacity of the reactants is the same as that of the products, and
further assume that this heat capacity is about the same as that of air we have
the following simplification.
Tout
Qc
q= w+ c p Air dT '
Air [101]
1 + Fuel
Tin

Recall that the control volume definition made the combustor the control volume.
In a heat transfer process, then, we expect the heat transfer to be negative
indicating that heat is transferred from the combustion gases. We want this to be
as large as possible and equation [101] tells us that we obtain this maximum heat
transfer when the inlet and outlet temperatures are the same. Increases in the
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 25

outlet temperature above the inlet temperature indicate a less efficient heat
transfer. The combustion efficiency may be defined as follows as the ratio of the
actual heat delivered by the combustion process (the absolute value of the right
side of equation [101] with w = 0) to the maximum heat transfer (the absolute
value of the right side of equation [101] with w = 0 and Tin = Tout).
T
out
Qc
Air T p Air
c dT '
Air
q
1 +
Fuel
in
1 + Fuel Tout
comb =
q max
=
Qc
=1
Qc c p Air dT '
Tin
[102]

Air
1 + Fuel

If we had not made the assumption that the reactant and product heat capacities
were the same, we could still obtain the same qualitative result. The combustion
efficiency is greatest when the inlet (reactant) and outlet (product) temperatures
are the same. Combustion efficiencies in practical systems attempt to reach this
goal by using the energy in the exhaust to preheat the incoming air.

COMBUSTION EFFICIENCY FOR INCOMPLETE COMBUSTION

Incomplete combustion products will reduce the combustion efficiency defined

above. The simplest (and most important) case to consider is the reduction in
efficiency due to the production of CO instead of complete combustion to CO2.
To analyze this case we use the simplification of the reaction equation [55] (for a
basis of 100 dry product moles) shown in equation [103], below, where all
incomplete combustion products except CO have been removed. For simplicity,
the presence of CO2 in the incoming air is ignored.

[
F C x H y S z O w N v + AF O 2 + r H 2O H 2 O + r Ar Ar + r N 2 N 2 ]
[103]
a CO 2 + b CO + d H 2 O + F z SO 2 + g O 2 + F A r N 2 N 2 + F A r Ar Ar

The element balances for sulfur, nitrogen and argon are already present in
equation [103]. The remaining element balances can be used to obtain the
following equations. The carbon balance gives.

a+b
x F = a+b F= [104]
x

The hydrogen balance gives

( )
F y + 2ArH 2 O = 2d yF = 2d 2FArH 2 O [105]

The oxygen balance gives

 Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 26

(w 2 z)F + (2 + r H 2O ) AF = 2 a + b + d + 2 g [106]

Because the basis was selected to be 100 dry moles, the following sum holds for
the product moles.

[ (
a + b + g + F z + A rN 2 + rAr = 100 )] [107]

Using the symbols for the moles of different species in this equation, we can
replace the first law energy balance in equation [94] by the following equation.

Tout Tout Tout

Q = W + a hCO2 (Tref ) + c pCO dT ' + b hCO (Tref ) + c pCO dT ' + d
& &

h (T ) + c p H O dT '

2 H 2O ref 2
Tref Tref Tref
Tout Tout


+ Fz hSO2 (Tref ) + c pSO dT ' + g hO2 (Tref ) + c pO dT '


2 2
Tref Tref
Tout Tout


+ h hN 2 (Tout ) + c p N dT ' + F A r Ar hAr (Tref ) + c p Ar dT '
2
Tref Tref
Tin Tin
F hFuel (Tref ) + c p Fuel dT ' AF hO2 (Tref ) + c pO dT '



2
Tref Tref
Tin Tin
h (T ) + c p H O dT ' FA r Ar hAr (Tref ) + c p Ar dT '

FArH 2O
H 2O ref 2
Tref Tref
Tin
FA rN 2 hN 2 (Tref ) + c p N dT '
[108]
2
Tref

We can simplify this equation by defining reactant and product heat capacities by
the equations below, which are similar to equations [95] and [96].

[
C pRe act = Fc p Fuel + AF c pO + + rH 2O c p H
2 2O
+ r Ar c p Ar + rN 2 c p N
2
] [109]

v
C pPr od = ac pCO + bc pCO + dc p H + zFc pSO + gc pO + ( + A r N 2 )c p N + A r Ar c p Ar [110]
2 2O 2 2 2 2

Substituting these heat capacity definitions into equation [108] gives the following
result.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 27

Tout Tin
Q& = W& + Cp Pr od
dT ' Cp Re act
dT '
[111]
Tref Tref
( )
+ ahCO2 (Tref ) + bhCO (Tref ) + d AFrH 2O hH 2O (Tref ) + zFhSO2 (Tref ) FhFuel (Tref )

Assuming a fuel with no ash content the mass of the fuel is equal to the moles of
the fuel, F, times the fuel molecular weight. Using the result from equation [104]
that F = (a + b)/x gives.

a+b
m fuel = FM fuel = M fuel [112]
x

The total mass, mair + mfuel, is given by the following equation.

Air Air
m = m fuel + mair = m fuel 1 + = FM fuel 1 + [113]
Fuel Fuel

Dividing equation [111] by this total mass gives the specific heat capacities
cp,react, and cp,prod, in the integrals, providing the following result.

Tout Tin
ahCO2 (Tref ) + bhCO (Tref )
q = w+ cp Pr od
dT ' cp Re act
dT ' +
Air
Tref Tref 1 + FM fuel
Fuel
+
(d AFrH O ) 2
hH 2O (Tref ) + zFhSO2 (Tref ) FhFuel (Tref )
[114]

Air
1 + FM fuel
Fuel

From equation [105] we see that the term multiplying hH2O in the second row of
equation [114] is simply equal to yF/2. Making this substitution and canceling the
F terms in the numerator and denominator in second row of [114] gives.

Tout Tin
ahCO2 (Tref ) + bhCO (Tref )
q = w+ c p Pr od dT ' c p Re act dT ' +
Air
Tref Tref 1 + FM fuel
Fuel
y [115]
hH 2 O (Tref ) + zhSO2 (Tref ) hFuel (Tref )
+ 2
Air
1 + M fuel
Fuel

The terms with the CO and CO2 enthalpies can be manipulated as follows, using
equation [104] that F = (a + b)/x.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 28

ahCO2 (Tref ) + bhCO (Tref ) (Fx b)hCO2 (Tref ) + bhCO (Tref )

=
Air Air
1 + FM fuel 1 + FM fuel
Fuel Fuel
=
xhCO2 (Tref )
+
[
b hCO (Tref ) hCO2 (Tref ) ] [116]

Air Air a + b
1 + M fuel 1 + M fuel
Fuel Fuel x

Substituting this result into equation [115] gives the enthalpy terms that define
the heat of combustion in equation [91].
Tout Tin
[
b hCO (Tref ) hCO2 (Tref ) ]
q = w+ c pPr od dT ' c pRe act dT ' +
Air a + b
Tref Tref
1 + M fuel
Fuel x
y
xhCO2 (Tref ) + hH O (Tref ) + zFhSO2 (Tref ) FhFuel (Tref )
+ 2 2 [117]
Air
1 + M fuel
Fuel
Tout Tin

= w + c pPr od dT ' c pRe act dT '

Qc
+
[
b hCO (Tref ) hCO2 (Tref ) ]
Air Air a + b
Tref Tref
1 + 1 + M fuel
Fuel Fuel x

In this case, the combustion efficiency equation [102] is replaced by equation

[118], to account for the presence of CO in the reaction products. As before, we
assume that the heat capacity of the reactants and the products can be
approximated as the heat capacity of air. The maximum heat transfer occurs
when the inlet and outlet temperatures are the same (so the integrals in equation
[117] vanish) and there is no CO produced (b = 0). We find this maximum heat
transfer from equation [117] and divide the result into equation [117] to obtain the
equation below. In that equation, the term with CO enthalpy is summarized as D
and D for convenience

Tout
Qc
Air
cp Air
dT ' D'
Air
1 + Fuel Tin 1 + Fuel Tout

c p dT ' D [118]
q
comb = = = 1 Air
q max Qc Qc
in
T
Air
1 + Fuel

Comparing equations [116] and [118] shows that we can write the D term as
follows.
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 29

Air
D=
1 +

[
Fuel b hCO (Tref ) hCO2 (Tref )
=
b 1 x ] [ ]
hCO (Tref ) hCO2 (Tref ) [119]
Qc Air a + b a + b Qc M fuel
1 + M fuel
Fuel x

In equation [119] the ratio b/(a+b) is the ratio of the CO concentration to the sum
of the CO and CO2 concentrations in the exhaust and x/Mfuel is the number of
carbon atoms in the fuel formula divided by the molecular weight of the fuel. The
value of the enthalpy difference hCO hCO2 is 282,990 kJ/kgmol = 121,665
Btu/lbmol at a reference temperature of 25oC. Defining this enthalpy difference
as HCO allows us to write the D in the following simplified manner.

b xH CO
D= [120]
a + b Qc M fuel

ADIABATIC FLAME TEMPERATURE

The maximum temperature achieved in a combustion process is called the

adiabatic flame temperature, TAFT. This temperature may be estimated from
equation [101] by setting q = w = 0, and assuming that the heat capacity is
constant at some mean value, c p Air . This gives the following result.

T AFTt

dT ' = c p Air (TAFT Tin ) =

Qc
c p Air
Air [121]
Tin 1 +
Fuel

For a typical liquid hydrocarbon fuel for which the lower heating value, QC =
18,000 Btu/lbm and the practical air-fuel ratio is about 18:1 we can compute the
adiabatic flame temperature from equation [103]. If we assume that the mean
heat capacity for air is about 0.27 Btu/lbm-F and the inlet temperature is 60 F, we
find the following result.

18,000 Btu
Qc lbm
TAFT = Tin + = 60 F + = 3569 F [122]

c p Air 1 +
Air 0.27 Btu
[1 + 18]]
Fuel lbm F

This calculation can be repeated, in a trial-and-error fashion, to ensure that a

correct value for the mean heat capacity is used. However, there is another
effect that takes place at high temperatures that tends to depress the adiabatic
flame temperature. CO2 dissociates into CO and oxygen. In addition, H2O
dissociates into H2, O2, and the hydroxyl radical. (There is also some
dissociation of diatomic gases H2, O2, and N2 into monatomic species H, O, and
N. All of these dissociation reactions produce species that have a large
Combustion Notes ME 483, L. S. Caretto, Spring 2010 Page 30

reference enthalpy. The production of these species reduces the adiabatic flame
temperature. The computation of complex chemical equilibrium, with multiple
species is readily handled by codes such as the NASA chemical equilibrium
code. Some results from that code are provided below.

The adiabatic flame temperatures for stoichiometric combustion of a series of

fuels in air are shown in the table below. In all cases the fuel is a gas and the
fuel and air are both at an initial temperature of 25 C.

Fuel H2 NH3 N2H4 CH4 C3H8 C8H18

TAFT (K) 2,384 2,074 2,435 2,227 2,268 2,277
TAFT (F) 3,832 3,274 3,923 3,549 3,623 3,639

If the combustion is fuel rich, it will not be possible to obtain the full energy
release from complete combustion. If the combustion is fuel lean, there will be
excess air that will absorb some of the chemical energy release from the fuel.
Maximum adiabatic flame temperatures tend to occur when the mixture is
stoichiometric. The table below shows the adiabatic flame temperature for a
variety of relative air/fuel ratios, , where < 1 indicates fuel-rich (air lean) and
> 1 indicates fuel-lean (air-rich) combustion.

0.667 1 1.25 1.667 2.5 5

TAFT (K) 1,982 2,302 2,046 1,697 1,298 840
TAFT (F) 3,108 3,684 3,223 2,595 1,877 1,052

These results assume that chemical equilibrium has been obtained in the
combustion reaction. This is often a good assumption for predicting the energy
release and adiabatic flame temperatures. However, the prediction of pollutant
formation requires an examination of the rate of the chemical reactions that are
involved in the combustion process.