Combustion and

Thermochemistry
SHEN-LIN CHANGw
Argonne National Laboratory
Argonne, Illinois, United States
CHENN QIAN ZHOU
Purdue University Calumet
Hammond, Indiana, United States

carbon fuel and an oxidant. Combustion generates

1. Introduction significant amounts of light, heat, and/or mechanical
2. Combustion Elements work. Furnaces and combustors have been developed
3. Thermochemistry to generate electricity and manufacture tools and
4. Hydrodynamics and Mixing equipment. Combustion engines have enabled trans-
5. Chemical Reactions portation in every region of Earth and even into
space. In recent years, concerns over energy avail-
6. Radiation Heat Transfer
ability and the environmental impacts of combustion
7. Tools for Combustion Analysis
processes have attracted more and more attention.
8. Pollution Control Techniques To use energy resources efficiently and responsibly
9. Concluding Remarks has become a main goal of many societies. To achieve
this goal, knowledge of combustion science has to be
learned and applied.
Glossary
adiabatic flame temperature The highest flame temperature
that is achievable under the condition of no external 1. INTRODUCTION
heat transfer.
combustion The burning of fuel and oxidant to produce Combustion includes thermal, hydrodynamic, and
heat and/or work. chemical processes. Combustion starts with the
computational fluid dynamics (CFD) Computer program mixing of fuel and oxidant, and sometimes in the
for calculating fluid dynamics properties of a flow. presence of additional compounds or catalysts. The
diffusive flame Separate fuel and oxidant inlets before
fuel/oxidant mixture can be ignited with a heat
burning takes place.
source; chemical reactions between fuel and oxidant
flammability Combustion reaction criteria.
gasification Incomplete fuel-rich combustion that pro- then take place and the heat released from the
duces CO and/or H2. reactions makes the process self-sustaining. Instabil-
ignition Initial conditions for sustained combustion. ity may occur, inhibiting or strengthening combus-
tion. Combustion products include heat, light,
chemical species, pollutants, mechanical work, and
Much solar energy is stored in hydrocarbons. Early plasma. Sometimes, a low-grade fuel, e.g., coal,
humans, seeking protection and comfort, learned to biomass, and coke, can be partially burned to
convert hydrocarbon energy to fire to survive. produce a higher grade fuel, e.g., methane. The
Combustion, the most important form of energy partial burning process is called gasification. Various
conversion, is a chemical reaction between a hydro- combustion systems, e.g., furnaces, combustors,
boilers, reactors, and engines, have been developed
w
Deceased. to utilize combustion heat, chemical species, and

Encyclopedia of Energy, Volume 1. r 2004 Elsevier Inc. All rights reserved. 595
596 Combustion and Thermochemistry
Solid, liquid,
or gas fuel
Mixing
Oxygen
Other species
nitrogen, etc.
Catalyst
FIGURE 1 Typical combustion processes.
work. Figure 1 shows a flow diagram of typical
combustion processes.
Advanced measurement/control devices have been
traditionally used as tools for analysis of combustion
systems. The analysis can lead to lower energy use
and lower pollutant emissions by a system. In recent
years, the computational analyses, including compu-
ter models of kinetics and fluid dynamics, have been
used as an added tool for combustion analysis. The
focus here is to assess the overall process of analyzing
a combustion system.
A computational combustion analysis starts with
the identification of the participating elements and
their thermochemical properties and relations. This
is followed by derivation of the governing equations
and development of the required phenomenological
models, including turbulent mixing, droplet evapora-
tion, particle devolatization, radiation heat transfer,
and interfacial interactions. Then, the governing
equations are solved numerically on a computer.
The results are validated with experimental data.
Thus, the validated computer code can be used to
evaluate the combustion system and to control
combustion products.
2. COMBUSTION ELEMENTS
The elements (or species) involved in a combustion
process include reactants, inert and intermediate
species, products, and catalysts. Reactants generally
include a fuel and an oxidant. Fuel can be in solid,
liquid, or gas phase. Solid fuels include coal and
biomass. Liquid fuels include hydrogen, gasoline,
diesel, kerosene, and jet fuels. Gas fuels include
Fuel
Heat Furnace
combustor
Heat boiler
Control
Ignition Pollutants
techniques
Chemical Reactors
Gasification species
Light
Combustion Work Engines
Plasma
Flame instability
natural gas, methane, and propane. The oxidant
is mostly oxygen but may include F2O, F2O2, NF3,
ClF3, ClF3, ClO3F, O3, and N2F4 in some rocket
applications. The fuel and the oxidant can also
be formed as a monopropellant in rocket applica-
tions. Catalysts are sometimes used to enhance com-
bustion.
Inert species are not directly involved in the
combustion process, but at high temperatures these
species can be dissociated or ionized. These species
include the nitrogen in the air and the ash in coal.
Major combustion products include CO2 and H2O.
Because these species can emit and absolve radiation
energy, they are regarded as greenhouse gases that
are related to the global warming issue. Many
intermediate species, such as OH, CO, CH, are
present during combustion. Combustion products
also include some minor species, i.e., NOx, SOx,
unburnt hydrocarbons (UHCs), and soot. These
species are regarded as pollutants. NOx and SOx
are believed to cause acid rain, UHCs play a role in
smog, and soot chemicals, including polynuclear
aromatics, may be carcinogenic.
In a combustion reaction, there can be so many
combustion elements that it is impossible to ana-
lyze them all. Therefore, many combustion elements
are lumped into one category for the convenience
of analysis. For example, coal consists of thousands
of hydrocarbons, but in most coal combustion
analyses, the hydrocarbons are grouped into four
categories: moisture, volatiles, char, and ash. The
moisture is water, the volatiles represent all of
the hydrocarbons that can be vaporized during
combustion, the char includes all hydrocarbons
that cannot be vaporized, and the ash is inert
material, mostly metals.

3. THERMOCHEMISTRY
Assume that Reaction (1) represents a combustion
reaction of I lumped reactants and J lumped products:
J
X
I X
ni Reactants- nj Products: ð1Þ
i¼1 j¼1
In the reaction, the ni values on the reactant side and
nj values on the product side are called the stoichio-
metric coefficients. The coefficients can be on a molar
or a mass basis. On a molar basis, the unit is moles;
on a mass basis, the unit is kilograms.
A computational combustion analysis calculates
the heat, work, and/or species generated from a
combustion process, which includes the combustion
reaction, fluid dynamics, and heat transfer. Thermo-
dynamic and chemical (thermochemical) properties
of the combustion elements are needed to calculate
the heat, work, and species. The thermochemical
properties most often used in a combustion analysis
include temperature, pressure, density, enthalpy,
specific heat, viscosity, diffusivity, thermal conduc-
tivity, Gibbs free energy, molecular weight, species
concentration, heat of combustion, latent heat, and
equilibrium constant.
3.1 Equations of State
The thermochemical properties of a combustion
species can be obtained by direct measurements or
theoretical calculation. These properties are not all
independent. Thermodynamic properties of a com-
bustion species are generally functions of tempera-
ture and pressure. In most practical applications,
these properties can be expressed in terms of
temperature only. Sometimes, even constant property
values are used. Most properties of a combustion
species have been determined and tabulated in tables
and other references produced by the joint inter-
agency (Army, Navy, NASA, and Air Force) commit-
tee, JANNAF (formerly JANAF, before NASA was
included). Properties of a mixture are determined by
adding the properties of its components according to
their concentrations. The partial pressure of a
component is defined as the total pressure times its
molar concentration.
Other than direct measurement, the thermochemi-
cal properties of members of a grouped (‘‘lumped’’)
combustion element (or species) can be obtained by
adding the properties of its major constituents
according to their proportion. For example, a fuel
composed of 90% methane (CH4) and 10% ethane
Combustion and Thermochemistry 597
(C2H6) becomes a lumped species C1.1H4.2. Its
molecular weight is 17.1 kg/mol, calculated by adding
90% of 16 kg/mol (molecular mass of methane) and
10% of 30 kg/mol (molecular mass of ethane).
Similarly, other properties of the lumped species can
be obtained from those of the chemical species.
3.2 Chemical Equilibrium
At constant temperature and pressure, a combustion
reaction such as Reaction (1) will reach an equili-
brium state. The equilibrium constant Kp is defined as
Y nj Y nij
Kp ¼ Pj = Pi ð2Þ
j¼p i¼r
in which the Pi values are partial pressures of the
reactants (r) and products (p). The equilibrium
constants of many combustion reactions have been
determined and are tabulated in most combustion
textbooks.
A combustion process generally consists of many
reactions. The equilibrium species concentrations
can be calculated from the equilibrium constants
and the initial species concentrations. Bittker and
Scullin developed a general chemical kinetics com-
puter (GCKP) program to perform equilibrium
calculations of hydrogen/air combustion and many
other combustion processes.
3.3 Adiabatic Flame Temperature
Combustion of a fuel produces heat. When all of the
heat is used to heat the products, without heat
transfer from external sources, the final temperature
is called the adiabatic flame temperature. The
temperature can be determined by balancing the
heat of combustion, the heat of dissociation, and the
total enthalpy of the combustion products. At a
combustion temperature higher than 2000 K, a small
portion of the combustion products CO2 and H2O
dissociates into intermediate species, such as CO, O,
and OH, and the dissociation uses up a significant
amount of the heat of combustion. Thus, the energy
balance equation needs to be solved in conjunction
with the equilibrium calculation to obtain an
adiabatic flame temperature. Assuming the initial
temperature and pressure are under standard condi-
tions, the adiabatic flame temperature of a methane/
air mixture is about 2200 K. Chang and Rhee
developed a set of empirical formulations that can
be used to estimate adiabatic flame temperature of
lean fuel/air mixtures. The adiabatic flame tempera-
ture is an important thermochemical property in a
598 Combustion and Thermochemistry
combustion analysis because it is the upper bound of
the temperature.
4. HYDRODYNAMICS AND MIXING
A fuel and an oxidant must mix to react. The mixing
process is a part of flow dynamics. Gas phase mixing
is mainly due to turbulence; liquid injection in
droplet sprays is commonly used to enhance the
mixing between liquid droplets and gas, and some
solid fuels are pulverized to increase the mixing
between the particles and gas.
4.1 Governing Equations
Combustion generates heat, work, and product
species. In a computational combustion analysis,
heat is calculated from the temperature and velocity;
work is calculated from pressure and density; and the
species are calculated from concentrations and
velocities. The governing equations of these proper-
ties are derived from fundamental thermodynamic,
hydrodynamic, and chemistry principles. The deriva-
tion can be on a fixed mass basis or a control volume
basis. In the following discussion, a control volume
approach is used.
The principles of mass, species, and momentum
conservation are used to determine pressure, con-
centration, and velocity. The first law of thermo-
dynamics (or conservation of energy) is used to
determine temperature. The equation of state is used
to determine density. In deriving the governing
equations, many derived properties are created. For
example, enthalpy is used in the energy equation and
specific heat is used in the caloric equations of state.
Equation (3) is a typical energy equation derived on a
Cartesian coordinate system:
X 3  
@ m @h
rui h þ e ¼ Scomb þ Srad þ Sint ; ð3Þ
i¼1
@xi sh @xi
in which xi is a coordinate, r is density, ui is velocity
components, h is enthalpy, me is effective viscosity, sh
is a turbulent scale factor for the enthalpy, Scomb is the
combustion heat release rate, Srad is net radiation heat
flux, and Sint is heat transfer from the liquid or solid
phase. Effective diffusivity is used in the momentum,
energy, and species equations. It is the sum of both
laminar and turbulent diffusivities. The source terms
of the governing equations need to be determined
from various models. In the energy equation (3), there
are three source terms. The combustion heat release
rate needs to be calculated from combustion kinetics,
radiation heat flux needs to be solved from a radiative
transport equation, and the last term needs to be
determined from an interfacial interactions model.
4.2 Turbulent Mixing
Diffusive flames, commonly used in a furnace or a
combustor, are mostly turbulent. Turbulence is under-
stood to be the small eddies that enhance mixing and
combustion, but understanding the physics of the
turbulence is still far from complete. An enclosure
type of the ke turbulence model is commonly used
for combustion analysis. The model expresses the
turbulent viscosity mt in terms of two turbulent
parameters, kinetic energy k and dissipation rate e,
me ¼ m þ mt ¼ m þ Cm rk2 =e;
in which Cm is an empirical constant.
Lauder and Spalding proposed two additional
transport equations to solve for these two turbulent
parameters. Turbulent diffusivities for the enthalpy
and species equations are also expressed in terms of
the turbulent viscosity with a scaling factor. In a
multiphase flow, solid particles or liquid droplets
tend to inhibit eddy motion and reduce turbulent
diffusion and the adjustment of the turbulent
viscosity is needed. In addition, statistical turbulence
models are used to describe the turbulence mixing
effects. In this approach, probability density func-
tions are chosen to represent the fluctuation of the
flow properties. Large eddy and direct numerical
simulations have been introduced with the hope of
improving the description of turbulent flow.
4.3 Liquid Spray and
Droplet Vaporization
Liquid fuel can be burned in pools or sprays. The
burning processes start with the vaporization of the
liquid fuel. Next, the fuel vapor is mixed with
oxygen. Finally, the combustion reaction takes place.
The pool burning is mostly fire. Because of limited
contact area, the mixing of fuel vapor and oxygen is
poor. Therefore, combustion is mostly fuel rich and a
lot of smoke is produced. A fuel injector breaks up
the liquid into tiny droplets and the high pressure
makes droplets penetrate deep into the gas flow.
Empirical models have been developed to describe the
droplet size and number distributions off the tip of an
injector. The penetration enhances the mixing of the
fuel and the oxygen and the high ratio of surface area
to volume speeds up the evaporation process.

Liquid fuel vaporizes in two modes. At low
temperature, vaporization occurs due to the diffusion
of mass. At a temperature higher than the boiling
point, the liquid boils and the vaporization rate is
controlled by the heat transfer rate from the
surroundings to the liquid. In most combustion
systems, the heat transfer is convective. Empirical
correlations have been developed to calculate the
interfacial heat transfer rate from other flow proper-
ties, such as, velocity, conductivity, and viscosity.
Liquid droplets are generally treated in a Lagran-
gian or an Eulerian approach. The Lagrangian
approach takes one droplet at a time. It traces the
motion of a single droplet in the flow and takes the
average effect of all the droplets. Zhou and Yao also
included the group effects on the spray dynamics.
The Eulerian approach treats a group of droplets as a
continuum. Governing equations are derived for
each droplet group for solving the flow field.
4.4 Devolatization of Solid Fuel
Pulverized coal is used in many utility boilers. Due to
the small particle size, pulverized coal can be
transported pneumatically. Coal particles contain
four major components: moisture, volatiles, char,
and ash. When heated, the moisture is dried and the
volatiles are devolatized. The volatile vapor mixes
with oxygen and the mixture burns. The char left on
the particles is burned with oxygen when contacted.
The drying and devolatilization processes are con-
trolled by the heat transfer from the gas to the
particles. Similar to the liquid vaporization, the heat
transfer is convective. Empirical correlations are used
to determine the interfacial heat transfer rate. Similar
Lagrangian and Eulerian approaches can be applied
for particles.
5. CHEMICAL REACTIONS
The mixture of fuel and oxidant is burned in
chemical reactions. A combustion reaction is the
effective collisions of reactants (and catalyst), break-
ing the chemical bonds of the reactants, forming the
products, and releasing heat. Three types of reactions
are significant in a combustion analysis: ignition,
heat release, and pollutant formation.
5.1 Ignition and Flammability
Fuel and oxidant can be self-ignited (autoignition) or
by an external heat source. For example, diesel
Combustion and Thermochemistry 599
engine combustion is autoignition and gasoline
engine combustion is ignited by a spark. At an
ignition temperature, the combustion reactions gen-
erate heat and the heat is lost to the surroundings by
conduction, convection, and radiation heat transfer.
If the heat generation is larger than the heat loss, the
combustion reactions are sustained.
There are mixture ratios of fuel and oxidant that
the combustion will not sustain after the ignition
source is removed. For premixed laminar flame,
there exist flammability limits that are frequently
defined as percentage fuel by volume in the mixture.
The lower limit is the leanest mixture that will allow
steady flame, and the upper limit represents the
richest mixture. Flammability limits in both air and
oxygen are found in the literature. For example,
the lower flammability limit of methane is about 5%
by volume.
5.2 Combustion Reactions
Assume that fuel is a hydrocarbon CmH4n. The
combustion of the fuel and oxygen is shown in
Eq. (4):
k
Cm H4n þ ðm þ nÞO2 - mCO2 þ 2nH2 O: ð4Þ
The extent of reaction, x, is defined as the molar
concentration of the consumed fuel. For each mole of
x consumed, the sum (m þ n) moles of oxygen is
consumed and m moles of CO2 and 2n moles of H2O
are produced. The reaction rate dx/dt of the
combustion reaction can be expressed in an Arrhe-
nius formulation:
dx d 1 d
¼  ½Cm H4n  ¼  ½O2 
dt dt m þ n dt
1 d 1 d
¼ ½CO2  ¼ ½H2 O; ð5aÞ
m dt 2n dt
dx
¼ k30 expðE=RTÞ½Cm H4n ½O2 ðmþnÞ ; ð5bÞ
dt
in which [ ] represents molar concentration of a
species, t is reaction time, k0 is a preexponential
constant, E is an activation energy, and R is the
universal gas constant. The preexponential constant
and the activation energy are empirical constants
extracted from experimental data. Thus, the species
consumption/generation rates can be obtained from
Eqs. (5a) and (5b) and the heat release rate becomes
dqcomb =dt ¼ ðdx=dtÞHo ; ð6Þ
in which Ho is the heat of combustion.
600 Combustion and Thermochemistry
5.2.1 Gasification Reactions
Gasification is an incomplete combustion of the fuel.
In a fuel-rich combustion, the intermediate species
such as CO becomes a major product species. If
water is added to the reaction, hydrogen is also
produced. Because both CO and H2 can be burnt
later with oxygen and can release heat, the gasifica-
tion has been used to convert low-grade fuels, such
as, coal and biomass, to a higher grade gaseous fuel,
CO and H2. The gasification process is now also used
to convert diesel or gasoline fuel to hydrogen for
fuel-cell applications.
5.2.2 Heterogeneous Reactions
Heterogeneous reactions include char burning with
oxygen and gaseous reactions on catalyst surfaces.
Char burning is regarded as similar to a combustion
reaction. Empirical constants are extracted from
experimental data. The catalytic reaction is generally
treated as a third-body reaction and an Arrhenius
formula is used for analysis.
5.3 Pollution Reactions
In addition to the major heat release reaction, many
intermediate species are produced in numerous
combustion reactions. Pitz and Wesbrook have
compiled hundreds of combustion reactions and the
list is still growing. Some of the intermediate species
attract more public attention because they are
pollutants. Pollution is defined as the contamination
of the environment. All matter emitted from combus-
tion chambers that alters or disturbs the natural
equilibrium of the environment must be considered
as a pollutant. Pollutants of concern include parti-
cular matter, the sulfur oxides, unburned and
partially burned hydrocarbons, nitrogen oxides,
carbon monoxide, and carbon dioxide.
5.3.1 Soot Kinetics
Soot is formed in the fuel-rich region of a combustion
flow. Because soot is a strong contributor to the
radiation heat transfer, a soot model is needed to
calculate soot concentration for the radiation heat
transfer calculation. The following simplified soot
model assumes that soot (st) is generated in the fuel-
rich flame by the cracking of the fuel and is burnt up
by oxygen. The soot formation/oxidation rate is
expressed as
dfst =dt ¼ AO2 ffu expðE2 =RTÞ
 AO3 fst fox T 1=2 expðE3 =RTÞ: ð7Þ
5.3.2 NOx Kinetics
NOx is formed by combustion in the presence of
nitrogen. There are three types of NOx formation:
thermal, prompt, and fuel. Thermal NOx is formed
in high-temperature reactions, prompt NOx comes
from reactions with intermediate species, and fuel
NOx comes from the nitrogen in the fuel, e.g., coal.
The Gas Research Institute (GRI) has compiled a
long list (over 300) of reactions related to NOx
formation. However, lumped reduce mechanisms
with many less reactions are used in practice.
5.3.3 SOx Formation
Many coals contain significant amount of sulfur. The
sulfur reacts with oxygen during combustion and
produces SOx. Sulfur is also contained in many
lubricants. In diesel combustion, SO is formed and
becomes a major source of soot particle nucleation.
6. RADIATION HEAT TRANSFER
At combustion temperature, radiation is an impor-
tant if not dominating mode of heat transfer. In a
combustion process, radiatively participating species
include soot and gaseous species such as CO2 and
H2O. Heat is emitted, absorbed, and scattered in
waves of various wavelengths. Assuming the scatter-
ing effect in the combustion flow is negligible, the
radiative heat transfer becomes the balance of
emissive and absorption powers. For each wave-
length, local net radiation heat power is obtained by
integrating the absorption of the incoming radiation
from all other locations and subtracting the emitted
power. A radiative transport equation is obtained by
integrating the net radiation heat power over all
wavelengths, Eq. (8):
Z NI R 00 00
qr ðx; y; zÞ ¼ k0l e0bl ðT 0 Þe k dl dv0
0
 kl ebl ðTÞ dl; ð8Þ
in which l is wavelength, k is volume absorptivity, l
is optical length, v is a control volume, and ebl(T) is
the blackbody radiation function. The spectral
volumetric absorptivities of these media must be
determined from gas and soot radiation models.
6.1 Gas Radiation Model
The H2O species has five strong radiation bands,
centered at wavelengths of 1.38, 1.87, 2.7, 6.3, and

20 mm, and the CO2 species has six bands, at 2.0,
2.7, 4.3, 9.4, 10.4, and 15 mm. A wideband model
was introduced to calculate total band absorptance
of these species. For each band, species concentra-
tions, pressure, and temperature are used to deter-
mine a set of semiempirical parameters: the
integrated band intensity, the bandwidth parameter,
and the line width parameter. A semiempirical
correlation is then used to calculate the total band
absorptance from these parameters.
6.2 Soot Radiation Model
If the scattering is negligible, the Rayleigh-limit
expression of the soot volume absorptance ksl can
be used:
36n2 kðp=lÞfv
ksl ¼ : ð9Þ
½n2 ð1 þ k2 Þ þ 22 þ 4n4 k2
Soot volume absorptance is proportional to the soot
volume fraction fv and inversely proportional to the
wavelength. The optical refraction indices, n and k,
are weak functions of wavelength that can be derived
from classical electromagnetic theory.
7. TOOLS FOR
COMBUSTION ANALYSIS
Measurement and testing have long been the ways to
analyze and evaluate combustion systems. However,
computational software has now become an addi-
tional tool for combustion analysis.
7.1 Computational Fluid Dynamics
Combustion flow calculations adopt a control
volume approach to convert the governing equations
to algebraic equations on a staggered, discretized
grid system. The algebraic equations are solved
iteratively with proper boundary conditions. Exit
flow conditions have a strong impact on the
convergence of the calculation. Because most flows
are not fully developed, the exit flow conditions that
satisfy global mass balance appear to improve
numerical convergence the most.
The major species flow calculation uses Patankar’s
SIMPLER computational scheme to solve the pres-
sure-linked momentum equations. A major species
flow calculation is considered to have converged if
the local and global mass balances are smaller than a
set of predetermined criteria. The subspecies flow is
solved using the flow properties calculated from the
Combustion and Thermochemistry 601
major species flow calculation. Free from the
interactions of the pressure and velocity fluctuations,
the calculation of the partially decoupled subspecies
transport equations becomes very stable numerically.
Chang and colleagues developed an advanced
methodology to solve the radiative transfer equation
(RTE) in a Cartesian coordinate system. The
methodology guarantees the integrity of the energy
balance between emitting and absorbing powers. The
RTE solution routine divides the radiation heat flux
into many bands of wavelength. The blackbody
radiation function can be discretized in the wave-
length domain by using a closed form solution. For
each wavelength band, a calculation is performed to
balance the emitted and absorbed energy. For each
node in the computational fluid dynamics (CFD) grid
system, energy emitted is calculated. This emitted
energy is then traced along the optical paths of all
angles. The energy absorbed in every node (including
the wall surface node) is calculated and added to the
absorption energy of the initial node.
7.2 Kinetics Calculations
Many schemes have been proposed for the number of
equations and reaction rates that may be used to
simulate combustion reactions. One of examples is
the GCKP program developed at the National
Aeronautics and Space Administration (NASA).
Another example is the CHEMKIN program, a
widely used general-purpose package for solving
chemical kinetics problems. CHEMKIN was devel-
oped at Sandia National Labs and provides a flexible
and powerful tool for incorporating complex chemi-
cal kinetics into simulations of fluid dynamics. The
latest version includes capabilities for treating multi-
fluid plasma systems that are not in thermal
equilibrium. These features allow researchers to
describe chemistry systems that are characterized
by more than one temperature, in which reactions
may depend on temperatures associated with differ-
ent species; i.e., reactions may be driven by collisions
with electrons, ions, or charge-neutral species.
Both thermodynamic and kinetic databases are
needed for the kinetics calculations. The GRI-Mech
combustion model is a widely used database of
detailed chemical kinetic data. The latest version is
an optimized mechanism designed to model natural
gas combustion, including NO formation and reburn
chemistry, containing 325 reactions and 53 species. It
provides sound basic kinetics and also furnishes the
best combined modeling predictability of basic
combustion properties.
602 Combustion and Thermochemistry
7.3 Measurements
Measurements of flame properties can be made by
the insertion of probes into a flame, by optical
methods applied to emissions from the flames, or by
laser probing. The techniques for probing in flames
include temperature measurement by thermocouples,
velocity measurement by pressure impact probes and
particle-tracking photography, and species concen-
tration measurements using suction probes followed
by gas analysis.
The optical methods for making measurements in
flames include interferometry, schlieren, and photo-
graphic methods. All of the probing methods may
cause some form of disturbance to the fluid flow, heat
transfer, and species concentrations. Optical methods
provide information that is integrated over the optical
length of the measurement and the spatial resolution
is poor. Lasers provide noninvasive probing of flames
and high spatial resolution of measurements. The
measurement of temperature and species concentra-
tion in flames can be carried out by laser spectro-
scopy. Laser anemometers are widely used to measure
velocity components, turbulent characteristics, and
particle size in flames. Various advanced combustion
sensors have been developed with the potential to
enable direct measurement of key combustion para-
meters for improved combustion control.
8. POLLUTION CONTROL
TECHNIQUES
Control of pollutant emissions is a major factor in
the design of modern combustion systems. Pollution
control techniques can be mainly classified as two
types. One involves process modification to prevent
or reduce the formation of pollutant emissions. The
other is postcombustion treatment to remove or
destroy pollutants from combustion before being
emitted into the ambient air.
8.1 Process Modification
The techniques to modify combustion for reducing
pollutant emissions include fuel changes and com-
bustion modifications. Switching vehicles from gaso-
line to compressed natural gas, propane, or ethanol
can reduce vehicular air pollutant emissions. Adding
oxygenated compounds to motor fuels can change
the combustion reaction to lower CO emissions
significantly. Using low-sulfur fuels can reduce sulfur
dioxides emissions.
The principle of combustion modification is
widely used in NOx emission control. Modifying
burner configuration or operation conditions can
change distributions of temperature, oxygen, and
nitrogen to reduce the formation of NOx. Such
techniques include using low excess air, staged
combustion, low NOx burners, water injection,
oxyfuel combustion, exhaust gas recirculation
(EGR), and reburn. These techniques can be eco-
nomical and effective. However, in some applica-
tions, combustion system modification alone is
unable to reduce pollutant emission levels below
legislated standards, and postcombustion treatment
may be required.
To reduce SO2 emissions, fluidized bed combus-
tion, in which limestone particles are used as bed
materials, is an alternative way to burn coal. Another
combustion modification alternative for SO2 reduc-
tion that is in the demonstration stage is the combi-
ned-cycle power plant.
8.2 Postcombustion Treatment
Postcombustion treatment involves installation of
pollution control devices downstream of the com-
bustor. For example, selective noncatalytic reduction
(SNCR) and selective catalytic reduction (SCR)
processes are widely used for NOx reduction. These
techniques involve a nitrogen-containing additive,
either ammonia, urea, or cyanuric acid, that is
injected and mixed with flue gases to effect chemical
reduction of NO to N2, without or with the aid of a
catalyst. Other postcombustion treatment techniques
utilize wet or dry limestone scrubbers and spray
dryers to reduce SO2 emissions; cyclones, electro-
static precipitators (ESPs), filters, and scrubbers for
particle removal; or three-way catalytic converters
for the control of NOx, CO, and hydrocarbon (HC)
emissions from automobiles.
To stabilize and ultimately reduce concentrations
of the greenhouse gas CO2, carbon sequestration
(carbon capture, separation, and storage or reuse) is
a major potential effective tool for reducing carbon
emissions from fossil fuel combustion.
9. CONCLUDING REMARKS
This article is intended to guide a reader through the
overall process of analyzing a combustion system,
especially using the newly added computational
tools, and to advocate the good use of combustion

analyses to convert combustion processes for cleaner
and more efficient energy production.
SEE ALSO THE
FOLLOWING ARTICLES
Acid Deposition and Energy Use Greenhouse Gas
Emissions from Energy Systems, Comparison and
Overview Heat Transfer Temperature and Its
Measurement
Further Reading
Bittker, D. A., and Scullin, V. J. (1972). ‘‘General Chemical
Kinetics Computer Program for Static and Flow Reactions, with
Application to Combustion and Shock-tube Kinetics,’’ NASA
TN D-6586. NASA, Washington, D.C.
Chang, S. L., and Rhee, K. T. (1983). Adiabatic flame temperature
estimates of lean fuel/air mixtures. Combust. Sci. Technol. 35,
203–206.
Chang, S. L., Golchert, B., and Petrick, M. (2000). Numerical
analysis of CFD-coupled radiation heat transfer in a glass
furnace, No. 12084. Proc. 34th Natl. Heat Transfer Conf.,
Pittsburgh, Pennsylvania.
Combustion and Thermochemistry 603
Glassman, I. (1977). ‘‘Combustion.’’ Academic Press, San Diego.
Kee, R. J., Rupley, F. M., Meeks, E., and Miller, J. A. (1996).
‘‘CHEMKIN-III: A Fortran Chemical Kinetics Package for the
Analysis of Gasphase Chemical and Plasma Kinetics,’’ Rep.
SAND96-8216. Sandia National Laboratories, Livermore, CA.
Lauder, B. E., and Spalding, D. B. (1974). The numerical
computation of turbulent flows. Comput. Meth. Appl. Mech.
Eng. 3, 269–289.
Patankar, S. V. (1980). ‘‘Numerical Heat Transfer and Fluid Flow.’’
Hemisphere, Washington, D.C.
Pitz, W. J., and Westbrokk, C. K. (1986). Chemical kinetics of the
high pressure oxidation of n-butane and its relation to engine
knock. Combust. Flame 63, 113–133.
Smith, G. P., Golden, D. M., Frenklach, M., Moriarty, N. W.,
Eiteneer, B., Goldenberg, M., Bowman, C. T., Hanson, R. K.,
Song, S., Gardiner, W. C., Jr., Lissianski, V. V., and Qin, Z.
(2002). GRI-Mech 3.0. Available on the Internet at http://
www.me.berkeley.edu/.
Stull, D. R., and Prophet, H. (1971). ‘‘JANAF Thermochemical
Tables,’’ 2nd ed., NSRDS-NBS 37. U.S. Dept. of Commerce,
National Reference Standard Data System-National Bureau of
Standards, Washington, D.C.
Turns, S. R. (2000). ‘‘An Introduction to Combustion: Concepts
and Applications.’’ McGraw Hill, New York.
Zhou, Q., and Yao, S. C. (1992). Group modeling of impacting
spray dynamics. Int. J. Heat Mass Transfer 35, 121–129.