Prog. Energy Combust. Sci. Vol. 23, pp.

95-132, 1997
Pergamon © 1997 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0360-1285/97 $29.00

PII:S0360-1285(97)00007-5

MODELS OF SOOT FORMATION A N D OXIDATION

IanM. Kennedy
D~artment of Mechan~al and Aeronautwal Engineering, Unive~i~ of Cal~ornm, Dav~, CA 95616, U.S.A.

Abstract--Advances in modeling soot formation and burnout in combustion systems are surveyed. The
types of models are divided up into three classes: empirical, semi-empiricaland detailed. Empirical models
use correlations of experimental data to predict trends in soot loadings. Semi-empiricalmodels solve rate
equations that are calibrated against experimentaldata. Detailed models seek to predict the concentrations
of all the important species in a flame, from fuel to polyaromatic hydrocarbons to soot. The three classes of
models have demonstrated success in predicting soot concentrations. However, our knowledge of some of
the fundamental underlying is still open to question and the success of the models has been obtained to
some degree by adjustments to fit measurements. © Elsevier Science Ltd.

CONTENTS

1. Introduction 95
2. Background to Soot Formation and Oxidation 95
3. Soot Models 99
3.1. Empirical Correlations 99
3.2. Semi-empiricalModels 102
3.3. Modelswith Detailed Chemistry 119
4. Concluding Remarks 129
References 129

1. I N T R O D U C T I O N into the controlling physical and chemical mechan-

Great strides have been made over the last few
decades in our understanding of the mechanisms and
the phenomenology of soot formation and burnout in
combustion systems. The attention that this problem
has received reflects the very difficult problem that
soot formation poses for combustion system
designers and operators of combustion systems.
Although progress has been achieved in understand-
ing the essential chemistry and physics, many
questions persist and some debate continues with
regard to the details of soot formation, growth and
oxidation. The relative importance of the various
stages of soot formation is open to question and may
well be system-dependent.
Despite a continuing uncertainty in some aspects of
soot phenomenology, combustion engineers are faced
with a pressing need to design systems in which the
amount of soot is controlled. Diesel engine designers
face a problem that is perhaps the most difficult of any
combustion based industry. They are confronted with
a severe regulatory limit on emissions of particulates
isms can be distilled into models that may be
formulated into either simple design guidelines,
empirical correlations, semi-empirical computer
models or full-blown attempts to describe the
detailed elementary chemical reactions and physics
of soot formation. The latter two approaches require
the use of computers that are used increasingly in the
design of advanced combustion systems.
This review offers a critical appraisal of the models
of soot formation that are currently available. The
models are grouped into three categories viz., (i)
purely empirical correlations, (ii) semi-empirical
approaches that solve rate equations for soot
formation with some input from experimental data
and (iii) detailed models that seek to solve the rate
equations for elementary reactions that lead to soot.
While there is inevitably overlap between these
categories, the classification is nevertheless useful in
bringing order to a large amount of material.
2. B A C K G R O U N D T O S O O T F O R M A T I O N A N D O X I D A T I O N

from their engines. At the same time, they must also

meet stringent limits on the emission of the oxides of
nitrogen. Conventional engineering solutions through
the development of numerous prototypes may no
longer be either economically attractive or, perhaps,
even feasible. The regulatory agenda require rapid
responses on the part of combustion designers.
The formulation of soot models has been a less than
rigorous science until recently. However, new insights
95
Soot is mostly carbon; other elements such as
hydrogen and oxygen are usually present in small
amounts. It is produced during the high temperature
pyrolysis or combustion of hydrocarbons. The
emission of soot from a combustor or from a flame
is determined by the competition between soot
formation and oxidation. A comprehensive model
of the soot process must include both phenomena.
96 I.M. Kennedy
A great deal of information has been obtained over
the years with regard to the formation step of soot in
shock tubes, laminar premixed flames and laminar
diffusion flames. The review by Haynes and Wagner l
remains one of the best sources for a full description
of this phenomenon. As hydrocarbons pyrolyze, they
produce primarily smaller hydrocarbons, in particu-
lar acetylene. The initial step in the production of soot
is the formation of the first aromatic species from
these aliphatic hydrocarbons. The details of this
process have been the subject of some considerable
debate over the years; discussion is deferred until a later
section in this review. The aromatic species grow by the
addition of other aromatic and smaller alkyl species to
form larger polyaromatic hydrocarbons (PAH). Con-
tinued growth of the PAH leads eventually to the smallest
identifiable soot particles with diameters of the order
of 1 nm and with masses of around 1000 amu.
The production of soot particles in a flame is
inherently a chemically-controlled phenomenon.
Low molecular weight (gaseous) hydrocarbons are
converted to essentially solid carbon in just a few
milliseconds. Thermodynamics alone cannot describe
this process since soot is formed beyond regimes
where it is thermodynamically stable relative to the
oxides of carbon. Hence, chemical kinetics play an
important role in soot production. Chemistry occurs
during nearly all phases of soot production: inception,
surface growth, aging, and surface oxidation. In
addition, it is now recognized that soot may
participate chemically in the reduction of another
undesirable pollutant, nitric oxide.
Particle inception initiates soot production in the
sense that the growth and oxidation of soot particles
occur in some qualitatively different manner to the
pre-particle, molecular chemistry. Some early soot
formation models were based entirely upon the
inception process. Conclusions drawn from these
models indicated that the net amount of soot
production was linearly dependent on the rate of
soot inception. This conclusion was based on the
argument that the surface growth rates were linearly
dependent upon the available surface area which was
dependent, in turn, upon the total number of particles
that were created during inception or nucleation.
Hence, many research groups focused efforts over the
last fifteen years towards developing an understand-
ing of these processes. On the other hand, Kennedy
et al. 2 used a semi-empirical model with a nucleation
rate that was only a function of mixture fraction to
show that for a coflow diffusion flame, the total
amount of soot was not strongly dependent on the
soot inception rate; instead surface growth processes
controlled soot production and total soot volume
fractions. They supported this contrary conclusion by
arguing that coalescence of a great number of
particles quickly hid the history related to the
inception process. This conclusion has significant
implications since it implies that knowledge of the
kinetic rates for initiation and the detailed associated
processes are unimportant when modeling soot
formation. Alternatively, models presented by
Colket and Hall 3 for premixed flames indicated that
an approximately direct proportionality exists
between the soot inception rate and the total mass
fraction of soot, at least for lightly sooting flames. As
soot mass fractions increased for increasingly rich
flames, this direct proportionality was lost as the
importance of surface growth processes increased.
More recently, Hall e t al. 4 have modeled soot
formation in a counterflow diffusion flame and
found a similar dependence on the inception process
at very low sooting levels. However, as soot volume
fractions increased, this dependence rapidly decreased.
Hence, the earlier conclusions of Kennedy et al. 2
require revision so as to account for the importance of
inception in lightly sooting flames.
An excellent example of the importance of the
inception/nucleation process and its attendant rate to
modeling soot formation under conditions of light
soot loading is the thorough analysis performed by
Markatou et al. 5 in their examination of sooting limits
in premixed flames. Using a detailed chemical kinetic
model of gas-phase chemistry, of soot particle
nucleation and of surface growth, they were able to
predict the thresholds (i.e. critical equivalence ratio)
at which visible (radiant) soot first appeared over a
range of flame temperatures and fuels. By showing
that the rates of surface growth, oxidation, and
coalescence varied slowly in the regime of the critical
sooting limit, while also showing a dramatic rise in the
computed concentration of the 'incepting' or 'nucle-
ating' species (in this case, acepyrene), they were able
to conclude 'that soot particle inception and hence the
sooting limit is determined by particle nucleation.'
Thermodynamics alone cannot adequately describe
soot formation phenomena; it is inherently a kinetically
limited process. However, thermodynamics, in parti-
cular those related to detailed balancing of reactions,
can dramatically affect the rates of initiation and
growth of soot. A simple example is the reversible
sequence
C6H5 + C2H2 *-* (C6HsC2H2)* ~ C6HsC2H + H
which interrelates the concentrations of phenyl
radicals, vinylphenyl radicals, acetylene, phenyl
acetylene and H-atoms. In other words, the net
forward rate of this reaction is in general limited by
reversible reactions. The kinetic expression, k[C2H2]
[C6H5] , represents an upper limit for the net rate of
production of phenyl acetylene and vinylphenyl
radicals. Predictions of PAH depend significantly on
the selected thermodynamics.
Stein 6 identified a series of stable PAHs, represent-
ing islands of stability during the growth process. He
predicted that PAH formation and soot formation
would proceed along this path. Frenklach et al. 7
identified similar species as key intermediates to the
PAH formation and growth process and argued that
these species essentially 'pulled' the chemistry along
 Models of soot formation and oxidation
the soot formation path. Other less stable species
would be subject to decomposition and remain in
equilibrium with lower molecular weight species. The
PAH stable isomers, however, were much less suscep-
tible to decomposition and hence, once formed, would
continue to grow towards larger species. A host of
experimental studies, together with the successes in
modeling soot formation via a PAH route (see later
discussions), provide strong evidence that PAHs are
the key ingredients leading to soot production. The
article by Howard s is an excellent source for a survey
of growth and oxidation of PAH and soot from a
fundamental viewpoint in which phenomena are
interpreted in terms of active sites.
Calcote and coworkers 9 have advocated the
importance of a link between ions in flames and
soot formation. Excellent arguments and data have
been presented showing a strong relationship between
soot and ions. Many of these arguments are similar to
those for the PAHs, in that the appearance of ions
occurs just before visible soot appears. Advocates for
a free radical mechanism of soot growth have
countered the arguments of the ionic mechanism
proponents, leading to an ongoing debate that is
beyond the scope of the present review. Suffice it to
say, the ionic viewpoint has not been implemented in
a predictive model of soot production in flames that
has met with wide acceptance.
Once soot particles are formed through the
inception process, they can grow by two mechanisms
viz., collisional coagulation and surface growth. The
former process is physical while the latter process is
chemical in nature. When particles are small and
surface growth is active, collisions between particles
generally lead to the formation of a larger spheroid
via the process of coalescence. Older particles
undergo agglomeration in which the individual
spheroids are retained in long chains with a fractal
like geometry. The rates of coagulation in the free
molecular limit of Knudsen number Kn ~ c~
(Kn = @ where the particle diameter is dp and the
mean free path of the gas is A) and in the continuum
regime ( Kn << 1 ) are fairly well understood. More
difficulties arise in the transition regime in which an
interpolation formula such as Fuch's expression is
applied, l0 van der Waals forces may play some role in
increasing the rate of coagulation as Harris and
Kennedy showed) U2 In the absence of surface
growth, an aerosol will tend to produce a so-called
self preserving size distribution under the impact
of coagulation. 13 The self preserving size distribution
leads to useful relationships between various moments
of the distribution. The form of the distribution may
be altered somewhat by van der Waals forces and by
surface growth.I t
Surface growth of particles proceeds in conjunction
with coagulation. Gas phase material is added
through chemical reactions with active sites on the
soot particles. It is generally agreed that the major
growth species in hydrocarbon flames is acetylene
97
(C2H2) , although PAHs may also play a role. 8 Rather
more controversy has arisen over the role played by
the aerosol surface area. Some researchers proposed
that the surface area of the soot aerosol determined
rates of growth) 4'15 In this view, the rate of growth is
described by the aerosol surface area and the
concentration of growth species. However, experi-
ments by Wieschnowsky et al.16 indicated that surface
area may not be the only relevant parameter. They
found that aerosols with the same apparent surface
areas exhibited different growth rates. They attributed
the differences to the important role of active sites on
the surface of particles in determining growth rates.
The growth rate of soot was described in terms of a
first order rate equation for the time rate of change of
soot volume (or mass ) fraction fv as ~ -- k(Jv* - f v )
where k is a rate constant and fv* is the maximum soot
volume fraction that is attained. While this equation
can represent the physical observations adequately, it
is not useful as a predictive relationship in a model of
soot formation since the maximum soot volume
fraction,fv*, is not known a priori.
Soot formation in diffusion flames usually occurs
low in the flame and is followed by oxidation as soot is
convected through the tip of the flame. Oxidation
occurs primarily as a result of attack by molecular
oxygen, 02, and the OH radical. Other oxygenated
species such as the O atom, H20 and CO2 may be
important under some conditions. Lee et al. 17
measured the O2 dependence and the temperature
dependence of the oxidation of soot in a laminar
diffusion flame. Samples of soot and the gases were
collected at different locations above the flame. The
gas samples were analyzed on a gas chromatograph.
The size of the soot particles was determined with an
electron microscope. The mass flow rate of soot was
found from the samples. They assumed that the
particles were small enough that diffusion did not
limit the rate of oxidation; the kinetics of surface
reactions were assumed to be the limiting mechanism.
Temperatures in the experiments ranged from 1200 to
almost 1700 K. The oxygen partial pressures ranged
from 4 × l0 -2 to 12 x 10-2atm. They arrived at the
following expression for the oxidation rate of soot
over the ranges of temperatures and 02 partial
pressures that they considered:
pd o dm
~Vo2 -
6 m~/3 m 2/3 dt
(1)
,As po2 ( 164,500
= 1.085 × lo ~T/ 2 e x p _ RT J
where
wo: is the surface specific oxidation rate (kg m -2
sec- 1)
do is the initial particle diameter (m)
p is the soot density (kg m -3)
m0 is the initial mass flow rate of soot (kg sec -1)
m is the mass flow rate of soot after time t (kg sec- I)
Po2 is the oxygen partial pressure (atm)
98 I.M. Kennedy
T is the temperature (K)
R is the universal gas constant (kJ kmol -l K - I )
The most widely used model for 02 oxidation comes
from Nagle and Strickland-Constable.lS They
measured the oxidation of a pyro graphite over
temperatures from 1000 to 2000°C and pressures from
0.1 to 0.6atm. The impact of mass transfer was
reduced by directing a high speed jet of 02 towards
a heated carbon rod. The measurements were
interpreted in terms of a model that assumed two
types of active sites were present on the carbon. Type
A sites reacted with 02 to give another A site plus
CO
A + 02 -* A + 2CO at a rate given b y ~ x
where p is the pressure in atmospheres.
Type B sites reacted with 02 to give a Type A site
plus CO
B + 02 --* A + 2CO at a rate of knp(1 - x).
Finally, Type A sites thermally rearranged to give
Type B sites
A --* B at a rate of kTx.
The parameter x was defined as x -_ l+-7-(ff/ff~"
I The
rate constants were assigned values of
k A = 2 x 104 e -130'000/Rr
kB = 4.46 e -~'°°°/Rr
kT = 1.51 x 108 e -4°6,°°°/Rr
k z = 2.14 x 104 e +17'°°°/Rr.
where R = 8.3144kJ kmo1-1 K - l . The units of the
rate constants were (kg-atoms of carbon, m 2, seconds,
atmospheres). The overall reaction rate was given by
= ( kAp ~x+ksp(l_x ) (2)
fi,°2 \ 1 + kz pJ
At low temperatures, the surface will be entirely
Type A sites with the reaction rate first order in 02
partial pressure for sub-atmospheric total pressures,
becoming independent of 02 concentration near one
atmosphere. Despite the wide acceptance of the
Nagle-Strickland-Constable model, some reserva-
tions are in order. The measurements and rate
constants were obtained under conditions that differ
significantly from the conditions under which soot is
oxidized in flames. The composition of soot is not the
same as the pyrographite that Nagle and Strickland-
Constable used. Their maximum 02 partial pressure
was 0.6 atm. Soot burn out in diesel engines and in
gas turbines may occur with much higher 02 partial
pressures although Radcliffe and Appleton 19 suggested
that the Nagle-Strickland-Constable formula could
be extended to higher pressures. A need clearly exists
to augment the data of Nagle and Strickland-
Constable for conditions more appropriate to
hydrocarbon combustion in modern engines. For
example, Najjar and Goodger 2° modified the rate
constants in the Nagle-Strickland-Constable
formulation to improve the prediction of smoke
levels from a gas turbine engine. Well-controlled
measurements under simpler conditions are desirable.
Modeling of OH attack on soot is currently on a
less fundamental level than 02 modeling, despite the
significant uncertainties that surround the latter issue.
Fenimore and Jones 21 pointed out the role of OH in
the burnout of soot in flames although they did not
have direct measurements of OH. Bradley et al. 22
measured oxidation rates of graphite powder in a flat,
laminar, methane-air premixed flame at sub-atmo-
spheric pressure. They concluded that radicals such as
OH and O were the main oxidants of graphite at
high temperatures. Mor~ direct measurements have
indicated OH to be an important oxidant of soot,
especially on the fuel side of a diffusion flame23. The
rate of OH attack on soot is usually taken from the
measurements of Neoh et al. 24 in the absence of other
relevant data. They found that the efficiency of a
collision of OH with a soot particle is of the order of
0.1. This result was confirmed by Roth et al. 2s For
comparison, Bradley et al. 22 reported a collision
efficiency of 0.28 for the reaction of OH with
powdered graphite. The difficulty in the prediction
of OH oxidation in diffusion flames is exacerbated by
the super-equilibrium levels of OH that are found to
exist in these conditions. 23 The accurate prediction of
non-equilibrium concentrations of OH poses a
challenge for modelers who hope to account
accurately for OH attack on soot.
Uncertainties in the modeling of soot formation
and oxidation are compounded by experimental
uncertainties in the determination of soot volume or
mass fractions in flames. The later stages of produc-
tion are generally characterized by the transition from
coalescent coagulation to agglomeration. Agglomera-
tion leads to the formation of chains of spherules
in which the basic units have diameters of about
30-50 nm. Soot that is emitted from combustors is
usually in an agglomerated form. The morphology of
the agglomerates may be important in predictions of
soot formation 26-3° and is certainly important in the
interpretation of light scattering data from the upper
reaches of laminar diffusion flames.
Soot volume fractions and number densities have
been measured typically by laser light extinction. It
was usually assumed that the particle scattering was in
the Rayleigh limit; in this case, light scattering was
negligible in comparison with light absorption for
soot particles. However, Choi et alfl and Koylii and
Faeth 2s'29 pointed out that soot aggregates in flames
are not well described by the Rayleigh limit. In fact,
the scattering cross section of soot that is emitted by
flames can be up to 41% of the absorption cross
section. For example, Dobbins et al. 32 found that
when optical data were analyzed with an aggregate
model instead of a Rayleigh model, the soot volume
fraction was 30% less at the midpoint of a diffusion
flame. The soot aerosol surface area was a factor of
two to four greater when an aggregate model was

//
1.2
0
~- 0.8
._o
0.6-
>
"5
0
03
0.4-
0.2-
f
0 . . . . [ . . . .
2.2 2.3 2.4
Equivalence ratio
Fig. 1. A comparison of soot volume fractions determined gravimetricatly and determined optically (from
Choi et al.31).
applied to the optical data in place of the usual
Rayleigh analysis. The value of the complex refractive
index of soot is also open to question, particularly
because it may change from fuel to fuel and even
within a given flame. 33
Choi et al. 31 determined soot volume fractions
gravimetrically and compared the results with laser
extinction measurements of the soot volume fraction
(Fig. 1). The optical measurements used the refractive
index that was reported by Dalzell and Sarofim 34 and
that has been applied widely in the analysis of light
extinction data to extract soot volume fractions.
The optical results typically overpredict the gravi-
metric results by about a factor of two. Therefore, one
must exercise some caution in comparing modeling
with experiments in light of the apparent uncertainty
in the interpretation of the light extinction data.
3. S O O T M O D E L S
The successful modeling of the soot yield or the
critical C/O ratio of a premixed flame, or the smoke
point of a diffusion flame, requires in general an
accurate account of both formation and oxidation.
Unlike NOx formation, soot production is also
inextricably linked to the flame structure through its
impact on flame temperatures via radiative heat
loss. 35 Predictions of soot yield or smoke point
height remain amongst the greatest challenges that
continue to face modelers. Advances will be ham-
pered by uncertainties in the fundamental rates of
processes such as 02 oxidation or surface growth.
Progress will depend on improvements in these areas.
Nevertheless, some useful predictions of soot forma-
tion can be obtained from relatively crude models.
3.1. E m p i r i c a l Correlations
Soot begins to form in a premixed flame at a critical
or threshold equivalence ratio, Xc. Several correla-
Models of soot formation and oxidation 99
-!1- Gravimetdc
-0- Optical
I' ' ' '1 .... I .... I ....
2.5 2.6 2.7 2.8
tions of X¢ been proposed over the years. 36'37 In
diffusion flames, the onset of soot emissions from a
flame is gauged in terms of the sooting height, the
flame height at which soot is emitted. It is important
to be able to estimate the sooting tendency of fuels
and mixtures of fuels that may be encountered in
practice. Calcote and Manos 3s proposed the use of a
threshold sooting index (TSI) as a way of removing
any system or burner dependence from measures of
the sooting tendency of fuels. The TSI was defined as
T S I = a - bXe (3)
where the apparatus dependent constants a and b
were determined by calibration. Gill and Olson 39
adopted this definition to predict soot thresholds for
fuel mixtures by using the individual TSIs of each
component. The mixing rule that they selected for
premixed flames was
(1.1) Tslm'' = EXj(1.1)TSb (4)
]
The T S I of each component of the fuel was T S I 2 and
mole fraction of component j in the mixture was Xj.
This correlation performed quite well for a ternary
fuel mixture of isooctane, decalin and l-methyl-
naphthalene. Olson et al. 36 reported on the extension
of the threshold soot index (TSI) to laminar diffusion
flames for a wide variety of fuels. The TSI approach
was able to account for the variation in measured
smoke point heights from different apparatus and
hence provided a useful means for assessing the
sooting tendencies of fuels and mixtures.
Many measurements have been made of the critical
C/O ratio at the onset of sooting in premixed flames.
Takahashi and Glassman 37 attempted to collapse
premixed flame data by considering an effective
equivalence ratio, • = [C + H/2)]/O. Their analysis
of the experimental results for the critical 9 at the
onset of soot led them to conclude that the sooting
tendency of a fuel was a function of its flame
temperature, the C/H ratio and the number of C
100
1.4
% 1.2--'1
11 . y
0.8 []
07 .
o.7
0 ' '012' ' '014" '018' ' '018 ' '
Predicted exhaust soot ( g rn"s )
Fig. 2. Comparison of measurements and predictions of soot in a diesel engine exhaust. 41 Points represent
predictions and measurements for the same engine conditions. (--) represents perfect agreement.
atoms but not the structure of the fuel. They
considered a wide range of aliphatic and aromatic
fuels that were burned in a premixed flame a fixed
value of the adiabtic flame temperature. The critical
was plotted as a function of the 'number of C - C
bonds' in which double carbon bonds were counted as
two and triple bonds as three. This simple analysis
yielded an excellent correlation of the experimental
data.
Harris et aL 4° reconsidered the experiments of
Takahashi and Glassman. 37 They made detailed
measurements of temperature by sodium D line
reversal in a premixed flame of various aliphatie
fuels. The measurements of this fundamental para-
meter permitted a realistic assessment to be made of
the impact of fuel type and temperature on soot
thresholds without resort to the assumption of
adiabatic flame temperatures. Harris et al. 4° assumed
that the onset of sooting was the manifestation of
competition between pyrolysis and oxidation, pri-
marily OH oxidation. This allowed them to develop a
satisfactory correlation of Xc for five aliphatic fuels
with the inverse measured flame temperature as the
independent variable and Xc normalized by the OH
concentration and C/H ratio of the fuel as the
dependent variable.
Most of the empirical modeling of soot formation
and emissions can be found in literature that is related
to gas turbine and diesel engines. Both types of devices
can suffer from unacceptable emissions of smoke under
certain conditions. The complexity of the combustion
processes in engines has generally precluded, until
recently, the use of detailed or semi - detailed modeling
of the basic soot formation mechanisms. On the other
hand, empirical models of soot formation that are
based on a phenomenological description have found
wide use in these communities.
Khan et al. 41 proposed a model for soot emissions
from diesel engines that has been widely cited in the
literature. Their scheme was based upon the notion
I.M. Kennedy
• 1100 RPM
[] A [] • 2000 RPM
• 2700 RPM
• 1100 RPM
[] 2000 RPM
O 2700 RPM
,x High swirl
O Med swirl
[] Low swirl
'1.2
that the diameters of soot particles from engines that
were operated over very different speeds and loads did
not vary. As a result, they further assumed that the
rate of soot formation is controlled entirely by the
formation of soot particles, i.e. by the soot inception
rate. The rate of particle formation was assumed to be
a function of the pressure, the equivalence ratio of
unburned gases and the temperature. They proposed
a general form of the soot equation as
n -E
dCs/dt = c Vu Pu X (5)
where Cs is the soot mass loading in (kg m-3), c is a
modeling parameter, Vu is the volume of the soot
formation zone in (m3), VNTP is the volume of the
cylinder contents at normal temperature and pressure
in (m3), Pu is the partial pressure of unburned fuel in
(Pa), X is the local unburned equivalence ratio, E is
the activation energy and Tu is the local temperature.
The modeling parameters c, n and E were determined
by comparing the output of the model with experi-
ments on a direct injection diesel engine with a
displacement of 966cm 3 and compression ratio of
16:1. A value of n = 3 was found to give the best
results although discrepancies of about a factor of 2
were apparent at injection timings of around 30 °
BTDC. A similar exercise yielded a value of c of about
0.468 kg. N - l m -1 sec -l.The activation energy E was
taken to be 1.7 x 105 kJ kmol - l . Two other important
parameters that needed to be considered were related
to the mixing model in the cylinder. An entrainment
ratio governed the rate of large scale mixing that
varied with engine speed and with swirl ratio. A
diffusivity constant determined the microscale mixing
of reactants and hence had an impact on heat release
rates. The diffusivity constant was determined from
fitting predicted heat release rates to measured rates.
The entrainment ratio was found from a similar
approach. The entrainment ratio had a strong impact
on predicted soot levels.
 Models of soot formation and oxidation
Khan et al. 42 compared the results of their model
with experiments for a direct injection diesel over a
range of speeds and injection timings. The solid line in
Fig. 2 indicates a perfect agreement with experiments;
the scatter demonstrates the error in the modeling.
In general, the agreement was good over a fairly
wide range of speeds and injection rates. The authors
considered some of the details of their modeling. In
particular, they examined the trends in predicted
exhaust soot with variations in the injection timing,
the injection period and the amount of fuel injected.
They were able to demonstrate the correct trends with
these parameters by comparison with measurements.
A notable omission in the model, as the authors
themselves acknowledged, related to oxidation of
soot. There was no account at all of this process. The
satisfactory agreement that they obtained must be
considered somewhat fortuitous in view of this
omission. The use of enough parameters in the
model to fit experimental data ensured some degree
of agreement. A similar agreement for other engine
types cannot be guaranteed by a model that omits a
fundamental process.
Mehta and Das 43 summarized earlier correlation
efforts for diesel engines and, in turn, proposed an
improved correlation of their own. They concluded
from their review of the literature that available
correlations included general operating parameters
such as the overall fuel-air ratio, the injection timing
and the engine speed but neglected the impact of fuel
injection and the in-cylinder air motion on soot
processes. Mehta and Das 43 proposed a seven
parameter correlation that included an account of
the spray mixing rate and the swirl mixing rate. The
other variables that they considered were the fueling
rate, the compression ratio, the temperature at
injection and the engine speed. A linear regression
analysis was applied to the results of tests on two
engines, a six cylinder and a single cylinder engine.
The comparison of predicted soot emissions with
measurements (Fig. 3) showed about the same quality
of agreement as shown in Fig. 2 from the results of the
computations of Khan et al. 41 The generality of the
correlation of Mehta and Das 43 is not likely to be
good although the use of an empirical correlation
certainly enjoys a significant advantage in economy
of calculations compared to the more detailed
approaches that have been attempted.
The gas turbine community has been interested in
soot emissions and radiant heat transfer from soot
for many years. In a review of flame radiation in
gas turbine engines, Lefebvre44 cited the work of
Khan and Greeves45 who applied Eq. (5) to the soot
formation problem. Soot oxidation was not consid-
ered in this model.
Edelman and Harsha 46 adopted a slightly more
sophisticated description of soot formation; they
included a separate first order dependence on
unburned molar fuel concentration (kmol m-3), Cf,
and oxygen, Co. The general global equation for soot
101
0.9
"~ 0.7
8 1 / •
~ 0.5
0.t
1 ./•
/
1 • f.
" •
if_ 0 . 1 ~
0 '1 .... I .... I .... I .... I .... I''''1 ....
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Experimental soot concentration (g m"3 )
Fig. 3. Predictions and measurements of exhaust soot
concentrations from diesel engines.43 Points represent
predictions and measurements for the same engine
conditions. (--) represents perfect agreement.
formation was given as
dCs/dt = A T a c b C ~ e x p ( - E / R T ) (6)
where for kerosene combustion the model had the
following specific form for soot formation
dCs/dt =4.4 × lOl7 Cfexp(-121OO/T)
- 3 × 109Coexp(-7800/T)
[kmol m-3sec -1] (7)
wherein the second, negative term accounted for soot
oxidation.
Soot production within gas turbines has been
modeled with empirical correlations that are coupled
to detailed predictions of the flow field within the
combustor. The detailed calculations of the flow
within the combustor were used as inputs to
correlations for CO, NO and soot formation and
oxidation. A three-dimensional code was tested on a
simulation of an Allison T56 combustor operated on
conventional aviation turbine fuels as well as high
density fuels. 47'48 The combustor was divided into
sub-regions in which the rates of CO, NO and soot
formation were calculated. The authors used 800 of
these sub-volumes.
Soot formation and soot oxidation were handled
separately in each sub-volume. Soot formation was
described by the empirical expression
fi~soot(mg/kg) = CP2(18 - H) 1.5 [ (F/A)mb ]
kTmg~.2~j (8)
where C was a modeling constant, P was the liner inlet
pressure (kPa), H was the weight percentage of
hydrogen in the fuel, F/A was the overall fuel-air
ratio, mb was the mass fraction of fuel that was
burned in the computational volume, mA was the
mass flow rate of air, T was the gas temperature and
Ck-e was a turbulence modeling constant that
described the rate of turbulent mixing. The oxidation
102
Table 1. Comparison of predicted and measured SAE smoke numbers from modified gas turbine combustors (from Rizk and
Mongia4s )
Baseline
Measured smoke number 38.0
Predicted smoke number 35.5
of soot was calculated from
, : rF/A Iv e0 lIT]
~b°x(mg/kg) = "~--V [,--T--J p z / m A - ( ~ - ~ / ( 1 8 - H) ''s
I . . I
where A was a modeling constant, Vwas volume (m a)
and subscript p z referred to the primary zone.
The correlations accounted for the impact of
pressure (p2), residence time (through mA), tempera-
ture and fuel composition on soot emissions. The
three-dimensional model was used to investigate
improvements to the performance of the T56
combustor with various modifications to the liner
and with the addition of a dome swirler. Measure-
ments were obtained with a combustor inlet pressure
of 1110 kPa, an inlet temperature of 618 K, an air flow
rate of 16.2kg sec -1 and an outlet temperature of
1491 K. The predictions of the soot emissions in terms
of the SAE Smoke number are compared with the
measurements in Table 1.
Although the model tended to underpredict the
soot emissions, the agreement was surprisingly good.
The modeling constants were adjusted to give
agreement with a set of baseline measurements so
that it is uncertain, as with all empirical models,
whether the model offers any general validity for
other combustors of significantly different design.
3.2. S e m i - e m p i r i c a l M o d e l s
The next level of soot modeling attempts to
incorporate some aspects of the physics and chem-
istry of the phenomenon, as opposed to a correlation
(albeit with physical insight) of experimental data.
This usually leads to the development of rate
equations for reactions of soot percursors and soot
particles with a simple description of the chemistry.
The formation of carbon from the pyrolytic
decomposition of gaseous carbon was modeled by
Hudson and Heicklen. 49 They considered an isother-
mal flow reactor and neglected axial diffusion so as to
avoid the complications of solving elliptical differ-
ential equations. The pyrolysis of the feedstock was
assumed to yield an active species that they tentatively
associated with either C2, C2H or C2H2. The formation
of the active species (referred to generically as C) was
followed by a series of growth reactions such as
C + Cn ~ Cn+l (10)
They assumed that all reactions of C and C~ resulted
in the larger species, Cn+l. The rate constant was
I.M. Kennedy
Modification Modification Modification Low smoke
1 2 3 mod
38.0 32.0 28.0 11.0
30.6 28.9 20.3 11.1
calculated simply from the kinetic theory of gases. As
a result, there was no activation energy for these
reactions; the only temperature dependence that
appeared was a 7 °.5 function that arose from the
(9) collision rate. In the first of their papers, they assumed
that the active species concentration was constant. A
later paper 5° included a rate equation to account for
the pyrolysis of the original feedstock to yield the
active species, C. A major goal of the authors was the
determination of the ideal conditions for the deposi-
tion of a high-density layer of graphite on the walls of
the reactor. A secondary interest was related to the
formation of gas phase carbon which they identified
as soot when the particle exceeded a critical size, i.e.
about l0 a monomer units or about 3 nm dia. The rates
that were used by Heicklen and co-workers49'50 were
based solely on kinetic theory collision rates; these
rates do not represent the slower chemical reactions
that we know to be an essential feature of soot
formation. It is expected, therefore, that their model
would tend to grossly overpredict the production of
soot in a pyrolytic system.
Smith 51 proposed a model of soot that assumed that
the particle inception was entirely due to a physical
nucleation process. Classical nucleation theory was
used to calculate the rate of particle nucleation; the
value of properties such as the surface tension of a
carbon cluster were estimated. The size of a soot
particle was assumed to be limited by the depletion of
the growth species. However, evidence exists that soot
formation is not represented accurately, in fact, as a
physical condensation process. The particle inception
process exhibits a relatively high activation energy
which is not consistent with physical condensation.
Tesner and co-workers 52's3 presented a model of
soot formation in 1971 that has been widely used.
Tesner et al. 52 interpreted their measurements of soot
particle formation in an acetylene-hydrogen flame in
terms of a simple kinetic model. They proposed a two
step mechanism that described the formation rate of
soot nuclei n (radical nuclei as they were called)
dn
d~ = no + ( f - g ) n - g o N n (1 1)
where
n o is a temperature dependent rate of spontaneous
generation of nuclei
f and g are branching and termination coefficients
go is the rate of loss of nuclei due to collisions with
soot particles
N is the number density of soot particles
 Models of soot formation and oxidation
and the particle number density N as
dN
d----{= (a - b N ) n (1 2)
This model has been applied widely over the years in a
range of combustion applications: 2'54'55
Surovikin 56 developed a more sophisticated model
that represented multiple steps for the production of
carbon black. Oxidation was included in this
formulation. The steps included: (1) the formation
of radical nuclei; (2) the growth of the nuclei to a
critical diameter at which point they become incipient
particles with a physical surface; (3) the growth of the
incipient particles into carbon particles. The rate of
formation of radical nuclei was written as
dn = V~ + f n - go nz - K (13)
dt
where V0 represented the rate of decomposition of
hydrocarbon molecules with an activation energy that
corresponded to the energy of a C - C or C - H bond.
The coefficient f represented the branching of the
nuclei formation reaction. The loss of nuclei due to
the collisions of one with another was represented by
the third term in Eq. (11) while the loss of nuclei on
the surface of particles was represented by K.
The rate of change of the diameter of a radical
nucleus was
dDrn 1 { 6 ~1/2 -z/3dm
-- / - - J m - - (14)
dt 3 \Trprn,I dt
where
Dm was the diameter of a radical nucleus
p~ was the density of a radical nucleus
m was the mass of a radical nucleus.
The rate of increase of the mass of the nucleus was
calculated from the rate of collisions of hydrocarbon
molecules with the nucleus and the mass of the
hydrocarbon molecule with an activation energy of
1.3 x 105 kJ kmol -t. Finally, the particle nuclei (also
referred to as seeds) grew as a result of surface
addition of hydrocarbon molecules. The growth rate was
assumed to be proportional to the particle surface area.
An activation energy of 1.3 x 105 kJ kmo1-1 was used.
The physical meaning of some terms in the formula-
tion of Tesner and Surovikin was not altogether clear,
Nonetheless, many authors have made use of Tesner's
model, including Magnussen et al. 54 They applied a
generalized eddy dissipation model to a sooting,
turbulent acetylene flame. The eddy dissipation model
treated chemical reactions as taking place in fine
structures in the flow within which the reactants were
assumed to be perfectly mixed. The fraction of the
flow that was occupied by these structures was
determined through scaling arguments. However,
not all the fine elements of fluid could react due to
insufficiently high temperatures. Therefore, an addi-
tional assumption was required to find the fraction of
fine structures that reacted. Mean rates of combustion
were determined on this basis.
Soot was assumed to form in both the fine
103
structures and in the surrounding fluid. The rates of
formation of soot nuclei and of soot mass were
calculated with the model of Tesner et al. 52'53 Soot
oxidation was assumed to be proportional to the rate
of combustion of fuel; no account was taken of OH or
02 concentrations. The complete model contained a
large number of 'constants'. The turbulence model
itself required the specification of 10 parameters,
more than the usual requirement in turbulence models
due to the inclusion of the equations for soot nuclei
number density and soot mass. In addition, the soot
model required the specification of a further six
parameters, most of which were taken from Tesner
et al. 53
Boundary layer forms of the governing equations
were solved. Two equations were solved for the soot
field viz., the mean number density of soot nuclei and
the mean mass concentration of soot. The numerical
results were compared with experimental data
obtained from light scattering. Reasonable agree-
ment was demonstrated over a range of Reynolds
numbers. However, some caution is required in
interpreting the results as a confirmation of the eddy
dissipation approach. The use of light scattering to
infer soot mass loadings in turbulent flames involved
uncertainty. Furthermore, the model contained many
parameters. The physical basis for an eddy dissipation
model in a turbulent diffusion flame may also be
questioned.
Kyriakides et a l : 7 and Mehta et al. 58 used similar
approaches to model soot emissions from diesel
engines. In both cases, they adopted the methodol-
ogy of Magnussen et al., 54 along with the soot model
of Tesner et al., 52 to calculate the soot formation in
the engine cylinder. Kyriakides et al. 57 made use of
the oxidation model of Lee et al. 17 to calculate soot
burnout. Mehta et al. 58 employed a somewhat simpler
model for soot burnout. In this case the local
oxidation rates of nuclei and soot particles were
related to the local rate of fuel consumption and the
mean concentration of nuclei and particles respec-
tively. This approach neglected the different tempera-
ture sensitivities of soot oxidation and fuel oxidation
as well as the impact of OH on soot burnout.
The agreement between predicted and measured
soot emissions for these models was similar to the
results obtained by Khan et al. 42 that were shown in
Fig. 2. Kyriakides et a l : 7 noted two important
shortcomings of their model. They assumed that all
soot particles were the same size and that the size was
a constant. Simulations with a particle size of 25 nm
yielded soot levels that were too low so the particle
size was increased in an ad hoe manner to 50 nm.
Better agreement was achieved. Accurate predictions
of spray mixing also presented a problem for soot
modeling in engines. The predictions of soot tended to
be rather sensitive to the details of the spray model.
Brown and Heywood 59 employed a stochastic
mixing model to account for inhomogeneous mixing
in a diesel engine cylinder. The stochastic model
104 I.M. Kennedy
considered the fluid to be made up of segregated
elements that were chosen at random and allowed to
mix on the molecular level following the approach of
Curl 6° and Pratt. 6~ The stochastic mixing model was
superimposed on a multi-dimensional calculation of
the cylinder flow with the KIVA code. Their goal was
to predict NO and soot emissions from a direct
injection diesel engine. The model was compared with
an engine that had a single cylinder with a 1173 cm -3
displacement volume.
Finite rate soot formation was modeled after the
results of Wang e t al. 62 that were obtained in a shock
tube study of soot formation from toluene. Oxidation
was predicted with the Nagle-Strickland-Constable
formula. Is The agreement of the model ranged from
remarkably good in one case (without EGR and low
swirl) to poor in three other cases. In the latter cases, the
model overpredicted the measured soot concentrations
by typically an order of magnitude. This was not
altogether surprising in view of the fact that the soot
sub-model was based upon shock tube results in toluene,
conditions rather far from those in a diesel engine.
The models that have been discussed so far were
applied to the simplest engine configuration, the
direct injection diesel, although multi-zone calcula-
tions were used in some cases. Indirect injection
diesels introduce an additional complication due to
the exchange of mass and energy between the
prechamber and the main combustion chamber.
Kouremenos et al.63 developed a model for this
more complex geometry to predict NO emissions and
soot emissions from a single cylinder, swirl precham-
ber Ricardo engine with displacement volume of
536cm 3. They used a two zone model in both
chambers to describe burned and unburned gases.
Combustion chemistry was described by equilibrium
between 11 chemical species. The simple soot model
of Hiroyasu et al.64was employed in their calculation.
The net rate of soot mass formation was found as the
difference between the rates of formation and
oxidation viz.,
dins (dms~ _(dms'~ (15)
\ dt /formation \ dt /oxidation
where Arrhenius expressions were used for the rates
of soot formation and oxidation
( - ~ t s ) formation= AfmfvP°5 exp ( ~ T f) (16)
(-~)oxidation= Aomovpl'Sexp(~ff-~) (17)
The activation energies were Ef = 8 x 104 kJ kmo1-1
and E0 = 12 x 104 kJ kmol - l . It was a little surprising
that they used an activation energy for oxidation that
was greater than for formation, an approach that runs
counter to other observations. The values of the
model parameters were chosen to match the results at
one experimental condition.
Predictions of exhaust soot were compared with
measurements that were obtained with a smoke meter
over a range of loads and injection timings. The
results showed the calculated soot concentrations in
the main chamber and in the pre-chamber for three
different mean effective pressures, i.e. three different
loads. It was evident that most of the soot was
formed in the pre-chamber because of the high overall
equivalence ratio and temperatures in the pre-chamber.
The agreement between measured and predicted
exhaust soot was good to within about 20% or
better. Similar agreement was achieved with varia-
tions in the injection timing. Predictions of NO
emissions from the engine were not as accurate as
the soot predictions. The results demonstrated the
usefulness of a relatively simple model, at least over a
limited range of conditions.
Jensen 65 presented a model that had a firmer basis
in the physics and chemistry of soot formation as they
are currently understood. The description included
most of the essential phenomena. He assumed that the
formation of soot was controlled by five processes.
The initial stage involved gas phase reactions that
produced radical fragments which constituted nuclei.
Nucleation was followed by coagulation, growth and
oxidation.
The initial nucleus was taken to be either C2 or
C2H. An 11 step, reversible, gas phase mechanism was
proposed to account for the formation of these
species. Mass growth of the nuclei occurred as a
result of the addition of C2, C2H, C3 or C2H2. The
rate of growth was proportional to the particle
surface area and the rate of arrival of growth species
at the surface. No activation energy was used for the
growth reactions. Coagulation was treated by sub-
dividing the soot aerosol into 15 size classes. The
coagulation rate was calculated in the free molecular
limit. Oxidation was not considered in view of the fuel
rich conditions that were of interest in rocket motors.
The model was applied to a rocket chamber that
was fueled on isopropyl nitrate. Measurements were
obtained of soot concentrations and gas composition
at the rocket nozzle exit plane. The observations
could be matched only if either (1) C2 were the nucleus
and C2H2 were the growth species or (2) C2H were the
nucleus and C2H2 were the growth species. Other
combinations of nucleating species and growth
species yielded soot concentrations that were much
too low compared to the measurements. He con-
cluded that for his conditions the controlling process
in soot formation was the rate of the gas phase
reactions, especially the rate of the initiation step
CH 4 + M -~ CH 3 + H + M (18)
The rates of the growth reactions and the rate of
coagulation were found to be of secondary impor-
tance. However, caution should be used in drawing
general conclusions from these results due to the
rather specialized application.
Graham 66 attempted to model the growth of soot
that was formed by the pyrolysis of aromatic
 Models of soot formation and oxidation
hydrocarbons in incident shock waves. 67 He assumed
that collisions of soot particles were coalescent, i.e.
they were perfectly sticky and formed spheres.
Furthermore, he assumed that a self-preserving size
distribution13 was maintained. Two fundamental
models for soot growth were considered. The simpler
model assumed that nucleation of new particles and
condensational growth onto existing particles gave
rise to zero net change in the mean volume of the soot
particle size distribution, i.e. they exactly balanced
each other with respect to mean particle size. The
somewhat more general model assumed nucleation
ceased at the beginning of shock heating and was
negligible for all time after that.
The two models were expressed in terms of the rate
of change of the mean volume (I7") of the soot aerosol
particles. The assumption of a self-preserving size
distribution led to the formulation of the first model
(coagulation only) as
dF k fv~,l/6 (19)
dt
where the rate constant, k, was expressed as
1 ( 3 x 1/6 (6XT'~ ~/e
k = ~ \~:) \~--/ o,C (20)
where ~ was Boltzmann's constant. The collision
integral was a and the enhancement of the collision
rate by long range dispersion forces 1132 was repre-
sented by G in Eq. (20). The coUisional enhancement
takes on values typically around 2. Equation (19) could
be integrated to yield an expression for the mean soot
particle volume as a function of time, t
"]6/5
g(t) = (go)5/6q-~kIi=tofv(t)dtj (21)
where V0 was the initial particle volume.
The second model included the effect of nucleation
and condensation and led to a formulation for the
rate of change of mean soot particle volume
d(r(t)-kfv(F')l/6+O~)dfVdt-~ (22)
which could not be integrated as simply as Eq. (19)
and had to be treated numerically. The scattered light
intensities that would be expected from each of
these models were compared with the results from
the shock tube experiments by obtaining best fits to
the data through varying parameters such as the soot
density, the particle refractive index and the colli-
sional enhancement factor, G. Good fits to the
experiments were obtained with both models. Graham
concluded that his results showed that particle
nucleation did not continue for a substantial time
following the shock. In other words, he concluded
that nucleation was extremely rapid and substantial,
leading him to the conclusion that soot particle
nucleation was physical rather than chemical.
Graham also concluded that the collisions of soot
particles were sticky and perfectly coalescent. From
this observation, he concluded that the particles were
105
part soot and in part liquid polynuclear aromatic
compounds. This conclusion was interesting in light
of the more recent observations of Dobbins et al.;68
they asserted that soot precursors were liquid droplets
that eventually underwent a graphitization process
to form mature soot particles. Graham further
concluded that this mechanism could account for
the observation that the primary particles in soot
agglomerates were of similar sizes. He believed that
the variation in the rate of graphitization with
temperature was important in determining the final
properties of the soot aerosol. Ultimately, his
modeling was not essentially predictive. Its purpose
was to deduce mechanisms of soot formation from
light scattering measurements in shock tubes.
The mathematical formulation of soot formation
models was continued by Mulholland.69 He proposed
a simple scheme in which soot nuclei were generated
by the pyrolysis of a fuel. The soot nuclei were
allowed to add to the fuel to form larger nuclei. Rate
equations were written in an Arrhenius form for the
production of the soot nuclei. The concentration of
soot particles was assumed to be given by the sum of
the concentrations of all nuclei. The surface growth
rate was assumed to be proportional to the particle
surface area. The growth species was the fuel itself so
the formulation was strictly correct only if the fuel
were acetylene. For other fuels, additional pyrolysis
steps that led to acetylene would be necessary. The
time dependence of various parameters such as
moments of the soot particle size distribution, the
number density, etc. were compared with experiments
under regimes in which the free radical growth of
nuclei or the surface growth or the coagulation
processes were switched off. It was found that a
satisfactory time dependence could not be obtained
with any combination of processes for all the
experimental conditions that were considered. This
conclusion was not altogether surprising in view of
the simplified nature of the model.
Some models of soot formation involve very little
mathematical formulation. Models such as that
proposed by Jones and Rosenfeld7° rely upon a
purely physical hypothesis about soot formation and
oxidation. Jones and Rosenfeld7° used Burke-
Schumann theory 71 to describe the gross features of
a laminar co-flow diffusion flame. They postulated
that the opening of the stoichiometric surface (the
flame front) indicated the onset of sooting. Theore-
tically, this would occur at an infinite flame height for
reactants that were supplied in stoichiometric propor-
tions. The stoichiometry could be varied in practice
through variations in the fuel and oxidizer partial
pressures in each stream of gas. The 02 partial
pressure that lead to a theoretically infinite flame
height was used as a measure of the conditions at
which the flame opened. This partial pressure was
compared with experimental values.
The partial pressure of 02 in the outer flow was
varied in a series of experiments. The maximum 02
106 I.M. Kennedy
partial pressure for which soot could be observed
above the flame was taken to be a measure of the soot
point for a number of fuels. The results showed a
rather remarkable agreement between the predicted
and the measured 02 partial pressures for a range of
different fuels. They argued that the results indicated
the importance of the diffusion flame structure in
determining sooting behavior. They relegated soot
kinetics to a secondary role. It is not clear why the
theoretical conditions for an infinite flame height
should relate so well to the experimentally observed
soot point, particularly because the kinetics of soot
formation and oxidation are slow. The assumption of
diffusion control is not appropriate in this case. The
amount of soot in a diffusion flame depends on the
time available to form soot, i.e. on the flame height.
Therefore, one might expect some greater dependence
on fuel type. The results were used by the authors to
point out the importance of controlling flame
characteristics in attempting to isolate chemical
effects in soot production. The simple model had no
real predictive capability.
The description of diffusion flames is facilitated by
the use of the concept of a mixture fraction. Many
models of soot formation in diffusion flames have
made use of the mixture fraction to describe the gas
phase composition and temperature of the
flame. 2'35'72-79 The mixture fraction is an example of
a Shvab-Zeldovich coupling function.7tAn essential
aspect of the Shvab-Zeldovich formulation is that all
species and energy diffuse at the same rate. An
alternative way to express this requirement is that the
Lewis numbers for all species should be unity. The
mixture fraction provides a very useful method to
describe the local thermochemical state of a diffusion
flame because it is a so-called 'conserved' scalar, i.e.
the equation for its conservation contains no source
term. Hence, the non-linear reaction rate terms in
combustion are eliminated. In order to relate the
mixture fraction to the species mole fractions and
temperature, some assumption is required with regard
to the thermochemistry. Chemical equilibrium is
often used to obtain this relationship. An alternative
method is to obtain the state relationships from
measurements s° or calculations in strained laminar
diffusion flames, sl A library of laminar flamelets is
then developed over a range of strain rates.
Delichatsioss2 formulated a theoretical model that
developed a scaling of soot formation with flame
height and with pressure. He focused on the evolution
of soot along the axis of a laminar diffusion flame.
The soot volume mass fraction was written as
drs'X
pu--d-x-x) = if' (23)
where the reaction rate ffs was a function of the
mixture fraction, ~ , temperature and the fuel mass
fraction at the nozzle exit
Ws = CP2 YFO exp(-E/RT) (24)
for mixture fractions ~ > ~* where ~* was the smallest
mixture fraction at which soot formed. The model
relied on the assumption that soot mass growth was
controlled solely by the availability of a gaseous
species such as acetylene. Growth in this view is
independent of the aerosol properties, including
surface area and number density of particles. There
has been no confirmation via more detailed computa-
tions that this is an accurate approximation. Indeed,
Lindstedt s3 found that a growth rate that was a
function of the particle number density performed
very well. In that case, particle nucleation may be an
important feature of the flow, at least in moderately
loaded flames such as the counterflow flames that
Lindstedt modeled.
The maximum soot volume fraction was assumed
to occur at the flame tip where ~ = ~st • The flow field
was handled by noting that the centerline velocity, u¢,
as a function of distance, x, in a laminar diffusion
flame was controlled by buoyancy forces so that
uo = ~ u v ~ (25)
By ignoring soot oxidation and by assuming that
temperature was a function of mixture fraction, Eq.
(23) could be integrated to yield a maximum soot
volume f r a c t i o n f max of
fvmax =Lf 1 (26)
O~uV~f T
where r was the time for soot formation that was
defined as
r-l= Ii,,f
~,T)f~st'I/2p~xll)l----~st)
f"
-E
~--~st' exp(~)d~
(27)
and the flame length was Lf. Delichatsios went on to
use the model to derive a scaling for the soot mass
flow rate in the Wolfhard-Parker flames of Kent and
Wagner. s4 The model collapsed the data in different
flames to a reasonable extent over two orders of soot
mass flow rate but the functional relationship was not
simple, particularly at large distances from the
burner.
Faeth and co-workers s° attempted to use the
mixture fraction concept to obtain a state relation-
ship with soot volume fraction. In other words, soot
volume fraction was correlated with mixture fraction.
A calculation of a turbulent diffusion flame then
involved the calculation of the mixture fraction and
the velocity field in the usual manner, s5
Unfortunately, soot does not diffuse at the same
rate as the molecular species. Furthermore, soot is the
product of a relatively slow reaction and is not in
equilibrium. Hence, it cannot be expected on
fundamental grounds that soot will be well corre-
lated with mixture fraction. For example, near the
base of the flame there is little soot although mixture
fractions cover the range from 0 in the free stream to
close to 1 on the axis of the flame. Significantly larger
amounts of soot are found over a similar range of
mixture fractions further along the flame. The use of
 Models of soot formation and oxidation
the mixture fraction state relationship is attractive in
computational terms but it neglects the impact of
chemistry and transport on the distribution of soot
throughout a flame.
A fundamentally more satisfactory approach uses
rate equations to account for the chemistry, albeit
often in a very crude fashion. An entire class of
models are characterized by their attempt to solve a
small number of differential equations for the
conservation of quantities such as soot particle
number density and soot volume fraction. In their
simplest manifestation, the models may include only
an account of the formation of soot nuclei. Kesten
et al. 86 used the model of Tesner et al. 52 to describe the
formation of soot around a fuel droplet. The only
reference to the soot process in this simple model was
to the production of' soot radical nuclei. Models
developed by other researchers include rates for soot
inception, surface growth, coagulation and soot
oxidation. Their common philosophy revolves
around the prescription of a minimum set of rate
equations that can describe important soot phenom-
ena. The ultimate goal is generally a model that can be
used in codes for turbulent combustion in an
industrial setting. Hence, the use of a full set of
detailed elementary reactions is impractical. The
differences amongst the models in this category are
relatively minor.
Kennedy et al. 2 attempted to use only one equation
to describe soot formation and oxidation in a laminar
diffusion flame as a forerunner to a model for
turbulent diffusion flames. The rationale called for
the minimum possible set of equations with a view to
ultimately applying the model in a PDF (probability
density function) calculation.75 Measurements in
many flames have shown that the number density of
particles decays very quickly as a result of rapid
coagulation near the particle inception zone. As a
result, Kennedy et al. 2 ignored the equation for
particle number density in favor of an average
number density and hence they did not account for
possible variations in nucleation rate with changing
flame conditions. They used only an equation for
conservation of the soot volume fraction throughout
the flame. As was noted earlier in this review, this
approach is most appropriate for flames that exhibit a
large soot loading. It is less likely to be satisfactory in
flames that do not exhibit large soot volume fractions.
The equation forfv contained two source and two
sink terms. Soot volume fraction increased as a result
of particle nucleation. The size of the smallest particle
was assumed to be I nm; the source of soot volume
was equal to the product of the particle inception rate
with the volume of the individual nuclei. The particle
inception rate was taken to be a function of mixture
fraction that located the inception zone just to the fuel
rich side of the flame. The inception rate was assigned a
narrow Gaussian distribution in mixture fraction space
with a peak rate that was derived from the measure-
ments of Wersborg et al. 87 T h e second source of soot
107
volume arose from surface growth. The surface growth
rate was taken to be a function of mixture fraction and
temperature. An activation temperature of 10,000K
was assumed on the basis of the measurements of
Tesner et al. 53 The functional relationship between the
growth rate per unit surface area and the mixture
fraction was obtained from measurements of soot
growth in a counterflow ethylene/air diffusion flame. As
a result, the approach was specific to a given fuel,
oxidizer and pressure at the conditions of the
measurements. The modeling assumed that the surface
growth rate depended on the soot aerosol surface area.
The model was initially applied to a laminar
ethylene diffusion flame in a co-flow configuration.
Predictions of soot volume fractions were obtained at
a number of axial stations. In general, good agreement
was obtained within about a factor of two of the peak
measured soot volume fractions. The authors did not
attempt to model the burnout zone of the flame and
hence did not subject the model to a full test.
The method of Kennedy et al. 2 was specific to
ethylene fuel. Said et al. 88 attempted to remove this
restriction by postulating the existence of a hypothe-
tical species, intermediate between the fuel and soot.
In reality, this imaginary species could be associated
with acetylene although Said et al. did not need to
make an explicit assignment of the intermediate to an
actual species. They followed the approach of
Kennedy et al. 2 in ignoring the dynamics of the soot
aerosol, i.e. they did not solve an equation for the
particle number density. However, two rate equations
were formulated in the model. The first equation
described the rate of formation and oxidation of the
intermediate species, denoted by '/'. The mass
fraction of I was found from
..... {- TAI"~
ddtYl _ kA ifueI Io x exp ~ - - - )
-k.Y,Y~oxeXp(-~)-k,(T)r, (28)
in which Yruel, Yox and Y1 were the mass fractions of
fuel, oxidizer and intermediate species respectively.
The other parameters in the equation were deter-
mined empirically. The production rate of soot was
found from the competition between the conversion
of I into soot and the oxidation of soot as shown in
the equation for soot mass fraction
dt ~ YoxY s P T - V 2 exp (29)
The oxidation rate of soot in Eq. (29) was derived
from the model of Lee et al. 17A constant value of soot
diameter, ds,was taken to be I nm in Eq. (29). This
value may be appropriate to freshly formed soot but it
is not likely to be representative of soot at the tip of a
diffusion flame where much larger particles are found.
The formation rate was found from experiments. A
value for ks was determined from examining experi-
mental resultss9 in a pre-mixed laminar flame. The
post flame temperature was assumed to be constant
108 I.M. Kennedy
and the concentration of oxidizers was assumed to
be zero. Equations (28) and (29) were simplified
considerably with these assumptions so that a simple
expression for ~ t was obtained. Hence, a comparison
with the data of Kent et aL allowed ks to be found.
Values for TA1 and TA2 were obtained from the work
of Leung et al. 76 while ct and 3 were assigned
arbitrary, but not unreasonable, values of 0 and 1,
respectively. The values of rate constants, kA and ka,
were determined by adjustment in comparison with
the experiments of Santoro et al. 9° through which
good agreement between the model and the measure-
ments was achieved. Oxygen mass fraction in Eq. (29)
was governed by an empirical relationship between
mixture fraction and oxygen mass fraction. 9~
The soot model was applied to the prediction of the
turbulent diffusion flame that was measured by Kent
and Honnery. 74 The agreement was very good,with
the peak in the mean soot volume fractions being
predicted accurately. The model included many
parameters, some of which were set abitrarily while
others were adjusted by comparison with laminar
flame experiments. The number of parameters was
significantly greater than that used by Kennedy et al. 2
so that somewhat better agreement with measure-
ments should be expected. Recalibration of the model
would be necessary if the fuel or pressure were
changed so it not clear that the inclusion of the psuedo
intermediate, /, adds greatly to the general applic-
ability of the model in comparison to simpler semi
empirical formulations.
Moss et al. 92 proposed a flamelet approach to
modeling soot formation in diffusion flames. The
usual flow field equations were solved. In addition,
balance equations were solved for the number density
of soot particles, n, and for the soot volume fraction,
fv, in the following form
d / n\
(30)
ai ~ o ) = a ( , ) - ~(,)(n/No) 2
dfv
ps--d7 = 7(~)n + 6(~) (31)
The density of soot, Ps, was taken to be 1800 kg m-a;
No was Avagadro's number. The first term in Eq. (30)
represented the increase in soot particle number due
to particle inception. The second term accounted for
the loss of particles as a result of coagulation. The first
term in Eq. (31) represented an increase in soot
volume as a result of surface growth while the second
term accounted for the increase in soot volume due to
nucleation of new particles. It should be noted that
the first growth term in Eq. (31) is proportional to the
number density, not a surface area. The number
density of an aerosol rapidly attains a nearly constant
value as a result of a balance between particle
inception and coagulation. Hence, if the number
density, n, is approximately constant, Eq. (31)
predicts that the soot volume fraction will increase
linearly with time if the temperature and the
concentrations are spatially homogeneous. If surface
growth is proportional to surface area, then a t 3
dependence is expected for the same conditions.
However, temperature and concentration inhomo-
geneities in a diffusion flame may overwhelm the
impact of any assumptions regarding the functional
form of surface growth on the temporal development
of soot volume fraction.
The source terms (c~, 3, 7, 6) for the number density
n and the volume fractionfv were written as functions
of the mixture fraction ~ and the temperature T as
c~ = Cc,p2T1/2Xc e x p ( - T,~/T) = ~/144 (32)
/~ = C 3 T I/2 (33)
7 = C'rpT1/2Xc e x p ( - T T / T ) (34)
where the Cis were constants that were determined,
along with the activation temperatures T;, from
measurements in laminar flames. The source terms
were also functions of the fuel mole fraction, Xc.
Temperatures in real combustors, especially gas
turbines, often exceed the peak temperatures that can
be achieved in laboratory flames burning hydrocar-
bons in air. Moss e t al. 77 applied the model to a
laminar ethylene diffusion flame burning on a
Wolfhard-Parker burner. The oxidizer was 52% 02
and 48% Ar. Peak flame temperatures were around
2600K. When the parameters that were obtained in
the original study 92 were used for this case, unrealistic
predictions of the mean particle size and number
density were obtained. Consequently, adjustments
were necessary to the original parameters (Ca, C 3 and
C~) in order to achieve satisfactory agreement with
the measured peak soot particle size and number
density. The activation energies for soot nucleation
and surface growth were unchanged. Oxidation by 02
and OH was included in this model. Radiation was
not included on the grounds that the flame was only
moderately sooting.
The two-dimensional flow field was calculated with
the thermochemistry derived from a flamelet
approach. The flamelets were calculated with a one-
dimensional code for a laminar diffusion flame.
Generally good agreement with measurements was
demonstrated for soot volume fractions and soot
particle diameters along the flame centerline. How-
ever, this is not altogether unexpected, given the fact
that the model parameters were adjusted to yield the
appropriate peak values. The correct distribution of
soot along the axis suggests that the essential physics
have been included in this model although the
requirement of adjusting the model parameters
indicates that semi-empirical models such as these
are not universal. Care must be taken when the model
is applied to conditions that do not precisely match
the conditions under which it was calibrated.
Syed e t al. 7s applied the flamelet modeling strategy
of Moss e t al. 92 to a turbulent methane diffusion
flame. Their particular interest was in predictions of
 Models of soot formation and oxidation
the thermal radiation from large buoyant flames.
Experiments were performed in a laminar methane
diffusion flame to verify the soot modeling. They
found that the surface growth model that Moss et
al. 92 used was incompatible with their observations in
the methane flame. Syed et aL 7s implemented a
surface growth model that contained a linear
dependence on aerosol surface area
d
Ps~tfv = "~(~)(Psfv)2/3n 1/3 (35)
where -~was a modified value of the numerical constant
C7 and the terms withfv and n accounted for the soot
surface area. When the number density n approached
a constant value, this equation led to a predicted t3
variation in soot volume fraction as Kennedy et al. 2
pointed out. The comparison of measurements with
the model predictions are shown in Fig. 4.
The agreement in the laminar diffusion flame was
generally quite satisfactory although the model
tended to underpredict the soot volume fraction on
the centerline of the flame. A similar problem existed
in the model of Kennedy et al. 2 Constraining particle
inception to small values of the mixture fraction
worked reasonably well low in a diffusion flame but
the correlation of inception with mixture fraction was
apparently less satisfactory higher in the flames. Saito
et al. 93 observed that benzene built up along the axis
of a laminar diffusion flame. This evidence suggested
that the assumptions behind the use of a Shvab-
Zeldovich coupling function,71 such as the mixture
fraction, were not appropriate in these circumstances,
certainly as far as the pre-particle chemistry was
concerned.
Syed et al. 7s applied the soot model to a turbulent
buoyant flame. A parabolic, k - e turbulence model
was used along with laminar flamelet chemistry. The
temperature-mixture fraction relationship was per-
turbed to account for the impact of radiation. Mean
predicted temperatures agreed quite well with
measurements that were obtained with a compen-
sated thermocouple. Less satisfactory agreement was
obtained for narrow band radiation. An accurate
treatment of the oxidation of soot was believed to be
an important reason for the discrepancy.
Alizadeh and MOSS94 evaluated the same model for
soot in a comparison of measurements and computa-
tions in an idealized combustor of the same design as
Heitor and Whitelaw. 95 State relationships were
obtained from both equilibrium and from a laminar
flamelet approach. They also predicted NOx by post-
processing, i.e. by calculating the NO concentrations
after the flow field had been calculated. A similar
approach was used with the soot but the authors
acknowledged that de-coupling the soot from the flow
field calculation was not likely to be successful due to
two effects: (I) the impact of soot radiation on the
temperature and density; (2) soot acting as a sink for
carbon in the flame.
They dealt with the first effect by ignoring radiative
JPEC$ 23:2-B
109
6 30
~ R 25 %
x
x
2O g
15 ~
0O
o~ . . . . . . .~. . . . . . . . . . . ; ---~0
0 1 2 3 4 5
Distance from centerline (mm)
Fig. 4. Soot volume fraction profiles in laminar Wolfhard-
Parker CH4-air flame at heights above burner of (a) 15 mm
(- - -) predictions, (m) measurements, (b) 30mm ( )
predictions, (&) measurements. From Syed et al. TM
heat loss; the latter issue was resolved in the manner
described by Young et al. 96 The mixture fraction was
decomposed into two components, one that was
related to the gas phase only and the other that was
related to the concentration of soot. The complexity
of the flow field precluded the use of a more realistic
approach.
The results showed a dramatic increase in soot
volume fraction as pressure increased. The pressure
effect was predominantly due to an increased rate of
particle nucleation. However, the conditions of the
simulation were well outside the range of calibration
of the soot model. The authors found that up to 75 %
of the locally available carbon was converted to soot.
In this case, it was important to account for the
modification of the local mixture fraction due to the
carbon bound up as soot. The use of the modified
mixture fraction restricted the production of soot to
the vicinity of the injector, inhibiting its production in
regions close to the primary zone jets.
The effect of pressure was explored by Young
97
et aL in a series of experiments that were designed to
yield property maps of the major variables viz.,
temperature, mixture fraction and soot volume
fraction. Microprobe sampling was used to measure
the mean mixture fraction in turbulent kerosene
flames at pressures up to 6.4 bar. The mean soot
volume fraction was found by laser extinction and
temperatures were measured with a fine wire thermo-
couple. Isolating the effects of pressure in a turbulent
diffusion flame is difficult because the history of a fluid
element changes drastically as variables such as the
flame length change. Young et al. reduced their data
to a standardized form by normalizing distance from
the nozzle with the location of the maximum soot
volume fraction and by correcting the measured soot
volume fractions to a standard pressure. This analysis
suggested an approximately linear dependence of soot
volume fraction and soot formation rate on pressure.
110 I.M. Kennedy
With measurements of the mean mixture fractions,
the results provided libraries of properties for use in a
flamelet approach to modeling soot formation and
radiation in high pressure flames. The maps of soot
volume fraction as a function of mixture fraction over
a range of pressures could be used in modeling soot
formation in gas turbine combustors.
Young and M o s s 98 have used an extended flamelet
approach to predict soot and radiation in turbulent
diffusion flames. Their goal was to fully couple the
soot formation and radiation processes to the flame
calculation without a post-processing strategy. They
adopted a conventional k - e turbulence model 85 to
which they added Favre averaged equations for the
soot particle number density and the soot volume
fraction
0-~xj(P~J~") - 0-~xj\~-~¢~x-jx:]= ~ - fi2~d (36)
0 _A(.t0cs
~ + N o P ~ , - N 10 / 3P'~ ~1/3~/3 (37)
= ox%n '~s
where the tilde denoted a Favre average and where
~n = ~ and ffs = ~fv- The particle number density
y~vo Y ,
was represented by n. No was Avagadro s Number, p~
was the density of a soot particle, fv was the soot
volume fraction. The parameters a and 6 represented
the impact of particle nucleation on the number
density n and on the soot volume fraction, fv. The
processes of coagulation, surface growth and oxida-
tion were represented by the parameters ~, 7 and Wox
respectively. The explicit evaluation of a,/3 and % as
described by Moss et al., 92 was presented in Eqs (32),
(33) and (34) above.
As in most other models of turbulent combustion,
the mean source terms presented the greatest closure
difficulty as a result of their non-linear dependence on
temperature. Young and M o s s 98 attacked this
problem with their flamelet approach whereby the
density, temperature and soot precursor/carbon
concentration were expressed as functions of a
mixture fraction via extended flamelet relationships.
It was possible to find the mean source terms such as
or ~'ox by averaging over a probability density
function for the mixture fraction so that the mean
source term was
Unfortunately, expressing the scalar quantities in
terms of mixture fraction alone precluded the
evaluation of possible correlations. For example, in
the case of surface growth, the term ~-~ was modeled
as "~N0~ which accounted for the non-linear
temperature dependence but neglected the effect of a
correlation between 7 and n, i.e. 7~n'. Effects such as these
could be captured correctly by methods that solve for
joint probability density functions. Kollmarm et al. 75 used
this approach to calculate soot formation and
radiation in a turbulent ethylene diffusion flame.
They were able to predict correlations between
various important quantities such as the temperature
and the soot volume fraction.
Young and M o s s 9s used a detailed calculation of
an adiabatic flame to obtain enthalpy and tempera-
ture as functions of mixture fraction. They adopted a
somewhat cumbersome adhoc method to account for
the effect of radiative heat loss on the temperature/
mixture fraction relationship. They reduced the
enthalpy at a given mixture fraction by some arbitrary
amount. The temperature was then obtained from the
enthalpy. The application of the flamelet library in the
turbulent case involved computing a mean mixture
enthalpy from a balance equation for energy with a
radiation sink term that accounted for soot luminosity.
The flamelet family was scanned for an enthalpy that
was close to the computed mean enthalpy and the
temperature of the mixture was obtained for that
value of the heat loss. It is not clear how this method
is implemented without an expensive iteration at each
grid point since the soot formation is temperature
dependent and, in turn, the radiation heat loss that
determines the enthalpy depends on the soot volume
fraction. The authors applied their methodology to a
turbulent ethylene diffusion flame. Trends in tem-
perature, mixture fraction and mean soot volume
fraction were reproduced reasonably well although
the quantitative agreement left room for improvement.
Lindstedt and co-workers have developed soot models
for laminar and turbulent diffusion flames. 72'73'76'83'99
Lindstedt76'99used a simple kinetic mechanism to predict
the soot volume fractions in co-flow and counterflow
laminar diffusion flames. He assumed that acetylene
was primarily responsible for the nucleation and the
growth of soot particles. The nucleation step was
treated simply as a one step process
C2H2 ~ 2Csoot + H2 (39)
The reaction ignored the fact that soot was not
composed purely of carbon but it is adequate for a
semi-empirical model. The rate of nucleation was
assumed to be first order in acetylene concentration so
that the rate was calculated as
I~n = 104e-21'l°°/T[c2H2] (40)
where [C2H2] was the concentration of acetylene and
the units were in kmol/ma/sec. The rate of surface
growth was also assumed to be first order in acetylene
concentration and dependent upon a function of the
aerosol surface area. Lindstedt did not assume that
the growth rate was simply directly proportional to
the aerosol surface area as some other authors
have. 2'72"1°° Bockhorn et all °l showed that soot
growth was not related only to surface area and
could, in fact, be independent of area. Their results
could be interpreted in terms of a mass growth that
was governed by the presence of active sites. Lindstedt
made the ad hoc assumption that the number of active
 Models of soot formation and oxidation
sites was proportional to the square root of the total
aerosol surface area. Hence, he wrote the soot growth
rate as
Wg = k(T)[f2n2][Cs]l/3[pg] I/6 (41)
where
k ( T ) = 6 x 10317r(6Mc/Trps)E/311/Ee-I2'l°°/r (42)
Mc was the molecular weight of carbon, Ps was the
density of soot, N was the number of soot particles per
unit mass of soot/gas mixture and [Cs] was given by
p Ycs/Mc in which Ycs is the soot mass fraction in
the flow and Mc is the molar weight (12.011 kg
kmol-l). The units were again in kmol/m/sec.
Soot oxidation was modeled with the method of
Lee e t al. 17 Leung e t al. 76 argued that oxidation was
not a particularly important factor in soot formation
in a counterflow flame. However, while 02 may not be
important in the case of a counterflow flame, it is
rather more likely that OH that diffuses back from the
reaction zone may be a significant oxidant in even the
counterflow geometry. The oxidation rate in the
model of Lindstedt 99 was adjusted by a factor of 14
to give adequate agreement with the measurements of
Garo et al. 102 This ad hoc adjustment is typical of the
semi-empirical models of soot formation in which it is
usually found to be necessary to adjust one or two
rates to achieve a reasonable agreement with data. In
this case, the adjustment was possibly necessitated by
the neglect of OH as an oxidant of soot. The rate of
the soot oxidation reaction
1
Cs + ~O2 ~ CO (43)
was written as
71" [6Mc]2/3
Wox = k( T) --~c
I 7rpc J [C02][Csl2/3[pN] 1/3 (44)
where [Co2] is the concentration of Oz and k(T) is
given, in units of [kmol/m/sec] by
k ( T ) = 1.25 x 105Tl/2e-19'68°/r (45)
Particle number density was calculated assuming that
the aerosol was monodisperse. The equation for
number density included the effects of particle
nucleation and particle coagulation.
The gas phase reactions were treated in a fairly
simple manner, although with greater detail than the
simple equilibrium approach that was used by
Kennedy et al. 2 An extended version of the global
mechanism of Jones and Lindstedt io3 was used with
additional steps to model the formation and destruc-
tion of acetylene.
The counterflow version of the code was used to
predict the results of Vandsburger et al. 1°4 The
experiments were performed at a fixed strain rate
but with a variable composition of the oxidizer
stream. The 02 mole fractions ranged from 18 to
28% in N2. The variation in Oz concentrations should
provide a good test of the accuracy of prediction of
111
acetylene and hence of soot. Unfortunately, the
experimental data included no information on gas
phase species concentrations so that comparisons
were made solely with the soot volume fraction and
number density. The agreement with the measured
soot volume fractions over the range of reported
oxygen concentrations was quite good. Less satisfac-
tory agreement was obtained with the particle number
density. In general, this is a difficult quantity for a
model to reproduce with fidelity. Particle dynamics in
flames are complicated by variations in coagulation
rates as a result of varying van der Waals forces, t2
sticking coefficients that may be less than one, and
significant uncertainties in the interpretation of light
scattering data on the basis of Rayleigh scattering
from a monodisperse aerosol.
Lindstodt 99 also applied his model to the prediction
of soot formation in the co-flowing, axisymmetric
methane air flame of Garo et al. 1°2 The soot model
was unchanged. Again, generally good agreement was
obtained for the distribution of the soot volume
fraction. Lindstedt ascribed the discrepancies to the
problem of specifying the initial profile of soot
volume fraction near the nozzle where there were no
measurements. It is not clear why the model could not
be used from a location close to the nozzle where soot
nucleation was not significant.
Fairweather e t al. 73 applied the model to the
prediction of soot formation in a turbulent propane
flame that issued into a co-flow of air. The approach
to the incorporation of the soot predictions into a
turbulence calculation was quite similar to the method of
Syed et al. 7s A conventional k - e turbulence model was
used with additional equations for the soot mass fraction
and the soot particle number density. The modeling by
Fairweather e t a / . 72'73 differed from the approach of
Moss and co-workers7s'92 mostly through the use of
acetylene as the precursor species for soot nucleation
and growth. Hence, the instantaneous rates of soot
nucleation and growth were proportional to the
acetylene concentration rather than to the parent
fuel concentration. This concept is physically more
plausible although it does complicate the modeling to
some extent by introducing the need to determine the
acetylene mass fraction. This is not a significant
burden if the laminar flamelet method is used.
However, it is important to note that the modeling
of Fairweather e t al. 72'73 and Syed e t al. 78 did not
account for the action of OH as an oxidant of soot.
This is potentially an important omission.
A counterflow flame code was used to generate
flamelet information for the acetylene concentration,
temperature, density and other scalars as functions of
the mixture fraction. The code was run at a low strain
rate (15sec -1) which yielded data for an effectively
unstrained flame. The mixture fraction-scalar rela-
tionships did not change much if the strain rate were
lowered. The counterflow flame calculations were
conducted under adiabatic conditions. Fairweather
e t al. 73 found that it was necessary to account for
112 I.M. Kennedy

0.8~
radiation in a rather a d hoc manner by adjusting the 1m
flamelet temperature by some arbitrary amount to
match the measured peak temperatures. They found
that the required temperature decrease did not have a
significant impact on the calculation of the acetylene
mass fractions when the laminar counterflow calcula-
tions were repeated with a prescribed radiant energy
loss.
Turbulent flame predictions were compared with
the measurements of Nishida and Mukohara.105 The
Jl
predictions of the acetylene and 02 mole fractions 0.
were in good agreement with the measurements. Such
agreement is necessary, of course, if good agreement
is to be obtained with predictions of soot volume
fractions because soot formation and oxidation are 0 10 20 30 40
directly related to these species. Figure 5 shows the r (mm)
quality of the predictions of the radial distributions of Fig. 5. Radial measurements of (11)CEH2, (@) 02 and
C2H2 and 02 in a flame with the incoming air predictions (--) at x / D = 150 in a turbulent propane flame
preheated to 323 K. Figure 6 indicates the quality of (from Fairweather et al.73).
the predictions of the mean soot volume fraction
along the centerline of the same flame. 30
It can be seen that the gas phase species and the
soot volume fractions are predicted quite well.
Fairweather et al. 73 found that the soot oxidation
rate that was predicted with the expression of Lee
et al. 17 was apparently excessive. They repeated the
calculations with the oxidation rate reduced by a
i £
factor of two (the dashed line in Fig. 6). The
agreement between the predicted and the measured J
soot volume fractions near the end of the flame was
improved significantly. It might be expected, however,
that the inclusion of the action of OH as a soot
t
oxidant would cause the agreement to worsen.
Nucleation in this model was related entirely to
acetylene as an indicator species. Lindstedt s3 0 100 200 300 400 500
extended the model to improve the calculation of x/O
soot nucleation and mass growth. In particular, he
Fig. 6. Soot concentrations along the centerline of a
added a kinetic mechanism for the production of C3 turbulent propane diffusion flame: (11) measurements, (--)
and C4 species that were able to produce benzene normal oxidation rate, (- - -) oxidation rate/2 (from
through reactions such as Fairweather et al.73).
C3H 3 + C3H 2 ---, C6H 5 (46)
reactions. The first model (I) followed the approach
nC4H3 + C2H2 --~ C6H 5 (47) set out by Frenklach and Wang 1°7 in which surface
chemistry was attributed to hydrogen abstraction/
Soot nucleation was then assumed to result from not
acetylene addition reactions. A certain number of
only a first order acetylene reaction but also a benzene
active sites per unit area of aerosol was assumed.
reaction
Growth then depended on the surface area of the soot
C6H 6 --~ 6Cs + 3H2 (48) aerosol and a steady state approximation to the rate of
with a reaction rate given by the hydrogen abstraction/acetylene addition reactions.
His second growth model (II) removed the
(Vn = k ( T)[Cc6H6 ] (49)
hydrogen abstraction mechanism so that growth
where was proportional to the acetylene concentration and
k ( T ) = 7.5 x 104e-21'°°°/rin units of the soot surface area. This model for surface growth
has found wide application in semi-empirical models
[kmol/m/sec/K]
of soot formation. 2'14'72'92'1°° The third model (III)
Lindstedt 83 also paid some attention to the problem assumed that the growth rate of soot was propor-
of modeling soot mass growth, where growth has tional to the number density of soot particles but
been denoted as 'mass' growth in view of evidence independent of the surface area. This model is
that it may, in fact, be independent of surface area. 1°6 consistent with the observations of Wieschnowsky
Lindstedt considered four models for the soot growth et al. 16 in premixed flames. The fourth and crudest
 Models of soot formation and oxidation
Table 2. Peak soot volume fractions predicted by the following soot growth models: I. growth proportional to surface area
plus the HACA mechanism; II. growth proportional" to surface area; III. growth proportional to number densitY,104independent
of surface area; IV. number density constant, compared to the experimental results of Vandsburger et al. for counterflow
ethylene diffusion flames with varying 02 mole fractions in the oxidizer stream. Taken from Lindstedts3
02 mole fraction Model I M o d e l II
0.18 2 . 3 8 - 10 -8 1.00- 10 -7
0.22 1 . 0 0 - 10 -6 1.03. 10 -6
0.28 1.11 • 10 -5 1.07. 10 -5
model (IV) assumed that the particle number density
was constant throughout the flame. This model had
the great advantage of removing the equation for
particle number density from the set of equations that
needed to be solved. Hence, it offered some
computational advantage, particularly in turbulent
flame calculations where computational cost is a
serious consideration. Kennedy e t al. 2 employed the
same approximation in their simplified modeling of
soot formation in a diffusion flame.
The code was again compared to the experimental
results of Vandsburger e t al. 1°4 in a counterflow
ethylene diffusion flame with a varying oxygen
concentration in the oxidizer stream. Lindstedt
compared his results with the peak soot volume
fractions that Vandsburger e t al. 1°4 measured. The
comparison of the four growth models with experi-
ments is shown in Table 2
Generally poor agreement was obtained with the
most sophisticated model (I). The good agreement in
the case with 22% 02 was considered by Lindstedt s3
to be fortuitous in view of the strong sensitivity of this
model to the modeling constant that related the
benzene concentration to the number of active growth
sites per unit area and the total soot surface area.
Further improvements to this model are apparently
required in order for it to achieve greater accuracy.
Lindstedt s3 proposed that the assumption of spherical
particles may pose a problem with the model; K6ylu
e t al. 3° have suggested that particle morphology is an
important property of the soot that is not considered
adequately in models. It is possible that a shape
dependent correction to surface areas is required
although one runs the risk of adding yet another level
of complexity and modeling uncertainty to the
calculation.
Very good agreement was obtained with model
(III) in which soot mass growth was simply a function
of particle number density and independent of aerosol
surface area. The small discrepancies were attributed
by Lindstedt to uncertainties in the soot nucleation
step. However, given the uncertainties in all aspects of
the flame modeling, the agreement should be
considered to be quite satisfactory and is likely to be
difficult to improve with general validity. Model (II)
in which growth was proportional to surface area did
not perform well. The results suggest that this model
of soot growth may not have general validity. Model
(IV), with a constant particle number density, actually
achieved better results than models (I) and (II) with
113
M o d e l III M o d e l IV E x p e r i m e n t a l results
3.38. 10 -7 5.11 • 10 -7 3 . 7 - 10 -7
1.02. 10 -6 9 . 7 8 . 10 -7 1.1 • 10 -6
2.40. 10 -6 1 . 6 4 . 10 -6 2 . 2 . 10 -6
errors of the order of 40%. Lindstedt correctly
pointed out that the model is attractive in simplified
models of soot formation (such as in turbulent flame
calculations) but it is likely to be less generally valid.
Its use will be restricted probably to fairly strongly
sooting flames in which particle coagulation is rapid.
The addition of the benzene route to soot nucleation
was found to be important. A mechanism that
incorporated only the acetylene nucleation step
resulted in errors of up to 50% when the surface
growth model (III), the most accurate model, was
used.
Sivathanu and Gore 35 applied the soot model of
Lindstedt, Jones and co-workers 72'76 to a laminar
acetylene air flame. They solved the axial momentum
equation, the gas phase mixture fraction, the energy
equation, the soot mass fraction and the soot particle
number density in their boundary layer form. Because
up to 30% of the carbon in an acetylene flame can be
converted to soot, the specification of the gas phase
mixture fraction required special treatment. It was
defined as the fraction of the local fluid mass that
originated from the nozzle and was in the gas phase.
As a result of this definition, it was not a conserved
scalar and was in fact increased by oxidation of soot
and reduced by the formation of soot. Hence, its
conservation equation required a source and sink
term that also appear in the equation for the soot
mass fraction. State relationships between the gas
phase mixture fraction and the mole fractions of
acetylene, 02 and chemical energy release were
obtained from the results of Gore l°s in an acetylene
flame. The energy equation contained three source
terms, one that accounted for the conversion of
acetylene into soot, another that accounted for the
heat released through oxidation and a final term to
account for radiation. Oxidation was assumed to
occur only though the action of 02; OH was not
included in calculations of soot oxidation.
Radiation, Qrad, was considered to consist of two
parts so that
Q r a d = Qabs - Qemi (50)
The emission
Oemi = CfvT5 (51)
was calculated from the soot volume fractionfv = e_~
Ps
and the temperature T, where Ys was the soot mass
fraction, p was the total density of both phases (gas
and soot) and ps was the density of a soot particle,
114 I.M. Kennedy
taken in this case to be 2000 kg m -3 . The constant, C,
was a function of the refractive index of soot.
The flame was not considered to be optically thin.
Rather, the details of absorption were included at all
points in the flame. This was achieved in an iterative
manner by first calculating an initial solution that
provided the radiation absorption terms without
coupling to the flame structure, i.e. adiabatically.
The absorption was calculated as
foo r2~r rTr
Qabs : J0 J0 J0 axI:~ sind0 dO dA (52)
where Ix was the incident spectral intensity and a~ was
the Planck absorption coefficient
(1 - exp(-KxfvAs)) (53)
a~ - As
The spatial discretization used in the calculations was
As; K~ was the specific absorption coefficient of soot.
After the initial estimate of the flame structure was
obtained, the entire calculation was repeated up to six
times with a radiative sink term in the energy equation
to obtain convergence of the radiation source terms to
within 2%. Clearly, this is not an approach that could
be used easily with a detailed chemical model. The
results of the calculation were compared with
experimental measurements of soot volume fraction
that were obtained with laser extinction and with
probe sampling measurements of the major species.
Aspects of the sampling of gas phase species in soot
laden flows necessitated the definition of an apparent
gas phase mixture fraction
is (54)
~ga - (1 - Ys)
where ~g was the actual mixture fraction that was
calculated.
The predicted soot volume fractions were com-
pared with experiments as a function of the apparent
gas phase mixture fraction, ~sa" The results were
shown for two different Reynolds numbers at a range
of distances from the nozzle. The predictions of soot
volume fraction were remarkably accurate, particu-
larly in view of the fact that oxidation by OH was
ignored.
The calculations of Sivathanu and Gore 35 high-
lighted the importance of including radiation in a
coupled manner in calculations of sooting flames. The
results suggested that the soot model of Leung et al. 76
was fairly robust, although some caution was in order
in view of the absence of a satisfactory sub-model for
oxidation that included the attack of OH on soot. One
may well expect a significant deterioration in the
quality of the predictions using the same model
parameters if OH attack were included.
The importance and the difficulties of including an
accurate model of OH oxidation were revealed in the
paper by Puri et al. 23 They measured laser induced
fluorescence of OH in methane, methane-butane and
in butene laminar diffusion flames. The measurements
were corrected for background soot scattering and for
PAH fluorescence by detuning the laser off resonance.
Quenching corrections were applied along the axis;
approximate corrections were applied to radial
profiles.
The profile of OH in relation to the other species in
the flame was worthy of note. The visible flame height
was about 107 mm. The radial profiles of all the major
molecular species exhibited a maximum on the
centerline at 102ram above the nozzle exit. How-
ever, the OH profile exhibited maxima off the axis.
The authors attributed this phenomenon to the loss of
OH on soot particles near the axis of the flame where
the soot was oxidized.
The concentration of OH in flames has often been
obtained from equilibrium calculations. 2 However,
the results of Puri et al. 23 showed that OH concentrations
can exceed equilibrium levels by one to two orders of
magnitude at atmospheric pressure. The presence of
superequilibrium concentrations poses a clear pro-
blem for soot models that treat OH attack in a
detailed manner. One approach may be to obtain the
thermochemical state relationships from a laminar
flamelet model.
The analysis of the experiments of Puri et al. 23
showed that the contribution of 02 to the soot
oxidation rate was small. The majority of the soot
oxidation was due to OH attack in their flames. Given
the importance of OH as an oxidizer of soot, it is
essential that an accurate rate for OH attack on soot
be used in a model of soot in flames. Many models
have used the reaction efficiency that was first
reported by Neoh et al. 24 Puri et al. 23 found that the
collision efficiency of OH with soot was a function of
the residence time of the soot in the flame, probably as
a result of a change in the soot reactivity. The
efficiency was as low as 0.05 at early times; it rose to
the value of 0.2 at later times.
Unfortunately, the estimation of the N a g l e -
Strickland-Constable rate by Puri e t al. 23 in their
1994 paper was based on an erroneous interpretation
of the original rate expression for 02 attack. A
subsequent short note 1°9 revised the estimate of the
O2 rate upward by a factor of 12. Consequently, the
original comparison of OH oxidation rates with O2
rates overstated the role of OH. Furthermore, the case
for a variation of the collision efficiency of OH with
soot could not be sustained although the data from
the CH4/C4HI0 flame continued to show a trend to
increasing collision efficiencies with height in the
flame. If the variation of collision efficiency with
time were substantiated, it would pose an additional
challenge to modelers of soot in flames. For example,
Kennedy et al. 11o found that a variation of OH collision
efficiency played a role in accurately capturing the
behavior of the soot aerosol during its formation
and its oxidation.
Miller et aL H1 attempted to calculate the growth of
PAHs, and hence soot, in a laminar diffusion flame by
 Models of soot formation and oxidation
extending the approach of Kennedy et al. 2 They
assumed that PAH did not diffuse and as a result,
these relatively large molecules followed streamlines
in the flame. A laminar flamelet concept was invoked
to correlate the concentrations of species such as H,
H2, C2H2, 02 and OH with the local mixture fraction
at some point in the flame. Measurements by Smyth
et al)12 in a methane-air flame provided an estimate
of the formation rate of benzene as a function of
mixture fraction. Benzene was considered to be the
inception species for soot particles; the formation of
benzene was followed by an irreversible growth of the
PAH. The growth rates of the PAH were determined
from a modified version of Frenklach's HACA
scheme. Oxidation of PAH or soot by 02 and by
OH was considered. The rate of OH attack was based
on the reported rate of OH reaction with benzene113
while the rate of O2 reaction was based on the
reported rate of reaction of oxygen with phenyl
radical. Soot was defined to be the sum of masses of
all species larger than coronene; the density of soot
was assumed to be 1800kg m -3.
Initial calculations with the model yielded dis-
appointingly small soot volume fractions, with peak
values of the order of 10-21 . The sensitivity to growth
rates and to oxidation rates was explored. The
ultimate peak soot volume fraction was sensitive to
the growth rate. Volume fractions of the order of 10-7
were obtained by increasing growth rates by a factor
of 200. The fastest growth of PAHs was along
streamlines on which H atoms and C2H2 overlapped
in the absence of OH or 02. This was true for mixture
fractions between 0.08 and 0.11.
It has been shown rather convincingly that simple
state relationships between soot volume fraction and
mixture fraction are not adequate. Kent and
Honnery74'114 sought to extend the utility of the
mixture fraction approach by mapping soot growth
rates in diffusion flames as functions of mixture
fractions and temperature. The original work of Kent
and HonneryTM used laser extinction measurements in
turbulent ethylene diffusion flames to obtain a
correlation between soot volume fraction and mean
mixture fraction. The mixture fraction at the location
where the soot volume fraction was measured was
inferred from a numerical calculation of the turbulent
flame.
The numerical model of the flame was written in
terms of a stream function115 formulation of the
axisymmetric boundary layer equations for a laminar
diffusion flame. Equations were solved for momen-
tum and energy. The energy equation contained a
term to account for the loss of enthalpy via radiation.
The radiation flux was found by solving the radiative
transfer equation in the horizontal plane. The
numerical simulation of the flame served two
purposes viz., to determine the velocity field and the
mixture fraction field so that soot mass growth rates
could be deduced along soot trajectories and also to
evaluate the accuracy of the model of soot growth
I 15
when it was incorporated into the numerical model of
the flame.
Measurements were performed in laminar ethane
and ethylene flames. Maps of the soot mass growth
rates per unit aerosol surface area (assuming a
monodisperse aerosol for the sake of measurement
interpretation) were produced from data for a
number of flames. The maps set out contours of
mass growth rates as functions of mixture fraction
and temperature. When the map data for the range of
flames of a given fuel type were combined, the root
mean square scatter was about 10-30% of the mean
growth rate. This result suggests that it may reason-
able to apply the growth function over a broader
range of conditions for a given fuel. The hypothesis
was tested by using the growth function as a source
term in the numerical model of the flame with an
additional equation for the soot mass.
The correlation of measured soot volume fractions
with predicted mixture fraction showed a significant
variation with height in the flame. This provided clear
proof that the use of mixture fraction alone is not
sufficient to yield useful predictions of soot loading.
Honnery and Kent 116 and Kent and Honnery t 14 in a
later study attempted to improve on the mixture
fraction approach by correlating measured soot
volume fractions with two variables viz., mixture
fraction and temperature. Honnery and Kent 1t6
analyzed the specific surface growth rate data of
Honnery et a l ) 17 in C2H4 and C2H6 diffusion flames.
The rates, wg were correlated in terms of mixture
fraction and temperature, i.e. wg = A s k s ( T , ~) where
As was the soot surface area, ks was the specific
growth rate and ~ was the mixture fraction. Equations
were solved for the mixture fraction, enthalpy and
soot volume fraction. An approximation for radiative
transfer, suitable for use with a parabolic code, was
applied. The soot surface area As was calculated from
a correlation of optically determined surface area
and soot volume fraction in a linear form viz.,
A s = a + bfv. For an ethylene flame, a = 55.5 and
b = 78.6 with units of [m] and [ppmv]. The use of the
empirical correlation of surface area with volume
fraction obviates the need to calculate the particle
number density. This approach is somewhat more
sophisticated than the approach adopted by Kennedy
et al. 2 who assumed a constant average number
density in which case the surface area varied with
fv 2/3. Oxidation was treated with the scheme of
Bradley et al. 22 and included 02 and OH attack. The
concentrations of these species were obtained from an
equilibrium calculation.
The model was used to predict the soot mass flow
rate, soot volume fractions and temperatures in
ethane and ethylene flames of various flame heights.
Generally impressive agreement with the measure-
ments of soot mass flow rates was found in the
formation zones of the flames although the agreement
was rather less satisfactory at large distances from the
nozzle, in the burnout zone. The measured soot mass
116 I.M. Kennedy
flow rates were overpredicted, possibly as a result of
uncertainties in the oxidation model. Honnery and
Kent 116 reaffirmed the sensitivity of soot volume
fraction predictions to the specific surface growth
rates that was reported by Kennedy et al. 2
Results in the later study 114 in ethane and ethylene
flames were encouraging, particularly in the more
heavily sooting ethylene flames. Fuel flow rates
covered an order of magnitude for the ethylene
flames, from non-sooting to heavily sooting. The
rate map model performed reasonably well in
reproducing trends of soot mass flow rates as
functions of height above the burner. The greatest
difficulty was in capturing the burnout of soot at the
end of the flame with the low flow rate. The model
predicted a sooting flame, whereas the experiments
showed that the flame was non-sooting. The authors
ascribed the discrepancy to superequilibrium concen-
trations of O and OH. The approach of Kent and
Honnery114 was not greatly different to that proposed
and tested by Kennedy et al. 2 and Villasenor and
Kennedy. v9 Both groups used measured rates of soot
growth as inputs to models of flames. Kent and
Honnery114 chose to work with a correlation between
growth rates and temperatures while Villasenor and
Kennedy 79 incorporated the effect of temperature via
an assumed activation energy. The quality of the
predictions was similar. Burnout of soot at the end of
a diffusion flame was difficult to capture accurately
due to uncertainties in the kinetic rates of oxidation
and more importantly, due to uncertainties in
predicted OH and O concentrations. This point was
emphasized by Kennedy et al.U°
Some authors have used a semi-empirical model of
soot formation to investigate the impact of soot
radiation on flame structure in detail. Kaplan et al.118
used a rather complete radiation model in a
calculation of a laminar ethylene diffusion flame.
They employed the Discrete Ordinate Method 119 to
calculate the radiation from CO2, H20 and soot.
Experimental data were used to estimate the absorp-
tion coefficient of these species.
They used the soot model of Moss et al. 92 Hence,
two equations were solved for the soot viz., the soot
volume fraction and the soot number density.
Oxidation was attributed entirely to the action of O2
through the use of the Nagle-Strickland-Constable
formulaJ s As a result, the rate of oxidation was
probably underestimated to some extent by ignoring
the important effect of OH on soot. A detailed
description of the flow field was used with equations
for continuity, momentum, energy and species
number densities. However, the chemical kinetics
were described in very simple terms with a one step
reaction of fuel to COz and H20.
A 'benchmark' calculation was undertaken to
compare the code with the measurements of Gore
and Faeth s° in a laminar, co-flow, ethylene diffusion
flame. The burner consisted of a 14.3 mm dia round
tube within a 102 mm outer tube. Fuel flowed through
the inner tube; air flowed through the outer tube. The
Reynolds numbers were about 50. Kaplan et al. l~s
found that their computations indicated that the
flame was unsteady, despite the relatively low
Reynolds number. The flicker at 16Hz was not
attributed to a numerical instability, rather to a
buoyancy driven instability of the flame itself. The
authors compared their calculations with the experi-
mental results of Gore and Faeth s° by analyzing their
results in terms of state relationships between mixture
fraction (or fuel equivalence ratio in this case) and
species mass fractions and soot volume fractions.
They reported a reasonable agreement for the major
species such as C2H4, 02, CO 2 and H20. It is very
difficult to ascertain the accuracy of the soot
calculation from the state relationship interpretation
of the results, particularly since the numerical results
exhibited some non-systematic scatter. The scatter
may be due to the inadequacy of the soot-mixture
fraction state relationship.
A second calculation was carried out for a larger
Reynolds number of about 5000. The results of this
study were used to illustrate the impact of radiation
on the structure of the diffusion flame. Radiative heat
losses reduced temperatures and chemical heat release
rates. As a result, the flame was shorter than the
corresponding adiabatic flame. The calculations were
computationally intensive, largely as a result of the
use of the DOM radiation model on the fine grid that
was required to resolve the flame structure.
Kennedy et aL ~l° modeled a sooting and a non-
sooting flame for the conditions of Santoro's
experiments. 9° The boundary layer forms of the
governing equations for a round laminar jet flame
were solved in primitive variable form with zero axial
pressure gradient. The energy equation was written in
terms of the temperature with the radiation repre-
sented by the assumption of an optically thin flame
without gas phase radiation, only soot radiation.
Equations were solved for N-I species mass
fractions
OYn OYn _ 1 0 {rpYnV,} +Muff' n (55)
pu Oxx + Try Or r Or
with the Ntb species being N2. The N-1 equations
included one for the soot mass fraction, Ys
ors oYs 1o
PU-~x +P'V Or rOr { r p V T Y s } + p S ( Y s ' T ' f )
(56)
In this equation, the thermophoretic velocity was
found from the appropriate expression for a free
molecular aerosol ~2°
VT = -0.55T00T (57)
The source term in Eq. (56) included the contributions
of soot nucleation (~nuc0, soot surface growth 0bs)
 Models of soot formation and oxidation
and soot oxidation (Wo)
S(Ys, T,f) = Wnucl+ fig - fro (58)
The latter term had two contributions viz., oxidation
of soot by 02 and by OH to form CO.
Earlier modeling studies of soot formation by
Kennedy et al. 2 used an average number density to
obtain an estimate of the soot aerosol surface area.
The more recent study followed the approach of
Fairweather et al. 72 in solving an equation for the
number density of particles. It should be noted that
their equation for the particle number density did not
incorporate the effect of thermophoresis.
The model of Fairweather et al. 72 was adopted in its
entirety with the following important difference. The
rate of soot surface growth was increased by a factor
of two to yield an adequate representation of the
measured soot volume fractions in the flame. This a d
hoc action was adopted because Fairweather et al. 72
did not incorporate the impact of OH in their model.
In their case, the oxidation of soot was attributed
entirely to 02. The parameters in their model were
calibrated against experiments on that basis. As a
result, their soot growth model underpredicted the
measured soot volume fractions when it was used by
Kennedy et a l . l l ° with OH oxidation.
Particular attention was given to the correct
formulation of the oxidation mechanism in the
model. The Nagle-Strickland-Constable18 formula
was used for 02 oxidation of soot. Oxidation of soot
by OH was generally more important in most of the
flame and, hence, it required greater attention than
the 02 mechanism. Calculations were originally
performed with the approach that was adopted by
Villasenor and Kennedy,79 i.e. a collision efficiency of
0.1 was used for the reaction of OH with soot.
However, it was found that a constant value for the
collision efficiency, regardless of its magnitude, could
not faithfully reproduce the characteristics of the soot
distribution in the flame. Consequently, reference was
made to the results of Puri et al. 23 who found that the
apparent collision efficiency of OH with soot changed
with time and/or temperature. The collision efficiency
was assumed to vary linearly with distance from the
fuel nozzle, from a minimum of 0.05 to a maximum of
0.2 at the flame tip. This model of OH reactivity
achieved reasonable results although it was quite
crude.
A simple mechanism was used to describe concisely
the Cl and the C2 reactions for ethylene oxidation.
The methane mechanism of Smooke et al. 121 was
implemented in the code with the rates for all the C2
chemistry from Frenklach et al. 122 The C2 chemistry
was described by a series of reactions that converted
C2H4 to C2H 3 and C2H2. The entire reaction
mechanism was composed of 62 reactions involving
24 species. The important oxidation steps by O, 02
and OH were included. The CO oxidation steps and
the H2-O2 steps were also included.
The governing differential equations were written
117
A
1.8
E
1.6-
× 1.4-
--~ 1.2'
o.6
0.41
mO.2 ~
_~ o .... I .... I .... I .... I .... I .... I .... I ....
0 1 2 3 4 5 6 7 8
x/D
Fig. 7. Integrated soot volume fractions in the non-sooting
flame of Santoro et al. 90 (--) Predictions from Kennedy
et al. n°
in a discrete form. The non-linear terms (convective
and rate terms) were linearized by using Newton's
method. The resulting Jacobian matrices were
determined numerically in the manner described by
Smooke and Giovangigli.123 Grid adaptation was
used in order to resolve the high gradient region in the
flow field with a minimum number of grid points.
Most of the results were obtained in the non-
sooting flame of Santoro et al. 90 Predictions of
temperature profiles and velocities were quite good.
Predicted profiles of major species compared quite
well with the measurements that were obtained by
probe sampling and GC/MS analysis. A measure of
the accuracy of the soot model is given by the
calculation of the integrated soot volume fraction
(Fig. 7) in a non-sooting flame. This quantity was
obtained by integrating the soot volume fraction
across a plane of the jet. It indicates the total amount
of soot at a given axial location in the flame. The
agreement between measurements and calculations
was good. The model was able to reproduce the peak
integrated soot volume fraction as well as predict the
burnout of soot at the flame tip. Detailed compar-
isons of the radial distribution of soot in the flame are
shown in Figs 8 and 9 at 15 and 50mm from the
nozzle, respectively. In both cases, the maximum soot
volume fraction was captured quite well by the model.
However, the presence of significant amounts of soot
on the centerline of the flame at a position 50 mm
from the nozzle was not predicted. In order to
reproduce this behavior, a more detailed soot model
is required, one that accounts for soot formation from
PAH that are known to form on the axis of diffusion
flames.
Hydroxyl mole fractions were measured with laser
induced fluorescence. The calculated hydroxyl mole
fractions were compared with the measurements at 7
and 70 mm. The model tended to overpredict the OH
mole fractions throughout the flame. However, it
should be borne in mind that LIF measurements
118 I.M. Kennedy

3.5 greatest for the minor, radical species such as O and

OH. These species are of particular interest in the
3 formation and oxidation of pollutants such as NO
% and soot. The ratio of computed OH mole
x 2.5 fractions to equilibrium mole fractions at the
C
O
local computed temperature were calculated at
2
40mm from the nozzle. At a radius of r / D = 0.745,
°Ht~'.~=' = 22 while ~ = 478. This location
~ 1.5
was ~n the air side of t'~e reaction zone at a mixture
fraction of around 0.03 (stoichiometric mixture
fraction is 0.064). It was apparent that large super-
o3
0.5 equilibrium concentrations could be achieved as a
result of the depressed temperatures in this radiating
0 t,,, i,,,, i,,,, i,,,, i,,,, i,,,,
flame. Puri et al. 124 found that the OH super-
0 0.1 0.2 0.3 0.4 0.5 0.6 equilibrium ratio was 9.4 at the peak OH location in
r/D this flame at a height of 70 mm. The results suggested
Fig. 8. Soot volume fractions at 15mm from nozzle. ( - - ) is that the assumption of equilibrium chemistry was
predictions from Kennedy et al.; 11° measurements from grossly inadequate for the prediction of the minor
Santoro et al. 9° species. This finding is particularly troublesome in
terms of the calculation of OH oxidation of soot.
12 One of the most difficult tests for any model of soot
behavior in diffusion flames is the prediction of the
% 1o • transition from a non-sooting to a sooting condition
as the fuel flow rate is increased. The correct
X reproduction of the transitional behavior requires
i8 a
° not only the accurate calculation of soot formation
but also the correct calculation of the soot burnout at
® 6- the tip of the flame. Experimental conditions for the
sooting flame of Santoro e t al. 9° were used in the
4, • calculation of Kennedy e t al. 11° The increased
production of soot with an increased flow rate of
09 2 fuel was captured quite well by the code, particularly
in regard to the peak soot volume fraction. The code
did a reasonable job of predicting the peak soot
0 '''' I'''' I'''' I'''' I'''' I''''
0 0.05 0.1 0.15 0.2 0.25 0.3 volume fraction in the flame. However, it was not able
r/D to correctly predict the emission of soot, as is evident
in Fig. 10 that shows the integrated soot volume
Fig. 9. Soot volume fractions at 50 mm from nozzle. (--) is
predictions from Kennedy et al.; 11° measurements from fractions in a sooting flame. This defect was attributed
Santoro et al. 9° to an excessively vigorous oxidation of soot that
proceeded too rapidly and persisted too long in the
involve uncertainties that are related to quenching cooling post flame gases. Kennedy et al. 12° believed
corrections and other errors. The errors were that the problem lay with the oxidation rate that was
estimated to be +50%. TM The numerical model calculated from the Nagle-Strickland-Constable
indicated the measured trend in OH mole fractions formula. 2s Evidence is available in the literature that
with distance from the nozzle although absolute the Nagle-Strickland-Constable formula overesti-
amounts were overpredicted. The concentrations of mates the oxidation rate of soot and char by
OH decreased as the flame tip was approached due to 02225'126 at temperatures below about 1800K;
the drop in temperature and due to the loss of OH by temperatures in postflame gases are typically about
reaction with soot particles and CO. 1600K or less. Evidently, the accurate prediction of
The use of a detailed kinetics model with a model the transition from non-sooting to sooting flames may
for soot formation and radiation permits the require an improved model for the low temperature
examination of questions regarding the impact of oxidation of soot by 02.
the soot process on flame chemistry in a manner that Kennedy et al.22° found that the inclusion of soot in
experiments alone cannot attempt. For example, the description of a diffusion flame could have a
calculations of turbulent flames require a model for significant impact on the structure of the flame. The
the thermochemistry. A convenient and very common rate of loss of OH on soot particles was comparable to
approach is to use chemical equilibrium. It is possible the rate of formation and destruction by the gas phase
to examine the accuracy of this assumption when chemistry, as shown in Fig. 11 at a location near the
there is substantial radiative heat loss from a tip of the non-sooting flame of Santoro e t al. 9° It was
hydrocarbon flame. The non-equilibrium effect is apparent from these results that soot is a significant
 Models of soot formation and oxidation 119

2 • phases of development was directed to modeling

fh
soot formation in laminar, premixed flames. More
recently, Yoshihara et al. 12s applied the model to the
industrially important problem of soot formation and
burnout in a diesel engine.

L \ Frenklach et al. 7 considered the detailed modeling

of soot formation during the shock tube pyrolysis of
acetylene. They extended the acetylene pyrolysis
mechanism of Tanzawa and Gardiner 129 to describe
the early hydrocarbon chemistry. The dominant route
8o. "i \"
\" for the formation of the first aromatic ring from an
atiphatic fuel was found to occur via vinyl addition to
acetylene, leading eventually to cyclization via the
o~,,,,,,,,,,,,,,,,,,,' "%,,. interaction of an unpaired electron with a triple
0 2 4 6 8 10 12 carbon bond. The aromatic ring then grew through
x/D the so-called HACA route (H abstraction-C2H2
Fig. 10. Integrated soot volume fractions in the sooting flame addition) in which thermodynamically stable species
of Santoro et al. 9° (--) predictions,U°points: measurements. such as acenaphthalene and coronene were formed
and were subsequently reactivated by H atom
3 1800 abstraction. Reactive coagulation of PAH could
also be important, i.e. the fusing of one or more
PAH to form a larger entity. This mechanism may be
1400 particularly important when the parent fuel is an
~tlJ
~, 1200 aromatic such as benzene. Frenklach et al. 7 found
E that the major 'bottleneck' in soot formation from
1000 -~
acetylene pyrolysis was at the step that led to
80O formation of the first aromatic ring. Their computa-
®
- I :
-60o E tional results showed reasonable agreement with
-2 II experiments in the shock tube, particularly if
8 II --14°° allowance were made for uncertainties in the inter-
ca -3- t -200 pretation of optical measurements of soot.
The growth of larger PAHs through many
-4 ,,i,,,~, ,),,,~,,,i,,,;,,,t,,,),,,),,, 0
0 0.2 0.4 0.6 (:).8 1 1.2 1.4 1.6 1.8 2 elementary reactions was accounted for via the
r/D method of linear lumping in which equations were
derived for the change in moments of the distributions
Fig. 11. Source and sink terms for OH at 70 mm from the nozzle
in the non-sooting flame of Santoro eta/. 9° and temperature
of concentration and size. 127The method of moments
profile. ( - - ) gas phase chemistry source of OH, (- - -) loss rate of is potentially more computationally efficient than a
OH on soot particles. From Kennedy et al. t=° sectional description 13° in which an aerosol distribu-
tion is divided into finite size groups that then
sink of OH near the end of the flame in comparison to represent a group of particles. The kth moment of
the gas phase chemistry. concentration was defined as
oo

3.3. Models with Detailed Chemistry Mk = Z mki Ni (59)

i=1

Models that rely on empirical inputs for soot where M k was the kth concentration moment, m~ was
nucleation, growth and oxidation rates are limited mass of PAH species of class i and Ni was the number
inherently to specific', conditions. They cannot be concentration of the same size class. The size
applied to conditions far from those under which the moments were defined as normalized concentration
rates were measured. Hence, they cannot be extended moments as follows
easily to different fuels or different pressures. A
complete description of the kinetics of PAH and soot
k mk
-- M~ (60)
growth is required for generality.
Frenklach and co-workers 7A°TA27have worked on Linear lumping was also applied to the evolution of
the development of detailed soot models over the last the size distribution of soot particles. A soot particle
decade or so. Their model has reached the greatest was taken to be formed when two PAH molecules
level of sophistication of any of the extant models. combined to form a dimer. Rate equations were
Frenklach treats the full panoply of phenomena, from written for the change in the moments of the soot
the initial pyrolysis of fuel to the nucleation of soot distribution; these equations included nucleation,
particles, their growth and coagulation and their coagulation and surface reactions in a form
ultimate oxidation. Most of the attention in the early compatible with the moment formulation.
120 I.M. Kennedy
Growth of soot particles by surface reaction was
described by the addition of acetylene to a radical
'arm chair' site on a particle) 27 The radical site was
formed by H atom abstraction as shown below
C r H + H ~ Ci • +H2 (61)
Ci • + H -~ Ci-H (62)
Ci • +C2H2 --' Ci+2-H + H (63)
Oxidation by 02 was also included
Ci • + 0 2 --, products (64)
The rate of reaction (64) was found by analogy with
the gas phase reaction of an aryl radical with 02
aryl • + 0 2 -~ products
The rates of reactions (61), (62) and (63) were found
by analogy with the gas phase reactions of H atoms
and C2H2 with aryl radicals under the assumption that
the collision efficiencies were the same per active site.
The rate of growth of a particle was formulated as
fig = kCgak~Csoot • Sn (65)
in which k was the per-site rate coefficient, C s was the
concentration of the growth species, a was an
empirical steric factor, S was the surface area of a
spherical particle and n was the number density of
particles of given size class. It assumed that the soot
particle could be represented as a sphere with
diameter that was based on its mass and the density
of bulk soot (taken as 1800kg m-a). Surface area of
the particle was multiplied by a factor, kVc~oot• , to
account for the number of surface radicals per unit
surface area. This factor was, in turn, derived from a
steady state assumption applied to reactions (61)-(64)
so that
k61 [H]
~/Csoot • =
k-61 [n2] + k62[n] + k63[C2H2] + k64[O2]
X ~ItCsoot_H (66)
The number of c i - a sites per unit area of soot
particle (kVCsoot_H) was estimated on the basis of
dimensions of PAH rings and distance between PAH
layers in soot to have a value of about 2.3 x 1019 to
2.9 x 1019 m -2.
Soot was oxidized due to the reaction of 02 with a
radical site
Ci • + 0 2 --* products (67)
and by the attack of OH on the soot surface
C i - H + OH ~ products (68)
The model employed the experimental results of Neoh
et al. 24 and hence used a reaction probability of OH
with soot of 0.13. The products of 02 and OH
reaction with soot were not given explicitly because
they did not play an important role in the chemistry
for the conditions that were studied. However, this
issue can be important in terms of the structure of the
flame as Kennedy et al)1o pointed out. The gas phase
products of soot oxidation in a heavily laden diffusion
flame may participate in the overall flame chemistry in
important ways. Our present understanding of the
details of OH reactions with soot is deficient.
Frenklach and Wang 1°7 compared their modeling
results with the measurements of Wieschnowsky et
al. 16 and Harris et al. 131 in premixed flames. The
irreversible coalescence of PAHs was enhanced by a
factor of 2.2, following the numerical results of Harris
and Kennedy ~1 for van der Waals forces between soot
particles. This may be an overestimate of the
collisional enhancement by dispersion forces because
the value of 2.2 was appropriate to small, like-sized
particles, not to the full panoply of collisional pairs.
Frenklach and Wang employed a value of a of 0.1 for
modeling Flame 1 of Wieschnowsky et a l ) 6 The
agreement with measurements of particle diameter
was good although predictions of the particle number
density were less satisfactory. The parameter, a , was
increased to 0.7 in order to achieve satisfactory
agreement with the measurements of Harris et a l l 3~
Several interesting conclusions were drawn from the
modeling efforts. Frenklach and Wang 1°7 were able to
reconcile the observations of Wieschnowsky et al. 16
with the measurements of Harris et al. ~4:5 Specifi-
cally, Wieschnowsky et al. 16 found that it was
possible to modify the growth of soot by inhibiting
coagulation through seeding flames with CsCI. They
concluded that the results of their experiments
indicated that soot growth was independent of
surface area. On the other hand, Harris et al. 14'15A31
claimed that soot growth rates were first order in
aerosol surface area. Furthermore, it should be noted
that under the conditions of the Wieschnowsky
experiment, the surface growth was dominated by
the addition of PAHs whereas growth in the
experiments of Harris et al. was predominantly due
to acetylene. The model of Frenklach and Wang 127
described soot surface reactions in terms of elemen-
tary reactions at active sites. The density of active sites
on soot particles was controlled by the gas phase
environment. For relatively low temperature flames,
such as those studied by Harris and co-workers, the
denominator of Eq. (66) was dominated by the term
k63 [C2H2] so that the surface growth rate due to
acetylene addition became
~g = 2Otff'Csoot_Hk61[H]Sn (69)
The rate of surface growth was then controlled by the
rate of H atom abstraction and was first order in
aerosol surface area. Frenklach and Wang 127 were
able to reproduce the experimental results of
Wieschnowsky et a l ) 6 in a higher temperature flame
in which growth rates were not a function of surface
area. Hence, the apparent contradiction was resolved
through a reasonable hypothesis that invoked a
mechanism of soot surface reactions in terms of
active sites.
Frenklach and Wang 127 gave attention to the
optical properties of the soot aerosol by using an
 Models of soot formation and oxidation 121

expansion of the Mie scattering coefficient and 2.2

rewriting it in terms of the soot aerosol moments, #
2.1'
and M, that were defined above. This approach O
allowed the authors to compare their predictions ._o 2. •
directly with measured scattering and extinction
coefficients. ~
,.-° 1.9-

Calculations were performed for the same condi- _e

tions as those used by Frenklach and W a n g ) °7 ._> 1.8.

Attention was focused on Flame 1 of Wieschnowsky 1.7:
e t al.; 16 it was a low pressure premixed flame of ~
t..)
•.~.

acetylene, oxygen and argon. By choosing a value of c~ :~ 1.6- "-

0 "
of 0.35, the authors were able to achieve impressive
1.5: •
agreement with the light scattering/extinction data. A
value ofc~ = 0.1 gave rise to discrepancies of an order 1.4 . ,, , . . . ,, . . , , , . , , . . , ,.,
of magnitude. It should be noted that the authors had 5.2 5.4 5.6 5.8 6 6.2 6.4
used a value of ~ of 0.1 in an earlier modeling effort t27 104/T ( K "1 )

for the same flame in which the optical data had been
interpreted in a simple fashion. The need to revise
the value of c~ highlighted the uncertainty in the
interpretation of optical data without an accurate
estimate of scattering and extinction cross sections.
An important test of a soot model for laminar
premixed flames is its ability to predict the critical
equivalence ratio, X¢, at which soot first appears.
Markatou e t al. 5 examined the laminar premixed
flames of Harris e t al. 40A32 who studied flames of
acetylene, ethylene and ethane. The temperatures of
the flames were controlled through the addition of N2.
The early flame chemistry was computed in two steps:
the Ci to C4 chemistry was calculated with 32 species
and 139 reactions for a free (non-burner stabilized)
flame. This yielded the temperature and the flow field.
The production of PAH up to coronene was then
calculated with a 'full' mechanism of 70 species and
337 reactions. Splitting the calculation in this manner
saved considerable computational time and yet it
yielded acceptable answers. The SANDIA burner
code 133 was used to perform the calculations.
The formation of the first aromatic ring was
described by reactions of acetylene with Ca species
n -- C4H 3 + C2H 2 ~ phenyl
n - C4H 5 + C2H2 ~ benzene + H
as well as the thermal route through
n - C4H 3 + C2H 2 ~ n - C6H 5 ~ phenyl
n - C4H 5 + C2H 2 ~ n - C6H 7 ~ benzene + H
The combination of propargyl (C3H 3 + C3H3) to
form benzene or phenyl was not included by
Markatou e t al. 5 because they calculated propargyl
mole fractions that were considered to be too low to
have an impact on the formation of benzene in their
flames.
The growth of PAH and soot particles followed the
route set out by Frenklach and Wang 127 with the
following notable exception: the steric factor that
was used by Frenklach and Wang 1°7 was not a
constant value in the calculations of Markatou e t aL 5
They assumed that the steric factor, a, exhibited a
Fig. 12. Critical equivalence ratios for N2 diluted flames.
Points are computed by Markatou et al. 5 Corresponding
lines are curve fits to tile experimental data of Harris
et al.4°'134(- - -) • C2H2, (--) • C2H4, (- . -) • C2H6.
temperature dependence
1t /12180 1]
= [tanh~- 7.19) + (70)
This function was obtained by fitting values of a at
two temperatures to values determined in an earlier
modeling effort j°7 and by noting that the hyperbolic
tangent function exhibited a physically reasonable
behavior in the limits of low and high temperatures.
In order to compare numerical results with experi-
ments, the authors computed luminous radiation
intensities with approximations to Mie theory. The
critical equivalence ratio was defined as the intercept
on the X axis by a tangent to the curve of luminous
radiation flux. The relationship to visual observations
of the onset of soot luminosity in experiments is
somewhat uncertain. The definition did provide,
however, a consistent manner in which to deal with
the numerical results.
A comparison of the predicted critical equivalence
ratios with a linear fit to the measurements of Harris
e t al. 4°A34 is shown in Fig. 12. The agreement is
remarkably good in view of the uncertainties in the
definition of critical equivalence ratio, both experi-
mental and computational, as well as the host of other
factors that are included in a complex model of soot
formation. Markatou e t al. 5 went on to use their
model of the premixed flames to investigate the
relative importance of nucleation, coagulation, sur-
face growth and oxidation in controlling the produc-
tion of soot in these flames. They concluded that the
formation of PAH and hence soot was controlled
largely by the relative abundance of acetylene and by
the thermal decomposition or growth of PAH species.
Oxidation of soot particles, p e r se, was not predicted
to be an important contributor to the overall response
of the soot process to equivalence ratio. The
major role for oxidation was ascribed to the early
chemistry of hydrocarbon oxidation and pyrolysis
122 I.M. Kennedy
that leads to the formation of the first aromatic
ring.
In a somewhat ambitious departure from modeling
simple laminar flames, Yoshihara et a l l 2s employed a
modified version of the soot model of Frenklach and
Wang ~27to calculate fuel oxidation, PAH growth and
soot formation in a natural gas-fueled, direct injection
diesel engine. The level of detail of the modeling was
significantly greater than previous attempts to model
soot formation in diesel engines. 43'57'63 The calcula-
tions were intended to match experimental conditions
for a single cylinder, naturally aspirated engine with a
compression ratio of 16 running at a speed of
1800 rpm.
A simple model of the turbulent mixing of fuel and
air within the engine cylinder was used. The contents
of the cylinder were divided into 197 computational
cells of equal mass, 190 cells of air and 7 of fuel. The
cells were allowed to mix and coalesce in the manner
described by Curl. 6° Two cells that underwent mixing
were replaced by two cells of a homogeneous mixture
determined by the state of the two cells that coalesced.
After mixing, the gases in the new cells reacted at a
finite rate according to a reduced chemical mechan-
ism. The collision frequency of cells was estimated by
fitting calculated heat release rates to measurements.
The model ignored entirely the complexities of the
fluid flow within the cylinder and apparently
considered the gases within the cylinder to constitute
an unmixed but macroscopically uniform distribution
of fuel and air. Hence, details of fuel spray dynamics
did not enter the calculation.
The chemical kinetics were treated in a logical
fashion by dividing the chemistry into three groups:
hydrocarbon oxidation kinetics, PAH growth and
soot formation and oxidation. The comprehensive
mechanism of Frenklach et alJ 22 for methane
oxidation was reduced systematically135 to 21 species
and 70 reactions. Reactions were added to account for
the reactions of O atoms with acetylene, dissociation
of propane, formation of C3Hx species and finally
formation of benzene via C3H3 + C3H3 --} benzene.
The more comprehensive PAH mechanisms of
Frenklach and co-workers 1°7'127 were subjected to a
reaction flux analysis to identify 12 key reactions that
formed PAHs up to pyrene. When steady state and
partial equilibrium assumptions were applied to this
reduced reaction set, an analytical expression for
pyrene concentrations was obtained in terms of
benzene concentrations. The results obtained with
this approximation were compared with a calculation
that used the complete reaction set for typical engine
conditions. The steady state/partial equilibrium
assumptions generally led to overpredicted pyrene
concentrations compared to the more complete
kinetics calculations. For example, the approximated
pyrene concentration was an order of magnitude
greater than the kinetically derived concentration at a
time of 0.2msec after initiation of reaction. PAH
growth was followed up to pyrene. It was deemed
unnecessary to consider larger PAHs in view of the
authors' observations that the size of the ultimate
PAH had a minor impact, less than a factor of two, on
predictions of soot concentrations. The soot model
itself followed closely the earlier work by Frenklach
and his co-workersJ °7'127 Growth of soot was
assumed to follow the H A C A model. The aerosol
dynamics were treated by the method of moments.
The only significant departure from the earlier models
was related to the model of OH oxidation of soot. A
temperature dependent rate of OH attack on soot was
developed to accommodate the experimental findings
of Puri et al. 23 The collision efficiency for OH with
soot (70~) was written as 12s
7oH = 0.42 [tanh ( - ~ - 2 . 8 ) + 1] (71)
It was found that 197 cells were sufficient to yield
statistically similar results. The only data point for
comparison with experiments consisted of a measure-
ment of soot mass fraction at the engine exhaust,
5 x 10-5. The model achieved a remarkably good
agreement with the measurement.
Some attention was given to the details of the OH
collision efficiency. The temperature dependent
efficiency shown in Eq. (71) was replaced with a
constant OH collision efficiency of 7oH = 0.13. The
soot mass fraction at the exhaust crank angle in this
case plummeted to about 10-7 , well below the
measured value. The validity of Eq. (71) is open to
question in light of the discovery by Puri e t al. 1°9 of an
error in their original estimation of the rate of 02
oxidation of soot and, hence, in their estimation of the
rate of OH attack. However, Kennedy et alJ l° also
found that it was necessary to include a temperature
dependence of the OH collision efficiency to match the
observed experimental data. The very good agree-
ment that Yoshihara et al.12s obtained with measured
exhaust soot levels must be considered rather
fortuitous in view of the uncertainty that surrounds
Eq. (71) and the rate of OH attack on soot.
Kazakov e t al. 136 returned to the issue of assigning
a value to the factor, a, in a study of soot formation in
high pressure, 10 bar, premixed ethene-air flamesJ 37
The equivalence ratio of the flames was adjusted in
the experiments to yield a range of temperatures from
1711 to 2017 K. The soot modeling of Frenklach and
Wang 1°7'127 was used for the high pressure flames.
Very good agreement with the experiments at 10 bar
was obtained by adjusting only one parameter,a. It
was argued that the mobility of the structural units of
soot would increase with temperature and hence a
would decrease with increasing temperature. This
hypothesis was tested by finding the value of a
that gave the best fit to experiments for a range of
conditions. The results in Fig. 13 appear to confirm
the physical reasoning. The functional form of a(T)
that was presented in Eq. (70) was revised by Kazakov
et al. 136 on the basis of the data shown in Fig. 13 to
 Models of soot formation and oxidation
0.7
0.6'
0.5.
0.4
• &
0.3-
0.2-
0.1-
0 fueled on liquid oxygen/hydrocarbon (LOX/HC).
1600 1¢00 ts'oo 19'00 20bo 2100
Maximum flame temperature (K)
Fig. 13. Fraction of radical sites available on soot surfaces,
a, as a function of the maximum flame temperature. From
Kazakov et aL 136 (m) ethene-air flameat 1 MPa, (O) ethene-
air flame at 101 kPa, (&) ethene-air flame at 12kPa. 127
read as
It is also worth noting that an obvious pressure
dependence does not. appear in Fig. 13. Unfortu-
nately, the model is very sensitive to the chosen value
of ~ and hence the validity of a p r i o r i calculations of
soot volume fractions for unmeasured conditions
must be called somewhat into doubt.
Frenklach 138 returned to the issue of reactivity of
soot and surface growth rate in a paper that
developed a detailed description of surface reac-
tions. A Monte Carlo simulation was run to simulate
the collisions of reactive gas species (H, HE and C2H2)
with a soot surface. A 13 step reaction scheme was
presented to represent the details of hydrogen
abstraction, C2H2 addition and cyclization that was
handled in a rudimentary manner by the original
HACA scheme [reactions (61)-(64)]. Of course, the
rate constants had to be estimated from analogous
gas phase PAH reactions with large uncertainties. In
some cases, reaction probabilities greater than unity
were obtained with this procedure. The Monte Carlo
simulation showed that surface growth rates
increased with temperature, even if reversibility of
reactions (62) and (63) were included. Hence,
Frenklach concluded that reversibility of the acety-
lene addition reaction and cyclization was not
important for soot particles and could not explain
the observed decay in soot reactivity. The growth of
PAH gaseous species was found to result in 'zig zag'
edges that were inconsistent with 'arm chair' sites that
were assumed in the HACA model. The apparent
inconsistency could be accommodated by the inclu-
sion of an additional graphitization step 6s'139 or by
assuming that five membered rings were formed that
participated in subsequent growth. There was no
direct physical evidence for the latter assumption
123
although it was argued that it was energetically
possible. The detailed growth modeling supported
earlier findings that growth, at least for the conditions
of the study, was proportional to the C2H2 concen-
tration. The use of Monte Carlo simulations of
surface growth was the most ambitious fundamental
modeling effort that has been applied to soot
processes. However, it is quite possible that rather
different conclusions may have been reached if some
adjustments to the rate constants were implemented.
A simplified version of Frenklach's early soot
modeling7 was used by Nickerson and Johnson 14° to
predict the formation of soot in a rocket gas generator
The problem was similar to the situation that
motivated Makel and Kennedyl°° to model a
laminar inverse diffusion flame. However, Nickerson
and Johnson attempted to predict the behavior of a
full scale rocket gas generator. The flow field in the
combustion chamber was calculated with a one-
dimensional code that is typical of the rocket
industry. Much greater detail was used to model the
fuel oxidation and the soot formation processes.
Jachiowski's mechanism 141 for propane oxidation
was used to deal with the fuel combustion.
The soot mechanism consisted of a series of
elementary steps that lead from acetylene and
hydrogen to the formation of an aromatic ring via
the production of C4 species. Growth of the aromatic
rings proceeded by acetylene addition and hydrogen
abstraction. The formation of a four ring compound
was taken to signify the onset of sooting. The details
of soot growth and oxidation were not considered,
although the latter effect was probably unimportant
under the very fuel rich conditions of a LOX/HC gas
generator. The predictions yielded qualitative agree-
ment with observations of the threshold equivalence
ratio for the onset of sooting. However, the experi-
mental data did not lend themselves easily to detailed
comparisons between predictions and computations
so that the results of the paper must be considered to
have limited use. They certainly did not afford a good
test of the soot model. More recent developments
from Frenklach's group 1°7'122 could be used to
supersede the early soot model that Nickerson and
Johnson used.
Mau8 e t al. 142 applied the soot model of Maul3
e t al. 143 (with a close relationship to the modeling
approach of Frenklach and co-workers 1°7) to a
laminar premixed flame with a particular interest in
the role of aerosol surface area and acetylene
concentration in controlling soot growth. Experi-
ments were conducted on a flat flame burner with
mixtures of Ar, 02 and C2H2 at low pressures from 9
to 18 kPa. The model used a 250 reaction mechanism
to calculate the aliphatic chemistry. The growth
reactions of benzene to small PAH were described
in the manner of Frenklach and Warnatz 144 although
the growth of PAH was assumed to be a fast
polymerization process. Consequently, the PAH were
124
assumed to be in a quasi-steady state and their
concentrations were found from algebraic expres-
sions. Comparisons of predicted quantities with the
experiments showed generally excellent agreement.
They concluded, in agreement with Frenklach and
Wang, 1°7 that the decrease in temperature, along with
the depletion of gaseous radicals and active sites on
the soot surface, could account for the observed
decrease in soot growth rate without resort to an
additional model of soot aging. The approach of
MauB et al.142"143 was applied to the prediction of the
reactivation of soot growth in the results reported by
Marquardt e t a / . 145 who measured the properties of
soot that was formed in 'back to back' premixed
counterflow flames of acetylene/oxygen/argon.
Colket and Hall developed a model of soot
formation and oxidation in a laminar, premixed
flame and applied it to the measurements of Harris
and Weiner 146 and Bockhorn et al. 106 The Sandia
burner c o d e 133 w a s used to calculate the flame structure.
The widely used aerosol program MAEROS 147 was
coupled to the output of the Sandia code to calculate
the growth, coagulation and oxidation of soot
particles. Pre-particle gas phase chemistry was
described with detailed kinetics. In the case of the
atmospheric ethylene flame of Harris and Weiner, 146
the mechanism of Harris et al.148 was used along with
an additional reaction to describe benzene formation
from the recombination of the propargyl radical viz.,
C3H 3 + C3H 3 *-* C6H 5 + H
A modified version of the mechanism of Miller and
Bowman 149 with propane reactions from Westbrook
and Dryer 15° was used to model the low pressure
flames of acetylene and propane of Bockhorn e t al.1°1
This scheme included the C3 chemistry [reaction (63)]
that was believed to be important to benzene
production.
Colket and Hall 3 followed a rather different
approach to that of Frenklach and co-workers with
regard to the issue of particle inception. They
considered that the calculation of the formation of
multi-ring compounds was fraught with considerable
uncertainty, as well as being quite expensive compu-
tationally. Furthermore, they correctly stated that the
choice of the so-called inception species was rather
arbitrary. In fact, the growth of PAH is a continuum
and the distinction between a soot particle and a large
molecule is uncertain. Hence, they defined the
inception species to have the same mass as a benzene
molecule and the inception rate to correspond to the
rate of production of benzene itself. It was obvious
that the nucleation flux must have been overestimated
to some extent by this assumption and the irreversible
kinetics of surface growth invoked too early in the
development of the soot.
Particle inception was followed by growth due to
acetylene addition and coalescence. Five surface
growth models were considered. The results of
Harris and Weiner (referred to as the Harris/Weiner
I.M. Kennedy
growth model 146) were used with an activation energy
of 1.33 x l0 s kJ kmo1-1 . Various modified versions of
the growth model of Frenklach and Wang 1°7 (referred
to as the Frenklach/Wang model) were also used. The
so-called 'modified Frenklach/Wang model' was
described in some detail by Colket and Hall; 3 they
included possible elimination of acetylene from the
soot radical. In addition, they separated the acetylene
addition process into a reversible formation of the
radical adduct and a cyclization process. In both
cases, the mass growth rate of soot was proportional
to the soot aerosol surface area. Predictions with the
five growth models were compared to the measured
specific surface growth rates, i.e. the rate of increase in
soot mass normalized by the soot aerosol surface
area. In general, the models underpredicted the
measured mass growth rates by factors of two or
three. It must be recalled, however, that the
measurements invoked assumptions in the interpreta-
tion of light scattering data that may have led to
errors in the estimation of the aerosol surface area
and hence in the specific growth rates. For example,
Dobbins et al. 32 estimated that the interpretation of
optical scattering measurements on the basis of
Rayleigh theory yielded surface areas that were two
to four times smaller than the areas found from a
more sophisticated analysis of aggregate scattering.
Larger surface areas would tend to shift the
experimental results for specific surface growth rates
to lower values and hence would improve the
(73) agreement with the predictions.
The apparent underestimation of the growth rates
was offset in the predictions of the soot volume
fractions by the use of benzene as the inception
species. This may have led to an artificially high
inception rate. Of perhaps greater concern than
absolute magnitudes of the specific growth rates was
the trend with time in the growth rate. None of the
growth models performed particularly well in this
regard. They did not reproduce the drop in growth
rates with time that the experimental data indicated.
This led Colket and Hall 3 to advocate the use of an
aging model in the belief that the drop in H atom
population did not provide an adequate account of
the decrease in apparent soot reactivity with time. It is
worth noting the contrast in this conclusion with the
conclusions drawn by MauB et al. 142 in a numerical
study of a premixed flame. They determined that the
change in the temperature and concentrations of
radicals accounted for the loss of soot reactivity
without the need for an aging model. The contra-
diction serves to highlight the uncertainty that continues
to surround fundamental aspects of soot modeling.
Soot oxidation was included in the model through
the use of the Nagle and Strickland-Constable
formula is for 0 2 attack and the use of a collision
efficiency of 0.13 for OH oxidation. 24 Oxidation was
not important in the Harris/Weiner flames but was
important in the flames that were studied by Bockhorn
et a l ) °l
 Models of soot formation and oxidation
Simulations of the Harris/Weiner flames were
carried out at C/O ratios of 0.8, 0.92 and 0.96.
Results were presented using the growth model
obtained from Harris and Weiner, 15'146 from Frenk-
lach and Wang 1°7 and with a modified version of the
growth model of Frenklach and Wang. In general, the
simulations overpredicted the measured soot volume
fractions close to the flame. The use of the Harris/
Weiner growth model and the modified Frenklach/
Wang model achieved reasonable predictions of the
trend in the ultimate soot volume fraction with
changes in the C/O ratio. On the other hand, the
unmodified Frenklach/Wang growth model did not
reproduce the correct variation in soot loading with
changes in C/O ratio. Colket and Hall 3 attributed
their lack of success with the Frenklach/Wang (FW)
model 1°7 to the observation that 'The F W model has
little or no dependence on acetylene pressure (under
the Harris and Weiner flame conditions), and cannot
therefore reproduce the relative stoichiometric depen-
dence with this inception model'. Colket and Hall
went on to argue that the relative failure of the
Frenklach/Wang growth model to account for the C/
O ratio effect could not be ascribed entirely to their
inception model. They believed that a growth model
with a greater sensitivity to acetylene partial pressures
was required; the impact of their inception model,
based on benzene, remains a contentious issue within
the soot modeling community. Furthermore, they
partly attributed their apparent lack of success with
this model, relative to the success achieved by
Frenklach and Wang, ~°7 to differences in the predic-
tions of benzene concentrations. A comparison of the
numerical predictions with the experimental data of
Bockhorn et al.l°l showed that the various versions of
the Frenklach/Wang growth models overpredicted
the soot volume fractions high above the burner by
about a factor of two. The predictions using the
Harris/Weiner growth model overpredicted the soot
volume fractions above the burner by about a factor
of 40. Coiket and Hall 3 attributed the failure of the
Harris/Weiner model to its extrapolation to the high
temperature conditions of the Bockhorn acetylene
flame with the same activation energy (1.33 x 105 kJ
kmol -~) that was obtained from lower temperature
measurements. They claimed that the use of a 'steric
factor' of 0.1 with the Harris/Weiner model yielded
very good results for the Bockhorn flame. However,
this was simply a curve fitting exercise with little
justification, although the same criticism could be
leveled at any model that invokes the use of an
empirical steric factor. The results of Colket and Hall 3
in the premixed flame served to point out the danger
in extrapolating an apparently successful model ( the
Harris/Weiner model for ethylene flames ) to other
conditions (such as the acetylene flames of Bockhorn
et al)°l).
Hall et al. 4 applied essentially the same model to the
calculation of soot formation in a counter flow
diffusion flame of methane and air. They included
125
full coupling of the soot formation with gas phase
chemistry and the temperature field with radiation.
The C1 and C2 chemistry was described by the
reaction set of Smooke et al. 15~ with an additional
19 reactions to account for the formation benzene.
The dominant reaction was the propargyl recombina-
tion [reaction (73)]. The governing equations for
momentum, energy and species were cast in a
similarity form and solved as a system of ordinary
differential equations. The energy equation included
the divergence of the radiation heat flux vector. With
the assumption of optical thinness, the radiation term
was written as
N N
dqR
- Cry T 5 + 41r ~ ~_, czijpilij (74)
-dfy i=I j=1
in which C was a parameter that depended on the
optical properties of the soot. Gas radiation was
calculated by the second term in Eq. (74) in which the
first summation in i was over all N species with
concentrations p; and the second summation in j was
over the active radiation bands of species i. Values of
C and the gas phase integrated band radiation
intensities were obtained from Grosshandler.152
The approach of Colket and Hall 3 to the issue of
particle inception was extended by Hall et al. 4 They
included reactions of benzene with acetylene and of
benzene with the phenyl radical to yield CloH7 • and
Cl4H10, respectively. The inception rate was taken to
be the sum of the rates of production of these species.
Although this approach appears to be more realistic
than assuming benzene to be the sole inception
species, the authors were nevertheless faced with the
necessity of increasing the inception rate by an
arbitrary factor of 8. Surface growth and oxidation
followed essentially the same routes as set out by
Colket and Hall. 3 MAEROS was used again to
calculate the development of the aerosol size
distribution.
The authors demonstrated the sensitivity of soot
formation and oxidation to energy loss and tempera-
ture reduction by radiation. They also showed the
potential importance of 'scrubbing' of gas phase
reactants by the soot aerosol, indicating the impor-
tant coupling between the aerosol phase and the gas
phase. The evaluation of different soot growth models
was of particular interest. Hall et al. presented a
comparison of the Harris/Weiner, the Frenklach/
Wang and the modified Frenklach models for the
counter flow flame. A comparison of the models with
the calculated oxidation rate is shown in Fig. 14.
It is apparent that the growth models yielded quite
different results. Hall et al. 4 pointed out that the two
Frenklach models did not yield any net growth rate;
the peak in the Frenklach/Wang model was close to
the flame itself where OH and 02 concentrations were
relatively high. The oxidation rate exceeded the
growth rates in this case. The Harris/Weiner growth
model succeeded in providing a positive net growth
126 I.M. Kennedy

4 5

-,= 2-
"o
E
~0-
0
"

i1 °
21
I.k
X -2" ID

•m . 4 . O

t/)
0
-8 I I I ' ' ' I ' ' ' t ' ' ' I ' ' ' I ' '

0 0.2 0.4 0.6 0.8 1 1.2 0 10 20 30 40 50 60

Normalized c o o r d i n a t e Axial Distance (ram)
Fig. 14. Calculated specific surface growth and oxidation Fig. 15. Predictions of soot volume fractions in a laminar
rates in a counter flow methane-air flame with three growth acetylene-N2 diffusion flame compared to the measurements of
models. (I-q) Harris/Weiner growth model, (O) Frenklach/ Gomez et al. TM (from Balthasar et a/.153~. (0) Measurements,TM
Wang growth model, (<>) modified Frenklach model, (x) (--) predictions.153
oxidation rate. The normalized coordinate in a direction
normal to the flame is 1 at the flame front and is 0 at the
stagnation plane. From Hall et al. 4 An equation for the mass fraction of soot in the
laminar diffusion flame was written as
because it was distributed over a wider region on the
fuel side of the flame. Given the inherent uncertainty
in the growth rates, a series of numerical experiments
--
o
=
o r ..drsl a[ lot]
0.54r/7 ~x~xj
were conducted that used growth rates enhanced by
powers of 2. The results showed that the sensitivity to + [~t (pJ~)] (75)
the inception rate decreased as growth rates increased,
providing some confirmation of the arguments and wherein the first term on the right hand side accounts
approach advocated by Kennedy e t aL 2 wherein for soot diffusion, the second accounts for thermo-
particle inception was ignored in a moderately phoresis and the final term is the net source term that
sooting ethylene diffusion flame. is derived from the flamelet library. Because the
The incorporation of detailed soot models into source term for soot volume fraction that appeared in
multi-dimensional flow codes, particularly with Eq. (75) required information about other moments
turbulence, is not feasible at present. However, of the aerosol size distribution, such as the aerosol
Balthasar e t al. 153 have attempted to incorporate surface area, the flamelet calculations required
elements of the detailed kinetics approach into a estimation of the rate of formation of at least two
simpler flamelet model for a laminar, acetylene air moments of the distribution, the first moment being
diffusion flame that was investigated experimentally the soot volume fraction itself. Fractional moments
by Gomez e t a l ) 54 The notion of flamelet modeling such as the soot aerosol surface area were found by
was retained, i.e. the thermochemical state could be interpolation. This may have introduced unknown
specified by the local mixture fraction and scalar errors into the procedure.
dissipation rate. Soot volume fractions are not well Predicted soot volume fractions were compared
correlated by these variables and hence it is necessary with measurements (Fig. 15). Although the measure-
to solve rate equations for the soot volume fraction. ments and predictions disagreed by as much as a
The flamelet method has been used for the gas phase factor of two low in the flame, a slight axial shift in the
thermochemistry by Moss and co-workers 77'78'sl who predicted profile would improve the agreement
developed rate equations for soot particle number significantly. It was possible that small errors in the
density and mass fraction. The parameters in these velocity field could contribute to such a shift.
equations included source and sink terms with Accurate predictions of soot volume fraction require
appropriate temperature dependence. The para- an accurate solution for the velocity, temperature and
meters were determined by comparison, or 'calibra- species fields, all of which are coupled through density
tion', against experiments. Hence, discussion of the and the impact of buoyancy forces. The approach
modeling of Moss e t al. was included under the that has been taken by Balthasar e t aL is3 suggests a
section devoted to semi-empirial methods. Balthasar potentially useful means for incorporating detailed
e t al. is3 departed from this approach by finding the kinetics of PAH and soot formation into a turbulent
source term for the soot mass fraction from a detailed flame calculation although the method cannot handle
calculation of soot formation and oxidation in a strongly sooting flames in which the presence of soot
counterflow diffusion flame. The detailed model can alter the flame chemistry and heat release profile.
followed the method of Frenklach and Wang TM and Soot can be a major sink for important species such as
its subsequent modificationsJ 4a OH and acetylene and it may generate significant
 Models of soot formation and oxidation 127

Table 3. Summary of modeling approaches

Reference Variables solved Fuel Chemistry model Application

Empirical models
Hudson and Concentration of -- -- Pyrolysis in isothermal
Heicklen49 carbon clusters flow reactor
Edelman and Molar soot Kerosene Arrhenius expressions Gas turbine engine
Harsha 46 concentration for soot formation
and oxidation
Khan et al. 4t Exhaust soot Diesel - - Diesel engine
concentration
Mehta and Das 43 ]Exhaust soot Diesel Diesel engine
concentration
Rizk and Smoke number/soot Aviation turbine Gas turbine engine
Mongia 47'48 mass concentration fuel

Semi-empirical models
Fairweather et al. 72 Soot mass fraction Natural gas Flamelet library based Turbulent diffusion
and particle number on detailed chemistry flame
density
Fairweather et al. 73 Soot mass fraction Propane Flamelet library based Turbulent diffusion
and particle number on detailed chemistry flame
density
Honnery and Soot mass fraction Ethane and ethylene Equilibrium for gas Laminar diffusion
Kent ~~6 phase; empirical flames
rates for soot
formation and
oxidation
Jensen 155 Concentrations of Isopropyl nitrate 12 step gas phase Rocket motor
15 sizes of carbon mechanism
clusters
Kennedy et al. 2 Soot volume fraction Ethylene-air Constrained Laminar ethylene/air
equilibrium (scalars diffusion flame (1 atm)
function of mixture
fraction and enthalpy-
radiation heat loss
included)
Kennedy et al. i10 Soot mass fraction Ethylene-air Short mechanism for Laminar ethylene/air
and particle number C1 and C2 chemistry diffusion flame (1 atm)
density
Kollmann et al. 75 Mean soot volume Ethylene-air Constrained Turbulent diffusion
fraction equilibrium (scalars flame (1 atm)
function of mixture
fraction and
enthalpy-radiation
heat loss included)
Kouremenos et al. 63 ]Massof soot with Diesel Equilibrium Diesel engine
model of
Hiroyasu 64
Kyriakides et al. 42 ]Nuclei and soot Diesel Direct injection diesel
particle number engines
densities (particle
mass assumed)
Leung et al. 76 Soot mass fraction C2H4/O2-N2 111 step C1-C3 Counterflow laminar
and number density hydrocarbon diffusion flame
mechanism
Makel and Soot volume fraction Ethylene-air Equilibrium Inverse laminar diffusion
Kennedy 1°° flame (air into fuel)
Moss et al. 77 Soot volume C2H4-O2-Ar Flamelet library Laminar diffusion flame
tYaetion and particle
number density
Said et al. ss Soot precursor mass Ethylene-air Single step fuel Laminar and turbulent
fraction; soot mass oxidation diffusion flame
fraction
Continued overleaf
128 I. M. Kennedy

Table 3 continued

Reference Variables solved Fuel Chemistry model Application

Syed et al. 7s Soot volume Methane/air Flamelet library Turbulent diffusion
fraction and particle flames
number density
Tesner et al. 52 Concentration of Acetylene/air Laminar diffusion flame
radical nuclei and
soot particles
Young and MOSS98 Soot particle number Ethylene-air Fiamelet library Turbulent ethylene
density and volume for density, diffusion flame (1 atm)
fraction temperature and
soot precursor
concentrations

Detailed models
Balthasar et a1.153 Soot volume fraction 32% acetylene- Flamelet model for Laminar diffusion flame
68% N2 in air thermoebemistry as
well as source terms
for soot volume
fraction
Colket and Hall 3 Species and soot C2H4-O2-Ar Detailed kinetics up Laminar, premixed
mass fractions (1 atm); C2H2 to benzene; various flames
(12 kPa); C3H8 soot growth models
(15 kPa)
Frenklach et al. 7 Soot yield 1.09% acetylene Detailed kinetics of Shock tube
-Ar acetylene pyrolysis;
PAH growth
Frenklach and Species mass C2H2-O2-Ar Detailed kinetics of Laminar, premixed
Wang 1°7 fractions; soot (12kPa); acetylene pyrolysis; flame
number, size and C2H4-O2-Ar PAH growth
volume fraction (101kPa)
Frenklach and Species mass CEH2-O2-Ar Detailed kinetics of Laminar, premixed
Wang 127 fractions; soot (12kPa) acetylene pyrolysis; flame
number, size and PAH growth
volume fraction
Hall et al. 4 Species and soot Methane-air 102 reactions for Laminar, counterflow
mass fractions aliphatic chemistry diffusion flames (1 atm)
and benzene
formation
Kazakov et al. 136 Species mass Ethylene-air Detailed gas phase Laminar, premixed
fractions; soot kinetics; Frenklach- flames (10 bar)
volume fractions Wang for PAH and
soot
Lindstedt s3 Soot mass fraction C2H4-O2-N2; 292 step kinetics Laminar counterflow
and particle number methane-air and co-flow flames
density
Markatou et aL s Mole fractions of Ethane, ethylene Detailed kinetics for Laminar, premixed
gas phase species and acetylene-air aliphatics and PAH flames (1 atm)
and soot; critical
equivalence ratio
MauB eta/. 143 Gas phase mass Acetylene-air-O2 Detailed gas phase Laminar, premixed
fractions; moments kinetics; modified flame; post flame soot
of soot aerosol Frenklach-Wang directed against
distribution; soot PAH growth and counterflow of pure
volume fraction soot growth oxygen (1 atm)
MauB et al. j42 Gas phase mass C2H2-O2-Ar Detailed gas phase Laminar, premixed
fractions; moments kinetics; modified flames at pressures of 9-
of soot aerosol Frenklach-Wang 18kPa
distribution; soot PAH growth and
volume fraction soot growth
Yoshihara et al.12s Exhaust soot mass 88% CH4-6% Reduced mechanism Direct injection diesel
fraction C2H6-6% C3Hs for fuel/air reaction; engine
Frenklach and Wang
for soot
 Models of soot formation and oxidation
amounts of CO or other species as it is oxidized. The
zone of heat release in the flame may be altered.
Important interactions of soot with the flame
structure are not handled at present by the flamelet
approach.
4. CONCLUDINGREMARKS
Modeling of complex phenomena such as chemi-
cally reacting flows or turbulence requires approx-
imations that can be formulated at varying degrees of
sophistication. For example, turbulence can be
modeled very simply with a mixing length approach,
with somewhat more difficulty by a k-e model or
higher order closure, with a Large Eddy Simulation or
finally, with a Direct Numerical Simulation. The
complexity of the flow, and the Reynolds number to
which these methods can be applied successfully, is
limited by current computational power. However, in
the case of Direct Numerical Simulations, the accuracy of
the solution is not compromised by uncertainties in the
underlying Navier-Stokes equations.
Modeling of soot formation in flames bears some
similarities to turbulence modeling in that a hierarchy
of methods may be applied. A summary of the extant
methods is provided in Table 3. The simplest
approach is that taken by engineers in the engine
community who adopt empirical correlations of soot
production as a function of engine operating condi-
tions. As with all correlations, the method is only
useful as an extrapolation for conditions close to
those under which the original data were first
obtained. Somewhat more sophisticated numerical
methods solve rate equations for the formation of
soot nuclei, soot particle growth and oxidation with
simple models for these processes that are derived
from experiments. Again, this approach can only be
used for conditions under which the original nuclea-
tion, growth and oxidation results were obtained or
calibrated. Recent years have seen a surge of interest
in attacking soot modeling with very detailed
descriptions of the soot physics and chemistry. An
analogy might be drawn in this case with the
application of Direct Numerical Simulations in
turbulence modeling. However, much greater reliance
can be placed in the Navier-Stokes equations of fluid
flow than in the detailed chemical schemes that are
used to describe soot formation because very few
elementary rate constants have been measured.
It is remarkable that all the methods that have been
reviewed in this survey have demonstrated the
potential for accurate predictions of soot formation
over a wide range of conditions. A healthy skepticism
is, of course, in order. All the results were compared
to measurements after some adjustment of para-
meters, whether it be an activation energy of soot
surface growth or a steric parameter or some other
less obvious modeling variable. To some extent, our
models of soot have been adjusted to fit the data.
129
Nonetheless, advances have been made in our
understanding of the underlying chemical and
physical processes of soot formation. Modeling has
been useful in determining the areas in which we are
currently still uncertain. More information is required
about some fundamental aspects of soot processes
such as the low temperature oxidation of soot by
oxygen in post flame regions, the potential necessity
of including another step for graphitization of liquid
soot precursors, the details of OH oxidation of soot,
the inclusion of the results of fractal analysis for soot
particle morphology, accurate modeling of radiative
heat loss in order to capture flame temperatures
correctly, etc. At present, semi-empirical models of
soot formation are useful design tools for a restricted
range of combustion conditions; detailed models of
soot formation hold out the prospect of predicting
soot formation over an unrestricted range of fuels,
temperatures and pressures. The challenge will be to
reduce them to a scope that can be handled by codes
that treat turbulent reacting flow.
In the course of reviewing the soot models that were
available, it became clear that in most cases authors
had chosen to consider unique experimental condi-
tions that differed from others in the literature. In
many cases, models were calibrated with and
compared against measurements by the authors
themselves. All the models contained either implicit
or explicit parameters that could be adjusted to
enhance agreement with experiments. Good agree-
ment with experimental data was achieved in almost
all cases after some adjustment. Hence, it was very
difficult to evaluate the inherent superiority of any
particular approach. It is apparent that it may be
worthwhile to emulate the turbulent reacting flow
community in attempting to develop a set of
universally acceptable experimental data sets.
Models could then be required to predict a subset of
these data or the full range over a variety of flame
types, fuels and pressures, depending on their claim to
generality. Only then would it be possible to evaluate
and compare the efficacy of models.
Acknowledgements--The input of Dr M. Colket of UTRC to
this paper is gratefully acknowledged. Conversations with
Dr D. Honnery of Monash University, Australia during the
early stages of planning the paper were also most helpful.
The support of the NIEHS Superfund Basic Research
program P42ES04699 for some of the author's research
into particulate formation in flames is appreciated.
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