Variation of Equivalence Ratio and Element Ratios With

Distance From Burner in Premixed One-Dimensional Flames

CHRISTOPHER J. POPE,** RICHARD A. SHANDROSS,*** and
JACK B. HOWARD*
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

Differential diffusion effects in a low-pressure premixed, laminar, one-dimensional benzene/oxygen/argon

flame are shown to lead to changes in the elemental mass fractions. The effect is caused by unequal diffusion
of reactants away from the burner and products towards the burner. Analysis of data previously collected from
this flame shows the local equivalence ratio to vary by as much as 25% from its inlet value, with similar
variations found for the atomic C/O ratio (up to 25%) and atomic C/H ratio (up to 10%). Variations of
comparable magnitude are predicted by detailed kinetic modeling of the same flame using a published
mechanism. The variations predicted for a similar flame but at atmospheric pressure are slightly smaller than
those at low-pressure, which is consistent with the constitutive equations. Similar effects would be expected for
any flame in which the mass average flame velocity is comparable to the diffusion velocities of the major flame
species. The results have implications for consideration of molecular-weight growth and soot formation in such
systems, since these processes are strongly dependent upon the C/O and equivalence ratios. © 1998 by The
Combustion Institute

NOMENCLATURE Mk molecular weight of species k

Mk,m weight of element m in species k
A area expansion ratio
p pressure
Am number of moles of atoms of element
R ideal gas constant
m per mole of gas
t time
Bk mass flux fraction of species k due to
T temperature
diffusion
v mass average velocity
Bk,m mass flux fraction of element m in
Vk diffusion velocity of species k
species k due to diffusion
Wm atomic weight of element m
Ball,m mass flux fraction of element m in all
xk mole fraction of species k
species due to diffusion
Yk mass fraction of species k
Dk1,k2 binary diffusion coefficient for species
Yk,m mass fraction of element m in species
k 1 and k 2
k
Dk,mix mixture diffusion coefficient of
Yall,m mass fraction of element m in all
species k
species
Fk molar flux of species k
z distance from burner
G mass flux fraction
Gk mass flux fraction of species k
Greek symbols
Gk,m mass flux fraction of element m in
species k ak,m number of atoms of element m per
Gall,m mass flux fraction of element m in all molecule of species k
species f equivalence ratio
K total number of species r mass density 5 M # p/RT
m inlet mass flux rate 5 r 0 n 0 5 rn A
#
M mean molecular weight of gas Subscripts
0 cold gas
*Corresponding author. E-mail: jbhoward@mit.edu k species index
**Present address: Laboratoire G.R.E., Université de
Haute-Alsace, 68200 Mulhouse, France. m element index
***Present address: Arthur D. Little, Inc., Acorn Park, all sum over all species
Cambridge, MA 02140.

COMBUSTION AND FLAME 116:605– 614 (1999)

© 1998 by The Combustion Institute 0010-2180/99/$–see front matter
Published by Elsevier Science Inc. PII S0010-2180(98)00062-5
606
INTRODUCTION
In diffusion flames, the elemental composition
is customarily described in terms of a spatially
varying equivalence ratio [1] or mixture fraction
[2], since the flame environment varies between
the extremes of pure fuel and pure oxidant.
Concentrations of most species in diffusion
flames (except products of molecular-weight
growth such as aromatics and soot) have been
found to correlate directly with the local equiv-
alence ratio [2– 6]. Furthermore, in the flame
zone of diffusion flames, fuel and oxidant dif-
fuse in opposite directions; if these diffusion
rates are not equal, usually due to differing
diffusion coefficients, the element ratios vary
across the reaction zone in different ways. The
effects of this so-called “differential diffusion”
on the element ratios have been seen by Bilger
[2] from analysis of the data of Tsuji and
Yamaoka [7], and by Moss and Roberts [8] from
analysis of the data of Melvin et al. [9].
In premixed flames, it has been assumed that
the equivalence ratio and elemental composi-
tion are spatially invariant [10, 11]. Although
knowledge of the importance of multicompo-
nent diffusion in premixed flames is widespread,
C/H and C/O ratios are invariably given as
single numbers, rather than ranges, in the liter-
ature. Even in soot formation, where elemental
composition receives much attention because of
its critical importance, the C/O ratio has been
assumed to have one single value in premixed
flames [12]. The present work shows that for
one-dimensional premixed laminar flames, con-
siderable variation of elemental composition
with respect to distance from the burner occurs
as the result of axial diffusion of major flame
species. Element ratios and the local equiva-
lence ratio are calculated using species concen-
tration profiles from (1) data from a low-pres-
sure laminar premixed benzene-oxygen-argon
flame [13, 14] and subsequent analysis of the
data [15], (2) model results obtained for the
same flame using a recent detailed kinetic
mechanism [16], and (3) model results for an
atmospheric-pressure flame similar to the low-
pressure flame considered.
While the variation in the local element ratios
and equivalence ratio is calculated from species
concentrations, it is caused by molecular diffu-
sion. For a truly one-dimensional system, i.e., no
C. J. POPE ET AL.
radial transport, the relevant processes occur-
ring are chemical reaction and axial convection
and diffusion. If diffusion did not occur, each
section of fluid volume could be described as a
closed system, i.e., as a batch reactor or a
segregated section of a plug flow reactor. Chem-
ical reactions do not transform elements, so
reactions within a closed fluid volume do not
change the elemental composition. Convection
in an ideal one-dimensional system would have
no radial gradients in axial velocity and would
merely translate fluid without affecting its com-
position. Therefore, it is only through diffusion
that variations in the elemental composition can
occur.
The one-dimensional flame equations [17]
are used below to show how diffusion leads to
changes in the mass fractions of the individual
elements (C, H, O, and Ar). Species diffusion
velocities are used in determining which flame
species contribute to the variation in equiva-
lence and element ratios, and the extent to
which pressure affects the variation of element
ratios is discussed.
EXPERIMENTAL DATA AND
COMPUTATIONS
The experimental data are from a near-sooting
benzene/oxygen/30% argon laminar flat flame
at a pressure of 20 Torr (2.67 kPa) [13, 14]. The
cold gas velocity and temperature are 50 cm/sec
and 298 K. The inlet equivalence ratio, defined
as the fuel/oxidant ratio in the cold gas divided
by the fuel/oxidant ratio required for stoichio-
metric conversion to CO2 and H2O, is 1.8. The
inlet atomic C/H ratio is unity and the inlet C/O
ratio is 0.72.
The modeling software used was the Sandia
flame code [18] with the CHEMKIN-II subrou-
tine package [19] and transport properties pro-
gram [20]. The detailed kinetic mechanism of
Zhang and McKinnon [16], which had been
tested on the same flame and found to repro-
duce successfully most of the major species, was
used without modification for all the simula-
tions performed in the present work. The exper-
imental temperature profile [13, 14] and area
expansion ratio [13] were used as input for the
simulation. Treatment of diffusion in the mod-
eling included the full calculation of multicom-
EQUIVALENCE RATIO IN PREMIXED 1-D FLAMES 607

ponent diffusion coefficients [21] and thermal x kM k,m

diffusion factors for H atom and H2. A second Y k,m 5 # , (2)
M
simulation was performed for a 1 atm flame
with the same cold gas composition and velocity where M k,m is the contribution of element m to
as the 20 Torr case, with the following modifi- the molecular weight of species k,
cations in the input parameters: (1) the inlet
M k,m 5 a k,mW m; (3)
mass flux, m, was increased 38-fold to compen-
sate for a 38-fold increase in pressure and (2) then Eq. 1 may be rewritten as
the temperature profile was spatially com-
#
Y all,mM
pressed by a factor of 38 and the experimental Am 5 (4)
profile was extrapolated in the post-flame zone. Wm
Both modifications are consistent with the as- with Y all,m (the total mass fraction of element
sumption that the reaction rates are linearly
m) defined as
proportional to pressure, which is reasonable if
bimolecular reactions predominate.
Diffusion velocities for mass flux fraction
Y all,m 5 OY
k
k,m. (5)

calculations using model results were obtained

via the FBR flat flame analysis program [22],
which uses subroutines from the Sandia
PREMIX flame code [18]. Dixon-Lewis mul-
ticomponent diffusion coefficients [21] and
thermal diffusivity were incorporated in these
calculations as well.
Experimental fluxes were calculated [13, 15]
from the measured mole fractions using the
one-dimensional flame equations described be-
low. The mole fractions were smoothed and
differentiated numerically [23]. Mixture diffu-
sion coefficients, computed by Wilke mixing
[24], were used. The main difference between
the calculated fluxes used in the present work
and those from the original calculation of Bitt-
ner [13] is the inclusion here of all 54 individual
species profiles measured, as well as profiles for
compounds heavier than 200 amu [15].
Therefore, the element ratios can be written as
A m1 Y all,m1W m2
5 . (6)
A m2 Y all,m2W m1
Equation 6 is useful for analyzing the source of
deviations from inlet conditions.
For the flames considered in the present
work, the only elements present are carbon,
hydrogen, oxygen, and argon: m 5 {C, H, O,
Ar}. Profiles of the atomic C/O ratio (5 A C/
A O) and C/H ratio (5 A C/A H) (Figs. 1 and 2,
respectively) show considerable variation, with
the largest perturbations appearing in the reac-
tion zone of the flame. For the purposes of
comparison with the 20 Torr data and modeling,
the results for the 1 atm modeling are expanded
by a factor of 38 in z (distance from burner).
The local equivalence ratio (f), as defined by
Mitchell et al. [1], can be expressed as

ELEMENT RATIOS AND LOCAL AH Y all,C Y all,H

2*A C 1 2* 1
EQUIVALENCE RATIOS 2 WC 2W H
f5 5 . (7)
AO Y all,O
The set of species mole fraction profiles and the WO
chemical composition of the species, as de-
scribed by ak,m, are needed for the analysis of Calculated values of f are shown in Fig. 3. The
equivalence and element ratios. The number of calculation of f from the data is identical to that
moles of atoms of element m per mole of gas is performed previously [25].
given by The above analysis shows the modeling re-
sults to be qualitatively consistent with the data

Oa
K
analysis, with the model predicting an even
Am 5 k,m x k. (1) greater perturbation in the C/H ratio and the
k51
local equivalence ratio. Results for the 1 atm
If the mass fraction of element m from species k modeling case are similar to those at 20 Torr,
is defined as with the peak heights being diminished slightly
608 C. J. POPE ET AL.

Fig. 1. Calculated atomic C/O ratio vs. distance from burn- Fig. 3. Calculated local equivalence ratio vs. distance from
er: thick line, data; diamonds, 20 Torr modeling; triangles, 1 burner: thick line, data; diamonds, 20 Torr modeling; trian-
atm modeling; dashed line, inlet value. (For this and all gles, 1 atm modeling; dashed line, inlet value.
subsequent figures, the results for the 1 atm modeling are
expanded by a factor of 38 in distance from burner for determine the source of variation in elemental
comparison with the 20 Torr results. Also, the data for all composition. Recall that the molar flux of spe-
figures are the original profiles drawn by Bittner [13, 14],
which have been treated by numerical smoothing [15, 23].)
cies k is defined by
xk p
Fk 5 @v 1 V k#A (8)
and the effect being slightly broadened (when RT
plotted using the expanded scale). Reasons for and the mass flux fraction of species k is
the differences between the 20 Torr and 1 atm
modeling results are discussed below. M kF k
Gk 5 . (9)
r 0v0
SOURCE OF VARIATION: FLUX ANALYSIS Equation 9 is equivalent to

One-Dimensional Flame Equations and

Variation in Yall,m
Gk 5
x kM k x kM k V k
M# 1 M # v F G
. (10)

The terms on the right-hand side of this equa-

The one-dimensional flame equations of Fris-
trom and Westenberg [17] were analyzed to
tion are the convective and diffusive contribu-
tions, respectively. In terms of the species mass
fractions, the convective and diffusive contribu-
tions to G k are Y k and Y k(V k/v).
Analysis of the equivalence and element ra-
tios also requires study of the mass flux fractions
of the elements. The portion of the total mass
flux fraction of element m arising from species k
is

G k,m 5
x kM k,m x kM k,m V k
M# 1
M# v F G
. (11)

Using Eq. 2 this can be written as

G k,m 5 Y k,m 1 Y k,m F G

Vk
v
. (12)
Fig. 2. Calculated atomic C/H ratio vs. distance from burn-
er: thick line, data; diamonds, 20 Torr modeling; triangles, 1 Conservation of mass requires that the total
atm modeling. (Inlet value 5 1.) mass flux remain constant:
EQUIVALENCE RATIO IN PREMIXED 1-D FLAMES
G5 O G 5 O Y 1 O Y vV 5 1.
k
k
k
k
k
k k
Since the individual atoms retain their identi-
ties, element conservation requires that the
total mass flux fraction of element m (G all,m)
also remain constant:
G all,m 5 OG k,m 5 OY k,m
k k
O Y vV
k,m k
1 5 constant.
k likely, because the mean molecular weight, be-
Since ¥ Y k 5 1, Eq. 13 shows that ¥ (Y kV k/v) is
constrained to be zero throughout the flame. In
the elemental balance, the only constraint which
applies to the diffusive contribution to G all,m,
¥ Y k,mV k/v (5 Ball,m), is that it approach zero as
z 3 `, however there is no reason to assume
that B all,m will be equal to zero in the reaction
and early post-flame zones (see below). There-
fore, ¥ Y k,m, which is equal to Y all,m, need not
remain constant to satisfy element conservation.
As mentioned above, diffusion is the driving
force of elemental composition variations. Vari-
ations in Y all,m due to B all,m Þ 0 are the source
of the changes in the local equivalence ratios
and element ratios (cf. Eqs. 6 and 7).
Variation of Measured and Computed
Element Mass Fractions
Variations of total element mass fractions,
Y all,m, with distance from the burner are shown
for carbon, hydrogen, oxygen, and argon in Fig.
4a– d, respectively. The variations are clearly
significant in comparison with the accuracy with
which the species mass balances are being com-
puted, i.e., four significant figures. Again, the
results from the modeling are comparable to
those obtained from the data, with the excep-
tion of the Ar mass fraction. Since the experi-
mental argon mole fraction is computed by
difference [13], it is affected by the errors in the
concentrations of all other flame species. The
data close to the burner surface ( z , ;0.3 cm)
are also more prone to experimental uncer-
tainty due to probe-burner interactions and flow
nonidealities. However, the variations in ele-
ment and equivalence ratios persist well beyond
0.3 cm, and there is sufficient agreement be-
609
(13)
tween the modeling results and the data analysis
to reinforce the assertion that the variations in
mass fractions are real.
One might expect that since argon is inert its
mass fraction would remain constant, but Fig.
4d shows that assumption to be incorrect. Given
the requirement that G all,Ar is constant, the only
way Y Ar can remain constant is for V Ar/v to
equal 0, which implies that V Ar 5 0. For this to
be true, x Ar must be a constant. However, if x Ar
# must also be
and Y Ar are both constant, M
(14) constant, since Y Ar 5 x Ar M Ar /M # . This is un-
ing the ratio of the total mass to the total
number of moles, can only remain constant if
the number of moles remains constant. In such
a case, the flow would either be non-reacting or
one in which the sum of all chemical reactions,
at all points in the flame, produces no net mole
change. Such systems might exist, but since
flames are driven by free-radical chain branch-
ing reactions, M# can be expected to vary widely.
Even when the stoichiometry of the overall
reaction implies no net mole change, for exam-
ple, Cx Hy 1 [ x 1 ( y/4)] O2 5 x CO2 1 y/ 2
H2O, with y 5 4, there would still be a net
change of moles in the reaction zone. There-
fore, even the mass fraction of an inert species
can change in a flame environment, due to
diffusion which arises when chemical reactions
cause a change in the total number of moles.
Element Flux Fractions and Species
Contributions
The normalized element flux fraction due to
diffusion, B all,m/G all,m, is a measure of the mag-
nitude and direction of the effect of diffusion on
equivalence and element ratio variations. Un-
fortunately, experimental G all,m values vary
from their inlet value by as much as 30% [13],
primarily because they involve differentiation of
measured data gathered in regions of high
gradients. Model calculations do not suffer from
this type of error, though there are small devi-
ations in the individual element fluxes due to
numerical errors. For the 20 torr modeling,
G all,m deviates by less than ;2% for z , 1 cm,
and by no more than 3.4% for z , 2 cm; for the
1 atm modeling, the maximum deviation in
G all,m is 5%. Therefore, B all,m/G all,m,0 from
610
Fig. 4. Mass fraction Y all,m vs. distance from burner—thick line, data; diamonds, 20 Torr modeling; triangles, 1 atm modeling;
dashed line, inlet value: (a) carbon, (b) hydrogen, (c) oxygen, and (d) argon.
modeling results are accurate enough to reveal
important trends.
The normalized diffusive flux fractions for 20
torr modeling results are shown in Fig. 5. The
normalized flux fraction is negative for carbon
and hydrogen, indicating a net flux due to
diffusion towards the burner for these elements,
while there is a net flux due to diffusion of both
oxygen and argon away from the burner. An
intuitive explanation can be found in the fact
that the fuel benzene is heavier than any of the
major carbon-containing products (CO, CO2,
and C2H2) and would diffuse more slowly away
from the burner than the products would diffuse
toward the burner, due to the differences in
diffusion coefficients. This would lead to a net
diffusive flux toward the burner, which would
require a larger convective flux—implying a
larger mass fraction of carbon—to conserve
total carbon flux. To quantify the above asser-
tions, Figure 6 shows the normalized diffusive
C. J. POPE ET AL.
element flux contributions (B k,m/G all,m,0) for
carbon-containing species. (Acetylene’s behav-
ior is explained by the fact that it is an interme-
diate species, reaching its maximum mole frac-
tion at z 5 0.9 cm, so it diffuses both towards
and away from the burner.)
A similar argument holds for hydrogen-con-
taining species: benzene would diffuse much
more slowly away from the burner than the
major hydrogen-containing products (H2O,
C2H2, H2, and H) would diffuse upstream.
Figure 7 shows the normalized element flux
fraction contributions from diffusion for hydro-
gen-containing species. From Fig. 5, the magni-
tude of the normalized diffusive oxygen flux is
considerably less than those of carbon and
hydrogen, but it still indicates the net effect of
O2 diffusing away from the burner faster than
CO, H2O, and CO2 are diffusing toward the
burner (Fig. 8).
The species contributing most to the diffusive
EQUIVALENCE RATIO IN PREMIXED 1-D FLAMES 611

Fig. 5. Normalized element flux fraction due to diffusion

Fig. 6. Normalized diffusive element flux fraction contribu-
(B all,m/G all,m,0) vs. distance from burner for the 20 Torr
tions (B k,m/G all,m,0) with m 5 carbon vs. distance from
modeling results: squares, carbon; diamonds, hydrogen;
burner for the 20 Torr modeling results: squares, C6H6;
triangles, oxygen; inverted triangles, argon.
diamonds, CO; triangles, C2H2; inverted triangles, CO2;
thick line, sum of all other species.
flux are those with the largest mole fractions.
All the species for which individual curves are
element ratios, can be seen by a detailed con-
drawn in Figs. 6 – 8 have peak mole fractions
sideration of the terms Y k,m and B k,m. As noted
greater than 0.01, except H atom, which has a
by Fristrom and Westenberg [17], in a flame
peak mole fraction of only 0.007 but has a large
dominated by bimolecular reactions the solu-
diffusion velocity. The reactants (C6H6 and O2)
tion of the flame equations is invariant with
and the major stable products (CO, CO2, H2O,
respect to pressure so long as mass flow rate
H2, and C2H2) contribute most strongly to the
scales linearly with pressure and distance from
variation of element ratios; the only intermedi-
the burner scales inversely with pressure. That
ates playing a significant role are C2H2 (also a
is, for a given cold gas velocity and composition,
product) and H, with the C2H2 diffusion veloc-
nearly identical sets of mole fraction and tem-
ity going from negative to positive within the
perature profiles are seen at all pressures where
reaction zone. Figures 6 – 8 show a concrete
bimolecular reactions predominate, except that
situation in which the diffusive fluxes for a given
the profiles are relatively compressed or ex-
element do not cancel each other: although
panded. Because all the x k would vary similarly
species containing carbon, hydrogen, and/or ox-
with pressure and their magnitudes would re-
ygen are diffusing in both directions, there is a
main unchanged, the mean molecular weight
net diffusive flux of these elements (B all,m Þ 0)
should behave similarly. Therefore, Eqs. 11 and
because of the differences in diffusion coeffi-
14 show that the pressure dependence of the
cients and mole fraction gradients, leading to
magnitude of B all,m/G all,m, which governs varia-
variations in the Y all,m.
tions in element and equivalence ratios, would
depend upon the pressure dependence of the
PRESSURE DEPENDENCE OF ratio V k/v. Since v 5 r0v0/rA, keeping the mass
EQUIVALENCE AND ELEMENT RATIO flow rate (5 r 0 v0) proportional to the pressure
VARIATIONS means that the factor p 0 /p implicit in this equa-
tion becomes p/p, and the velocity profile
The effect of pressure on the magnitude of the should also expand (or contract) with the dis-
diffusive flux, and thus the equivalence and tance-from-burner scale.
612
Fig. 7. Normalized diffusive element flux fraction contribu-
tions (B k,m/G all,m,0) with m 5 hydrogen vs. distance from
burner for the 20 Torr modeling results: squares, C6H6;
diamonds, H2O; triangles, C2H2; inverted triangles, H2;
circles, H; thick line, sum of all other species.
Next, consider the diffusion velocity V k( z).
Whether the diffusion coefficients (D k,mix) are
calculated by Wilke mixing [24], as in the data
flux analysis, or by the more rigorous method of
Dixon-Lewis [21], which was used in the mod-
eling and the FBR flat flame analysis program
[22], the diffusion velocity is of the form
d@ln x k~ z!#
V k~ z! 5 D k,mix~ z! . (15)
dz
In both cases D k,mix is calculated from the set of
mole fractions and the binary diffusion coeffi-
cients. The mole fraction profiles, as argued
above, would retain the same relative shapes,
but the z-scale and the D k,mix both scale as p 21 ,
so the diffusion velocities should also be invari-
ant. Therefore, the ratio V k/v, and consequently
the variation in equivalence and element ratios,
should be unaffected by pressure.
According to the modeling results, the varia-
tion of element ratios is slightly less at atmo-
spheric pressure than at 20 Torr. The difference
may be due to the failure of the variation of the
chemical composition (i.e., the rate of reaction)
to scale as suggested above. A global measure of
C. J. POPE ET AL.
Fig. 8. Normalized diffusive element flux fraction contribu-
tions (B k,m/G all,m,0) with m 5 oxygen vs. distance from
burner for the 20 Torr modeling results: squares, O2;
diamonds, CO; triangles, H2O; inverted triangles, CO2;
thick line, sum of all other species.
the extent of reaction is the mean molecular
weight M # . From Fig. 9, the slower decrease in M
#
for the 1 atm case indicates a relatively slower
overall rate of reaction. Examination of the
individual species profiles supports this notion.
Figures 10 and 11 show the mass fractions of O2
and CO, respectively, as examples of the slower
consumption of the initial reactants and slower
production of the major products. A likely rea-
son for the slower-than-expected rate of
progress is the importance of termolecular rad-
ical recombination reactions, whose depen-
dence on pressure is one power higher than
bimolecular reactions. For example, the pre-
dicted peak mole fraction of H atom at 1 atm is
only 31% of that predicted for 20 Torr. With a
decreased radical pool, all the flame reactions
would slow down. Therefore, the proposed scal-
ing of chemical composition is not quite correct,
explaining the slightly decreased variation of
element ratios for the 1 atm modeling results.
Note that the lack of an experimental tempera-
ture profile for the 1-atm case introduces some
uncertainty in any comparison of the modeling
results for the two cases.
EQUIVALENCE RATIO IN PREMIXED 1-D FLAMES
Fig. 9. Mean molecular weight (M # ) vs. distance from
burner: thick line, data; diamonds, 20 Torr modeling; trian-
gles, 1 atm modeling; dashed line, inlet value.
CONCLUSIONS AND DISCUSSION
The elemental composition of laminar pre-
mixed flat flames can vary widely (up to ;25%)
due to axial diffusion of the initial reactants, the
major products, and key intermediates such as
H and C2H2. While diffusion is occurring in
both directions in such a way as to conserve
both the total mass flux and the total element
fluxes, the net flux fractions due to diffusion for
the individual elements can be nonzero, leading
to changes in the elemental mass fractions and
thus variations in the elemental ratios and the
local equivalence ratio. The key parameter de-
termining the magnitude of the effect of diffu-
sion on the elemental composition is the V k/v
factor multiplying the Y k,m. Therefore, for
Fig. 10. O2 mass fraction vs. distance from burner: thick
line, data; diamonds, 20 Torr modeling; triangles, 1 atm
modeling.
613
Fig. 11. CO mass fraction vs. distance from burner: thick
line, data; diamonds, 20 Torr modeling; triangles, 1 atm
modeling.
flames in which the diffusion velocities of the
flame species are of comparable magnitude to
or greater than the flame velocity, similar effects
can be expected. While the variation of element
ratios was first noticed [25] by analyzing data
from a low-pressure flame, modeling results and
scaling arguments show that similar behavior is
expected to occur in atmospheric-pressure flat
flames.
These results are not only of theoretical in-
terest but are also pertinent to flame chemistry,
for example, in molecular weight growth leading
to the formation of polycyclic aromatic hydro-
carbons (PAH) and soot, since the equivalence
ratio is a key parameter in characterizing a
flame’s tendency to form soot. In the 20 Torr
benzene flame considered here, the C/O ratio
and N are noticeably above their inlet values for
z up to ;1.0 cm, which is also the region where
the observed PAH (up to 202 amu) are formed
and destroyed [13, 14]. The increased C/O ratio
in the reaction zone could be contributing to the
formation of PAH or key intermediates in mo-
lecular weight growth chemistry. As an example
of the strong effect of the equivalence ratio on
molecular-weight growth processes, Bittner [13,
14] found that by varying the inlet equivalence
ratio from 1.8 to 2.0 the flame went from
non-sooting to sooting, and the concentration of
compounds heavier than 700 amu increased
roughly 100-fold.
There is no simple way to determine, a priori,
the direction of the variation of the element
ratios in a given flame. Conceivably, there are
614
flames in which the observed trends for one or
more of the elements is the opposite of that
seen in the present work. While the total flux of
a given element remains constant, the magni-
tude and direction of the total diffusive flux of
an element is a composite of the diffusive fluxes
of all the species containing that element. What
the present work has demonstrated is that, in
the general case, such a diffusive flux is not zero
throughout the flame. Therefore, it is not safe to
assume that the element ratios in a laminar flat
flame remain the same as their inlet values.
While it has long been known [2, 8] that
differential diffusion leads to unequal variation
of element ratios in diffusion flames, the results
of the present work provide additional insights
on the interpretation of diffusion flame data. In
the analysis of Bilger [2] the carbon mass frac-
tion (as expressed by the mixture fraction)
exhibited no apparent changes as might be
caused by differential diffusion. Given the
present finding that the mass fractions of all the
elements in the flame studied were found to
vary, we conjecture that the behavior of the
carbon mass fraction in Bilger’s study is specific
to the flame considered [7]. Accordingly, any
generalization that the carbon mass fraction in
diffusion flames is somehow unaffected by dif-
ferential diffusion may deserve reconsideration
in light of the present work.
We are grateful to the Division of Chemical
Sciences, Office of Basic Energy Sciences, Office
of Energy Research, U.S. Department of Energy,
for financial support under grant number DE-
FG02-84ER13282; and to the National Energy
Research Supercomputer Center for CPU time.
The authors would also like to thank Prof. J. T.
McKinnon and H.-Y. Zhang of the Colorado
School of Mines for providing us with copies of
their kinetic mechanism and associated thermo-
chemical and transport parameters.
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Received August 18, 1997; revised March 31, 1998; accepted
April 15, 1998