Computers and Mathematics with Applications 65 (2013) 1625–1632

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Computers and Mathematics with Applications

journal homepage: www.elsevier.com/locate/camwa

Simplifying the complexity of diffusion flames through

interpretation in C/O ratio space
Fei Xia, Richard L. Axelbaum ∗
Washington University in St. Louis, St. Louis, MO 63130, United States

article info abstract

Keywords: Understanding the structure of diffusion flames is often complicated by the dependence of
C/O ratio
flame structure on the boundary conditions, e.g. composition, temperature and flow field
Diffusion flame
(e.g., strain rate in a counterflow flame.) In this paper, the local carbon-to-oxygen atom
Stoichiometric mixture fraction
Soot inception ratio (C/O ratio) is applied as a variable to interpret the flame and soot zone structures of
counterflow diffusion flames from numerical results with detailed chemical kinetics and
transport. Radical pool and soot precursor zones are shown to be clearly delineated in C/O
ratio space. The boundary of these two zones, as well as the flame location, are shown to be
independent of both stoichiometric mixture fraction (Zst ) and strain rate when interpreted
in C/O space. The kinetic ratio is used to study the characteristics of key chemical reactions
and to identify regions of equilibrium for these reactions. The results of this paper indicate
that the C/O ratio is a valuable variable for interpreting flame structure and soot precursor
chemistry for diffusion flames.
© 2013 Elsevier Ltd. All rights reserved.

1. Introduction and review

Most practical combustion processes involve diffusion flames, where the fuel and oxidizer are initially separate (non-
premixed) and the reactions take place in a thin reaction zone where the fuel and oxidizer mix in nearly stoichiometric
proportions [1]. Diffusion flames have been studied extensively in physical space and mixture fraction space. The structure
of a diffusion flame for a given fuel is dependent on the system geometry and boundary conditions. Studying diffusion
flames in physical space has practical value, but the complex coupling between fluid flow, heat transfer, mass transfer and
chemical reactions in flames makes it difficult to obtain a fundamental understanding of the effects of parametric changes
to the boundary conditions. This can at least partially be addressed by interpreting flame structure in mixture fraction space.
Mixture fraction is the local mass fraction of the mass originated from the fuel stream and can be expressed as
YH −YH ,ox YC −YC ,ox YO,ox −YO
nWH
+ mWC
+ (m+n/4)WO
Z = YH ,fu −YH ,ox YC ,fu −YC ,ox Y ,ox −YO,fu
(1)
nWH
+ mWC
+ (mO+ n/4)WO

where Yi and Wi represent the mass fraction and molecular weight of species i, and m and n respectively refer to number
of carbon and hydrogen atoms, in the fuel Cm Hn [2,3]. As such, mixture fraction is an indication of the extent of mixing
locally [1]. Interpreting flame structure in mixture fraction space can largely eliminate system geometry dependences and
can facilitate physical interpretations of flame structure [4], as well as illustrate the dependence of flame characteristics on
compositions [1].

∗ Corresponding author. Tel.: +1 314 935 7560.

E-mail address: axelbaum@wustl.edu (R.L. Axelbaum).

0898-1221/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
doi:10.1016/j.camwa.2013.01.008
1626 F. Xia, R.L. Axelbaum / Computers and Mathematics with Applications 65 (2013) 1625–1632

In diffusion flames, the flame sheet resides in the vicinity of the stoichiometric mixture fraction, where Z = Zst , and Zst
is given by

Zst = (1 + YF ,0 WO υO /YO,0 WF υF )−1 (2)

where YF ,0 and YO,0 refer to fuel and oxidizer mass fractions at the inlet boundaries, WF and WO represent species
molecular weight, and υF and υO are the fuel and oxygen stoichiometric coefficients, respectively. Changes to the boundary
compositions will affect the value of Zst , but the flame sheet will always reside in the vicinity of Z = Zst . Nonetheless, the
flame structure in mixture fraction space is dependent on boundary composition for a given fuel. In other words, varying the
fuel or oxygen mass fractions at the boundaries will vary the flame structure in Z space. Thus, interpreting flame structure,
and the effects of boundary composition on flame structure, is complicated in Z space. While Z space has general utility
in the field of chemical engineering, it is not necessarily the most appropriate variable for interpreting flame structure.
Alternatively, we have proposed expressing flame structure in terms of carbon-to-oxygen atom ratio (C/O ratio) space [5,6].
The definition of Z includes inerts, while that of C/O ratio does not. The benefit of this approach is that while the C/O ratio
includes the benefits of Z space in terms of describing the state of mixedness, and thereby eliminating system geometry
dependences, it also is intrinsically defined from a flame perspective. In other words, since the essential aspects of a flame
are the fuel, as represented by C atoms, and the oxidizer, as represented by O atoms, the C/O ratio is a direct measure of the
state of mixing of the fuel and oxidizer and is not dependent on the concentrations of the fuel and oxidizer in describing the
mixedness of the reactants.
As a means of demonstrating the utility of C/O ratio space, radical production zone and the zone of soot precursor
formation will be evaluated when Zst is varied. The reason for using Zst as a parameter is that it characterizes flame structure
in that varying Zst leads to a change in the relationship between local temperature and local species profiles, which in
turn affects processes like soot inception [7]. It has been previously demonstrated that increasing Zst can inhibit and even
eliminate soot formation in non-premixed systems even if the adiabatic flame temperature is held constant [8–12]. Soot
formation and its relationship to flame structure have been the subject of many investigations and much progress has been
made [13–16]. However, soot inception in diffusion flames is still not completely understood. In this paper, the soot inception
zone is studied in C/O ratio space.

2. Numerical model

A sketch of the counterflow diffusion flame burner is shown in Fig. 1. The counterflow flame was modeled with the
OPPDIF flame code assuming plug flow at the boundaries [17]. Thermodynamic and transport properties for the gas-phase
species were obtained from the Chemkin software package [18]. The code calculates temperature, species concentration
and velocity profiles in the flame along the burner axis. The boundary conditions applied are summarized in Table 1, where
XF ,0 and XO,0 refer to fuel and oxidizer mole fraction at the inlet boundaries, T0 the inlet boundary temperature for both
streams, VF ,0 and VO,0 the inlet velocity at the fuel and oxidizer boundaries, respectively. When changing Zst the adiabatic
flame temperature was maintained at the value for pure fuel burning in air by ensuring that the amount of inert at the flame
was constant. This was accomplished by changing the amount of inert in the boundaries in a predetermined manner, as
described in [19]. The separation distance between nozzles was 2 cm and the inlet boundary velocity was held at 15 cm/s
for all runs except those where the effect of strain rate was being analyzed. A total of 143 species and 938 reactions are
included in the mechanism, which combines the Appel et al. [20] and USC Mech Version II [21] mechanisms with chemistry
up to pyrene from Wang and Frenklach [22].

3. Results and discussion

3.1. Interpret flame structure in C/O ratio space

Using the results from the numerical calculations, flame structure is shown in physical space, mixture fraction space
and C/O ratio space in Figs. 2–4 respectively. In these figures Zst is varied from 0.064 (that of fuel/air) to as high as 0.75 for
C2 H4 flames. Presenting diffusion flames in physical space is straightforward, but the interpretation is challenging because
the flame location and flame structure are radically altered by Zst . In mixture fraction space, the flame location occurs at
Z = Zst . However, as shown in Fig. 3, when plotting results in Z space it is still difficult to interpret the effects of Zst on
flame structure, much as it is in physical space. The shift and variation of maximum flame temperature can be explained as
indicated in Ref. [23].
In Fig. 4, results are plotted in C/O ratio space. The C/O ratio applied here is obtained from
 
C/O = x∗ χCi x Hy Oz z ∗ χCi x Hy Oz (3)
i i

where χCi x Hy Oz is the mole fraction of the ith species calculated from OPPDIF. For diffusion flames, the oxidizer boundary
corresponds to a C/O ratio of zero, while the fuel boundary corresponds to a C/O ratio of infinity. Since most of the important
aspects of the flame occur at small values of C/O ratio (less than 1), the data are plotted in the range of 0–4 in C/O ratio space.
 F. Xia, R.L. Axelbaum / Computers and Mathematics with Applications 65 (2013) 1625–1632 1627

Fig. 1. Schematic of counterflow diffusion flame burner.

Table 1
Boundary conditions for the flames of C2 H4 and C3 H8 .
Inlet temperature was 300 K and the exit velocity was
15 cm/s for both nozzles except where noted.
Fuel Zst XF ,0 XO,0 Tad [K]

0.064 1.0 0.21

0.2 0.32 0.25
C2 H 4 0.4 0.16 0.33 2370
0.6 0.106 0.512
0.75 0.085 0.858
0.06 1.0 0.21
0.2 0.215 0.248
C3 H 8 0.4 0.101 0.335 2267
0.6 0.066 0.514
0.75 0.053 0.861

As shown in Fig. 4, regardless of the extent to which the fuel and oxidizer compositions are varied, the C/O ratio at the flame
sheet location is always at (C/O)st , where,

(C/O)st = m/(2m + n/2) (4)

for a hydrocarbon fuel with the molecular formula Cm Hn . This is anticipated since the flame resides at (or very near) the
location of stoichiometry and the C/O ratio at stoichiometry is not a function of boundary composition. Another important
advantage of C/O space is that the zone of interest, the reaction zone, is expanded and is always in the same region. Clearly
this is not the case when the variable is the physical dimension or mixture fraction.
To appreciate the utility of C/O space, fuel pyrolysis will be described for varying Zst . To understand how this change
affects pyrolysis it is necessary to know how the local temperatures as well as the local concentrations of major species
vary. First considering the fuel side of the flame, Fig. 4 clearly shows that, as Zst increases, the temperature on the fuel side
decreases and, beyond a C/O ratio of 1.25, the fuel concentration also decreases. Thus, by plotting the results in C/O ratio
space we are able to readily show that the increase in Zst , caused by moving the diluent from the oxidizer to the fuel, leads to
a change in temperature and fuel concentration, both of which decrease the rate of pyrolysis. Referring back to Figs. 2 and 3,
we see that while it may be possible to extract the same information from these plots, it is far more ambiguous.
More details demonstrating the advantages of interpreting flame structure in C/O ratio space are shown in Fig. 5. It can
be observed from Fig. 5 that there are two separated zones easily identified in the region near the flame, namely the radical
pool zone and the soot precursor zone. Also, the edge of the soot precursor zone is coincident with the location of depletion
of radicals. The demarcation of these two zones is located at around C/O = 0.47 for all five flames of C2 H4 . It is also seen
in Fig. 5 that, for a given fuel, the contours of temperature, and the mole fractions of O2 radicals and precursors (C6 H5 and
C6 H6 ) have similar features regardless of Zst . For example, the location where certain critical radicals, such as OH and O, and
1628 F. Xia, R.L. Axelbaum / Computers and Mathematics with Applications 65 (2013) 1625–1632

Fig. 2. Temperature, fuel and oxygen mole fraction profiles in physical space for Zst of 0.064, 0.4, and 0.75 for ethylene (C2 H4 ) flames.

Fig. 3. Temperature, fuel and oxygen mole fraction profiles in mixture fraction space for Zst of 0.064, 0.4, and 0.75 for ethylene (C2 H4 ) flames.

Fig. 4. Temperature, fuel and oxygen mole fraction profiles in C/O ratio space for Zst of 0.064, 0.4, and 0.75 for ethylene (C2 H4 ) flames.

intermediate species, such as C2 H2 are depleted (their ‘‘depletion points’’) is independent of Zst in C/O ratio space. The onset
of soot precursors is located at a C/O ratio of approximately 0.47 for all of the C2 H4 flames.
The above results suggest that, unlike physical and mixture fraction space, the C/O ratio is a valuable variable that filters
out complexity and clearly depicts the flame structure even when boundary concentrations are varied.

3.2. The effects of strain rate on flame structure and soot inception in C/O ratio space

Increasing the jet velocities in counterflow flames leads to larger strain rates, which in turn reduces residence time [24].
The effects of strain rate on the soot precursor zone can be clearly discerned in C/O ratio space, as shown in Figs. 6 and 7,
 F. Xia, R.L. Axelbaum / Computers and Mathematics with Applications 65 (2013) 1625–1632 1629

Fig. 5. Temperature, radical and soot precursor mole fraction profiles in C/O ratio space for Zst of 0.064, 0.4, and 0.75 for ethylene (C2 H4 ) flames.

Fig. 6. Ethylene flames — temperature, O2 , critical radical and precursor mole fraction profiles in C/O ratio space for Zst = 0.064 with inlet velocities of
15 cm/s for fuel and oxidizer streams and global strain rate of 15/s (solid line); fuel 100 cm/s and oxidizer 15 cm/s and global strain rate of 57/s (dot-dashed
line); 100 cm/s for fuel and oxidizer streams and global strain rate of 100/s (dashed line); 150 cm/s for fuel and oxidizer streams and global strain rate of
150/s (dotted line).

Fig. 7. Propane flames – temperature, O2 , critical radical and precursor mole fraction profiles in C/O ratio space for Zst = 0.06 with inlet velocities of
15 cm/s for fuel and oxidizer streams and global strain rate of 16.7/s (solid line); fuel 60 cm/s and oxidizer 30 cm/s and global strain rate of 52/s (dot-
dashed line); 50 cm/s for fuel and oxidizer streams and global strain rate of 56/s (dashed line); 80 cm/s for fuel and oxidizer streams and global strain rate
of 90/s (dotted line).
1630 F. Xia, R.L. Axelbaum / Computers and Mathematics with Applications 65 (2013) 1625–1632

where the fuel and oxidizer inlet velocities have been varied. Note that the location of the stagnation planes for these cases
differs significantly in physical space. Numerical results shown in C/O ratio space in Figs. 6 and 7 demonstrate the similarity
in structure, i.e., radicals O and OH are depleted at the same location and the onset of soot precursors (C6 H5 and C6 H6 )
resides at approximately C/O = 0.47 for C2 H4 and 0.37 for C3 H8 . It is also seen that soot precursor concentrations decrease
with increasing strain rate, as has been demonstrated previously [25,26]. Therefore, the strain rate does not qualitatively
influence the flame and soot zone structures in C/O ratio space. Nonetheless, it does change the quantitative characteristics,
i.e., the magnitudes of precursors in C/O ratio space and this in turn affects soot formation.

3.3. Kinetic study of key chemical reactions

Recognizing the clearly defined flame structure in C/O ratio space with respect to the radical pool, it is instructive to
evaluate if equilibrium exists for any of the key radical reactions in this region. Reactions (R1)–(R4) below are considered
because they represent key radical reactions — the first two being key branching reactions and the last two being key heat
release reactions in the near flame region.

O + H2 ↔ H + OH (R1)
H + O2 ↔ OH + O (R2)
OH + H2 ↔ H2 O + H (R3)
OH + CO ↔ CO2 + H. (R4)

To evaluate the extent of equilibrium, the ‘‘kinetic ratio’’, given by

Qi
Λi = (5)
Keq,i

is studied, where Λi is the kinetic ratio for the ith chemical reaction, Qi is the reaction quotient, i.e. the characteristic of
c d
chemical reaction a A + b B = c C + d D, which is written as follows Q = [[CA]]a [[DB]]b , and Keq,i is the equilibrium constant for
the ith chemical reaction. Qi and Keq,i can be calculated using the results from OPPDIF.
From Figs. 8 and 9, the kinetic ratios follow the same pattern in C/O ratio space for low and high Zst (Figs. 8 and 9,
respectively). Recall that conditions are such that the adiabatic flame temperature is the same in both figures. In the
region near (C/O)st , (i.e., the location of the flame sheet, which in this case is C/O = 1/3) the kinetic ratio is close to
or equal to unity. In other words, these reactions can be approximated as being in equilibrium in this region. The mole
fractions of O2 and O are also plotted in the figure to indicate that the domain in the vicinity of equilibrium is followed
by the depletion of oxygen. Both reactions (R3) and (R4) are close to equilibrium in certain regions of C/O ratio space.
Therefore, the corresponding global reaction generated by the reverse (R3) reaction together with the forward (R4) reaction,
i.e. CO+H2 O → CO2 +H2 (the water–gas shift reaction) is also in the vicinity of equilibrium. The ratio Λ3 /Λ4 gives the kinetic
ratio of the water–gas-shift reaction and it is interesting to note from Fig. 10 that the water–gas-shift reaction is nearly in
equilibrium from 0.2 < C/O < 0.6, which is the region of most of the important reactions in the flame. This approximate
equilibration of water–gas shift reaction at high-temperature reaction zone was also confirmed experimentally in
Refs. [27,28].

Fig. 8. Kinetic ratio for reactions from (R1) to (R4) for C2 H4 with Zst of 0.064.
 F. Xia, R.L. Axelbaum / Computers and Mathematics with Applications 65 (2013) 1625–1632 1631

Fig. 9. Kinetic ratio for reactions from (R1) to (R4) for C2 H4 with Zst of 0.6.

Fig. 10. Kinetic ratio for water–gas-shift reaction for C2 H4 with Zst of 0.064, 0.3 and 0.6.

4. Conclusions

The carbon to oxygen atom ratio, the C/O ratio, was applied as a variable to better understand flame structure and
soot inception chemistry using numerical results from OPPDIF. The complex coupling between species and temperature in
diffusion flames often makes it difficult to understand how flame structure is affected by a change in boundary conditions.
Without an unambiguous interpretation of flame structure it is often difficult to discern how the local chemistry is affected
by the boundary conditions. We have shown that the C/O ratio, which is effectively a mixture fraction that is specifically
scaled to diffusion flames, is the appropriate scale to interpret flame structure. Critical zone boundaries, like the flame
location, radical depletion boundary and precursor formation boundary, are shown to be independent of stoichiometric
mixture fraction (i.e., changes in boundary concentrations), and strain rate. The method of ‘‘kinetic ratio’’ was used to study
the equilibrium behavior of certain important chemical reactions in the near flame zone and regions of equilibrium for key
radical reactions were identified. Overall, the C/O ratio is a quantity of powerful value to the study of flame structure and
soot formation.

Acknowledgments

This work was supported by NASA and the Consortium for Clean Coal Utilization. The authors are indebted to Drs. Gregory
Yablonsky, Peter Sunderland, Beei-Huan Chao, Vivien Lecoustre and Benjamin Kumfer for many helpful discussions.

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