Академический Документы
Профессиональный Документы
Культура Документы
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
G k,m 5
x kM k,m x kM k,m V k
M# 1
M# v F G
. (11)
G5 O G 5 O Y 1 O Y vV 5 1.
k
k
k
k
k
k k
(13)
tween the modeling results and the data analysis
to reinforce the assertion that the variations in
mass fractions are real.
Since the individual atoms retain their identi- One might expect that since argon is inert its
ties, element conservation requires that the mass fraction would remain constant, but Fig.
total mass flux fraction of element m (G all,m) 4d shows that assumption to be incorrect. Given
also remain constant: the requirement that G all,Ar is constant, the only
Variations of total element mass fractions, Element Flux Fractions and Species
Y all,m, with distance from the burner are shown Contributions
for carbon, hydrogen, oxygen, and argon in Fig.
4a– d, respectively. The variations are clearly The normalized element flux fraction due to
significant in comparison with the accuracy with diffusion, B all,m/G all,m, is a measure of the mag-
which the species mass balances are being com- nitude and direction of the effect of diffusion on
puted, i.e., four significant figures. Again, the equivalence and element ratio variations. Un-
results from the modeling are comparable to fortunately, experimental G all,m values vary
those obtained from the data, with the excep- from their inlet value by as much as 30% [13],
tion of the Ar mass fraction. Since the experi- primarily because they involve differentiation of
mental argon mole fraction is computed by measured data gathered in regions of high
difference [13], it is affected by the errors in the gradients. Model calculations do not suffer from
concentrations of all other flame species. The this type of error, though there are small devi-
data close to the burner surface ( z , ;0.3 cm) ations in the individual element fluxes due to
are also more prone to experimental uncer- numerical errors. For the 20 torr modeling,
tainty due to probe-burner interactions and flow G all,m deviates by less than ;2% for z , 1 cm,
nonidealities. However, the variations in ele- and by no more than 3.4% for z , 2 cm; for the
ment and equivalence ratios persist well beyond 1 atm modeling, the maximum deviation in
0.3 cm, and there is sufficient agreement be- G all,m is 5%. Therefore, B all,m/G all,m,0 from
610 C. J. POPE ET AL.
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 element flux contributions (B k,m/G all,m,0) for
important trends. carbon-containing species. (Acetylene’s behav-
The normalized diffusive flux fractions for 20 ior is explained by the fact that it is an interme-
torr modeling results are shown in Fig. 5. The diate species, reaching its maximum mole frac-
normalized flux fraction is negative for carbon tion at z 5 0.9 cm, so it diffuses both towards
and hydrogen, indicating a net flux due to and away from the burner.)
diffusion towards the burner for these elements, A similar argument holds for hydrogen-con-
while there is a net flux due to diffusion of both taining species: benzene would diffuse much
oxygen and argon away from the burner. An more slowly away from the burner than the
intuitive explanation can be found in the fact major hydrogen-containing products (H2O,
that the fuel benzene is heavier than any of the C2H2, H2, and H) would diffuse upstream.
major carbon-containing products (CO, CO2, Figure 7 shows the normalized element flux
and C2H2) and would diffuse more slowly away fraction contributions from diffusion for hydro-
from the burner than the products would diffuse gen-containing species. From Fig. 5, the magni-
toward the burner, due to the differences in tude of the normalized diffusive oxygen flux is
diffusion coefficients. This would lead to a net considerably less than those of carbon and
diffusive flux toward the burner, which would hydrogen, but it still indicates the net effect of
require a larger convective flux—implying a O2 diffusing away from the burner faster than
larger mass fraction of carbon—to conserve CO, H2O, and CO2 are diffusing toward the
total carbon flux. To quantify the above asser- burner (Fig. 8).
tions, Figure 6 shows the normalized diffusive The species contributing most to the diffusive
EQUIVALENCE RATIO IN PREMIXED 1-D FLAMES 611
Fig. 7. Normalized diffusive element flux fraction contribu- Fig. 8. Normalized diffusive element flux fraction contribu-
tions (B k,m/G all,m,0) with m 5 hydrogen vs. distance from tions (B k,m/G all,m,0) with m 5 oxygen vs. distance from
burner for the 20 Torr modeling results: squares, C6H6; burner for the 20 Torr modeling results: squares, O2;
diamonds, H2O; triangles, C2H2; inverted triangles, H2; diamonds, CO; triangles, H2O; inverted triangles, CO2;
circles, H; thick line, sum of all other species. thick line, sum of all other species.
Next, consider the diffusion velocity V k( z). the extent of reaction is the mean molecular
Whether the diffusion coefficients (D k,mix) are weight M # . From Fig. 9, the slower decrease in M
#
calculated by Wilke mixing [24], as in the data for the 1 atm case indicates a relatively slower
flux analysis, or by the more rigorous method of overall rate of reaction. Examination of the
Dixon-Lewis [21], which was used in the mod- individual species profiles supports this notion.
eling and the FBR flat flame analysis program Figures 10 and 11 show the mass fractions of O2
[22], the diffusion velocity is of the form and CO, respectively, as examples of the slower
consumption of the initial reactants and slower
d@ln x k~ z!#
V k~ z! 5 D k,mix~ z! . (15) production of the major products. A likely rea-
dz son for the slower-than-expected rate of
In both cases D k,mix is calculated from the set of progress is the importance of termolecular rad-
mole fractions and the binary diffusion coeffi- ical recombination reactions, whose depen-
cients. The mole fraction profiles, as argued dence on pressure is one power higher than
above, would retain the same relative shapes, bimolecular reactions. For example, the pre-
but the z-scale and the D k,mix both scale as p 21 , dicted peak mole fraction of H atom at 1 atm is
so the diffusion velocities should also be invari- only 31% of that predicted for 20 Torr. With a
ant. Therefore, the ratio V k/v, and consequently decreased radical pool, all the flame reactions
the variation in equivalence and element ratios, would slow down. Therefore, the proposed scal-
should be unaffected by pressure. ing of chemical composition is not quite correct,
According to the modeling results, the varia- explaining the slightly decreased variation of
tion of element ratios is slightly less at atmo- element ratios for the 1 atm modeling results.
spheric pressure than at 20 Torr. The difference Note that the lack of an experimental tempera-
may be due to the failure of the variation of the ture profile for the 1-atm case introduces some
chemical composition (i.e., the rate of reaction) uncertainty in any comparison of the modeling
to scale as suggested above. A global measure of results for the two cases.
EQUIVALENCE RATIO IN PREMIXED 1-D FLAMES 613
flames in which the observed trends for one or 4. Mitchell, R. E., Sarofim, A. F., and Clomburg, L. A.,
more of the elements is the opposite of that Combust. Flame 37:227–244 (1980).
5. Smyth, K. C., Miller, J. H., Dorfman, R. C., Mallard,
seen in the present work. While the total flux of W. G., and Santoro, R. J., Combust. Flame 62:157–181
a given element remains constant, the magni- (1985).
tude and direction of the total diffusive flux of 6. Sivathanu, Y. R., and Faeth, G. M., Combust. Flame
an element is a composite of the diffusive fluxes 82:211–230 (1990).
of all the species containing that element. What 7. Tsuji, H., and Yamaoka, I., Thirteenth Symposium
(International) on Combustion, The Combustion Insti-
the present work has demonstrated is that, in tute, Pittsburgh, 1971, pp. 723–731.
the general case, such a diffusive flux is not zero 8. Moss, J. B., and Roberts, P. T., Combust. Flame
throughout the flame. Therefore, it is not safe to 34:335–338 (1979).
assume that the element ratios in a laminar flat 9. Melvin, A., Moss, J. B., and Clarke, J. F., Combust. Sci.
flame remain the same as their inlet values. Technol. 4:17–30 (1971).
10. Gaydon, A. G., and Wolfhard, H. G., Flames: Their
While it has long been known [2, 8] that structure, radiation and temperature (4th Ed.), Chap-
differential diffusion leads to unequal variation man and Hall, London, 1979, p. 39.
of element ratios in diffusion flames, the results 11. Liñán, A., and Williams, F. A., Fundamental Aspects of
of the present work provide additional insights Combustion, Oxford University Press, New York, 1993,
on the interpretation of diffusion flame data. In p. 62.
12. Wagner, H. Gg., in Soot Formation in Combustion,
the analysis of Bilger [2] the carbon mass frac-
Bockhorn, H., Ed., Springer-Verlag, 1994, p. 163.
tion (as expressed by the mixture fraction) 13. Bittner, J. D., Sc.D. thesis, Massachusetts Institute of
exhibited no apparent changes as might be Technology, 1981.
caused by differential diffusion. Given the 14. Bittner, J. D., and Howard, J. B., Eighteenth Sympo-
present finding that the mass fractions of all the sium (International) on Combustion, The Combustion
Institute, Pittsburgh, 1981, pp. 1105–1116.
elements in the flame studied were found to
15. Pope, C. J., M. S. thesis, Massachusetts Institute of
vary, we conjecture that the behavior of the Technology, Cambridge, MA, 1988.
carbon mass fraction in Bilger’s study is specific 16. Zhang, H.-Y., and McKinnon, J. T., Combust. Sci.
to the flame considered [7]. Accordingly, any Tech. 107:261–300 (1995).
generalization that the carbon mass fraction in 17. Fristrom, R. M., and Westenberg, A. A., Flame Struc-
ture, McGraw-Hill, New York, 1965.
diffusion flames is somehow unaffected by dif-
18. Kee, R. J., Grcar, J. F., Smooke, M. D., and Miller,
ferential diffusion may deserve reconsideration J. A., A Fortran Program for Modeling Steady Laminar
in light of the present work. One-Dimensional Premixed Flames, Sandia National
Laboratories Report No. SAND85-8240, 1985.
We are grateful to the Division of Chemical 19. Kee, R. J., Rupley, F. M., and Miller, J. A., Chemkin-
II: A Fortran Chemical Kinetics Package for the Analysis
Sciences, Office of Basic Energy Sciences, Office of Gas-Phase Chemical Kinetics, Sandia National Lab-
of Energy Research, U.S. Department of Energy, oratories Report No. SAND89-8009, 1989.
for financial support under grant number DE- 20. Kee, R. J., Dixon-Lewis, G., Warnatz, J., Coltrin,
FG02-84ER13282; and to the National Energy M. E., and Miller, J. A., A Fortran Computer Code
Research Supercomputer Center for CPU time. Package for the Evaluation of Gas-Phase Multicompo-
nent Transport Properties, Sandia National Laborato-
The authors would also like to thank Prof. J. T. ries Report No. SAND86-8246, 1986.
McKinnon and H.-Y. Zhang of the Colorado 21. Dixon-Lewis, G., Proc. R. Soc. A 307:111–135 (1968).
School of Mines for providing us with copies of 22. Shandross, R. A., Ph.D. thesis, Massachusetts Institute
their kinetic mechanism and associated thermo- of Technology, Cambridge, MA, 1995.
chemical and transport parameters. 23. Savitsky, A., and Golay, M. J. E., Anal. Chem. 36:1627–
1639 (1964). See also corrections by Steinier, J., Ter-
monia, Y., and Deltour, J., Anal. Chem. 44:1906 –1909
REFERENCES (1972).
24. Wilke, C. R., Chem. Eng. Prog. 46:95 (1950).
1. Mitchell, R. E., Sarofim, A. F., and Clomburg, L. A., 25. Pope, C. J., Ph.D. thesis, Massachusetts Institute of
Combust. Flame 37:201–206 (1980). Technology, Cambridge, MA, 1993.
2. Bilger, R. W., Combust. Flame 30:277–284 (1977).
3. Moore, J. G., and Moore, J., Sixteenth Symposium
(International) on Combustion, The Combustion Insti- Received August 18, 1997; revised March 31, 1998; accepted
tute, Pittsburgh, 1976, pp. 1123–1132. April 15, 1998