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Twenty-Seventh Symposium (International) on Combustion/The Combustion Institute, 1998/pp.

495504

A RE-EVALUATION OF THE MEANS USED TO CALCULATE TRANSPORT PROPERTIES OF REACTING FLOWS


RGEN WARNATZ2 PHILLIP PAUL1 and JU 1Combustion Research Facility Sandia National Laboratories Livermore Livermore, CA 94550, USA 2Interdisciplinary Center of Scientic Computing (IWR) Heidelberg University D-69120 Heidelberg, Germany

Simulations of laminar combustion and other reactive ow processes (like chemical vapor deposition, plasma etching, etc.) are presently carried out in most cases using the transport code TRANFIT attached to the CHEMKIN package. The approach used is based on experimental data from 1975 and is now outdated, especially in view of recent work presented in the literature. The new approach described here seeks to remove the deciencies of former transport models by using the following features: (1) representation of transport data of light species at high temperature by switching to an exponential repulsive potential, (2) use of effective potential parameters to handle the intermolecular forces in an easy and elegant way, if polar molecules are considered, and (3) use of a simplied formula for binary thermal diffusion factors, based on an expansion for large values of the mass ratio of the species included. This paper presents the new transport model in terms of a complete set of equations. The molecular parameters provided allow a complete treatment of the oxidation of H2 and H2/CO mixtures (data for species taking place in the oxidation of hydrocarbons and in other reaction systems are not yet available). To demonstrate the consequences of the new transport model for combustion processes, results have been generated by implementing the model in a code for the simulation of premixed laminar ames.

Introduction Simulations of laminar combustion and other reactive ow processes (like chemical vapor deposition, plasma etching, etc.) are presently carried out in most cases using the transport code TRANFIT [1,2] attached to the CHEMKIN package [3]. The approach taken [4] is based on the ChapmanEnskog theory (see, e.g., Ref. [5]). It uses a Stockmayer 12-6-3 potential (equivalent to the well-known LennardJones 12-6 potential for the interaction of nonpolar molecules) and was tested extensively in the simulation of laminar premixed ames (with the MIXFLA package [68]). The underlying database [4] was developed on the basis of the experimental data existing in 1975 and is now outdated, especially in view of recent work done by Mason and coworkers [912]. The need to use a new approach stems from the fact that transport properties of light particles cannot be appropriately described by the 1/r12 repulsive part of the Stockmayer or LennardJones potential, which seems to be too stiff at high characteristic temperatures [5]. This is quantitatively demonstrated by Paul [13] on the basis of experimental results and ab initio calculations on H2 viscosity and

on H-atom diffusivity given in the literature. Thus, the new approach described here seeks to remove this and some other deciencies of former transport models by using the following features [13]: 1. representation of transport data of light species at high temperature T (i.e., at high characteristic temperatures T* kBT/e 10; e potential well depth, kB Boltzmann constant) by switching to an exponential repulsive potential; 2. use of effective potential parameters to handle the intermolecular forces in an easy and elegant way if polar molecules are considered; and 3. use of a simpliedbut sufciently accurate formula for binary thermal diffusion factors, based on an expansion for large values of the mass ratio of the species included. In light of the serious problems with species or pair transport properties, the discussion on whether full multicomponent formulations for mixture transport properties need to be used turns out to be minor. This paper presents the new transport model in terms of a complete set of equations (reduced collision integrals are given in the literature [9,13]). The molecular parameters presented allow a complete treatment of the oxidation of H2 and H2/CO

495

496

LAMINAR PREMIXED FLAMES

mixtures (data for species involved in the oxidation of hydrocarbons and other reaction systems are not yet available). To demonstrate the consequences of the new transport model for combustion processes, results have been generated by implementing the model in a code for the simulation of premixed laminar ames. The New Transport Model Molecular Interaction Potentials In recent transport program packages [1,2,4], molecular interaction between two molecules i and j was described by the Stockmayer 12-6-3 potential, which is equivalent to the well-known Lennard Jones 12-6 potential for the interaction of nonpolar molecules (fd-id and fd-d 0),
uij(r, xij) 4eij

which is an effective LennardJones 12-6 potential and allows easy incorporation of dipoledipole and dipoleinduced dipole interaction terms into the reduced collision integrals by dening effective LennardJones and exponential repulsive parameters. Formally, the expansion delivers a value k 1; however, a value k 1/4 works much better [13,16]. For the reasons discussed in the Introduction, at high characteristic temperatures T* kBT/e 10, it is advisable to switch to an exponential repulsive potential uij(r) Vij exp(r/qij) (see, e.g., Ref. [9]). An analogous treatment leads to an effective potential uij(r) V(eff.) exp(r/q(eff.) ) ij ij (4)

For the determination of effective potential parameters (and then of reduced collision integrals), rst the quantities (i polarizability) vij

rr
ij

12

[ 1 n* ij fdid(xij)]

i lj2 j l2 l2 l2 i and Dij i j6 6 4eijrij 24eijrij

(5)

rr
ij

d* ij fdd(xij)

rr
ij 3

(1)

where uij is the interaction potential (dependent on intermolecular distance r and angle xij between the induced and permanent dipoles), eij is the potential well depth, rij is a mean molecule diameter, fd-id and fd-d are angle-dependent functions for dipoleinduced dipole and dipoledipole interaction, and n* ij 2 3 (not used in the following) and d* ij lij/2eijrij are mean reduced polarizability and mean reduced dipole moment (l dipole moment). Usually this potential is integrated with respect to the angle-dependent part (assuming constant fdid and fdd) to yield an angle-independent Krieger potential [5], for which reduced collision integrals X(m,n)* are available [14]. It is equally plausible to perform this integration with respect to the angle-dependent potential parts using a thermally orientation-averaged potential of the form [15]

are dened. vij is dimensionless and is zero if both species i and j are nonpolar; Dij is zero unless both species are polar. Then the effective parameters become e(eff) eij(1 vij Dij//T)2, r(eff) ij ij rij(1 vij Dij/T)1/6 V(eff) ij V*(1 vij Dij/T) , ij
2

(6)

q(eff) qij *(1 vij Dij/T)1/6 ij Thus, the transport property calculation is in terms of 6 reduced parameters for every collision pair: eij, rij, V* * qij /rij, ij, and lij. A collection ij Vij /eij, qij of potential parameters for species involved in the oxidation of H2 and H2/CO mixtures is presented in Table 1; the combination rules for species pairs (including a seventh parameter, the normalized inter6 action dispersion energy C* 6 C6/er ) are given in a later section. Pure Species and Species Pair Transport Coefcients For the computation of pure species viscosities and binary diffusion coefcients, the usual relations are used together with higher order corrections (hi and dij) [5]. The shear viscosity gi is given by (mi mass of molecule i; expressions for the reduced collision integral Xij * and for Eii * are given in Refs. [9,13]) ni 5 16

uij(r)

u(r, x) exp[u(r, x)/(k T)]dx


x

exp[u(r, x)/(k T)]dx


x

(2) The huge advantage of this central (or spherical) potential is that it can be expanded in a series that gives at low order
uij(r) 4eij
(eff.) 4eij

r
rij

12

1 n* ij

2c eij d* ij 3 T

r
rij
6

12 r(eff.) ij

r
(3)

6 r(eff.) ij

mi kBT 1 hi with hi 2 X(2,2)* (t*) p rii ii 3 (8 Eii * 7) 196 (7)

RE-EVALUATED TRANSPORT PROPERTIES OF REACTING FLOWS TABLE 1 Molecular data for the determination of intermolecular potentials [13] Species CO CO2 H H2 H2O H2O2 HO2 O O2 OH N2 e/k[K] 98.40 245.30 5.42 23.96 535.21 368.11 365.56 57.91 121.10 281.27 98.40 r [1010 m] 3.652 3.769 3.288 3.063 2.673 3.499 3.433 3.064 3.407 3.111 3.652 l [Debye] 0.1098 0.0 0.0 0.0 1.847 1.573 2.09 0.0 0.0 1.655 0.0

497

[1030 m3]
1.95 2.65 0.667 0.803 1.45 2.230 1.950 0.802 1.600 0.980 1.750

V* 5.31 104 2.80 106 3.70 104 1.14 105 3.50 107 8.23 105 5.30 105 5.06 105 1.32 106 7.73 104 5.31 104

q* 0.1080 0.0720 0.1010 0.1030 0.0640 0.0830 0.0860 0.0840 0.0745 0.1010 0.1080

C* 6 2.630 1.860 6.586 4.245 1.612 2.322 2.450 2.740 2.270 3.226 2.180

TABLE 2 Coefcients of Pi(T) for the determination of ki [13] (Pi (T) 1 for the monatomics) Species CO CO2 H2 H2O H2O2 HO2 O2 OH N2 P1 0.9133026 1.5518010 1.1004753 0.5931511 0.0243916 0.422988 0.7759023 0.7319990 1.0367960 P2 0.3384788 0.2911856 0.3268305 0.1095666 0.2087738 0.1763043 0.3787674 0.3669068 0.3182594 P3 0.26450910 0.54380010 0.32212841 0.03359944 0.07258789 0.16050169 0.23802530 0.21580729 0.29313580 P4 0.03584491 0.02452900 0.03198276 0.0 0.01300192 0.01131380 0.04579047 0.04311154 0.03122558 P5 0.01961665 0.05427209 0.02408867 0.0 0.0 0.0 0.01837284 0.01598934 0.02160071 P6 0.00108565 0.0 0.00075892 0.0 0.0 0.0 0.00170918 0.00157644 0.00079964

In an analogous way, the coefcients for binary diffusion of a species i into species j are given by the expression (q total mass density) Dij with mij 3 8

2kBTmij 1 dij 2 X(1,1)*(T*) p qrij ij (8)

The thermal conductivities actually are not computed in a similar way due to the difculties connected with transport of internal degrees of freedom (Eucken correction [1,2,4,5]). Instead, polynomials Pj are used to describe the deviation of the heat conductivity ki from its monatomic part k(mon) , i ki Pi(T)k(mon) with Pi(T) i (Pi,1 Pi,3)(y Pi,5)y2 (1 Pi,2)(y Pi,4)(y2 Pi,6)y3 (10)

mi mj mi mj

again, with a higher order correction (an expression for Cij * is given in Refs. [9,13]) dij 1.3(6Cij * 5)2 ci 1 ci cib (9)

where y ln(T/K). Values of the Pi,1 . . . Pi,6 are given in Table 2. The monatomic part k(mon) is dei termined in the usual way from the viscosity of species i (equation 7) by the relation k(mon) i 15 kB gi 4 mi (11)

with (xi mole fraction of species i; the indices are ordered such that mj mi) ci

2 xi X(1,1)* , 2 xi xj 8(1 1.8mj /mi) X(2,2) ii *


and b 10[1 1.8mj /mi 3(mj /mi)2]

It remains to derive an expression for the binary thermal diffusion factors T ij , which are secondorder transport properties with a complicated dependence on composition, molecular mass, and collision integrals. Bzowski et al. [9], for example, nd

498

LAMINAR PREMIXED FLAMES

that calculated values of T ij may involve uncertainties that are an order of magnitude larger than the uncertainties in calculated values for viscosity or binary diffusion coefcients. They also note that errors in the experimental data for the thermal diffusion factor involve uncertainties of similar magnitude. To avoid complicated computations with doubtful results, one can use the fact that thermal diffusion is important only for light species [4,5], that is, for H and H2 in combustion processes. Therefore, the thermal diffusion factor T ij (as given in Refs. [5,13]) may be expanded for large values of the ratio mi/mj to give the approximation (n particle number density, B* ij given in Refs. [9,13])

The problem of internal degrees of freedom (Eucken correction) was already mentioned; it is also relevant, if mixture heat conductivities are considered. To avoid this problem here (see, e.g., the wellknown EuckenHirschfelder approach [19]), for mixture heat conductivities, a formulation of Mason and Saxena is taken [20] (N number of species involved):
kmix xjUij xikixi 1.065 j i 1 1, j i

with Uij 1

m k 81 m
mi
j 1/4 (mon) ki (mon) j 1/2 2

mi
j

1/2

T ij

nij[1 F(nij)](6C* ij 5) (5 12B*) ij ci ( 4nij /3)(mjnDij /gj)cj xi , xi xj nij m m m


i i j 1/2

(13) In an analogous way, the mixture shear viscosity gmix is given by the semiempirical expression (12)
gmix xjUij xigi xi j i 1 1, j i

with ci

The function F(n) is an empirical correction that makes the approximation reasonably accurate for values of mj /mi up to a value of 1/2 and is given as F(n) 7.99027(1 n)2 76.0603(1 n)4 In these equations, the indices, again, are ordered such that mj mi, which is consistent with the normal sign convention for the thermal diffusion factor (i.e., above the inversion temperature T ij is a positive number; thus, the thermal diffusion of heavy species will be toward a cooler region). Combination Rules for Species Pairs The usual combination rules for species-pair potential parameters (arithmetic mean for diameters, geometric mean otherwise) are extended here by corrections described in Refs. [9,13,17,18]. The following procedure gives the information needed for the treatment of species pairs: 1. Determine rij ( ri rj), ai ri[1 ( C6 *,i/ 2.2)1/6] for all C6 *,i 2.2 and ai 0 otherwise; 2. determine eij eiej (ri ai)3(rj aj)3/[rij ( ai aj)/2]6 2/Xij 1/Xij with Xij i/j (C6,j/ C6,i)1/2; * qi *ri q* 3. and, nally, determine qij j rj/2r* ij q q qj/2qij and V* . ij qij/eij (Vi/qi) t/2 y Vj/qj) Mixture Transport Coefcients Full multicomponent formulations for mixture transport properties are avoided here; the relations given later do not vary from the multicomponent treatment by more than the error limits attributed to the species transport properties.

with Uij 1

m g 81 m
mj
1/4

gi
j

1/2 2

mi
j

1/2

(14)

For diffusion coefcients of a species i into the mixture, the old formalism of Stefan [21] agrees well with full multicomponent models [22] (within the uncertainty of the input data and models used to compute the binary diffusion coefcients):

Di,mix

xjmj j 1, j i

j1

xj/Dij xjmj j 1, j i

(15)

For the mixture thermal diffusion factor, the usual expression (following Chapman and Cowling [23]) kT i,mix xi

xjT ij j 1

(16)

is taken, where the sum of the kT i over the mixture is zero. In analogy to the binary expression [5]
T DT i,binary ki

c2M1M2 D12 with i 1,2 q

(17)

the thermal diffusion coefcient is evaluated as (c total molar concentration, Mi molar mass, M mean molar mass)
T DT i,mix ki,mix

c2 MiM Di,mix q

(18)

This should be sufciently accurate as only thermal diffusion of H and H2 are important in combustion processes, which thus the mixture behaves like a binary one, formed by the light species considered and the rest of the mixture.

RE-EVALUATED TRANSPORT PROPERTIES OF REACTING FLOWS

499

Premixed Flames Considered, Choice of the Reaction Mechanism As previously mentioned, transport properties of light species like H and H2 and of polar species like H2O experience the largest modications, if the sophisticated transport model described earlier is applied to reacting ow systems. Therefore, consequences of the new formulation can be tested best, if the combustion of hydrogen (or mixtures of hydrogen with carbon monoxide) is considered. A further (preliminary) reason for this choice is that data for species involved in the oxidation of hydrocarbons and other reaction systems are not yet available. The reaction mechanism used is based on a data compilation by Baulch et al. [27,28], which had been slightly modied for practical application [24,25]. This mechanism attributes rather high rate coefcients to the sensitive reactions H O2 OH O and OH CO CO2 H to be able to simulate experimental data on H2-air and H2-CO-air ames. This procedure has been harshly criticized [29], but in light of the results of this paper, it is evident that deciencies of the (slow) old transport model had to be compensated by fast rate-limiting reactions. This tting now can be removed, and the desired slow rate coefcients can be used for the reactions mentioned earlier [26], which are similar to those used in the GRI mechanism [30]. The reaction mechanism is listed in Table 3.

The consequence of these results is that the changes of both heat conductivities and diffusion coefcients can (partially) compensate. Thus, the prediction of a general trend for reactive ows is difcult and dependent on the actual conditions, as shown below for some selected premixed ames. H2Air and H2O2 Flames To demonstrate the consequences of the new transport model for combustion processes, the inuence on premixed hydrogenair and hydrogenoxygen ame velocities (at atmospheric pressure and room temperature in the unburned gas) is shown in Figs. 3 and 4. To guarantee a fair comparison, the same mixture transport model is taken (equation 13 for kmix, equation 15 for Di,mix, and equations 16 and 18 for DT i,mix). There is no essential change in thermal diffusion (0.5% change of the ame velocity of a stoichiometric H2air ame) but up to 4% change in the ame velocity in the H2air system (up to 8% in moderately rich H2O2 mixtures) as a result of the new heat conductivities and diffusion coefcients. This reects the well-known dependency vL /s, where the thermal diffusivity is given by k/qcp, which is approximately equivalent to a mean diffusion coefcient [38]. There is good agreement of experiment and simulation now in the H2air ames, where precise measurements (including extrapolation to strain-free conditions) are available; older measurements (and all experimental results for H2O2 ames; see Fig. 4) tend to be too high because of strain effects. Sensitivity analysis for the fastest H2air and H2 O2 ames shows that the relative sensitivity of the ame velocity with respect to the rate coefcients of the reactions H O2 OH O and H O2 M HO2 M are 0.25 and 0.18, respectively. This means that the modications introduced by the new transport model have to be compensated by a decrease of the rate coefcient of one of these reactions of up to one-third. H2-O2-CO-N2 Flames The consequences of the new transport model for premixed hydrogencarbon monoxideair ame velocities (at atmospheric pressure and room temperature in the unburned gas) are demonstrated in Fig. 5. As expected, the changes are highest when fast ames (i.e., hotter ames) are considered. Again, comparison with precise measurements including extrapolation to strain-free conditions are available. Sensitivity analysis of the 50% fuel ame gives the result that the largest relative sensitivities of the ame velocity with respect to the rate coefcients of the reactions H O2 OH O and CO OH CO2 H are 0.27 and 0.55, respectively.

Results and Discussion Pure Species and Species Pair Transport Coefcients As already mentioned in the Introduction, this new approach changes (1) the data for light species at high temperature by switching to an exponential repulsive potential, (2) data for polar molecules by using effective potentials, and (3) thermal diffusion factors, using an expansion for large values of the mass ratio of the species included. Whereas the thermal diffusion coefcients (leading to a rather small correction in any case) do not change considerably, there are noticeable changes with respect to the other points addressed. The rst important fact is (see Fig. 1) that the heat conductivities in the new formulation are slightly larger for stable nonpolar species (and much more for H and O) and 5% smaller for stable polar species (and much more for OH). The second difference is (see Fig. 2) that diffusion coefcients of light species are much larger (up to 40% for diffusion of H atoms), if the new approach is used. The only exceptions are binary diffusion coefcients of the radical OH, which slightly decrease (10% for DOHN2).

500

LAMINAR PREMIXED FLAMES TABLE 3 Reaction mechanism for the oxidation of H2 and CO [2426]

Reaction 1. H2-O2 Reactions (HO2, H2O2 not included) O2 H OH O H2 O OH H H2 OH H2O H OH OH H2O O H H M* H2 M* O O M* O2 M* H OH M* H2O M* 2. HO2 Formation/Consumption H O2 M* HO2 M* HO2 H OH OH HO2 H H2 O2 HO2 H H2O O HO2 O OH O2 HO2 OH H2O O2 3. H2O2 Formation/Consumption HO2 HO2 H2O2 O2 OH OH M* H2O2 M* H2O2 H H2 HO2 H2O2 H H2O OH H2O2 O OH HO2 H2O2 OH H2O HO2 4. CO Formation/Consumption CO OH CO2 H CO HO2 CO2 OH CO O M* CO2 M* CO O2 CO2 O 5. CHO Formation/Consumption CHO M* CO H M* CHO H CO H2 CHO O CO OH CHO O CO2 H CHO OH CO H2O CHO O2 CO HO2 CHO CHO CH2O CO 6. CH2O Formation/Consumption CH2O M* CHO H M* CH2O H CHO H2 CH2O O CHO OH CH2O OH CHO H2O CH2O HO2 CHO H2O2 CH2O CH3 CHO CH4 CH2O O2 CHO HO2

A [cm, mol, s]

E/kJ mol1

8.70 1013 5.06 1004 1.00 1008 1.50 1009 1.80 1018 2.90 1017 2.20 1022 2.30 1018 1.50 1014 2.50 1013 3.00 1013 1.80 1013 6.00 1013 2.50 1011 3.25 1022 1.70 1012 1.00 1013 2.80 1013 5.40 1012 4.76 1007 1.50 1014 7.10 1013 2.50 1012 7.10 1014 9.00 1013 3.00 1013 3.00 1013 1.00 1014 3.00 1012 3.00 1013 5.00 1016 2.30 1010 4.15 1011 3.40 1009 3.00 1012 1.00 1011 6.00 1013

0.0 2.67 1.6 1.14 1.0 1.0 2.0 0.8 0.0 0.0 0.0 0.0 0.0 0.0 2.0 0.0 0.0 0.0 0.0 1.23 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.05 0.57 1.2 0.0 0.0 0.0

60.3 26.3 13.8 0.42 0.00 0.00 0.00 0.00 4.20 2.90 7.20 1.70 0.00 5.20 0.00 15.7 15.0 26.8 4.20 0.29 98.7 19.0 200. 70.3 0.00 0.00 0.00 0.00 0.00 0.00 320. 13.7 11.6 1.90 54.7 25.5 171.

[M*] [ H2] 6.5 [ H2O] 0.4 [ O2] O.4 [ N2] 0.75 [ CO] 1.5 [ CO2]

RE-EVALUATED TRANSPORT PROPERTIES OF REACTING FLOWS

501

Fig. 1. Heat conductivities for H2 and H2O as function of the temperature. Gray line: old transport model (see Refs. [4,68]); black line: new transport model; points: experimental results [3137]. The CHEMKIN package [13] is better for H2 due to a different choice of its LJ potential parameters, but worse for H2O due to the neglect of a resonance correction for polar species interaction [5].

Fig. 2. Binary diffusion coefcients (related to p 1 bar) for mixtures with N2 as function of the temperature. Gray line: old transport model (see Refs [4,68]); black line: new transport model (the results for O2N2 are not distinguishable).

This prominent dependence on the OH CO2 reaction means that the modications introduced by the new transport model (8% increase of the ame velocity at maximum) now leaves place for a decrease of the (rather high) rate coefcient of one of these steps up to 15%. Conclusions and Outlook A new transport model in terms of a complete set of equations is presented. The molecular parameters provided allow a complete treatment of the oxidation of H2 and H2/CO mixtures. To demonstrate the consequences of the new transport model for combustion processes, results have been generated by implementing the model in a code for the simulation of premixed laminar ames. Data for species taking place in the oxidation of hydrocarbons and in other reaction systems (e.g., to

Fig.. 3. Flame velocity (at p 1 bar, Tu 298 K) for H2air mixtures as function of the H2 mole fraction. Points: experiments after 1970 (see Refs. [6,30]); gray line: old transport model: black line: new transport model.

502

LAMINAR PREMIXED FLAMES

for all hydrocarbon intermediates), showing an increase of the ame velocity of a stoichiometric ame from 38.1 to 39.1 cm/s or 2.5%; the reaction mechanism used is similar to that presented in Ref. [25]*). Furthermore, the implementation in non-premixed amewhere changes in the transport coefcients can be much more importantis in preparation.
Acknowledgments Ph. P. acknowledges the support of the U.S. Department of Energy, Basic Sciences, Chemical Sciences Division and support from the Deutsche Forschungsgemeinschaft (DFG) (LEIBNIZ program) for an extended stay at Heidelberg University. J. W. is thankful for support of this work by the DFG (SFB 359, LEIBNIZ program) and the Fonds der Chemischen Industrie, and also for the hospitality of the Combustion Research Facility, Sandia National Laboratories in Livermore.

Fig. 4. Flame velocity (at p 1 bar, Tu 298 K) for H2O2 mixtures as function of the H2 unburned gas mole fraction. Points: experiments (see Ref. [6]); gray line: old transport model; black line: new transport model.

REFERENCES 1. Kee, R. J., Warnatz, J., and Miller, J. A., A FORTRAN Computer Package for the Evaluation of Gas Phase Viscosities, Heat Conductivities, and Diffusion Coefcients, Sandia report SAND83-8209. 2. Kee, R. J., Dixon-Lewis, G., Warnatz, J., Coltrin, M. E., and Miller, J. A., A FORTRAN Computer Code Package for the Evaluation of Gas-Phase Multicomponent Transport Properties, Sandia report SAND86-8246. 3. Kee, R. J., Rupley, F. M., and Miller, J. A., CHEMKIN-II: A Fortran Chemical Kinetics Package for the Analysis of Gas-Phase Chemical Kinetics, Sandia National Laboratories report SAND89-8009. 4. Warnatz, J., Berechnung der Flammengeschwindigkeit und der Struktur von laminaren Flammen, Habilitationsschrift, Technische Hochschule Darmstadt, 1977. 5. Hirschfelder, J. O., Curtiss, C. F., and Bird, R. B., Molecular Theory of Gases and Liquids, Wiley, New York, 1964. 6. Warnatz, J., Ber. Bunsen-Ges. Phys. Chem. 82:643649 (1978). 7. Warnatz, J., Ber. Bunsen-Ges. Phys. Chem. 83:950957 (1979). 8. Warnatz, J., in Eighteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, 1981, pp. 369384. 9. Bzowski, J., Kestin, J., Mason, E. A., Uribe, F. J., J. Phys. Chem. Ref. Data 19:11791232 (1990). 10. Uribe, F. J., Mason, E. A., and Kestin, J., Phys. A 156:467491 (1989). *An actual version of the mechanism is given under: http://reaow.iwr.uni-heidelberg.de/(keyword: ftp server)

Fig. 5. Flame velocity (at p 1 bar, Tu 298 K) for H2COair mixtures as function of the fuel percentage in the unburned gas. Points: experiments by McLean et al. [29], and by Scholte and Vaags [39] with [CO]u 19[H2]u; gray line: old transport model; black line: new transport model.

describe CVD, plasma etching, chemical reactors, etc.) are not yet available but will be providedat least for hydrocarbon oxidationin future. Consequences for hydrocarbon combustion can be drawn from preliminary results for methaneair ames (where the methane molecular data have been taken

RE-EVALUATED TRANSPORT PROPERTIES OF REACTING FLOWS 11. Uribe, F. J., Mason, E. A., and Kestin, J., J. Phys. Chem. Ref. Data 19:11231136 (1990). 12. Assael, G. J., Mixafend, S., Wakeham, W. A., J. Phys. Chem. Ref. Data 15:13151322 (1986). 13. Paul, P., DRFMA New Package for the Evaluation of Gas-Phase Transport Properties, Sandia report SAND98-8203, Sandia National Laboratories, Livermore, 1997. 14. Monchick, L. and Mason, E. A., J. Chem. Phys. 55:16761697 (1961). 15. Keesom, W. H., Phys. Z. 22:129 (1921). 16. Gray, C. G., Gubbins, K. E., The Theory of Molecular Fluids, Clarendon Press, Oxford, 1984. 17. Bzowski, J., Mason, E. A., and Kestin, J., Int. J. Thermophys. 9:131143 (1988). 18. Tang, K. T. and Toennies, J. P., J. Chem. Phys. 80:37263741 (1984). 19. Hirschfelder, J. O., in Sixth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, 1957, pp. 351366. 20. Mason, E. A. and Saxena, S. C., Phys. Fluids 5:361 369 (1958). 21. Stefan, J., Sitzungsberichte Akad. Wiss. Wien II 68:325 (1874). 22. Paul, P., Personal communication. 23. Chapman, S. and Cowling, T. G., The Mathematical Theory of Non-Uniform Gases, Cambridge University Press, Cambridge, 1970. 24. Warnatz, J., in Twenty-Fourth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, 1992, pp. 553579. 25. Warnatz, J., Maas, U., and Dibble, R. W., Combustion, Springer, Heidelberg, 1996. 26. Baulch, D. L., Bowman, C. T., Cox, R. A., Just, Th., Kerr, J. A., Pilling, M. J., Stocker, D. W., Troe, J., Tsang, W., Walker, R. W., and Warnatz, J., unpublished work.

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COMMENTS
Daniel E. Rosner, Yale University, USA. One of the most sensitive tests of the validity of a particular intermolecular potential is its ability to predict the magnitude and temperature dependence of the LudwigSoret coefcient T (thermal diffusion factor), a dimensionless quantity needed to predict mass transfer rates in disparate molecular weight, highly nonisothermal systems [1,2]. Have such experimental data been used to guide present generalizations of the more familiar 12:6 LennardJones potential and selection of the associated species-specic parameters? Authors Reply. It is well known that the thermal diffusion factor T is quite sensitive to the form of the potential. Bzowski et al. [1] nd that calculated values of the thermal diffusion factor may involve uncertainties an order of magnitude greater than the uncertainties in calculations of rstorder transport properties. They also note that the errors in the experimental data for the thermal diffusion factor involve uncertainties of a similar magnitude. This group has recently published an extensive review and revaluation of transport property experimental data. As a result, they have prescribed the use of a more advanced set of potential parameter combination rules as well as the use of a hybrid potential (i.e., modied LennardJones at temperatures less than 10 times the well-depth energy of the collision pair and an exponential repulsive potential at higher temperatures). For our transport model, we have adopted their full set of recommendations that include a new set of potential parameters, new combination rules, a new potential, the inclusion of higher order corrections to rst-order

REFERENCES 1. Rosner, D. E., et al., Combust. Sci. Technol. 20:87106 (1979). 2. Rosner, D. E., et al., Electrochem. Soc. 88-4:11138 (1998).

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LAMINAR PREMIXED FLAMES these advanced models appear to correct the deciencies of prior models and substantially improve the predictability of transport properties. REFERENCE 1. Bzowski, J., Kestin, J., Mason, E. A., and Uribe, F. J., J. Phys. Chem. Ref. Data 19:11791232 (1990).

properties (i.e., Kihara corrections), and the use of a Kihara formulation for the thermal diffusion factor. In comparisons with experimental data, they found and we conrm that the representations for pure species, binary, mixture, and multicomponent properties, as currently used in reacting ow simulations, perform poorly especially as regards mixtures containing disparate mass ratios and the thermal diffusion factor. Within all of the available data,