Physica A 260 (1998) 49–72

The kinetic chemical equilibrium regime
a

Alexandre Ern a; b; ∗ , Vincent Giovangigli b
CERMICS, ENPC, 6 et 8 av. Blaise Pascal, Cite Descartes, 77455 Marne la Vallee cedex 2, France
b CMAP, CNRS, Ecole Polytechnique, 91128 Palaiseau cedex, France
Received 29 December 1997; received in revised form 4 June 1998

Abstract
We investigate reactive gas mixtures in the kinetic chemical equilibrium regime. Our starting point is a generalized Boltzmann equation with a chemical source term valid for arbitrary
reaction mechanisms and yielding a positive entropy production. We

rst study the Enskog
expansion in the kinetic chemical equilibrium regime. We derive a new set of macroscopic
equations in the zeroth- and

reserved.V. we derive the entropy conservation equation in the Navier–Stokes equilibrium regime and show that the source term is positive and c 1998 Elsevier Science B. Introduction Extensive interest in the kinetic theory of gas mixtures with chemical reactions has grown signi. expressing conservation of element densities. The transport uxes arising in the Navier–Stokes equilibrium regime are the element di usion velocities. PACS: 82A40. momentum and energy. 82A70 Keywords: Boltzmann equation. however.rst-order regimes. the kinetic equilibrium regime appears to be formally equivalent to the one obtained for gas mixtures in chemical nonequilibrium and then letting the chemical reactions approach equilibrium. Transport coecients. The actual values of the transport coecients are. di erent. Entropy 1. All rights that it is compatible with Onsager’s reciprocal relations. Enskog expansion. the heat ux vector and the pressure tensor and are written in terms of transport coecients. Kinetic equilibrium. Upon introducing species di usion velocities. Finally. Chemical reactions.

plasma physics. c 1998 Elsevier Science B. combustion processes and chemical reactors.V. E-mail: ern@cermics.3 .enpc. CERMICS.: +331-64153570.4 3 7 1 ( 9 8 ) 0 0 3 0 3 . ENPC (see above addressa ) Tel. All rights reserved. An attractive approach for modeling gas mixtures with chemical reactions relies upon a generalized Boltzmann equation with chemical source term and the Enskog expansion. The subject is indeed related to a wide range of practical applications. fax: 33 1 64 15 35 86.fr. the collision term in the Boltzmann ∗ Correspondence address: Alexandre Ern. including spacecraft ights.cantly over the past few years. 0378-4371/98/$ – see front matter PII: S 0 3 7 8 . With this approach.

Most applications are concerned with the zeroth.and . Ern. Giovangigli / Physica A 260 (1998) 49–72 equation is split into fast and slow processes. thus giving rise to a formal expansion of the species distribution functions and the kinetic equations. V.50 A.

2]. When the chemistry times are much larger than the relaxation times for translational and internal energy exchange.rst-order terms in the expansion. This regime has been introduced formally by Ludwig and Heil [6] for dissociation and ionization of gas mixtures. On the other hand. in particular. thus excluding cases such as external magnetic and electric . but these authors did not introduce the appropriate collisional invariants associated with the chemical elements. In this context. several kinetic regimes may arise for chemically reactive gas mixtures [1. the chemical source term in the Boltzmann equation accounts for slow processes while the nonreactive source term results from fast processes. a kinetic chemical equilibrium regime arises. to the tempered and slow reaction regimes. In the next section we present the generalized Boltzmann equation for chemically reactive mixtures in a semi-classical framework. isotropic mixtures with fast relaxation of all the internal energy modes. Our analysis is concerned with dilute. This regime has been studied extensively in the past and gives rise. Our paper is organized as follows. when the chemical characteristic times are of the same order of magnitude as the relaxation times of translational and internal energy. The main goal of this work is now to derive a general theoretical framework for gas mixtures in the kinetic chemical equilibrium regime. 3 –6]. for which expressions of transport coecients have been given [1.

We present the macroscopic equations expressing conservation of element densities. We discuss the form of the chemical source term for arbitrary chemical reaction mechanisms and show that all nonreactive and reactive collisions arising at the microscopic level yield a positive contribution to the entropy production. in Section 4 we investigate the Navier–Stokes regime corresponding to the . momentum and energy.elds or strong vibrational desequilibrium [7]. Finally. but the species number densities are constrained by the chemical equilibrium conditions. In this regime. We then introduce the collisional invariants associated with chemical elements. the species distribution functions are given by local Maxwellian distribution functions. momentum and energy and study the Enskog expansion in the kinetic chemical equilibrium regime. In Section 3 we investigate the Euler regime corresponding to the zeroth-order Enskog expansion.

The macroscopic equations for element densities. We express these uxes in terms of various transport coecients including.rst-order Enskog expansion. in particular. we show that the . momentum and energy involve several transport uxes: the element di usion velocities. Upon introducing the species di usion velocities. the pressure tensor and the heat ux vector. the element di usion matrix.

rst order kinetic equilibrium regime is formally equivalent to the one obtained from a .

di erent. Finally. . however. we derive the conservation equation for the entropy and show that the source term is positive and that it is compatible with Onsager’s reciprocal relations.rst order expansion with nonequilibrium chemistry and then letting the chemical reactions approach equilibrium. The actual values of the transport coecients are.

Ern. V. We . Theoretical framework In this section we derive a theoretical framework for the kinetic chemical equilibrium regime. Giovangigli / Physica A 260 (1998) 49–72 51 2.A.

It preaverages the collision cross-sections over all the magnetic quantum numbers and can be derived from the Waldmann–Snider quantum mechanical Boltzmann equation [9. (2. Di is the usual di erential operator Di (fi ) = @t fi + (ci · @x )fi + (bi · @ci )fi . ci . the dependence on (t. x) is made implicit. We next present the collisional invariants for reactive mixtures at equilibrium. The state of the mixture is described by the species distribution functions denoted by fi (t. we investigate the Enskog expansion in the kinetic chemical equilibrium regime. x the three-dimensional spatial coordinate.10]. Finally. where t is the time.e.2) where bi is the external force acting on the ith species. The family of species distribution functions f = (fi )i∈S is the solution of a generalized Boltzmann equation written in the form Di (fi ) = Bi (f) + Ci (f). This equation is obtained in a semiclassical framework. where i depends on ci and I . we refer to [11]. I . n] is the set of species indices. accounting for element. In the above equation. The starting point of our analysis is the Boltzmann equation derived in [8] for polyatomic gas mixtures without chemical reactions. the nonreactive and reactive source terms. and Bi (f) and Ci (f) are. I ). ci the velocity of the ith species and I the index for the internal energy state. i. For a relativistic kinetic gas theory.. the translational motion of the particules is treated classically and the internal degrees of freedom are treated quantum mechanically. (2. We then show that both nonreactive and reactive source terms are compatible with the positivity of entropy production.3) Bi (f) = 0 0 a a iI jJ 0 0 j∈S J. i∈S .1. momentum and energy conservation.1) where S = [1. J where I and J are the indices for the quantum energy states of the ith and jth species before collision.rst derive a generalized Boltzmann equation for chemically reactive mixtures and present explicitly the form of the chemical source term for an arbitrary reaction mechanism. (2. For brevity. For a family of functions i . x.8]  X X Z  0 0 0 0 aiI ajJ fi fj − fi fj WijIJI J dcj dci0 dcj0 . i ∈ S. The nonreactive source term is given by [1. respectively. aiI the degeneracy . we introduce the compact notation  = (i )i∈S . I 0 and J 0 the corresponding numbers after collision. Generalized Boltzmann equation We consider a dilute isotropic reactive gas mixture consisting of n chemical species having internal degrees of freedom. 2.

4) It is also possible to consider a formalism based on collision cross-sections rather than transition probabilities. triple reactive collisions are retained since recombination reactions cannot often proceed otherwise [6. but the present formalism is more convenient for reactive collisions [2.52 A. Triple reactive collisions can also be viewed as a sequence of two bimolecular reactions proceeding extremely fast [2]. Giovangigli / Physica A 260 (1998) 49–72 0 0 of the I th quantum energy shell of the ith species and WijIJI J the transition probability for the nonreactive collision. We consider both bimolecular and trimolecular chemical reactions.6]. Ern. V. In particular. The reactive source term Ci (f) results from chemical reactions between species in the mixture. we present some examples. Consider . Before giving the general form of the reactive source term.12]. Note that the transition probabilities have been preaveraged over all the magnetic quantum numbers and satisfy the reciprocity relations [8] WijIJI 0 0 J 0 0 aiI ajJ = WijI J IJ aiI 0 ajJ 0 : (2. although triple nonreactive collisions have been neglected in the nonreactive source term (2:3).

j.rst a bimolecular reaction of the form i + j k + l . (2. Let I. J.11.6.12]  XZ  .2. K. The reactive source term then reads [1.5) with species indices i. l assumed to be distinct and with i denoting the chemical symbol for the ith species. L denote the indices for the internal energy states of the species. k.

kK .

lL IJKL fk fl − fi fj Wijkl dcj dck dcl .6) Ci (f) = . (2.

.

iI jJ J. K. L where the statistical weight .

iI is given by .

iI = h3P .5). mi the mass of the particules of the ith species IJKL and Wijkl the transition probability for the forward reaction in Eq.2.7) and where hP is the Planck constant.12] IJKL Wijkl . (2.6). aiI m3i (2.6. we have used the reciprocity relation between the forward and reverse transition probabilities which reads [1. (2. In Eq.

iI .

jJ = KLIJ Wklij .

kK .

respectively.9) the forward and reverse reaction delete or produce. where i and j are the same in reaction (2:5).lL : (2. two molecules of the ith species so that the reactive source term becomes [2.12]  XZ  .8) In the case. i + i k + l . (2.e.. i.6.

kK .

10) Ci (f) = 2 .lL I I˜KL ˜ fk fl − fi fi Wiikl dc˜i dck dcl . (2.

iI .

K. L .iI˜ I˜.

12]  X Z  . In the case of a chemical reaction involving three products. c˜i . Giovangigli / Physica A 260 (1998) 49–72 53 with f˜i denoting f˜i (t. (2. x.6. as in i + j k + l + m . the reactive source term reads [2. V.11) with all the indices assumed to be distinct. Ern.A. I˜).

kK .

lL .

mM IJKLM Ci (f) = fk fl fm − fi fj Wijklm dcj dck dcl dcm . (2.12) .

.

i. iI jJ J. Finally. Note that the Planck constant does no longer cancel out in Eq. in the case where the ith species is present as reactant and product in reaction (2:5)..6. M with obvious notation. L. i + j i + l . (2.12).13) the forward and reverse reactions do not account for the same statistical event regarding species i so that the source term reads [2.e. (2.12] XZ   . K.

iI˜.

lL IJ I˜L ˜ Ci (f) = fi fl − fi fj Wijil dcj dc˜i dcl .

iI .

L  XZ  . I˜.jJ J.

iI .

lL I˜JIL ˜ fi fj − + fi fl Wijil dc˜i dcj dcl : .

iI˜.

(2. I˜. i} and P (r) = {k. For example. Ci (r) (f) is the source term for the rth elementary reaction written in the form X j∈R (r) j X k .16) k∈P (r) where R (r) and P (r) are. l}.14) L. l}. and we also denote by R and P the indices of internal energy states for reactants and products. we have R (r) = {i. The reactive source term for the ith species reads Ci (f) = X Ci (r) (f) : (2. we have Ri(r) = {j} and for reaction (2:9) we have Ri(r) = {i}. J We now generalize the above expressions into a single formalism valid for arbitrary reaction mechanisms.15) (r) Here. respectively. For instance. for reaction (2:5).jJ (2.9). the indices for reactants and products. whereas for reaction (r) (r) (2. For a given species i ∈ S. for reaction (2:5). we have R (r) = {i. respectively. respectively. we introduce . We denote by iR and iP the stoichiometric coecients of the ith species among reactants and products. j} and P (r) = {k. Finally. we denote by Ri(r) the set of reactant indices where the index i has been removed only once.

V. RI and PI . Pi (r) Q R (r) . P × Y Ri(r) . for instance. Ern. P (r) + P i × (r) with. With this notation. Giovangigli / Physica A 260 (1998) 49–72 a similar notation for Pi (r) . R (r) . Pi (r)  WRP (r) (r) QR P .54 A. the source term for the rth elementary reaction reads Ci (r) (r) (f) = R i X Z Y RI .

f jJ j R (r) R (r) .

jJ Y dcj dck X Z Y R. PI Y P .

kK fk − (r) R (r) .

jJ fj − Y P (r)  WRP (r) (r) .

kK fk Q R P (r) R .

WRRP(r) P (r) is the transition probability for a reactive collision in which the reactants R (r) with internal energy states R are transformed into products P (r) with internal energy states P. dcj dck standing for (2. Note that the following reciprocity relation holds for the transition probabilities [2]: WPR(r) (r) WRP(r) (r) QR P = Q P R : R (r) .jJ dcj dck .17) Q R (r) dcj Q Pi (r) dck . In addition.

jJ P (r) .

Entropy production We now show that the nonreactive source term (2:3) and the reactive source term (2:17) are both compatible with the H -theorem or.2.kK (2. that they yield a positive entropy production.18) 2. we introduce the kinetic entropy per unit volume given by XZ fi (log(. in other words. To this purpose.

I Multiplying the Boltzmann equation (2:1) by −kB log(.iI fi ) − 1) dci : (2.19) S kin = −kB i.

(2.20) where v is the mean average velocity de. integrating over dci and summing over i and I yields the entropy conservation equation in the form @t S kin + @x · (S kin v) + @x · J kin = kin .iI fi ).

ned later. J kin the entropy di usive ux given by XZ kin J = −kB (ci − v)fi (log(.

21) i. (2. B + kin. The source term reads kin = kin.22) . I and kin the kinetic entropy source term. C . (2.iI fi ) − 1) dci .

B  Bi (f) log(. V.A. Ern. Giovangigli / Physica A 260 (1998) 49–72 55 with the nonreactive source term given by XZ kin.

J 0 fi0 fj0 fi fj . I 1 = kB 4 X X Z  i. I 0 . J.iI fi ) dci = −kB i. j∈S I. aiI 0 ajJ 0 aiI ajJ  0 0 WijIJI J dci dcj dci0 dcj0 .23) and the reactive source term by XZ kin. (aiI ajJ )−1 (2.C = −kB Ci (f) log(.

P R (r) . I = kB XXZ (r) × Y R. P (r) Y P .iI fi ) dci i.

kK fk . (r)  WRP (r) (r) QR P .

f jJ j R (r) (r) R .

ii = i i dci : (2. l = ne + . The generalized Boltzmann equation (2:1) is thus compatible with the H -theorem and yields a dissipative structure. The ne + 4 collisional invariants are then given by  l ∈ E. 2. B and kin. 3 . y) = log(x=y)(x−y).26) i. given by the sum of the energy of formation plus the internal energy. yield a positive contribution to the kinetic entropy production. For two families  = (i )i∈S and  = (i )i∈S . where Eil is the number of element l in the ith species. In other words. all the collisions arising at the microscopic level. and EiI the total internal energy of the ith species in the I th quantum energy shell. ci the component of ci in the th spatial coordinate. l = ne + 4 . Collisional invariants and macroscopic properties As opposed to the nonreactive case where species. in the reactive case only elements.25) = (mi ci )i∈S . I .  1 ( 2 mi ci · ci + EiI )i∈S . We denote by ne the number of elements in the mixture and by E = [1. It is readily seen that both  kin.3.  (Eil )i∈S . we introduce the scalar product XZ hh. either nonreactive or reactive. momentum and energy are conserved by any microscopic collision. This property is particularly important in the modeling of reactive gas mixtures where special care should be taken so that all the terms arising in the entropy production yield a positive contribution.  = 1. (2. we denote by I the space spanned by the collisional invariants. momentum and energy are conserved. l (2. For later convenience. ne ] the set of element indices. 2. C are a sum of positive terms.jJ Y dcj dck .24) with (x.

Ern.56 A. I i . Giovangigli / Physica A 260 (1998) 49–72 More generally.R when dealing with tensor quantities  and . the scalar product becomes P hh. ii = i. V.

i dci . where i .

e 2 P e le nl the density where e nl denotes the number density for the lth element. l = n + 4 .  = l∈E m e l the molecular mass of the lth element. Hi = 52 kB T + E i .29) We also introduce the averaged internal energy of the ith species Ei = 1 X aiI EiI exp(−EiI =kB T ) Qiint I (2. 1 v · v + E. We introduce the partition function for internal energy Qiint for the ith species Qiint = X aiI exp(−EiI =kB T ) . i∈S : The species number densities are de. 2. 3 . v the component in the of the mixture.27) f. (2. l = ne + . Qi = Qitr Qiint : (2. m th spatial coordinate of the mean average velocity v. e (2. l = v . l∈E . and E the total internal energy per unit volume of the mixture. The macroscopic properties are given by  nl .28) I where kB is the Boltzmann constant and T the temperature. i denotes the maximum contracted product between tensors i and i .  = 1. as well as the translational and full partition functions Qitr  = 2mi kB T h2P 3=2 .30) as well as the internal energy of the ith species and its enthalpy Ei = 32 kB T + E i .

ned as XZ fi dci . ni = (2. i ∈ S .33) i∈S The total internal energy per unit volume of the mixture then reads E= X i∈S ni Ei : (2.34) . l∈E : (2.31) (2.32) I in such a way that e nl = X ni Eil .

(2.37) and (2. The kinetic chemical equilibrium regime In this work we are concerned with the kinetic chemical equilibrium regime in which both the chemistry times and the relaxation times for translational and internal energy are much smaller than the characteristic times of the ow.38) = f. (2. the species distribution functions are expanded as fi = fi0 (1 + ”i + O(”2 )). Giovangigli / Physica A 260 (1998) 49–72 57 2. Ern. i∈S : (2.37) In order to determine f 0 uniquely. (2. it is classical to impose that f 0 yield the local macroscopic properties 0 l l f . ” i∈S . Rewriting Eq.4. We will see in Section 3 that Eqs.38) uniquely determine the zerothorder distribution functions f 0 and give rise to the Euler equilibrium regime. i∈S : (2.A. l . The . ∈I : (2.35) where ” is a formal expansion parameter.1) in the form 1 Di (fi ) = (Bi (f) + Ci (f)). An approximate solution to the Boltzmann equation (2:1) is then obtained using an Enskog expansion. V.36) The family of zeroth-order distribution functions f 0 = (fi0 )i∈S is the solution of Bi (f 0 ) + Ci (f 0 ) = 0.

l = 0.42) In order to determine uniquely the perturbation . =i denotes the linearized collision operator for the ith species. which reads C =i () = =B i () + =i () . i∈S : (2. f 0  . 0 fi =C i () = − 1 @f Ci (f 0 ). (2.rst-order perturbations  = (i )i∈S are the solution of non-homogeneous integral equations written in the form =i () = i . f 0  : 0 fi (2.39) where the right member i uniquely depends on f 0 and reads i = −Di (log fi0 ). (2. the integral equations (2:39) are completed with the ne + 4 constraints 0 l f . ∈I : (2.41) where the nonreactive and reactive collision operators are given by =B i () = − 1 @f Bi (f 0 ).40) In addition.43) The . i∈S .

i∈S . (2.44) .rst-order species distribution functions f1 = (fi1 )i∈S given by fi1 = fi0 (1 + i ).

1.4.4 that they satisfy Eqs. Giovangigli / Physica A 260 (1998) 49–72 are then such that 1 l 0 = f . This regime results from the zeroth order Enskog expansion discussed in Section 2. Ern. (2.38).58 A. l = f. V. l . we have seen in Section 2.45) and give rise to the Navier–Stokes equilibrium regime discussed in Section 4. 3. (2.37). Indeed. f . Generalized Maxwellian distribution functions The zeroth-order distribution functions f 0 are generalized Maxwellian distribution functions. (2.37) and (2. 3. Using Eq. The Euler equilibrium regime In this section we discuss the Euler equilibrium regime for reactive mixtures in kinetic chemical equilibrium. we . l ∈I .

rst deduce that XZ (Bi (f 0 ) + Ci (f 0 )) log(.

iI fi0 ) dci = 0 . it is readily seen from Eqs.23) and (2.1) 0 = −kB i. Since 0 is a sum of nonnegative terms. I and hence the entropy production corresponding to f 0 is zero. (3. (2.24) that 0 can vanish if and only if the vector (log(.

We may therefore write (log(.iI fi0 ))i∈S is conserved in both nonreactive and reactive collisions.

25) we obtain that log(.2) Using Eq.iI fi0 ))i∈S ∈ I : (3. (2.

iI fi0 ) = nX e +4 l l i. i∈S . (3.3) l=1 and the constants l are determined from the macroscopic constraints (2:38). (3.5) log Qi i∈S . except that the species number densities are now constrained by the relations   ni ∈E .4) exp − 2kB T 2kB T kB T Qiint These expressions are similar to those obtained for ows in both tempered and slow reaction regimes. After some algebra we get   aiI m3i ni mi EiI 0 2 (ci − v) − exp − fi = 3 2kB T kB T hP Qi  3=2   mi EiI aiI ni mi 2 = (ci − v) − : (3.

(3. It is important to point out that the constraints (3:5) actually yield the usual chemical equilibrium conditions for the species number densities. V. Indeed. Ene ) . Giovangigli / Physica A 260 (1998) 49–72 59 where we have introduced the element space E = Vect(E1 .6) where El = (Eil )i∈S for l ∈ E.A. Ern. upon introducing the zeroth order entropy per unit volume XZ 0 fi0 (log(. : : : .

14) . (3.16]. (3. T Qi i∈S : (3. I we obtain after some algebra that S0 = X ni Si0 . D(f 0 ) = 0. the resulting equilibrium constant is exactly the same as would be obtained using the rules of statistical mechanics [1.2.12) where we have introduced the family D(f 0 ) = (Di (fi0 ))i∈S . In addition.iI fi0 ) − 1) dci . Macroscopic conservation equations The macroscopic conservation equations in the Euler regime are obtained from the relations l l . 3.10) and it is readily seen from Eq. (3. (3.11) This relation simply states the usual equilibrium conditions for the chemical reactions. After some algebra.8) i∈S with the zeroth order molecular entropies Si0 given by Si0 = Hi ni − kB log .13) X i∈S i bi . @t (v) + @x · (v ⊗ v) = @x p + (3.15]. we obtain nl + @x · (e nl v) = 0. the species chemical potentials read i0 = 1 kB T ni (Hi − TSi0 ) = log . mi mi Qi (3.5) that the vector M0 with components mi i0 is in the element space M0 = (mi i0 )i∈S ∈ E : (3.7) S = −kB i. (3. as detailed for instance in [14.9) At the zeroth order. ∈I . @t e l∈E .

Upon introduing the particular derivative Dt = @t + v · @x . Ern. mol X chem.15) i∈S where i = ni mi is the density of the ith species.17) i∈S P i∈S where n = i∈S ni is the total number density. The . (3. momentum and energy. These equations express conservation of element densities.60 A.16) @e nl i∈S l∈E mol which appears in Eq. Giovangigli / Physica A 260 (1998) 49–72 @t ( 12 v2 + E) + @x · (( 12 v2 + E)v) = −@x · (pv) + X i bi · v . V. (3. An equation for the temperature is easily recovered from the energy equation (3:15). mol cmol = 32 kB n + ni ci + ni c i .16) consists of three contriThe molecular heat capacity c butions X int. a straightforward calculation yields !) ( X @ni X e cmol Dt T = −(p + E) + nl @x · v : Ei (3. (3.

17) accounts for the translational heat capacity. dT cichem. the internal and chemical molecular heat capacity of the ith species given by ciint. while ciint.rst term in Eq. mol and cichem. This regime results from the . mol = 1 @ni Ei : ni @T (3.18) 4. (3. respectively. The Navier–Stokes equilibrium regime In this section we discuss the Navier–Stokes equilibrium regime for reactive mixtures in kinetic chemical equilibrium. mol = dE i . mol are.

I 0 . Using Eq.rst-order Enskog expansion discussed in Section 2. (3. P (r) Ri(r) fj0 dcj dck X R (r) j − X P (r) ! k WRRP(r) P (r) . (4. J 0 and R (r) =C i () = i XZ Y RI . P × Y Ri(r) . Linearized Boltzmann equations The species perturbed distribution functions  = (i )i∈S are the solution of the integral equations (2:39) completed by the constraints (2:43).2). 4.1.1) =i () = j∈S J.4. the nonreactive and reactive collision operators now read X X Z 0 0 B fj0 (i + j − 0i − 0j )WijIJI J dcj dci0 dcj0 .

(ii) it is positive semi-de.A. (i) it is symmetric: <. = = f 0 . =() . keeping in mind that  and  may be either scalar or tensor quantities.2) The linearized collision operator = = = B += C has important structure properties which generalize those discussed in [13] for nonreactive mixtures.3) <. It is readily seen from Eqs. V.2) that the bracket operator has the following fundamental properties. Ern. =. Giovangigli / Physica A 260 (1998) 49–72 (r) + iP × Y XZ Y R. = = <. PI R (r) . (4. We introduce the bracket operator (4.1) and (4. Pi (r) Pi (r) fk0 X k − P (r) X 61 ! j WPPR(r) R (r) R (r) dcj dck : (4.

p l ∈ E. (2. = = 0 ⇔  ∈ I. On the other hand. the right member i in Eq. pi = ni kB T.2. (iii) its kernel is spanned by the collisional invariants: <. =¿0.nite: <. we introduce the partial pressure of the lth element and the partial pressure of the ith species given by el = e nl kB T. i∈S : With the ne + 4 macroscopic variables .39) may now be evaluated using the zeroth-order macroscopic conservation equations derived in Section 3. For convenience.

p l .l given by  el. l∈E .

= v . l = ne + 4 (4.  = 1.  1=kB T. 3 . 2. l = ne + .4) (4.5) we obtain i = nX e +4 l=1 il (Dt .

l + (ci − v) · @x .

6) with 1 @fi0 fi0 @.l ) − mi (ci − v) · bi . kB T (4.

 pi @T 2 il = (4. it is easily veri. 2. 3 .  = 1. l = ne + 4 . l = ne + .   p pl  i @e    mi (ci − v ).7) for i ∈ S.l  1 @pi   . l∈E . Using the relations presented in the appendix. = kB T     2    Hi − kB T @pi − 1 mi (ci − v)2 − EiI .

ed that for all  l l = 1. : : : . the vector i i∈S is a linear combination of the collisional invariants . ne +4.

. After some lengthy calculations. × Hi − pi @T pi @e pl 2 l∈E   X @pj  1  @pi Dl − Yi (ci − v) . namely X e 0 1 l e l − i · @x (1=kB T ) i = −i : @x v − i @x · v − D i · @x p 3 l∈E X Dj + i · (j bj ) . i = Hi −   pi @T @T 2 i mi = kB T j∈S D i j = 1 (ij − Yi )(ci − v) .8) j∈S with   1 2 (ci − v) ⊗ (ci − v) − (ci − v) I . e i = pi  @e pl @e pl  j∈S       2 X 0 @p 1 k @p T j B  i − Yi − mi (ci − v)2 − EiI (ci − v) . we deduce from the expansion (4:8) for i a similar expansion for i . Giovangigli / Physica A 260 (1998) 49–72 (2:25). 0 . V. Ern. = 0. or Dj for j ∈ S.11) 0  l l ∈I : f  .9) el where I is the identity matrix and ij the Kronecker symbol. . (4.62 A. =i (  ) = i . (4. pi (4. 3 X e l @pi 1 mi p (ci − v)2 − i = 3 kB T pi @e pl l∈E  !    X X @nj 1 e n + − n E p + j l j  kB T 2 cmol  @e nl j∈S l∈E ) ( e l @pi kB T 2 @pi X p 1 2 − kB T − mi (ci − v) − EiI . we obtain the following expansion for i in terms of the macroscopic variable gradients: X e 0 1 l e l − i · @x (1=kB T ) i = − i : @x v − i @x · v − D i · @x p 3 l∈E X Dj + i · (j bj ) . Letting  = . (4.10) is the solution of the constrained integral equations ( i ∈ S. (4.10) j∈S and each of the expansion coecients   = (i )i∈S in Eq. D for l ∈ E.

A. Ern. Giovangigli / Physica A 260 (1998) 49–72 63 It is easily veri. V.

D(f1 ) = 0.ed that the above systems are well posed for all . i ∈ S .12) where we have introduced the family D(f1 ) = (Di (fi1 ))i∈S . Macroscopic conservation equations The macroscopic equations in the Navier–Stokes regime are obtained from the relations l l . 4. i. We introduce two types of di usion uxes. the right member i is in the range of the operator =i and the solution   is unique. ∈I .e.2. (4. the classical species di usion uxes given by XZ (ci − v)fi0 i dci . (4.13) ni Vi = I and the element di usion uxes de..

These transport uxes are expressed in terms of the species perturbed distribution functions as follows: DD EE Di . (4. I in such a way that X el = e nl V Eil ni Vi . l ∈ E .17) i∈S  @t     1 2 1 2 v + E + @x · v + E v + @x · (Q + P · v) 2 2 X i bi · (v + Vi ) : = (4. 3 (4.ned as XZ el = e nl V Eil (ci − v)fi0 i dci .f  I .15) i∈S After some algebra.19) Vi = kB T P = pI + .  = kB T .18) i∈S With the element di usion velocities given by Eq. @t (v) + @x · (v ⊗ v) + @x · P = (4. (4.20) . momentum and energy in the form el ) = 0. l∈E : (4.15). the heat ux vector Q and the pressure tensor P.14) i. f 0 + kB T  0 . we obtain the macroscopic equations expressing conservation of element densities. we still need to specify the species di usion velocities Vi for i ∈ S. f 0  .16) (4. nl v) + @x · (e nl V @t e nl + @x · (e X i bi . l ∈ E . (4. i ∈ S .

3. V.64 A. Giovangigli / Physica A 260 (1998) 49–72 Q=− DD 0 EE 0 .f  + X i∈S kB T 2 @pi Hi − pi @T  ni Vi . Transport coecients We . In the next section we express the transport uxes Eqs. (4. 4. Ern.19)–(4.21) in terms of various transport coecients. (4.21) where  is the viscous stress tensor.

and the heat ux vector Q. We introduce the shear viscosity  and the volume viscosity  given by kB T   < .22) and the viscous stress tensor then reads   2  = − @x v + (@x v)t − (@x · v)I − (@x · v)I : 3 (4.23) We next turn to the species di usion velocities Vi . 10 kB T   = < . i ∈ S. We de. 9 = (4.  = .  = .rst consider the viscous stress tensor .

ne the species multicomponent and the thermal di usion coecients as pkB T Di Dj < . 3 Dij = (4.26) l∈E The species di usion velocities may then be written as Vi = − X Dij dj − i @x log T. j ∈ S. 3 1 0 i = − < . 2 3kB T (4.  = .27) j∈S and the heat ux vector as Q = −0 @x T − p X i∈S i di + X i∈S Hi − kB T 2 @pi pi @T  ni Vi : (4. i∈S . j∈S : (4. i ∈ S .24) the partial thermal conductivity as 0 = 0 0 1 < .  =. (4. i.  Di =.25) and the di usion driving forces as 1 dj = p X @pj e l − j bj @x p @e pl ! .28) .

We .A. Giovangigli / Physica A 260 (1998) 49–72 65 It is also possible to use a formalism identical to the one arising for mixtures with nonequilibrium chemistry. Ern. V.

29) j∈S Thus.32) Upon introducing the integral equations b 0 ) = b 0 . by linearity.rst notice that X D @pj Dl = j : e @e pl (4. = 0. we obtain by linearity that b  − kB T 2  =  0 0 X j∈S  Dj @pj : @T (4. l (4. the corresponding solutions of the integral Boltzmann equations (4:11) are such that X D @pj Dl e =  j : @e pl (4.33) ∈I .34) We then de.31) in such a way that b  − kB T 2  = 0 0 X Dj j∈S @pj : @T (4. i ∈ S. =i ( i DD EE 0 b 0 l f  . (4. i 2 i∈S .30) j∈S We also introduce the quantities b 0 =(Hi − 1 mi (ci − v)2 − EiI )(ci − v).

38) .36) ! .  = = i − Dij 3 p @T (4. i∈S .  = . i ∈ S . .37) (4. j∈S (4.35) j∈S the partial thermal conductivity as b 0 = 1 b 0 b 0 < . 3kB T 2 and the species di usion driving forces as 1 dbj = p X @pj l∈E @pj el + @x T − j bj @x p @e pl @T (4.ne the thermal di usion coecients as @pj 1 b  0 Di T X b i = − <  . j∈S : The species di usion velocities Vi are then given by X Vi = − Dij dbj − b i @x log T.

39) i∈S It is possible to rewrite the species di usion velocities and the heat ux vector in terms of the thermal di usion ratios and the thermal conductivity [17].  =. 3kB T 2 mi b  =.42) j∈S we may write 1 b b < .40) b j = 0 . for i ∈ S.44) i∈S The transport coecients introduced above satisfy several important properties which result from those of the bracket operator < . j∈S while the thermal conductivity reads p Xb b j : j b =b 0 − T (4. are the unique solution of the constrained singular system X j = b Dij b i . i ∈ S.41) j∈S Upon introducing b 0 + pkB T b =   X b  j  Dj .45) p b p (  ) (D ) i i∈S ij i. with i = ((ci −v)ij )i∈S . j∈S T T is symmetric positive semi-de. =. Using the thermal conductivity and the thermal di usion ratios. i ∈ S. the matrix of order n + 1   p b 1 b0 T (i )i∈S T2    (4. First. The thermal di usion ratios b i . the species di usion velocities and the heat ux vector read X Dij (dbj + b  j @x log T ).  i = 3pkB T b = (4. (4. Ern.66 A. Giovangigli / Physica A 260 (1998) 49–72 and the heat ux vector by Q = −b 0 @x T − p X b i dbi + i∈S X Hi ni Vi : (4. Vi = − j∈S Q = −b @x T − p X i∈S b i Vi + X Hi ni Vi : (4. and we recover the formalism derived in [17] for nonreactive mixtures. j∈S X (4. b <i .43) i∈S . V.

nite with kernel spanned by the vector (0. Yn ). we may state that the thermal conductivity b  is positive and that the . Equivalently. : : : . Y1 .

V. Giovangigli / Physica A 260 (1998) 49–72 67 di usion matrix D = (Dij )i.A. j∈S is symmetric positive semi-de. Ern.

Finally. : : : .nite with kernel spanned by the mass fraction vector (Y1 . the latter being zero only if there are no polyatomic species in the mixture. we point out that it is possible to de. the shear viscosity  is positive and the volume viscosity  is nonnegative. On the other hand. Yn ).

. as follows: V ek = − V X l∈E e kl 1 @x p el − e D k @x log T + p X ni Dij j bj . j∈S and the thermal di usion coecients for the elements e k = X ni i Eik . bi = b for i ∈ S. i. (4. the last term in Eq. Introducing the matrix ( lm )l.46) vanishes. m∈E de.46) i. j∈S where we have introduced the element multicomponent di usion coecients e kl = D X ni @pj Dij Eik . (4. Indeed.e.48) i∈S Note also that when all the species external forces are equal.47) i. e nk @e pl k. k ∈E. we may write the element di usion velocities ek . Eik e nk p (4. l ∈ E .ne multicomponent and thermal di usion coecients for the elements. e nk k ∈E : (4.

ned in the appendix. the element multicomponent di usion coecients may be expressed as e kl = D X kB T lm m∈E X 1 Dij ni Eik nj Ejm : e nk (4. l∈E As opposed to the di usion matrix D. such as symmetry or positive de. j∈S e = (D e kl )k.49) i. the element di usion matrix D does not appear to have any simple structure properties.

4. As a result. it is more convenient e to use the species di usion matrix D rather than the element di usion matrix D. Entropy production and Onsager’s reciprocal relations It is well-known that at the .4. We will see in the next section that this matrix does not appear directly in the framework of Onsager’s reciprocal relations.niteness.

rst order in the Enskog expansion. The . the entropy may be evaluated using the zeroth order Maxwellian distribution functions.

denoted by S. reads S = −kB = X i∈S XZ fi1 (log(.rst-order entropy per unit volume.

I ni Si0 + O(”2 ) .50) .iI fi1 ) − 1) dci i. (4.

V. Giovangigli / Physica A 260 (1998) 49–72 where the zeroth-order molecular entropies are given by Eq. Ern. First. Qi (4. The Gibbs free energy per unit volume of the species Gi = Hi − TSi0 = kB T log ni . as a result of the chemical equilibrium conditions (3:5) we have (Gi )i∈S ∈ E : (4.9). (3.51) has several important properties.68 A. as a direct consequence of the .52) In addition.

we obtain the orthogonality property X Gi i∈S @ni =0 : @T (4. (A.2).rst relation in Eq.53) We then de.

59) . (4.58) l∈E This relation generalizes the Gibbs di erential relation to the kinetic chemical equilibrium regime. one can easily show that X X el . @e pl l∈E . we deduce that the di erential of the volumetric entropy in the Navier–Stokes equilibrium regime is given by the relation X e l de G T dS = dE − nl : (4.ne the Gibbs free energy per unit volume for the elements as el = G X Gi i∈S @pi .54) as well as the enthalpy per unit volume for the elements el = H X i∈S Hi @pi .57) Using the above relations. A straightforward calculation yields that @t S + @x · (vS) + @x · Js =  .55) Using the relations given in the appendix. e nl G ni Gi = G= i∈S l∈E X X and that H= i∈S ni Hi = el + T e nl H l∈E   @p : @T e pl (4. @e pl l∈E : (4.56) (4. (4. A conservation equation for S is then easily obtained from Eq.2. (4.58) and the macroscopic conservation equations stated in Section 4.

In order to expand the last term in Eq.60) l∈E and the entropy source term  reads X Q · @x T 1X :@x v e l · @x e nl V =− + − i Vi · bi − 2 T T T i∈S l∈E el G T ! : (4. read 0. we may write X X el = − 0. m ∈ E : i.A. m = i @pi . 0 @x T − ele ek . e le G nl V Js = Q− T (4. (4. 06k.61). l ∈ E . (4. (4. l∈E Using the expressions for the transport uxes obtained in the previous section. Ern. 0 = X i∈S k.62) @T T T pl e and el G T @ @e pk ! T. we assume that all the external forces are equal. we use the following relations: ! el el G H @ =− 2. @e pk k ∈ E. bi = b for i ∈ S. pT @e pk @e pm (4. 1 X @pi @pj Dij . so that the third term in the right member of Eq. 0. l∈E .67) k. m @x p 2 T k ∈E. m6ne . k. k = k. m .66) m∈E and the coecients k. V. nl V kB kle k. (4. . Giovangigli / Physica A 260 (1998) 49–72 69 where Js is the entropy ux vector given by ! X 1 el .64) =− x T2 T k. l∈E is symmetric and given explicitly in the appendix.61) For the sake of simplicity.61) vanishes. nl V H 0.63) where the matrix ( kl )k. The entropy source term may now be written as P el ele X nl V Q − l∈E H :@x v e l · @x p el : nl V − · @ T − kB kle (4. k @x p (4. e pm . m6=k = kB kl . (4. j∈S The above relations show that the entropy source term in the Navier–Stokes equilibrium regime is compatible with Onsager’s reciprocal relations. 0 @x T − em.65) Q− T2 l∈E and X l∈E k∈E X el = − k. 0 = T 2 0 .

however. the simplest structure in these equations is recovered by introducing species di usion velocities. as opposed to the linearized Boltzmann operator that would be obtained if the chemical reactions were considered as a slow process. (1) The preceding sections show that the underlying structure of the governing equations for gas mixtures in the kinetic chemical equilibrium regime is formally identical to the one obtained for gas mixtures in chemical nonequilibrium and then letting the chemical reactions approach equilibrium.68) 2T 3 3 From the properties of the transport coecients stated in Section 4. Indeed. we readily obtain that the entropy production term  is a sum of positive terms.3. Concluding remarks In this paper we have derived a theoretical framework for the kinetic chemical equilibrium regime introduced formally by Ludwig and Heil and we have presented a detailed investigation of the associated Euler and Navier–Stokes regimes. V. we present some useful di erential relations needed in this work. it is interesting to consider the following points. the mean average ow velocity. that the actual value of the transport coecients is di erent in each case. After some algebra.70 A. (2) It is also interesting to point out that although the macroscopic governing equations in the kinetic equilibrium regime express conservation of element densities instead of species densities. j∈S      2 2 @x v + (@x v)t − (@x · v)I : @x v + (@x v)t − (@x · v)I : + (4. This remark is valid for both the transport uxes and the entropy production. we get p X  @x T · @x T + Dij (dbi + b i @x log T ) · (dbj + b  j @x log T ) + (@x · v)2 =b  2 T T T i. Ern. It is actually impossible to eliminate completely the species from the governing equations since the volumetric energy of the mixture cannot be expressed as a combination of quantities only depending on the elements. It is important to notice. Giovangigli / Physica A 260 (1998) 49–72 Finally. We restate that in the kinetic chemical equilibrium regime the macroscopic independent variables are the element number densities. Di erential relations In this appendix. 5. Appendix. and the . As a conclusion. the linearized Boltzmann operator = contains terms accounting for reactive collisions. in the kinetic chemical equilibrium regime. we point out that the entropy source term may also be written using the same formalism as for gas mixtures in chemical nonequilibrium.

V. the species number densities ni . recalling that E is the element space de. As a result. i ∈ S. are functions of the element number densities e nl . They are given by X ni Eil = e nl . Ern. l ∈ E.A. Giovangigli / Physica A 260 (1998) 49–72 71 temperature.1)  i∈S ∈E . and the temperature T . i∈S  log ni Qi (A.

1) with respect to T .6). (3.ned by Eq. Di erentiating Eq. (A.

4)  i∈S ∈E .rst yields   @ni ∈ E⊥ . e l . @e nm i∈S   1 @ni ∈ E. (A. With the macroscopic variables (4:5).1) with respect to e nm . m ∈ E . as given by Eq. m ∈ E .2)   kB T 2 @ni Ei − ∈E . m ∈ E : pi @e pm i∈S (A. m ∈ E : ni @e nm i∈S (A. Eqs. (4. pi @T i∈S (A. yields X @ni Eil = lm . @T i∈S   kB T 2 @pi Hi − ∈E . @T i∈S (A. for m ∈ E. (A. the species partial pressures are functions of the element partial pressures p and the temperature T .1) now read X el . l ∈ E. @e pm i∈S   1 @pi ∈ E. pi Eil = p i∈S  pi log kB TQi (A. for m ∈ E.5) and X @pi Eil = lm .3) Rather than number densities.4) with respect to T and p   @pi ∈ E⊥ . it is also possible to consider partial pressures for the elements and the species.4).6) . yields and di erentiating Eq. ni @T i∈S while di erentiating Eq. e m . (A.

Z. 295–514. I. Alexeev. Physica 15 (1949) 913–932. Physica A 176 (1991) 542–556. i ∈ S.T.Th.J. Transporterscheinungen in Gasen von mittlerem Druck. . new series monographs. V. Appl. Mazur. Giovangigli. Ern. [11] W. W. 1936.8) i∈S References [1] A. Xhrouet. Prigogine. A. Rev. P. Ludwig. Ern. Springer. [12] I. 1994. E 49 (1994) 2809–2825. Giovangigli / Physica A 260 (1998) 49–72 From the second relation in Eq. (A. Springer.F. pp. Grushin.). Handbuch der Physik. Phys. V. Trubenbacher. Fowler. Cambridge. Giovangigli. E. [8] L. Phys. [14] F. Snider. m24. Physica A 214 (1995) 526–546. Krambeck. van Leeuwen. V. V. Shapiro.72 A. Kusc er. L. Cambridge Univ. 13 (1965) 353–375. Shapley. in: S. Physica A 224 (1996) 613–625. Ern. [16] R. Statistical Mechanics. [3] I. Phys. Physica 16 (1950) 51–64. 39–118. Phys. New York. [5] J. 12. [17] A. M. Waldmann. Zeitschr.H. [9] L. S. 35 (1961) 19–28. Rev. (A. Hermens. E. Chem. 32 (1960) 1051–1060. 1958. M.6) we deduce that there exist a matrix = ( kl )k. 38 (1970) 317–347. Giovangigli. Anal. Multicomponent Transport Algorithms.7) pi @e pl l∈E and a straightforward calculation shows that kl = lk = X 1 @pi @pi : pi @e pk @e pl (A. l∈E such that X 1 @pi = kl Eil . [13] A. vol. J. in: Advances in Applied Mechanics. Berlin. Math. [15] N.A. Flugge (Ed. de Groot.R. 1960. Heil. pp. [6] G. vol. [10] R. Press. Ch. SIAM J. l ∈ E .V. Chikhaoui. Giovangigli. E 53 (1996) 485– 492. [4] I. Waldmann. J. Ross. Mahieu. V. [2] B. Physica 60 (1972) 472– 487. van Weert. Naturforschg 17a (1962) 363–376. Ern. Prigogine. vol. Academic Press. Berlin. Chem.S. 6. Ern. Arch.G. Rational Mech. [7] A.