Calculation of two-temperature thermodynamic and transport properties for argon, oxygen, nitrogen and air plasmas at atmospheric pressure

Ph. Teulet1, Y. Cressault1, H. Hingana1, M. Bouyssi1, A. Gleizes1 and A. Piquemal2

1

Laplace, UMR 5213, Universit Paul Sabatier, 118 Rte de Narbonne, 31062 Toulouse cx 9, France.
2

CEA DAM Ile de France, BP 12, 91680 Bruyres Le Chatel, France.

Abstract: This paper deals with the calculation of two-temperature (2T) oxygen, nitrogen, air and argon plasma properties (compositions, thermodynamic properties and transport coefficients). 3 different techniques are developed and confronted to obtain the plasma composition: a steady-state collisional-radiative (CR) model, a transient kinetic model and a simplified model based upon a 2T mass action law. Thermodynamic properties are than calculated analytically and transport coefficients are obtained from recent theoretical developments. Keywords: Argon; Air; 2T composition; thermodynamic and transport properties.

1. Introduction
Electric arcs and thermal plasmas are often studied under the assumption of local thermodynamic equilibrium (LTE). However, it is well known that the LTE assumption is not valid any more in some particular areas of the plasma: in the close vicinity of the electrodes and the walls and in the external zones of the arc where the turbulence phenomenon and the pumping of surrounding cold gas play a significant role. The LTE assumption is also dubious during arc decay or within the plasma column in the case of low power arcs. In this last case, the temperature on the axis of the plasma remains relatively low. Thus the collisions are not enough efficient to ensure an equal distribution of the energy between the various chemical species. The consequence is that the electrons have a kinetic temperature Te higher than that of the heavy species Tg. To study theoretically this kind of discharge taking into account the possible occurrence of departures from thermal equilibrium, it is necessary to develop multi temperature hydrodynamic models. There are currently several publications in the literature dealing with 2T fluid models such as the works of El Morsli and Proulx [1] concerning a RF ICP torch or Ghorui et al. [2] for the study of the gas flow inside the nozzle of a metal cutting device. The implementation of these multi temperature models is often based upon 2T thermodynamic and transport property databases as a function of Te and of the

ratio = Te/Tg. The present work falls under these problems as it concerns the calculation of 2T plasma properties for argon, nitrogen, oxygen and air plasma. In spite of the large number of previous works dealing with this problem, there is no consensus in the literature and the theory allowing the computation of 2T plasma compositions, thermodynamic properties and transport coefficients is not yet clearly established.

2. Theory and methods

The first step to obtain the 2T properties of the plasma is the calculation of the composition. In the present work, several approaches have been developed to obtain the 2T composition: a steadystate collisional-radiative (CR) model, a transient kinetic (K) model and a simplified model based upon a 2T mass action (MA) law. 2.1. The 2T mass action (MA) law model The model presented here is built on the formalism of Godin and Trpanier [3]. 31 chemical species are considered: N2O3, N2O4, N2O5, NO3, NO2, N2O, O3, N3, NO2-, N2O+, N2, O2, NO, N2+, O2+, O2- and NO+, O, N and Ar, O+, O++, O+++, O-, N+, N++, N+++, Ar+, Ar++ and Ar+++ and the electrons. The four basic equations of the model are the electrical neutrality, the conservation of the stoechiometric proportions between N and O and N and Ar, and the Daltons law. These relations can be written as:

Z n
i =1 i

=0

(1)

Where N is the total number of chemical species. Zi and ni are respectively the charge and the population number density of the ith species.

j ni C i ,k = k ni C i , j
i =1 i =1

(2)

Where j and k are the relative proportions of two elementary species and Ci,j and Ci,k are the elements of the composition matrix [3].

where all the electronic levels are coalesced for each chemical species. In this work, the following levels or species are considered : O2(X, a, b, A, B), O2+ (X, a, A, b), O2- (X), N2 (X, A, B, C), N2+ (X, A, B, C), NO (X, A, B, C, B, F), NO+ (X, a, b, b, A), 24 levels for the oxygen atom, 35 levels for N, 20 levels for Ar, the fundamentals states of O+(4S), N+(3P) Ar+(2P) and O-(2P) and the electrons. The system of equations to be solved is constituted of relations (1), (2) and (3) and of a conservation equation for each electronic level or chemical species given by:

P = kTe ne + kTg

i =1, i e

(3)

ni = C i ni Di = 0 t CR

(6)

It is possible to write relations (1), (2) and (3) as a function of the population number densities of the electrons and the atoms (ne, nN, nO and nAr). All other densities can be expressed from these four densities through the mass action law (this law can be written for each chemical reaction occurring in the plasma):

n = Q
i

(4)

i =1

i =1

Where M is the number of chemical species involved in the considered chemical reaction. i are the stoechiometric coefficients of the reaction and Qi the total volumic partition function given by:
E 2mi kTtr int Qi = Qi (Tex , Tv , Tr ) exp 2 kT h ex
ref i 3 2

Where ni is the population number density of the level or species i. The terms Ci and Di depend on the population densities of the other species and on the forward and reverse rate coefficients of the chemical reactions occurring in the plasma. The reaction rate coefficient database used in the present study is taken from [5-6]. In the case of a multi-temperature plasma, the critical point for the development of a CR model concerns the 2T laws (Boltzmann, Saha and Guldberg-Waage laws) used for the calculation of the reverse rate coefficients (detailed balance principle). In this work the have chosen the following formalism:
Ei E j ni g = i exp kT * nj g j
1.5

th

(7)

(5)
ne ni+ 2 g i+ 2me kTe Ii = exp * ni gi h 2 kT

(8)

Where E

ref i

is the reference energy of the i species

(i.e. the enthalpy of formation at 298K) and Qiint the internal partition function. The translation temperature Ttr is equal to Te for electrons and to Tg for heavy particles. The rotation temperature Tr = Tg. Tex (electronic excitation temperature) and Tv (vibration temperature) are varying between Te and Tg. They are determined from chemical kinetics considerations (see [4] for details). 2.2. The collisional-radiative (CR) model Two CR codes have been developed: a complex model taking into account several electronic levels for each chemical species and a simplified model

n AnB g A g B 2 AB kTg = n AB g AB h2

DAB exp kT *

1.5

(9)

Where g is the degeneracy of the electronic level or the internal partition function of the chemical species. AB is the reduced mass of the molecule AB. Ei and Ej are the energies of the electronic levels i and j. Ii and DAB are respectively the ionization energy of the state i and the dissociation energy of the molecule AB. T* is a temperature characteristic of the chemical process: if an electron is involved in the reverse reaction T* = Te.

if the mechanism occurs only with heavy particles T* = Tg.

H e C Pe ( , Te ) = T e
H g C Pg ( , Te ) = T g

P
P

(13)

2.3. The transient kinetic (K) model With this approach, 15 chemical species are considered: N2, O2, NO, N2+, O2+, O2-, NO+, O, N, Ar, O+, O-, N+, Ar+ and the electrons. A conservation equation is written for each chemical species:
N n kT n ni n = Ci ni Di i g e + i coll t P t coll i = 2 t rad rad n T (10) i i Ti t P

(14)

According to Brand and Kopainsky [7], the two last terms of this equation have to be added to the two first one of creation and destruction (Ci and niDi) to ensure pressure conservation during the temperature decay. This set of equations is solved with the CHEMEQ2 algorithm [8] assuming a cooling temperature low enough in order to obtain a solution corresponding to the steady-state case. 2.4. Thermodynamic and transport properties Recent works dealing with hydrodynamic modeling of 2T plasmas have shown that it is necessary to write two distinct and coupled energy conservation equations (one for the electrons and the other for heavy particles). It is thus necessary to calculate separately the transport coefficients and the thermodynamic properties of the electrons and heavy species involved in the energy conservation equations. The enthalpies (J/kg) are then given by:

The calculation of the transport coefficients, i.e. the electrical conductivity (S/m), the viscosity (kg.m1 -1 .s ) and the thermal conductivity of electrons e(W.m-1.K-1) and heavy particles g(W.m-1.K-1) is based upon the Chapman-Enskog theory [9] and on the works of Bonnefoi [10], Rat et al. [11] and Ghorui et al. [12]. All the details concerning the method of calculation and the analytical expressions of the 2T transport coefficients presented in this work are available in [13].

3. Results and discussions

The population number densities of ionized species for a 2T atmospheric pressure air plasma ( = Te/Tg = 2) obtained with the complex CR model are presented in the Figure 1. Abrupt transitions in the population densities are clearly observable and it is also evident that there is not a single solution for the 2T composition in the temperature range 9600K < Te < 10400K. Indeed, population densities are different in this temperature interval in the case of the down convergence (i.e. the computation is started at high temperature with a 100K decreasing step) and for the up convergence (calculation with an increasing temperature). This temperature area (9600K < Te < 10400K) corresponds to the transition between the domination of the heavy particle reactions (at low temperature) and the predominance of the electron collisions (at high temperature). This result will have a significant effect on the transport and thermodynamic properties. The figures 2 and 3 present the enthalpy and the thermal conductivity of heavy particles for 2T air and argon plasmas respectively. As expected, the enthalpy exhibits rapid changes located at the same electron temperature as the population number density transitions observable in the figure 1. Concerning the thermal conductivity of heavy species (figure 3), we can see a decrease of g with increasing . Differences are also clearly observable

H g ( , Te ) =
+ kTg2

N 5 kTg N i 2 i =1 ( i e )
N ln Qiint + N i Eiref Tg i =1( i e )

i =1( i e )

Ni

(11)

H e ( , Te ) =

5 kTe N e 2

(12)

Where Ni (kg-1) = ni/. The specific heats at constant pressure CP (J.kg-1.K-1) are then calculated as numerical derivatives of the enthalpies:

between the different models used to obtain the 2T composition. Moreover, strong breaks are visible with the MA model in the case of up convergence.
10 10
23 22

4. Conclusion
Several methods have been developed to determine the composition in the case of a multi-temperature plasma. These results are then used to calculate the thermodynamic and transport properties in the case of argon, oxygen, nitrogen and air plasmas with the aim to test the influence of the method of calculation of the composition on the plasma properties.

Population number density (m )

10 10 10 10 10 10 10 10 10 10

21

P = 0.1 MPa =2

Air plasma
NO
+

-3

20

19

NO

18

17

References
N
+

16

15

14

[1] El Morsli M, Proulx P, J. Phys. D: Appl. Phys., 40, 4810 (2007)

9000 9500 10000 10500 11000

13

12

7500

8000

8500

[2] Ghorui S, Heberlein J.V.R, Pfender E, J. Phys. D Appl. Phys., 40, 1966 (2007) [3] Godin D and Trpanier J Y, Plasma Chem. Plasma Proc. 24, 447 (2004) [4] Gleizes A, Chervy B and Gonzalez J J, J. Phys. D appl. Phys. 32, 2060 (1999) [5] Teulet Ph, Sarrette J P and Gomes A M, J. Quant. Spectrosc. Radiat. Transfer, 70, 159 (2001)

Electron temperature Te (K)

Figure 1. Population number densities of charged species (complex CR model). Arrows indicate up or down convergence.

1,0x10

Enthalpy of heavy species Hg (J.kg )

8,0x10

=1 =2

Air plasma P = 0.1 MPa

-1

6,0x10

[6] Teulet Ph, Gonzalez J J, Mercado-Cabrera A, Cressault Y and Gleizes A, J. Phys. D: Appl. Phys., 42, 175201 (2009) [7] Brand K P and Kopainsky J, Appl. Phys., 16, 425 (1978) [8] Mott D R and Oran E E, CHEMEQ2: A solver for the stiff ordinary differential equations of chemical kinetics, NRL memorandum Report 640001-8553 (2001)

4,0x10

2,0x10

0,0 2000 4000 6000 8000 10000 12000 14000

Electron temperature Te (K)

Figure 2. Enthalpy of heavy species (complex CR model). Arrows indicate up or down convergence.

[9] Hirschfelder J O, Curtis C F, Bird R B, Molecular theory of gases and liquids, John Wiley and Sons, New York (1964) [10] Bonnefoi C, Contribution ltude des mthodes de rsolution de lquation de Boltzmann dans un plasma deux tempratures: exemple le mlange argon-hydrogne, PhD Thesis n15-83, Universit de Limoges (1983) [11] Rat V, Andre P, Aubreton J, Elchinger M F, Fauchais P, Lefort A, Phys. Rev. E, 64, 026409 (2001) [12] Ghorui S, Heberlein J V R, Pfender E, Plasma Chem. Plasma Proc., 27, 267 (2007) [13] Hingana H, Contribution ltude des proprits des plasmas deux tempratures Application lArgon et lAir PhD thesis, Universit Paul Sabatier (2010)

Figure 3. Thermal conductivity of heavy species for argon.