Nonequilibrium vibration-dissociation phenomena behind a propagating shock wave: Vibrational population calculation
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Abstract
An analysis of nonequilibrium phenomena behind a plane shock is presented concerning the vibrational relaxation and the dissociation of a pure diatomic gas. In the first part, the temperature range is 600 K–2500 K and the dissociation processes are neglected. The population of each vibrational level is computed by solving relaxation and conservation equations. The relaxation process is described by the master equations of each vibrational level. The vibrational transition probabilities appearing in the relaxation equations are calculated analytically and take into account the anharmonicity of molecular vibration and the potential angular dependence. The populations obtained are compared to those calculated using a Treanor model and to those calculated with a nonequilibrium Boltzmann distribution. For moderately high levels significant differences may be observed. The importance of the V-V process is found to be weak for the transitions involving the lowest levels. In the second part, the temperature range is 2500 K–5500K and the dissociation process is taken into account as well as the gas dynamic behavior which did not appear in several recent works. The kinetic equations are transformed to obtain a first order differential system and the resolution of such a system coupled with the conservation equations leads to the population of each vibrational level. The vibrational transition probabilities associated with the atom-molecule interaction are deduced from the cross section calculation used in the first part. The bound-free transition probabilities are obtained, following Marrone and Treanor, assuming that dissociation must occur preferentially from the higher vibrational states: the Marrone and Treanor probability model is extended and employed with an anharmonic oscillator. In the present investigation, behind the shock wave, the evolution of the population distribution expressed as a function of the distance is not monotonous: a lag time appears as shown experimentally in previous works for the macroscopic parameters. For moderately high levels the influence of the anharmonicity and those of the V-V processes appear significant and strongly related. In a general way, in both temperature ranges investigated, the V-V processes reduce the effects of the T-V transfer. Finally the influence of the“characteristic probability temperature” U of Marrone and Treanor is analyzed and a method of determination of local varying U is proposed.
Key words
Vibration-dissociation Vibrational populations Rate constants Vibrational cross-sectionsPreview
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References
- 1.Breshears WD, Bird PF, Kiefer JH (1971) Density gradient measurements of 02 dissociation in shock waves. J Chem Phys 55:4017–4026Google Scholar
- 2.Brun R, Zappoli B (1977) Model equations for a vibrationally relaxing gas. Phys Fluids 20:1441–1448Google Scholar
- 3.Brun R (1986) Transport et Relaxation dans les Ecoulements Gazeux Chap. 1, 2, 3, Masson, ParisGoogle Scholar
- 4.Camac M (1961) 02 Vibrational relaxation in Oxygen-Argon mixtures. J Chem Phys 34:448–459Google Scholar
- 5.Center RE, Caledonia GE (1971) Vibrational distribution functions in anharmonic ocillators. J Chem Phys 55:552–561Google Scholar
- 6.Cubley SJ, Mason E A (1975) Atom-molecule and molecule-molecule potentials and transport collision integrals for high-temperature air species. Phys Fluids 18:1109–1111Google Scholar
- 7.Gonzales D, Varghese PL (1992) Master equation calculations of vibrational nonequilibrium and dissociation kinetics. I U T A M Symposium, Marseille, FranceGoogle Scholar
- 8.Herzfeld KF, Litovitz TA (1959) Absorbsion and dispersion of ultrasonic waves. Chap. 7 Academic Press, New YorkGoogle Scholar
- 9.Hirschfelder J, Curtis C, Bird R (1954) Molecular theory of gases and liquids. Chap. 13, 14, Wiley Inc., New-YorkGoogle Scholar
- 10.Kafri A, Levine RD (1976) Comment on the dynamics of dissociation of diatomic molecules: mass and temperature effects. J Chem Phys 64:5320–5321Google Scholar
- 11.Keck J, Carrier G (1965) Diffusion theory of nonequilibrium dissociation and recombination. J Chem Phys 43:2284–2298Google Scholar
- 12.Kiefer JH, Hajduk JC (1976) A vibrational bias mechanism for diatomic dissociation: induction times and steady rate for O2, H2 and D2 diluate in Ar. J Chem Phys 64: 5320–5321.Google Scholar
- 13.Lambert JD (1977) Vibrational and rotational relaxation in gases. Chap. 3, 4. Clarendon Press, OxfordGoogle Scholar
- 14.Landau L, Teller E (1936) Theory of sound dispersion. Phys Zeit Sowj 10:34–43.Google Scholar
- 15.Landrum BD, Candler GV (1992) Vibration-dissociation coupling in nonequilibrium flows. J Therm and Heat Transf 6:643–649Google Scholar
- 16.Marrone PV, Treanor CE (1963) Chemical relaxation with preferential dissociation from excited vibrational Level. Phys Fluids 6:1215–1221Google Scholar
- 17.Meolans JG, Chauvin AH (1976) Matrice de vibration du potentiel d'interaction pour des molécules considerées comme des oscillateurs de Morse. Physica C 84:432–438Google Scholar
- 18.Meolans JG, Chauvin AH (1991) Scattering cross sections for homonuclear diatomic molecule collisions: influence of the angular potential dependence. AIAA-91-1340 26th Thermophysics Conf Honolulu, Hawaii.Google Scholar
- 19.Meolans JG (1992) Echanges vibrationnels dans les gaz diatomiques. Thèse de doctorates-sciences physiques. Université de Provence, Marseille, FranceGoogle Scholar
- 20.Millikan RC, White RD (1963) Systematics of vibrational relaxation. J Chem Phys 64:3209–3213Google Scholar
- 21.Park C (1988) Two-temperature interpretation of dissociation rate data for N2 and O2. AIAA-88-0459, Thermophysics Conf USA.Google Scholar
- 22.Park C (1990) Nonequilibrium hypersonic aerothermodynamics. Chap. 3, Sect. 3. 4 and 3. 5. John Wiley and Sons, New York.Google Scholar
- 23.Park C (1993) Review of chemical kinetic problems of future NASA missions, I: Earth entries. J Therm and Heat Transf 7:385–398Google Scholar
- 24.Reddy NM (1969) A modified model for vibration-dissociation coupling phenomena. AIAA J 7:1179–1180Google Scholar
- 25.Schwartz RM, Slawky ZI, Herzfeld KF (1952) Calculations of vibrational relaxation times in gases. J Chem Phys 20:1591–1599Google Scholar
- 25a.Schwartz RN, Herzfeld KF (1954) Vibrational relaxation times in gases. J Chem Phys 22:767–773.Google Scholar
- 26.Sharma SP, Huo WM, Park C (1988) The rate parameters for coupled vibration-dissociation in a generalized S.S.H aproximation. AIAA-88-2714, Thermophysics, Plasmadynamics and Lasers, San Antonio, TexasGoogle Scholar
- 27.Stupochenko YV, Losev SA, Osipov AI (1967) Relaxation in shock waves. Springer-Verlag, New-YorkGoogle Scholar
- 28.Tanczos FI (1956) Calculation of vibrational times of the Chloromethanes. J Chem Phys 25:439–446Google Scholar
- 29.Treanor CE, Rich JW, Rehm RG (1967) Vibrational relaxation of oscillators with exchange-dominated collisions. J Chem Phys 42:1798–1807Google Scholar