Reaction rate coefficients and thermodynamic and transport properties are provided for the 11-species air model which can be used for analyzing flows in chemical and thermal nonequilibrium. Such flows will likely occur around currently planned and future hypersonic vehicles. Guidelines for determining the state of the surrounding environment are provided. Approximate and more exact formulas are provided for computing the properties of partially ionized air mixtures in such environments.

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A review of reaction rates and thermodynamic and transport properties for the 11-species air model for chemical and thermal nonequilibrium calculations to 30000 K

A two-temperatur e chemical-kinet ic model for air is assessed by comparing theoretical results with existing experimental data obtained in shock tubes, ballistic ranges, and flight experiments. In the model, one temperature (T) is assumed to characterize the heavy-particle translational and molecular rotational energies, and another temperature (Tv) the molecular vibrational, electron translational, and electronic excitation energies. The theoretical results for nonequilibrium flow in shock tubes are obtained using the computer code STRAP (shock-tube radiation program) and for flow along the stagnation streamline in the shock layer over spherical bodies using the newly developed code SPRAP (stagnation-point radiation program). Substantial agreement is shown between the theoretical and experimental results for relaxation times and radiative heat fluxes. At very high temperatures, the spectral calculations need further improvement. The present agreement provides strong evidence that the two-temperature model characterizes principal features of nonequilibriu m airflow. New theoretical results using the model are presented for the radiative heat fluxes at the stagnation point of 6 m radius sphere, representing an aeroassisted orbital transfer vehicle, over a range of freestream conditions. Assumptions, approximations, and limitations of the model are discussed. Nomenclature = average molecular speed ^/$kT/nm, cm s ~ ! = pre-exponential factor in reaction rate coefficient, cm3mole~ 1 s~ * - average vibrational energy per particle, erg = average vibrational energy per particle under equilibrium, erg = reaction energy, erg

Assessment of two-temperature kinetic model for ionizing air

The rate of molecular dissociation behind strong shock waves is calculated with the assumption that dissociation can occur preferentially from the higher vibrational levels. An exponential probability of dissociation from the various vibrational levels is employed using an anharmonic oscillator model. Results for the dissociation of oxygen in an argon diluent are presented. Vibrational non‐equilibrium introduces a T−3 temperature dependence into the oxygen dissociation rate constant in the range 4000°–8000°K. A dissociation lag‐time of the order of the extrapolated vibrational relax ation time is predicted immediately behind the shock front. The computed results are shown to be in agreement with available experimental results.

Chemical Relaxation with Preferential Dissociation from Excited Vibrational Levels

The validity of the author's two-temperature, chemical/kinetic model which the author has recently improved is assessed by comparing the calculated results with the existing experimental data for nitrogen in the dissociating and weakly ionizing regime produced behind a normal shock wave. The computer program Shock Tube Radiation Program (STRAP) based on the two-temperature model is used in calculating the flow properties behind the shock wave and the Nonequilibrium Air Radiation (NEQAIR) program, in determining the radiative characteristics of the flow. Both programs were developed earlier. Comparison is made between the calculated and the existing shock tube data on (1) spectra in the equilibrium region, (2) rotational temperature of the N2(+) B state, (3) vibrational temperature of the N2(+) B state, (4) electronic excitation temperature of the N2 B state, (5) the shape of time-variation of radiation intensities, (6) the times to reach the peak in radiation intensity and equilibrium, and (7) the ratio of nonequilibrium to equilibrium radiative heat fluxes. Good agreement is seen between the experimental data and the present calculation except for the vibrational temperature. A possible reason for the discrepancy is given.

Assessment of a two-temperature kinetic model for dissociating and weakly ionizing nitrogen

The coupled vibration—dissociation—recombination process for molecules and atoms has been examined. Techniques for solving the appropriate master equations for both quantum (discrete) and classical (continuous) models are given. It is shown that the process is most easily treated classically and that in this case the master equation can be reduced to an equivalent diffusion equation. It is assumed that, after an initial vibration transient, during which reactions are negligible, the process may be treated using the steady‐state approximation. During the steady‐state phase, the usual phenomenological rate equations are valid and the ratio of the forward and reverse rate constants is the equilibrium constant, though the individual rate constants are depressed below their equilibrium values.Comparison of the results with other theoretical work shows general agreement for similar models; comparison with shock‐tube experiments on molecular dissociation and stellarator experiments on ionic recombination is enco...

Diffusion theory of nonequilibrium dissociation and recombination

The rate of dissociation behind strong shock waves in N2 and O2 is calculated using a revised model for the coupling of vibration and dissociation. In previous calculations a model which coupled the rate of dissociation to the degree of vibrational excitation was used. The present model adds to the coupled vibration‐dissociation model the fact that the rate of vibrational excitation is in part determined by the rate of dissociation. Since the average energy of molecules which are dissociated is greater than the average energy of the remaining molecules, this coupling results in a drain on the average vibrational energy. It is shown that this coupling reduces the strong overshoot in vibrational energy that was previously obtained, and decreases the rate of dissociation behind strong shocks.

Effect of Dissociation on the Rate of Vibrational Relaxation

: The coupling between vibrational relaxation and dissociation is discussed. A model for computations of dissociation behind strong shock waves is presented. It is shown that the loss of vibrational energy during dissociation introduces an inverse temperature dependence into the observed dissociation rate of O2 between 4000 and 8000K. Changing the model so that dissociation from higher vibrational levels is enhanced results in a dissociation-incubation time immediately behind the shock. The vibrational-energy distribution behind the shock is calculated, and shown to depart considerably from a Boltzmann distribution. The molecular model, which uses a Boltzmann distribution, is shown to give the same result as the non-Boltzmann model for both the nonequilibrium dissociation rate and the dissociation incubation time. (Author)

Charles E. Treanor

Papers

Chemical Relaxation with Preferential Dissociation from Excited Vibrational Levels

Effect of Dissociation on the Rate of Vibrational Relaxation

Vibrations and dissociation coupling behind strong shock waves