Rovibrational internal energy transfer and dissociation of high-temperature oxygen mixture.

This work constructs a rovibrational state-to-state model for the O2 + O2 system leveraging high-fidelity potential energy surfaces and quasi-classical trajectory calculations. The model is used to investigate internal energy transfer and nonequilibrium reactive processes in a dissociating environment using a master equation approach, whereby the kinetics of each internal rovibrational state is explicitly computed. To cope with the exponentially large number of elementary processes that characterize reactive bimolecular collisions, the internal states of the collision partner are assumed to follow a Boltzmann distribution at a prescribed internal temperature. This procedure makes the problem tractable, reducing the computational cost to a comparable scale with the O2 + O system. The constructed rovibrational-specific kinetic database covers the temperature range of 7500-20 000 K. The reaction rate coefficients included in the database are parameterized in the function of kinetic and internal temperatures. Analysis of the energy transfer and dissociation process in isochoric and isothermal conditions reveals that significant departure from the equilibrium Boltzmann distribution occurs during the energy transfer and dissociation phase. Comparing the population distribution of the O2 molecules against the O2 + O case demonstrates a more significant extent of nonequilibrium characterized by a more diffuse distribution whereby the vibrational strands are more clearly identifiable. This is partly due to less efficient mixing of the rovibrational states, which results in more diffuse rovibrational distributions in the quasi-steady-state distribution of O2 + O2. A master equation analysis for the combined O2 + O and O2 + O2 system reveals that the O2 + O2 system governs the early stage of energy transfer, whereas the O2 + O system takes control of the dissociation dynamics. The findings of the present work will provide a strong physical foundation that can be exploited to construct an improved reduced-order model for oxygen chemistry.

Thermochemical nonequilibrium flow analysis in low enthalpy shock-tunnel facility.

A thermochemical nonequilibrium analysis was performed under the low enthalpy shock-tunnel flows. A quasi-one-dimensional flow calculation was employed by dividing the flow calculations into two parts, for the shock-tube and the Mach 6 nozzle. To describe the thermochemical nonequilibrium of the low enthalpy shock-tunnel flows, a three-temperature model is proposed. The three-temperature model treats the vibrational nonequilibrium of O2 and NO separately from the single nonequilibrium energy mode of the previous two-temperature model. In the three-temperature model, electron-electronic energies and vibrational energy of N2 are grouped as one energy mode, and vibrational energies of O2, O2+, and NO are grouped as another energy mode. The results for the shock-tunnel flows calculated using the three-temperature model were then compared with existing experimental data and the results obtained from one- and two-temperature models, for various operating conditions of the K1 shock-tunnel facility. The results of the thermochemical nonequilibrium analysis of the low enthalpy shock-tunnel flows suggest that the nonequilibrium characteristics of N2 and O2 need to be treated separately. The vibrational relaxation of O2 is much faster than that of N2 in low enthalpy condition, and the dissociation rate of O2 is manly influenced by the species vibrational temperature of O2. The proposed three-temperature model is able to describe the thermochemical nonequilibrium characteristics of N2 and O2 behind the incident and reflected shock waves, and the rapid vibrational freezing of N2 in nozzle expanding flows.

Electronic-state-resolved analysis of high-enthalpy air plasma flows.

In the present study, three different electronic state-to-state methods are proposed to analyze nonequilibrium air plasma flows behind a strong shock wave. In the first approach representing the conventional method, a two-temperature model combined with the electronic quasi-steady-state assumption is adopted. In the second and the third methods, atomic and molecular electronic master equations are coupled with a conservation equation to describe the electronic state-to-state kinetics. State-of-the-art electronic transition rates for atmospheric gas species are compiled with comparisons of existing data. A prediction of the measured nonequilibrium radiation is made for the flow conditions of recent electric-arc shock tube experiments. In a comparison with the measured spectrum, the present electronic master equation coupling methods are more accurate than the conventional approach when used to estimate the initial rising rate and peak value of the diatomic intensity and small amounts of atomic radiation when the diatomic nonequilibrium condition is dominant. Moreover, the spatial distributions of the intensity and electron number density are more accurately predicted by the present methods when the flow fields are dominated by atomic nonequilibrium.