Master equation study of three-body recombination of nitrogen and oxygen in non-equilibrium hypersonic flows

TL;DR

This study uses master equations to analyze non-equilibrium energy transfer and recombination in nitrogen and oxygen systems during rapid cooling, providing detailed insights into relaxation processes and rate constants.

Contribution

It offers a state-to-state analysis of non-equilibrium recombination in N₂+N and O₂+O systems, highlighting differences in relaxation times and proposing improved binning strategies.

Findings

Rotational relaxation is faster than vibrational in N₂+N.

Relaxation times differ between heating and cooling, with faster cooling.

Effective recombination rate constants are derived for quasi-steady states.

Abstract

This work aims to study the energy transfer and recombination processes in N$_{2}$$\left(^{1}\sum^{+}_{g}\right)$+N$\left(^{4}S_{u}\right)$ and O$_{2}$$\left(^{3}\sum^{+}_{g}\right)$+O$\left(^{3}P_{2}\right)$ chemical systems when the system is suddenly cooled in a 0-D isothermal reactor thereby inducing strong non-equilibrium. A state-to-state (StS) study of the non-equilibrium phenomenon is crucial for developing accurate and efficient reduced-order models that can accurately capture the thermophysics involved. The gas mixture, consisting primarily of atoms at a high initial temperature of 10,000 K, is suddenly plunged into a low-temperature heat bath to simulate non-equilibrium recombination conditions. The population distribution of microscopic energy levels for each system is determined by solving a system of master equations. The conventional assumption of faster equilibration of rotational mode as compared to the vibrational mode holds for $ N_2 +N$, while it is not a very strong assumption for $ O_2 +O$ as the two relaxation time scales are comparable. Effective recombination rate constants for the quasi-steady state (QSS) period are calculated using the population distribution obtained by solving the master equations. It was also observed that the relaxation time constants for heating and cooling are different, with the time constant being lower for the cooling case due to anharmonicity effects in expanding flows. An attempt has also been made to use the insights from the StS analysis to determine an accurate binning strategy for the recombination processes involved in the two chemical systems.