A macroscopic chemistry method for the direct simulation of non-equilibrium gas flows

The macroscopic chemistry method for modelling non-equilibrium reacting gas flows with the direct simulation Monte Carlo (DSMC) method is developed and tested. In the macroscopic method, the calculation of chemical reactions is decoupled from the DSMC collision routine. The number of reaction events that must be performed in a cell is calculated with macroscopic rate expressions. These expressions use local macroscopic information such as kinetic temperatures and density. The macroscopic method is applied to a symmetrical diatomic gas. For each dissociation event, a single diatom is selected with a probability based on internal energy and is dissociated into two atoms. For each recombination event, two atoms are selected at random and replaced by a single diatom. To account for the dissociation energy, the thermal energies of all particles in the cell are adjusted. The macroscopic method differs from conventional collision-based DSMC chemistry procedures, where reactions are performed as an integral part of the collision routine. The most important advantage offered by the macroscopic method is that it can utilise reaction rates that are any function of the macroscopic flow conditions. It therefore allows DSMC chemistry calculations to be performed using rate expressions for which no conventional chemistry model may exist. Given the accuracy and flexibility of the macroscopic method, it has significant potential for modelling reacting non-equilibrium gas flows. The macroscopic method is tested by performing DSMC calculations and comparing the results to those obtained using conventional DSMC chemistry models and experimental data. The macroscopic method gives density profiles in good agreement with experimental data in the chemical relaxation region downstream of a strong shock. Within the shock where strongly non-equilibrium conditions prevail, the macroscopic method provides good agreement with a conventional chemistry model. For the flow over a blunt axisymmetric cylinder, which also exhibits strongly non-equilibrium conditions, the macroscopic method also gives reasonable agreement with conventional chemistry models. The ability of the macroscopic method to utilise any rate expression is demonstrated by using a two-temperature rate model that accounts for dissociation-vibration coupling effects that are important in non-equilibrium reacting flows. Relative to the case without dissociation-vibration coupling, the macroscopic method with the two-temperature model gives reduced dissociation rates in vibrationally cold flows, as expected. Also, for the blunt cylinder flow, the two-temperature model gives reduced surface heat fluxes, as expected. The macroscopic method is also tested with a number density dependent form of the equilibrium constant. For zero-dimensional chemical relaxation, the resulting relaxation histories are in good agreement with those provided by an exact Runge-Kutta solution of the relaxation behaviour. Reviews of basic DSMC procedures and conventional DSMC chemistry models are also given. A method for obtaining the variable hard sphere parameters for collisions between particles of different species is given. Borgnakke-Larsen schemes for modelling internal energy exchange are examined in detail. Both continuous rotational and quantised vibrational energy modes are considered. Detailed derivations of viscosity and collision rate expressions for the generalised hard sphere model of Hassan and Hash [Phys. Fluids 5, 738 (1993)] and the modified version of Macrossan and Lilley [J. Thermophys. Heat Transfer 17, 289 (2003)] are also given.