The role of products and a reverse reaction in analysis of nonequilibrium effects in a bimolecular chemical reaction in a dilute gas

Abstract

A thermally activated bimolecular reaction in a dilute gas is analyzed. The Shizgal–Karplus perturbation method of solution of the Boltzmann equation for reactions A+A→B+B and A+A⇆B+B is used to obtain the analytical expressions for the nonequilibrium temperatures of reactants and for the rate of chemical reaction. For both the reactions the temperatures of components obtained within one and two Sonines approximations depend on concentration of products. The rate constant of chemical reaction depends on concentration of products for the first reaction only and for the second reaction is constant. The analytical results for the temperature of the reactant A are compared with those obtained from the Monte Carlo computer simulations with use of the Bird method. It is shown that all analytical expressions simplify to those previously discussed if the concentration of products is negligible.