Nonstandard reaction kinetics: microscopic simulations of system with product removal

We perform Monte Carlo microscopic simulations of reactive gas system in wh ich products are removed. The chemical reaction induces deformation of the equilibrium particle velocity distribution which in turn results in perturb ation of reaction kinetics. The nonequilibrium corrections to the standard chemical kinetics are deduced from the Monte Carlo simulations. For reactio ns sufficiently slow, the results of the simulations confirm the theoretica l predictions obtained from the perturbation solution of the Boltzmann equa tion. The simulations are also used to examine the range of convergence of the perturbation solution for fast reactions with low activation energies. The reason for the difference between the results for reaction with product s neglected or included is discussed. (C) 2001 Elsevier Science B.V. All ri ghts reserved.