Chemical reactions in non-equilibrium gas mixtures and mass action law breakdown

Strong deviation of chemical reaction rates from their equilibrium values in vibrationally non-equilibrium gas is shown. Performed analysis is based on a new approach for solving the generalized Boltzmann equation. It allows to overstep the limits of a traditional method, where the part of the collisional integral responsible for chemical reactions is assumed to be small (of the order of the Knudsen number). Another generalization consists in considering both the monomolecular and collisional reaction paths. The influence of non-equilibrium vibrational distributions, which are caused by the chemical reactions, on the chemical reactions themselves is studied. Strong correlation between parallel reactions (when one molecule reacts with a number of others) is shown. The situation when one reaction blocks another one is described. Such a behavior of the reaction rates means the mass action law breakdown.