Nonequilibrium Contributions to the Rate of Reactions. II. Isolated Multicomponent Systems

The nonequilibrium rates of reaction in multicomponent reactive systems are obtained by solving the Champman–Enskog equation. A Sonine polynomial expansion is used for the solution and its convergence is demonstrated for a wide range of system variables. It is found that the perturbation of the velocity distribution function for each reactive component depends on the deviation of the reactive collision frequency $R^{\text{(0)}}({\mathbf{c}}_{\gamma })$ from a special form ${\mathrm{R̄}}^{\text{(0)}}({\mathbf{c}}_{\gamma })$ . A model reactive system was examined with line‐of‐centers reactive cross sections and hard‐sphere elastic cross sections chosen to fit the available data for the reaction H₂+Cl=HCl+H. The deviation of the ratio of the forward and reverse rate coefficients ${\mathrm{(k}}_f{\mathrm{\hspace{0.17em}/\hspace{0.17em}k}}_r)$ from the equilibrium value ${\mathrm{(k}}_f^{\text{(0)}}{\mathrm{\hspace{0.17em}/\hspace{0.17em}k}}_r^{\text{(0)}})$ was shown to be much smaller than the experimental deviation; this suggests that translational nonequilibrium is not significant, but does not exclude vibrational effects which could be more important.