Chemical reactions from the point of view of statistical thermodynamics far from equilibrium

Authors:

• Michał Kurzyński

Abstract

A formal derivation of equations of chemical kinetics in statistical terms is presented. In the case of reactions proceeding according to activated mechanisms, it is shown that equations of conventional kinetics, as well as time correlation function formulas for the rate constants, are valid arbitrarily far from equilibrium. Contrary to activated reactions, the time course of reactions controlled by processes of internal equilibration depends on the distance from equilibrium. A general theory requires nonlinear corrections to the equations of conventional chemical kinetics. Close to equilibrium, the kinetics of controlled reactions differs from the kinetics of activated ones in that direct transitions between any pair of species are generally allowed without the equilibration of transient species. Open problems for the controlled reactions are the necessity of satisfying the detailed balance condition and the possibility of inertial effects being manifested on a thermodynamic scale. © 1990 American Institute of Physics.