Statistical rate theory of interfacial transport. I. Theoretical development

Abstract

After assuming that the transport of molecules between phases at thermal equilibrium results primarily from single molecular events, the expression for the rate of molecular transport between phases is developed by using a first order perturbation analysis of the Schrödinger equation and the Boltzmann definition of entropy. This leads to an Einstein-type relation with the constant of proportionality being the average rate of exchange between microscopic states of different molecular distributions. A hypothesis is introduced which leads to the conclusion that this exchange rate is unchanged as the system moves through the molecular distributions leading to equilibrium, and to it being equal to the molecular rate of exchange between phases in the final equilibrium state. This allows a complete expression for the rate of molecular transport between phases to be developed. The validity of the hypothesis can be examined by comparing the predictions that follow from the derived rate expressions with the available experimental data. This comparison is reported in subsequent parts of this work. © 1982 American Institute of Physics.