Enskog theory for chemically reacting fluids

Abstract

Presented here is a theory of nonequlibrium processes for a dense fluid composed of chemically reactive, rigid-sphere molecules. Explicit consideration is given to the relocations of the molecular centers of mass that result from the occurrence of reaction and the accompanying rearrangements of chemical bonds. The collision operators are separated into source and flux parts in order to produce equations of motion which faithfully mimic those of continuum mechanics. As a consequence of this we are led naturally to the discovery of ’’collisional transfer’’ contributions to the mass fluxes of the reactive species. To transform these concepts into a computationally tractable theory we invoke the approximate Enskog functional relationship between the singlet and pair-space distribution functions. This is followed by the development of a procedure for estimating the nonequilibrium corrections to the reaction rates as well as the coefficients of viscosity and diffusion, with special attention being devoted to the collisional transfer contributions to the species’ mass fluxes.