Equilibrium of Multi-Phase Systems in Gravitational Fields

Abstract

Four necessary conditions for equilibrium of an isolated solid-liquid-vapor system in a gravitational field were derived by Ward and Sasges (1998) in a unified setting, by using an entropy maximization approach, and under the assumption that the liquid-vapor surface tension does not depend on elevation. These are thermal equilibrium, the Laplace and Young equations, and a condition on the chemical potentials of the components present in the system. Gibbs (1876) had obtained the Young equation in a derivation separate from the derivation of the other three conditions and by using an energy minimization approach. However, Gibbs had derived a more general form of the Laplace equation than Ward and Sasges's. Gibbs's equation contained a term expressing the contribution of the variation of surface tension with elevation. This equation has since been neglected by most of the scientific community. In the present paper, the same approach as Ward and Sasges's is used to derive, in an unified setting, the conditions for equilibrium of an isolated solid-liquid-vapor system in a gravitational field but under the assumption that the liquid-vapor surface tension may depend on elevation. The four well-known conditions for equilibrium are obtained, with Gibbs's generalized Laplace equation instead of the classical Laplace equation. The derivations in this paper were carried out for two different system geometries, namely, for a sessile drop and for a conical capillary tube, and similar conditions for equilibrium were obtained.