Application of the thermodynamics of curved boundary layers to the scaled particle theory of hard-sphere fluids

Abstract

The thermodynamics of curved boundary layers, with the assumption that the distance between the surface of a fluid cavity and its surface of tension is a quadratic function of the cavity radius, is applied to the exact thermo-dynamic expression forG, the central function of scaled particle theory. The coefficients in the quadratic representation are determined so as to satisfyall five of the known exact conditions onG valid for cavity radii between one-half and one molecular diameter. The results of the calculation are displayed as the hard-sphere equation of state, the boundary tension associated with the surface of tension, and the distance between the cavity surface and the surface of tension. Although the hard-sphere equation of state obtained by this method using all five conditions onG is more accurate than in the case where only two or three conditions are used, the original scaled particle theory, in whichG itself was represented simply by a quadratic function of inverse powers of cavity radius, still yields the more accurate equation of state. Nevertheless, the present approach limits approximations to the distance between the cavity surface and the surface of tension, a small quantity in itself. The path to a still more improved theory remains well defined, contingent upon the discovery of additional exact conditions, and does not depend, as in the original scaled particle theory, on a form forG arrived at in a somewhat ad hoc manner.