Spherical Interface. II. Molecular Theory

The statistical mechanical theory of plane and spherical interfaces is developed on the basis of the virial theorem and the Gibbsian mechanical and thermodynamic definitions of surface tension. The expressions for the relevant thermodynamic functions in terms of molecular variables are employed in a discussion of the curvature dependence of surface tension which leads to an asymptotic expansion of the grand partition function in terms of the geometrical parameters that characterize the interface and thus provide a criterion for the range of validity of macroscopic concepts.