Frank H. Stillinger
Bell Laboratories, Murray Hill, New Jersey 07974

(Received 30 October 1972)

J. Solution Chem. 2, 141-158 (1973).

Abstract

The scaled-particle theory of classical fluids offers a powerful conceptual and computational framework within which to examine molecular order and thermodynamic properties. This method was originally devised to describe only the rigid-sphere model without attractive forces. Nevertheless, its scope has since been increased to include models for a wide class of real substances. Furthermore, the underlying theory has been substantially strengthened and deepened in comparison to its early version. The initial attempts to apply scaled-particle theory to liquid water were disappointing. Both the surface tension and the isothermal compressibility, along the saturation line from 0° to 100°C, were predicted to be too low and to have improper temperature variations. In view of the strong, directional, and nonadditive interactions that operate in water to produce extensive hydrogen bonding, this failure seems hardly surprising.