XXI.—A New Approach to the Statistical Thermodynamics of Liquids

Abstract

An attempt is made to develop the statistical mechanics of the liquid state based not on the usual concept of a “radial distribution function” but on that of a “next neighbour distribution function” which is closely linked up with Bernal's ideas on the characteristic features of liquid structure. Making certain simplifying assumptions it is indeed possible to construct a partition function for an atomic liquid in this way and from this to derive the thermodynamic properties of the system according to the principles of classical statistical mechanics. It is shown that the free energy, the equation of state, the specific heat and entropy as obtained from the theory are consistent with the expected behaviour of such liquids. It is further shown that the computed next neighbour distribution function for close packing is in good agreement with the one derived empirically from a model by Bernal and Mason.