Critical-point thermodynamics of fluids without hole-particle symmetry

Abstract

We have examined an infinite class of fluids which exhibit a liquid‐vapor critical point, with regard to corrections to thermodynamic scaling of critical phenomena. These ``penetrable‐sphere models'' possess an underlying bilateral symmetry in their equivalent binary fluid mixture versions. After postulating a suitable scaling for these mixtures, we show that the transciption to the penetrable‐sphere models produces a generalization of the conventional pure‐fluid scaled equation of state. Some leading corrections to the scaled form of thermodynamic properties are derived and tabulated. These corrections are presented in a form that makes no explicit reference to their modelistic source, so in fact they may apply to real substances.