Extension of the Neoclassical Theory of Capillarity to Advanced Cubic Equations of State

Abstract

The neoclassical Redlich–Kwong (RK) theory of capillarity is extended to the Soave–Redlich–Kwong (SRK) and Peng–Robinson (PR) equations of state. Use of the SRK and PR fluid models results in poorer predictions of interfacial tension compared to the RK model because the RK overpredicts vapor densities to a greater extent than SRK or PR, reducing the corresponding RK interfacial tension predictions to be in better agreement with accepted values. The limits of the theory applied to cubic equations are reached by proposing modified SRK and PR fluid models based on a known interfacial tension datum and knowledge of the fluid molecular structure. These modified fluid models provide improved accuracy in interfacial tension predictions of 6% (SRK) and 10% (PR) for the fluid set in this study when compared to applying the RK model (17%). These modified fluid models also provide improved predictions of bulk liquid density, but sacrifice accuracy in pressure and vapor density predictions.