J Colloid Interface Sci. 2015 May 01;445:48-59. doi: 10.1016/j.jcis.2014.12.069. Epub 2014 Dec 31.

Gradient Theory simulations of pure fluid interfaces using a generalized expression for influence parameters and a Helmholtz energy equation of state for fundamentally consistent two-phase calculations.

Journal of colloid and interface science

Rainer N Dahms

PMID: 25596368 DOI: 10.1016/j.jcis.2014.12.069

Abstract

The fidelity of Gradient Theory simulations depends on the accuracy of saturation properties and influence parameters, and require equations of state (EoS) which exhibit a fundamentally consistent behavior in the two-phase regime. Widely applied multi-parameter EoS, however, are generally invalid inside this region. Hence, they may not be fully suitable for application in concert with Gradient Theory despite their ability to accurately predict saturation properties. The commonly assumed temperature-dependence of pure component influence parameters usually restricts their validity to subcritical temperature regimes. This may distort predictions for general multi-component interfaces where temperatures often exceed the critical temperature of vapor phase components. Then, the calculation of influence parameters is not well defined. In this paper, one of the first studies is presented in which Gradient Theory is combined with a next-generation Helmholtz energy EoS which facilitates fundamentally consistent calculations over the entire two-phase regime. Illustrated on pentafluoroethane as an example, reference simulations using this method are performed. They demonstrate the significance of such high-accuracy and fundamentally consistent calculations for the computation of interfacial properties. These reference simulations are compared to corresponding results from cubic PR EoS, widely-applied in combination with Gradient Theory, and mBWR EoS. The analysis reveals that neither of those two methods succeeds to consistently capture the qualitative distribution of obtained key thermodynamic properties in Gradient Theory. Furthermore, a generalized expression of the pure component influence parameter is presented. This development is informed by its fundamental definition based on the direct correlation function of the homogeneous fluid and by presented high-fidelity simulations of interfacial density profiles. The new model preserves the accuracy of previous temperature-dependent expressions, remains well-defined at supercritical temperatures, and is fully suitable for calculations of general multi-component two-phase interfaces.

Copyright © 2015. Published by Elsevier Inc.

Keywords: Equation of state; Gradient Theory; Influence parameter; Interfacial tension; Metastability; Pure fluid

Publication Types

• Journal Article