Can liquid-liquid equilibria be predicted by the combination of a cubic equation of state and a gE model not suitable for liquid-liquid equilibria?

Romain Privat, Jean-Noël Jaubert, Georgios M. Kontogeorgis

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Abstract

In modern versions of cubic equations of state (EoS), the mixing rules for EoS parameters are derived from an activity coefficient model using either the Huron-Vidal or the Zero Reference Pressure (ZRP) approach. As it is a fact that Wilson's activity coefficient model cannot predict liquid-liquid equilibria (LLE), this article attempts to answer the question: if Wilson's model is coupled with a cubic EoS, is the resulting model capable of predicting LLE?
This question is actually becoming increasingly important as recent EoS rely on such a coupling (e.g., the tc-PR EoS). We show that although Wilson's model is mathematically unable to predict instable liquid phases, this is not true for Wilson-EoS models (i.e., EoS incorporating Wilson's model). However, it is also shown that the capacity of Wilson-EoS to predict LLE depends not only on the approach chosen (Huron-Vidal or ZRP) but also on mixture characteristics (such as the ratio of covolumes, the ratio of critical attractive parameters, the binary interaction parameters etc.).
Original languageEnglish
Article number114249
JournalFluid Phase Equilibria
Volume589
Number of pages19
ISSN0378-3812
DOIs
Publication statusPublished - 2025

Keywords

  • Huron-Vidal
  • MHV1
  • Mixing rules
  • Wilson
  • Zero reference pressure

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