The cubic-plus-association (CPA) equation of state (EoS) is applied, using different combining rules, to vapor-liquid equilibria (VLE) and liquid-liquid equilibria (LLE) of alcohol-water systems. It is demonstrated that the Elliott combining rule (ECR) with a common temperature-independent interaction parameter provides very adequate VLE correlations over extended temperature and pressure ranges, yielding also a very satisfactory description of the azeotropic behavior. LLE of heavy alcohol-water systems is best described with the CR-1 combining rule and a single interaction parameter. Satisfactory predictions of multicomponent, multiphase equilibria of water-alcohol-alkane systems at various conditions are achieved using solely one interaction parameter per binary. A study of the dominant binary systems for the prediction of the multicomponent systems demonstrates that both the binary alcohol-water and alcohol-hydrocarbon systems are crucial for the prediction of the partition coefficients of alcohols. Finally, the CPA EoS combined with a model for the solid-complex formation can successfully describe solid-liquid equilibria of glycol/methanol-water systems including the description of the solid-complex phase, which is known to exist at intermediate concentrations.
Folas, G., Gabrielsen, J., Michelsen, M. L., Stenby, E. H., & Kontogeorgis, G. (2005). Application of the cubic-plus-association (CPA) equation of state to cross-associating systems. Industrial & Engineering Chemistry Research, 44(10), 3823-3833. https://doi.org/10.1021/ie048832j