Towards predictive association theories

Abstract

Association equations of state like SAFT, CPA and NRHB have been previously applied to many complex mixtures. In this work we focus on two of these models, the CPA and the NRHB equations of state and the emphasis is on the analysis of their predictive capabilities for a wide range of applications. We use the term predictive in two situations: (i) with no use of binary interaction parameters, and (ii) multicomponent calculations using binary interaction parameters based solely on binary data. It is shown that the CPA equation of state can satisfactorily predict CO 2–water–glycols–alkanes VLE and water–MEG–aliphatic hydrocarbons LLE using interaction parameters obtained from the binary data alone. Moreover, it is demonstrated that the NRHB equation of state is a versatile tool which can be employed equally well to mixtures with pharmaceuticals and solvents, including mixed solvents, as well as phase equilibria in mixtures containing glycols. The importance of considering the solvation of CO 2–water (in CPA) when the model is applied to multicomponent mixtures as well as of the multiple associations in heavy glycol–water mixtures (in NRHB) is investigated.