A Review of Electrolyte Equations of State with Emphasis on Those Based on Cubic and Cubic-Plus-Association (CPA) Models

Abstract

Electrolyte thermodynamics is a complex and broad subject of immense importance in very diverse applications. The models proposed for electrolyte solutions have some similarities to those for non-electrolytes but also significant differences. Not just due to additional contributions but also because of the way the models are developed for electrolytes vs. non-electrolytes. Moreover, there are still fundamental issues unresolved in electrolyte thermodynamics. It is still today the activity coefficient models, often extensions of local-composition models that are used in engineering practice for electrolytes e.g., the Pitzer, electrolyte NRTL and extended UNIQUAC. In this review, however, we investigate the area of equations of state (EoS) for electrolytes, a very rich field which essentially started with the Fürst and Renon model in 1993. Since then numerous electrolyte EoS (e-EoS) have been proposed; the literature is both rich and confusing. We have decided in this work to review mostly electrolyte versions of cubic and CPA (Cubic-Plus-Association) EoS, although some of the observations made may be applicable to e-EoS of the SAFT type as well, and some of them are also briefly discussed. Reviewing e-EoS is not an easy task due to especially the diversity of modeling and parameter estimation approaches which are followed as well as the way the models have been validated. Almost none of the e-EoS proposed in literature can be compared “on equal terms” with another e-EoS. Thus, a critical comparative analysis is proposed here, including some recent developments of the e-CPA approach. When possible, different modeling—parameter estimation—validation approaches are compared. It is hoped that this review can provide an insight on the current state-of-the-art of some e-EoS proposed in literature and point out areas where further research is needed.