ePC-SAFT advanced - Part I: Physical meaning of including a concentration-dependent dielectric constant in the born term and in the Debye-Huckel theory

The transition from aqueous electrolyte systems to non-aqueous electrolyte systems is highly demanded in industrial applications and especially challenging for physics-based thermodynamic models. Electrolyte thermodynamics is a complex matter, and still not all physico-chemical effects are accounted for in state-of-the-art equations of state. The dielectric constant of non-aqueous electrolyte systems changes drastically compared to aqueous systems. One main consequence is that ions are very differently solvated in non-aqueous medium compared to aqueous medium. The Born term represents a methodology to account for the influence of solvation energies of ions, which is based on influences of solvent and salt on the dielectric constant. Utilizing the Born term in electrolyte models is extensively debated, and it is often reasonably neglected in predominantly aqueous systems. Yet, it has a significant influence on transferability from aqueous to non-aqueous media i.e., systems with a large difference in polarity or permittivity compared to aqueous systems. In this work, a modified Born term was combined with electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT) by introducing additionally a salt concentration-dependent dielectric constant, henceforth called altered Born contribution. The new methodology was validated against infinite dilution properties for ion-solvent interactions: Gibbs energy of hydration and Gibbs energy of transfer of alkali halides from water to alcoholic solvents. Further, mean ionic activity coefficients (MIACs) of alkali halides in alcoholic solvents were quantitatively correct predicted with the advanced ePC-SAFT approach. Original ePC-SAFT parameters were applied for all predictions, and no further binary parameters were adjusted. Based on the success of the model predictions, the transferability of pure-ion ePC-SAFT parameters to organic solvents was verified and the incorporation of concentration-dependent dielectric constant into the altered Born contribution and Debye-Huckel theory was proven to be meaningful methods for the transfer of electrolyte thermodynamic models from aqueous to non-aqueous systems. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

The transition from aqueous to non-aqueous electrolyte systems poses significant challenges in electrolyte thermodynamics. The change in dielectric constants can alter ion solvation significantly. The use of the Born term in electrolyte models has a notable impact on transferability between aqueous and non-aqueous systems.