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arXiv · 2303.16987

Calculation of Thermodynamic Equilibria with the Predictive Electrolyte Model COSMO-RS-ES: Improvements for Low Permittivity Systems

Simon Müller·Andrés González de Castilla·Christoph Taeschler·Andreas Klein·Irina Smirnova
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Abstract

The predictive electrolyte model COSMO-RS-ES is refined to improve the description of systems at 25{\deg}C in which strong ion pairing is expected due to a low static permittivity of the liquid phase. Furthermore, the short-range ion energy interaction equations have been modified to better describe the misfit and energy interaction terms between ions and solvent molecules. In addition, the salt solubility database is extended with additional non-aqueous systems containing solvents that have a low (\epsilon_s<15) dielectric constant and promote near to full ion association. Throughout this work it is demonstrated that liquid-liquid equilibrium calculations and solid-liquid equilibrium predictions for electrolyte systems can be markedly improved with the inclusion of Bjerrum treatment based phenomenological considerations while introducing only one general additional parameter. Our modified approach reinforces the capabilities of COSMO-RS ES as a powerful predictive tool for the calculation of phase equilibria in systems with scarce experimental data.

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Simon Müller, Andrés González de Castilla, Christoph Taeschler, Andreas Klein, Irina Smirnova. 2023-03-29. Calculation of Thermodynamic Equilibria with the Predictive Electrolyte Model COSMO-RS-ES: Improvements for Low Permittivity Systems. https://doi.org/10.1016/j.fluid.2019.112368

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