On the analogy between the restricted primitive model and capacitor circuits. Part II: A generalized Gibbs-Duhem consistent extension of the Pitzer-Debye-Hückel term with corrections for low and variable relative permittivity

Abstract

We present a novel, thermodynamically consistent modification of the Pitzer-Debye-Hückel term and its extension for concentration dependent density, molar mass and relative permittivity. This extension is validated for ionic liquids by comparison with a reference model from the literature and, in contrast to similar extensions, also applied to conventional salts with small spherical ions in aqueous, mixed and non-aqueous solvents. The central novelty is the inclusion of a modified parameter of closest approach, which improves the overall qualitative performance of the Pitzer-Debye-Hückel term over the complete relative permittivity range. Gibbs-Duhem consistency is retained in the modified extension and sample calculations for aqueous [BMIM][BF4] and aqueous NaCl are provided. The novel, modified and extended term with concentration dependent properties is combined with the predictive COSMO-RS-ES model for the calculation of phase equilibria and activity coefficients in electrolytes with conventional salts. The performance of the COSMO-RS-ES model for predictions of salt solubility in fully non-aqueous media improves significantly upon introduction of concentration dependent properties within the long-range electrostatics. Modelling performance with the modified extended Pitzer-Debye-Hückel term outperforms modelling with the unmodified extension as well as with the conventional term with no extension. The correlated relative permittivity of the mixture is overestimated with respect to experimental values and kinetic depolarization effects provide a plausible explanation for this observation. Overall, our results support the consistent introduction of concentration dependent properties within the electrostatic theory in order to improve the modelling of electrolytes with particular emphasis on non-aqueous electrolytes.