Development of a COSMO‐RS based model for the calculation of phase equilibria in electrolyte systems

Abstract

A new electrolyte model, which is based on the predictive thermodynamic model COSMO-RS, is presented. For this purpose, an implementation of COSMO-RS that allows the integration of multiple segment descriptors was developed. To aid in the development of the electrolyte model, a new technique is presented that allows the evaluation of the different contributions of the interaction terms of COSMO-RS to the partial molar enthalpies. General empirical interaction energy equations are introduced into the electrolyte model. They are parameterized based on a large training set of mean ionic activity coefficients as well as liquid-liquid equilibrium data close to ambient conditions. The model is shown to be capable of predicting properties of systems containing anions that were not part of the training set of the model. Furthermore, it is demonstrated that the model can also lead to satisfying predictions if compared to vaporliquid equilibrium data.

Experimental solubility and density studies on aqueous solutions of quaternary ammonium halides, and thermodynamic modelling for melting enthalpy estimations

“…This was somehow expected as it has been shown that COSMO-RS presents serious difficulties describing ion interactions, particularly those for small and highly charged ions like chloride [77]. Contributing to overcome this problem Gerlach et al [78] combined COSMO-RS with a Pitzer-Debye-Hückel term to account for long-range electrostatic interactions between the ions obtaining very satisfactory results in the description of the mean ionic activity coefficients of the salts, and both liquid-liquid and vapor-liquid equilibrium of systems containing ions.…”

Deep eutectic solvents for efficient capture of cyclohexane in volatile organic compounds: Thermodynamic and molecular mechanism

“…The COSMO-RS model, [43][44][45] as a prior predictive molecular thermodynamic model independent of experimental data, has been widely used to predict various thermodynamic properties of single-or multicomponent systems, such as solubility, Henry's constant, activity coefficient, vapor pressure, and excess enthalpy. It can also be used to predict the vapor-liquid equilibrium 46,47 and liquid-liquid equilibrium 48,49…”

“…The COSMO‐RS model, 43–45 as a prior predictive molecular thermodynamic model independent of experimental data, has been widely used to predict various thermodynamic properties of single‐ or multi‐component systems, such as solubility, Henry's constant, activity coefficient, vapor pressure, and excess enthalpy. It can also be used to predict the vapor–liquid equilibrium 46,47 and liquid–liquid equilibrium 48,49 data in processing the issues on fluid‐phase equilibrium. In this work, the solubility, excess enthalpy, and Henry's constants of cyclohexane gas in various DESs were predicted within the COSMOthermX software (version C30_1301).…”

Ideal-Gas Thermochemical Properties for Alkanolamine and Related Species Involved in Carbon-Capture Applications

“…These include the Conductor-like Screening Model for Realistic Solvents (COSMO-RS) 18,19 and Solvation Models based on Density (SMD, SMDx). 20 The deficiencies of these contin-uum solvation models can be partially overcome by incorporating explicit solvent molecules in the first solvation shell.…”

“…One method employs implicit solvent models, which have been used to study individual reaction mechanisms and the carbamate reaction. 22−25 These include the conductor-like screening model for realistic solvents (COSMO−RS) 26,27 and solvation models based on density (SMD, SMDx). 28 The deficiencies of these continuum solvation models can be partially overcome by incorporating explicit solvent molecules in the first solvation shell.…”