Cluster-Continuum Model as a Sanity Check of Sodium Ions’ Gibbs Free Energies of Transfer

Arseniy A. Otlyotov, Luigi Cavallo, Yury Minenkov

Research output: Contribution to journalArticlepeer-review

Abstract

An approach to estimate the uncertainty of the calculated through the monomer cycle cluster-continuum model Gibbs free energy of transfer has been developed and suggested to be used as a quantitative measure of the reliability of the predictions. A set of experimental Na+ free energies of transfer from water to 18 solvents (ΔGtr(Na+, W → S)) has been assessed. For all solvents, we find Na+(S)n clusters to be thermodynamically unstable if n > 5. For 1,2-dichloroethane (1,2-DCIE), we have resolved considerable (ca. 10 kcal mol–1) discrepancies between available experimental ΔGtr(Na+, W → S). For 1,1-DCIE, we reject the only available experimental value and recommend our own estimate instead. We strongly propose experimental revisiting of ΔGtr(Na+, W → S) for ethylene glycol and hexamethylphosphoramide. The statistical analysis performed on a set of predicted and recommended experimental ΔGtr(Na+, W → S) values, in this work, results in the mean unsigned and signed deviations of 3.4 and −1.3 kcal mol–1, respectively. The squared Pearson correlation coefficient of 0.91 encourages the extension of the utilized theoretical approach to other available experimental data on ion solvation.
Original languageEnglish (US)
JournalInorganic Chemistry
DOIs
StatePublished - Nov 7 2022

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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