title: Probing carboxylate Gibbs transfer energies via liquid|liquid transfer at triple phase boundary electrodes: ion-transfer voltammetry versus COSMO-RS predictions.
abstract: Understanding liquid|liquid ion transfer processes is important in particular for naturally occurring species such as carboxylates. In this study electrochemically driven mono-, di-, and tri-carboxylate anion transfer at the 4-(3-phenylpropyl)pyridine|aqueous electrolyte interface is investigated experimentally for a triple phase boundary system at graphite electrodes. The tetraphenylporphyrinato-Mn(III/II) redox system (Mn(III/II)TPP) dissolved in the water-immiscible organic phase (4-(3-phenylpropyl)pyridine) is employed for the quantitative study of the structure-Gibbs transfer energy correlation and the effects of the solution pH on the carboxylate transfer process. For di- and tri-carboxylates the partially protonated anions are always transferred preferentially even at a pH higher than the corresponding pK(a). COSMO-RS computer simulations are shown to provide a quantitative rationalisation as well as a powerful tool for predicting Gibbs free energy of transfer data for more complex functionalised carboxylate anions. It is shown that the presence of water in the organic phase has a major effect on the calculated Gibbs free energies.
authors.affiliation: Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
authors.forename: Stuart M
authors.initials: SM
authors.lastname: MacDonald
authors.forename: Marcin
authors.initials: M
authors.lastname: Opallo
authors.forename: Andreas
authors.initials: A
authors.lastname: Klamt
authors.forename: Frank
authors.initials: F
authors.lastname: Eckert
authors.forename: Frank
authors.initials: F
authors.lastname: Marken