Probing carboxylate Gibbs transfer energies via liquid|liquid transfer at triple phase boundary electrodes: ion-transfer voltammetryversus COSMO-RS predictions

Physical Chemistry Chemical Physics Pub Date: 2008-05-22 DOI: 10.1039/B803582B

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 pKa. 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.

Graphical abstract: Probing carboxylate Gibbs transfer energies via liquid|liquid transfer at triple phase boundary electrodes: ion-transfer voltammetryversus COSMO-RS predictions
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