MacDonald, Stuart M. and Opallo, Marcin and Klamt, Andreas and Eckert, Frank and Marken, Frank (2008) Probing carboxylate Gibbs transfer energies via liquid vertical bar liquid transfer at triple phase boundary electrodes: ion-transfer voltammetry versus COSMO-RS predictions. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 10 (26). pp. 3925-3933. ISSN 1463-9076, 1463-9084
Full text not available from this repository. (Request a copy)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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | LIQUID/LIQUID INTERFACE; REDOX LIQUID; SOLVENTS; WATER; MICRODROPLETS; SYSTEMS; DRIVEN; ANIONS; APPROXIMATION; MICROSCOPY; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 23 Nov 2020 08:23 |
| Last Modified: | 23 Nov 2020 08:23 |
| URI: | https://pred.uni-regensburg.de/id/eprint/31754 |
Actions (login required)
 |
View Item |
