Gulaboski, Rubin and Ferreira, E.S. and Pereira, Carlos M. and Cordeiro, M Natália D S and Garau, A. and Lippolis, V. and Silva, A. Fernando (2008) Coupling of Cyclic Voltammetry and Electrochemical Impedance Spectroscopy for Probing the Thermodynamics of Facilitated Ion Transfer Reactions Exhibiting Chemical Kinetic Hindrances. Journal of Physical Chemistry C, 112 (1). pp. 153-161. ISSN 1932-7447
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Abstract
Mathematical models under conditions of cyclic staircase voltammetry and electrochemical impedance
spectroscopy (EIS), which consider the kinetic effects due to the complexation reaction by the facilitated
transfer of metal ions at polarized interfaces, are presented. Criteria for qualitative recognition of these kinetic
effects from the features of simulated cyclic voltammograms are given. In case of the existence of these
effects, only the EIS can bring access to the thermodynamics and kinetics of the complexation chemical
reaction. Analytical equations for estimating the thermodynamic parameters by such systems under EIS
conditions are evaluated. The theoretical results are compared with the experimental results of the facilitated
Cu2+ transfer at the polarized water-1,2-dichlorethane interface, assisted by two phenanthroline-containing
macrocycles. In the experimental case where kinetic effects due to the complexation step exist, we show how
elegantly EIS can be used as a tool for estimation of the complexation constant of Cu2+ and 5-oxo-2,8-dithia
[9],(2,9)-1,10-phenanthrolinophane (PhenOS2).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | square-wave voltammetry, electrochemical impedance spectroscopy, kinetic of ion transfer, interfacial complexation, methamatical modeling |
| Subjects: | Natural sciences > Chemical sciences |
| Divisions: | Faculty of Agriculture |
| Depositing User: | Rubin Gulaboski |
| Date Deposited: | 31 Oct 2012 13:10 |
| Last Modified: | 21 Oct 2014 09:52 |
| URI: | https://eprints.ugd.edu.mk/id/eprint/139 |
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