Coupling of Cyclic Voltammetry and Electrochemical Impedance Spectroscopy for Probing the Thermodynamics of Facilitated Ion Transfer Reactions Exhibiting Chemical Kinetic Hindrances

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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Official URL: http://dx.doi.org/10.1021/jp076203s

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: http://eprints.ugd.edu.mk/id/eprint/139

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