Subject: Chemical sciences
Year: 2008
Type: Article
Type: PeerReviewed
Title: Coupling of Cyclic Voltammetry and Electrochemical Impedance Spectroscopy for Probing the Thermodynamics of Facilitated Ion Transfer Reactions Exhibiting Chemical Kinetic Hindrances
Author: Gulaboski, Rubin
Author: Ferreira, E.S.
Author: Pereira, Carlos M.
Author: Cordeiro, M Natália D S
Author: Garau, A.
Author: Lippolis, V.
Author: Silva, A. Fernando
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).
Publisher:
Relation: https://eprints.ugd.edu.mk/139/
Identifier: oai:eprints.ugd.edu.mk:139
Identifier: https://eprints.ugd.edu.mk/139/1/__ugd.edu.mk_private_UserFiles_rubin.gulaboski_Desktop_GULABOSKI-MY%20pdf%20PUBLICATIONS_CV%20and%20EIS-JPC-2008.pdfIdentifier: 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
Identifier: doi:10.1021/jp076203s
