A Comparative Study of the Anion Transfer Kinetics Across a Water/Nitrobenzene Interface by Means of Electrochemical Impedance Spectroscopy and Square-Wave Voltammetry at Thin Organic Film-Modified Electrodes

Gulaboski, Rubin and Mirceski, Valentin and Pereira, Carlos M. and Cordeiro, M Natália D S and Silva, A. Fernando and Quentel, François and L'Her, Maurice and Lovrić, Milivoj (2006) A Comparative Study of the Anion Transfer Kinetics Across a Water/Nitrobenzene Interface by Means of Electrochemical Impedance Spectroscopy and Square-Wave Voltammetry at Thin Organic Film-Modified Electrodes. Langmuir, 22 (7). pp. 3404-3412. ISSN 0743-7463

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Official URL: http://dx.doi.org/10.1021/la052565k

Abstract

The kinetics of the transfer of a series of hydrophilic monovalent anions across the water/nitrobenzene (W/NB) interface has been studied by means of thin organic film-modified electrodes in combination with electrochemical impedance spectroscopy and square-wave voltammetry. The studied ions are Cl-, Br-, I-, ClO4 -, NO3 -, SCN-, and CH3COO-. The electrode assembly comprises a graphite electrode (GE) covered with a thin NB film containing a neutral strongly hydrophobic redox probe (decamethylferrocene or lutetium bis(tetra-tert-butylphthalocyaninato)) and an organic supporting electrolyte. The modified electrode is immersed in an aqueous solution containing a supporting electrolyte and transferring ions, and used in a conventional three-electrode configuration. Upon oxidation of the redox probe, the overall electrochemical process proceeds as an electron-ion charge-transfer reaction coupling the electron transfer at the GE/NB interface and compensates ion transfer across the W/NB interface. The rate of the ion transfer across the W/NB interface is the limiting step in the kinetics of the overall coupled electron-ion transfer reaction. Moreover, the transferring ion that is initially present in the aqueous phase only at a concentration lower than the redox probe, controls the mass transfer regime in the overall reaction. A rate equation describing the kinetics of the ion transfer that is valid for the conditions at thin organic film-modified electrodes is derived. Kinetic data measured with two electrochemical techniques are in very good agreement.

Item Type: Article
Uncontrolled Keywords: ion transfer, EIS, Square-wave voltammetry, biomimetic membranes, kinetics of ion transfer
Subjects: Natural sciences > Biological sciences
Natural sciences > Chemical sciences
Natural sciences > Matematics
Natural sciences > Physical sciences
Divisions: Faculty of Agriculture
Depositing User: Rubin Gulaboski
Date Deposited: 31 Oct 2012 13:15
Last Modified: 05 Nov 2012 11:06
URI: http://eprints.ugd.edu.mk/id/eprint/160

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