Determination of the standard Gibbs energies of transfer of cations across the nitrobenzene|water interface utilizing the reduction of iodine in an immobilized nitrobenzene droplet

被引：42

作者：

Mirceski, V ^{[1
]}

Gulaboski, R ^{[1
]}

Scholz, F ^{[1
]}

机构：

[1] Ernst Moritz Arndt Univ Greifswald, Inst Chem & Biochem, D-17489 Greifswald, Germany

来源：

ELECTROCHEMISTRY COMMUNICATIONS | 2002年 / 4卷 / 10期

关键词：

voltammetry; iodine; three-phase junction; cation transfer;

D O I：

10.1016/S1388-2481(02)00456-3

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

When a nitrobenzene (NB) droplet containing iodine is attached to a graphite electrode and immersed into a chloride containing aqueous (AQ) solution, the electrochemical reduction of iodine is accompanied by a transfer of chloride ions from NB to water. These chloride ions enter the NB phase in a preceding partition between the AQ and the NB phases, supported by formation of I2Cl- ions in NB and accompanied by the transfer of stoichiometric amounts of cations. The overall electrode reaction is of CErev type, where C refers to the preceding chemical step forming I2Cl- and E-rev refers to the reversible reduction of iodine at the graphite\NB interface and the simultaneous transfer of chloride from NB to water. If the chloride concentration in NB is insufficient to compensate by leaving the NB the amount of electrochemically produced iodide, a second voltammetric signal occurs at more negative potentials due to the transfer of iodide from NB to water. The kinetics and thermodynamics of the preceding chemical step C, determine the voltarnmetric behaviour of the system in such way that the ratio of peak currents of the first and second signals depends linearly on the Gibbs energy of transfer of the co-partitioned cations. The method was validated for cations of known Gibbs energies of transfer, and it was applied to cations of amino acids. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：814 / 819

页数：6

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