Coupling of Cyclic Voltammetry and Electrochemical Impedance Spectroscopy for Probing the Thermodynamics of Facilitated Ion Transfer Reactions Exhibiting Chemical Kinetic Hindrances
Coupling of Cyclic Voltammetry and Electrochemical Impedance Spectroscopy for Probing the Thermodynamics of Facilitated Ion Transfer Reactions Exhibiting Chemical Kinetic Hindrances
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循环伏安法与电化学阻抗谱的耦合用于探索具有化学动力学障碍的促进离子转移反应的热力学
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发表时间：
2008
期刊：
影响因子：
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通讯作者：
A. F. Silva
中科院分区：
文献类型：
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作者：
R. Gulaboski;Elisabete S C Ferreira;C. Pereira;M. Cordeiro;A. Garau;A. Lippolis;A. F. Silva
建立了循环阶梯伏安法和电化学阻抗谱（EIS）条件下的数学模型，该模型考虑了金属离子在极化界面上的促进转移引起的络合反应的动力学效应。根据模拟循环伏安图的特征，给出了定性识别这些动力学效应的准则。在这些效应存在的情况下，只有EIS才能获得络合化学反应的热力学和动力学。在EIS条件下，给出了估算系统热力学参数的解析方程。在两个含菲罗啉的大环的辅助下，在极化水-1,2-二氯乙烷界面上促进Cu 2+转移的实验结果与理论结果进行了比较。在实验情况下，由于络合步骤的动力学效应存在，我们展示了如何优雅的EIS可以作为一个工具来估计cu2 +和5-氧-2,8-二甲酸[9]，(2,9)-1,10-菲罗啉（PhenOS2）的络合常数。
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 Cu 2+ 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 Cu 2+ and 5-oxo-2,8-dithia [9],(2,9)-1,10-phenanthrolinophane (PhenOS2).