用双筒微量移液管技术对液/液界面处电子转移和电荷转移耦合过程的研究。

Studies of electron-transfer and charge-transfer coupling processes at a liquid/liquid interface by double-barrel micropipet technique.

作者信息

Chen Yong, Gao Zhao, Li Fei, Ge Liaohai, Zhang Meiqin, Zhan Dongping, Shao Yuanhua

机构信息

State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.

出版信息

Anal Chem. 2003 Dec 1;75(23):6593-601. doi: 10.1021/ac034674e.

DOI:10.1021/ac034674e

PMID:16465713

Abstract

Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN)63- in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO3-, NO2-, Cl-, COO-, TBA+, TPAs+, Cs+, Rb+, K+, Na+, and Li+, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.

摘要

报道了采用双管微量移液管技术对水/1,2 - 二氯乙烷界面处的异质电子转移（ET）反应进行的研究。所选择的体系是水相（W）中的Fe(CN)₆³⁻与1,2 - 二氯乙烷（DCE）中的二茂铁之间的反应。根据生成电流、收集电流以及收集效率，可以研究该界面处的ET - 离子转移（IT）耦合过程以及与有机相中的有机支持电解质的竞争反应。此外，已发现该技术是区分和测量在液/液界面同时发生的两个离子之间的电荷转移耦合反应（IT - IT）过程的有效方法。在此基础上，定量评估了一些离子（如NO₃⁻、NO₂⁻、Cl⁻、COO⁻、TBA⁺、TPAs⁺、Cs⁺、Rb⁺、K⁺、Na⁺和Li⁺）跨W/DCE界面转移的形式吉布斯自由能，由于IT - IT耦合过程，通常难以直接获得它们的转移情况。