Department of Chemistry and Biochemistry, Queens College-City University of New York, Flushing, New York 11367, USA.
Anal Chem. 2010 Jan 1;82(1):77-83. doi: 10.1021/ac902244s.
Steady-state voltammetry at the pipet-supported liquid/liquid interface has previously been used to measure kinetics of simple and facilitated ion transfer (IT) processes. Recently, we showed that the conventional experimental protocol and data analysis produce large uncertainties in kinetic parameters of rapid IT processes extracted from pipet voltammograms. Here, we used a new mode of nanopipet voltammetry, in which a transferable ion is initially present as a common ion in both liquid phases, and improved methodology for silanization of the outer pipet wall to investigate the kinetics of the rapid transfer of tetraethylammonium (TEA(+)) at the 1,2-dichloroethane/water interface. This reaction was often employed as a model system to check the IT theory. The determined standard rate constant and transfer coefficient of the TEA(+) transfer are compared with previously reported values to demonstrate limitations of conventional nanopipet voltammetry with a transferrable ion present only in one liquid phase.
以前曾使用在支持的液体/液体界面处的稳定状态伏安法来测量简单和促进离子转移（IT）过程的动力学。最近，我们表明，从微电极伏安图中提取快速 IT 过程的动力学参数时，常规实验方案和数据分析会产生很大的不确定性。在这里，我们使用了一种新的纳米微电极伏安法模式，其中可转移离子最初作为两种液相中的同离子存在，并且改进了对外管壁硅烷化的方法，以研究四乙基铵（TEA(+))在 1,2-二氯乙烷/水界面的快速转移动力学。该反应通常被用作检查 IT 理论的模型系统。确定的 TEA(+)转移的标准速率常数和转移系数与先前报道的值进行了比较，以证明仅在一种液相中存在可转移离子的传统纳米微电极伏安法的局限性。
