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Voltammetric Kinetic Studies of Electrode Reactions: Guidelines for Detailed Understanding of Their Fundamentals

计时安培法 化学 塔菲尔方程 动能 电极 循环伏安法 伏安法 阶跃势薛定谔方程的解 限制电流 电化学 传质 分析化学(期刊) 化学物理 热力学 物理化学 物理 经典力学 色谱法
作者
Joaquı́n González,Eduardo Laborda,Á. Molina
出处
期刊:Journal of Chemical Education [American Chemical Society]
卷期号:100 (2): 697-706 被引量:16
标识
DOI:10.1021/acs.jchemed.2c00944
摘要

Theoretical and practical foundations of basic electrochemical concepts of heterogeneous charge transfer reactions that underline electrochemical processes are presented for their detailed study by undergraduate and postgraduate students. Several simple methods for calculating key variables, such as the half-wave potential, limiting current, and those implied in the kinetics of the process, are explained, discussed, and put in practice through simulations making use of an Excel document. The current-potential response of electron transfer processes of any kinetics (i.e., any degree of reversibility) are deduced and compared for electrodes of different size, geometry, and dynamics, namely: static macroelectrodes in chronoamperometry and normal pulse voltammetry, and static ultramicroelectrodes and rotating disc electrodes in steady state voltammetry. In all cases, a universal, normalized current-potential response is obtained in the case of reversible (fast) electrode reactions, whereas this is not possible for nonreversible processes. For this last situation, different widely used protocols for the determination of the kinetic parameters (the mass-transport corrected Tafel analysis and the Koutecký-Levich plot) are deduced, proposing learning activities that highlight the foundations and limitations of such protocols, as well as the influence of the mass transport conditions. Discussions on the implementation of this framework and on the benefits and difficulties found are also presented.
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