SIMPLE ANALYSIS OF QUASI-REVERSIBLE STEADY-STATE VOLTAMMOGRAMS
SIMPLE ANALYSIS OF QUASI-REVERSIBLE STEADY-STATE VOLTAMMOGRAMS
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DOI：
10.1021/ac00043a020
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发表时间：
1992-10-01
影响因子：
7.4
通讯作者：
BARD, AJ
中科院分区：
文献类型：
--
作者：
MIRKIN, MV;BARD, AJ
The kinetic parameters (k-degrees and alpha) of a uncomplicated quasi-reversible electrochemical reaction studied by any steady-state voltammetric technique can be found directly from the values of two easily accessible experimental parameters, (E1/4 - E1/2) and (E1/2 - E3/4), where E1/2 is the experimental half-wave potential and E1/4 and E3/4 are伏安级四分之一的电势。对于任何类型的稳态（或伪稳态）电流曲线，该曲线通过均匀访问的工作电极（例如，旋转盘或半球微电极，极性微图，极性，样品电流伏安和样品电流伏安和样品伏击的伏型伏安级数）的标准级别的标准率和列表的标准级别的标准级别，以下标准率，从以上两个实验值中传递系数，α以及正式的e-Degrees。给出了一个小小的微型电极的类似表。与以前报道的方法不同，对标准（正式）潜力的独立评估是不必要的。该分析还不依赖电极表面积的值和通常降低结果准确性的电活性物种的批量浓度。还讨论了所提出的方法在其他电化学系统中的应用，包括扫描电化学显微镜（SECM）和按照锥形或球形段形状的超大型电极。
The kinetic parameters (k-degrees and alpha) of a uncomplicated quasi-reversible electrochemical reaction studied by any steady-state voltammetric technique can be found directly from the values of two easily accessible experimental parameters, (E1/4 - E1/2) and (E1/2 - E3/4), where E1/2 is the experimental half-wave potential and E1/4 and E3/4 are voltammetric quartile potentials. For any type of steady-state (or pseudo-steady-state) current-potential curve obtained with a uniformly accessible working electrode, e.g., voltammetry at a rotating disk or hemispherical microelectrode, polarography, sample current voltammetry, and thin-layer voltammetry, a table is given which shows the kinetic parameters, i.e., standard rate constant, k-degrees, and the transfer coefficient, alpha, and also the formal potential, E-degrees', from the two above experimental values. An analogous table is presented for the nonuniformly a microdisk electrode. Unlike previously reported approaches, an independent evaluation of the standard (formal) potential is unnecessary. This analysis also does not rely on values of the electrode surface area and the bulk concentration of electroactive species which usually decrease the accuracy of the results. The application of the proposed methodology to other electrochemical systems including scanning electrochemical microscopy (SECM) and ultramicroelectrodes shaped as a cone or spherical segment is also discussed.