Use of the ferrocene oxidation process to provide both reference electrode potential calibration and a simple measurement (via semiintegration) of the uncompensated resistance in cyclic voltammetric studies in high resistance organic solvents
Use of the ferrocene oxidation process to provide both reference electrode potential calibration and a simple measurement (via semiintegration) of the uncompensated resistance in cyclic voltammetric studies in high resistance organic solvents
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DOI：
10.1021/ac000020j
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发表时间：
2000-08-01
影响因子：
7.4
通讯作者：
Snook, GA
中科院分区：
文献类型：
--
作者：
Bond, AM;Oldham, KB;Snook, GA
由于其理想的可逆行为，二茂铁的氧化被广泛用于高阻有机溶剂中的循环伏安研究，作为参比电极电位校准的一种手段。在这项研究中，它表明，一个很好的估计，需要参考电位校正，也经常是一个输入参数，在模拟的理论，可以得到一个很好的估计，同时与二茂铁参考电位测量使用一个简单的分析的基础上，半积分，应用于循环伏安氧化二茂铁在二氯甲烷中（0.1 M NBu4PF6），在未补偿的电阻类似于2.5 k Ω遇到的条件下，被用来说明分析的半积分方法的保真度。将该估计的电阻值作为输入参数包括在市售的数字模拟包中，证实了二茂铁在二氯甲烷中的氧化代表了接近理想的扩散控制的可逆过程。然而，使用的半积分的数据分析方法，也使检测的微妙形式的非理想性遇到的二茂铁氧化过程中，在其他介质中，动力学控制的铁阳离子的吸附可能会发生。
Because of its presumed ideal reversible behavior, the oxidation of ferrocene is widely used in cyclic voltammetric studies in highly resistive organic solvents as a means of reference electrode potential calibration. In this study, it is shown that a good estimate of the uncompensated resistance value, needed for reference potential correction and also frequently an input parameter in simulation of the theory, can be obtained simultaneously with the ferrocene reference potential measurement using a simple analysis based on the semiintegral, Application to cyclic voltammetric oxidation of ferrocene in dichloromethane (0.1 M NBu4PF6), under conditions where uncompensated resistances of similar to 2.5 k Omega are encountered, is used to illustrate the fidelity of the semiintegral method of analysis. Inclusion of this estimated resistance value as the input parameter in a commercially available digital simulation package confirms that the oxidation of ferrocene in dichloromethane represents a close-to-ideal diffusion-controlled reversible process. However, use of the semiintegral method of data analysis also enables detection of subtle forms of nonideality encountered with the ferrocene oxidation process in other media where kinetically controlled adsorption of the ferricenium cation may occur.