The electrooxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) is dependent on the pH value of Britton-Robinson (B-R) buffer solution. In this work, the electrooxidation behavior of TMB was investigated with a SnO2:F film optically transparent thin-layer spectroelectrochemical cell. TMB underwent one two-electron electrooxidation process in the pH range from 2.0 to < 4.0, and two successive one-electron electrooxidation processes in the pH range from 4.0 to < 7.0 in the B-R buffer solution. At pH 6.5, the electrooxidative product of TMB generated a subsequent chemical reaction to yield an azo compound. Several spectroelectrochemical techniques, such as thin-layer cyclic voltammetry, thin-layer cyclic voltabsorptometry, thin-layer potential-controlled electrolysis absorptometry, thin-layer single-potential-step chronoabsorptometry, thin-layer dou-ble-potential-step chronoabsorptometry, thin-layer single-potential-step open-circuit relaxation chronoabsorptometry, were applied to this investigation. The formal potential E0’ and the electron transfer number corresponding to the electrooxidation of TMB in B-R buffer solution, and the reaction rate constant of the subsequent chemical reaction were determined.
JIAO Kui1, YANG Tao2 & NIU Shuyan1,2 1. College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
The electrooxidation behavior of 3, 3′,5, 5′-tetramethylbenzidine(TMB) was investigated using a platinum minigrid optically transparent thin-layer spectroelectrochemical cell. TMB underwent one two-electron electrooxidation process to yield quinonediimine in the pH range from 2.0 to < 4.0, and two consecutive one-electron electrooxidation processes, gave the mediate product free radical of TMB first, then gave the oxidation product quinonediimine in the pH range from 4.0 to < 7.0. In the pH range from 7.0 to 10.0, the electrooxidation of TMB was also one two-electron electrooxidation process to yield an azo compound. The formal potential E0'and the electron transfer number of the electrooxidation of TMB at pH 2.0 and pH 8.4 were determined by spectroelectrochemical techniques.
