A rotating disc voltammetry study of the 1,8-dihydroxyanthraquinone mediated reduction of colloidal indigo

Colloidal indigo is reduced to an aqueous solution of leuco-indigo in a mediated two-electron process converting the water-insoluble dye into the water-soluble leuco form. The colloidal dye does not interact directly with the electrode surface, and to employ an electrochemical process for this reduction, the redox mediator 1,8-dihydroxyanthraquinone (1,8-DHAQ) is used to transfer electrons from the electrode to the dye. The mediated reduction process is investigated at a (500-kHz ultrasound-assisted) rotating disc electrode, and the quantitative analysis of voltammetric data is attempted employing the Digisim numerical simulation software package. At the most effective temperature, 353 K, the diffusion coefficient for 1,8-DHAQ is (0.84±0.08)×10−9 m2 s−1, and it is shown that an apparently kinetically controlled reaction between the reduced form of the mediator and the colloidal indigo occurs within the diffusion layer at the electrode surface. The apparent bimolecular rate constant kapp=3 mol m−3 s−1 for the rate law % MathType!Translator!2!1!AMS LaTeX.tdl!TeX -- AMS-LaTeX! % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbbjxAHX % garmWu51MyVXgatuuDJXwAK1uy0HwmaeHbfv3ySLgzG0uy0Hgip5wz % aebbnrfifHhDYfgasaacH8qrps0lbbf9q8WrFfeuY-Hhbbf9v8qqaq % Fr0xc9pk0xbba9q8WqFfea0-yr0RYxir-Jbba9q8aq0-yq-He9q8qq % Q8frFve9Fve9Ff0dmeaabaqaciGacaGaaeqabaWaaeWaeaaakeaada % WcaaqaaiaadsgadaWadaqaaiaabYgacaqGLbGaaeyDaiaabogacaqG % VbGaeyOeI0IaaeyAaiaab6gacaqGKbGaaeyAaiaabEgacaqGVbaaca % GLBbGaayzxaaaabaGaamizaiaadshaaaGaeyypa0Jaam4AamaaBaaa % leaacaqGHbGaaeiCaiaabchaaeqaaOGaey41aq7aamWaaeaacaqGTb % GaaeyzaiaabsgacaqGPbGaaeyyaiaabshacaqGVbGaaeOCaaGaay5w % aiaaw2faaiabgEna0oaadmaabaGaaeyAaiaab6gacaqGKbGaaeyAai % aabEgacaqGVbaacaGLBbGaayzxaaaaaa!617E!$$\frac{{d{\left[ {{\text{leuco}} - {\text{indigo}}} \right]}}} {{dt}} = k_{{{\text{app}}}} \times {\left[ {{\text{mediator}}} \right]} \times {\left[ {{\text{indigo}}} \right]}$$ is determined and attributed to a mediator diffusion controlled dissolution of the colloid particles. The average particle size and the number of molecules per particles are estimated from the apparent bimolecular rate constant and confirmed by scanning electron microscopy.

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