Voltammetric determination of dihydroxybenzenes at a mechanically renewed electrode made from a graphite-epoxy composite

Abstract

Differences of potentials of anodic and cathodic peaks (ΔEp) are determined in cyclic voltammograms of dihydroxybenzene/p-benzoquinone redox systems at an electrode made of a graphite-epoxy composite in a wide pH range. The data obtained (ΔEp = 29 ± 1 mV) are close to the thermodynamic values for two-electron reversible reactions. This indicates that the electrode mechanically renewed by cutting a 0.5-μm surface layer directly in a test solution exhibits a high activity in such electrochemical reactions. The potentials of anodic and cathodic peaks are proportional to the pH of the supporting electrolyte solution in the range from 1.0 to 9.0. A change of 58 ± 1 mV in Ep per unit pH for all isomers shows that the first stage of the oxidation of each dihydroxybenzene isomer involves one electron and is accompanied by the detachment of one hydrogen ion, that is, an intermediate oxidation product, semiquinone, is formed. Despite the closeness of the potentials of hydroquinone and pyrocatechol peaks (ΔE = 100 mV), a scheme is proposed for the selective voltammetric determination of dihydroxybenzene isomers in a 0.1 M HCl solution in hydroquinone-pyrocatechol, pyrocatechol-resorcinol, and hydroquinone-resorcinol binary mixtures. The concentrations of hydroquinone and pyrocatechol are found from cathodic peaks and that of resorcinol, from the anodic peak. The results are well reproducible and contain no systematic error.