Study of electrochemical bleaching of <Emphasis Type="Italic">p</Emphasis>-nitrosodimethylaniline and its role as hydroxyl radical probe compound

In the present paper, research on the electrochemical bleaching of p-nitrosodimethylaniline (RNO) in different electrolyte systems is presented with special attention to the role of RNO as a selective hydroxyl radical probe compound. At a Ti/Pt₉₀–Ir₁₀ anode, RNO was found to be bleached in 0.050 M sodium sulphate electrolyte due to lattice active oxygen without hydroxyl radicals being intermediately present. In 0.050 M sodium chloride, the bleaching rate was greatly enhanced due to indirect bulk oxidation by active chlorine species, again without the presence of hydroxyl radicals in the oxidation mechanisms. Under galvanostatic electrolysis, a linear relationship was found between the concentration of added chloride to a supporting sodium sulphate electrolyte and the first order rate constant of the bleaching reaction, showing the importance of the indirect bulk chlorine bleaching in chloride electrolyte systems. In this fashion both the chemically bonded active oxygen and the chemical bulk oxidation by active chlorine species proved to be valid bleaching pathways of RNO that according to these findings cannot be regarded as a fully selective hydroxyl radical probe compound. In addition, the difference in the mechanisms of chloride electrolysis at Ti/Pt₉₀–Ir₁₀ and Si–BDD anodes was clearly demonstrated using t-BuOH as hydroxyl radical scavenger.