Reductive Reaction Mechanisms of the Azo Dye Orange II in Aqueous Solution and in Cellulose: From Radical Intermediates to Products

Abstract

Reductive reaction mechanisms of the azo dye Orange II (Acid Orange 7) in aqueous solution have been studied from radical intermediates through to the final products using a combination of nanosecond time-resolved UV-visible absorption spectroscopy, steady-state photolysis, and HPLC techniques. The dye is reduced by photochemically produced 2-hydroxy-2-propyl radicals at a near-diffusion-controlled rate (k2 = 2.2 x 10(9) dm3 mol(-1) s(-1)) to give the dye radical anion, which then disproportionates (k3 = 2.6 x 10(8) dm3 mol(-1) s(-1)) to re-form the parent dye and a hydrazine. The hydrazine decomposes to 4-aminobenzenesulfonate and a naphthylimine species, which hydrolyses to give 1,2-naphthoquinone; this naphthoquinone and 4-aminobenzenesulfonate react to give a species that reacts further in the presence of air to form an indophenol dye. The reduction of Orange II has also been studied in cellophane, where the rate constant for dye reduction by 2-hydroxy-2-propyl radicals is approximately two orders of magnitude lower than that in aqueous solution.