Photo‐reductive fading of disperse azo dyes on nylon substrate: thermochemical analyses of reactions of photo‐induced radicals using the semiempirical molecular orbital method†

When the excited triplet states of disperse azo dyes with nitro groups abstract hydrogen to generate hydrazinyl (from azo groups) and nitrosyl hydroxide radicals (from nitro groups), both the radicals as H‐acceptors carry out azo scission, conversion to nitrogen dioxide via disproportionation reactions and self‐decomposition via rearrangement. A kinetic equation was formulated by the sum of these reactions, which describes the initial rates (K_PA) of reductive fading. The K_PA values were controlled by the rate constants of the reactions of hydrazinyl and nitrosyl hydroxide radicals as H‐acceptors, which were estimated by thermochemical analyses of the reactants, intermediates and end products using the semiempirical molecular orbital PM5 method, and by the concentrations of the reactants: H‐acceptors and H‐donors. The K_PA values observed for 12 dyes were explained semi‐quantitatively by multiple routes of reactions depending upon to what extent each radical reaction was thermochemically favoured.