Quantitative prediction of direct and indirect dye ozonation kinetics

A quantitative estimation of direct ozonation and indirect free radical oxidation of dyes with assorted chromophores was studied through the examination of reaction kinetics in the ozonation process. The reaction kinetics of dye ozonation under different conditions was determined by adjusting the ozone doses, dye concentration, and reaction pH. The ozonation of dyes was found dominant by pseudo-first-order reaction, and the rate constants decreased as the dye/ozone ratio increased. For all selected azo dyes, the dye decay rates increased as the initial pH of the solution increased, yet the decay rates of anthraquinone dyes would decrease in the same situation because of their insensible structure for ozone oxidation, formation of leuco-form, and higher solubility at a lower pH. The ozonation of dyes at a high pH contributed by hydroxyl free radicals was qualitatively verified by the use of a free radical scavenger. A proposed model, in another way, quantitatively determines the fraction of contribution for dye decomposition between free radical oxidation and direct ozonation. (C) 2000 Elsevier Science Ltd.