Kinetic and mechanistic aspects of the oxidation of chlorophenols by ozone

In Advanced oxidation processes (AOPs) radicals are considered to play an important role. Organic contaminations can in AOPs generally be converted to carbon dioxide, water, etc, The most important limitation to the application of AOPs, however, is their high costs, especially when complete mineralisation of the pollutants is pursued. The costs can be reduced by using the oxidant more efficiently, which can be achieved by introducing selectivity. Kinetic and mechanistic data are the basic requirements for optimization of the process. In this work, the influence of several different parameters (temperature, pH, UV irradiation and carbonate concentration) on the kinetics of the degradation of ortho-chlorophenol and para-chlorophenol by ozone was investigated. The pH is the most important parameter. Strongly related to the pH is the degree of ionisation of the phenol, which might be of importance since the shift from a slow to a fast reaction occurs at a higher pH in the case of para-chlorophenol as compared to the case with the more acidic ortho-chlorophenol. A strong indication for a radical mechanism is found in the decrease of the reaction rate in the presence of carbonate, a well known radical scavenger. A further indication is seen in the first step of the reaction, which is dechlorination of the aromatic compound. (C) 1997 IAWQ, Published by Elsevier Science Ltd.