Ozonation of Drinking Water: Part I. Oxidation Kinetics and Product Formation

The oxidation of organic and inorganic compounds during ozonation can occur via ozone or OH radicals or a combination thereof. The oxidation pathway is determined by the ratio of ozone and OH radical concentrations and the corresponding kinetics. A huge database with several hundred rate constants for ozone and a few thousand rate constants for OH radicals is available. Ozone is an electrophile with a high selectivity. The second-order rate constants for oxidation by ozone vary over 10 orders of magnitude, between < 0.1 M(-1)s(-1) and about 7 x 10(9) M(-1)s(-1). The reactions of ozone with drinking-water relevant inorganic compounds are typically fast and occur by an oxygen atom transfer reaction. Organic micropollutants are oxidized with ozone selectively. Ozone reacts mainly with double bonds, activated aromatic systems and non-protonated amines. In general, electron-donating groups enhance the oxidation by ozone whereas electron-withdrawing groups reduce the reaction rates. Furthermore, the kinetics of direct ozone reactions depend strongly on the speciation (acid-base, metal complexation). The reaction of OH radicals with the majority of inorganic and organic compounds is nearly diffusion-controlled. The degree of oxidation by ozone and OH radicals is given by the corresponding kinetics. Product formation from the ozonation of organic micropollutants in aqueous systems has only been established for a few compounds. It is discussed for olefines, amines and aromatic compounds.