In a water ozonation process, dissolved organics undergo two reactions at least: direct ozone attack and oxidation with hydroxyl radicals generated from the ozone decomposition. In the particular case of urban wastewater contaminated with pharmaceuticals, competition between these two reactions can be studied through application of gas–liquid reaction kinetics. However, there is a lack in literature about kinetic modeling of ozone processes in water specially in photocatalytic ozonation. In this work, lumped reactions of ozone and hydroxyl radicals with total organic carbon have been proposed. Urban wastewater containing a mixture of eight pharmaceutical compounds has been used to establish the kinetic model that simulates the mineralization process. The kinetic model is based on a mechanism of free radical and molecular reactions and the knowledge of mass transfer, chemical reaction rate constants, and radiation transfer data. According to the model, both single ozonation and photocatalytic ozonation present two distinct reaction periods characterized by the absence and presence of dissolved ozone. In the first period (less than 10 min), pharmaceuticals mainly disappear by direct ozone reactions and TOC variation due to these compounds has been modeled according to gas–liquid reaction kinetics through a lumped ozone-pharmaceutical TOC fast second order reaction. The corresponding rate constant of this reaction was found to change with time from 3 × 105 to 200 M−1 s−1 with Hatta values higher than 0.3. In the second period (nearly 5 h), competition between direct and hydroxyl radical reactions takes place and a kinetic model based on a direct and free radical reaction mechanism is proposed. Main influencing parameters to be known were: Direct ozone reaction rate constant, catalyst quantum yield, and hydroxyl radical scavengers. The first two take values of 0.5 M−1 s−1 and 5 × 10−4 mol·photon−1, respectively, while a fraction of TOC between 10% and 90% that changes with time was found to possess hydroxyl radical scavenger nature.
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