Modeling the Kinetics of UV/Peracetic Acid Advanced Oxidation Process

Abstract

Abstract Peracetic acid combined with UV (i.e., UV/PAA) has emerged as a novel advanced oxidation process (AOP) for water disinfection and micropollutant degradation, but kinetic modeling for this AOP was lacking. In this study, a comprehensive model was developed to elucidate the reaction mechanisms and simulate reaction kinetics of UV/PAA process. By combining radical scavenging experiments and kinetic modeling, accurate quantum yield of PAA under UV254 (Φ = 0.88 ± 0.04 mol-Einstein–1) was determined via simultaneously quenching •OH and CH3C­(O)­O• with 2,4-hexadiene. The comparison between experimental observations and model predictions over a wide range of conditions allowed estimation of the rate constants of PAA with •OH (k•OH/PAA = 1.3 ± 0.2 × 109 M–1 s–1) and HO2• (kHO2•/PAA ≤ 5 × 102 M–1 s–1) with good accuracy. With derived Φ, k•OH/PAA and kHO2•/PAA, the kinetic model accurately predicts PAA decay under UV254 photolysis across varying PAA and H2O2 concentrations and water pH (5.8–7.2). Meanwhile, the model reveals that UV/PAA generates a lower •OH concentration than UV/H2O2 at equivalent oxidant concentrations, with CH3C­(O)­OO• as the most abundant carbon-centered radical. This study significantly improves the knowledge of reactive species generation and reaction kinetics and mechanisms under UV/PAA, and provides a useful kinetic model for this AOP in water treatment.