S(IV)-based systems used for advanced oxidation processes (AOPs) have been constructed for the degradation of organic contaminants via oxysulfur radicals, including SO3•-, SO4•-, and SO5•-. Although SO5•- is proposed as an active species in AOPs processes, research on the reactivity of SO5•- has remained unclear. In this work, 53 target aromatic micropollutants (AMPs), including 13 phenols, 27 amines, and 13 PPCPs were selected to determine the second-order reaction rate constants for SO5•- using the competitive kinetics method, in which the [Formula: see text] values, observed at pH 4 ranged from (2.44 ± 0.00) × 105 M-1 s-1 to (4.41 ± 0.28) × 107 M-1 s-1. Quantitative structure-activity relationship (QSAR) models for the oxidation of AMPs by SO5•- were developed based on 40 [Formula: see text] values of amines and phenols, and their molecular descriptors, using the stepwise multiple linear regression method. This comprehensive model exhibited the excellent goodness-of-fit (Radj2 = 0.802), robustness (QLOO2 = 0.749), and predictability (Qext2 = 0.656), and the one-electron oxidation potential (Eox), energy of the highest occupied molecular orbital energy (EHOMO), and most positive net atomic charge on the carbon atoms (qC+) were considered the most influential descriptors for the comprehensive model, indicating that SO5•- oxidizes pollutants via single electron transfer reaction and exhibits a strong oxidation capacity, especially for pollutants containing electron-donating groups. Moreover, the [Formula: see text] values of 13 PPCPs were predicted using this comprehensive model, which suggested the practical application significance of the QSAR model. This study emphasizes the direct oxidation capacity of SO5•-, which is important to evaluate and simulate AOPs based on S(IV).
Keywords: Aromatic micropollutants; Competitive kinetic method; Peroxymonosulfate radical; Quantitative structure-activity relationship; S(IV)-based AOPs.
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