Kinetic and Mechanistic Considerations on the Superoxide-Mediated Transformation Of Phenol and Nitrobenzene

In this study, the kinetics and mechanisms of [[EQUATION]] ‒mediated transformation of two monosubstituted aromatic contaminants with diametrically opposed electronic effect, namely phenol (PhOH) and nitrobenzene (NB), were investigated through combined experimental and theoretical approaches. The reaction rate constant between [[EQUATION]] and PhOH was determined to be 269 M ‒1 s ‒1 via competition kinetic method. Such weak role of [[EQUATION]] is confirmed by density functional theory (DFT) calculations of the reaction at SMD/CAM−B3LYP/6−311++G**//CAM−B3LYP/6−31+G** level of theory. However, NB exhibited a higher reactivity towards [[EQUATION]] than that with PhOH, demonstrating the selectivity of [[EQUATION]] to interact with aromatic compounds with a low electron density. These results were also in reasonably good agreement with an indication from a quantitative structure–property relationship model. With these quantitative and mechanistic results, we provided a more comprehensive understanding on the [[EQUATION]] ‒mediated transformation of organic pollutants bearing different electron donating/withdrawing groups