Effects of common inorganic anions on the ozonation of polychlorinated diphenyl sulfides on silica gel: Kinetics, mechanisms, and theoretical calculations

Abstract

In this work, the ozonation properties of 2,2',3',4,5-pentachlorodiphenyl sulfide (PeCDPS) was systematically studied, with special emphasis on the underlying mechanism for the effects of inorganic ions. Kinetic experiments show that common ions can significantly reduce the oxidative properties of ozone, except for SO₃^2- and Cu²⁺. The inhibition effect of anions has been explained through the scavenging effect of free radicals and the generation of other free radicals with weaker oxidation potentials, but no research has reported on the effect of free radicals generated by anions on the degradation pathway. However, SO₃^2- and Cu²⁺ exerted a promoting effect through enhanced formation of ·OH via the hydrolysis effect and the catalyzed decomposition of O₃, respectively. According to the intermediate products identified by high performance liquid chromatography-mass spectrometry/mass spectrometry (HPLC-MS/MS) analysis, direct oxidation of S atom, substitution of Cl atom with -OH group, and hydroxylation of the benzene ring were commonly observed. The addition of NO₂^- and SO₃^2- produced new free radicals like ·NO₂, ·SO₃ and ·SO₄^-, which would attack the parent compound or its primary product, thus influencing the degradation efficiency and pathways. The radicals initiated reactions and the structures of the corresponding products were further rationalized by density functional theory (DFT) calculations. These findings provide new insights into the effects of common anions on ozone oxidation of organic compounds.

Keywords: Free radicals; Ions; Mechanisms; Ozone oxidation; Theoretical calculations.