Kinetics and Mechanism of Degradation of Reactive Radical-Mediated Probe Compounds by the UV/Chlorine Process: Theoretical Calculation and Experimental Verification

The UV/chlorine process, by combining chlorination with UV irradiation, has been recently considered as a highly efficient advanced oxidation process (AOP) technology in water treatment. Nitrobenzene (NB), benzoic acid (BA), and p-chlorobenzoic acid (pCBA) are widely used as model probe compounds in the UV/chlorine system to calculate the second-order rate constants of the specific radical reaction with target contaminates by a competitive kinetics method. A comprehensive understanding of probe compounds' reaction mechanism with reactive radicals is critical for investigation of the UV/chlorine reaction system. Here, we evaluated the radical-mediated reaction kinetics and mechanism of NB, BA, and pCBA in the UV/chlorine process using theoretical calculations and experimental studies. The main reactive radicals center dot OH, center dot ClO, and center dot Cl in the UV/chlorine process for the initial reaction with NB, BA, and pCBA can be explained by H-abstraction and addition pathways. The Delta E-0,E-not equal values for the center dot OH reaction with NB, BA, and pCBA were in the range of 5.0-8.0, 3.7-8.2, and 3.4-8.2 kcal mol(-1), respectively. The Delta E-0,E-not equal values for center dot ClO and center dot Cl reactions with these three probe compounds were higher than those of center dot OH, indicating slower center dot ClO-and center dot Cl-initiated reactions than that of the center dot OH-initiated reaction. The theoretically calculated radical-mediated reaction kinetic rate constants (k(CP)(C)) for NB, BA, and pCBA were 4.58 x 10(-3), 1.28 x 10(-2), and 1.6 x 10(-2) s(-1), respectively, which was consistent with the experimentally determined pseudo -first-order rate constant (kCP RR) in the UV/chlorine process. Interestingly, theoretical calculations showed that center dot ClO and center dot Cl played an important role in subsequent reactions of NB-OH radicals, converting to hydroxylated and chlorinated products, which were further confirmed by experimental products' identification. The findings from this study indicated that quantum chemistry calculations provide an effective means to investigate the reaction kinetics and mechanism of chemicals in the UV/chlorine process.

Automated summary

The UV/chlorine process is an efficient advanced oxidation process in water treatment. This study evaluated the reaction kinetics and mechanism of nitrobenzene, benzoic acid, and p-chlorobenzoic acid in the UV/chlorine process using theoretical calculations and experimental studies. The results showed that the reactions in the UV/chlorine process are mainly initiated by H-abstraction and addition pathways, with slower reactions initiated by chlorine radicals. The theoretically calculated rate constants were consistent with experimental results.