The kinetic and thermodynamic study on the OH-initiated degradation mechanism of polychlorinated dibenzo-p-dioxins

摘要

Quantum chemical method is adopted to elucidate the OH-initiated degradation mechanism of polychlorinated dibenzo-p-dioxins. Among the entire possible product channels, the main reaction pathways are discussed and show that the concerted isomerization reaction of druidical adduct is more favored than the step-by-step decomposition of monoradical adduct. The kinetic calculation is performed and the rate constants are calculated over a temperature range of 200~1200 K. The forward and reverse rate constants and the equilibrium constants are obtained. The four-parameter formulas of rate constants with the temperature are fitted.