Solving the discrepancy between the direct and relative-rate determinations of unimolecular reaction kinetics of dimethyl-substituted Criegee intermediate (CH3)2COO using a new photolytic precursor

Abstract

We have performed direct kinetic measurements of the thermal unimolecular reaction of (CH₃)₂COO in the temperature range 243–340 K and pressure range 5–350 Torr using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, 2-bromo-2-iodopropane ((CH₃)₂CIBr), which photolysis at 213 nm in the presence of O₂ produces acetone oxide, (CH₃)₂COO. The results show that the thermal unimolecular reaction is even more important main loss process of (CH₃)₂COO in the atmosphere than direct kinetic studies have suggested hitherto. The current experiments show that the unimolecular reaction rate of (CH₃)₂COO at 296 K and atmospheric pressure is 899 ± 42 s⁻¹. Probably more importantly, current measurements bring the direct and relative-rate measurements of thermal unimolecular reaction kinetics of (CH₃)₂COO into quantitative agreement.