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Utilization of Stop-flow Micro-tubing Reactors for the Development of Organic Transformations
Published on: January 4, 2018
Solving the discrepancy between the direct and relative-rate determinations of unimolecular reaction kinetics of
Jari Peltola1, Prasenjit Seal1, Niko Vuorio1
1Department of Chemistry, University of Helsinki, P.O. Box 55 (A.I. Virtasen aukio 1), Helsinki, FI-00014, Finland. arkke.eskola@helsinki.fi.
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.
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