Kinetics of the simplest Criegee intermediate reaction with ozone studied by mid-infrared quantum cascade laser spectrometer

Abstract

The kinetics of CH${}_2$OO reaction with ozone has been studied by monitoring CH${}_2$OO with time-resolved infrared (IR) absorption spectroscopy, which utilized fast chirped IR pulse train from a quantum cascade laser [J. Chem. Phys. 146, 244302 (2017)]. CH${}_2$OO was prepared by photolyzing a gas mixture of CH${}_2$I${}_2$/O${}_2$/O${}_3$ at 352 nm; the photolysis wavelength was chosen to minimize the photodissociation of O${}_3$. The measured rate coefficient at 298 K and 30 Torr is (6.7$\pm$0.5)x10${}^{-14}$ cm${}^3$sec${}^{-1}$, independent of pressure from 30 to 100 Torr. The result indicates that previous ab initio calculations either underestimated or overestimated this reaction rate by one order of magnitude or more. The result also implies that in laboratory studies of ozonolysis of alkenes, the reaction of Criegee intermediate with ozone may play a role. However, this reaction would not compete with other CH${}_2$OO sinks in the atmosphere.

References in corpus (1)

• High resolution quantum cascade laser spectroscopy of the simplest Criegee intermediate, CH${}_2$OO, between 1273 cm${}^{-1}$ and 1290 cm${}^{-1}$