Infrared Characterization of the Products of the Reaction between the Criegee Intermediate CH₃CHOO and HCl

Abstract

The rapid reactions between Criegee intermediates and hydrogen halides play important roles in atmospheric chemistry, particularly in the polluted urban atmosphere. Employing a step-scan Fourier transform spectrometer, we recorded infrared absorption spectra of transient species and end products of the reaction CH 3 CHOO + HCl in a flowing mixture of CH 3 CHI 2 /HCl/O 2 /N 2 irradiated at 308 nm.

Detailed mechanism and kinetics of reactions of anti- and syn-CH3CHOO with HC(O)OH: infrared spectra of conformers of hydroperoxyethyl formate

“…It is interesting to note that the reaction syn -CH 3 CHOO + HC(O)OH ended up with the formation of the anti -conformer of HPEF, similar to the case of syn -CH 3 CHOO + HCl to form the anti -conformer of chloroethyl hydroperoxide ( anti -CH 3 CHClOOH). 70 In both cases, the internally excited syn -conformers of the hydrogen-transferred adducts convert to the low-energy anti -conformer.…”

Collection on the Spectroscopy, Structure, and Reactivity of Stabilized Criegee Intermediates

“…The unusual electronic character of the sCIs influences their chemical reactions, which typically proceed via cyclic transition states associated with cycloaddition or 1,2- or 1,4-insertion pathways. − The latter insertion reactions tend to be faster, in some cases approaching the gas-kinetic limit. Not only is there fundamental interest in the structural and conformer dependence of the bimolecular reaction rates, but many of the studies of the rates of these bimolecular reactions are also motivated by their potential importance in atmospheric oxidation chemistry.…”