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• W3199293460 abstract "The reactions of carbonyl oxide Criegee intermediates with acids proceed predominantly by an insertion mechanism. We characterise the products from one of the simplest reactions of carbonyl oxides with inorganic acids, CH2OO + hydrogen chloride, which occurs via a 1,2-insertion in the H–Cl bond. Reactions of both HCl and DCl isotopologues yield product signal at the mass of the insertion product chloro(hydroperoxy)methane and a dissociative ionisation peak at the mass of the protonated (or deuteronated) Criegee intermediate. The isotopic composition of the insertion product has been measured for reaction mixtures where both HCl isotopologues are present, and the H/D ratio of the product is consistently higher (by a factor of 1.6 ± 0.3) than that of the reactants. This isotope selectivity in the products has smaller uncertainty than the ratio of measured rate coefficients and suggests a normal (kH > kD) kinetic isotope effect in the reaction. Theoretical kinetics calculations predict a small normal kinetic isotope effect for the overall reaction (kH / kD = 1.35 at 20 Torr N2 and kH / kD = 1.2 at 1 atm N2) but predict a substantial inverse kinetic isotope effect (kD > kH) for the stabilisation fraction, in disagreement with the experimental observation." @default.
• W3199293460 created "2021-09-27" @default.
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• W3199293460 date "2021-09-16" @default.
• W3199293460 modified "2023-10-16" @default.
• W3199293460 title "Insertion products in the reaction of carbonyl oxide Criegee intermediates with acids: Chloro(hydroperoxy)methane formation from reaction of CH₂OO with HCl and DCl" @default.
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• W3199293460 doi "https://doi.org/10.1080/00268976.2021.1975199" @default.
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