title: Direct kinetic measurements of Criegee intermediate (CH₂OO) formed by reaction of CH₂I with O₂.
abstract: Ozonolysis is a major tropospheric removal mechanism for unsaturated hydrocarbons and proceeds via "Criegee intermediates"--carbonyl oxides--that play a key role in tropospheric oxidation models. However, until recently no gas-phase Criegee intermediate had been observed, and indirect determinations of their reaction kinetics gave derived rate coefficients spanning orders of magnitude. Here, we report direct photoionization mass spectrometric detection of formaldehyde oxide (CH(2)OO) as a product of the reaction of CH(2)I with O(2). This reaction enabled direct laboratory determinations of CH(2)OO kinetics. Upper limits were extracted for reaction rate coefficients with NO and H(2)O. The CH(2)OO reactions with SO(2) and NO(2) proved unexpectedly rapid and imply a substantially greater role of carbonyl oxides in models of tropospheric sulfate and nitrate chemistry than previously assumed.
authors.affiliation: Combustion Research Facility, Mail Stop 9055, Sandia National Laboratories, Livermore, CA 94551-0969, USA.
authors.forename: Oliver
authors.initials: O
authors.lastname: Welz
authors.forename: John D
authors.initials: JD
authors.lastname: Savee
authors.forename: David L
authors.initials: DL
authors.lastname: Osborn
authors.forename: Subith S
authors.initials: SS
authors.lastname: Vasu
authors.forename: Carl J
authors.initials: CJ
authors.lastname: Percival
authors.forename: Dudley E
authors.initials: DE
authors.lastname: Shallcross
authors.forename: Craig A
authors.initials: CA
authors.lastname: Taatjes