title: Direct measurements of conformer-dependent reactivity of the Criegee intermediate CH3CHOO.
abstract: Although carbonyl oxides, "Criegee intermediates," have long been implicated in tropospheric oxidation, there have been few direct measurements of their kinetics, and only for the simplest compound in the class, CH2OO. Here, we report production and reaction kinetics of the next larger Criegee intermediate, CH3CHOO. Moreover, we independently probed the two distinct CH3CHOO conformers, syn- and anti-, both of which react readily with SO2 and with NO2. We demonstrate that anti-CH3CHOO is substantially more reactive toward water and SO2 than is syn-CH3CHOO. Reaction with water may dominate tropospheric removal of Criegee intermediates and determine their atmospheric concentration. An upper limit is obtained for the reaction of syn-CH3CHOO with water, and the rate constant for reaction of anti-CH3CHOO with water is measured as 1.0 × 10(-14) ± 0.4 × 10(-14) centimeter(3) second(-1).
authors.affiliation: Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551-0969, USA. cataatj@sandia.gov
authors.forename: Craig A
authors.initials: CA
authors.lastname: Taatjes
authors.forename: Oliver
authors.initials: O
authors.lastname: Welz
authors.forename: Arkke J
authors.initials: AJ
authors.lastname: Eskola
authors.forename: John D
authors.initials: JD
authors.lastname: Savee
authors.forename: Adam M
authors.initials: AM
authors.lastname: Scheer
authors.forename: Dudley E
authors.initials: DE
authors.lastname: Shallcross
authors.forename: Brandon
authors.initials: B
authors.lastname: Rotavera
authors.forename: Edmond P F
authors.initials: EP
authors.lastname: Lee
authors.forename: John M
authors.initials: JM
authors.lastname: Dyke
authors.forename: Daniel K W
authors.initials: DK
authors.lastname: Mok
authors.forename: David L
authors.initials: DL
authors.lastname: Osborn
authors.forename: Carl J
authors.initials: CJ
authors.lastname: Percival