title: The OH-initiated oxidation of 1,3-butadiene in the presence of O2 and NO: a photolytic route to study isomeric selective reactivity.
abstract: We report the study of the isomeric selective OH-initiated oxidation of 1,3-butadiene in the presence of O2 and NO using the LP/LIF technique. The photolysis of monodeuterated 1-iodo-3-buten-2-ol provides only one of the possible OD-butadiene adducts, the minor addition channel product, simplifying the oxidation mechanism. We find, based on analysis of OD time-dependent traces that prompt rearrangement of initial beta-hydroxyalkyl radicals to alpha-hydroxyalkyl radicals occurs in agreement with RRKM/ME theoretical predictions. We report a rate constant of (3.3+/-1.0) x 10(-11) cm3 molecules(-1) s(-1) for deuterium abstraction from the alpha-hydroxyalkyl radical at 298 +/-2 K. Our approach demonstrates the feasibility of isomeric selective kinetic studies of the OH-initiated oxidation of unsaturated hydrocarbons.
authors.affiliation: Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842, USA.
authors.forename: Erin E
authors.initials: EE
authors.lastname: Greenwald
authors.forename: Jiho
authors.initials: J
authors.lastname: Park
authors.forename: Katie C
authors.initials: KC
authors.lastname: Anderson
authors.forename: Hahkjoon
authors.initials: H
authors.lastname: Kim
authors.forename: B Jesse E
authors.initials: BJ
authors.lastname: Reich
authors.forename: Stephen A
authors.initials: SA
authors.lastname: Miller
authors.forename: Renyi
authors.initials: R
authors.lastname: Zhang
authors.forename: Simon W
authors.initials: SW
authors.lastname: North