title: Resonance Stabilization Effects on Ketone Autoxidation: Isomer-Specific Cyclic Ether and Ketohydroperoxide Formation in the Low-Temperature (400-625 K) Oxidation of Diethyl Ketone.
abstract: The pulsed photolytic chlorine-initiated oxidation of diethyl ketone [DEK; (CH3CH2)2C═O], 2,2,4,4-d4-DEK [d4-DEK; (CH3CD2)2C═O], and 1,1,1,5,5,5-d6-DEK [d6-DEK; (CD3CH2)2C═O] is studied at 8 torr and 1-2 atm and from 400-625 K. Cl atoms produced by laser photolysis react with diethyl ketone to form either primary (3-pentan-on-1-yl, RP) or secondary (3-pentan-on-2-yl, RS) radicals, which in turn react with O2. Multiplexed time-of-flight mass spectrometry, coupled to either a hydrogen discharge lamp or tunable synchrotron photoionizing radiation, is used to detect products as a function of mass, time, and photon energy. At 8 torr, the nature of the chain propagating cyclic ether + OH channel changes as a function of temperature. At 450 K, the production of OH is mainly in conjunction with formation of 2,4-dimethyloxetan-3-one, resulting from reaction of the resonance-stabilized secondary RSwith O2. In contrast, at 550 K and 8 torr, 2-methyl-tetrahydrofuran-3-one, originating from oxidation of the primary radical (RP), is observed as the dominant cyclic ether product. Formation of both of these cyclic ether production channels proceeds via a resonance-stabilized hydroperoxy alkyl (QOOH) intermediate. Little or no ketohydroperoxide (KHP) is observed under the low-pressure conditions. At higher O2concentrations and higher pressures (1-2 atm), a strong KHP signal appears as the temperature is increased above 450 K. Definitive isomeric identification from measurements on the deuterated DEK isotopologues indicates the favored pathway produces a γ-KHP via resonance-stabilized alkyl, QOOH, and HOOPOOH radicals. Time-resolved measurements reveal the KHP formation becomes faster and signal more intense upon increasing temperature from 450 to 575 K before intensity drops significantly at 625 K. The KHP time profile also shows a peak followed by a gradual depletion for the extent of experiment. Several tertiary products exhibit a slow accumulation in coincidence with the observed KHP decay. These products can be associated with decomposition of KHP by β-scission pathways or via isomerization of a γ-KHP into a cyclic peroxide intermediate (Korcek mechanism). The oxidation of d4-DEK, where kinetic isotope effects disfavor γ-KHP formation, shows greatly reduced KHP formation and associated signatures from KHP decomposition products.
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , MS 9055, Livermore, California 94551, United States.
authors.forename: Adam M
authors.initials: AM
authors.lastname: Scheer
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , MS 9055, Livermore, California 94551, United States.
authors.forename: Arkke J
authors.initials: AJ
authors.lastname: Eskola
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , MS 9055, Livermore, California 94551, United States.
authors.forename: David L
authors.initials: DL
authors.lastname: Osborn
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , MS 9055, Livermore, California 94551, United States.
authors.forename: Leonid
authors.initials: L
authors.lastname: Sheps
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , MS 9055, Livermore, California 94551, United States.
authors.forename: Craig A
authors.initials: CA
authors.lastname: Taatjes