title: Synchrotron photoionization mass spectrometry measurements of product formation in low-temperature n-butane oxidation: toward a fundamental understanding of autoignition chemistry and n-C4H9 + O2/s-C4H9 + O2 reactions.
abstract: Product formation in the laser-initiated low-temperature (575-700 K) oxidation of n-butane was investigated by using tunable synchrotron photoionization time-of-flight mass spectrometry at low pressure (∼4 Torr). Oxidation was triggered either by 351 nm photolysis of Cl2 and subsequent fast Cl + n-butane reaction or by 248 nm photolysis of 1-iodobutane or 2-iodobutane. Iodobutane photolysis allowed isomer-specific preparation of either n-C4H9 or s-C4H9 radicals. Experiments probed the time-resolved formation of products and identified isomeric species by their photoionization spectra. For stable primary products of butyl + O2 reactions (e.g., butene or oxygen heterocycles) bimodal time behavior is observed; the initial prompt formation, primarily due to chemical activation, is followed by a slower component arising from the dissociation of thermalized butylperoxy or hydroperoxybutyl radicals. In addition, time-resolved formation of C4-ketohydroperoxides (C4H8O3, m/z = 104) was observed in the n-C4H9 + O2 and Cl-initiated oxidation experiments but not in the s-C4H9 + O2 measurements, suggesting isomeric selectivity in the combined process of the "second" oxygen addition to hydroperoxybutyl radicals and subsequent internal H-abstraction/dissociation leading to ketohydroperoxide + OH. To further constrain product isomer identification, Cl-initiated oxidation experiments were also performed with partially deuterated n-butanes (CD3CH2CH2CD3 and CH3CD2CD2CH3). From these experiments, the relative yields of butene product isomers (cis-2-butene, trans-2-butene, and 1-butene) from C4H8 + HO2 reaction channels and oxygenated product isomers (2,3-dimethyloxirane, 2-methyloxetane, tetrahydrofuran, ethyloxirane, butanal, and butanone) associated with OH formation were determined. The current measurements show substantially different isomeric selectivity for oxygenated products than do recent jet-stirred reactor studies but are in reasonable agreement with measurements from butane addition to reacting H2/O2 mixtures at 753 K.
authors.affiliation: Combustion Research Facility, Sandia National Laboratories , Mail Stop 9055, Livermore, California 94551-0969, United States.
authors.forename: Arkke J
authors.initials: AJ
authors.lastname: Eskola
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: Craig A
authors.initials: CA
authors.lastname: Taatjes