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JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 107, NO. D15, 4268, doi:10.1029/2001JD000716, 2002

Product analysis of the OH oxidation of isoprene and 1,3-butadiene in the presence of NO

Michele Sprengnether

State University of New York at Albany, New York, USA


Kenneth L. Demerjian

State University of New York at Albany, New York, USA


Neil M. Donahue

Harvard University, Cambridge, Massachusetts, USA


James G. Anderson

Harvard University, Cambridge, Massachusetts, USA


Abstract

The oxidation mechanisms of isoprene and butadiene initiated by OH in the presence of NO have been explored under “wall-less” flowing conditions, with products observed a few seconds after reaction by infrared spectroscopy. Since only ∼1% of alkene is reacted, any secondary chemistry is negligible. The use of reaction modulation spectroscopy permits the accurate measurement of a percent change in high alkene concentration and of 1013 molecules/cm3 concentrations for products. Measured carbonyl species agree with previous studies, while alkyl nitrate yields are consistent with upper values reported in the literature. NO sensitivity studies performed exclude the possibility of competing chemistry. Isoprene is not observed to form 3-methyl furan, indicating that this is not a prompt oxidation product. However, butadiene does form furan. In an auxiliary experiment, peroxy radicals in the second stage of butadiene oxidation are fully converted to peroxynitrates. Average cross sections for integrated peroxynitrate bands are determined from this experiment.

Published 13 August 2002.

Index Terms: 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0317 Atmospheric Composition and Structure: Chemical kinetic and photochemical properties; 0315 Atmospheric Composition and Structure: Biosphere/atmosphere interactions.

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Citation: Sprengnether, M., K. L. Demerjian, N. M. Donahue, and J. G. Anderson (2002), Product analysis of the OH oxidation of isoprene and 1,3-butadiene in the presence of NO, J. Geophys. Res., 107(D15), 4268, doi:10.1029/2001JD000716.