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DOI: 10.1039/A702364B (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1997, 93, 3021-3027

Products and mechanism of the gas-phase reaction of NO3 radicals with α-pinene

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Torsten Berndt and Olaf Böge

Abstract

The gas-phase reaction of NO3 radicals with α-pinene has been studied under flow conditions in the pressure range 20<p/mbar <200 at 298 K using gas chromatography–mass spectrometry/flame ionisation detection (GC–MS/FID), MS and long-path FTIR spectroscopy as detection techniques. NO3 radicals were generated by thermal decomposition of N2O5. He, N2 or O2–N2 mixtures served as carrier gas. In the absence of O2 in the carrier gas, α-pinene oxide (ca. 60%) and an organic nitrate (ca. 40%) were found to be the main products with minor amounts of α-campholene aldehyde. The yields were slightly pressure dependent. In the presence of O2, pinonaldehyde was the predominant product. When NO was added for conversion of the formed peroxyl radicals via RO2+NO→RO→NO2, the following product yields were obtained at p=200 mbar and [O2]>1017 molecule cm-3, pinonaldehyde 75±6%, α-pinene oxide 15±3%, organic nitrates (total) 14±3%, α-campholene aldehyde 3±1%. In the absence of NO, nitroperoxy-group-containing substances were observed, arising from the reaction RO2+NO2→RO2NO2 . A reaction mechanism is proposed and a tropospheric application of the results is discussed.

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