期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 114, 期 50, 页码 13102-13107出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1707564114
关键词
autooxidation; peroxides; ignition; secondary organic aerosol; mass spectrometry
资金
- King Abdullah University of Science and Technology, Office of Sponsored Research (OSR) [OSR-2016-CRG5-3022]
- Saudi Aramco under the FUELCOM program
- Office of Energy Research, Office of Basic Energy Sciences (BES), Chemical Sciences Division of the US Department of Energy (USDOE) [DE-AC02-05CH11231]
- Division of Chemical Sciences, Geosciences and Biosciences, BES/USDOE
- Deutsche Forschungsgemeinschaft [KO1363/31-1]
- European Research Council (ERC)/ERC [291049-2G-CSafe]
- USDOE's National Nuclear Security Administration [DE-NA0003525]
- Office of BES, of the USDOE [DE-AC02-05CH11231]
Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500-600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound's molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.
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