期刊
PROCEEDINGS OF THE COMBUSTION INSTITUTE
卷 35, 期 -, 页码 291-298出版社
ELSEVIER SCIENCE INC
DOI: 10.1016/j.proci.2014.05.011
关键词
Ketohydroperoxide; n-Butane; Autoignition; Chain branching; Time-resolved
资金
- Saudi Aramco Kinetics Cluster of Excellence under a cooperative research and development agreement (CRADA) [CRADA SC10/01773.00, 6500007287]
- Office of Science, Office of Basic Energy Sciences of the U.S. Department of Energy (BES/USDOE) [DE-AC02-05CH11231]
- Argonne-Sandia Consortium on High-Pressure Combustion Chemistry (SNL FWP) [014544]
- Division of Chemical Sciences, Geosciences, and Biosciences, BES/USDOE
- National Nuclear Security Administration [DE-AC04-94-AL85000]
Ketohydroperoxide formation in Cl-atom initiated low-temperature (550-700 K) oxidation of n-butane was investigated using a time-of-flight mass spectrometer and either tunable synchrotron radiation or a H-2 discharge for photoionization. Experiments were performed at 1-2 atm pressure using a new high-pressure reactor and also at similar to 5 Torr pressure for comparison. Direct kinetic observations of ketohydroperoxide formation qualitatively agree with previous atmospheric pressure jet-stirred reactor studies of Battin-Leclerc et al. (Angew. Chem. Int. Ed., 49 (2010) 3169-3172) where the maximum ketohydroperoxide signal was observed near 600 K. Oxidation of partially deuterated n-butanes provided additional information on the QOOH radical intermediates that proceed to form ketohydroperoxides. The photoionization spectrum of the observed ketohydroperoxide is independent of pressure and is the same when using different deuterium substituted n-butanes, suggesting that one ketohydroperoxide isomer dominates in n-butane oxidation. We conclude that 4-hydroperoxy-2-butyl + O-2 is the main reaction leading to ketohydroperoxide and 3-hydroperoxybutanal is the sole ketohydroperoxide that is observed. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
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