期刊
COMBUSTION AND FLAME
卷 246, 期 -, 页码 -出版社
ELSEVIER SCIENCE INC
DOI: 10.1016/j.combustflame.2022.112414
关键词
Alkene oxidation; Autoxidation; Chain branching; Hydroperoxide; Keto-hydroperoxide
类别
资金
- National Natural Science Foun-dation of China
- Hefei Science Center, CAS
- [51976028]
- [2020HSC-KPRD001]
- [2021HSC-UE005]
This study investigates the low temperature oxidation of alkenes and identifies two different chain branching reaction networks initiated by alkenyl keto-hydroperoxide and hydroxyl keto-hydroperoxide.
The low temperature oxidation of alkenes exhibits some distinct reaction pathways that may form differ-ent kinds of keto-hydroperoxides to start the chain-branching by further decomposition. This is mainly due to the existence of the double bond that the OH radical could add to it. This work explores that phenomenon by investigating the low temperature oxidation of three alkenes (1-hexene, 1-heptene and 1-decene) in a jet-stirred reactor (JSR) at atmospheric pressure. The synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) experiments combined with hydrogen-deuterium (H-D) exchange reactions were used to evaluate the chain branching pathways. Alkenyl keto-hydroperoxide (AnKHP) and hydroxyl keto-hydroperoxide (HyKHP) are identified. They represented two different chain branching reaction networks that are initiated from the H-abstraction of the primary and secondary C -Hs and via OH addition to the double bond. The experimental estimated and model predicted ratios of AnKHP to HyKHP are compared, and the result indicates that the literature model underpredicts the chain branching reactions via the formation of AnKHP, but overpredicts the chain branching reactions via HyKHP.(c) 2022 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
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