Kinetics of reaction RH + O-2 = R + HO2 (RH = normal C1-C14 alkanes): A DFT investigation

doi:10.1016/j.fuel.2018.07.153

	Kinetics of reaction RH + O-2 = R + HO2 (RH = normal C1-C14 alkanes): A DFT investigation
	Fan, Hongjun; Xu, Wei
刊名	FUEL
	2018-12-15
卷号	234 页码:1165-1172
关键词	Fuel combustion Long alkane Kinetics First-principle
ISSN号	0016-2361
DOI	10.1016/j.fuel.2018.07.153
通讯作者	Fan, Hongjun(fanhj@dicp.ac.cn)
英文摘要	Alkane dehydrogenation by O-2 molecule is a one of the key elementary reactions for combustion, while the reliable reaction rates are very limited. Here UM06-2X/ccpv-dz calculations are carried out on reaction RH + O-2 = R + HO2 (RH = normal C1-C14(1) alkanes), the rate constants of these reactions at 500-2000 K are then simulated with canonical variational transition state theory and compared with those from experiments and kinetic models. The parameters of Arrhenius equation were fitted using the calculated rate constants and reaction barriers. For primary H, we found that the barrier decreases from C1 to C5, and then does not change obviously from C5 to C14. The barriers of the secondary H are smaller, and are all similar from C3 to C14. Consequently, the rate constants of the primary H of C5-C14 are slightly larger than C1-C4 at low temperature, and the secondary H have larger rate constants than the primary H. The barrier is not always the only decisive factor to judge the trends of the rate constants. We found that the pre-exponential factor for secondary H increases dramatically from C10 to C14, resulting a higher rate constants than other smaller alkanes. We also found that the pre-exponential factor is highly dependent on temperature, therefore the rate constant is better fitted by Arrhenius equations with T-n term. We believe these studies could provide valuable information for increasing the reliability of the current combustion model of alkanes, as well as constructing new combustion model for long alkanes.
资助项目	National Natural Science Foundation of China[21673224] ; National Key Research and Development Program of China[2016YFB0600301] ; DICP[DICP DMTO201404] ; Strategic pilot science and technology project of the Chinese Academy of Sciences[XDB17000000]
WOS关键词	TRANSITION-STATE THEORY ; LOW-TEMPERATURE OXIDATION ; N-DECANE ; TORSIONAL ANHARMONICITY ; JET FUEL ; HYDROGEN ABSTRACTION ; COMBUSTION ; PYROLYSIS ; MECHANISM ; THERMOCHEMISTRY
WOS研究方向	Energy & Fuels ; Engineering
语种	英语
出版者	ELSEVIER SCI LTD
WOS记录号	WOS:000445253100117
资助机构	National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Key Research and Development Program of China ; National Key Research and Development Program of China ; DICP ; DICP ; Strategic pilot science and technology project of the Chinese Academy of Sciences ; Strategic pilot science and technology project of the Chinese Academy of Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Key Research and Development Program of China ; National Key Research and Development Program of China ; DICP ; DICP ; Strategic pilot science and technology project of the Chinese Academy of Sciences ; Strategic pilot science and technology project of the Chinese Academy of Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Key Research and Development Program of China ; National Key Research and Development Program of China ; DICP ; DICP ; Strategic pilot science and technology project of the Chinese Academy of Sciences ; Strategic pilot science and technology project of the Chinese Academy of Sciences ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Key Research and Development Program of China ; National Key Research and Development Program of China ; DICP ; DICP ; Strategic pilot science and technology project of the Chinese Academy of Sciences ; Strategic pilot science and technology project of the Chinese Academy of Sciences
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/167012]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Fan, Hongjun
作者单位	Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, 457 Zhongshan Rd, Dalian 116023, Liaoning, Peoples R China
推荐引用方式 GB/T 7714	Fan, Hongjun,Xu, Wei. Kinetics of reaction RH + O-2 = R + HO2 (RH = normal C1-C14 alkanes): A DFT investigation[J]. FUEL,2018,234:1165-1172.
APA	Fan, Hongjun,&Xu, Wei.(2018).Kinetics of reaction RH + O-2 = R + HO2 (RH = normal C1-C14 alkanes): A DFT investigation.FUEL,234,1165-1172.
MLA	Fan, Hongjun,et al."Kinetics of reaction RH + O-2 = R + HO2 (RH = normal C1-C14 alkanes): A DFT investigation".FUEL 234(2018):1165-1172.