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DOI	10.1016/j.atmosenv.2021.118915
	Theoretical investigation on atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon ketones and alcohols
	Wang Q.; Ni S.; Bai F.; Pan X.
发表日期	2022
ISSN	1352-2310
卷号	271
英文摘要	The oxidation mechanism, thermochemistry and kinetics of 3-hydroxy-2-butanone (3H2B) and 2-methyl-1-propanol (2M1P) initiated by NO3 radicals were theoretically investigated at the CCSD(T)//BH&HLYP/6–311++G(d,p) level. The thermodynamic calculation results show that the channels of α-CH and α-CH2 sites are dominant for 3H2B and 2M1P. The strategy of experiment-SAR-DFT combined was proposed for the first time to discuss reaction kinetic information. The estimated rate constants of hydroxylketones and saturated alcohols with the total carbon number of four to six were provided by using the SAR method. The revised and supplemented group substituent factors F(–CH<) and F(–CH2OH) were provided to the original NO3 database, and the values obtained are 1.67 and 18.3. The rate constants for H-atom abstraction reactions of 3H2B and 2M1P with NO3 were evaluated over the temperature range of 250–350 K to verify the experiment-SAR-DFT strategy. The calculated values of 3H2B and 2M1P are 6.93 × 10−16 and 2.67 × 10−15 cm3 molecule−1 s−1 at 298 K, which are in close agreement with the reported experimental results and updated estimated values. Our theoretical research outcomes further attest that the new group substituent factor F(–CH2OH) is reliable. The nighttime atmospheric lifetime of 3H2B and 2M1P were estimated to be around 33 and 9 days, indicating that 3H2B has an effect on the atmospheric environment at night. The results can improve the reliability and accuracy of NO3 radicals kinetic data required to predict the contributions of 3H2B and 2M1P to the atmospheric environment. © 2021 Elsevier Ltd
关键词	Atmospheric fate Hydroxylketones Kinetics Reaction mechanism Saturated alcohols Structure-activity relationship
语种	英语
scopus关键词	Carbon; Ketones; Rate constants; 1-propanol; 2-butanone; Atmospheric environment; Atmospheric fates; Atmospheric reaction mechanisms; Hydroxylketone; Reaction mechanism; Saturated alcohols; Structure-activity relationships; Theoretical investigations; Kinetics; acetoin; alcohol derivative; carbon; isobutanol; ketone; radical; ketone; oxidation; reaction kinetics; synthetic aperture radar; theoretical study; thermodynamics; Article; atmosphere; chemical reaction kinetics; rate constant; reaction analysis; substitution reaction; theoretical study
来源期刊	ATMOSPHERIC ENVIRONMENT
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/248098
作者单位	Institute of Functional Material Chemistry, National & Local United Engineering Lab for Power Battery, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China; Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang, 110034, China
推荐引用方式 GB/T 7714	Wang Q.,Ni S.,Bai F.,et al. Theoretical investigation on atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon ketones and alcohols[J],2022,271.
APA	Wang Q.,Ni S.,Bai F.,&Pan X..(2022).Theoretical investigation on atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon ketones and alcohols.ATMOSPHERIC ENVIRONMENT,271.
MLA	Wang Q.,et al."Theoretical investigation on atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon ketones and alcohols".ATMOSPHERIC ENVIRONMENT 271(2022).