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DOI	10.1016/j.atmosenv.2021.118821
	Rate coefficient and mechanism of the OH-initiated degradation of cyclobutanol: A combined experimental and theoretical study
	Garavagno M.D.L.A.; Hernández F.J.; Jara-Toro R.A.; Mahecha G.; Barrera J.A.; Taccone R.A.; Pino G.A.
发表日期	2022
ISSN	1352-2310
卷号	268
英文摘要	The degradation process of cyclobutanol (cButOH) by hydroxyl radical (OH), under atmospheric conditions, (750 ± 10) Torr of air and (296 ± 2) K, has been studied. The rate coefficient for the title reaction (k296K = (7.3 ± 0.6) x 10−12 cm3 molecule−1 s−1) was determined at 296 K by the conventional relative-rate method. Electronic structure calculations with uCCSD(T)/uBHandHLYP/aug-cc-PVDZ were conducted to study the reaction mechanism. The global rate coefficient was also calculated using the transition state theory with tunnelling corrections, obtaining a value of 5.4 × 10−12 cm3 molecule−1 s−1 in agreement with the experimental determination. Additionally, reaction products identification in clean and NOx-contaminated atmospheres was performed for the first time. The identified reaction products and their corresponding yields (YP) depend on the environment composition in which the reaction is studied. In the absence of NOx, cyclobutanone (cButanone) was the only identified product, with YcButanone = (0.66 ± 0.08). In NOx-contaminated atmospheres, in addition to cButanone, tetrahydrofuran (THF), 2-nitro-1-butanol (2N1B), 3-nitro-2-butanol (3N2B) and 2-methyl-2-nitro-1-propanol (2M2N1P), were also identified as primary reaction products. Under this condition, we were able to determine only the yields of cButanone and THF (YcButanone = 0.38 ± 0.05 and YTHF = 0.28 ± 0.02). A likely reaction mechanism for the observed products is proposed and the atmospheric implications are discussed. © 2021
关键词	Cyclic-alcohol Cyclobutanone Nitro-alcohol NOx contaminated atmosphere Tetrahydrofuran
语种	英语
scopus关键词	Electronic structure; Molecules; Nitrogen oxides; Organic solvents; Reaction products; Cyclic alcohols; Cyclobutanols; Cyclobutanones; Nitro-alcohol; NO x; NOx contaminated atmosphere; Rate coefficients; Reaction mechanism; Tetra-hydrofuran; Tetrahydrofurans; Ketones; 2 methyl 2 nitro 1 propanol; 2 nitro 1 butanol; 3 nitro 2 butanol; 4 ol tetrahydro 4h pyrane; butanol; butyrolactone; cyclobutanol; cyclobutanone derivative; hydroxyl radical; methanol derivative; pyran derivative; tetrahydro 2 furan methanol; tetrahydrofuran; unclassified drug; atmospheric chemistry; degradation; hydroxyl radical; organic compound; reaction kinetics; Article; atmospheric pressure; calculation; chemical structure; controlled study; degradation; experimental study; flame ionization detection; oxidation; photolysis; quadrupole mass spectrometry; rate constant; reaction analysis; reaction time; retention time; solid phase microextraction; 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/248145
作者单位	INFIQC: Instituto de Investigaciones en Fisicoquímica de Córdoba (CONICET – UNC) - Haya de la Torre y Medina Allende, Ciudad Universitaria, Córdoba, X5000HUA, Argentina; Departamento de Fisicoquímica, Facultad de Ciencias Químicas– Universidad Nacional de Córdoba – Haya de la Torre y Medina Allende, Ciudad Universitaria, Córdoba, X5000HUA, Argentina; Centro Láser de Ciencias Moleculares - Universidad Nacional de Córdoba - Haya de la Torre y Medina Allende, Pabellón Argentina, Ciudad Universitaria, Córdoba, X5000HUA, Argentina
推荐引用方式 GB/T 7714	Garavagno M.D.L.A.,Hernández F.J.,Jara-Toro R.A.,et al. Rate coefficient and mechanism of the OH-initiated degradation of cyclobutanol: A combined experimental and theoretical study[J],2022,268.
APA	Garavagno M.D.L.A..,Hernández F.J..,Jara-Toro R.A..,Mahecha G..,Barrera J.A..,...&Pino G.A..(2022).Rate coefficient and mechanism of the OH-initiated degradation of cyclobutanol: A combined experimental and theoretical study.ATMOSPHERIC ENVIRONMENT,268.
MLA	Garavagno M.D.L.A.,et al."Rate coefficient and mechanism of the OH-initiated degradation of cyclobutanol: A combined experimental and theoretical study".ATMOSPHERIC ENVIRONMENT 268(2022).