气候变化领域集成服务门户(CCPortal): Reaction between CH3C(O)OOH (peracetic acid) and OH in the gas phase: A combined experimental and theoretical study of the kinetics and mechanism

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DOI	10.5194/acp-20-13541-2020
	Reaction between CH3C(O)OOH (peracetic acid) and OH in the gas phase: A combined experimental and theoretical study of the kinetics and mechanism
	Berasategui M.; Amedro D.; Vereecken L.; Lelieveld J.; Crowley J.N.
发表日期	2020
ISSN	16807316
起始页码	13541
结束页码	13555
卷号	20 期号:21
英文摘要	Peracetic acid (CH3C(O)OOH) is one of the most abundant organic peroxides in the atmosphere; yet the kinetics of its reaction with OH, believed to be the major sink, have only been studied once experimentally. In this work we combine a pulsed-laser photolysis kinetic study of the title reaction with theoretical calculations of the rate coefficient and mechanism. We demonstrate that the rate coefficient is orders of magnitude lower than previously determined, with an experimentally derived upper limit of 4×10-14 cm3 molec.-1 s-1. The relatively low rate coefficient is in good agreement with the theoretical result of 3×10-14 cm3 molec.-1 s-1 at 298 K, increasing to ≈ 6× 10-14 cm3 molec.-1 s-1 in the cold upper troposphere but with associated uncertainty of a factor of 2. The reaction proceeds mainly via abstraction of the peroxidic hydrogen via a relatively weakly bonded and short-lived prereaction complex, in which H abstraction occurs only slowly due to a high barrier and low tunnelling probabilities. Our results imply that the lifetime of CH3C(O)OOH with respect to OHinitiated degradation in the atmosphere is of the order of 1 year (not days as previously believed) and that its major sink in the free and upper troposphere is likely to be photolysis, with deposition important in the boundary layer. © Author(s) 2020.
语种	英语
来源期刊	Atmospheric Chemistry and Physics
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/143811
作者单位	Division of Atmospheric Chemistry, Max Planck Institute for Chemistry, Mainz, 55128, Germany; Institute for Energy and Climate Research: IEK-8, Forschungszentrum Juelich, Juelich, 52425, Germany
推荐引用方式 GB/T 7714	Berasategui M.,Amedro D.,Vereecken L.,et al. Reaction between CH3C(O)OOH (peracetic acid) and OH in the gas phase: A combined experimental and theoretical study of the kinetics and mechanism[J],2020,20(21).
APA	Berasategui M.,Amedro D.,Vereecken L.,Lelieveld J.,&Crowley J.N..(2020).Reaction between CH3C(O)OOH (peracetic acid) and OH in the gas phase: A combined experimental and theoretical study of the kinetics and mechanism.Atmospheric Chemistry and Physics,20(21).
MLA	Berasategui M.,et al."Reaction between CH3C(O)OOH (peracetic acid) and OH in the gas phase: A combined experimental and theoretical study of the kinetics and mechanism".Atmospheric Chemistry and Physics 20.21(2020).