Reaction between CH<sub>3</sub>C(O)OOH (peracetic acid) and OH in the gas-phase: A combined experimental and theoretical study of the kinetics and mechanism

doi:10.5194/acp-2020-658

GSTDTAP > 地球科学

DOI	10.5194/acp-2020-658
	Reaction between CH₃C(O)OOH (peracetic acid) and OH in the gas-phase: A combined experimental and theoretical study of the kinetics and mechanism
	Matias Berasategui, Damien Amedro, Luc Vereecken, Jos Lelieveld, and John N. Crowley
	2020-07-14
发表期刊	Atmospheric Chemistry and Physics
出版年	2020
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 been studied only 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 molecule⁻¹ s⁻¹. The relatively low rate coefficient is in good agreement with the theoretical result of 3 × 10⁻¹⁴ cm³ molecule⁻¹ s⁻¹ at 298 K, increasing to ~ 6 × 10⁻¹⁴ in the cold upper troposphere, but with associated uncertainty of a factor-two. The reaction proceeds mainly via abstraction of the peroxidic-hydrogen via a relatively weakly bonded and short-lived pre-reaction complex, in which H-abstraction occurs only slowly due to a high barrier and low tunneling probabilities. Our results imply that the lifetime of CH₃C(O)OOH with respect to OH-initiated degradation in the atmosphere is of the order of one year (and not days as previously believed) and that its major sink in the free and upper troposphere is likely to be photolysis, with dry-deposition important in the boundary layer. Similar conclusions can be made for other, saturated peroxy-acids.
领域	地球科学
URL	查看原文
引用统计
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/284196
专题	地球科学
推荐引用方式 GB/T 7714	Matias Berasategui, Damien Amedro, Luc Vereecken, Jos Lelieveld, and John N. Crowley. 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]. Atmospheric Chemistry and Physics,2020.
APA	Matias Berasategui, Damien Amedro, Luc Vereecken, Jos Lelieveld, and John N. Crowley.(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.
MLA	Matias Berasategui, Damien Amedro, Luc Vereecken, Jos Lelieveld, and John N. Crowley."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 (2020).