English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  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. (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), 13541-13555. doi:10.5194/acp-20-13541-2020.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Berasategui, Matias1, Author              
Amedro, Damien1, Author              
Vereecken, Luc, Author
Lelieveld, Jos1, Author              
Crowley, John N.1, Author              
Affiliations:
1Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society, ou_1826285              

Content

show
hide
Free keywords: -
 Abstract: 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 OH-initiated 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.

Details

show
hide
Language(s): eng - English
 Dates: 2020-11-13
 Publication Status: Published online
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: -
 Identifiers: DOI: 10.5194/acp-20-13541-2020
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Atmospheric Chemistry and Physics
  Abbreviation : ACP
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Göttingen : Copernicus Publications
Pages: - Volume / Issue: 20 (21) Sequence Number: - Start / End Page: 13541 - 13555 Identifier: ISSN: 1680-7316
CoNE: https://pure.mpg.de/cone/journals/resource/111030403014016