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https://doi.org/10.5194/acp-2020-658
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2020-658
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

  14 Jul 2020

14 Jul 2020

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This preprint is currently under review for the journal ACP.

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 Berasategui1, Damien Amedro1, Luc Vereecken2, Jos Lelieveld1, and John N. Crowley1 Matias Berasategui et al.
  • 1Division of Atmospheric Chemistry, Max-Planck-Institute for Chemistry, 55128 Mainz, Germany
  • 2Institute for Energy and Climate Research: IEK-8, Forschungszentrum Juelich, 52425 Juelich, Germany

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 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.

Matias Berasategui et al.

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Matias Berasategui et al.

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Short summary
Peracetic acid is one of the most abundant organic peroxides in the atmosphere. We combine experiment and theory to show that peracetic acid reacts orders of magnitude more slowly with OH than presently accepted, which results in a significant extension of its atmospheric lifetime.
Peracetic acid is one of the most abundant organic peroxides in the atmosphere. We combine...
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