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Discussion papers
https://doi.org/10.5194/acp-2019-1030
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2019-1030
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 28 Nov 2019

Submitted as: research article | 28 Nov 2019

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This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).

Kinetic and mechanistic study of the reaction between methane sulphonamide (CH3S(O)2NH2) and OH

Matias Berasategui, Damien Amedro, Achim Edtbauer, Jonathan Williams, Jos Lelieveld, and John N. Crowley Matias Berasategui et al.
  • Division of Atmospheric Chemistry, Max-Planck-Institut für Chemie, 55128 Mainz, Germany

Abstract. Methane sulphonamide (MSAM), CH3S(O)2NH2, has recently been detected for the first time in ambient air over the Red Sea and the Gulf of Aden where peak mixing ratios of ~ 60 pptv were recorded. Prior to this study the rate constant for its reaction with the OH radical and the products thereby formed were unknown, precluding assessment of its role in the atmosphere. We studied the OH-initiated photo-oxidation of MSAM in air (298 K, 700 Torr total pressure) in a photochemical reactor using in situ detection of MSAM and its products by FTIR absorption spectroscopy. The relative rate technique, using three different reference compounds, was used to derive a rate coefficient of (1.4 ± 0.3) ×10−13 cm3 molecule−1 s−1. The main end products of the photo-oxidation observed by FTIR were CO2, CO, SO2 and HNO3 with molar yields of (0.73 ± 0.11), (0.28 ± 0.04), (0.96 ± 0.15) and (0.62 ± 0.09), respectively. N2O and HC(O)OH were also observed in smaller yields (0.09 ± 0.02), (0.03 ± 0.01). Both the low rate coefficient and the products formed are consistent with hydrogen abstraction from the -CH3 group as the dominant initial step. Based on our results MSAM has an atmospheric lifetime with respect to loss by reaction with OH of about 80 days.

Matias Berasategui et al.
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Matias Berasategui et al.
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Short summary
We have determined the rate coefficient and mechanism for the reaction of the OH radical with methane sulphonamide, a trace-gas which has recently been found in the atmosphere. The rate coefficient is 1.4 × 10−13 cm3 molec−1 s−1 which indicates a tropospheric lifetime of > 2 months. The observation of CO, CO2, SO2, HNO3, HCOOH and N2O products enabled us to derive a detailed reaction mechanism for the reaction, which proceeds predominantly by H-abstraction from the CH3-group.
We have determined the rate coefficient and mechanism for the reaction of the OH radical with...
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