Temperature‐dependent kinetics of the simplest Criegee intermediate reaction with dimethyl sulfoxide

Yu‐Lin Li; Chun‐Yu Lin; Yen‐Hsiu Lin; Jim Jr-Min Lin

doi:10.1002/jccs.202000206

journal article Aug 25, 2020

Temperature‐dependent kinetics of the simplest Criegee intermediate reaction with dimethyl sulfoxide

Yu‐Lin Li Chun‐Yu Lin Yen‐Hsiu Lin Jim Jr-Min Lin

Journal of the Chinese Chemical Society Vol. 67 No. 9 pp. 1563-1570 · Wiley

View at Publisher Save 10.1002/jccs.202000206

Abstract

AbstractCriegee intermediates are thought to play roles in atmospheric chemistry, including OH radical formation, oxidation of SO2, NO2, etc. CH2OO is the simplest Criegee intermediate, of which the reactivity has been a hot topic. Here we investigated the kinetics of CH2OO reaction with dimethyl sulfoxide (DMSO) under 278–349 K and 10–150 Torr. DMSO is an important species formed in the oxidation of dimethyl sulfide in the biogenic sulfur cycle. The concentration of CH2OO was monitored in real‐time via its mid‐infrared absorption band at about 1,286 cm−1 (Q branch of the ν4 band) with a high‐resolution quantum cascade laser spectrometer. The 298 K bimolecular rate coefficient was determined to be k298 = (2.3 ± 0.3) × 10−12 cm3/s at 30 Torr with an Arrhenius activation energy of −3.9 ± 0.2 kcal/mol and a weak pressure dependence for pressures higher than 30 Torr (k298 = (2.8 ± 0.3) × 10−12 cm3/s at 100 Torr). The reaction is speculated to undergo a five‐membered ring intermediate, analogous to that of CH2OO with SO2. The negative activation energy indicates that the rate‐determining transition state is submerged. The magnitude of the reaction rate coefficient lies in between those of CH2OO reactions with (CH3)2CO and with SO2.

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References

33

[1]

10.1063/1.4923165

[2]

10.1080/0144235x.2015.1055676

[3]

10.1146/annurev-physchem-052516-050739

[4]

10.1039/c7cs00336f

[5]

Criegee intermediates and their impacts on the troposphere

M. A. H. Khan, C. J. Percival, R. L. Caravan et al.

Environmental Science: Processes & Impacts 10.1039/c7em00585g

[6]

10.1126/science.1213229

[7]

10.1038/nature11278

[8]

10.1002/jccs.201700049

[9]

10.1021/cr500488p

[10]

10.1021/acs.jpca.5b06565

[11]

10.1063/1.5019205

[12]

10.1021/acs.jpca.6b07810

[13]

10.1039/c3cp52598h

[14]

10.1039/c2cp40294g

[15]

10.1039/c5cp02224j

[16]

10.1002/kin.21007

[17]

10.1021/acsearthspacechem.9b00213

[18]

10.1039/c3cp54391a

[19]

10.1021/jp407058b

[20]

10.1039/c4cp04198d

[21]

10.1021/jz402191w

[22]

10.1126/science.1234689

[23]

10.1039/c4cp04408h

[24]

10.1073/pnas.1513149112

[25]

10.1063/1.4986536

[26]

10.1039/c7cp06653h

[27]

10.1021/acs.jpca.8b12553

[28]

10.1039/d0cp00988a

[29]

10.1021/acs.jpca.5b12124

[30]

10.1021/jp0276911

[31]

10.1126/science.1261549

[32]

Sander S. P. (2011)

[33]

10.1016/j.chemphys.2006.11.017

Metrics

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Citations

33

References

Details

Published: Aug 25, 2020
Vol/Issue: 67(9)
Pages: 1563-1570
License: View

Authors

Y

Yu‐Lin Li

Institute of Atomic and Molecular Sciences Academia Sinica Taipei Taiwan; Department of Chemistry National Taiwan University Taipei Taiwan

C

Chun‐Yu Lin

Institute of Atomic and Molecular Sciences Academia Sinica Taipei Taiwan; Department of Physics National Taiwan University Taipei Taiwan

Y

Yen‐Hsiu Lin

Institute of Atomic and Molecular Sciences Academia Sinica Taipei Taiwan; Department of Chemistry National Taiwan University Taipei Taiwan

J

Jim Jr-Min Lin

Institute of Atomic and Molecular Sciences Academia Sinica Taipei Taiwan; Department of Chemistry National Taiwan University Taipei Taiwan

Funding

Ministry of Science and Technology, Taiwan Award: MOST 106‐2113‐M‐001‐026‐MY3

Academia Sinica

Cite This Article

Yu‐Lin Li, Chun‐Yu Lin, Yen‐Hsiu Lin, et al. (2020). Temperature‐dependent kinetics of the simplest Criegee intermediate reaction with dimethyl sulfoxide. Journal of the Chinese Chemical Society, 67(9), 1563-1570. https://doi.org/10.1002/jccs.202000206

Temperature‐dependent kinetics of the simplest Criegee intermediate reaction with dimethyl sulfoxide

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