Lade, R.E., Onel, L., Blitz, M.A. et al. (2 more authors) (2024) Kinetics of the Gas-Phase Reactions of syn- and anti-CH3CHOO Criegee Intermediate Conformers with SO2 as a Function of Temperature and Pressure. The Journal of Physical Chemistry A, 128 (14). pp. 2683-2908. ISSN 1089-5639
Abstract
Kinetics of reactions between SO2 and CH3CHOO Criegee intermediate conformers have been measured at temperatures between 242 and 353 K and pressures between 10 and 600 Torr using laser flash photolysis of CH3CHI2/O2/N2/SO2 gas mixtures coupled with time-resolved broadband UV absorption spectroscopy. The kinetics of syn-CH3CHOO + SO2 are pressure-dependent and exhibit a negative temperature dependence, with the observed pressure dependence reconciling apparent discrepancies between previous measurements performed at ∼298 K. Results indicate a rate coefficient of (4.80 ± 0.46) × 10–11 cm3 s–1 for the reaction of syn-CH3CHOO with SO2 at 298 K and 760 Torr. In contrast to the behavior of the syn-conformer, the kinetics of anti-CH3CHOO + SO2 display no significant dependence on temperature or pressure over the ranges investigated, with a mean rate coefficient of (1.18 ± 0.21) × 10–10 cm3 s–1 over all conditions studied in this work. Results indicate that the reaction of syn-CH3CHOO with SO2 competes with unimolecular decomposition and reaction with water vapor in areas with high SO2 concentration and low humidity, particularly at lower temperatures.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2024 The Authors. This is an open access article under the terms of the Creative Commons Attribution License (CC-BY 4.0), which permits unrestricted use, distribution and reproduction in any medium, provided the original work is properly cited. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Funding Information: | Funder Grant number NERC (Natural Environment Research Council) NE/L010798/1 NERC (Natural Environment Research Council) NE/P012876/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 15 Mar 2024 15:28 |
Last Modified: | 16 Apr 2024 11:25 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.jpca.4c00199 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:210281 |