Mechanism of the Reaction of CH 3 SO with NO 2 in Relation to Atmospheric Oxidation of Dimethyl Sulfide: Experimental and Theoretical Study
| Autor: | Alexander Kukui, Georges Le Bras, Valérie Bossoutrot, G. Laverdet |
|---|---|
| Přispěvatelé: | Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences de l'Ingénierie et des Systèmes (INSIS) |
| Jazyk: | angličtina |
| Rok vydání: | 2000 |
| Předmět: |
010304 chemical physics
Chemistry Photodissociation Thermal decomposition Ab initio Analytical chemistry 010402 general chemistry 01 natural sciences 7. Clean energy Decomposition 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Reaction rate constant 13. Climate action Torr Yield (chemistry) 0103 physical sciences Molecule Physical and Theoretical Chemistry ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Journal of Physical Chemistry A Journal of Physical Chemistry A, American Chemical Society, 2000, 104 (5), pp.935-946. ⟨10.1021/jp993158i⟩ |
| ISSN: | 1089-5639 1520-5215 |
| Popis: | CH{sub 3}SO{sub 2} radical decomposition and the mechanism of SO{sub 2} and CH{sub 3} formation in the reaction of CH{sub 3}SO with NO{sub 2} were experimentally investigated in the pressure range 1--612 Torr of He using laser pulsed photolysis/laser-induced fluorescence and discharge flow mass spectrometry/laser-induced fluorescence techniques. The upper limit for the thermal decomposition rate of CH{sub 3}SO{sub 2} in the investigated pressure range has been found to be 100 s{sup {minus}1} at 300 K. High-pressure limit, k{sup infinity} = 2.08 x 10{sup 3} x{sup {minus}1}, and low-pressure limit, k{sup 0} = 2.72 x 10{sup {minus}17} cm{sup 3} molecule{sup {minus}1}s{sup {minus}1}, of the rate coefficient of the CH{sub 3}SO{sub 2}decomposition have been derived from ab initio and RRKM calculations. The CH{sub 3}SO{sub 2} decomposition rate at 760 Torr and 300 K has been estimated to be about 200 s{sup {minus}1} from falloff calculations. Reaction of CH{sub 3}SO with NO{sub 2} has been found to form CH{sub 3} and SO{sub 2} with a yield varying from (0.33 {+-} 0.05) at 13 Torr to (0.18 {+-} 0.03) at 612 Torr of He. The rate constant for the reaction of CH{sub 3}SO with NO{sub 2} has been found to be (1.5 {+-} 0.4)more » x 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} at 300 K, independent of pressure. On the basis of ab initio and RRKM calculations, the experimental results have been interpreted by assuming the reaction of CH{sub 3}SO with NO{sub 2} to form chemically activated CH{sub 3}SO{sub 2}* radical followed by its thermal stabilization or prompt decomposition to CH{sub 3} and SO{sub 2}. The implication of the obtained results for the atmospheric oxidation of dimethyl sulfide is discussed.« less |
| Databáze: | OpenAIRE |
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