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Título: | Gas-phase reactions of chlorine atoms and CIO radicals with dimethyl sulfide. Rate coefficients and temperature dependences |
Autor: | Díaz-de-Mera, Y.; Aranda, Antonio; Rodríguez, D.; López, R.; Cabañas Galan, Beatriz; Martínez, E. | Fecha de publicación: | 2002 | Editor: | American Chemical Society | Citación: | Journal of Physical Chemistry A 106(37): 8627-8633 (2002) | Resumen: | The results of a discharge flow-mass spectrometric (DF-MS) kinetic study of the reaction between Cl and dimethylsulfide (DMS) (1) over the temperature range 259−364 K at low total pressure between 0.5 and 1 Torr with helium as carrier gas are reported. At room temperature and 1.0 Torr the main products of reaction 1 correspond to an abstraction channel leading to HCl and CH3SCH2 with k(1) = (6.9 ± 1.3) × 10-11 cm3 molecule-1 s-1. The association channel has also been confirmed by mass spectroscopic detection of the adduct CH3S(Cl)CH3 with a yield <0.05 under the experimental conditions used. It is now shown that the abstraction channel requires a slight activation energy, k(1) = (2.0 ± 1.2) × 10-10 exp[−(332 ± 173)/T] cm3 molecule-1 s-1. The kinetics and mechanism of the reaction ClO + DMS → products (2) over the temperature range 259−335 K at total pressures between 0.5 and 2 Torr have also been studied by DF-MS. By mass spectroscopic calibration of dimethyl sulfoxide, DMSO, the branching ratio of the channel leading to this product has been measured (0.90 ± 0.49). The rate constant of reaction 2 has been measured under pseudo-first-order conditions in excess of DMS over ClO: k(2) = (1.2 ± 0.7) × 10-15 exp[(354 ± 163)/T] cm3 molecule-1 s-1 with k(2) = (3.9 ± 1.2) × 10-15 cm3 molecule-1 s-1 at 298 K. The reaction is postulated to proceed through a channel involving a long-lived intermediate [CH3S(OCl)CH3]* which may decompose back to reactants or to products. Finally, the atmospheric implications through the DMS chemistry of both reactions are discussed. | Versión del editor: | https://doi.org/10.1021/jp014570c | URI: | http://hdl.handle.net/10261/282494 | DOI: | 10.1021/jp014570c | ISSN: | 1089-5639 |
Aparece en las colecciones: | (IREC) Artículos |
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