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http://hdl.handle.net/10261/282494
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Campo DC | Valor | Lengua/Idioma |
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dc.contributor.author | Díaz-de-Mera, Y. | es_ES |
dc.contributor.author | Aranda, Antonio | es_ES |
dc.contributor.author | Rodríguez, D. | es_ES |
dc.contributor.author | López, R. | es_ES |
dc.contributor.author | Cabañas Galan, Beatriz | es_ES |
dc.contributor.author | Martínez, E. | es_ES |
dc.date.accessioned | 2022-11-08T10:46:59Z | - |
dc.date.available | 2022-11-08T10:46:59Z | - |
dc.date.issued | 2002 | - |
dc.identifier.citation | Journal of Physical Chemistry A 106(37): 8627-8633 (2002) | es_ES |
dc.identifier.issn | 1089-5639 | - |
dc.identifier.uri | http://hdl.handle.net/10261/282494 | - |
dc.description.abstract | 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. | es_ES |
dc.description.sponsorship | We thank the European Commission for financial support within the “Energy, Environment and Sustainable Development” V Framework program (EVK2-CT-1999-00033 contract) and the Spanish Ministry of Science and Technology for the PB97-0432 contract. | es_ES |
dc.format | application/pdf | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.rights | closedAccess | es_ES |
dc.title | Gas-phase reactions of chlorine atoms and CIO radicals with dimethyl sulfide. Rate coefficients and temperature dependences | es_ES |
dc.type | artículo | es_ES |
dc.identifier.doi | 10.1021/jp014570c | - |
dc.description.peerreviewed | Peer reviewed | es_ES |
dc.relation.publisherversion | https://doi.org/10.1021/jp014570c | es_ES |
dc.contributor.funder | Ministerio de Ciencia y Tecnología (España) | es_ES |
dc.contributor.funder | European Commission | es_ES |
dc.relation.csic | No | es_ES |
oprm.item.hasRevision | no ko 0 false | * |
dc.identifier.funder | http://dx.doi.org/10.13039/501100006280 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100000780 | es_ES |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.grantfulltext | none | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.fulltext | No Fulltext | - |
item.cerifentitytype | Publications | - |
item.languageiso639-1 | en | - |
item.openairetype | artículo | - |
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