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| Titel |
Kinetic isotope effects in the gas phase reactions of OH and Cl with CH3Cl, CD3Cl, and 13CH3Cl |
| VerfasserIn |
A. A. Gola, B. D'Anna, K. L. Feilberg, S. R. Sellevåg, L. Bache-Andreassen, C. J. Nielsen |
| Medientyp |
Artikel
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| Sprache |
Englisch
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| ISSN |
1680-7316
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| Digitales Dokument |
URL |
| Erschienen |
In: Atmospheric Chemistry and Physics ; 5, no. 9 ; Nr. 5, no. 9 (2005-09-19), S.2395-2402 |
| Datensatznummer |
250003065
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| Publikation (Nr.) |
 copernicus.org/acp-5-2395-2005.pdf |
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| Zusammenfassung |
| The kinetic isotope effects in the reactions of CH3Cl,
13CH3Cl and CD3Cl with OH radicals and Cl atoms were studied
in relative rate experiments at 298±2 K and 1013±10 mbar. The
reactions were carried out in a smog chamber using long path FTIR detection
and the spectroscopic data analyzed employing a non-linear least squares
spectral fitting method using measured high-resolution infrared spectra as
well as absorption cross sections from the HITRAN database. The reaction
rates of 13CH3Cl and CD3Cl with OH and Cl were determined
relative to CH3Cl as: kOH+CH3ClkOH+CH3Cl/kOH+13CH3Cl}kOH+13CH3Cl=1.059±0.008,
kOH+CH3ClkOH+CH3Cl/kOH+CD3ClkOH+CD3Cl=3.9±0.4, kCl+CH3ClkCl+CH3Cl/kCl+13CH3ClkCl+13CH3Cl
=1.070±0.010
and kCl+CH3ClkCl+CH3Cl/kCl+CD3ClkCl+CD3Cl=4.91±0.07. The uncertainties given are 2σ from the
statistical analyses and do not include possible systematic errors. The
unexpectedly large 13C kinetic isotope effect in the OH reaction of
CH3Cl has important implications for the global emission inventory of
CH3Cl. |
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