The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere.
Phys Chem Chem Phys
; 14(42): 14682-95, 2012 Nov 14.
Article
em En
| MEDLINE
| ID: mdl-23032271
The reaction of Criegee intermediates (CI) with NO and RO(2) radicals is studied for the first time by theoretical methodologies; additionally, the reaction of CI with SO(2) molecules is re-examined. The reaction of CI with NO was found to be slow, with a distinct energy barrier. Their reaction with RO(2) radicals proceeds by the formation of a pre-reactive complex followed by addition of the RO(2) radical on the CI carbon over a submerged barrier, leading to a larger peroxy radical and opening the possibility for oligomer formation in agreement with experiment. The impact of singlet biradicals on the reaction of CI with SO(2) is examined, finding a different reaction mechanism compared to earlier work. For larger CI, the reaction with SO(2) at atmospheric pressures mainly yields thermalized sulfur-bearing secondary ozonides. The fate of the CI in the atmosphere is examined in detail, based on observed concentration of a multitude of coreactants in the atmosphere, and estimated rate coefficients available from literature data. The impact of SCI on tropospheric chemistry is discussed.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Compostos Orgânicos
/
Atmosfera
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Dióxido de Enxofre
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Óxido Nítrico
Idioma:
En
Revista:
Phys Chem Chem Phys
Assunto da revista:
BIOFISICA
/
QUIMICA
Ano de publicação:
2012
Tipo de documento:
Article
País de afiliação:
Alemanha