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Sleiman, Chantal
Universite de Rennes 1, Ecole doctorale Science de la Matiere, UMR CNRS 6251, UFR Sciences et Proprietes de la Matiere, Departement de Physique Moleculaire, Institut de Physique de Rennes - IPR, Bat. 11 C, Campus de Beaulieu, 35042 Rennes Cedex (France)2014
Universite de Rennes 1, Ecole doctorale Science de la Matiere, UMR CNRS 6251, UFR Sciences et Proprietes de la Matiere, Departement de Physique Moleculaire, Institut de Physique de Rennes - IPR, Bat. 11 C, Campus de Beaulieu, 35042 Rennes Cedex (France)2014
AbstractAbstract
[en] This thesis reports the experimental kinetic study of the gas phase reactions of atmospheric and astrophysical interests. The knowledge of the reactions rate constants is useful to understand the mechanisms of formation and destruction of molecules in the Earth's atmosphere and in the interstellar medium. On the atmospheric side, we have studied the reactions of a series of hydroxyketones (4-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone and 4-hydroxy-4-methyl-2-pentanone), a large category of hydroxy-carbonyls with OH radicals and chlorine atoms Cl in order to determine their atmospheric fate. We have measured the absolute rate constants of the reactions of hydroxyketones with OH radicals by using the cryogenic cell coupled to PLP-LIF technique (Pulsed Laser Photolysis - Laser Induced Fluorescence) at room temperature and as function of pressure. The relative rate constants of the reactions of the compounds investigated with Cl atoms were measured at room temperature and atmospheric pressure by using the atmospheric simulation chamber coupled to the analytical detection techniques: FTIR and GC-MS. In addition, a mechanistic study was also conducted in order to identify and quantify the products formed from these reactions. The whole results are discussed in order to assess the atmospheric implications of these hydroxyketones (lifetimes and environmental impact). On the astrophysical side, the kinetic of the reactions involving CN radical and a series of nitrogen-containing molecules (methylamine, dimethylamine, trimethylamine and acetonitrile) was studied over a wide range of temperature (23 K - 354 K) using CRESU technique (a French acronym standing for Cinetique de Reaction en Ecoulement Supersonique Uniforme) and the cryogenic cell coupled to the detection technique PLP-LIF. These experimental studies were accompanied by theoretical studies to better understand the reaction mechanisms. Possible astrophysical implications of the whole results have been discussed in this study. (author)
[fr]
Cette these reporte l'etude experimentale de la cinetique en phase gazeuse de plusieurs reactions d'interet atmospherique et astrophysique. La connaissance des constantes de vitesse de ces reactions est utile a la comprehension des processus de synthese et de destruction des molecules dans l'atmosphere terrestre et dans le milieu interstellaire. Sur le plan atmospherique, nous avons etudie les reactions d'une serie d'hydroxycetones, une sous-famille de COV carbonyles, (4-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone and 4-hydroxy-4-methyl-2-pentanone) avec le radical OH et l'atome de Chlore Cl afin de definir leur devenir atmospherique. Nous avons determine les constantes de vitesse des reactions de ces hydroxycetones avec le radical OH en absolue a temperature ambiante et en fonction de la pression en utilisant la cellule cryogenique couplee a la technique PLP-LIF (Photolyse a Laser Pulse - Fluorescence Induite par Laser). Les constantes de vitesse des reactions de ces hydroxycetones avec Cl ont ete mesurees en relative a temperature ambiante et a pression atmospherique en utilisant les chambres de simulation atmospherique couplees aux techniques analytiques de detection: FTIR et GC-MS. En plus, une etude mecanistique a ete menee egalement afin d'identifier et quantifier les produits issus de ces reactions. L'ensemble des resultats obtenus est discute et nous a permis d'evaluer les implications atmospheriques de ces hydroxycetones (duree de vie et impact sur l'environnement). Sur le plan astrophysique, la cinetique des reactions impliquant le radical CN et une serie de molecules azotees (methyamine, dimethylamine, trimethylamine et acetonitrile) a ete etudiee sur une large gamme de temperature (23 K - 354 K) en utilisant la technique CRESU (Cinetique de Reaction en Ecoulement Supersonique Uniforme) et la cellule cryogenique couplees a la technique de detection PLP-LIF. Ces etudes experimentales ont ete accompagnees par des etudes theoriques afin de mieux comprendre les mecanismes reactionnels. Les eventuelles implications astrophysiques de l'ensemble de ces resultats ont fait l'objet d'une discussion detaillee. (auteur)Original Title
Reactivite chimique en phase gazeuse de molecules organiques d'interet atmospherique et astrophysique
Primary Subject
Source
25 Nov 2014; 365 p; 150 refs.; Available from the INIS Liaison Officer for France, see the INIS website for current contact and E-mail addresses; These Docteur de l'Universite de Rennes 1, Mention: Physique
Record Type
Miscellaneous
Literature Type
Thesis/Dissertation
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AMINES, CHEMICAL REACTIONS, CHEMISTRY, CHROMATOGRAPHY, DECOMPOSITION, ELEMENTS, EMISSION, FLUID FLOW, HALOGENS, KINETICS, LUMINESCENCE, MATTER, NITRILES, NONMETALS, ORGANIC COMPOUNDS, ORGANIC NITROGEN COMPOUNDS, PHOTOCHEMICAL REACTIONS, PHOTON EMISSION, RADICALS, REACTION KINETICS, SEPARATION PROCESSES, SPACE, SPECTROSCOPY
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