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<dc:title xml:lang="en">Spectroscopic methods for concentration measurements and calibration of reactive gases</dc:title>
<dcterms:alternative xml:lang="fr">Méthodes spectroscopiques pour les mesures de concentration et la calibrage de gaz réacttifs</dcterms:alternative>
<dc:subject xml:lang="fr">Ion radicalaire</dc:subject>
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<tef:elementdEntree autoriteExterne="027860108" autoriteSource="Sudoc">Hydrocarbures halogénés</tef:elementdEntree>
<tef:subdivision autoriteExterne="029648890" autoriteSource="Sudoc" type="subdivisionDeSujet">Réactivité</tef:subdivision>
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<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="031182860" autoriteSource="Sudoc">Sulfure de carbone</tef:elementdEntree>
<tef:subdivision autoriteExterne="029648890" autoriteSource="Sudoc" type="subdivisionDeSujet">Réactivité</tef:subdivision>
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<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="031182178" autoriteSource="Sudoc">Cyanures</tef:elementdEntree>
<tef:subdivision autoriteExterne="029648890" autoriteSource="Sudoc" type="subdivisionDeSujet">Réactivité</tef:subdivision>
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<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="027905934" autoriteSource="Sudoc">Ammoniac</tef:elementdEntree>
<tef:subdivision autoriteExterne="029648890" autoriteSource="Sudoc" type="subdivisionDeSujet">Réactivité</tef:subdivision>
</tef:vedetteRameauNomCommun>
<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="029670888" autoriteSource="Sudoc">Spectroscopie de microondes</tef:elementdEntree>
</tef:vedetteRameauNomCommun>
<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="032575017" autoriteSource="Sudoc">Spectroscopie infrarouge à transformée de Fourier</tef:elementdEntree>
</tef:vedetteRameauNomCommun>
<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="027576558" autoriteSource="Sudoc">Chimie de l'atmosphère</tef:elementdEntree>
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<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="031665888" autoriteSource="Sudoc">Cosmochimie</tef:elementdEntree>
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<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="031435645" autoriteSource="Sudoc">Spectroscopie optoacoustique</tef:elementdEntree>
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<tef:vedetteRameauNomCommun>
<tef:elementdEntree autoriteExterne="027829944" autoriteSource="Sudoc">Radicaux (chimie)</tef:elementdEntree>
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<dcterms:abstract xml:lang="fr">Le sujet de ma thèse concerne l´application des méthodes spectroscopiques utilisées pour la détection et la mesure de concentration de différentes espèces intéressantes du point de vue de leur réactivité et pour leur rôle dans des domaines très variés comme en chimie atmosphérique, en astrochimie ou encore dans le corps humain. Pour la première fois l´analyse de la bande de vibration asymétrique v4 du radical FCO2 a été effectuée ainsi que celle de la bande v2 . FCO2 est un des produits intermédiaires importants dans les processus de dégradation des carbures d´halogène. Ce travail à conduit à la détermination précise des constantes moléculaires (y compris celles de structure fine) des deux bandes de vibration.Nous avons également effectué l´identification de l´ion radicalaire CS+ par spectroscopie millimétrique, dans la gamme de fréquence 414 - 622 GHz. L´analyse globale avec les données infrarouges disponibles a permis de déterminer précisément les valeurs de la constante de rotation et de la constante de structure fine. J’ai ensuite effectué la mesure des spectres des cyanures BrCN et CH3CN par spectroscopie infrarouge à transformée de Fourier. J´ai aussi étudié la réactivité de ces molécules ainsi que leurs produits de décomposition dans un plasma à basse température. Finalement, j´ai étudié l´impact écologique de l´ammoniaque sur l´environnement ainsi que le rôle des arbres sur la concentration en ammoniaque atmosphérique. Une cuve opto-acoustique a ainsi été conçue pour mesurer les concentrations de l´ammoniaque et d´autres gaz présents en très faible quantité.</dcterms:abstract>
<dcterms:abstract xml:lang="en">Description of the work is divided into four thematic parts describing four independently performed experiments. The analyses of the asymmetrical vibration ν4 band and the symmetrical ν2 band of the FCO2 radical, that belong to significant intermediate products of degradation processes of halogen hydrocarbons, were performed for the first time within this work. The detailed analysis led to the determination of the rotational constants, centrifugal distortion constants and fine structure constants for both bands. For the first time we performed the unambiguous identification of the radical ion CS+ by high resolution millimetrewave spectroscopy in the frequency range 414 - 622 GHz. The complex analysis allowed us to accurately determine the values of the rotational constant as well as the fine structure constant. Experiments were also perform to measure spectra of cyan BrCN and CH3CN using time resolved Fourier transform infrared spectroscopy. These molecules as well as their disintegration products in the low temperature plasma environment were carefully studied. Finally, I have studied the ecological impact of ammonia (NH3) on the environment and the influence of trees on the amount of ammonia in the air. For this purpose, an optoacoustic cell was designed and assembled to measure trace amounts of ammonia and other gaseous substances.</dcterms:abstract>
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