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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
31

Etude multi-échelle des phénomènes physico-chimiques aux interfaces gaz – surfaces métalliques / Multiscale study of the chemical and physical phenomena’s at the gas – metal surface interfaces.

Grenier, Romain 26 October 2015 (has links)
Dans le contexte des écoulements micro- et nano-fluidiques, ce travail porte sur l'étude des interactions à l'interface entre des flux de gaz rares et des surfaces métalliques via une approche de modélisation multi-physique et multi-échelle. Elle se concentre tout particulièrement sur l'interaction entre l'argon et une surface d'or. Pour ce faire la modélisation a été effectuée en deux étapes, une première partie utilisant la mécanique quantique à l'échelle atomique et une deuxième partie de dynamique moléculaire à l'échelle nanométrique. La première partie est consacrée à l'obtention de potentiels d'interaction entre un atome d'argon et les atomes d'or de la surface par des méthodes de calculs théoriques basés sur la DFT comportant des effets à longues distances. Deux approches, donnant des résultats comparables, ont été utilisées : la première est liée à la description périodique de la surface d'or par un modèle basé sur la description des électrons par des ondes planes alors que la seconde permet de récupérer séparément les parties répulsives et attractives de l'interaction d'un atome d'argon avec un petit cluster d'or. Ces potentiels d'interactions ont été décomposés en potentiels de paires Ar-Au utilisables par des simulations de dynamique moléculaire. Ces simulations ont consisté en la projection d'atomes d'argon sur des surfaces d'or ‘parfaites' dites lisses ou des surfaces rugueuses plus représentatives de la technologie actuelle. L'analyse statistique des vitesses réfléchies permet de déterminer le coefficient d'accommodation tangentiel de l'argon sur des surfaces d'or. Ce coefficient est la traduction du phénomène de glissement qui peut ainsi être modélisé dans une description plus macroscopique de l'écoulement d'un gaz dans une micro-conduite. L'approche multi-physique utilisée dans ce travail a permis la détermination numérique de coefficients d'accommodations tangentiels très précis et comparables à l'expérience pour le couple argon-or, et doit pouvoir être appliquée à d'autres couples / In the context of micro- and nano-flows, this work concentrates on the study of interactions at the interface of noble gas and metal surfaces by a multi-physics and multiscale model. Particularly, the interaction of an argon atom with a gold surface is the focus of the study. The work has been made in two steps: the first one occurred at the atomic scale in which Quantum Mechanics is employed and the second one at the nanoscale with the use of Molecular Dynamics.The first part of the work was devoted to the determination of interaction potentials between an argon atom and gold atoms from the surface by DFT calculation methods comporting long range effects. Two approaches, leading similar results, have been used: the first one is linked to a periodic description of the gold surface where electrons are defined by plane waves, the second one gives independently repulsive and attractive parts of the interaction of an argon atom with a small gold cluster. Those interaction potentials are then decomposed in pair potentials suitable for Molecular Dynamics simulations. These last ones consisted in multiple times projecting argon atoms on smooth or rough gold surfaces (which are more representative of the roughness of actual technologies). The statistical analysis of the reflected velocities yielded the tangential momentum accommodation (TMAC) coefficient of argon on gold surfaces. This coefficient is the transcription of slip phenomena which occur at the interface, and it can then be used in nano-flow simulations. The multi-physics approach of the thesis gives accurate TMAC values which are comparable to experiments. The accounted method could then be applied to other noble gas metal surface couples
32

Fluorite (U-Th-Sm)/He thermochronology

Wolff, Reinhard 09 September 2015 (has links)
No description available.
33

Novas investigações de propriedades elétricas realizadas por meio da teoria quântica de átomos em moléculas / New investigations of electric properties by the Quantum Theory of Atoms and Molecules

Terrabuio, Luiz Alberto 11 July 2017 (has links)
Nesta tese de doutorado apresentamos os resultados de quatro tópicos referentes a estudos de propriedades elétricas que são interpretados com o auxílio da Teoria Quântica de Átomos em Moléculas (QTAIM). No primeiro deles, foram calculados momentos de dipolo e suas derivadas através de um novo formalismo de divisão de átomos em moléculas, baseado em campos de forças de Ehrenfest (CFE), sendo que estes dados são comparados com aqueles advindos da QTAIM. Desta forma, um modelo alternativo de partição em carga - fluxo de carga - fluxo de dipolo (CFCFD) é discutido para derivadas do momento dipolar. Os resultados gerais obtidos pelo formalismo CFE foram satisfatórios em termos quantitativos, embora QTAIM ainda fornece uma descrição mais apropriada destes fenômenos das polarizações atômicas e de suas variações durante vibrações. Na sequência, investigamos os Atratores Não Nucleares (NNAs), que são identificados através de uma análise QTAIM da densidade eletrônica. O nosso intuito foi descobrir novas moléculas que apresentam essa peculiaridade, bem como encontrar padrões entre os casos encontrados que permitam contribuir para o entendimento dos fatores que levam ao seu aparecimento. Para isso trabalhamos com moléculas diatômicas homonucleares de elementos representativos com números atômicos que variavam de Z=1 até Z=38 e moléculas heteronucleares formadas pela combinação dos mesmos. Os nossos dados mostram que NNAs podem ser encontrados em alguns pontos dentro da faixa de distâncias internucleares investigada para quase todos os sistemas diatômicos homonucleares, exceto para as moléculas de Hidrogênio, Hélio e Estrôncio. Por sua vez, encontramos trinta casos de NNAs em sistemas heteronucleares, muitos dos quais ainda inéditos na literatura. Descobrimos também que a polarizabilidade atômica aparentemente tem um papel importante na explicação dos casos encontrados. Tratamos também de moléculas contendo interações fracas como as de Van der Waals (moléculas tri-atômicas contendo um gás nobre ligado a um composto diatômico iônico) de modo a investigar os valores de dipolos atômicos QTAIM de uma maneira mais direta, ou seja, via comparação com um modelo simples para estes compostos. Por fim, estudamos moléculas em estados excitados, sendo que nossa análise focou em dois casos peculiares (CO e de CF2N2) que apresentam momento de dipolo nulo no estado fundamental, enquanto valores significativos desta propriedade são observados em seus primeiros estados excitados. Desta forma, QTAIM foi fundamental para compreender como o processo de excitação pode levar à mudanças tão significativas em tais propriedades elétricas. / In this PhD thesis we present the results of four different topics that refer to a study of electric properties interpreted with The Quantum Theory of Atoms and Molecules (QTAIM). First, dipole moments and their derivatives were calculated from a new formalism based on Ehrenfest Force Fields (EFF) and a comparison with data from QTAIM is carried out. Therefore, the Charge-Charge Flux-Dipole Flux (CCFDF) model was discussed for the dipole moment derivatives. The results from EFF were satisfactory in quantitative terms although QTAIM still seems to be better for the description of atomic polarization and its variations during vibrations. In the sequence, we investigated the Non-Nuclear Attractors (NNAs) that could be identified with the QTAIM formalism. Our intention was to discover new molecules that present this peculiarity, as well as to find trends among these cases that allow contributing for the understanding of the factors that lead to their appearance. For this purpose, we selected homonuclear diatomic molecules of elements presenting atomic numbers ranging from Z=1 to Z=38 and heteronuclear diatomic molecules containing these same elements. Our data shows that NNAs could be found in almost every homonuclear molecule expect by the systems formed by Hydrogen, Helium, and Strontium. On other hand, we have found 30 cases of NNAs in heteronuclear molecules, many of them seen for the first time. We also have noticed that the atomic polarizabilities play a main role in the understanding of these cases. We also treated molecules containing weak Van der Waals interactions (triatomic complexes presenting a noble gas bonded to a diatomic ionic molecule) in order to investigate the atomic dipole values obtained with QTAIM in a direct way, that is, by means of a comparison using a simple model for this kind of bonding. Finally, we studied molecules in excited states. Our focus was in two peculiar cases (CO and CF2N2), which present null dipole moments in their ground states but exhibit significant dipole moment values in their first excited states. Therefore, QTAIM was fundamental to understand how the excitation process can lead to important changes in electric properties.
34

Caractérisation, quantification et modélisation du transport et des interactions du CO₂ dans une zone vadose carbonatée : application à une fuite diffuse de CO₂ en contexte de séquestration géologique / Characterisation, quantification and modelling of CO₂ transport and interactions in a carbonate vadose zone : application to a CO₂ diffusive leakage in a geological sequestration context

Cohen, Grégory 18 November 2013 (has links)
Le réchauffement climatique est lié aux augmentations des concentrations de gaz à effet de serre dans l'atmosphère terrestre et en particulier aux émissions anthropiques de CO₂. La séquestration géologique a la capacité et la longévité potentielles pour diminuer de façon significative les émissions anthropiques de CO₂. Cette séquestration à grande profondeur induit des risques de fuite des réservoirs géologiques. Parmi les scénarios de fuite envisagés, celui d'une fuite diffuse est le plus inquiétant puisque sans surveillance, cette fuite pourrait perdurer et entrainer des séquelles sur l'environnement ainsi que des risques pour les populations. Des outils et protocoles de surveillance doivent donc être mis au point pour la surveillance en proche surface. Ce travail de thèse s'inscrit dans le cadre de cette problématique. Il a pour objectif la caractérisation, la quantification et la modélisation du transport et des interactions du CO₂ dans une zone non saturée carbonatée. Ce travail a suivi une approche expérimentale sur un site pilote naturel à Saint-Emilion (Gironde, France), avec la réalisation de fuites diffuses en ZNS carbonatée. Cette étude aborde plusieurs thématiques: la description et l'instrumentation du site pilote naturel ; la caractérisation physico-chimique de l'hétérogénéité du réservoir carbonaté ; l'étude du fonctionnement naturel de la ZNS carbonatée et en particulier la mise en place d'une ligne de base des concentrations en CO₂ ; la caractérisation de l'extension des panaches de gaz suite à des expériences de fuite diffuse dans la ZNS carbonatée et l'étude par simulation numérique des interactions gaz-eau-roche lors d'une fuite diffuse de CO₂ dans une ZNS carbonatée. Les résultats de ces travaux montrent l'importance de la caractérisation de l'hétérogénéité du réservoir carbonaté ainsi que des techniques d'échantillonnage et d'analyse des différentes phases en présence. L'établissement de la ligne de base a une importance particulière pour permettre de distinguer les variations naturelles de celles induites par une fuite diffuse de CO₂ dans la ZNS carbonatée. Les modes de transport du CO₂ vont évoluer en fonction des paramètres physico-chimiques. Ce transport se fait par advection et/ou par diffusion. L'utilisation de gaz inertes au niveau du site de séquestration géologique est très importante puisque la détection de ces traceurs permettrait de prédire les arrivées de panaches de CO₂ en proche surface. Par ailleurs, les interactions chimiques doivent être prises en compte dans les modèles de transport afin de pouvoir définir les facteurs de retard et l'impact d'une fuite diffuse de CO₂ sur une ZNS carbonatée. / Global warming is related to atmospheric greenhouse gas concentration increase and especially anthropogenic CO₂ emissions. Geologic sequestration has the potential capacity and the longevity to significantly diminish anthropogenic CO₂ emissions. This sequestration in deep geological formation induces leakage risks from the geological reservoir. Several leakage scenarios have been imagined. Since it could continue for a long period, inducing environmental issues and risks for human, the scenario of a diffusive leakage is the most worrying. Thus, monitoring tools and protocols are needed to set up a near-surface monitoring plan. The present thesis deals with this problematic. The aims are the characterisation, the quantification and the modelling of transport and interactions of CO₂ in a carbonate unsaturated zone. This was achieved following an experimental approach on a natural pilot site in Saint-Emilion (Gironde, France), where diffusive gas leakage experiments were set up in a carbonate unsaturated zone. Different aspects were investigated during the study: natural pilot site description and instrumentation; the physical and chemical characterisation of carbonate reservoir heterogeneity; the natural functioning of the carbonate unsaturated zone and especially the set-up of a CO₂ concentrations baseline; the characterisation of gas plume extension following induced diffusive leakage in the carbonate unsaturated zone and the study of gas-water-rock interactions during a CO₂ diffusive leakage in a carbonate unsaturated zone through numerical simulations. The results show the importance of the carbonate reservoir heterogeneity characterisation as well as the sampling and analysing methods for the different phases. The baseline set-up is of main interest since it allows discrimination between the induced and the natural CO₂ concentrations variations. The transfer of CO₂ in a carbonate unsaturated zone is varying in function of physical and chemical properties. This transfer is done by diffusion and/or advection. Because the detection of the noble gases allows the prediction of CO₂ plume arrival, the use of tracers in the sequestration site is of main importance. The chemical interactions have to be taken under account in transport models in order to predict delay factors and the impact of a CO₂ leakage in a carbonate unsaturated zone.
35

Materie-Optik mit Edelgasmolekülen an Nanostrukturen / Matter Optics with Noble Gas Molecules and Nanostructures

Stoll, Werner Martin 18 December 2003 (has links)
No description available.
36

Novas investigações de propriedades elétricas realizadas por meio da teoria quântica de átomos em moléculas / New investigations of electric properties by the Quantum Theory of Atoms and Molecules

Luiz Alberto Terrabuio 11 July 2017 (has links)
Nesta tese de doutorado apresentamos os resultados de quatro tópicos referentes a estudos de propriedades elétricas que são interpretados com o auxílio da Teoria Quântica de Átomos em Moléculas (QTAIM). No primeiro deles, foram calculados momentos de dipolo e suas derivadas através de um novo formalismo de divisão de átomos em moléculas, baseado em campos de forças de Ehrenfest (CFE), sendo que estes dados são comparados com aqueles advindos da QTAIM. Desta forma, um modelo alternativo de partição em carga - fluxo de carga - fluxo de dipolo (CFCFD) é discutido para derivadas do momento dipolar. Os resultados gerais obtidos pelo formalismo CFE foram satisfatórios em termos quantitativos, embora QTAIM ainda fornece uma descrição mais apropriada destes fenômenos das polarizações atômicas e de suas variações durante vibrações. Na sequência, investigamos os Atratores Não Nucleares (NNAs), que são identificados através de uma análise QTAIM da densidade eletrônica. O nosso intuito foi descobrir novas moléculas que apresentam essa peculiaridade, bem como encontrar padrões entre os casos encontrados que permitam contribuir para o entendimento dos fatores que levam ao seu aparecimento. Para isso trabalhamos com moléculas diatômicas homonucleares de elementos representativos com números atômicos que variavam de Z=1 até Z=38 e moléculas heteronucleares formadas pela combinação dos mesmos. Os nossos dados mostram que NNAs podem ser encontrados em alguns pontos dentro da faixa de distâncias internucleares investigada para quase todos os sistemas diatômicos homonucleares, exceto para as moléculas de Hidrogênio, Hélio e Estrôncio. Por sua vez, encontramos trinta casos de NNAs em sistemas heteronucleares, muitos dos quais ainda inéditos na literatura. Descobrimos também que a polarizabilidade atômica aparentemente tem um papel importante na explicação dos casos encontrados. Tratamos também de moléculas contendo interações fracas como as de Van der Waals (moléculas tri-atômicas contendo um gás nobre ligado a um composto diatômico iônico) de modo a investigar os valores de dipolos atômicos QTAIM de uma maneira mais direta, ou seja, via comparação com um modelo simples para estes compostos. Por fim, estudamos moléculas em estados excitados, sendo que nossa análise focou em dois casos peculiares (CO e de CF2N2) que apresentam momento de dipolo nulo no estado fundamental, enquanto valores significativos desta propriedade são observados em seus primeiros estados excitados. Desta forma, QTAIM foi fundamental para compreender como o processo de excitação pode levar à mudanças tão significativas em tais propriedades elétricas. / In this PhD thesis we present the results of four different topics that refer to a study of electric properties interpreted with The Quantum Theory of Atoms and Molecules (QTAIM). First, dipole moments and their derivatives were calculated from a new formalism based on Ehrenfest Force Fields (EFF) and a comparison with data from QTAIM is carried out. Therefore, the Charge-Charge Flux-Dipole Flux (CCFDF) model was discussed for the dipole moment derivatives. The results from EFF were satisfactory in quantitative terms although QTAIM still seems to be better for the description of atomic polarization and its variations during vibrations. In the sequence, we investigated the Non-Nuclear Attractors (NNAs) that could be identified with the QTAIM formalism. Our intention was to discover new molecules that present this peculiarity, as well as to find trends among these cases that allow contributing for the understanding of the factors that lead to their appearance. For this purpose, we selected homonuclear diatomic molecules of elements presenting atomic numbers ranging from Z=1 to Z=38 and heteronuclear diatomic molecules containing these same elements. Our data shows that NNAs could be found in almost every homonuclear molecule expect by the systems formed by Hydrogen, Helium, and Strontium. On other hand, we have found 30 cases of NNAs in heteronuclear molecules, many of them seen for the first time. We also have noticed that the atomic polarizabilities play a main role in the understanding of these cases. We also treated molecules containing weak Van der Waals interactions (triatomic complexes presenting a noble gas bonded to a diatomic ionic molecule) in order to investigate the atomic dipole values obtained with QTAIM in a direct way, that is, by means of a comparison using a simple model for this kind of bonding. Finally, we studied molecules in excited states. Our focus was in two peculiar cases (CO and CF2N2), which present null dipole moments in their ground states but exhibit significant dipole moment values in their first excited states. Therefore, QTAIM was fundamental to understand how the excitation process can lead to important changes in electric properties.
37

Oxide and Oxide Fluoride Chemistry of Xenon(VIII), Xenon(VI), and Iridium

Goettel, James T. January 2017 (has links)
This Thesis extends our fundamental knowledge of high-oxidation-state chemistry and in particular compounds of Xe(VIII), Xe(VI), and Ir(V). The crystal structure of XeVIIIO4 was obtained and provides important information on this fundamentally interesting endothermic and shock-sensitive compound. Macroscopic amounts of XeO3F2 have been prepared for the first time. Although the low-temperature Raman spectrum of solid XeO3F2 exhibits some frequency shifts and band splittings of the bending modes, the spectrum is similar to the Raman spectrum of the previously reported matrix-isolated compound. The crystal structures of decomposition and byproducts resulting from the syntheses of XeO3F2 have been obtained for [XeF5][HF2]∙XeOF4 and XeF2∙XeO2F2. The solid-state structure of xenon trioxide, XeO3, was reinvestigated by low-temperature single-crystal X-ray diffraction and shown to exhibit polymorphism that is dependent on crystallization conditions. The previously reported α-phase (orthorhombic, P212121) only forms upon evaporation of aqueous HF solutions of XeO3. In contrast, two new phases, β-XeO3 (rhombohedral, R3) and gamma-XeO3 (rhombohedral, R3c) have been obtained by slow evaporation of aqueous solutions of XeO3. The extended structures of all three phases result from Xe=O----Xe bridge interactions among XeO3 molecules that arise from the amphoteric donor-acceptor nature of XeO3. The Xe atom of the trigonal pyramidal XeO3-unit has three Xe---O secondary bonding interactions. The orthorhombic α-phase displays the greatest degree of variation among the contact distances and has a significantly higher density than the rhombohedral phases. The ambient-temperature Raman spectra of solid α- and gamma-XeO3 have also been obtained and assigned for the first time. Xenon trioxide interacts with CH3CN and CH3CH2CN to form O3XeNCCH3, O3Xe(NCCH3)2, O3XeNCCH2CH3, and O3Xe(NCCH2CH3)2. Their low-temperature single-crystal X-ray structures show that the xenon atoms are consistently coordinated to three electron-donor atoms which result in pseudo-octahedral environments around their xenon atoms. The adduct series provides the first examples of a neutral xenon oxide bound to nitrogen bases. Energy-minimized gas-phase geometries and vibrational frequencies were obtained for the model compounds O3Xe(NCCH3)n (n = 1−3) and O3Xe(NCCH3)n∙[O3Xe(NCCH3)2]2 (n = 1, 2). The natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses were carried out to further probe the nature of the bonding in these adducts. Xenon trioxide forms adducts with the polytopic nitrogen base ligands: hexamine, DABCO, 2,2’-bipyridine, 1,10-phenanthroline, and 4,4’-bipyridine. The adducts were conveniently synthesized in aqueous or CH3CN solutions and are stable at room temperature. The crystal structures of hexamine∙2XeO3, hexamine∙XeO3∙H2O, 2,2’-bipyridine∙XeO3, 1,10-phenanthroline∙XeO3, and 4,4’-bipyridine∙XeO3 have been determined by low-temperature single-crystal X-ray diffraction. The structures consist of XeO3 molecules bridged by the ligands to form extended supramolecular networks with Xe---N bonds which range from 2.634(3) to 2.829(2) Å. Raman spectroscopy was used to characterize and probe the room-temperature stabilities of these adducts. The reaction of 1,4-diazabicyclo[2.2.2]octane (DABCO) with XeO3 in aqueous solutions yields thin, plate-shaped crystals which are severely twinned whereas the reaction of DABCO with XeO3 in the presence of HF forms [DABCOH]2[F2(XeO3)2]∙H2O and [DABCOH2][F][H2F3] which were also characterized by low-temperature X-ray crystallography and Raman spectroscopy. A reversible temperature-dependent phase transition occurred for [DABCOH]2[F2(XeO3)2]∙H2O. The structures of 2,2’-bipy∙XeO3 and 1,10-phen∙XeO3 provide the first examples of noble-gas chelates. The structure of hexamine∙XeO3∙H2O provides the first instance in which a noble-gas centre is coordinated by water. These compounds also represent the first examples of sp2- and sp3-hybridized N---Xe(VI) bonds and are rare examples of noble-gas compounds that are air-stable at ambient temperatures. Adducts between XeO3 and three molar equivalents of the nitrogen bases, pyridine and 4-dimethylaminopyridine (4-DMAP), have been synthesized and characterized. The crystal structures of (C5H5N)3XeO3, {(CH3)2)2NC5H4N}3XeO3∙H2O have been determined by low-temperature single-crystal X-ray diffraction. The reaction of hydrolyzed XeF6 in acetonitrile with pyridine or 4-DMAP afforded [C5H5NH]4[HF2]2[F2(XeO3)2] and [(CH3)2NC5H4NH][HF2]∙XeO3 which were characterized by low-temperature X-ray crystallography and Raman spectroscopy. The structures contain pyridinium cations that are hydrogen bonded to the fluoride coordinated to XeO3 and can be viewed as pyridinium fluoroxenates. The structure of (CH3)2NC5H5N∙XeO3∙H2O contains a water molecule that is hydrogen bonded to two oxygen atoms of two adjacent XeO3 molecules. The pyridine adduct, (C5H5N)3XeO3, was found to be relatively insensitive to shock, whereas the 4-DMAP adduct was extremely shock sensitive. The number of isolable compounds which contain different noble-gas−element bonds is limited for xenon and even more so for krypton. Examples of Xe−Cl bonds are rare and prior to this work, no definitive evidence for a Xe−Br bonded compound existed. The syntheses, isolation, and characterization of the first compounds to contain Xe−Br bonds ([N(C2H5)4]3[Br3(XeO3)3] and [N(CH3)4]4[Br4(XeO3)4]) and their chlorine analogues are described. The bromo- and chloroxenate salts are stable in the atmosphere at room temperature and were characterized in the solid state by Raman spectroscopy, low-temperature single-crystal X-ray diffraction, and in the gas phase by quantum-chemical calculations. They are the only known examples of cage anions that contain a noble-gas element. The Xe−Br and Xe−Cl bonds are weakly covalent and can be viewed as σ-hole interactions, similar to halogen bonds. Xenon trioxide reacts with alkali metal fluorides and chlorides to form a variety of room-temperature stable fluoro- and chloroxenate salts. The reaction of XeO3 with various ratios of KF in water afforded three new compounds. The crystal structures of α-K[F(XeO3)2], β-K[F(XeO3)2], α-K[FXeO3], K2[F2(XeO3)] have been determined. The reaction of XeO3 with aqueous CsF resulted in Cs3[F3(XeO3)2]. The XeVI−F bond lengths range from 2.3520(18) to 2.5927(17) Å. No stable product was isolated when [N(CH3)4]F was the fluoride source, but in the presence of HF, crystals of [N(CH3)4]3[HF2]2[H2F3]∙2XeO3 were obtained. The reaction of KCl with XeO3 in equimolar amounts resulted in the formation of K[ClXeO3] whereas the analogous reaction with CsCl yielded Cs3[Cl3(XeO3)4]. Attempts to synthesize Xe–P and Xe–S bonded compounds were unsuccessful and instead resulted in adducts between XeO3 and O-bases such as the phosphine oxide adduct, {(C6H5)3PO}2XeO3 and dimethylsulfoxide (DMSO) adduct {(CH3)2SO}3(XeO3)2. Although DMSO was found to be resistant to oxidation by XeO3, no significant Xe---S bonding interactions were observed. Acetone was found to be highly resistant to oxidation by XeO3 and forms {(CH3)2CO}3XeO3 at low temperatures. The reaction of pyridine-N-oxide yielded large crystals of (C5H5NO)3(XeO3)2 in which the structure contains short chains in contrast with ((CH3)2SO)3(XeO3)2 whose structure consists of discrete dimers. The reaction of XeO3 with the oxidatively resistant main-group oxide anion source, [N(CH3)4][OTeF5] in CH3CN solvent afforded [N(CH3)4][F5TeOXeO3(CH3CN)2]. Xenon trioxide reacts with potassium hydroxide to form the previously known K4[XeO6]∙2XeO3 salt which was characterized by Raman spectroscopy and low-temperature X-ray crystallography. The reaction of MgO with XeO3 yielded single crystals of [Mg(OH2)6]4[XeO6(XeO3)12O2]∙12H2O, which also contains perxenate-XeO3 interactions. Alkali metal carbonates also incorporate XeO3 into their crystal lattices. Raman spectra of M2[CO3(XeO3)n]∙xH2O (M = Na, K, Rb) were recorded and contain intense bands assigned to the XeO3 stretching modes and very weak bands assigned to the [CO3]2− modes. The reaction of dilute aqueous solutions of XeO3 with RbOH and atmospheric CO2 afforded single crystals of Rb2[CO3(XeO3)2]∙2H2O which were characterized by low-temperature X-ray crystallography. Attempts to incorporate XeO3 into other polyatomic anion salts such as KMnO4, NaClO3, and NaNO3 were unsuccessful. The reaction of IrO2 with XeF6 in aHF provided [Xe2F11][IrF6], whereas the reaction of IrO2 with KrF2 with ClF3 in anhydrous HF solvent provided [ClO2][Ir2F11] and [ClO2][(μ-OIrF4)3]. The structure of [(μ-OIrF4)3]− consists of a six membered Ir3O3 ring with four terminal fluorine atoms on each Ir atom. It was also found that ClF3 forms an adduct with [Xe2F11][HF2] in which the structural parameters of ClF3 are very similar to that of solid ClF3. The [ClO2][Ir2F11] salt provides the first structural information on the [Ir2F11]− anion and the [(μ-OIrF4)3]− anion represents the first isolated iridium oxide fluoride species. / Thesis / Doctor of Philosophy (PhD) / Xenon is a noble-gas element which is located in the far right-hand column of the periodic table and was previously thought to be chemically unreactive and incapable of forming compounds. In 1962, it was shown that xenon reacts with the most reactive compounds, such as elemental fluorine, but the resulting xenon compounds are themselves highly reactive. This Thesis extends the chemistry of some of the most unstable and chemically reactive xenon compounds that are currently known. One such compound, xenon trioxide, tends to easily detonate unless carefully handled. Methods of stabilizing xenon trioxide were developed and its behaviour with compounds which resulted in formation of new xenon compounds was studied. The molecular structures of these compounds were investigated in the solid with particular emphases on their chemical bonding. Iridium is one of the most chemically resistant metals known. Highly reactive xenon and krypton compounds were used synthesize new iridium compounds.
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Contraintes sur les processus de dégazage des dorsales océaniques par la géochimie des volatils et la pétrologie des laves basaltiques / Constraints on degassing processes at mid-oceanic ridges using volatile geochemistry and petrology

Colin, Aurélia 06 December 2010 (has links)
Afin de préciser l'origine des volatils terrestres et les flux actuels et passés vers l’atmosphère, de nombreuses études s’intéressent à la composition du manteau. Ce réservoir est échantillonné naturellement lors des éruptions volcaniques, mais une grande partie des gaz est alors émise dans l'atmosphère, de sorte que la composition des volatils du manteau reste peu contrainte. Nous cherchons à préciser les mécanismes de dégazage sous les dorsales océaniques afin de corriger ces fractionnements. L'analyse (He-Ne-Ar-CO2) de verres basaltiques issus de la dorsale des Galápagos, dans la zone d'influence du point chaud des Galápagos, montre que la composition en volatils des laves s'explique par distillation de Rayleigh d'une source unique. Cette source est distincte de celle du point chaud (isotopes du néon), impliquant un dégazage en profondeur du panache ou une hétérogénéité spatiale de sa composition.Plusieurs verres volcaniques issus de la dorsale Atlantique et Est Pacifique ont été imagés par micro-tomographie aux rayons X. L'étude met en évidence des mécanismes de nucléation et de croissance des bulles différents sous les deux dorsales. De la convection en périphérie de la chambre magmatique avant l’éruption a été mise en évidence par l’étude pétrologique des verres. Les vésicules imagées ont ensuite été ouvertes individuellement sous vide par ablation laser et analysées (CO2, 4He, isotopes de l'argon). La composition des bulles est hétérogène dans certains échantillons et compatible avec une distillation de Rayleigh. Les tendances de dégazage obtenues permettent d'obtenir localement la composition de la source mantellique, qui est hétérogène.L'étude permet également d'appréhender l'hétérogénéité des rapports 40Ar/36Ar dans les chambres magmatiques par la technique d’ablation laser qui diminue la contamination atmosphérique par rapport à la technique classique de broyage / The composition of mantle volatiles is related to the origin of Earth's volatiles and to the past and present volatile fluxes to the atmosphere. Although this reservoir is naturally sampled during volcanic eruptions, most of the volatiles are lost to the atmosphere during this event, thus the composition of mantle volatiles is still uncertain. We try here to precise the processes of degassing below mid-oceanic ridges to correct the lava compositions for degassing.The He-Ne-Ar-CO2 analyses of basaltic glasses sampled along the Galapagos Spreading Center, in the area of influence of the Galapagos hotspot, show that the volatile composition of lavas is fully explained by a Rayleigh distillation of a unique source distinct from the plume source. These results imply that the plume degasses at depth or is heterogeneous.Several volcanic glasses from Mid-Atlantic ridge and East Pacific Rise have been imaged by X-rays microtomography. The mechanisms of vesicle nucleation and growth appear to be different below the two ridges. A step of convection at the magma body margin has been evidenced by the petrologic study of the glasses. Imaged vesicles have been subsequently opened under vacuum by laser ablation and analysed (CO2, 4He, argon isotopes). We observe, depending on the samples, either a single composition for all bubbles, or variations in composition between bubbles consistent with a trend of equilibrium degassing in an open system. The trends of degassing allow extrapolating locally to the volatile composition of the mantle source, which is heterogeneous. We also studied the heterogeneity of 40Ar/36Ar ratios in magmatic chambers using the laser opening method, which lowers the contribution of atmospheric gases compared to the classical crushing method
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Caractérisation, quantification et modélisation des processus de transfert et des interactions CO₂-eau-roche en milieu poreux non saturé en contexte de forage lors d'un stockage géologique / Characterization, quantification and modeling of transfer process and CO₂-water-rock interactions in the unsaturated carbonate vadose and in a drilling well during carbon storage

Rhino, Kévins 07 December 2017 (has links)
Le stockage géologique du carbone est l’une des techniques les plus prometteuses pour réduire le taux de CO₂ dans l’atmosphère. La séquestration géologique possède la capacité et la longévité potentielles pour diminuer les émissions de CO₂ vers l’atmosphère. Dans le cadre d’injections à l’échelle industrielle, les réservoirs carbonatés peuvent faire partie des sites aptes à stocker du CO₂. Toutefois, ces injections à grandes profondeurs sont sujettes à des risques de fuites du piège géologique lui-même ou des infrastructures liés à l’exploitation du site de stockage. Ainsi, il existe principalement deux types de fuite : brutale et diffuse. Dans les deux cas, elles sont susceptibles d’entrainer des risques pour l’environnement et de mettre en danger les populations. Il est ainsi nécessaire de développer des outils capables de prévenir une fuite de CO₂ quel que soit son type. Par ailleurs, il est particulièrement indispensable de comprendre les mécanismes de transport réactif qui rentrent en jeu lors de l’arrivée de cette fuite en contexte de proche surface (zone vadose) et ainsi d’essayer d’étudier comment cette fuite peut s’amortir. Ces travaux de thèse traitent donc de la caractérisation, de la quantification et de la modélisation des processus de transferts et des interactions CO₂-H₂O-CaCO₃ dans la zone vadose en contexte de fuite à partir d’un puits de forage. Cette problématique a été d’abord abordée par une approche expérimentale sur un site pilote à Saint-Emilion. Puis, les interactions CO₂-H₂O-CaCO₃ ont été étudiées au travers d’une approche expérimentale à l’échelle de la carotte en laboratoire. L’approche expérimentale a conduit à la réalisation de deux fuites dans la zone vadose du site pilote : une fuite diffuse et une fuite ultra diffuse. Elles furent réalisées dans la continuité des expériences qui avaient déjà eu lieu auparavant. Une comparaison de l’ensemble des fuites a montré la nécessité d’utiliser des gaz nobles comme précurseurs de l’arrivée en surface du CO₂. Selon le type de fuite, l’hélium peut servir de précurseur temporel du CO₂, tandis que le krypton prévient de l’étendue du panache de gaz durant la fuite. Plus la pression d’injection du CO₂ est importante et plus le gaz migre par advection. Par ailleurs, une pression d’injection importante favorise l’existence de passage préférentiel dans la zone vadose. L’utilisation d’isotopes tels que ceux de l’hélium et du carbone permet de mettre en évidence la présence locale de phases aqueuses dans le massif et de déterminer l’origine biologique ou anthropique du CO₂. Les expériences à l’échelle de la carotte permettent d’estimer le pouvoir tampon des calcaires oligocènes en fonction du faciès de la roche. La perméabilité et la porosité de celle-ci conditionnent la dissolution des calcaires. De même, la réactivité des carbonates en contexte de fuite dépend du pH de la phase aqueuse, du débit qui traverse le réseau poreux, de la saturation en eau et des caractéristiques pétro-physiques des carbonates. / Carbon storage is one of the most encouraging methods to decrease CO₂ concentration into the atmosphere. Carbon storage provides the longevity and the capacity needed to decrease CO₂ emissions toward the atmosphere. When dealing with storage on an industrial scale, carbonated reservoirs can be among the most suitable storage sites. However, these high depth injections are subject to leakage risks from the geologic trap itself or from the framework created by the establishment of the site. Two main types of leakage exist: brutal and diffusive leakage. In both cases, they are likely to endanger the environment and the population. Therefore, it is essential to develop tools that are able to anticipate any types of CO₂ leakage. Furthermore, it is also necessary to understand the reactive transport mechanism that take place when the leakage arrives in the shallow subsurface (vadose zone)and to see how the leakage can be buffered. This work deals with the characterization, the quantification and the modelling of transfer processes and CO₂-H₂O-CaCO₃ interactions into the vadose zone in a context of a leakage from a drilling well. This issue was first dealt through field experiment on the site of Saint Emilion. Then, the CO₂-H₂O-CaCO₃ interactions were studied through an experimental approach in laboratory. Two leakage experiments were performed on the site: a diffusive leakage and an ultra-diffusive leakage. They were performed as a sequel of former experiments carried on the pilot site. A comparison of all the leakage experiments revealed the necessity to use noble gases as precursor of the CO₂ arrival at the surface. Depending of the type of the leakage, helium can be a temporal precursor while krypton can anticipate the spread of the CO₂ gas plume. The higher the injection pressure, the more the gas migrates through advective flux. Moreover, a high injection pressure favors the existence of preferential paths in the vadose zone. The use of helium and carbon isotopes makes it possible to reveal the presence of a local aqueous phase within the porous media and to identify the origin of CO₂. The core scale experiments lead to the estimation of the buffering power of Oligocene limestone according to the rock facies. The permeability and the porosity influence the dissolution of the limestone. The reactivity of carbonates during a leakage depends on the pH of the aqueous phase, the flow rate that goes through the porous media, the water saturation and petrophysical characteristics of the carbonates.
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A Treatise on the Geometric and Electronic Structure of Clusters : Investigated by Synchrotron Radiation Based Electron Spectroscopies

Lindblad, Andreas January 2008 (has links)
<p>Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (<i>i.e.</i> nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques.</p><p>The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures.</p><p>Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well.</p><p>Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger <i>vis-à-vis</i> Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups.</p><p>Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.</p>

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