L'objet de cette thèse est l'étude des interactions du formaldéhyde avec l'eau, système qui possède à la fois un intérêt fondamental et des applications dans les domaines de la chimie atmosphérique et de l'astrochimie. Nous avons déterminé par spectroscopie d'absorption infrarouge la constante de Henry du formaldéhyde, qualifiant sa solubilité dans l'eau ou la glace, pour des solutions aqueuses de fraction molaire inférieure à 1%, et des températures entre 270 et 295 K, représentantes des conditions atmosphériques.La composition de ces solutions a été étudiée par calorimétrie différentielle à balayage, diffraction des rayons X et spectroscopie Raman pour différentes concentrations (1-30 % en mol. frac.) et températures (183-453 K). L'analyse des solutions gelées a montré différentes phases cristallines selon les conditions expérimentales. Nous avons fait la première observation, par spectroscopie Raman, du formaldéhyde en phase liquide sous sa forme H2CO, pour des températures supérieures à 363 K.Le mécanisme d'hydratation de formaldéhyde en méthylène glycol CH2(OH)2 a été étudié par calculs ab initio dans les phases gazeuse et liquide. Un mécanisme coopératif a été mis en évidence et les effets de l'ajout de molécules d'eau autour du soluté sur les géométries et les énergies ont été analysés. Des simulations de dynamique moléculaire ab initio ont été réalisées pour étudier les systèmes comprenant des molécules d'eau et de méthylène glycol ou de H(CH2O)2OH, à 300 K. Les structures préférentielles des solutés et les effets de polarisation dus à l'interaction du soluté avec le solvant ont été déterminés. Les spectres Raman calculés ont été comparés aux expérimentaux. / The subject of this work is the study of the interactions of formaldehyde with water, which has both a fundamental interest and applications in the fields of atmospheric chemistry and astrochemistry. We focused first on the determination, by infrared absorption spectroscopy, of Henry's law constant for formaldehyde, characterizing its solubility into water or ice, for aqueous solutions of molar fraction below 1%, and temperatures between 270 and 295 K, representative of the atmospheric conditions. The composition of the formaldehyde aqueous solutions has also been studied, using differential scanning calorimetry, X-ray diffraction and Raman spectroscopy, for a large range of concentrations (1-30 % mol. frac.) and temperatures (183-453 K). The analysis of the frozen solutions showed different crystallized phases depending on the experimental conditions. We made the first observations, by Raman spectroscopy, of formaldehyde in the liquid phase under its gas form, for temperatures above 363 K. The hydration mechanism of formaldehyde into methylene glycol CH2(OH)2 has been investigated by ab initio calculations in the gas and liquid phases. A cooperative mechanism has been highlighted and the effects of additional water molecules around the solute on the geometries and on the energies have been analyzed. We also used ab initio molecular dynamics to study systems comprising water molecules and methylene glycol or the next oligomer HCH2O)2OH, at 300 K. The preferred structures of the solute and the polarization effects due to the interaction of the solute with the solvent have been determined. Calculated Raman spectra were compared to the experimental ones.

Voir 4ème de couverture / Voir 4ème de couverture

Diss.--Giessen Universität, 1996. / Notes bibliogr. Bibliogr. p. 177-186. Index.

Reproduction de : Thèse de doctorat : Sciences Mathématiques : Faculté des sciences de Paris : 1889. / Titre provenant de la page de titre du document numérisé.

La sorption du cadmium sur la calcite est étudiée en système ternaire, en présence, simultanément d’un ligand organique (malonate) et du cadmium. D’abord nous avons étudié l’interaction entre le malonate et la calcite. L’influence du malonate sur la solubilité de la calcite, le signal du malonate en spectroscopie infrarouge et enfin la modélisation des isothermes d’adsorption par un modèle de complexation de surface à trois plans (CD-MUSIC) nous ont permis de proposer un modèle pour la spéciation du malonate à la surface de la calcite et d’estimer quantitativement l’adsorption. Ensuite, nous avons étudié la sorption du cadmium sur la calcite, respectivement en absence et en présence de malonate. En absence de malonate, l’adsorption du cadmium donne lieu à une isotherme classique, de valeurs connues. La modélisation néanmoins révèle quelques difficultés de paramètrage. L’étude de la sorption en réacteur à écoulement continu sous conditions proches de l’équilibre CaCO3-H2O-CO2 met en évidence une parfaite réversibilité adsorption/désorption du cadmium. Notons que aucune expérience de sorption ne dépassait une durée totale de 60 heures. En présence de malonate, expériences et modélisations indiquent un effet négatif du malonate sur la sorption du cadmium. La cinétique de sorption est notablement ralentie et le cadmium est, en partie, fixé plus fortement à la surface. Les résultats tendent à montrer que la présence de malonate ralentit considérablement l’atteinte d’un équilibre de sorption du cadmium sur la calcite. / The sorption of cadmium by calcite was studied in a ternary system, with an organic ligand (malonate) and cadmium simultaneously present in solution. First we studied the interaction between malonate and calcite. The influence of malonate on the solubility of calcite, malonate spectra in infrared spectroscopy, and the modelling of isotherms by a 3-plane surface complexation model (CD-MUSIC) allowed us to propose a model for the speciation of malonate at the surface of calcite and to estimate adsorption quantitatively. In a second step, we have studied the sorption of cadmium by calcite, without and with malonate respectively. When malonate was not present, cadmium sorption by calcite gave rise to an isotherm with known values. Modelling however revealed some difficulties with parametrisation. Studying sorption under continuous flow in a “Stirred Flow Through Reactor” under conditions close to CaCO3-H2O-CO2 equilibrium, showed perfectly reversible adsorption/desorption of cadmium. Note that sorption experiments were conducted over 15 to 60 hours at maximum. When malonate was present, experiments and modelling indicated that malonate reduced the sorption of cadmium. Sorption kinetics were significantly lower and cadmium, in part, sorbed more strongly on the calcite surface. The results tend to show that the presence of malonate slows down the reach of sorption equilibrium of cadmium with calcite.

Thesis (Ph. D.)--University of Chicago. / Also available on the Internet.

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Tecnologia, Departamento de Engenharia Civil e Ambiental, 2016. / Submitted by Albânia Cézar de Melo (albania@bce.unb.br) on 2016-06-02T13:47:12Z No. of bitstreams: 1 2016_CristinaMartinezUribe.pdf: 7588676 bytes, checksum: 9ebbe0761f7688450e8bc4895ff9f12e (MD5) / Approved for entry into archive by Raquel Viana(raquelviana@bce.unb.br) on 2016-07-21T18:06:43Z (GMT) No. of bitstreams: 1 2016_CristinaMartinezUribe.pdf: 7588676 bytes, checksum: 9ebbe0761f7688450e8bc4895ff9f12e (MD5) / Made available in DSpace on 2016-07-21T18:06:43Z (GMT). No. of bitstreams: 1 2016_CristinaMartinezUribe.pdf: 7588676 bytes, checksum: 9ebbe0761f7688450e8bc4895ff9f12e (MD5) / Nesta pesquisa é apresentado o desenvolvimento, montagem e teste de um permeâmetro de parede flexível e carga constante construído. Este equipamento é uma ferramenta de qualidade que permite a determinação da permeabilidade em materiais de baixa condutividade hidráulica, o qual se compõe de uma câmara de confinamento de acrílico e sistemas de aplicação de pressão de confinamento, de aplicação de contrapressão, imposição de gradientes hidráulicos elevados e aquisição de dados automatizada. Este equipamento foi construído seguindo uma metodologia dividida em quatro etapas: i) projeto, ii) construção, iii) instrumentação e iv) operação do equipamento. Para o projeto do equipamento, objetivou-se atingir a reprodução das condições reais do campo tendo-se, assim aplicabilidade em diferentes áreas de pesquisa. Algumas considerações no projeto foram: a possibilidade de aplicação de tensão desviadora, a possibilidade de realização de ensaios em diferentes materiais e maior representatividade de materiais com frações granulares devido ao uso de amostras de maior diâmetro (130 mm). Nas etapas de construção e instrumentação do permeâmetro foi realizada toda a montagem dos componentes do equipamento, assim como o sistema de aquisição de dados. A quarta etapa envolveu a realização de ensaios pelo método de carga constante, que permitiram a validação da operação do equipamento. Para isto foram utilizadas amostras indeformadas obtidas no Campo Experimental do PPG-UnB. Os resultados obtidos da condutividade hidráulica para este tipo de material se situaram na ordem de 2,63x10- 7 até 9,01x10-7 m/s, coerentes com os valores publicados na literatura para este material. O equipamento permite realizar medições de permeabilidades entre 1x10-4 e 1x10- 12 m/s. ________________________________________________________________________________________________ ABSTRACT / In this research, the development, assembly and test of a constant head and flexible wall permeameter which was built for the laboratory of the Postgraduate Program in Geotechnics of the University of Brasilia (PPG-UnB), is presented. This equipment is a quality tool that allows the determination of the permeability of materials with low hydraulic conductivity. The permeameter consists of a confining acrylic cell and systems for the application of confining pressure, for the application of backpressure, setting of high hydraulic gradients and automated data acquisition. This equipment was made following a methodology, developed in four stages: i) design, ii) construction, iii) instrumentation and iv) equipment's operation. For the design of the equipment, it was sought to reach the reproduction of the real ground conditions, having thus applicability in different research areas. Some of the design considerations were: the possibility of application of deviator stress, possibility to perform tests in different types of materials, a better representation of the materials with granular fractions due to the use of greater diameter samples (130 mm), among others. In the construction and instrumentation stage, all the components of the permeameter and of the data acquisition system were assembled. The fourth stage involved the performance of head constant tests that allows the validation of the operation of the equipment. For this, undisturbed soil samples obtained from the experimental field of the PPG-UnB were used. The obtained results of the hydraulic conductivity for this type of material were in the range of 2,63 x10-5 to 9,01x10-5 cm/s, coherent with the values of this material published in the literature. The equipment allow to made measurement of permeability between 1x10-4 e 1x10- 12 m/s.

Neste trabalho são tratados alguns resultados sobre superfícies com curvatura média constante, imersas na R3, sendo destacadas os teoremas de DELAUNAY (1841), LIEBMANN (1900), H. HOPF (1956), A.D. ALEXANDROV (1957) e J. RIPOLL (1985). Demonstra-se, com algum detalhamento, o leorema de DELAUNA Y para o caso da cônica -que rola, sobre urna reta, sem deslizar, ser uma elipse e não uma hipérbole, como no trabalho original, bem como prova-se 1que para gue a superfície de revolução com curvatura média constante seja completa, tal cônica deve ser, obrigatoriamanente, uma elipse. Utiliza-se, neste último teorema, resultados mais recentes como o de'i'ido a W. HSIANG (1981). São também demonstrados o clássico teorema de ALEXANDROV de caracterização da esfera, como única superfície compacta e conexa que possui curvatura média constante não nula, e o de J. RIPOLL que generaliza o anterior pais substitui a hipótese de compaticidade por outra mais fraca que é a sua completude, embora exija que seja propriamente mergulhada na R 3, bem como sua inclusão num cone plano.

Neste trabalho apresentamos resultados de existência e unicidade para gráficos de curvatura média constante em H² x R, com bordo prescrito em planos paralelos, obtidos através da resolução de problemas de Dirichlet para a equação da curvatura média. / In this work we investigate the existence and uniqueness of constant mean curvature graphs in H² x R, with boundary in parallel planes, by solving a Dirichlet problems for the mean curvature equation.

Neste trabalho, investigamos a existência e unicidade de gráficoscos parabólicos de curvatura média constante H em H³ cujo bordoé dado a priori, sobre hipóteses que relacionam H com a geometria do domínio e uma condição sobre o dado no bordo, que por analogia com um problema similar para gráficos em R³, a denominamos condição de declividade limitada. / In this work, we investigate the existence and uniqueness of parabolic graphs of constant mean curvature H in H³ whose boundary is given a priori, under hypothesis relating H with the geometry of the domain and a condition on the boundary data that, by anal- ogy with a similar problem for vertical graphs in R³, we denominated it by bounded slope condition.