I present an experimental study on the formation and dissociation characteristics of carbon dioxide (CO2) gas hydrates using Raman spectroscopy. The CO2 hydrates were formed from aqueous salt solutions with salinities ranging from 0-11 wt-%, and the salts used were sodium chloride (NaCl), potassium chloride (KCl), magnesium chloride (MgCl2) and calcium chloride (CaCl2). The experiments were conducted in a high-pressure vessel, in which the aqueous solution was pressurized with liquid CO2 to 6 MPa. First, I investigated how the addition of salts to a CO2-hydrate forming system inhibits the hydrate formation thermodynamically. For this purpose, the molar enthalpy of reaction between strongly and weakly hydrogen bonded water molecules was determined. I observed a decrease in the molar reaction enthalpy of up to 30 % for the highest salt concentration investigated. In addition, the influence of the salts on the solubility of CO2 in water was studied, which was reduced up to 40 %. The results showed that both properties could be well correlated with the effective mole fraction of salt in solution. Furthermore, the decrease in molar reaction enthalpy could be directly correlated with the equilibrium temperature of gas hydrates. This showed that the shift in equilibrium temperature induced by thermodynamic inhibitors was a direct result from the weakened hydrogen bonded network in the water-rich liquid phase before the onset of gas hydrate formation. Additionally, the growth mechanisms of CO2 hydrates were investigated by determining the amount of solid hydrate formed and the respective reaction constant. The reaction constant was not affected by the addition of salts, whereas the maximum amount of solid hydrate formed also showed a good correlation with the effective mole fraction. This finding leads to the assumption that salt does not affect the intrinsic growth mechanisms of hydrate formation, but that the weakened hydrogen bonded network leads to a decrease in the conversion of liquid water to hydrate and more water molecules stay in a liquid in the form of inclusions between the hydrate cages. Lastly, I analyzed the ratio of CO2 and water and the development of hydrogen bonds after the complete dissociation of hydrate. I observed a supersaturation of CO2 in the water-rich phase and found evidence that the excess CO2 exists as dispersed micro- or nanoscale liquid droplets in the liquid water-rich phase. The development of hydrogen bonds in the liquid water-rich phase was the same as before the hydrate formation. These results could be a possible explanation for the memory effect originating from residual nano- and mircodroplets. With this study, I aim to provide a better understanding of the mode of action of thermodynamic inhibitors and to contribute further insights to the controversially debated phenomenon of the memory effect.

Die Bildung und Beständigkeit von CSH-Phasen wurde in Abhängigkeit von Zeit, Ca/Si-Verhältnis, Temperatur, SiO2-Reaktivität, w/s-Verhältnis und NaCl-Sättigung der Lösung untersucht. Semikristalline CSH-Phasen bilden tobermoritähnliche Schichtstrukturen aus und weisen trotz ihrer Metastabilität hohe Beständigkeit bei 25 °C auf. Durch Erhöhung von Temperatur und w/s-Verhältnis wird deren Umwandlung zu kristallinen CSH-Phasen begünstigt, während NaCl-Sättigung der wässrigen Lösung die Kristallisation hemmt. Die Löslichkeit von CSH-Phasen ändert sich ebenfalls durch Variation von Temperatur und NaCl-Konzentration. Die NaCl-Sättigung führt in Folge der teilweisen Substitution von Ca2+ durch Na+ in den Festphasen zu einer deutlichen Erhöhung der Ca2+-Konzentrationen in Lösung. Mischphasenmodelle beschreiben dieses Verhalten in Berechnungen zumeist nicht hinreichend. Die Erweiterung der Datenbasis und Anpassungen der Modelle sind nötig. Mg2+-haltige Kontaktlösungen führen zur Auflösung von CSH- unter Bildung von MSH-Phasen.

Formation of gas hydrates is an important feature of water systems. It occurs undesirably in natural gas pipelines, but also in deep-sea deposits and unfreezing permafrost. However, the natural occurrence is of particular interest because methane hydrates have one of the highest energy densities of all naturally occurring forms of methane. Therefore, an accurate description of its thermodynamic properties is required. In this work, we demonstrate how the material properties of methane hydrate can be more easily calculated compared to ab initio methods. Furthermore, it is shown how the material properties depend on the cage occupancy by using the comparably fast self-consistent-charge density-functional tight-binding (SCC-DFTB) method. The cell potential is calculated and compared to a numerical as well as an ab initio model, and is in good agreement with the literature.

Seafloor compliance is a non-intrusive geophysical method sensitive to the shear modulus of the sediments below the seafloor. A compliance analysis requires the computation of the frequency dependent transfer function between the vertical stress, produced at the seafloor by the ultra low frequency passive source-infra-gravity waves, and the resulting displacement, related to velocity through the frequency. The displacement of the ocean floor is dependent on the elastic structure of the sediments and the compliance function is tuned to different depths, i.e., a change in the elastic parameters at a given depth is sensed by the compliance function at a particular frequency. In a gas hydrate system, the magnitude of the stiffness is a measure of the quantity of gas hydrates present. Gas hydrates contain immense stores of greenhouse gases making them relevant to climate change science, and represent an important potential alternative source of energy. Bullseye Vent is a gas hydrate system located in an area that has been intensively studied for over 2 decades and research results suggest that this system is evolving over time. A partnership with NEPTUNE Canada allowed for the investigation of this possible evolution. This thesis describes a compliance experiment configured for NEPTUNE Canada’s seafloor observatory and its failure. It also describes the use of 203 days of simultaneously logged pressure and velocity time-series data, measured by a Scripps differential pressure gauge, and a Güralp CMG-1T broadband seismometer on NEPTUNE Canada’s seismic station, respectively, to evaluate variations in sediment stiffness near Bullseye. The evaluation resulted in a (- 4.49 x10-3± 3.52 x 10-3) % change of the transfer function of 3rd October, 2010 and represents a 2.88% decrease in the stiffness of the sediments over the period. This thesis also outlines a new algorithm for calculating the static compliance of isotropic layered sediments.

Seafloor compliance is a non-intrusive geophysical method sensitive to the shear modulus of the sediments below the seafloor. A compliance analysis requires the computation of the frequency dependent transfer function between the vertical stress, produced at the seafloor by the ultra low frequency passive source-infra-gravity waves, and the resulting displacement, related to velocity through the frequency. The displacement of the ocean floor is dependent on the elastic structure of the sediments and the compliance function is tuned to different depths, i.e., a change in the elastic parameters at a given depth is sensed by the compliance function at a particular frequency. In a gas hydrate system, the magnitude of the stiffness is a measure of the quantity of gas hydrates present. Gas hydrates contain immense stores of greenhouse gases making them relevant to climate change science, and represent an important potential alternative source of energy. Bullseye Vent is a gas hydrate system located in an area that has been intensively studied for over 2 decades and research results suggest that this system is evolving over time. A partnership with NEPTUNE Canada allowed for the investigation of this possible evolution. This thesis describes a compliance experiment configured for NEPTUNE Canada’s seafloor observatory and its failure. It also describes the use of 203 days of simultaneously logged pressure and velocity time-series data, measured by a Scripps differential pressure gauge, and a Güralp CMG-1T broadband seismometer on NEPTUNE Canada’s seismic station, respectively, to evaluate variations in sediment stiffness near Bullseye. The evaluation resulted in a (- 4.49 x10-3± 3.52 x 10-3) % change of the transfer function of 3rd October, 2010 and represents a 2.88% decrease in the stiffness of the sediments over the period. This thesis also outlines a new algorithm for calculating the static compliance of isotropic layered sediments.

Solubility prediction usually refers to prediction of the intrinsic aqueous solubility, which is the concentration of an unionised molecule in a saturated aqueous solution at thermodynamic equilibrium at a given temperature. Solubility is determined by structural and energetic components emanating from solid-phase structure and packing interactions, solute–solvent interactions, and structural reorganisation in solution. An overview of the most commonly used methods for solubility prediction is given in Chapter 1. In this thesis, we investigate various approaches to solubility prediction and solvation model development, based on informatics and incorporation of empirical and experimental data. These are of a knowledge-based nature, and specifically incorporate information from the Cambridge Structural Database (CSD). A common problem for solubility prediction is the computational cost associated with accurate models. This issue is usually addressed by use of machine learning and regression models, such as the General Solubility Equation (GSE). These types of models are investigated and discussed in Chapter 3, where we evaluate the reliability of the GSE for a set of structures covering a large area of chemical space. We find that molecular descriptors relating to specific atom or functional group counts in the solute molecule almost always appear in improved regression models. In accordance with the findings of Chapter 3, in Chapter 4 we investigate whether radial distribution functions (RDFs) calculated for atoms (defined according to their immediate chemical environment) with water from organic hydrate crystal structures may give a good indication of interactions applicable to the solution phase, and justify this by comparison of our own RDFs to neutron diffraction data for water and ice. We then apply our RDFs to the theory of the Reference Interaction Site Model (RISM) in Chapter 5, and produce novel models for the calculation of Hydration Free Energies (HFEs).

La connaissance des processus physiologiques, soit dans la phase de repos, soit pendant le développement végétatif, est important dans l'adaptation des angiospermes ligneuses tempérées, plutôt sur la question de la gestion de l'eau par la plante. Les objectifs de cette étude étaient d’évaluer la teneur de l’eau et le métabolisme des hydrates de carbone pendant l'état d'avancement de la dormance chez les poiriers, d'évaluer les stratégies d'utilisation de l'eau chez deux espèces ligneuses (pommier et noyer), qui ont été soumis à trois niveaux de déficit hydrique, et finalement, d’évaluer la fiabilité de la technique d'injection d'air pour provoquer la cavitation dans trois espèces d'angiospermes ligneuses. Lors de la première expérience, menée pendant l'automne et l'hiver 2008 au Brésil, nous avons utilisé les cultivars de poiriers et de ‘Packham Triumph’ et ‘Housui’. La deuxième expérience a été développée en France au cours de l'été 2009, avec des pommiers et des noyers sous stress hydrique. La troisième expérience a été réalisée en France en 2009 avec trois espèces d'angiospermes ligneuses avec différentes longueurs de vaisseaux du xylème, Betula pendula, Prunus persica et Quercus robur. D'après les résultats, on a pu conclure que la teneur de l’eau dans les tissus peut être un marqueur de la progression de dormance de la ‘Packham Triumph’. Cependant, les données ne sont pas concluantes pour la ‘Housui’. La fermeture des stomates peut être un paramètre important dans la prévention de la cavitation du xylème chez les noyers et pommiers soumis à un déficit hydrique du sol. Lors du régime de sécheresses sévères, le pommier conserve les stomates partiellement ouverts, ce qui indique une plus grande tolérance de cette espèce à la sécheresse par rapport au noyer. Enfin, la technique d'utilisation de l'injection d'air avec des caméras d’air à deux sorties est fiable pour les espèces dont le xylème a une porosité diffuse, dès qu’on utilise des caméras courtes et des échantillons de branches qui ont une longueur plus grande que les vaisseaux du xylème. / The knowledge of physiological processes during both dormancy and vegetative growth is important for adaptation processes in temperate zone woody angiosperms, especially in water management by those plants. The objectives of this work were to evaluate the water content and carbohydrate metabolism during the progress of dormancy in pears, to evaluate strategies of water use in two woody species (apple and walnut), which were subjected to three di fferent levels of water deficit, and also to evaluate reliability of air injection technique to induce cavitation in three woody angiosperms. The fi rst experiment was conducted during autumn and winter of 2008 in Brazil, and it was used plants of pears cultivars Packham's Triumph and Housui. The second study was carried out during the summer season of 2009 in France, with apple and walnut trees under water stress. The third experiment was done in France in 2009, and three species of woody angiosperms with different lengths of xylem were used Betula pendula, Prunus persica and Quercus robur. From the results it was concluded that the water content in tissues might be a marker of dormancy progression for cv. Packham's Triumph. However, the data were not conclusive and clear in cv. Housui. Stomatal closure might be an important parameter for preventing xilemian cavitation in walnut and apple trees subjected to soil water deficit. Apple trees stomata grown under severe drought regime remained partially open, indicating a greater tolerance of this species to drought in comparison to walnut. Finally, the doubleended pressure sleeve technique is reliable for species with diffuse-porous xylem by using short chambers and also branches longer than the xylem vessels. / O conhecimento dos processos fisiológicos, tanto na fase de repouso quanto no desenvolvimento vegetativo, é importante na adaptação das angiospermas lenhosas de clima temperado, especialmente na questão da gestão da água pela planta. Os objetivos deste trabalho foram avaliar o conteúdo da água e o metabolismo de carboidratos durante o progresso da dormência em pereiras, avaliar estratégias do uso da água em duas espécies lenhosas (maciei ra e noguei ra), que foram submetidas a três níveis de déficit hídrico, e por fim, avaliar a confiabilidade da técnica de injeção de ar para indução à cavitação em três espécies de angiospermas lenhosas. No primei ro experimento, conduzido durante o outono e inverno de 2008 no Brasil, utilizou-se plantas de pereira cultivares Hous ui e Packham´s Triumph. O segundo experimento foi desenvolvido na França durante o verão de 2009, com macieiras e nogueiras sob estresse hídrico. O tercei ro experimento foi conduzido na França em 2009 com três espécies de angiospermas lenhosas com di ferentes comprimentos dos vasos do xilema, Betula pendula, Prunus persica e Quercus robur. A partir dos resultados concluiu-se que o conteúdo de água nos tecidos pode ser um marcador do progresso da dormência para cv. Packham’s Triumph. Porém os dados não foram conclusivos para cv. Housui. O fechamento estomático pode ser um importante parâmetro na prevenção à cavitação xilemática em nogueiras e macieiras submetidas a déficit hídrico no solo. Em regime de secas severas, a maciei ra mantém os estômatos parcialmente abertos, indicando maior tolerância desta espécie à seca quando comparado à nogueira. E por fim, a técnica de injeção de ar utilizando câmara de ar com duas saídas é fiável para espécies com xilema de porosidade difusa, utilizando câmaras curtas e amostras de ramo que tenha comprimento superior aos vasos do xilema.

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