Arctic climate is changing fast, but weather forecast and climate models have serious deficiencies in representing the Arctic atmosphere, because of the special conditions that occur in this region. The cold ice surface and the advection of warm air aloft from the south result in a semi-continuous presence of a temperature inversion, known as the “Arctic inversion”, which is governed by interacting large-scale and local processes, such as surface fluxes and cloud formation. In this thesis these poorly understood interactions are investigated using observations from field campaigns on the Swedish icebreaker Oden: The Arctic Summer Cloud Ocean Study (ASCOS) in 2008 and the Arctic Clouds in Summer Experiment (ACSE) in 2014. Two numerical models are also used to explore these data: the IFS global weather forecast model from the European Center for Medium-range Weather Forecasts and the MIMICA LES from Stockholm University. Arctic clouds can persist for a long time, days to weeks, and are usually mixed-phase; a difficult to model mixture of super-cooled cloud droplets and ice crystals. Their persistence has been attributed to several mechanisms, such as large-scale advection, surface evaporation and microphysical processes. ASCOS observations indicate that these clouds are most frequently decoupled from the surface; hence, surface evaporation plays a minor role. The determining factor for cloud-surface decoupling is the altitude of the clouds. Turbulent mixing is generated in the cloud layer, forced by cloud-top radiative cooling, but with a high cloud this cannot penetrate down to the surface mixed layer, which is forced primarily by mechanical turbulence. A special category of clouds is also found: optically thin liquid-only clouds with stable stratification, hence insignificant in-cloud mixing, which occur in low-aerosol conditions. IFS model fails to reproduce the cloud-surface decoupling observed during ASCOS. A new prognostic cloud physics scheme in IFS improves simulation of mixed-phase clouds, but does not improve the warm bias in the model, mostly because IFS fails to disperse low surface-warming clouds when observations indicate cloud-free conditions. With increasing summer open-water areas in a warming Arctic, there is a growing interest in processes related to the ice marginal zones and the summer-to-autumn seasonal transition. ACSE included measurements over both open-water and sea-ice surfaces, during melt and early freeze. The seasonal transition was abrupt, not gradual as would have been expected if it was primarily driven by the gradual changes in net solar radiation. After the transition, the ocean surface remained warmer than the atmosphere, enhancing surface cooling and facilitating sea-ice formation. Observations in melt season showed distinct differences in atmospheric structure between the two surface types; during freeze-up these largely disappear. In summer, large-scale advection of warm and moist air over melting sea ice had large impacts on atmospheric stability and the surface. This is explored with an LES; results indicate that while vertical structure of the lowest atmosphere is primarily sensitive to heat advection, cloud formation, which is of great importance to the surface energy budget, is primarily sensitive to moisture advection. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.</p>

Fundamental studies on thermodynamic properties of vanadium-containing oxides systems are essential to understand practical vanadium metallurgical process. The CALPHAD technique is here applied to the thermodynamic modelling of the V-O, Ca-V-O and Ti-V-O systems. The compound energy formalism is used for all the solution phases. All optimization processes and calculations are performed using the Thermo-Calc software package. The present work attempts to develop a self-consistent thermodynamic database of all phases in the studied systems. The obtained datasets can be used to calculate thermodynamic properties, stable as well as metastable phase equilibria and driving forces for oxidation etc. Steelmaking slag is an important secondary source for vanadium extraction. The phase relationships and vanadium distribution in the CaO-SiO2-MgO-V2O3-Al2O3 synthetic slags, whose compositions were chosen based on the relevance to the steel producers, are also studied. Phase equilibria in the temperature range of 1773 to 1823 K at oxygen partial pressure of 10-10 bar and 0.21 bar were characterized. An investigation of the volatilization of vanadium oxide was also carried out in the present work. Isothermal evaporation of vanadium pentoxide in the temperature range between 1723 and 1873 K was investigated by Thermogravimetric Analysis under different oxygen partial pressures, viz. oxygen, air or CO2. The Arrhenius activation energy for the evaporation reaction in various atmospheres was calculated from the experimental results. A mathematical model was developed to describe the kinetics of the evaporation process. Evaporation coefficients and enthalpies in various atmospheres were also estimated. The present results may have some implications in recovering vanadium from different vanadium-bearing sources. / <p>QC 20161202</p>

This research aims to investigate how particles assemble together through thermodynamic and kinetic control. Particle assembly with thermodynamic control is achieved in part due to electrostatic attraction between particles. Electrostatic attraction between particles can be achieved by functionalizing polystyrene or SiO2 particles with different charges. Particles with different charges will come together in solution slowly and self-assemble to form ordered crystals with different patterns based on size and charge ratios of two oppositely charged particles. Kinetic control of particle assembly is achieved by pattern aided exponential amplification of nanoscale structures. Some of these nanoscale structures are difficult to build with other conventional synthetic methods. On the other hand, as for kinetically controlled particle replication, the patterns can be synthesized by one of two ways i) crystal products which are produced by thermodynamically controlled particle assembly or ii) single particle deposition. Specifically, kinetically controlled particle assembly focuses on constructing SiO2 particles. Exponential replication of SiO2 particles is achieved by growing a "bridge layer", between templates of SiO2 particles and next generation SiO2 replicas. By dissolving the bridge layer, two times the amount of the SiO2 particles with the shape of the original templates can be formed. In the next generation, all the particles serve as template particles. Thus, after n cycles of replication, 2n amount of products can be formed. If successful, particle assembly can be thermodynamic controlled and particle exponential replication can be kinetical controlled, which will enable new ways to build particles with well-defined shapes from readily available building blocks.

Le captage du CO2 représente un enjeu industriel majeur et scientifique du siècle. Il existe différentes méthodes de séparation et de captage du CO2, telles que, l'absorption aux amines et l’adsorption. Bien que ces processus soient bien développés au niveau industriel, ils sont très consommateurs d’énergie. Le procédé de captage du CO2 par formation d’hydrates de gaz consomme moins d’énergie et semble être très prometteur pour la séparation du CO2 Les hydrates de gaz sont des composés cristallins de la famille des clathrates dans lesquels des molécules d'eau se relient entre elles par des liaisons hydrogène pour former des cavités qui peuvent contenir des molécules de gaz. La formation d'hydrates de gaz est favorisée par une haute pression et basse température.Cette étude est menée dans le cadre du projet ANR SECOHYA. L'objectif est d'étudier les conditions thermodynamiques et cinétiques du procédé de captage du CO2 par cristallisation d'hydrates de gaz.Premièrement, nous avons développé un dispositif expérimental pour réaliser des expériences afin de déterminer les conditions thermodynamiques et cinétiques de formation des hydrates mixtes CO2-N2 dans l'eau comme phase liquide. Nous avons montré que la pression opératoire peut être très élevée et la température très basse. Pour la faisabilité du projet, nous avons utilisé le TBAB (TétraButylAmmonium Bromure) en tant qu'additif thermodynamique dans la phase liquide. L'utilisation du TBAB peut réduire considérablement la pression opératoire.Dans la deuxième partie de cette étude, nous avons présenté un modèle thermodynamique, basé sur le modèle de van der Waals et Platteeuw. Ce modèle permet de prédire les conditions d'équilibre thermodynamique de formation des hydrates de gaz. Des données expérimentales d'équilibre de mélanges CO2-CH4 et de CO2-N2 sont présentées et comparées à des résultats théoriques. / CO2 capture and sequestration represent a major industrial and scientific challenge of thiscentury. There are different methods of CO2 separation and capture, such as solid adsorption, amines adsorption and cryogenic fractionation. Although these processes are welldeveloped at industrial level, they are energy intensive. Hydrate formation method is a lessenergy intensive and has an interesting potential to separate carbon dioxide. Gas hydrates are Document crystalline compounds that consist of hydrogen bonded network of water molecules trapping a gas molecule. Gas hydrate formation is favored by high pressure and low temperature. This study was conducted as a part of the SECOHYA ANR Project. The objective is to study the thermodynamic and kinetic conditions of the process to capture CO2 by gas hydrate crystallization. Firstly, we developed an experimental apparatus to carry out experiments to determine the thermodynamic and kinetic formation conditions of CO2-N2 gas hydrate mixture in water as liquid phase. We showed that the operative pressure may be very important and the temperature very low. For the feasibility of the project, we used TBAB (TetraButylAmmonium Bromide) as thermodynamic additive in the liquid phase. The use of TBAB may reduce considerably the operative pressure.In the second part of this study, we presented a thermodynamic model, based on the van der Waals and Platteeuw model. This model allows the estimation of thermodynamic equilibrium conditions. Experimental equilibrium data of CO2-CH4 and CO2-N2 mixtures are presented and compared to theoretical results.

Dans les années 2000, les matériaux de conversion sont apparus comme une alternative intéressante aux matériaux d'insertion actuellement utilisés dans les batteries Li-ion. Ils réagissent avec le lithium pour former une électrode constituée de nanoparticules métalliques encapsulées dans une matrice lithiée. Pour comprendre ces réactions, le phosphure de cobalt (CoP) a été étudié au moyen de techniques théoriques et expérimentales. La complexité de ces systèmes nanocomposites n'a pas permis de caractériser toutes les espèces présentes dans l'électrode. Cependant, les calculs DFT ont prédit la formation de composés intermédiaires dont les potentiels de formation sont cohérents avec l'expérience. De plus, ces travaux ont mis en évidence l'importance de la réactivité de surface quant à l'origine de l'hystérésis de potentiel qui nuit au rendement énergétique de ce type d'électrode. La méthodologie développée spécialement pour les réactions de conversion, mais transférable vers d'autres réaction électrochimique, a été validée par les mesures expérimentales. / In the 2000s, conversion materials appeared as an interesting alternative to the insertion materials currently used in Li-ion batteries. They react with lithium to form an electrode constituted of metallic nanoparticles embedded into a lithiated matrix. To understand those reactions, cobalt phosphide (CoP) has been studied by theoretical and experimental techniques. The complexity of those nanocomposite systems does not allow to characterize all the species present inside the electrode. However, DFT calculations predicted the formation of intermediate compounds whose the formation potentials are in agreement with the experiment. Moreover, these studies have highlighted the importance of surface reactivity about the voltage hysteresis which harms to the electrode efficiency.The methodology especially developed for conversion reactions, but transferable to others electrochemical reaction, was validated by experimental measures.

E système Mo-Ni-Re est un sous-système majeur des superalliages à base de Ni conçus pour une utilisation dans les applications à haute température. Compte tenu des contradictions entre les informations publiées antérieurement, cette étude a été consacrée à la détermination expérimentale complète des équilibres entre phases dans le système Mo-Ni-Re, à la caractérisation structurale des phases intermétalliques et à la modélisation thermodynamique du système à l'aide de la méthode CALPHAD. L'étude expérimentale des équilibres entre phases a été effectuée en utilisant des alliages à l'équilibre, et les diagrammes de phases du système Ni-Re et Mo-Ni-Re (à 1200°C et à 1600°C) ont été proposées. En comparaison avec les études précédentes, le diagramme de phases Ni-Re déterminé au cours de ce travail a montré des différences significatives en termes de domaines d'homogénéité, des domaines de cristallisation et de température de réaction péritectique. La coupe isotherme à 1200°C du système Mo-Ni-Re proposée lors de cette étude a montré l'extension importante de la phase σ du système binaire Mo-Re et de la phase δ du système Mo-Ni dans le diagramme ternaire. En outre, la présence de deux phases ternaires jusque-là inconnues a également été observée. La coupe isotherme du système Mo-Ni-Re à 1600°C a également montré une grande extension de la phase σ dans le diagramme ternaire tandis que l'extension de la phase χ du système Mo-Re dans les deux coupes isothermes est limitée à un étroit domaine de composition. Les phases ternaires observées dans la coupe isotherme à 1200°C ne sont pas présentes dans la coupe isotherme à 1600°C. D'autre part, les études partielles des domaines de composition des phases dans les systèmes binaires Mo-Ni et Mo-Re ainsi que la détermination de la projection du liquidus du système Mo-Ni-Re ont également été effectuées. La projection du liquidus du système Mo-Ni-Re proposée lors de la présente étude a également montré des champs de cristallisation primaire de la phase σ de système Mo-Re et la solution solide de Re dans la région ternaire qui sont largement étendus. Puisque la coupe isotherme du système Mo-Ni-Re a montré un domaine d'homogénéité de la phase σ très étendu, la caractérisation structurale de la phase σ du système ternaire Mo-Ni-Re a été effectuée en mettant l'accent sur la détermination de l'occupation des sites en fonction de la composition par affinement de Rietveld combiné des données de diffraction des rayons X et des neutrons. Les résultats expérimentaux recueillis au cours de cette étude ainsi que les informations disponibles dans la littérature ont été utilisés comme données d'entrée pour la modélisation thermodynamique du système Mo-Ni-Re. La description thermodynamique du système Mo-Re a été prise de la littérature tandis que les optimisations thermodynamiques des systèmes Mo-Ni, Ni-Re et Mo-Ni-Re ont été effectuées au cours de ce travail avec la méthode CALHAD.Mots-clés: Mo-Ni, Mo-Re, Ni-Re, Mo-Ni-Re; diagramme de phases; coupe isotherme; caractérisation structurale; modélisation thermodynamique; méthode CALPHAD / The Mo-Ni-Re system is one of the important subsystems of the Ni based superalloys engineered for use in high temperature applications. Considering the contradictions among previously reported information, the present study was devoted to the complete experimental determination of the phase equilibria in the Mo-Ni-Re system, structural characterization of its intermetallic phases and thermodynamic modeling of the system with the help of the CALPHAD method. The experimental investigation of phase equilibria was carried out with the help of equilibrated alloys and phase diagrams of the Ni-Re and Mo-Ni-Re system (at 1200°C and 1600°C) were proposed. In comparison with previous investigations, the Ni-Re phase diagram determined during the present study showed significant difference in terms of homogeneity domains, freezing ranges and peritectic reaction temperature. The 1200°C isothermal section of the Mo-Ni-Re system proposed during the present study showed large extension of the Mo-Re σ phase and Mo-Ni δ phase in the ternary region. In addition, presence of two previously unknown ternary phases was also observed. The isothermal section of the Mo-Ni-Re system at 1600°C also showed large extension of σ phase in the ternary region whereas extension of the Mo-Re χ phase in both isothermal sections was restricted to narrow composition range. The presence of the ternary phases observed in the 1200°C isothermal was not evidenced in 1600°C isothermal section. On the other hand, partial investigations of phase boundaries in the Mo-Ni and Mo-Re binary systems and determination of liquidus projection of the Mo-Ni-Re system was also carried out. The liquidus projection of the Mo-Ni-Re system proposed during present study also showed largely extended primary crystallization fields of the Mo-Re σ phase and Re solid solution in the ternary region. Since isothermal sections of the Mo-Ni-Re system showed largely extended homogeneity domain of σ, structural characterization of the Mo-Ni-Re σ with particular emphasis on determination of site occupancy trends as a function of composition was carried out by combined Rietveld refinement of the X-ray and neutron diffraction data. The experimental results gathered during the present study along with the information available in the literature were used as input for thermodynamic modeling of the Mo-Ni-Re system. The thermodynamic description of the Mo-Re system was taken from literature whereas thermodynamic modeling of the Mo-Ni, Ni-Re and Mo-Ni-Re system was carried out during the present study with the help of the CALHAD method.Keywords: Mo-Ni; Mo-Re; Ni-Re; Mo-Ni-Re; phase diagram; isothermal section; structural characterization; thermodynamic modeling; CALPHAD method

L’objectif de cette thèse était la modélisation numérique de la torche à plasma à couplage inductive. (ICP). Nous avons établi les bases de données nécessaires : composition, propriétés thermodynamiques et de transport appliqués aux mélanges d’argon, d’acide nitrique et d’eau. Le modèle hydrodynamique de la torche ICP (7 spires) considère le plasma à l'équilibre thermodynamique et couple les équations de Navier-Stokes pour décrire l'écoulement du plasma aux équations de Maxwell pour décrire l'évolution du champ électrique et du champ magnétique. / The purpose of the work was the numerical modeling of the inductive coupling plasma torch. (ICP). We have established the necessary databases: composition, thermodynamic and transport properties applied to argon mixtures of nitric acid and water. The hydrodynamic model of the ICP torch (7 coils) considers the plasma at thermodynamic equilibrium and uses the Navier-Stokes equations to describe the plasma flow and the Maxwell equations to describe the evolution of the electric field and the magnetic field.

Title: Symmetrical aminophosphinates Author: Bc. Soňa Procházková Department of Inorganic Chemistry, Faculty of Science, Charles University Supervisor: RNDr. Vojtěch Kubíček, Ph.D. Supervisor's email address: kubicek@natur.cuni.cz ABSTRACT Two types of α-aminophosphinates were prepared and studied: phosphinate analogues of iminodiacetic acid − aminobis(methyl(hydroxymethyl)phosphinic acid) (IDPhm ) and aminobis(methyl(2-carboxyethyl)phosphinic acid) (IDPce ), and bis(aminomethyl- phosphinates) − (hydroxy(fenyl)methylen)bis(aminomethylphosphinic acid) (PheOHABPin) and (methylen)bis(aminomethylphosphinic acid) (ABPin). All prepared compounds were fully characterized (by NMR, MS, elemental analysis). One crystal structure was determined by X-ray singlecrystal analysis. The diphosphinates were synthesized by Mannich type reaction, whereas the bis(aminomethylphosphinates) were prepared by multistep synthesis including reactive silylesters. Compounds were prepared in moderate or good yields Acid-base and coordination properties of ligands were investigated and compared by potentiometric and NMR titrations. The values of protonation constants of aminogroups, which determine stability of complexes, showed surprising results. An extremely low basicity of nitrogen atom was found in diphosphinates. So, these compounds...

Title: Bifunctional ligands for copper(II) complexation Author: Bc. Martina Benešová Supervisor: doc. RNDr. Jan Kotek, Ph.D. Institution: Department of Inorganic Chemistry, Faculty of Science, CU in Prague Author's e-mail: EvaGlaser@seznam.cz ABSTRACT The main aim of this thesis was preparation of macrocyclic ligands based on 1,4,8,11- tetraazacyclotetradecane skeleton, which is suitable for selective complexation of divalent copper, and study of their properties. These ligands are suggested for potential utilization in nuclear medicine. Cyclam macrocycle was modified to bear one coordinating aminobenzylphospinate pendant arm (compound L1) or monophosphinate-bis(phosphonate) pendant arm (compound L2). During the synthesis, the skeleton was protected in positions 1, 4 and 8. In the frame of this work the synthesis of both targeted products was developed. Furthermore, a study of the thermodynamic, kinetic and coordination properties of ligand L2 was investigated by UV/VIS spectrophotometry and potentiometric titrations. A model bioconjugation of ligand L1 with primary amine was also studied. KEYWORDS Cyclam, phosphinates, phosphonates, nuclear medicine, copper(II) complexes, kinetic inertness, thermodynamic stability.

To study especially the influence of a forest canopy on thermodynamic processes in the Atmospheric Boundary Layer (ABL) an one-dimensional model was developed for an ABL including forest as a vertically high resoluted canopy. In contrast to very expensive mesometeorological and LES (Large-Eddy Simulation)-models it is the aim of our study to construct practical simple applicable ABL-model-versions for a rather detailed non steady-state simulation of energy fluxes as well as of windvector, temperature-, humidity- and turbulence-parameter- profiles within and above a forest canopy. The obtained results show clearly that characteristic features of the meteorological fields as temperature are in a general agreement with observations (BEMA). Numerical experiments also describe the considerable influence of the closure approach used and the values for vegetation parameters on the simulation results. / Um den Einfluß eines Waldbestandes auf die thermodynamischen Prozesse in der Atmosphärischen Grenzschicht (AGS) zu untersuchen, wurde ein eindimensionales Modell für eine AGS mit einem Waldbestand als vertikal hoch aufgelöster Vegetationsschicht entwickelt. Im Gegensatz zu den sehr aufwendigen mesoskaligen und LES (Large-Eddy Simulation)-Modellen ist es Ziel dieser Untersuchung, praktisch leicht anwendbare Modellversionen der AGS für die detaillierte instationäre Simulation von Energieflüssen sowie des Windvektors, von Temperatur-, Feuchte- und Turbulenzparameterprofilen inner- und oberhalb des Waldbestandes zu konstruieren. Die erhaltenen Resultate zeigen deutlich, daß die charakteristischen Eigenschaften der meteorologischen Felder, z.B. Temperatur, in genereller Übereinstimmung mit Messungen (BEMA) sind. Die numerischen Experimente geben außerdem den bedeutenden Einfluß der verwendeten Schließungsannahme und der Werte für die Vegetationsparameter auf die Ergebnisse der Simulationen wieder.