Cette thèse présente les mesures et l'analyse thermodynamique d'équilibres de phases de systèmes d'hydrates contenant du dioxyde de carbone (CO2), dans le contexte de procédés alternatifs de captage du CO2. Le développement de nouveaux procédés de séparation par voie de cristallisation par hydrates est un point crucial de cette thématique. Les conditions de température et de pression requises et l'utilisation de promoteurs thermodynamiques sont au-delà des opérations habituelles et des bases de données existantes. La connaissance précise des conditions de formation et dissociation d'hydrates de gaz en présence d'additifs chimiques constitue une contrainte importante d'un point de vue thermodynamique et est nécessaire pour la modélisation et l'établissement de la faisabilité de nouveaux procédés industriels impliquant des hydrates de gaz. Dans cette thèse, nous présentons un nouveau dispositif expérimental qui combine techniques statiques et techniques analytiques, ce dernier a été spécialement développé pour mesurer des données d'équilibres des phases hydrate-liquide-gaz à des températures variant entre 233 et 373 K et à des pressions jusqu' à 60 MPa. De nouvelles données d'équilibre de phases des systèmes (CO2 + méthane), (CO2 + azote) et (CO2 + hydrogène) ont été mesurées dans des conditions de formation d'hydrates en suivant la méthode isochorique avec variation de la pression en fonction de la température, et en analysant la composition en phase gazeuse. Les données d'équilibre et les conditions de dissociation d'hydrates générées dans ce travail sont comparées avec les données de la littérature. La fiabilité des modèles thermodynamiques les plus couramment utilisés est aussi étudiée. Les comparaisons entre les données expérimentales et prédites de dissociation d'hydrates suggèrent la nécessité de réajuster les paramètres des modèles thermodynamiques pour les systèmes contenant des hydrates de CO2. En outre, l'effet promoteur du bromure de tetrabutylammonium (TBAB) sur les équilibres des phases des gaz purs et de mélanges contenant du CO2 a été étudié. L'effet le plus important de promotion (réduction de la pression de formation des hydrates > 90%) est observé pour le système (TBAB + azote). Les résultats expérimentaux suggèrent que le CO2 peut être séparé de mélanges de gaz industriels ou de combustion à des températures douces et à de basses pressions à l'aide de TBAB en tant que promoteur thermodynamique. La pression requise pour la formation d'hydrates à partir de mélanges de (CO2 + azote) est réduite de 60 % en présence de TBAB. / This thesis addresses the measurement and thermodynamic analysis of the phase equilibrium behavior of carbon dioxide (CO2) hydrate-forming systems in the context of alternative capture engineering approaches. The development of new technologies based on gas hydrates requires specific temperature and pressure conditions and the utilization of thermodynamic promoters that are beyond usual operations and existing databases. Accurate knowledge of gas hydrates formation and dissociation from thermodynamics point of view in the presence of chemical additives is necessary for modeling purposes and to establish the feasibility of emerging industrial processes involving gas hydrates. In this thesis, a new experimental set-up and method for measuring pressure, temperature and compositional phase equilibrium data of high accuracy are presented. The equipment is based on the ‘static-analytic' technique with gas phase capillary sampling and it is suitable for measurements in a wide temperature range (i.e. 233 to 373 K) and pressures up to 60 MPa. New phase equilibrium data in the (CO2 + methane), (CO2 + nitrogen) and (CO2 + hydrogen) systems under hydrate formation conditions were measured following an isochoric pressure-search method in combination with gas phase compositional analysis. The equilibrium data generated in this work are compared with literature data and also with the predictions of two thermodynamic literature models. Comparisons between experimental and predicted hydrate dissociation data suggest a need of readjusting model parameters for CO2 hydrate-forming systems. In addition, the thermodynamic stability of Tetra-n-Butyl Ammonium Bromide (TBAB) semi-clathrates (sc) with pure and mixed gases was investigated. The largest promotion effect (> 90% reduction in hydrate formation pressure) is observed for (TBAB + nitrogen) sc. The experimental results suggest that CO2 can be separated from highly to low concentrated industrial/flue gas mixtures at mild temperatures and low pressures by using TBAB as thermodynamic promoter. The pressure required for hydrate formation from (CO2 + nitrogen) gas mixtures is reduced by 60% in the presence of TBAB.

Dans le domaine d’optimisation de forme de structures, la réduction des coûts et l’amélioration des produits sont des défis permanents à relever. Pour ce faire, le procédé de mise en forme doit être optimisé. Optimiser le procédé revient alors à résoudre un problème d’optimisation. Généralement ce problème est un problème d’optimisation multicritère très coûteux en terme de temps de calcul, où on cherche à minimiser plusieurs fonctions coût en présence d’un certain nombre de contraintes. Pour résoudre ce type de problème, on a développé un algorithme robuste, efficace et fiable. Cet algorithme, consiste à coupler un algorithme de capture de front de Pareto (NBI ou NNCM) avec un métamodèle (RBF), c’est-à-dire des approximations des résultats des simulations coûteuses. D’après l’ensemble des résultats obtenus par cette approche, il est intéressant de souligner que la capture de front de Pareto génère un ensemble des solutions non dominées. Pour savoir lesquelles choisir, le cas échéant, il est nécessaire de faire appel à des algorithmes de sélection, comme par exemple Nash et Kalai-Smorodinsky. Ces deux approches, issues de la théorie des jeux, ont été utilisées pour notre travail. L’ensemble des algorithmes sont validés sur deux cas industriels proposés par notre partenaire industriel. Le premier concerne un modèle 2D du fond de la canette (elasto-plasticité) et le second est un modèle 3D de la traverse (élasticité linéaire). Les résultats obtenus confirment l’efficacité de nos algorithmes développés. / One of the current challenges in the domain of the multiobjective shape optimization is to reduce the calculation time required by conventional methods. The high computational cost is due to the high number of simulation or function calls required by these methods. Recently, several studies have been led to overcome this problem by integratinga metamodel in the overall optimization loop. In this thesis, we perform a coupling between the Normal Boundary Intersection -NBI- algorithm and The Normalized Normal constraint Method -NNCM- algorithm with Radial Basis Function -RBF- metamodel in order to have asimple tool with a reasonable calculation time to solve multicriteria optimization problems. First, we apply our approach to academic test cases. Then, we validate our method against two industrial cases, namely, shape optimization of the bottom of a can undergoing nonlinear elasto-plastic deformation and an optimization of an automotive twist beam. Then, in order to select solutions among the Pareto efficient ones, we use the same surrogate approach to implement a method to compute Nash and Kalai-Smorodinsky equilibria.

Cette thèse étudie les performances du marché du travail dans une économie susceptible de présenter plusieurs équilibres, et les implications d’une telle configuration pour la politique économique. Elle comporte quatre essais, traitant chacun d’un aspect spécifique de cette problématique. En premier lieu, l’analyse économétrique des séries temporelles de taux de chômage de quelques pays de l’OCDE, permettant notamment l’identification des changements de régimes et de leurs caractéristiques, apporte des évidences significatives à l’appui de l’hypothèse d’une multiplicité d’équilibres. En second lieu, on étudie les effets de l’introduction d’un salaire minimum obligatoire et d’une hausse de celui-ci dans un modèle statique de concurrence imparfaite avec négociations salariales au niveau de la firme, le facteur travail étant hétérogène. Si la hausse du salaire minimum est défavorable à l’emploi,l’introduction d’un salaire minimum en présence d’une multiplicité d’équilibres permet d’éliminer l’équilibre Pareto-inférieur. En troisième lieu, on étudie également les implications de l’existence d’équilibres multiples pour les politiques économiques, du fait de l’altération des propriétés dynamiques de l’économie, à travers l’analyse complète d’un modèle dynamique de concurrence imparfaite avec des négociations salariales individuelles et des frictions d’appariement sur le marché du travail. Enfin, on montre grâce à l’outil expérimental dans quelle mesure l’introduction d’une variable dite de tâche solaire, peut être source de défaut de coordination et d’inefficience dans une économie possédant deux équilibres Pareto-ordonnés. / This thesis analyzes the performances of labor market in an economy subject to multiple equilibria and the implications of such a configuration for economic policy. It contains four pieces of research, each dealing with a particular aspect of the general setting. First, the econometric analysis of the unemployment time series for several OECD countries,which allows the identification of regime switches and their characteristics, brings forth some significant evidence that the multiple equilibria framework is relevant. Second, the effect of the implementation and of the rise of the minimum wage are investigated through a static model, assuming imperfect competition, heterogeneous labor input and wage negotiations at the firm level. Though minimum wage hikes have an adverse effect on employment, the implementation of a binding minimum wage turns out to be an efficient tool for excluding the Pareto- inferior equilibrium. Third economic policy conditions are also affected because the existence of multiple equilibria alters the dynamic properties of the economy. This case has been investigated in the framework of a fully dynamic model assuming imperfect competition individual wage negotiations and matching frictions. Finally, a coordination game experiment confirms that the introduction of a sunspot can be a source of coordination failure and inefficiency in an economy with two Pareto-ranked equilibria.

Lors de l'extraction de l'uranium par lixiviation acide, AREVA fait face à des phénomènes transitoires de précipitation de phases mal cristallisées entrainant un colmatage des installations. Les analyses de ces précipités ont mis en évidence la formation d'un solide jaune minoritaire et d'un blanc majoritaire composé de sulfate de calcium et d'hydroxysulfate d'aluminium. Afin de comprendre les phénomènes menant à la précipitation et pour prévoir, éviter ou limiter leur apparition, les travaux de thèse ont consisté en l'étude expérimentale des équilibres solides-liquide du système complexe Al–Fe–K–P–S–H2O (± Ca et Mg) en milieu acide à 25°C, avec pour objectif l'identification des solides susceptibles d'apparaître en conditions industrielles. Les résultats permettront ainsi de compléter les bases de données thermodynamiques utilisées pour modéliser le comportement global du milieu lors des opérations. Après la mise au point de techniques analytiques appropriées, le travail s'est porté sur la délimitation des équilibres liquide-solides du système relatif au précipité blanc et particulièrement sur l'analyse des ternaires impliquant les hydroxysulfates d'aluminium. Le colmatage se produisant durant la phase d'acidification, l'évolution de la précipitation de ces hydroxysulfates en fonction du pH a été étudiée, afin de caractériser les solides formés en présence de cations minoritaires (Na+, K+, Mg2+, Ca2+) et de définir leurs constantes de solubilités à partir d'un modèle de calcul des coefficients d'activités des ions en solution. Des tests dynamiques sur colonne à partir de minerai naturel ont également été effectués et comparés aux résultats statiques / During the uranium extraction by acid leaching, AREVA observed the precipitation of not well crystallized solid phases, leading to the clogging of various equipment. The analyses of these precipitates highlighted the formation of a minor yellow precipitate and a major white precipitate containing calcium sulphate and aluminium hydroxisulphate. To understand the phenomena leading to the precipitation and to predict, prevent or at least limit their formation, this thesis work consisted of the solid-liquid equilibria experimental study of the Al–Fe–K–P–S–H2O (± Ca and Mg) system in an acidic environment at 25°C, with the identification of solid phases which may appear in natural ore as the major goal. The results could complete the thermodynamic database used to model global behaviour of the environment during acid mining. Based on the observed precipitates, two quaternary systems were defined, such as the H2O-Al3+, Ca2+ // O2-, SO42- system. After the development of appropriate analytical techniques, the work focused on the delimitation of the liquid-solid equilibria of the system based on the white precipitate and particularly on the analysis of the ternaries involving aluminium hydroxisulphates. As clogging occurs during acidification, the hydroxisulphate precipitation depending on the pH was studied in the presence of minority cations (Na+, K+, Mg2+, Ca2+), in order to characterise the solid phases which were formed, and to define their solubility constants. For the solubility constant determination, a calculation model of the ion activity coefficients in solution was used. A dynamic survey on a column containing natural ore was done and compared to static results

This thesis is organized into two parts, one for my main area of research in the field of stochastic games, and the other for my contributions in the area of service systems. We first provide an abstract for my work in stochastic games. The field of stochastic games has been actively pursued over the last seven decades because of several of its important applications in oligopolistic economics. In the past, zero-sum stochastic games have been modelled and solved for Nash equilibria using the standard techniques of Markov decision processes. General-sum stochastic games on the contrary have posed difficulty as they cannot be reduced to Markov decision processes. Over the past few decades the quest for algorithms to compute Nash equilibria in general-sum stochastic games has intensified and several important algorithms such as stochastic tracing procedure [Herings and Peeters, 2004], NashQ [Hu and Wellman, 2003], FFQ [Littman, 2001], etc., and their generalised representations such as the optimization problem formulations for various reward structures [Filar and Vrieze, 1997] have been proposed. However, they suffer from either lack of generality or are intractable for even medium sized problems or both. In our venture towards algorithms for stochastic games, we start with a non-linear optimization problem and then design a simple gradient descent procedure for the same. Though this procedure gives the Nash equilibrium for a sample problem of terrain exploration, we observe that, in general, it need not be true. We characterize the necessary conditions and define KKT-N point. KKT-N points are those Karush-Kuhn-Tucker (KKT) points which corresponding to Nash equilibria. Thus, for a simple gradient based algorithm to guarantee convergence to Nash equilibrium, all KKT points of the optimization problem need to be KKT-N points, which restricts the applicability of such algorithms. We then take a step back and start looking at better characterization of those points of the optimization problem which correspond to Nash equilibria of the underlying game. As a result of this exploration, we derive two sets of necessary and sufficient conditions. The first set, KKT-SP conditions, is inspired from KKT conditions itself and is obtained by breaking down the main optimization problem into several sub-problems and then applying KKT conditions to each one of those sub-problems. The second set, SG-SP conditions, is a simplified set of conditions which characterize those Nash points more compactly. Using both KKT-SP and SG-SP conditions, we propose three algorithms, OFF-SGSP, ON-SGSP and DON-SGSP, respectively, which we show provide Nash equilibrium strategies for general-sum discounted stochastic games. Here OFF-SGSP is an off-line algorithm while ONSGSP and DON-SGSP are on-line algorithms. In particular, we believe that DON-SGSP is the first decentralized on-line algorithm for general-sum discounted stochastic games. We show that both our on-line algorithms are computationally efficient. In fact, we show that DON-SGSP is not only applicable for multi-agent scenarios but is also directly applicable for the single-agent case, i.e., MDPs (Markov Decision Processes). The second part of the thesis focuses on formulating and solving the problem of minimizing the labour-cost in service systems. We define the setting of service systems and then model the labour-cost problem as a constrained discrete parameter Markov-cost process. This Markov process is parametrized by the number of workers in various shifts and with various skill levels. With the number of workers as optimization variables, we provide a detailed formulation of a constrained optimization problem where the objective is the expected long-run averages of the single-stage labour-costs, and the main set of constraints are the expected long-run average of aggregate SLAs (Service Level Agreements). For this constrained optimization problem, we provide two stochastic optimization algorithms, SASOC-SF-N and SASOC-SF-C, which use smoothed functional approaches to estimate gradient and perform gradient descent in the aforementioned constrained optimization problem. SASOC-SF-N uses Gaussian distribution for smoothing while SASOC-SF-C uses Cauchy distribution for the same. SASOC-SF-C is the first Cauchy based smoothing algorithm which requires a fixed number (two) of simulations independent of the number of optimization variables. We show that these algorithms provide an order of magnitude better performance than existing industrial standard tool, OptQuest. We also show that SASOC-SF-C gives overall better performance.

L'existence de différentes phases, polymorphes, sels, solvates et co-cristaux génère de nombreuses questions concernant la caractérisation des matériaux à l'état solide, en particulier pour l'industrie pharmaceutique. Les problématiques relatives à l'identification des phases et à la surveillance des processus de crist(allisation et de transitions de phase ne peuvent toutefois pas toujours être résolues à l'aide de techniques d'analyse conventionnelles. Dans ce travail, nous développons une approche analytique basée sur le phénomène d'optique non-linéaire de génération de seconde harmonique (GSH). La GSH est une technique sensible et précise pour détecter l'absence de centre d'inversion au sein d'une structure cristalline et pour suivre des modifications subtiles de symétrie. A travers plusieurs exemples, nous montrons comment les mesures de GSH résolues en température (TR-SHG) peuvent être utilisées pour étudier les diagrammes de phases et pour suivre les mécanismes et cinétiques des transitions de phase, y compris pour des transitions de type ordre-désordre. La combinaison de la TR-SHG avec les techniques classiques (XRPD, DSC et microscopie) permet ainsi de démontrer l'utilité et le potentiel de l'optique non-linéaire dans la caractérisation des propriétés physico-chimiques des matériaux. / The existence of different phases, including polymorphs, salts, solvates and co-crystals generates concerns in the characterization of solid-state materials, especially for the pharmaceutical industry. Issues related to the identification of phases and the monitoring of phase transitions and crystallisation processes cannot be always solved using conventionnal techniques. In this work, a complementary analytical approach based on the nonlinear optical phenomena of second harmonic generation (SHG) is developed. SHG is a sensitive and accurate technique to detect the absence of inversion center in the crystalline structure and to capture subtle symmetry changes. Herein, through several examples we show how Temperature-Resolved SHG (TR-SHG) measurements van be used to study phase diagrams and for tracking mechanisms and kinetics of phase transitions including order-disorder phase transitions. The combination of TR-SHG with classical techniques (XRPD, DSC and microscopy) reveals in this study the usefulness and the potentials of nonlinear optics in material characterization.

Wie vermischen sich Kraftstoff und Luft, wenn ein flüssiger Kraftstoff in einer Umgebung eingespritzt und zerstäubt wird, deren Parameter Druck und Temperatur den kritischen Druck und die kritische Temperatur des Kraftstoffs überschreiten? In dieser Arbeit wurden Experimente basierend auf Raman-spektoskopischen Methoden zur Gemischbildung unter eben solchen Bedingungen durchgeführt. Ziel der Arbeit war der experimentelle Nachweis der Möglichkeit einphasiger Gemischbildung, d.h. des Übergangs von eingespritztem Kraftstoff in das überkritische Regime, und von da Mischung mit der umgebenden initial überkritischen Stickstoffphase ohne Auftreten von Phasengrenzen. Dazu war es nötig, das Zweiphasengebiet der eingesetzten Stoffe exakt zu charakterisieren (die Gas-Flüssig-Gleichgewichte zu messen), und die Temperatur der Flüssigphase zuverlässig während der Gemischbildung zu messen. Mittels eines Mikrokapillar-Aufbaus wurden Daten zu Gas-Flüssig-Gleichgewichten (engl. Vapor-liquid-equilibria, VLE) bei hohen Drücken und Temperaturen erhoben. Dazu wurden unter kontrollierten Bedingungen phasenspezifische Raman-Spektren der Gas- und der Flüssigphase gemessen, aus denen sich in-situ die Gemischzusammensetzung der Phasen ermitteln ließ. Desweiteren wurden Methoden zur Bestimmung der Temperatur der Flüssigphase erarbeitet, sowie eine Methode zur Unterscheidung von Gas- und Flüssiganteil anhand der Raman-Spektren. Die letzten Methoden basieren auf einer Auswertung des Signals der Hydroxyl-Gruppe von Ethanol, welches in der vorliegenden Arbeit als Kraftstoff-Surrogat verwendet wurde. Danach wurden diese Methoden in einer Hochdruck-Hochtemperatur-Einspritzkammer eingesetzt. Hier wurde Kraftstoff unter realistischen Motorbedingungen eingespritzt, und Raman-Spektroskopie zeitlich und örtlich aufgelöst im entstehenden Spray angewandt. Dies erlaubte die Untersuchung der Gemischbildung ohne Beeinträchtigung des Systems, wie etwa durch Zugabe von Marker-Stoffen oder den Einsatz invasiver Messtechniken. Die gewonnenen VLE-Daten stellen eine erhebliche Verbesserung der Datengrundlage in diesem Druck- und Temperaturbereich dar, da Literaturdaten hier rar sind. Der realisierte Mikrokapillar-Aufbau benötigt nur minimale Volumina an Flüssigkeit und Gas, und lässt vielfältige weitere Einsatzmöglichkeiten wie etwa die Messung von VLE-Daten anderer Stoffe oder auch ternärer Gemische, oder die Untersuchung chemischer Reaktionen zu. Gleichgewichte stellen sich aufgrund des hohen Oberflächen-Volumen-Verhältnisses und der insgesamt kurzen Weglängen schnell ein. Die Zuverlässigkeit der gewonnenen Daten konnte durch Vergleich mit den wenigen vorhandenen Literaturdaten gezeigt werden. Bei Vorliegen von Wasserstoffbrückenbindungen konnte die Zuverlässigkeit und Überlegenheit der Raman-Thermometrie basierend auf der „integrated absolute difference spectroscopy“ gezeigt werden, außerdem erlaubt das charakteristische Raman-Signal der Hydroxyl-Gruppe in Wasserstoff-brückenbindung eine Unterscheidung von Gas- und Flüssigphase in überlagerten Spektren. Zum Nachweis der Durchführbarkeit einer solchen Unterscheidung wurde eine Methode entwickelt, um mittels unterschiedlicher Trigger-Signale phasenspezifische Messungen ohne Überlagerung durch eine alternierende Phase durchzuführen. Die gemessenen, örtlich und zeitlich aufgelösten Daten zur Gemischbildung im Spray erlauben die thermodynamische Charakterisierung der Gemischbildung anhand der ermittelten Parameter „globale Gemischzusammensetzung“, „Flüssigphasenanteil“ und „Flüssigphasentemperatur“. Die Ergebnisse zeigten für hohe Umgebungsdrücke und Temperaturen, dass die Flüssigphase Temperaturen jenseits ihrer kritischen Temperatur erreichen kann. Dies lieferte den Nachweis des Auftretens einphasiger Gemischbildung.:I Abbreviations and symbols II Figures III Tables 1. Introduction 2. State of the art 2.1.1. Objective of this thesis 3. Application-oriented fundamentals 3.1. Thermodynamic states 3.1.1. Single-component systems 3.1.2. Multi-compound systems 3.2. Micro-fluidic systems 3.3. Spray break-up 3.4. Raman spectroscopy 3.4.1. Fundamentals 3.4.2. Quantifiability of Raman signals 3.4.3. Liquid fraction determination 3.4.4. Raman thermometry 4. Vapor-Liquid-Equilibra – Experimental setup 4.1. Overview and auxiliary equipment 4.2. Heating system 4.3. Raman probe 4.4. Light guard technique 4.5. Materials and Experiments 5. Vapor-Liquid-Equilibria – Results and discussion 5.1. Data evaluation 5.2. Calibration 5.3. Liquid film correction 5.4. Results ethanol/nitrogen 5.5. Results decane/nitrogen 5.6. Raman thermometry 6. Sprays – Experimental Setup 6.1. Overview and auxiliary equipment 6.2. Calibration setup 6.3. Spray excitation and detection 6.4. Investigated conditions 7. Sprays – Results and discussion 7.1. Data evaluation 7.1.1. Fuel fraction determination 7.1.2. Liquid fraction determination 7.1.3. Liquid temperature determination 7.2. Calibration results 7.3. Spray results 8. Conclusion 9. References / How do fuel and air mix, when liquid fuel is injected and atomized in an environment with parameters pressure and temperature exceeding the respective critical ones of the fuel? In this work, experiments on mixture formation at such conditions based on methods of Raman spectroscopy were performed. Objective of the work was the experimental proof of single-phase mixing, i.e. the transition of injected fuel into the supercritical regime, and therein mixture with the surrounding initially supercritical nitrogen atmosphere without the formation of phase boundaries. To this end, the characterization of the two-phase regime was necessary (i.e. the measurement of the vapor-liquid-equlibria), and the reliable determination of the temperature of the liquid phase during mixture formation. Data on vapor-liquid-equilibria (VLE) were measured in a micro-capillary setup at high temperatures and pressures. To this end, phase-specific Raman spectra of the liquid and the vapor phase were measured at well-controlled conditions, from which the mixture composition of the respective phases was derived in-situ. Furthermore, Methods for the determination of the liquid phase temperature were developed, as well as an approach for the differentiation of the liquid phase signal from the vapor phase signal. The two latter methods exploit the specific signal of the hydroxyl-group of ethanol, which served as a fuel surrogate in this work. In the next step, these methods were applied in a high pressure, high temperature injection chamber. Here, fuel was injected at realistic engine-like conditions, and Raman spectroscopy was applied temporally and spatially resolved across the created spray cone. This approach allowed the Investigation of the mixture formation without affecting the system, compared to e.g. the addition of markers or the use of invasive measurement techniques. The gathered data are a significant addition to the scarce data base available in this pressure and temperature range. The realized micro-capillary setup needs only minimal volume of fluids, and allows various other operational Scenarios like the measurement of VLE data of other components, binary or ternary, or the Investigation of chemical reactions. Equilibria form very fast due to the high surface-to-volume ratio and the short path lenghts. The reliability of the gathered data were shown by comparison with literature. With the presence of hydrogen bonds, the reliability and superiority of the Raman thermometry based on the 'integrated absolute difference spectroscopy' was shown. Furthermore, the characteristic Raman signal of the hydroxyl-group allows for the differentiation of the vapor- and liquid-phase contributions in superimposed spectra from vapor- and liquid-phase. For the proof of feasibility of such a differentiation, a sophisticated method for the phase-specific measurements was developed by exploiting distinctive trigger Signals from the phases, allowing measurements in one phase without cross-talk from the alternating phase. The temporally and spatially resolved data measured during mixture formation in the spray lead to the thermodynamic characterization of the mixture formation with respect to the Parameters 'global mixture composition', 'liquid phase fraction', and 'liquid phase temperature'. The results for high pressures and temperatures inside the chamber show that the liquid or liquid-like phase can reach temperatures exceeding the critical temperature of the fuel. This provides the proof a the existance of single-phase mixing.:I Abbreviations and symbols II Figures III Tables 1. Introduction 2. State of the art 2.1.1. Objective of this thesis 3. Application-oriented fundamentals 3.1. Thermodynamic states 3.1.1. Single-component systems 3.1.2. Multi-compound systems 3.2. Micro-fluidic systems 3.3. Spray break-up 3.4. Raman spectroscopy 3.4.1. Fundamentals 3.4.2. Quantifiability of Raman signals 3.4.3. Liquid fraction determination 3.4.4. Raman thermometry 4. Vapor-Liquid-Equilibra – Experimental setup 4.1. Overview and auxiliary equipment 4.2. Heating system 4.3. Raman probe 4.4. Light guard technique 4.5. Materials and Experiments 5. Vapor-Liquid-Equilibria – Results and discussion 5.1. Data evaluation 5.2. Calibration 5.3. Liquid film correction 5.4. Results ethanol/nitrogen 5.5. Results decane/nitrogen 5.6. Raman thermometry 6. Sprays – Experimental Setup 6.1. Overview and auxiliary equipment 6.2. Calibration setup 6.3. Spray excitation and detection 6.4. Investigated conditions 7. Sprays – Results and discussion 7.1. Data evaluation 7.1.1. Fuel fraction determination 7.1.2. Liquid fraction determination 7.1.3. Liquid temperature determination 7.2. Calibration results 7.3. Spray results 8. Conclusion 9. References

Gegenstand dieser Arbeit ist die Frage wie thermische und photochemische Gleichgewichte verbunden werden können und sich gegenseitig beeinflussen. Dazu wurden zwei Projekte bearbeitet, zum einen das Konzept der „säure-katalysierten Zykloreversion“ und zum anderen das Konzept der „licht-induzierten pKs Veränderung“. Im ersten Konzepte wurde eine extern steuerbare, thermische Rückreaktion genutzt, um die Zusammensetzung im photostationären Zustand zu kontrollieren. Durch Zugabe von katalytischen Mengen einer starken Säure wurde die Ringöffnung eines Diarylethens, welches mit einem Flurenol substituiert ist, eingeleitet. Der zugrundeliegende Prozess wurde kinetisch und thermodynamisch, sowohl durch Experimente als auch durch computergestützte Rechnungen beschrieben. Eine säure-induzierte Dehydratation öffnet einen neuen Reaktionspfad, wodurch die normalerweise sehr hohe Reaktionsbarriere der Ringöffnung umgangen werden kann. Die quantitative Umsetzung mit Säure führt zu einer kompletten Löschung der photochemischen Reaktivität. Dieses Konzept kann in der Speicherung von Lichtenergie in photochromen metastabilen Systemen genutzt werden. Durch die Nutzung von 3-H-Thiazol-2-on als Rest im Diarylethen konnte eine signifikante pKs Änderung von 2.8 Einheiten in wässriger Umgebung erreicht werden. Dabei wurden zwei Säure-Base Gleichgewichtssysteme miteinander gekoppelt, welche an der thermischen Umwandlung gehindert sind, jedoch photochemisch ineinander überführt werden können. Des Weiteren wurde eine hohe Abhängigkeit der Quantenausbeute von dem Protonierung festgestellt. Diese wurde genutzt um die Performance der Photoreaktion zu beeinflussen. Die Beeinflussung der Photoreaktion erfolgt nicht durch Veränderung der Energetik des Grundzustandes, sondern durch Veränderung der Potentialhyperfläche des angeregten Zustandes. Durch neue molekulare Designs konnte eine signifikante Verbesserung im Vergleich zu bekannter Molekülen und Konzepten in beiden Projekten erreicht werden. / Two projects are implemented in this work, which share the goal to interconnect acid-base equilibria with the photoreactions of diarylethene (DAE) photoswitches. This task can be divided into two logic questions: How can photochemical equilibria be controlled or rather influenced via an acidic or basic stimulus and how can a photoreaction induce control over an acid-base equilibrium? In the first project, “Acid-Catalyzed Cycloreversion”, an externally tunable thermal back reaction was designed to influence a photochemical equilibrium. Upon addition of catalytic amounts of acid, a closed DAE carrying a fluorenol moiety undergoes facile thermal ring opening. The underlying thermodynamics and kinetics of the entire system have been analyzed experimentally as well as computationally. Appling an excess of acid leads to a complete inhibition of the photoreaction through the introduction of a charge-transfer. My work suggests that acid catalysis provides a useful tool to bypass thermal barriers, potentially usable to efficiently trigger the release of light energy stored in photoswitches. In the second project, entitled “Light-induced pKa Modulation”, a significant pKa change of 2.8 units in an aqueous medium was achieved by connecting two different acid-base equilibria. These thermodynamic equilibria are separated by a high activation barrier, overcome by a photoreaction. The developed system which is based on the incorporation of a 3 H thiazol 2 one moiety into a DAE, shows a strong dependency of the quantum yield and hence, of the photoconversion on the protonation state. Adjusting the pH within the range of the pKa change, a substantial enhancement of the photoconversion is achievable as well as a distinct alteration of the performance of the photoreaction. This effect does not originate from different reaction paths on the ground state potential energy surface (PES), but results presumably from a protonated state dependent difference in the excited PES.

Motion of ions under the influence of electric field has been a subject of scientific interest for many decades. Capillary electrophoresis in particular benefited greatly from this research and mathematical models of electromigration applicable to capillary electrophoresis have been developed. As the sophistication of the models grew, so did the computational demands to evaluate them. In order to fully exploit the possibilities of advanced mathematical models a computer implementation capable of solving non-trivial problems at sufficient speed is necessary. This dissertation thesis explores applications of computer implementations of mathematical models re- lated to electromigration in two different areas. The main focus of this thesis is on the topic of linear theory of electromigration. We discuss the extension of the linear theory of electromigration beyond of just acid-base equilibria and computer implementation of this extented theory which is specialized to include complex-forming equilibria in order to be able to deal with affinity capillary electrophoresis prob- lems. Some technical aspects of the computer implementation are also discussed. This is followed upon by investigating certain selected affinity capillary electrophoresis systems. The purpose of this investi- gation is to re-derive...

<p>Contest outcomes often involve some mix of skill and chance.  In three essays, I vary the sources of noise and show how player actions either influence, or are influenced by, noise.  I begin with a classic multi-battle contest, the Colonel Blotto game.  Due to his disadvantage in resources, the weak player in this contest stochastically distributes resources to a subset of battlefields while neglecting all others in an attempt to achieve a positive payoff.  In contrast, the strong player evenly distributes his resources in order to defend all battlefields, while randomly assigning extra resources to some.  Because the weak player benefits from randomizing over larger numbers of battlefields, a strong player has incentive to decrease the range over which the weak player can randomize.  When battlefields are exogenously partitioned into subsets, or \textit{fronts}, he is able to do this by decentralizing his forces to each front in a stage prior to the distribution of forces to battlefields and actual conflict.  These allocations are permanent, and each subset of battlefields effectively becomes its own, independent Blotto subgame.  I show that there exist parameter regions in which the strong player's unique equilibrium payoffs with decentralization are strictly higher than the unique equilibrium payoffs without decentralization.</p> <p><br></p> <p>In my second paper, I show how sources of exogenous noise, what Clausewitz referred to as the ``fog of war," obscure developments on the battlefield from the view of a military leader, while individual inexperience and lack of expertise in a particular situation influence his decisionmaking.  I model both forms of uncertainty using the decentralized Colonel Blotto game from the first chapter.  To do so, I first test the robustness of allocation-stage subgame perfect equilibria by changing the contest success function to a lottery, then I find the players' quantal response equilibria (QRE) to show how individual decision-making is impacted by bounded rationality and noisy best responses, represented by a range of psi values in the logit QRE.  I find that player actions rely significantly less on decentralization strategies under the lottery CSF compared to the case of the all-pay auction, owing mainly to the increased exogenous noise.  Moreover, agent QRE and heterogeneous QRE approximate subgame perfect equilibria for high values of psi in the case of an all-pay auction, but under the lottery CSF, QRE is largely unresponsive to changes in psi due to the increase in exogenous noise.</p> <p><br></p> <p>Finally, I examine a potential method for introducing noise into the all-pay auction (APA) contest success function (CSF) utilized in the Colonel Blotto games of the first two chapters.  Many contests are fundamentally structured as APA, yet there is a tendency in the empirical literature to utilize a lottery CSF when stochastic outcomes are possible or the tractability of pure strategy equilibria is desired.  However, previous literature has shown that using a lottery CSF sacrifices multiple distinguishing characteristics of the APA, such as the mixed strategy equilibria described by Baye, Kovenock, and de Vries (1996), the exclusion principle of Baye, Kovenock, and de Vries (1993), and the caps on lobbying principle of Che and Gale (1998).  I overcome this by formulating an APA that incorporates noise and retains the defining characteristics of an auction by forming a convex combination of the APA and fair lottery with the risk parameter lambda.  I prove that equilibria hold by following the proofs of Baye et al. (1996, 1993) and Che and Gale (1998), and I show the new CSF satisfies the axioms of Skaperdas (1996).  While player and auctioneer actions, payments, and revenues in the noisy APA adhere closely to the those of the APA for low levels of noise, the effect of discounted expected payoffs results in lower aggregate payments and payoffs when noise is high.  Finally, I show the noisy APA is only noise equivalent to the lottery CSF when lambda = 0, i.e., the fair lottery.</p>