In recent years, the enthalpy raise hot channel factor limit has decreased significantly due to the power upgrade of Ringhals 4 and the use of shielding fuel assemblies. The shielding fuel assemblies task are to reduce the neutron leakage to the reactor vessel and in that way extend the reactor lifetime. This is achieved by replacing a few fuel rods with steel rods. Experiences from the last fuel cycles show that the core design procedure has been hampered because of this and that it’s hard to stay under the design limit. A way to overcome this problem and to improve the fuel economy is to introduce the use of radial enrichment distribution in the fuel assembly. This master thesis shows, through a case study of three fuel cycles at Ringhals 4,  that the internal peaking factor can be improved by roughly 2–3 % and that the maximum enthalpy raise hot channel factor can be improved by about 2.0–2.5 % if the fuel assemblies contain three different levels of enrichments instead of currently one. This can be achieved without any noticeable decrease in cycle length. / Genom en fallstudie av tre driftcykler för Ringhals 4 visar den här rapporten att max FΔH under cykeln kan sänkas med 2,0–2,5 % om bränsleknippena radiellt anrikningsoptimeras med minst tre delanrikningar. Totalt under cykeln kan FΔH sänkas med upp till 4 %. Om radiell anrikningsoptimering införs för Vattenfalls PWR:er skulle arbetet med att designa härdarna förenklas och utrymme ges för att ladda reaktorerna på ett mer ekonomiskt sätt.

Les simulations numériques sont devenues un outil indispensable dans la conception des chambres de coupure des disjoncteurs électriques haute tension. Elles sont utilisées non seulement dans le dimensionnement des différentes pièces, mais elles fournissent également une aide précieuse dans la compréhension des phénomènes intervenant entre les deux électrodes au moment de la coupure. L’arc électrique généré entre ces deux électrodes rassemble de nombreux domaines de la physique plus ou moins complexes. Tous ces phénomènes ne sont pas encore parfaitement compris. Avec l’évolution de la puissance de calcul, ces simulations peuvent prendre en compte de plus en plus de phénomènes. Mais pour des raisons de temps de développement, la question des phénomènes à prendre en compte dans ces simulations se pose. Le but de telles simulations est de déterminer de manière rapide si une configuration est plus ou moins capable qu’une autre de couper sous une contrainte donnée. Ainsi, il est important de prendre en compte uniquement les phénomènes physiques importants et nécessaires pour avoir une réponse la plus décisive possible et la plus rapide possible, de la réussite ou non à la coupure d’une configuration testée. Dans cette thèse, nous nous sommes particulièrement intéressés aux déséquilibres thermiques et chimiques qui pourraient intervenir dans les disjoncteurs électriques haute tension au moment de la coupure. En effet, pour des raisons de temps et de coût de calcul, la plupart des simulations numériques actuelles sont réalisées en faisant une hypothèse forte : l’hypothèse d’Equilibre Thermodynamique Local (ETL). Cette hypothèse consiste à considérer que dans chaque maille de notre domaine d’étude et à chaque pas de temps, on a un équilibre thermodynamique réalisé. Faire cette hypothèse nous permet d’utiliser les lois de conservation (masse, quantité de mouvement et énergie) en allégeant le problème. Mais en réalité, cette hypothèse est mise à mal dès que l’on est en présence de forts gradients de température ou de densité. Pour réaliser ces simulations, le code numérique CARBUR a été utilisé. Des modules d’arc électrique (effet Joule et rayonnement) et d’électrode mobile ont été implémentés afin de pouvoir simuler au mieux le comportement du gaz présent dans les disjoncteurs électriques haute tension. Six études différentes ont été réalisées et sont présentées. Ces études portent sur les influences de la forme du bout des électrodes, d’une modélisation en Navier-Stokes par rapport à une modélisation en Euler, de la nature du gaz (SF6, CO2 et N2), du déséquilibre thermique dans le cas de l’azote ou encore du positionnement des termes sources de l’arc électrique dans les différentes équations d’évolution des énergies. Dans ce travail, une étude sur différents modèles cinétiques chimiques est proposée. Dans ces modèles, 5 espèces chimiques sont présentes : N2, N, N+, N2+ et e-. En ce qui concerne la température, on en distingue 4 : T, TVib-N2, TVib-N2+ et Te. / The numerical simulations are become a very important tool to design the high voltage circuit breaker (HVCB) chamber. They help for the understanding of the different phenomena which can take place between the 2 electrodes during an interruption process. The electric arc brings together many fields of physics more or less complex and many of these phenomena are still poorly studied. So many aspects remain to be explored to improve simulations. With the increase of the calculation power, these numerical simulations can take into account more phenomena. However, for reasonable simulation times, we need to know which phenomena are preponderant. The aim of these numerical simulations is to rapidly conclude on the capacity of geometry to success an interruption process compared to different other geometries, under a given stress. In this PhD dissertation, we are particularly interested on thermal and chemical non equilibrium that can occur in HVCB during an interruption process. Currently, most simulations are carried out with a strong hypothesis: the hypothesis of Local Thermodynamic Equilibrium (LTE). This assumption allows us to alleviate the problem and to reduce the computing time. But this assumption becomes not valid when high temperature or density gradients occur. To do these simulations, the CARBUR numerical code has been used. In order to simulate flow behaviors in HVCB, an electrical arc (Joule effect and radiation) model and a module of mobile electrode have been added. Six different studies have been done and are presented: influence of the electrode shape, influence of the Navier-Stokes equations compared to the Euler equations, influence of the gas (SF6, CO2 et N2), influence of the thermal non equilibrium in a nitrogen case, influence of the position of the arc source terms in the different energy equations. In this work, a study on different nitrogen chemical kinetics is proposed. In these models, 5 chemical species are distinguished: N2, N, N+, N2+ and e-. Finally, 4 different temperatures are used: T, TVib-N2, TVib-N2+ and Te.

Ce travail porte sur la contribution à la modélisation thermodynamique d'un atelier de purification d'acide acrylique. Après l'identification des principaux produits intervenant dans l'étape de purification et la collecte de leurs propriétés thermodynamiques disponibles dans la littérature, nous avons effectué une série de mesures expérimentales pour un ensemble de mélanges contenant des acides carboxyliques (en particulier : diagrammes d'équilibres liquide-liquide et équilibres liquide-vapeur, enthalpies d'excès et volumes d'excès). L'ensemble des données (nos mesures et les valeurs de la littérature) a été exploité selon deux approches de modélisation des équilibres liquide-vapeur : une approche symétrique (φ-φ) appliquée aux équations d'état de Peng-Robinson (P-R) et de PC-SAFT et une approche dissymétrique (γ-φ) appliquée aux modèles de coefficients d'activité en phase liquide NRTL, UNIQUAC et Van Laar associés à diverses équations d'état en phase vapeur (gaz parfait, Viriel, Hayden et O'Connell et Nothnagel). Nous avons finalement retenu le modèle UNIQUAC associé à la corrélation de Hayden et O'Connell en phase vapeur. Des nouveaux paramètres d'interaction ont été déterminés et conduisent à des résultats homogènes et satisfaisants en comparaison avec nos mesures expérimentales et aux données de la littérature. Ils permettent également de décrire convenablement les diagrammes d'équilibres liquide-vapeur et les volatilités relatives des mélanges étudiés / This work focuses on the contribution in the thermodynamic modeling of an acrylic acid purification unit. After identifying the main products involved in the purification step and collecting their thermodynamic properties available in the literature, we conducted a series of experimental measurements for a range of mixtures containing carboxylic acids(mainly liquid-liquid equilibrium and vapor-liquid equilibrium diagrams, excess enthalpies and excess volumes).The data set-our measurements and literature values-was used according to two approaches for modeling vapor-liquid equilibrium: a symmetric approach(φ-φ) applied to the equations of state Peng-Robinson (P-R) and PC-SAFT and an asymmetrical approach (γ-φ) applied to the models of activity coefficients in the liquid phase NRTL, UNIQUAC and Van Laar associated with various equations of state in the vapor phase(ideal gas, Viriel, Hayden O'Connell and Nothnagel). We have finally chosen the UNIQUAC thermodynamic model associated with the correlation of Hayden O'Connell in vapor phase. New binary parameters were determined and led to consistent and satisfactory results in comparison with our experimental measurements and literature data. These parameters can also be used to adequately describe the diagrams of vapor-liquid equilibrium and the relative volatilities of the mixtures studied

The Ph.D. project compiled in this thesis has focused on the role of the solvent in solid-liquid phase equilibria and in nucleation kinetics. Six organic substances have been selected as model compounds, viz. ortho-, meta- and para-hydroxybenzoic acid, salicylamide, meta- and para-aminobenzoic acid. The different types of crystal phases of these compounds have been explored, and their respective solid-state properties have been determined experimentally. The solubility of these crystal phases has been determined in various solvents between 10 and 50 oC. The kinetics of nucleation has been investigated for salicylamide by measuring the metastable zone width, in five different solvents under different experimental conditions. A total of 15 different crystal phases were identified among the six model compounds. Only one crystal form was found for the ortho-substituted compounds, whereas the meta-isomeric compounds crystallized as two unsolvated polymorphs. The para-substituted isomers crystallized as two unsolvated polymorphs and as several solvates in different solvents. It was discovered that the molar solubility of the different crystal phases was linked to the temperature dependence of solubility. In general, a greater molar solubility corresponds to a smaller temperature dependence of solubility. The generality of this relation for organic compounds was investigated using a test set of 41 organic solutes comprising a total of 115 solubility curves. A semi-empirical solubility model was developed based on how thermodynamic properties relate to concentration and temperature. The model was fitted to the 115 solubility curves and used to predict the temperature dependence of solubility. The model allows for entire solubility curves to be constructed in new solvents based on the melting properties of the solute and the solubility in that solvent at a single temperature. Based on the test set comprising the 115 solubility curves it was also found that the melting temperature of the solute can readily be predicted from solubility data in organic solvents. The activity of the solid phase (or ideal solubility) of four of the investigated crystal phases was determined within a rigorous thermodynamic framework, by combining experimental data at the melting temperature and solubility in different solvents and temperatures. The results show that the assumptions normally used in the literature to determine the activity of the solid phase may give rise to errors up to a factor of 12. An extensive variation in the metastable zone width of salicylamide was obtained during repeated experiments performed under identical experimental conditions. Only small or negligible effects on the onset of nucleation were observed by changing the saturation temperature or increasing the solution volume. The onset of nucleation was instead considerably influenced by different cooling rates and different solvents. A correlation was found between the supersaturation ratio at the average onset of nucleation and the viscosity of the solvent divided by the solubility of the solute. The trends suggest that an increased molecular mobility and a higher concentration of the solute reduce the metastable zone width of salicylamide. / QC 20100831

Two gas-phase ion-molecule reaction systems are presented here based on measurements done in a temperature variable 22-pole trapping machine. In the first case, the proton affinity of methane is determined based on a new technique for measuring the equilibrium constant of the HCO2+ + CH4 <=> CH5+ + CO2 reaction. The second case reports to the (Ar + N2 )+ reaction system, with reaction rate temperature dependencies measurements made both in the forward and reverse direction with different and complementary methods. The temperature variable 22-pole trapping machine allows one to determine equilibrium constants and reaction rate coefficients over a wide range of temperatures. The coupling of an effusive beam to the setup overcomes the problem of neutral gas wall condensation and extends the temperature range measurements beyond condensation point. The introduction (Chapter 1) gives a short overview about the rf technology and parallel experimental techniques developed in order to better characterize and understand the several mechanisms related to ion-molecule reactions. It also focuses some aspects of reaction rate temperature dependencies determination as well as thermodynamical equilibrium in laboratory environment. A short description of the setup and experimental methods are presented in Chapter 2. Based on equilibrium constant measurements, Chapter 3 is dedicated to the proton affinity of methane. This concept has applications on several fields such as atmospheric and combustion modelling, or testing empirical and ab initio theories for electronic structures. The (Ar − N2 )+ system presented in Chapter 4, is known for being a good case study for inferring the role of vibrational excitation in reaction dynamics and to the existence of non-adiabatic coupling. The experimental results here presented for the N2+ + Ar reaction demonstrate that it is possible to avoid parallel reactions with first vibrational excited state of nitrogen (N2 (ν = 1)). On the other hand, the reverse reaction experiments confirm the existence of a minimum of the reaction rate in the 30 to 300 K range, due to the existence of two reaction channels. The question of the high rate coefficient towards lower temperatures being related to the N2 rotational ground state population is raised. A summary and outlook are presented in Chapter 5, where some new possible paths of investigation are pointed out.

The majority of structural studies on DNA have been carried out using fibre diffraction, while studies of its dynamics and thermal behaviour have been mainly performed in solution. When the DNA double helix is heated, it exhibits local separation of the two strands that grow in size with temperature and lead to their complete separation. This work has investigated various aspects of this phenomenon. The experiments reported in this thesis were carried out on films of oriented fibres of DNA prepared with the Wet Spinning Apparatus. Thus, sample preparation and characterisation are essential parts of the research. The structures of two forms of DNA, A and B, have been explored as a function of relative humidity at fixed ionic conditions. A method to eliminate traces of ever-present B-form contamination in A-form samples was established. The high orientation of the DNA molecules within the samples allowed us to investigate dynamical fluctuations and the melting transition of DNA using neutron scattering, which can provide the spatial information crucial to understand a phase transition, probing the static correlation length along the molecule as a function of temperature. The transition has been investigated for A and B-forms in order to understand its dependence on molecular configuration.Furthermore, after the first melting, denatured DNA films show typical glass behaviour. Their thermal relaxation has been explored using calorimetry.Neutron and X-ray inelastic scattering (INS and IXS) were used in the past to measure longitudinal phonons in fibre DNA, and the results shown disagreement. Recent INS measurements supported with phonon simulations have been crucial to understand the different dispersion curves reported to date. Experiments using INS and IXS have been carried out to continue with this investigation. Attempts to observe the transverse fluctuations associated to the thermal denaturing of DNA, never experimentally investigated before, have been made.

Previous studies of short DNA hairpins have revealed that loop and stem sequences can significantly affect the thermodynamic stability of short DNA hairpins. Nevertheless, there has not been sufficient investigation into the pressure-temperature stability of DNA hairpins, and the current thermodynamic knowledge of DNA hairpins’ stability is limited to the temperature domain. In this work, we report the effect of hydrostatic pressure on the helix-coil transition temperature (TM) for eleven short DNA hairpins at different salt concentrations by performing UV-monitored melting. The studied hairpins form by intramolecular folding of 16-base self-complementary DNA oligo¬deoxy¬ribonucleotides. Model dependent (van’t Hoff) transition parameters such as ΔHvH and transition volume (ΔV) were estimated from analysis of optical melting transitions. Experiments revealed the ΔV for denaturation of these molecules range from -2.35 to +6.74 cm3mol-1. The difference in the volume change for this transition is related to differences in the hydration of these molecules.

Previous studies of short DNA hairpins have revealed that loop and stem sequences can significantly affect the thermodynamic stability of short DNA hairpins. Nevertheless, there has not been sufficient investigation into the pressure-temperature stability of DNA hairpins, and the current thermodynamic knowledge of DNA hairpins’ stability is limited to the temperature domain. In this work, we report the effect of hydrostatic pressure on the helix-coil transition temperature (TM) for eleven short DNA hairpins at different salt concentrations by performing UV-monitored melting. The studied hairpins form by intramolecular folding of 16-base self-complementary DNA oligo¬deoxy¬ribonucleotides. Model dependent (van’t Hoff) transition parameters such as ΔHvH and transition volume (ΔV) were estimated from analysis of optical melting transitions. Experiments revealed the ΔV for denaturation of these molecules range from -2.35 to +6.74 cm3mol-1. The difference in the volume change for this transition is related to differences in the hydration of these molecules.

In dieser Arbeit wurde die Möglichkeit untersucht, Bortrihalogenide mit Wasserstoff unter milden Bedingungen (T < 100 °C, p(H2) < 50 bar) zu hydrieren. Um eine Triebkraft für die thermodynamisch ungünstige Reaktion zu erhalten, wurden Amine als Hilfsbasen zugesetzt, welche den bei der Reaktion entstehenden Halogenwasserstoff als Ammoniumsalz binden und damit das Reaktionsgleichgewicht in Richtung der Produkte verschieben. Es wurden dafür verschiedene Amin-Boran bzw. Amin-HCl Addukte synthetisiert und mittels IR, NMR und DSC charakterisiert. Bei den anschließenden Hydrierungsversuchen wurden verschiedene Katalysatoren auf ihre Eignung getestet und weiterentwickelt. Unterstützt wurden die experimentellen Arbeiten durch Berechnungen mit Gaussian 03. IR- und NMR-Spektren vieler Addukte wurden berechnet und freie Reaktionsenthalpien der Hydrierung in Abhängigkeit des verwendeten Amins und Borhalogenids bestimmt. Mögliche Übergangszustände wurden diskutiert und ihre Aktivierungsenergien ermittelt.

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