Natural Gas (NG) plays an important role in the energy demand in the United States and throughout the world. Its characteristics as a clean, versatile and a sustainable source of energy makes it an important alternative within the spectra of energy resources. Addressing industrial and academic needs in the natural gas research area requires an integrated plan of research among experimentation, modeling and simulation. In this work, high accuracy PpT data have been measured with a high pressure single sinker magnetic suspension densimeter. An entire uncertainty analysis of this apparatus reveals that the uncertainty of the density data is less that 0.05% across the entire ranges of temperature (200 to 500) K and pressure (up to 200 MPa). These characteristics make the PpT data measured in this study unique in the world. Additionally, both a low pressure (up to 35 MPa) and a high pressure (up to 200 MPa) isochoric apparatus have been developed during the execution of this project. These apparatuses, in conjunction with a recently improved isochoric technique, allow determination of the phase envelope for NG mixtures with an uncertainty of 0.45% in temperature, 0.05% in pressure and 0.12% in density. Additionally, an innovative technique, based upon Coherent Anti-Stokes Raman Scattering (CARS) and Gas Chromatography (GC), was proposed in this research to minimize the high uncertainty introduced by the composition analyses of NG mixtures. The collected set of P?T and saturation data are fundamental for thermodynamic formulations of these mixtures. A study at the molecular level has provided molecular data for a selected set of main constituents of natural gas. A 50-50% methane-ethane mixture was studied by molecular dynamics simulations. The result of this study showed that simulation time higher than 2 ns was necessary to obtain reasonable deviations for the density determinations when compared to accurate standards. Finally, this work proposed a new mixing rule to incorporate isomeric effects into cubic equations of state.

The scale of the energy business today and a favorable and promising economic environment for the production of natural gas, requires study of the thermophysical behavior of fluids: sophisticated experimentation yielding accurate, new volumetric data, and development and improvement of thermodynamic models. This work contains theoretical and experimental contributions in the form of 1) the revision and update of a field model to calculate compressibility factors starting from the gross heating value and the mole fractions of diluents in natural gas mixtures; 2) new reference quality volumetric data, gathered with state of the art techniques such as magnetic suspension densimetry and isochoric phase boundary determinations; 3) a rigorous first-principles uncertainty assessment for density measurements; and 4) a departure technique for the extension of these experimental data for calculating energy functions. These steps provide a complete experimental thermodynamic characterization of fluid samples. A modification of the SGERG model, a standard virial-type model for prediction of compressibility factors of natural gas mixtures, matches predictions from the master GERG-2008 equation of state, using least squares routines coded at NIST. The modification contains new values for parametric constants, such as molecular weights and the universal gas constant, as well as a new set of coefficients. A state-of-the-art high-pressure, single-sinker magnetic suspension densimeter is used to perform density measurements over a wide range of temperatures and pressures. This work contains data on nitrogen, carbon dioxide, and a typical residual gas mixture (95% methane, 4% ethane, and 1% propane). Experimental uncertainty results from a rigorous, first-principles estimation including composition uncertainty effects. Both low- and high-pressure isochoric apparatus are used to perform phase boundary measurements. Isochoric P-T data can determine the phase boundaries. Combined with density measurements, isochoric data provides isochoric densities. Further mathematical treatment, including noxious volume and thermal expansion corrections, and isothermal integration, leads to energy functions and thus to a full thermodynamic characterization.

L'interaction d'impulsions lasers brèves et intenses avec un plasma est une source intéressante d'ions énergétiques. Les travaux effectués au cours de cette thèse s'articulent autour de deux grandes thématiques : la production de protons par laser, et leur utilisation pour le chauffage isochore, avec, pour principal outil d'étude, la simulation à l'aide de codes numériques (cinétique particulaire et hydrodynamique). Dans un premier temps, nous avons étudié le comportement de l'énergie cinétique maximale des protons qu'il est possible d'accélérer avec le mécanisme du Target Normal Sheath Acceleration (TNSA), en régime sub-ps, en fonction de différents paramètres, notamment de la durée d'impulsion laser. Nous avons montré que l'allongement de la durée d'impulsion, à énergie laser constante, est responsable du préchauffage et de la détente du plasma avant l'arrivé du pic d'intensité. Les gradients de densité ainsi produits (face avant et face arrière) peuvent favoriser, ou au contraire pénaliser, le gain en énergie cinétique des protons. Les résultats obtenus ont servi à l'interprétation d'une étude expérimentale réalisée au Laboratoire d'Optique Appliquée. Nos efforts se sont ensuite concentrés sur l'élaboration d'un modèle semi-analytique rendant compte de l'énergie cinétique maximale des protons accélérés par le biais du TNSA. Ce modèle permet de retrouver l'ordre de grandeur des intensités nécessaires, de l'ordre de 6x1021 W/cm², pour atteindre des énergies de proton supérieures à 150 MeV avec des impulsions laser de quelques joules et plusieurs dizaines de fs. Dans la dernière partie de cette thèse, nous nous sommes intéressés à l'utilisation de ces faisceaux de protons pour le chauffage isochore. Nous avons caractérisé, dans un premier temps, les fonctions de distribution produites par des cibles composées d'un substrat lourd (A >> 1) sur la face arrière duquel est déposé un plot d'hydrogène (schéma d'Esirkepov). Ensuite, à partir de simulations hydrodynamiques, nous avons étudié le temps caractéristique de détente de la cible chauffée en modifiant des paramètres tels que la distance à la source de protons, l'intensité et la tache focale du laser, et la densité surfacique du plot. Nous avons enfin étendu cette étude aux cibles cylindriques et nous avons montré qu'il est possible de réduire les effets liés à la divergence naturelle du faisceau de protons et ainsi d'obtenir des températures plus élevées. / The interaction of ultra-high intensity, ultra-short laser pulses with matter is an interesting source of energetic ions. During this work, we studied the production of energetic protons and their application to isochoric heating using kinetics and hydrodynamics code. We first considered the behavior of the maximum proton kinetic energy with the Target Normal Sheath Acceleration (TNSA) mechanism, in the sub-ps interaction regime, as a function of different parameters, especially the laser pulse duration. We showed that stretching the pulse duration, with a constant laser energy, led to the preheating and the expansion of the plasma slab. This expansion can be beneficial or detrimental regarding the maximum proton kinetic energy. The results we obtained helped to explain an experimental study carried out at the Laboratoire d'Optique Appliquée. We then developed a semi-analytical model trying to describe the maximum proton kinetic energy that can be produced in the TNSA regime. The results we obtained can retrieve the minimum intensity, of the order of 6x1021 W/cm², that is required to reach proton energies of 150 MeV with femtosecond, few joules laser pulses. As a final step, we were interested in the use of these proton beams for isochoric heating. We first characterized the proton distribution function produced by targets consisting in an heavy substrate with an hydrogen is deposited at the rear side. By the mean of hydrodynamics simulations, we studied the characteristic expansion time of the heated target by varying several parameters such as the heated sample distance from the proton source, the intensity and focal spot size of the laser, and the areal density of the dot. Finally, we extended the previous study to cylindrical targets and we demonstrated that it is possible to counterbalance the natural divergence of the proton beam and hence, to reach higher temperatures.