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Analyses de microvolumes de gaz par spectroscopie Raman : expériences quantitatives et modélisation des mélanges CO₂-CH₄-N₂

Abstract : Quantitative knowledge of species trapped within fluid inclusions provides key information to better understand geological processes as well as to reconstruct the conditions of paleofluid circulation. CO₂, CH₄, and N₂ are among the most dominant gas species omnipresent in various geological environments, but their quantitative PVX calibration data are not fully established yet. Using the previously published data can therefore lead to non-quantified errors, especially when applied to geological fluids containing generally several substances at elevated pressure and density. The aim of this work is to provide accurate calibration data for the simultaneous determination of PVX properties of pure gases or any binary and ternary mixtures of CO₂, CH₄, and N₂ over 5 to 600 bars at a fixed temperature, directly from Raman spectra. For this, gas mixtures were prepared and compressed using a mixer (GasMix AlyTech) coupled with a homemade pressurization system. Raman in situ analyses of gas mixtures were performed at controlled conditions using an improved HPOC system (High-Pressure Optical Cell) with a transparent microcapillary containing the prepared gas mixtures, placed on a heating-cooling stage (Linkam CAP500). Overall, the uncertainty of the measurement of the PVX properties of fluid inclusions from our calibration equations at 22 or 32 °C is < ± 1 mol%, ~ ± 20 bars, and ~ ± 0.02³ for molar proportion, pressure and density, respectively. The ensuing aim of the project is to interpret the variation trends of the peak position of the CH₄ and N₂ ν1 band for an in-depth understanding. Two theoretical models, i.e., Lennard-Jones 6-12 potential energy approximation and Perturbed hard-sphere fluid model were involved to quantitatively assess the contribution of the attractive and repulsive intermolecular interaction forces to the pressure-induced frequency shifts. A predictive model was also provided to predict the variation trend of the CH₄ ν1 band over a pressure range up to 3000 bars as a function of pressure and composition. Furthermore, the applicability of our calibration data to other laboratories and apparatus and to gas mixtures that contain a small amount of other species (e.g., H2, H2S) was discussed and evaluated. New universal calibration data applicable for other laboratories were then provided. A computer program “FRAnCIs” was also developed to make the application of our calibration data as convenient as possible via a user-friendly interface.
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Submitted on : Friday, February 26, 2021 - 1:09:47 PM
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Van-Hoan Le. Analyses de microvolumes de gaz par spectroscopie Raman : expériences quantitatives et modélisation des mélanges CO₂-CH₄-N₂. Géochimie. Université de Lorraine, 2020. Français. ⟨NNT : 2020LORR0178⟩. ⟨tel-03153454⟩



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