Molecular Dynamics Simulations and Flow Injection Studies of Hydrothermal Fluids

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Plugatyr, Andriy
hydrothermal , molecular dynamics , flow injection
Hydrothermal fluids near and above the critical point of water have unique and potentially very useful thermophysical properties. At present, the lack of knowledge of supercritical water chemistry hinders implementation of innovative hydrothermal technologies. The development of new experimental methods and application of molecular modeling tools is clearly warranted to provide a better understanding of the complex properties of aqueous systems at elevated temperatures and pressures. The thermodynamic, dielectric and transport properties of hydrothermal fluids are investigated using Molecular Dynamics (MD) simulation and flow injection techniques. The spatial hydration structures and self-diffusion coefficients of phenol, aniline and naphthalene in aqueous infinitely dilute solution are examined from ambient to supercritical conditions by means of MD simulations. It is shown that the solvation shell around aromatic molecules undergoes significant changes along the liquid-vapour coexistence curve and, essentially, disappears at supercritical conditions. The changes in hydration structures are reflected in the values of the self-diffusion coefficients which dramatically increase near the critical point of water. The thermodynamic and dielectric properties of the Simple Point Charge Extended (SPC/E) water model are examined over a broad range of sub- and supercritical states. Accurate thermodynamic and dielectric equations of state (EOS) for the SPC/E water model are presented. The parameterizations provide the most accurate, up-to-date description of the properties of high-temperature SPC/E water, thus enabling for the direct comparison of molecular simulation results with experimental data via the corresponding states principle. The experimental methodology for the study of aqueous fluids at extreme conditions by using the ex situ flow injection technique is presented. The methodology significantly simplifies the technical aspects of flow injection analysis in hydrothermal fluids as sample injection and detection are performed at ambient temperature, thus allowing the use of standard on-line detection methods. The proposed ex situ experimental technique is applied to the examination of the hydrodynamic regime of a flow-through tubular reactor from ambient to supercritical water conditions. Application of the ex situ Taylor dispersion technique to measurements of the binary diffusion coefficients in hot compressed water is also presented. The ex situ flow injection methodology provides a basis for further development of flow injection analysis techniques at supercritical water conditions.
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