Thermodynamics and hydrogen storage ability of binary hydrogen + help gas clathrate hydrate

Storage of hydrogen as hydrogen hydrate is a promising alternative technology to liquefied hydrogen at cryogenic temperatures or compressed hydrogen at high pressures. In this paper, computer simulation is performed based on the solid solution theory of clathrates of van der Waals and Platteeuw with some modifications that include in particular the account of multiple cage occupancies and host relaxation. The quasiharmonic lattice dynamics method employed here gives the free energy of clathrate hydrate to first order in the anharmonicity of intermolecular potential and permits to take into account quantum zero-point vibration of host lattice and hydrogen in the cages. It is employed to study the thermodynamic functions of binary (mixed) H ₂CH₄ hydrates of cubic structure II (sII) and hexagonal structure H (sH). It is shown that at divariant equilibrium "gas phasegas hydrate" with increasing pressure the filling of large cavities by hydrogen proceeds gradually from single filling to the maximal number of hydrogen molecules in clusters included in large cages (four in sII and five in sH) preserving stability of the hydrogenmethane hydrates sII and sH. The results show that mass fraction of hydrogen in the mixed sH hydrate is significantly lower than in the mixed sII hydrate. Pressure of monovariant equilibrium "IceIhgas phasemixed sII hydrate" with increasing methane concentration in the gas phase lowers in comparison with the pressure of pure hydrogen hydrate formation. For the mixed hydrogen + methane sH hydrates, it was demonstrated that thermodynamic stability depends on the filling degree of small cavities by methane molecules and stability area shifts to lower pressure with increasing filling.