A model has been developed permitting to accurately predict on molecular level phase diagram of the clathrate hydrates. This model allows to take into account the influence of guest molecules on the host lattice and to extend the interval of temperatures and pressures of computed thermodynamic potentials and significantly improves known van der Waals and Platteeu theory. The theoretical study of phase equilibrium in gas-gas hydrate-ice Ih system for methane and xenon hydrates has been performed. The obtained results are in a good agreement with experimental data. A new interpretation of so-called self-preservation effect has been proposed. The self-preservation of gas hydrates can be connected with differences in thermal expansions of ice Ih and gas hydrates. This is confirmed by calculations performed for methane and mixed methane-ethane hydrates.
The theory developed in our earlier papers is extended to predict dynamical and thermodynamic properties of clathrate structures by accounting for the possibility of multiple filling of cavities by guest molecules. The method is applied to the thermodynamic properties of argon and krypton hydrates, considering both structures I (sI) and II (sII), in which the small cages can be singly occupied and large cages of sII can be singly or doubly occupied. It was confirmed that the structure of the clathrate hydrate is determined by two main factors: intermolecular interaction between guest and host molecules and the configurational entropy. It is shown that for guests weakly interacting with water molecules, such as argon or krypton, the free energy of host lattices without the contribution of entropy is the main structure-determining factor for clathrate hydrates, and it is a cause of hydrate sII formation at low pressure with these guests. Explicit account of the entropy contribution in the Gibbs free energy allows one to determine the stability of hydrate phases and to estimate the line of structural transition from sII to sI in P-T plane. The structural transition between sII and sI in argon and krypton hydrates at high pressure is shown to be the consequence of increasing intermolecular interaction and the degree of occupancy of the large cavities.
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