Calculation of Liquid Water-Hydrate-Methane Vapor Phase Equilibria from Molecular Simulations
Publication: Research - peer-review › Journal article – Annual report year: 2010
Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled using the TIP4P/ice potential and a united-atom Lennard-Jones potential. respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials. (ii) calculation of the chemical potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated for pressures ranging from 20 to 500 bar and is shown to follow the Clapeyron behavior, in agreement with experiment; coexistence temperatures differ from the latter by 4-16 K in the pressure range studied. The enthalpy of dissociation extracted from the calculated P-T curve is within 2% of the experimental value at corresponding conditions. While computationally intensive, simulations such as these are essential to map the thermodynamically stable conditions for hydrate systems.
| Original language | English |
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| Journal | Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical |
| Publication date | 2010 |
| Volume | 114 |
| Journal number | 17 |
| Pages | 5775-5782 |
| ISSN | 1520-6106 |
| DOIs | |
| State | Published |
| Citations | Web of Science® Times Cited: 18 |
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ID: 4496819