Determining the three-phase coexistence line in methane hydrates using computer simulations

Molecular dynamics simulations have been performed to estimate the three-phase (solid hydrate-liquid water-gaseous methane) coexistence line for the water-methane binary mixture. The temperature at which the three phases are in equilibrium was determined for three different pressures, namely, 40, 100, and 400 bar by using direct coexistence simulations. In the simulations water was described by using either TIP4P, TIP4P/2005, or TIP4P/Ice models and methane was described as simple Lennard-Jones interaction site. Lorentz-Berthelot combining rules were used to obtain the parameters of the cross interactions. For the TIP4P/2005 model positive deviations from the energetic Lorentz-Berthelot rule were also considered to indirectly account for the polarization of methane when introduced in liquid water. To locate the three-phase coexistence point, two different global compositions were used, which yielded (to within statistical uncertainty) the same predictions for the three-phase coexistence temperatures, although with a somewhat different time evolution. The three-phase coexistence temperatures obtained at different pressures when using the TIP4P/Ice model of water were in agreement with the experimental results. The main reason for this is that the TIP4P/Ice model reproduces the melting point of ice I-h. (C) 2010 American Institute of Physics. [doi:10.1063/1.3466751]