Experimental and computational investigation of the sII binary He-THF hydrate

The objective of this work is to study the binary He-THF hydrate with both experimental and theoretical approaches. Experimental data for the hydrate equilibrium at pressures up to 12.6 MPa are reported for the binary He-THF hydrate with stoichiometric THF composition (i.e., 5.56 mol % THF). These data are used to calibrate a thermodynamic model [J. Phys. Chem. C2009, 113, 422] for the prediction of hydrate equilibrium that is based on the van der Waals-Platteeuw statistical thermodynamic theory. Then this model is used to extrapolate the obtained experimental data to much higher pressures, and good agreement is observed with other available experimental data at pressures up to 150 MPa. This model is also capable of estimating the cavity occupancies for He and THF. The results show that the large cavities are completely occupied by THF molecules, whereas the small ones are partially occupied by He atoms. The He occupancy of the small cavities is less than 60%, even at high pressures (100 MPa). The occupancies predicted from this model are in close agreement with similar results from molecular simulations and a previously reported thermodynamic approach.