title: Phase relations and binary clathrate hydrate formation in the system H2-THF-H2O.
abstract: Experimentally determined equilibrium phase relations are reported for the system H2-THF-H2O as a function of aqueous tetrahydrofuran (THF) concentration from 260 to 290 K at pressures up to 45 MPa. Data are consistent with the formation of cubic structure-II (CS-II) binary H2-THF clathrate hydrates with a stoichiometric THF-to-water ratio of 1:17, which can incorporate modest volumes of molecular hydrogen at elevated pressures. Direct compositional analyses of the clathrate phase, at both low (0.20 mol %) and stoichiometric (5.56 mol %) initial THF aqueous concentrations, are consistent with observed phase behavior, suggesting full occupancy of large hexakaidecahedral (51264) clathrate cavities by THF, coupled with largely complete (80-90%) filling of small dodecahedral (512) cages by single H2 molecules at pressures of >30 MPa, giving a clathrate formula of (H2) < or =2.THF.17H2O. Results should help to resolve the current controversy over binary H2-THF hydrate hydrogen contents; data confirm recent reports that suggest a maximum of approximately 1 mass % H2, this contradicting values of up to 4 mass % previously claimed for comparable conditions.
authors.affiliation: Centre for Gas Hydrate Research, Institute of Petroleum Engineering, Heriot-Watt University, Edinburgh EH14 4AS, U.K.
authors.forename: Ross
authors.initials: R
authors.lastname: Anderson
authors.forename: Antonin
authors.initials: A
authors.lastname: Chapoy
authors.forename: Bahman
authors.initials: B
authors.lastname: Tohidi