Clathrate and other solid phases in the tetrahydrofuran–water system: thermal conductivity and heat capacity under pressure

Abstract

Solid phases in the tetrahydrofuran–water (THF–H 2 O) system were investigated in the temperature range 100–260 K and at pressures up to 1.5 GPa. Thermal conductivity, λ, and heat capacity per unit volume, ρc p , were measured, using the transient hot-wire method. We made measurements on solid phases having nominal compositions THF•17H 2 O, THF•7 • 1H 2 O, and THF•4 • 6H 2 O, which we refer to as phases α, β, and γ, respectively. Phase α is known to be a structure II clathrate hydrate, and λ for this phase was found to be similar to other crystalline solids which are glass-like in relation to their thermal properties. Low-energy excitations are known to be relevant to the properties of glass-like solids, and, in the case of phase α, were probably rotational vibrations of the THF guest molecules. Phase β was similar, and we inferred that it was probably a structure I clathrate hydrate. Phase γ behaved nearly like a normal crystal phase at low temperatures, but λ became almost independent of temperature near melting. At 1.1 GPa and 130 K, we found evidence that phase α transformed, on pressurization, to a metastable modification which may be a new high-density form of clathrate hydrate. The astrophysical implications of our results were mentioned briefly.