Clathrate Ices—Recent Results

Abstract

Abstract The last five years have seen an increasing interest in clathrate ices as a result of the discovery of extensive deposits of natural gas hydrates in permafrost regions. Twenty-six new clathrate hydrates have been identified, mainly by NMR, including a tetragonal hydrate of dimethyl ether. N-butane and neopentane have been found to be enclathrated in natural gas hydrates, the former as a gauche conformer. As a result of their high symmetries, encaged neopentane, CF4, SF6, and SeF6 exhibit a Resing apparent-phase-change effect in the temperature range of NMR line narrowing. There is increasing evidence that reorientational jumps of water molecules are more frequent than translational jumps in clathrate ices. This is certainly so for ethylene oxide-d4 and tetrahydrofuran-d8 hydrates for which two regions of proton line narrowing and two T 1ρ minima have been observed. The reorientational motions of most guest molecules in structure II hydrates only become isotropic on a time scale long enough to permit the cage configurations to be averaged to 4 3m symmetry by reorientation of the water molecules. The orientations of the water molecules remain disordered to the lowest temperatures.