Dielectric properties of the hydrates of argon and nitrogen

Abstract

The dielectric relaxation of water in the structure I clathrate hydrates of argon and nitrogen was studied over a range of temperature and pressure. Hydrates were slowly grown at pressures of 1 to 2 kbar in a coaxial cell enclosed in a pressure vessel. The complex permittivity loci resemble circular arcs with static dielectric constants of ~56 at 0 °C and high-frequency dielectric constants of 2.85 ± 0.05. Relaxation near 0 °C is about as slow as in ice I, but activation energies and entropies are much smaller. Formation of Bjerrum defects probably takes place preferentially near the occasional sites at which argon and nitrogen molecules have replaced water molecules in the lattice. The much faster relaxations found previously in the isostructural hydrates of ethers arise from orientational defects induced in the water lattice by the encaged molecules, a small proportion of which may form hydrogen bonds with water. The effect of small gaps in series with samples showing circular-arc dispersion behavior was evaluated.