Characterization of natural gas hydrates by nuclear magnetic resonance and dielectric relaxation

Abstract

Continuous-wave proton nmr spectra of the clathrate hydrates and/or deuteriohydrates of methane, ethane, propane, isobutane, and neopentane–D2S have been recorded down to 2 K. Between 50 and 200 K each H2O hydrate spectrum consists of a line 3 to 4 G wide from reorienting guest molecules and a broader band from rigid water molecules. Line shapes characteristic of non-rotating guests are obtained in D2O hydrates at low temperatures, except for methane which gives a narrow line to 2 K. Neopentane, shown for the first time to be capable of enclathration, exhibits a Resing effect and other features related to its tetrahedral symmetry. Low-temperature dielectric absorption from reorienting guest-molecule dipoles has been measured in H2S, propane, isobutane, and n-butane–H2S hydrates. For steric reasons n-butane is encaged as a gauche rather than the trans isomer. Average barriers to reorientation estimated from nmr and dielectric data are 1.2 kcal/mol for ethane in type I hydrate and 0.6, 1.2, 1.4, and 0.8 kcal/mol for propane, isobutane, n-butane, and neopentane in type II.