NMR study of methane + ethane structure I hydrate decomposition.

The thermally activated decomposition of methane + ethane structure I hydrate was studied with use of 13C magic-angle spinning (MAS) NMR as a function of composition and temperature. The observed higher decomposition rate of large sI cages initially filled with ethane gas can be described in terms of a model where a distribution of sI unit cells exists such that a particular unit cell contains zero, one, or two methane molecules in the unit cell; this distribution of unit cells is combined to form the observed equilibrium composition. In this model, unit cells with zero methane molecules are the least stable and decompose more rapidly than those populated with one or two methane molecules leading to the observed overall faster decomposition rate of the large cages containing ethane molecules.

Direct measure of the hydration number of aqueous methane.

A hydration number of 20 has been measured for aqueous CH4 in the temperature range 273-298 K on the basis of the simultaneous observation of the 13C isotropic resonance lines of CH4 in both aqueous solution and the dodecahedral cage of CH4 structure I hydrate. Additional experimental evidence and analysis reported in this paper suggest that the dominant aqueous hydration number of methane is 20.