In situ X-ray diffraction measurements of the self-preservation effect of CH4 hydrate

In situ observations of CH4 hydrate dissociation using X-ray diffraction we re carried out at atmospheric pressure and at both 168 and 189 K. Dissociat ion rates of the hydrate and the rate of transformation into hexagonal ice were measured using time-resolved energy-dispersive X-ray diffraction. The dissociation of CH4 hydrate had an initially fast regime followed by slower dissociation. Thus, the data support a previously suggested two-step proce ss. In addition, we observed dynamic behavior of the X-ray diffraction inte nsities of ice lh, which implies a transient crystal structure at the begin ning of the dissociation. Our analyses indicates that the first step, which lasted several tens of minutes, was the formation of an ice Ih layer aroun d the CH4 hydrate, and the second step was relatively slow because the CH4 had to diffuse through the thickening ice layer. This second step determine d the hydrate lifetime. The resulting diffusion coefficients were estimated at 2.2 x 10(-11) m(2)/s at 189 K and 9.6 x 10(-12) m(2)/s at 168 K.