Measurements of physical properties of gas hydrates and in situ observations of formation and decomposition processes via Raman spectroscopy and X-ray diffraction

Gas hydrate properties and phase transition kinetics were studied using Raman spectroscopic and X-ray diffraction methods. These techniques have the advantage of measuring physical properties such as crystal structure, gas composition, and cage occupancy of gas molecules without decomposing the sample. In situ observations using these techniques are indicative of formation and decomposition processes in gas hydrates. Raman spectroscopy is used for the analysis of gas concentrations and gas compositions of gas hydrates. The nu(1) symmetrical C-H stretching vibration mode of methane molecules in the hydrate phase shows a doublet, and the relative intensity of the peaks determines the cage-occupancy ratio. However, as the Raman method is not standard for this application, we evaluated the method by analyzing the same methane hydrate sample using NMR and Raman scattering in a laboratory in Canada and also comparing the data with the Raman measurements made on the same sample in a laboratory in Japan. The data were consistent with all three measurements. In addition, in situ measurements of hydrate formation and decomposition were done by X-ray diffraction. The transformation of ice into CO2 hydrates occurred in two steps: at first a CO2 hydrate layer rapidly formed a coating on the ice surface and then the CO2 hydrate slowly grew according to the diffusion rates of CO2 and H2O molecules through the hydrate layer to the reaction sites. The same methods were used to observe the self-preservation effect of methane hydrates.