An overview of recent structural work focusing on the gas hydrates of methane and carbon dioxide is given. Both the crystal structure and the microstructure are considered. We report on the pressure-dependent molecular structure of methane clathrate hydrate using laboratory-made hydrogenous and deuterated samples investigated by neutron and hard-X-ray synchrotron diffraction experiments. The isothermal compressibilities are determined for hydrogenated and deuterated CH4 hydrate, and isotopic differences between both compounds are established for the first time. The cage filling of carbon dioxide and methane hydrate is determined and compared with predictions from statistical thermodynamic theory. In the case of small cages in methane hydrate, experimental results and predictions do not agree. Field-emission scanning electron microscopy reveals the meso- to macro-porous nature of gas hydrates formed with an excess of free gas. Furthermore, in situ measurements of the formation kinetics of porous hydrates are reported in which differences between methane and carbon dioxide are established quantitatively and the transient existence of a type II carbon dioxide structure is found. PACS Nos.: 82.75-z, 61.10Nz, 61.12Ld, 68.37Hk
Insights into Kinetics of Methane Hydrate Formation in the Presence of Surfactants
