Clathrate Hydrate - Structure

Structure

Gas hydrates usually form two crystallographic cubic structures – structure (Type) I and structure (Type) II of space groups and respectively. Seldom, a third hexagonal structure of space group may be observed (Type H).

The unit cell of Type I consists of 46 water molecules, forming two types of cages – small and large. The small cages in the unit cell are two against six large ones. The small cage has the shape of a pentagonal dodecahedron (512) and the large one that of a tetradecahedron, specifically a hexagonal truncated trapezohedron (51262), together forming a Weaire-Phelan structure. Typical guests forming Type I hydrates are CO2 in carbon dioxide clathrate and CH4 in methane clathrate.

The unit cell of Type II consists of 136 water molecules, forming also two types of cages – small and large. In this case the small cages in the unit cell are sixteen against eight large ones. The small cage has again the shape of a pentagonal dodecahedron (512) but the large one is a hexadecahedron (51264). Type II hydrates are formed by gases like O2 and N2.

The unit cell of Type H consists of 34 water molecules, forming three types of cages – two small of different type and one huge. In this case, the unit cell consists of three small cages of type 512, two small ones of type 435663 and one huge of type 51268. The formation of Type H requires the cooperation of two guest gases (large and small) to be stable. It is the large cavity that allows structure H hydrates to fit in large molecules (e.g. butane, hydrocarbons), given the presence of other smaller help gases to fill and support the remaining cavities. Structure H hydrates were suggested to exist in the Gulf of Mexico. Thermogenically-produced supplies of heavy hydrocarbons are common there.

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