  Clathrate hydrates are believed to play a significant role in various solar
system environments, e.g. comets, and the surfaces and interiors of icy
satellites, however the structural factors governing their formation and
dissociation are poorly understood. We demonstrate the use of a high pressure
gas cell, combined with variable temperature cooling and time-resolved data
collection, to the in situ study of clathrate hydrates under conditions
relevant to solar system environments. Clathrates formed and processed within
the cell are monitored in situ using synchrotron X-ray powder diffraction and
Raman spectroscopy. X-ray diffraction allows the formation of clathrate
hydrates to be observed as CO2 gas is applied to ice formed within the cell.
Complete conversion is obtained by annealing at temperatures just below the ice
melting point. A subsequent rise in the quantity of clathrate is observed as
the cell is thermally cycled. Four regions between 100-5000cm-1 are present in
the Raman spectra that carry features characteristic of both ice and clathrate
formation. This novel experimental arrangement is well suited to studying
clathrate hydrates over a range of temperature (80-500K) and pressure
(1-100bar) conditions and can be used with a variety of different gases and
starting aqueous compositions. We propose the increase in clathrate formation
observed during thermal cycling may be due to the formation of a quasi
liquid-like phase that forms at temperatures below the ice melting point, but
which allows easier formation of new clathrate cages, or the retention and
delocalisation of previously formed clathrate structures, possibly as amorphous
clathrate. The structural similarities between hexagonal ice, the quasi
liquid-like phase, and crystalline CO2 hydrate mean that differences in the
Raman spectrum are subtle; however, all features out to 5000cm-1 are diagnostic
of clathrate structure.
