Co-deposition of gas hydrates by pressurized thermal evaporation

Gas hydrates are usually synthesized by bringing together a pressurized gas and liquid or solid water. In both cases, the transport of gas or water to the hydrate growth site is hindered once an initial film of hydrate has grown at the water-gas interface. A seemingly forgotten gas-phase technique overcomes this problem by slowly depositing water vapor on a cold surface in the presence of the pressurized guest gas. Despite being used for the synthesis of low-formation-pressure hydrates, it has not yet been tested for hydrates of CO₂ and CH₄. Moreover, the potential of the technique for the study of hydrate decomposition has not been recognized yet. We employ two advanced implementations of the condensation technique to form hydrates of CO₂ and CH₄ and demonstrate the applicability of the process for the study of hydrate decomposition and the phenomenon of self-preservation. Our results show that CO₂ and CH₄ hydrate samples deposited on graphite at 261-265 K are almost pure hydrates with an ice fraction of less than 8%. Rapid depressurization experiments with thin deposits (approx. 330 μm thickness) of CO₂ hydrate on an aluminum surface at 265 K yield identical dissociation curves when the deposition is done at identical pressure. However, hydrates deposited at 1 MPa almost completely withstand decomposition after rapid depressurization to 0.1 MPa, while samples deposited at 2 MPa decompose 7 times faster. Therefore, this synthesis technique is not only applicable for the study of hydrate decomposition but can also be used for the controlled deposition of a super-preserved hydrate.