Thermodynamics of carbon dioxide hydrate formation in media with broad pore-size distributions.

Equilibrium pressures for the dissociation of carbon dioxide hydrates confined in silica gel pores of nominal radii 7.5, 5.0, and 3.0 nm were measured over a wide temperature range and were observed to be higher than those for bulk carbon dioxide hydrate. Models that have been previously reported in the literature are used to determine the pore radius involved in each equilibrium associated with these data, exactly reproducing the experimental equilibrium pressure. Based on these models, pore volume distributions are reconstructed and compared to those obtained from nitrogen desorption isotherms. This comparison indicates that in the nominal 7.5 nm pores the hydrate formed nearly uniformly in the available pores, while in the nominal 5.0 and 3.0 nm pores it did not.