Modeling Hydrate Formation in Media with Broad Pore Size Distributions

Abstract

We show how the modification by Henry et al. of the earlier van der Waals−Plateeuw thermodynamic model can be used to interpret data for hydrates in small pores even when there is a broad distribution of pore sizes. Pore size distribution effects explain the previously reported discrepancy between calculated and measured equilibrium pressures for nominal 7.5 nm radius pores. On the basis of the model, pore volume distributions are reconstructed for the silica gel samples in which the hydrates were formed and compared with distributions constructed from desorption isotherms. The excellent agreement between the calculations and experimental data supports the interpretation of how the pore size distribution present in the silica gel samples affects the observed equilibrium pressures.