<i>In situ</i> Study of Mass Transfer in Aqueous Solutions under High Pressures via Raman Spectroscopy: A New Method for the Determination of Diffusion Coefficients of Methane in Water near Hydrate Formation Conditions

A new method was developed for in situ study of the diffusive transfer of methane in aqueous solution under high pressures near hydrate formation conditions within an optical capillary cell. Time-dependent Raman spectra of the solution at several different spots along the one-dimensional diffusion path were collected and thus the varying composition profile of the solution was monitored. Diffusion coefficients were estimated by the least squares method based on the variations in methane concentration data in space and time in the cell. The measured diffusion coefficients of methane in water at the liquid (L)–vapor (V) stable region and L–V metastable region are close to previously reported values determined at lower pressure and similar temperature. This in situ monitoring method was demonstrated to be suitable for the study of mass transfer in aqueous solution under high pressure and at various temperature conditions and will be applied to the study of nucleation and dissolution kinetics of methane hydrate in a hydrate–water system where the interaction of methane and water would be more complicated than that presented here for the L–V metastable condition.