title: Molecular modeling of the dissociation of methane hydrate in contact with a silica surface.
abstract: We use constant energy, constant volume (NVE) molecular dynamics simulations to study the dissociation of the fully occupied structure I methane hydrate in a confined geometry between two hydroxylated silica surfaces between 36 and 41 Å apart, at initial temperatures of 283, 293, and 303 K. Simulations of the two-phase hydrate/water system are performed in the presence of silica, with and without a 3 Å thick buffering water layer between the hydrate phase and silica surfaces. Faster decomposition is observed in the presence of silica, where the hydrate phase is prone to decomposition from four surfaces, as compared to only two sides in the case of the hydrate/water simulations. The existence of the water layer between the hydrate phase and the silica surface stabilizes the hydrate phase relative to the case where the hydrate is in direct contact with silica. Hydrates bound between the silica surfaces dissociate layer-by-layer in a shrinking core manner with a curved decomposition front which extends over a 5-8 Å thickness. Labeling water molecules shows that there is exchange of water molecules between the surrounding liquid and intact cages in the methane hydrate phase. In all cases, decomposition of the methane hydrate phase led to the formation of methane nanobubbles in the liquid water phase.
authors.affiliation: Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia, V6T 1Z3, Canada.
authors.forename: S Alireza
authors.initials: SA
authors.lastname: Bagherzadeh
authors.forename: Peter
authors.initials: P
authors.lastname: Englezos
authors.forename: Saman
authors.initials: S
authors.lastname: Alavi
authors.forename: John A
authors.initials: JA
authors.lastname: Ripmeester
mesh_terms: D008697:Methane / Q000737:chemistry*; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D012822:Silicon Dioxide / Q000737:chemistry*; D013499:Surface Properties; D013696:Temperature; D014867:Water / Q000737:chemistry
chemical_list: D014867:Water; D012822:Silicon Dioxide; D008697:Methane