title: Augmented stability of hydrogen clathrate hydrates by weakly polar molecules.
abstract: Thermodynamic stability of hydrogen clathrate hydrates has been examined in a wide range of pressure based solely on the intermolecular interactions involved. We show that the stability is indeed augmented by a second guest species (here acetone) called a promoter, a consequence of which is notable reduction in the dissociation pressure of the hydrates encaging hydrogen alone. This evaluation is made by extension of the van der Waals-Platteeuw theory combined with semi-grand-canonical Monte Carlo (GCMC) simulations where the number of hydrogen molecules is allowed to vary while those of host water and promoter acetone molecules are fixed. The GCMC simulations then provide various types of cage occupancies of hydrogen from single to quadruple, from which the chemical potential of water in the clathrate hydrate is obtained as a function of the cage occupancy by acetone and the pressure. These occupancies are used to calculate the chemical potential of water in the clathrate hydrate. The stability is estimated by comparison of the chemical potential of water in the clathrate hydrate with that in hexagonal ice. We show the extent to which the dissociation pressure is reduced with increasing the occupancy of the larger cages by acetone.
authors.affiliation: Department of Chemistry, Faculty of Science, Okayama University, 3-1-1 Tsushima-naka, Kitaku, Okayama 700-8530, Japan.
authors.forename: Takato
authors.initials: T
authors.lastname: Nakayama
authors.forename: Kenichiro
authors.initials: K
authors.lastname: Koga
authors.forename: Hideki
authors.initials: H
authors.lastname: Tanaka