title: Effects of thermodynamic inhibitors on the dissociation of methane hydrate: a molecular dynamics study.
abstract: We investigate the effects of methanol and NaCl, which are known as thermodynamic hydrate inhibitors, on the dissociation kinetics of methane hydrate in aqueous solutions by using molecular dynamics simulations. It is shown that the dissociation rate is not constant but changes with time. The dissociation rate in the initial stage is increased by methanol whereas it is decreased by NaCl. This difference arises from the opposite effects of the two thermodynamic inhibitors on the hydration free energy of methane. The dissociation rate of methane hydrate is increased by the formation of methane bubbles in the aqueous phase because the bubbles absorb surrounding methane molecules. It is found that both methanol and NaCl facilitate the bubble formation. However, their mechanisms are completely different from each other. The presence of ions enhances the hydrophobic interactions between methane molecules. In addition, the ions in the solution cause a highly non-uniform distribution of dissolved methane molecules. These two effects result in the easy formation of bubbles in the NaCl solution. In contrast, methanol assists the bubble formation because of its amphiphilic character.
authors.affiliation: Department of Chemistry, Faculty of Science, Okayama University, Okayama, 700-8530, Japan.
authors.forename: Takuma
authors.initials: T
authors.lastname: Yagasaki
authors.affiliation: Department of Chemistry, Faculty of Science, Okayama University, Okayama, 700-8530, Japan.
authors.forename: Masakazu
authors.initials: M
authors.lastname: Matsumoto
authors.affiliation: Department of Chemistry, Faculty of Science, Okayama University, Okayama, 700-8530, Japan and Research Center of New Functional Materials for Energy Production, Storage and Transport, Okayama, 700-8530, Japan. htanakaa@okayama-u.ac.jp.
authors.forename: Hideki
authors.initials: H
authors.lastname: Tanaka