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Published on: May 15, 2017
Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface
Xiaojing Fu1, Luis Cueto-Felgueroso1,2, Ruben Juanes1
1Massachusetts Institute of Technology, 77 Massachusetts Avenue, Building 1, Cambridge, Massachusetts 02139, USA.
Abstract:
We develop a continuum-scale phase-field model to study gas-liquid-hydrate systems far from thermodynamic equilibrium. We design a Gibbs free energy functional for methane-water mixtures that recovers the isobaric temperature-composition phase diagram under thermodynamic equilibrium conditions. The proposed free energy is incorporated into a phase-field model to study the dynamics of hydrate formation on a gas-liquid interface. We elucidate the role of initial aqueous concentration in determining the direction of hydrate growth at the interface, in agreement with experimental observations. Our model also reveals two stages of hydrate growth at an interface-controlled by a crossover in how methane is supplied from the gas and liquid phases-which could explain the persistence of gas conduits in hydrate-bearing sediments and other nonequilibrium phenomena commonly observed in natural methane hydrate systems.
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