Interfacial free energy of the structure II cyclopentane hydrate in cyclopentane liquid from the capillary wave fluctuation method

Abstract

The interfacial stiffness of structure II cyclopentane hydrate in cyclopentane liquid has been measured by the Capillary Wave Fluctuation (CWF) method for an equilibrated system with temperature of T=280K and pressure of P~20bar, close to the upper (L${}_w$-Hyd-Vap-L${}_{HC}$) Quadruple-point, on the boundary of the hydrate stable region. The hydrate-II/cyclopentane interfacial stiffness results fall broadly in the range ${\Gamma }_{ho}$=(35-55)$\times 10^{-3}$J/m${}^2$, with an average over all simulations giving ${\Gamma }_{ho}$=45(5)$\times 10^{-3}$J/m${}^2$. Earlier work of the author has determined the cubic harmonic expansion of the natural crystalline oscillations in structure II hydrate. Using this work, the stiffness value translates directly into an orientation-averaged interface free energy of ${\gamma }_{ho}$=45(5)$\times 10^{-3}$J/m${}^2$. The latter is in excellent agreement with the experimentally based estimates of ${\gamma }_{ho}$=47(5)$\times 10^{-3}$J/m${}^2$ from particle-particle adhesion force measurements of Aman et. al. (Langmuir, 29(8):2676-2682, 2013) This provides further evidence for the feasibility and robustness of the simulation approach to measure interfacial free energies in molecular systems.

arXiv comment9 pages, 4 figures

References in corpus (1)

• Canonical sampling through velocity-rescaling