Hydrate nucleation in water nanodroplet: size dependence

Lei Wang and Peter Kusalik

Department of Chemistry, University of Calgary, 2500 University drive NW, Calgary, Alberta T2N 1N4, Canada

Clathrate hydrates are ice-like structures in which hydrogen-bonded cages formed by water encapsulate guest molecules (e.g., methane). Understanding of clathrate nucleation in water nanodroplets is not only of great scientific interest, it also has significant implications for industrial processes (e.g., the hydrate blockage inside the oil/gas pipeline, \(CO_2\) sequestration and natural occurrence of clathrates in sedimental environments). Yet, despite recent efforts devoted into the understanding the molecular level mechanisms, these have remained elusive. To examine the impact of the size of water nanodroplets on the microscopic mechanisms of nucleation of gas hydrates, extensive MD simulations have been performed with systems where a water nanodroplet is surrounded by a non-aqueous liquid comprising one of the pure guest species (\(H_2S\), \(C_3H_8\), \(CH_4\), \(CO_2\), \(C_2H_6\)) or their mixtures. For all the systems studied, the nucleation events have been observed under the current simulation time scales (~500ns) with only pure \(H_2S\) guest species systems or with nuclei dominated by the \(H_2S\) species in mixed-guest systems. With pure \(H_2S\) guest systems, the impact of the size of water nanodroplets on the hydrate nucleation behavior has been studied over a range of temperatures. The dissociation temperature dependence of the crystallite size for \(H_2S\) sI is well described by the Gibbs-Thomson equation and provides a reasonable estimate for the interfacial tension. Our results show that a decrease in size or increase in temperature not only causes an increase in the induction time for the nucleation but also results in a tendency of the nuclei appear at the center of the nanodroplet. Additionally, according to analyses of the hydrate structures, we find that the hydrate nuclei initiated with incomplete cages subsequently grow to essentially fill the water nanodroplet and are eventually dominated by complete cages. These amorphous hydrate nuclei exhibit motifs of both sI and sII structures. This work provides new insights into the kinetic behavior of hydrate nucleation practically within water nanodroplets

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