Theoretical studies of the kinetics of methane hydrate crystallization in external electromagnetic fields

• Published in: The Journal of Chemical Physics
• Main Authors: English, Niall J., MacElroy, J. M. D.
• Format: Article in Journal/Newspaper
• Language: English
• Published: AIP Publishing 2004
• Subjects: Methane hydrate
• Online Access: http://dx.doi.org/10.1063/1.1730092; https://pubs.aip.org/aip/jcp/article-pdf/120/21/10247/19031828/10247_1_online.pdf

Nonequilibrium molecular-dynamics (MD) simulations have been performed for the growth and dissolution of a spherical methane hydrate crystallite, surrounded by a saturated water–methane liquid phase, in both the absence and presence of external electromagnetic (e/m) fields in the microwave to far infrared range (5–7500 GHz) at root-mean square (rms) electric field intensities of up to 0.2 V/Å. A rigid/polarizable potential was used to model water and a rigid/nonpolarizable model was utilized for methane. In the absence of a field, it was found that the average growth rate of the crystallite was ∼0.32 water and 0.045 methane molecules per picosecond, evaluated over a 500 ps NPT simulation for three different initial geometries. Upon the application of an e/m field, it was found that no significant deviations from the zero-field crystal growth patterns were observed for rms electric field intensities of less than about 0.1 V/Å, regardless of the field frequency. At, and above, this “threshold” intensity, it was found that dissolution took place. The mobility of the molecules in the system was enhanced by the e/m field, to the greatest extent for frequencies of 50–100 GHz. Furthermore, it was observed that there was a systematic frequency variation in the pattern of dipole alignment with the external field and this led to marked differences in the rate of dissolution.