Prediction of the univariant two-phase coexistence line of the tetrahydrofuran hydrate from computer simulation

TL;DR

This study uses molecular dynamics simulations to determine the two-phase coexistence line of tetrahydrofuran hydrate across a range of pressures, comparing different models and interaction parameters to match experimental data.

Contribution

It introduces a detailed simulation approach with model comparisons and interaction modifications to accurately predict hydrate phase behavior.

Findings

Rigid THF model is computationally faster than flexible model.

Modified dispersive interactions improve agreement with experimental data.

Both models show small differences at high pressures.

Abstract

In this work, the univariant two-phase coexistence line of the hydrate of tetrahydrofuran (THF) is determined from 100 to 1000 bar by molecular dynamics simulations. The study is carried out by putting in contact a THF hydrate phase with a stoichiometric aqueous solution phase. Following the direct coexistence technique, the pressure has been fixed, and the coexistence line has been determined by analyzing if the hydrate phase grows or melts at different values of temperature. The model of water used is the well-known TIP4P/Ice model. We have used two different models of THF based on the transferable parameters for phase equilibria-united atom approach (TraPPE-UA), the original (flexible) TraPPe-UA model as well as a rigid and planar version of it. Overall, at high pressures, small differences have been observed in the results obtained by both models. Also, large differences have been observed in the computational efforts required by the simulations performed using both models, being the rigid and planar version much faster than the original one. The effect of the unlike dispersive interactions between the water and THF molecules has been also analyzed at 250 bar using the rigid and planar THF model. In particular, we have modified the Berthelot combining rule by adding a factor ({\xi}O-THF) that modifies the unlike water-THF dispersive interactions and we have analyzed the effect on the dissociation temperature when {\xi}O-THF is modified from 1.0 (original Berthelot combining rule) to 1.4 (modified Berthelot combining rule). We have extended the study using {\xi}O-THF = 1.4 and the rigid THF model to the rest of the pressures considered in this work, finding an excellent agreement with the scarce experimental data taken from the literature.