Stability of tetra-n-butyl ammonium bromide (TBAB) and tetra-n-butyl phosphonium bromide (TBPB) semiclathrate hydrates with a hydration number of 38 is studied by the molecular dynamics (MD) simulation in the absence and presence of methane, carbon dioxide, methanol, and ethanol molecules. All of the simulation runs are performed under NVT (constant number of atoms, volume, and temperature) and NPT (constant number of atoms, pressure, and temperature) conditions using optimized potentials for liquid simulations-all-atom (OPLS-AA) force field with nonpolarizable water models (including SPC, TIP3P, TIP4P, and TIP4P/Ice), where the operating conditions include a temperature range of 250−350 K and pressures of 0.1 and 50 MPa. The potential energy and structural analysis, mean square displacement (MSD), diffusion coefficient, radial distribution function (RDF), lattice parameter, and the average number of hydrogen bonds between water−water molecules are evaluated by employing MD strategy. According to the potential energy results, the order for the water models in both TBAB and TBPB hydrate stabilities is as follows: TIP4P/Ice > TIP4P ≈ SPC > TIP3P. This order agrees well with the previous studies of gas hydrates and ices. In the absence and presence of methane and carbon dioxide guest molecules, the height of the peaks in the RDF of oxygen−oxygen atoms decreases with lowering pressure and increasing temperature; greater MSD, diffusion coefficient, and lattice parameter values are also achieved. Thus, in the absence and/or presence of guest gas molecules, the stability of TBAB and TBPB hydrate cages decreases with increasing temperature and reducing pressure. A good match is noticed between the results of MD simulation and previous experimental and theoretical studies, confirming the accuracy and validation of the simulation method. Reduction of the hydrogen bond balance between water molecules and formation of new hydrogen bonds between the water and the hydroxyl groups of methanol and/or ethanol molecules in the cages indicate that methanol and ethanol molecules have an inhibitory effect on TBAB and TBPB hydrates. Due to different hydrophilic versus hydrophobic behaviors of alcohols, the extent of disruption of hydrogen bonds between water−water molecules of TBAB and TBPB hydrates in the presence of methanol is larger than that in the presence of ethanol, which is consistent with the MD simulation results of clathrate hydrate. This study can help to further understand the semiclathrate hydrate stability or dissociation conditions at a molecular scale for better design and operation of corresponding processes.
The rise of partially wetting liquids along the corners of noncircular capillary tubes is observed in many practical science and engineering applications such as wastewater treatment using membranes, remediation, oil recovery from petroleum reservoirs, and blood flow. In this paper, rivulet rise at the corners of polygonal capillary tubes is studied for partially wetting liquids with contact angles below the critical value. The presence of corners changes the distribution of a liquid in an incomplete wetting condition. In this study, geometrical models are proposed to better understand the capillary rise and flow behavior at the corners. A geometrical solution for the capillary rivulet height and profile is derived under gravity in triangular, square, and pentagonal capillary tubes. The effects of several factors including contact angle, number of polygon sides, and liquid properties on the capillary rivulet height are examined. It was found that the ratio of liquid surface tension to density directly affects the corner rise, while it has an inverse relationship with other factors. The maximum rivulet height of 91.6 mm is obtained in the triangular capillary tube with a side length of 1 mm and a contact angle of 30° for polydimethylsiloxane (PDMS-20)-air fluid pair. The minimum capillary rivulet height of 6.2 mm, on the other hand, is achieved in the pentagonal capillary tube, with a side length of 3 mm and a contact angle of 30°. To validate the developed analytical approach, comparisons are made between the model results, literature predictions, and experimental data. In addition, the geometrical model for a square capillary tube is compared with previous published studies, revealing a good agreement. This study provides quantitative results for the influence of capillary tube shape on the flow behavior of fluids in noncircular tubes that can be useful for control and optimization of transport phenomena in corresponding systems.
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