The interfacial tensions of liquid−liquid mixtures are rarely measured, despite their importance, for example, in extraction processes. In this work, we applied classical density functional theory to liquid−liquid interfaces of binary mixtures and evaluated the predicted interfacial tensions. The functional was based on the statistical associating fluid theory with a polar perturbed-chain contribution to the dispersive term (PCP-SAFT). To ensure a good representation of the liquid−liquid equilibrium of the bulk phases, we applied two binary interaction parameters. Interfacial tensions were predicted without adjusting any model parameter to interfacial properties. For several methanol and ethylene glycol systems, we found good agreement with existing experimental data on interfacial tensions. Limitations in the accuracy of the Helmholtz energy functional were seen for aqueous liquid mixtures, for which phase equilibria were not modeled with sufficient agreement to experimental data, preventing a meaningful prediction of interfacial tensions.

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Abstract. In our previous study [Planková et al., EPJ Web. Conf. 92, 02071 (2015)], several molecular simulations of vapor-liquid phase interfaces for pure water were performed using the DL POLY Classic software. The TIP4P/2005 molecular model was successfully used for the modeling of the density profile and the thickness of phase interfaces together with the temperature dependence of the surface tension. In the current study, the extended simple point charge (SPC/E) model for water was employed for the investigation of vapor-liquid phase interfaces over a wide temperature range from 250 K to 600 K. The TIP4P/2005 model was also used with the temperature step of 25 K to obtain more consistent data compared to our previous study. Results of the new simulations are in a good agreement with most of the literature data. TIP4P/2005 provides better results for the saturated liquid density with its maximum close to 275 K, while SPC/E predicts slightly better saturated vapor density. Both models give qualitatively correct representation for the surface tension of water. The maximum absolute deviation from the IAPWS standard for the surface tension of ordinary water is 10.4 mN · m −1 and 4.1 mN · m −1 over the temperature range from 275 K to 600 K in case of SPC/E and TIP4P/2005, respectively.

Abstract. The paper describes molecular dynamics study of nucleation of water in NVE ensemble. The numerical simulation was performed with the DL_POLY. The metastable steam consisting of 10976 water molecules with TIP4P/2005 potential was driven on the desired energy level by a simulation at constant temperature, and then the nucleation at constant energy was studied for several tens of nanoseconds, which was sufficient for clusters to evolve at hundred molecules size. The results were compared with the previously published results and the classical nucleation theory predictions.

Abstract:The study presents some preliminary results of the density gradient theory (GT)

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Abstract. Molecular dynamics simulations for water were run using the TIP4P/2005 model for temperatures ranging from 250 K to 600 K. The density profile, the surface tension and the thickness of the phase interface were calculated as preliminary results. The surface tension values matched nicely with the IAPWS correlation over wide range of temperatures. As a partial result, DL POLY Classis was successfully used for tests of the new computing cluster in our institute.

Abstract. In this work, we used the density gradient theory (DGT) combined with the cubic equation of state (EoS) by Peng and Robinson (PR) and the perturbed chain (PC) modification of the SAFT EoS developed by Gross and Sadowski [1]. The PR EoS is based on very simplified physical foundations, it has significant limitations in the accuracy of the predicted thermodynamic properties. On the other hand, the PC-SAFT EoS combines different intermolecular forces, e.g., hydrogen bonding, covalent bonding, Coulombic forces which makes it more accurate in predicting of the physical variables. We continued in our previous works [2,3] by solving the boundary value problem which arose by mathematical solution of the DGT formulation and including the boundary conditions. Achieving the numerical solution was rather tricky; this study describes some of the crucial developments that helped us to overcome the partial problems. The most troublesome were computations for low temperatures where we achieved great improvements compared to [3]. We applied the GT for the n-alkanes: nheptane, n-octane, n-nonane, and n-decane because of the availability of the experimental data. Comparing them with our numerical results, we observed great differences between the theories; the best results gave the combination of the GT and the PC-SAFT. However, a certain temperature drift was observed that is not satisfactorily explained by the present theories.