This work is framed within the Ninth Industrial Fluid Properties Simulation Challenge, with the aim of assessing the capability of molecular simulation methods and force fields to accurately predict the interfacial tension of oil + water mixtures at high temperatures and pressures. The challenge focused on predicting the liquid-liquid interfacial tension of binary mixtures of dodecane + water, toluene + water and a 50:50 (wt%) mixture of dodecane:toluene + water at 1.825 MPa (250 psig) and temperatures from 110 to 170 °C. In our entry for the challenge, we employed coarse-grained intermolecular models parametrized via a top-down technique in which an accurate equation of state is used to link experimentally observed macroscopic properties of fluids with the force-field parameters. The state-of-the-art version of the statistical associating fluid theory (SAFT) for potentials of variable range as reformulated in terms of the Mie potential is employed here. Interfacial tensions are calculated through a direct method, where an elongated simulation cell is sampled through molecular dynamics in the isobaric-isothermal constant area ensemble (NP zz AT). The coarse-grained nature of the force field allows for the accelerated calculation of relatively large systems. The binary interaction parameters that describe the crossinteractions have been obtained in previous works by fitting to interfacial tensions of the constituent binaries at lower pressures and temperatures; these are taken as constant for all conditions and mixtures studied. After disclosure of the challenge results, we observe that the interfacial properties of the mixtures are described with an error of less than 5 mN/m over the whole range of conditions, demonstrating the accuracy and transferability of the top-down SAFT-γ Mie force field approach.

Coarse-grained molecular simulation has become a popular tool for modelling simple and complex fluids alike. The defining aspects of a coarse grained model are the force field parameters, which must be determined for each particular fluid. Since the number of molecular fluids of interest in nature and in engineering processes is immense, constructing force field parameter tables by individually fitting to experimental data is a futile task. A step towards solving this challenge was taken recently by Mejia et al., who proposed a correlation that provides SAFT-γ Mie force field parameters for a fluid provided one knows the critical temperature, the acentric factor and a liquid density, all relatively accesible properties. Building on this, we have applied the correlation to more than 6000 fluids, and constructed a web application, called "Bottled SAFT" which makes this data set easily searchable by CAS number, name or chemical formula. 1Alternatively, the application allows the user to calculate parameters for components not present in the database. Once the intermolecular potential has been found through Bottled SAFT, code snippets are provided for simulating the desired substance using the "raaSAFT" framework, which leverages established molecular dynamics codes to run the simulations. The code underlying the web application is written in Python using the Flask microframework; this allows us to provide a modern high-performance web app while also making use of the scientific libraries available in Python. Bottled SAFT aims at taking the complexity out of obtaining force field parameters for a wide range of molecular fluids, and facilitates setting up and running coarse-grained molecular simulations. The web application is freely available at http://www.bottledsaft.org.The underlying source code is available on Bitbucket under a permissive license.

We present a perturbation theory that combines the use of a third-order Barker–Henderson expansion of the Helmholtz energy with Mie-potentials that include first- (Mie-FH1) and second-order (Mie-FH2) Feynman–Hibbs quantum corrections. The resulting equation of state, the statistical associating fluid theory for Mie potentials of variable range corrected for quantum effects (SAFT-VRQ-Mie), is compared to molecular simulations and is seen to reproduce the thermodynamic properties of generic Mie-FH1 and Mie-FH2 fluids accurately. SAFT-VRQ Mie is exploited to obtain optimal parameters for the intermolecular potentials of neon, helium, deuterium, ortho-, para-, and normal-hydrogen for the Mie-FH1 and Mie-FH2 formulations. For helium, hydrogen, and deuterium, the use of either the first- or second-order corrections yields significantly higher accuracy in the representation of supercritical densities, heat capacities, and speed of sounds when compared to classical Mie fluids, although the Mie-FH2 is slightly more accurate than Mie-FH1 for supercritical properties. The Mie-FH1 potential is recommended for most of the fluids since it yields a more accurate representation of the pure-component phase equilibria and extrapolates better to low temperatures. Notwithstanding, for helium, where the quantum effects are largest, we find that none of the potentials give an accurate representation of the entire phase envelope, and its thermodynamic properties are represented accurately only at temperatures above 20 K. Overall, supercritical heat capacities are well represented, with some deviations from experiments seen in the liquid phase region for helium and hydrogen.

With the advent of CO 2 capture and storage (CCS) as an important remedy for reducing atmospheric CO 2 emissions, it has become necessary to develop accurate and efficient simulation tools. Among other things, such tools should handle the depressurization from supercritical pressures down to atmospheric conditions. This might involve the formation of solid CO 2 (dry ice) as the state passes the triple point. In this work, we propose a dynamic simulation method that handles the dry-ice formation. The method uses the Span-Wagner reference equation of state, with additional relations for thermodynamic properties along the sublimation line. A density-energy state function formulation is employed, which naturally follows from mass and energy conservation. To illustrate the method's capabilities, demanding test cases are considered, both for the depressurization of a vessel and for fluid dynamics in a pipeline, where phase change occurs due to changing boundary conditions.

The level-set method is a popular interface tracking method in two-phase flow simulations. An often-cited reason for using it is that the method naturally handles topological changes in the interface, e.g. merging drops, due to the implicit formulation. It is also said that the interface curvature and normal vectors are easily calculated. This last point is not, however, the case in the moments during a topological change, as several authors have already pointed out. Various methods have been employed to circumvent the problem. In this paper, we present a new such method which retains the implicit level-set representation of the surface and handles general interface configurations. It is demonstrated that the method extends easily to 3D. The method is validated on static interface configurations, and then applied to two-phase flow simulations where the method outperforms the standard method and the results agree well with experiments.