A quasi-stationary molecular dynamics simulation method for studying mass transfer through vapourliquid interfaces of mixtures driven by gradients of the chemical potential based on the dual control volume (DCV) method is described and tested. The rectangular simulation volume contains three bulk domains: a liquid domain in middle with vapour on each side such that there are two vapour-liquid interfaces. The mass flux is generated by prescribing the chemical potential in control volumes in the vapour domains close to the outer boundary of the simulation volume. The simulation method was applied for studies of two binary Lennard-Jones mixtures: one in which a strong enrichment of the lowboiling component at the vapour-liquid interface is observed and another in which there is practically no enrichment. The two mixtures differ only in the dispersive interactions; their bulk diffusion coefficients are similar. Furthermore, the prescribed chemical potential difference was the same in all simulations.Nevertheless, important differences in the mass flux of the low-boiling component were observed for the two mixtures at all studied temperatures which might be related to the enrichment at the interfaces.

Molecular dynamics (MD) simulations are highly attractive for studying the influence of interfacial effects, such as the enrichment of components, on the mass transfer through the interface. In a recent work, we have presented a steady-state MD simulation method for investigating this phenomenon and tested it using model mixtures with and without interfacial enrichment. The present study extends this work by introducing a nonstationary MD simulation method. A rectangular simulation box that contains a mixture of two components 1 + 2 with a vapor phase in the middle and two liquid phases on both sides is used. Starting from a vapor−liquid equilibrium state, a non-stationary molar flux of component 2 is induced by inserting particles of component 2 into the center of the vapor phase in a pulse-like manner. During the isothermal relaxation process, particles of component 2 pass through the vapor phase, cross the vapor−liquid interface, and enter the liquid phase. The system thereby relaxes into a new vapor−liquid equilibrium state. During the relaxation process, spatially resolved responses for the component densities, fluxes, and pressure are sampled. To reduce the noise and provide measures for the uncertainty of the observables, a set of replicas of simulations is carried out. The new simulation method was applied to study mass transfer in two binary Lennard-Jones mixtures: one that exhibits a strong enrichment of the low-boiling component 2 at the vapor− liquid interface and one that shows no enrichment. Even though both mixtures have similar transport coefficients in the bulk phases, the results for mass transfer differ significantly, indicating that the interfacial enrichment influences the mass transfer.

A set of molecular models for the alkali nitrates (LiNO3, NaNO3, KNO3, RbNO3, and CsNO3) in aqueous solutions is presented and used for predicting the thermophysical properties of these solutions with molecular dynamics simulations. The set of models is obtained from a combination of a model for the nitrate anion from the literature with a set of models for the alkali cations developed in previous works of our group. The water model is SPC/E and the Lorentz–Berthelot combining rules are used for describing the unlike interactions. This combination is shown to yield fair predictions of thermophysical and structural properties of the studied aqueous solutions, namely the density, the water activity and the mean ionic activity coefficient, the self-diffusion coefficients of the ions, and radial distribution functions, which were studied at 298 K and 1 bar; except for the density of the solutions of all five nitrates and the activity properties of solutions of NaNO3, which were also studied at 333 K. For calculating the water the activity and the mean ionic activity coefficient, the OPAS ( osmotic pressure for the activity of selvents) method was applied. The new models extend an ion model family for the alkali halides developed in previous works of our group in a consistent way.

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