Molecular dynamics simulation study on the mass transfer across vapor-liquid interfaces in azeotropic mixtures.

Mass transfer through fluid interfaces is an important phenomenon in industrial applications as well as in naturally occurring processes. In this work, we investigate the mass transfer across vapor-liquid interfaces in binary mixtures using molecular dynamics simulations. We investigate the influence of interfacial properties on mass transfer by studying three binary azeotropic mixtures known to have different interfacial behaviors. Emphasis is placed on the effect of the intermolecular interactions by choosing mixtures with the same pure components but different cross-interactions such that different azeotropic behaviors are obtained. The molar flux is created by utilizing a non-stationary molecular dynamics simulation approach, where particles of one component are inserted into the vapor phase over a short period of time before the system's response to this insertion is monitored. From a direct comparison of the density profiles and the flux profiles in close proximity to the interface, we analyze the particles' tendency to accumulate in the interfacial region throughout the different stages of the simulation. We find that for mixtures with strong attractive cross-interactions, the inserted particles are efficiently transported into the liquid phase. For systems with weak attractive cross-interactions, the inserted particles show a tendency to accumulate in the interfacial region, and the flux through the system is lower. The results from this work indicate that the accumulation of particles at the interface can act as a hindrance to mass transfer, which has practical relevance in technical processes.

Molecular modeling and simulation of aqueous solutions of alkali nitrates.

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.

Mass Transfer through Vapor-Liquid Interfaces Studied by Non-Stationary Molecular Dynamics Simulations.

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 non-stationary 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.