Diffusion in liquid mixtures.

The understanding of transport and mixing in fluids in the presence and in the absence of external fields and reactions represents a challenging topic of strategic relevance for space exploration. Indeed, mixing and transport of components in a fluid are especially important during long-term space missions where fuels, food and other materials, needed for the sustainability of long space travels, must be processed under microgravity conditions. So far, the processes of transport and mixing have been investigated mainly at the macroscopic and microscopic scale. Their investigation at the mesoscopic scale is becoming increasingly important for the understanding of mass transfer in confined systems, such as porous media, biological systems and microfluidic systems. Microgravity conditions will provide the opportunity to analyze the effect of external fields and reactions on optimizing mixing and transport in the absence of the convective flows induced by buoyancy on Earth. This would be of great practical applicative relevance to handle complex fluids under microgravity conditions for the processing of materials in space.

Diffusion in Multicomponent Liquids: From Microscopic to Macroscopic Scales.

In spite of considerable research on the nature of aqueous alcohol mixtures that are characterized by microscopic inhomogeneity or incomplete mixing at the molecular level, transport properties have received little attention. We report the results of a study on diffusion in the ternary mixture of water with two alcohols, that is, water + methanol + ethanol, which is investigated on microscopic and macroscopic scales by means of molecular simulation and Taylor dispersion experiments. A novel protocol is developed for the comparison of mutual diffusion coefficients sampled by two fundamentally different approaches, which allows for their critical analysis. Because of complex intermolecular interactions, given by the presence of hydrogen bonding, the analysis of transport processes in this mixture is challenging for not only on the microscopic scale for simulation techniques but also on the macroscopic scale due to unfavorable optical properties. Binary limits of the Fick diffusion matrix are used for validation of the experimental ternary mixture results together with the verification of the validity of the phenomenological Onsager reciprocal relations. The Maxwell-Stefan diffusion coefficients and the thermodynamic factor are sampled by molecular simulation consistently on the basis of given force field models. The protocol for the comparison of the results from both approaches is also challenging because Fick diffusion coefficients of ternary mixtures depend on the frame of reference. Accordingly, the measured coefficients are transformed from the volume-averaged to the molar-averaged frame of reference, and it is demonstrated that both approaches provide not only similar qualitative behavior along two concentration paths but also strong quantitative agreement. This coordinated work using different approaches to study diffusion in multicomponent mixtures is expected to be a significant step forward for the accurate assessment of cross-diffusion.