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.