Interplay of structure and diffusion in ternary liquid mixtures of benzene + acetone + varying alcohols

The Fick diffusion coefficient matrix of ternary mixtures containing benzene + acetone + three different alcohols, i.e., methanol, ethanol, and 2-propanol, is studied by molecular dynamics simulation and Taylor dispersion experiments. Aiming to identify common features of these mixtures, it is found that one of the main diffusion coefficients and the smaller eigenvalue do not depend on the type of alcohol along the studied composition path. Two mechanisms that are responsible for this invariant behavior are discussed in detail, i.e., the interplay between kinetic and thermodynamic contributions to Fick diffusion coefficients and the presence of microscopic heterogeneities caused by hydrogen bonding. Experimental work alone cannot explain these mechanisms, while present simulations on the molecular level indicate structural changes and uniform intermolecular interactions between benzene and acetone molecules in the three ternary mixtures. The main diffusion coefficients of these ternary mixtures exhibit similarities with their binary subsystems. Analyses of radial distribution functions and hydrogen bonding statistics quantitatively evidence alcohol self-association and cluster formation, as well as component segregation. Furthermore, the excess volume of the mixtures is analyzed in the light of intermolecular interactions, further demonstrating the benefits of the simultaneous use of experiment and simulation. The proposed framework for studying diffusion coefficients of a set of ternary mixtures, where only one component varies, opens the way for further investigations and a better understanding of multicomponent diffusion. The presented numerical results may also give an impulse to the development of predictive approaches for multicomponent diffusion.