Influence of Liquid Structure on Fickian Diffusion in Binary Mixtures of n‑Hexane and Carbon Dioxide Probed by Dynamic Light Scattering, Raman Spectroscopy, and Molecular Dynamics Simulations

• Published in: The journal of physical chemistry. B Vol. 122; no. 28; pp. 7122 - 7133
• Main Authors: Klein, Tobias, Wu, Wenchang, Rausch, Michael H, Giraudet, Cédric, Koller, Thomas M, Fröba, Andreas P
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 19-07-2018
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.8b03568

This study contributes to a fundamental understanding of how the liquid structure in a model system consisting of weakly associative n-hexane (n-C6H14) and carbon dioxide (CO2) influences the Fickian diffusion process. For this, the benefits of light scattering experiments and molecular dynamics (MD) simulations at macroscopic thermodynamic equilibrium were combined synergistically. Our reference Fickian diffusivities measured by dynamic light scattering (DLS) revealed an unusual trend with increasing CO2 mole fractions up to about 70 mol %, which agrees with our simulation results. The molecular impacts on the Fickian diffusion were analyzed by MD simulations, where kinetic contributions related to the Maxwell–Stefan (MS) diffusivity and structural contributions quantified by the thermodynamic factor were studied separately. Both the MS diffusivity and the thermodynamic factor indicate the deceleration of Fickian diffusion compared to an ideal mixture behavior. Computed radial distribution functions as well as a significant blue-shift of the CH stretching modes of n-C6H14 identified by Raman spectroscopy show that the slowing down of the diffusion is caused by a structural organization in the binary mixtures over a broad concentration range in the form of self-associated n-C6H14 and CO2 domains. These networks start to form close to the infinite dilution limits and seem to have their largest extent at a solute–solvent transition point at about 70 mol % CO2. The current results not only improve the general understanding of mass diffusion in liquids but also serve to develop sound prediction models for Fick diffusivities.