Summary: On the Role of Solute Solvation and Excluded-Volume Interactions in Coupled Diffusion
Department of Chemistry, Texas Christian UniVersity, Fort Worth, Texas 76129
ReceiVed: May 6, 2008; ReVised Manuscript ReceiVed: July 16, 2008
Coupled diffusion is observed in multicomponent liquid mixtures in which strong thermodynamic interactions
occur. This phenomenon is described by cross terms in the matrix of multicomponent diffusion coefficients.
This paper reports a theoretical analysis on the relative role of thermodynamic factors and Onsager cross-
coefficients on cross-diffusion coefficients relevant to ternary mixtures containing macromolecules or colloidal
particles in the presence of salting-out conditions. A new model based on frictional coefficients between
solvated solutes is reported. This model predicts that the Onsager cross-coefficient is negative and contributes
significantly to cross-diffusion coefficients even at infinite dilution for solutes with a large difference in size.
These predictions are consistent with recent experimental results. The role of preferential solvation and excluded-
volume interactions on the thermodynamic factors are also examined. Excluded-volume interactions are
introduced through the use of the McMillan-Mayer thermodynamic framework after emphasizing some
important aspects of diffusion reference frames and thermodynamic driving forces. Finally, new expressions
for cross-diffusion coefficients are proposed.
Diffusion plays an important role in many industrial, geochem-
ical, and biochemical processes.1 Modeling these processes
include the knowledge of the diffusion coefficients.2 The