Abstract
A hydrodynamic bead model based on Kirkwood-Riseman theory has been used to calculate the translational diffusion constant, D, for solutes with polymethylene chains in solutions with a polar component. A comparison with the experimental values for nonpolar n-alkanes in polar 2-propanol, tetrahydrofuran, chlorobenzene, chloroform, 1-octanol, quinoline, and chloroform (78 D values) and polar primary alcohols in nonpolar benzene and n-octane (24 D values) gives an average absolute percentage difference of ∼3% between the 102 experimental and calculated D values. Consideration of the solvent's temperature-dependent changes in the degree of aggregation due to hydrogen bonding was necessary for the n-alkanes in 1-octanol. Good agreement was not found for primary alcohols in 1-octanol due to solute-solvent hydrogen bonding. A correlation that depends on the solutes' molar volumes instead of their chain lengths gives worse agreement than the bead model for the n-alkanes in polar solvents and primary alcohols and n-alkanes in nonpolar solvents.
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