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Importance of the Debye interaction in organic solutions: Henry's law constants for polar liquids in nonpolar solvents and vice versa
Authors:J. Howard Rytting  Danny R. McHan  Takeru Higuchi  David J. W. Grant
Affiliation:(1) Department of Pharmaceutical Chemistry, University of Kansas, Malott Hall, 66045 Lawrence, KS;(2) Faculty of Pharmacy, University of Toronto, M5S 1A1 Toronto, Ontario, Canada
Abstract:Henry's law constants have been determined for gamma-butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, DeltaG20 of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, DeltaG20 decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of DeltaG20 against the change in pair potential energy calculated from the classical expressions suggests that DeltaG20 seriously underestimates the strength of the Debye interactions in comparison with the London interactions.
Keywords:Henry's law constants  free energies of transfer  activity coefficients  dipole-dipole and dipole-induced dipole interactions  London dispersion forces  polarizability  refractive index  butyrolactone, ethyl acetate, 2-methyl-3-pentanol, iso-octane, toluene, cinnamaldehyde
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