Abstract
The heats of solution at infinite dilution, ΔH s, of more than 40 solvents of widely different structure and polarity (from n-hexane to 2,2,2-trifluoroethanol) in liquid poly (ethylene oxide) PEO, derived from gas-liquid chromatography, were quantitatively analysed within the general framework of linear solvation energy relationships: − ΔH s(kcal mol −1) = 0.48 × 10 24 P + 1.725 μ + 4.29 α, R(26 solvents) = 0.9566. This linear multiparametric approach allows us to separate the contributions of dispersion-cavitation forces (probe polarizability P), of dipolar interactions (probe dipole moment μ) and of hydrogen bonding (H-bond donating power α of the probe measured by the Taft empirical parameter). It affords reliable values for the heat of H-bonding formation between protic probes and PEO. The potential value of such a correlation analysis as a general strategy to quantify solute-polymer interactions in polar systems at a molecular level is emphasized.
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