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Solubility in binary solvent systems III: predictive expressions based on molecular surface areas.

W E Acree, J H Rytting

    Journal of Pharmaceutical Sciences
    |March 1, 1983
    PubMed
    Summary
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    This study enhances the nearly ideal binary solvent model by incorporating molecular surface areas. The improved model accurately predicts solute solubilities in mixed solvents, outperforming previous methods based on molar volumes.

    Area of Science:

    • Physical Chemistry
    • Thermodynamics
    • Solution Chemistry

    Background:

    • The nearly ideal binary solvent model effectively predicts solute properties in mixed solvents.
    • Existing models often use molar volumes as weighting factors, with limitations in certain systems.

    Purpose of the Study:

    • To extend the nearly ideal binary solvent model using molecular surface areas as weighting factors.
    • To compare the predictive accuracy of new equations against existing ones for solute solubilities.

    Main Methods:

    • Derived two new predictive equations incorporating molecular surface areas.
    • Compared these with equations using molar volumes for weighting.
    • Evaluated predictions against experimental solubilities of anthracene and naphthalene in binary solvent mixtures.

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    Main Results:

    • An equation using surface fraction averaging of excess Gibbs free energy showed the best fit.
    • This model predicted solubilities in 25 systems with an average deviation of 1.7% and a maximum of 7.5%.
    • Molar volume-based equations performed well generally but failed for anthracene in benzene-containing mixtures.

    Conclusions:

    • Molecular surface area weighting significantly improves the predictive capability of the nearly ideal binary solvent model.
    • The surface fraction averaging approach offers superior accuracy for predicting solute solubilities in diverse solvent mixtures.
    • This enhanced model provides a more robust tool for thermodynamic calculations in solution chemistry.