Solubility of coumarin in (ethanol plus water) mixtures: Determination, correlation, thermodynamics and preferential solvation

Abstract

Equilibrium mole fraction solubility of coumarin in nine aqueous-ethanolic mixtures, as well as in neat water and neat ethanol, was determined at seven temperatures from (293.15 to 323.15) K. Coumarin solubility in was adequately correlated with several well-known correlation models with the mean percentage deviations of 5.1-10.8%. The respective apparent thermodynamic functions (Gibbs energy, enthalpy, and entropy) for the dissolution, mixing and solvation processes were computed using the van't Hoff and Gibbs equations. The enthalpy-entropy relationship for coumarin was non-linear in the plot of enthalpy vs. Gibbs energy of dissolution with negative slope from neat water to the mixture of w(1) = 0.10 but positive from this mixture to neat ethanol. Accordingly, in the first case the coumarin transfer from neat water to the mixture of w(1) = 0.10 is entropy-driven, which could be attributed to water molecules release originally bounded as "icebergs" around the non-polar groups of this drug. Otherwise, in mixtures of w(1) >= 0.10 the driving mechanism for the transfer of coumarin from the more polar solvent systems to those less polar is the enthalpy, probably owing the better drug solvation. Moreover, by means of the inverse Kirkwood-Buff integrals is observed that apparently coumarin is preferentially solvated by water molecules in water-rich mixtures but preferentially solvated by ethanol molecules in mixtures of 0.23 < x(1) < 1.00. (C) 2021 Elsevier B.V. All rights reserved.