Construction of solid–liquid phase diagrams in ternary systems by titration calorimetry

Titration calorimetry was used to construct the solid–liquid equilibrium line in ternary systems containing the solute and an aqueous mixed solvent by measuring the heat of dissolution of the solid solute during successive additions of the liquid solvent. The plot of cumulated heats versus the mole ratio, nsolvent/nsolute, yields two (almost) linear increases of different slopes. These two lines represent successively the enthalpy of dissolution then the enthalpy of dilution of the medium; their intersection gives the solubility and the enthalpy of dissolution of the solute. Phase diagrams have been established over the whole concentration range for o-anisaldehyde, 1,3,5-trimethoxybenzene and vanillin, in water + methanol, +ethanol, or +n-propanol at 303, 313 and 318 K.