Effect of Solvent Composition on Solubility, Thermodynamics, Metastable Zone Width (MSZW) and Crystal Habit of L-Ascorbic Acid

Abstract

This work investigates the effect of different solvent systems on solubility, thermodynamics, metastable zone width (MSZW), and crystal habit of ascorbic acid, in order to help optimize its crystallization process. The solubility curves and metastable zone (MSZ) limits were determined experimentally using the polythermal method in pure solvents: water and alcohols (methanol/ethanol/isopropanol), as well as water-alcohol binary solvent systems. The solubility decreases with increasing alcohol composition for all solvent systems. The solubility data were well correlated using the Jouyban–Acree model as a function of two variables: temperature and solvent composition. The dissolution enthalpy ((Formula presented.)), dissolution entropy ((Formula presented.)), and Gibbs free energy ((Formula presented.)) were determined using Van’t Hoff and Jouyban–Acree models. The thermodynamic properties increase with increasing alcohol composition. The lowest and highest values of enthalpy were obtained for water (20.52 kJ mol (Formula presented.)) and isopropanol (35.33 kJ mol (Formula presented.)), respectively. Pure alcohols as solvents widen the metastable zone width, indicating high supersaturation required for the nucleation. Crystal images captured during cooling crystallization in water confirm the cubic crystal habit formation, whereas increasing alcohol composition in the solvent system promotes preferential growth along one crystallographic axis, leading to elongated prism-shaped crystals in methanol and ethanol and needle-shaped crystals in isopropanol.