A Phase Study of the System: Oxalic Acid/Acetic Acid/Water; Its Significance in Oxalic Acid Crystal Growth

The presence of limited amounts of water appears to improve the quality of anhydrous oxalic acid single crystals grown from acetic acid solutions. Water concentrations in the saturated solutions which allow crystallization of the anhydrous acid have been determined from the phase study of this ternary system. Near 50 °C the anhydrous acid crystallizes from solutions containing up to 5.2 weight percent water, while the dihydrate appears when water is in excess of this amount. The phase diagram shows a minimum content of oxalic acid in solution at a solvent composition near 83 percent acetic acid, 17 percent water. The solubility increases with increased acetic acid to the isothermal invariant point, found experimentally at a measured temperature of 50.21 °C to have the composition 20.94 percent oxalic acid, 73.89 percent acetic acid, 5.17 percent water. Decreasing solubility occurs at higher acetic acid concentrations. The maximum water content which allows crystallization of anhydrous acid increases with increasing crystallization temperature. The solubility of oxalic acid in acetic acid/water mixtures at 40° and 50 °C is reported.