Ostwald-Meyers Metastable Region in LiBr Crystallization-Comparison of Measurements with Predictions

Experiments have been performed to measure the Ostwald-Meyers metastable region during crystallization from concentrated LiBr solutions. Solution thermodynamics shows that several hydrated LiBr salts and ice can crystallize depending upon the concentration of LiBr in aqueous solution. The available solubility data were interpreted to give solubility products of several hydrated LiBr salts using the formulation of Helgeson, which accounts for the activity of water. The crystallization temperature was measured by monitoring to +/-0.01 degrees C the temperature of solutions inside test tubes placed in a cooling bath programmed at a cooling rate of 20 degrees C/h. A release of the heat of crystallization identifies the temperature of crystallization. The equilibrium solubility was verified by crystallization with seed crystals present. The crystallization temperature without seeds present was 10 to 20 degrees C less than the equilibrium solubility temperature corresponding to the Ostwald-Meyers metastable region. This crystallization temperature measured at 20 degrees C/h was shown to correspond to nucleation on the surface of the test tube with an interface energy of 40+/-1.2 erg/cm(2). Homogeneous nucleation from solution data shows the crystallization temperature to be from 40 to 50 degrees C below the equilibrium solubility curve and to be accurately predicted by homogeneous nucleation with an interface energy of 26 erg/cm(2), the literature value of the ice/water interface. Since the hydrated LiBr salts have surfaces that expose structured water molecules to the solution, this value is believed to be an appropriate value of the interface energy of the hydrated LiBr crystals. Crystallization temperature measurements were performed at different cooling rates, showing that slower cooling rates gave a narrower Ostwald-Myers metastable zone as is expected. Induction time measurements showed that the time to spontaneous crystallization increases as the supersaturation is decreased. Copyright 2001 Academic Press.