Solvent-induced phase transformations of hydrates

An increase of the specific surface area of solid phases is often desirable e.g. for the bioavailability of pharmaceuticals or in chemical processes. Such an increase can a.o. be achieved by suspending crystalline substances in a solvent that induces phase transformations. Hence, the original substance has to be in a metastable state in the solvent. If the stable phase after transformation has in addition a very low solubility in the solvent, a dendritic growth is forced to occur because of the high local supersaturations during the phase change. This dendritic growth of the stable phase in term leads to needle- or whisker-like crystals, which have the desired larger specific surface area in comparison to the initial crystalline substance. In order to investigate this phenomenon several hydrates of salts were chosen, which undergo phase transformations to their anhydrates accompanied by a corresponding loss of crystal water when suspended in excess in lower alcohols. Consequently, anhydrous forms were created by dehydrating these hydrates. The transformation rate or in this case the dehydration level can thus be indirectly measured by Karl-Fischer titration. The thermodynamic background of the dehydration phenomena can be clarified by solubility studies of the hydrates and anhydrates in water/alcohol-mixtures.