Interactions of water with the surfaces of crystal polymorphs

The purpose of this study is to investigate the interactions of water adsorption on the surfaces of different crystal forms of the same drug. The energy of interaction between water vapor and the surfaces of the two crystal polymorphs has been investigated as a function of temperature and water activity. One of the adsorbents, the metastable form of the monotropically related pair used here, showed greater adsorptive capacity in terms of both the amount of water uptake as well the integral heat of adsorption. However, the specific heat of adsorption values revealed that even though the surface of the thermodynamically stable crystal adsorbs less water, water molecules are actually more strongly bound when adsorbed on the surface of the stable crystal form. This means that the metastable crystal form adsorbs a greater amount of more weakly bound water. Conversely, the thermodynamically stable form, presents on its surface a smaller number of stronger adsorption sites for water. This study also shows that the crystalline character of the surfaces of the two polymorphs, shown as quantifiable differences in their surface interactions, is maintained despite the presence of any crystal defects incorporated upon milling. (C) 2005 Elsevier B.V. All rights reserved.