Heat capacity and glass transition in P₂O₅-H ₂O solutions: Support for Mishima's conjecture on solvent water at low temperature

The P₂O₅-water system has the widest range of continuously glass-forming compositions known for any glassformer + water binary system. Despite the great range of structures explored by the glasses and liquids in this system, the glass transition temperature (T_g) itself varies in a simple monotonic fashion. However the values of T_g reported in the literature show wide disagreement, linked to the different methods of measurement employed. In this work we use differential scanning calorimetry (DSC) to obtain both T_g itself and the jump in heat capacity that occurs as the metastable equilibrium of the supercooled liquid relieves the non-ergodic glassy state. Our study covers the molar ratio range of H₂O/P₂O₅ from 1.5 to 14 (corresponding to the mass fraction of P₂O₅ between 0.36 and 0.84), which includes the compositions corresponding to pyrophosphoric acid (H ₄P₂O₇) and orthophosphoric acid (H ₃PO₄). The theoretical model of Couchman and Karasz predicts very well the glass transition temperatures of the P₂O ₅-H₂O system over the whole composition range if the relatively large heat capacity change associated with water in aqueous solutions at the glass transition temperature is adopted, instead of the vanishingly small value observed for vapor deposited or hyperquenched pure water. Therefore, solvent water in this ambient pressure P₂O₅-H ₂O system behaves like a different liquid, more closely resembling a high-density liquid (HDL) polyamorph, as suggested by Mishima for electrolytes at high pressures.