The thermodynamics and kinetics of the dehydration of CsH2PO4 studied in the presence of SiO2

The thermodynamic and kinetics of the dehydration and hydration of CsH2PO4 is investigated by thermogravimetric, differential scanning calorimetry and X-ray diffraction analysis in the temperature range of 200 to 400 degrees C, water partial pressure range of 0.06 to 0.90 atm. SiO2 powder was added to CsH2PO4 to accelerate both dehydration and hydration. When dehydrated in the presence of SiO2, CsH2PO4 has a fine microstructure (similar to 200 nm feature size), and no reaction between CsH2PO4 and SiO2 is observed. By making use of the enhanced kinetics afforded by SiO2, the phase boundary between CsH2PO4, CsPO3 and dehydrated liquid was precisely determined. The triple point connecting these phases is located at p(H2O) = 0.35 +/- 0.2 atm and T = 267.5 +/- 1.0 degrees C. The stability of CsH2PO4 and the liquid dehydrate, CsH2(1-x)PO4-x(l), were confirmed by the complete reversal of dehydration to recover these phases in the appropriate temperature and water partial pressure ranges. Rehydration and conversion of CsPO3(s) to CsH2PO4(s) occur over a period of several hours, depending on temperature, water partial pressure, and morphology of the metaphosphate. High p(H2O) and small particles favor rapid dehydration, whereas the temperature dependence of the rehydration kinetics is non-monotonic, reaching its fastest rate in the vicinity of the superprotonic transition. (c) 2011 Elsevier B.V. All rights reserved.