Abstract
Relative-enthalpy measurements have been made on the hexagonal, tetragonal, glass and liquid phases of GeO2. The glass transition is very sensitive to the impurity content, with a T g ranging from 980 K for a pure product to 780 K for a Li-doped sample with 0.06 mol % Li. The relative C p change at T g of about 5% increases with the impurity content as a result of lower glass transition temperatures. Above 298 K the derived heat capacities are similar for all forms, with slightly higher values for the amorphous phases and two C p cross-overs at 400 and 1000 K between the hexagonal and tetragonal modifications. For both GeO2 and SiO2 the coordination state markedly affects C p and the entropy below 300 K, where the properties are much lower for the tetragonal than for the hexagonal modifications, i.e., S 298 = 39.7 vs 55.3 J/mole K and 27.8 vs 41.4 J/ mole K for GeO2 and SiO2, respectively. The high-temperature C p's of coesite and stishovite are likely similar to those of the low-pressure SiO2 forms. Finally, these results, low-temperature C p data and enthalpy-of-solution measurements have been used to derive a consistent set of thermodynamic properties for the GeO2 modifications.
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Richet, P. GeO2 vs SiO2: Glass transitions and thermodynamic properties of polymorphs. Phys Chem Minerals 17, 79–88 (1990). https://doi.org/10.1007/BF00209228
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DOI: https://doi.org/10.1007/BF00209228