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Wenjun Yong E. Dachs A. C. Withers E. J. Essene 《Contributions to Mineralogy and Petrology》2008,155(2):137-146
The low-temperature heat capacity (C
p) of Si-wadeite (K2Si4O9) synthesized with a piston cylinder device was measured over the range of 5–303 K using the heat capacity option of a physical
properties measurement system. The entropy of Si-wadeite at standard temperature and pressure calculated from the measured
heat capacity data is 253.8 ± 0.6 J mol−1 K−1, which is considerably larger than some of the previous estimated values. The calculated phase transition boundaries in the
system K2O–Al2O3–SiO2 are generally consistent with previous experimental results. Together with our calculated phase boundaries, seven multi-anvil
experiments at 1,400 K and 6.0–7.7 GPa suggest that no equilibrium stability field of kalsilite + coesite intervenes between
the stability field of sanidine and that of coesite + kyanite + Si-wadeite, in contrast to previous predictions. First-order
approximations were undertaken to calculate the phase diagram in the system K2Si4O9 at lower pressure and temperature. Large discrepancies were shown between the calculated diagram compared with previously
published versions, suggesting that further experimental or/and calorimetric work is needed to better constrain the low-pressure
phase relations of the K2Si4O9 polymorphs.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
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Wenjun Yong E. Dachs A. C. Withers E. J. Essene 《Physics and Chemistry of Minerals》2006,33(3):167-177
The low-temperature heat capacity (C
p
) of KAlSi3O8 with a hollandite structure was measured over the range of 5–303 K with a physical properties measurement system. The standard entropy of KAlSi3O8 hollandite is 166.2±0.2 J mol−1 K−1, including an 18.7 J mol−1 K−1 contribution from the configurational entropy due to disorder of Al and Si in the octahedral sites. The entropy of K2Si4O9 with a wadeite structure (Si-wadeite) was also estimated to facilitate calculation of phase equilibria in the system K2O–Al2O3–SiO2. The calculated phase equilibria obtained using Perple_x are in general agreement with experimental studies. Calculated phase relations in the system K2O–Al2O3–SiO2 confirm a substantial stability field for kyanite–stishovite/coesite–Si-wadeite intervening between KAlSi3O8 hollandite and sanidine. The upper stability of kyanite is bounded by the reaction kyanite (Al2SiO5) = corundum (Al2O3) + stishovite (SiO2), which is located at 13–14 GPa for 1,100–1,400 K. The entropy and enthalpy of formation for K-cymrite (KAlSi3O8·H2O) were modified to better fit global best-fit compilations of thermodynamic data and experimental studies. Thermodynamic calculations were undertaken on the reaction of K-cymrite to KAlSi3O8 hollandite + H2O, which is located at 8.3–10.0 GPa for the temperature range 800–1,600 K, well inside the stability field of stishovite. The reaction of muscovite to KAlSi3O8 hollandite + corundum + H2O is placed at 10.0–10.6 GPa for the temperature range 900–1,500 K, in reasonable agreement with some but not all experiments on this reaction. 相似文献
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