Abstract:
The heat capacity of synthetic, stoichiometric wadeite-type K2Si4O9 has been measured by DSC in the 195≤T(K)≤598 range. Near the upper temperature limit of our data, the heat capacity observed by DSC agrees with that reported by Geisinger et al. (1987) based on a vibrational model of their infrared and Raman spectroscopic data. However, with decreasing temperature, the Cp observed by DSC is progressively higher than that predicted from the vibrational model, suggesting that the standard entropy of K2Si4O9 is likely to be larger than 198.9 ± 4.0 J/K · mol computed from the spectroscopic data. A fit to the DSC data gave: Cp(T) = 499.13 (±1.87) − 4.35014 · 103(±3.489 · 101) · T −0.5, with T in K and average absolute percent deviation of 0.37%. The room-temperature compressibilities of kalsilite and leucite, hitherto unknown, have been measured as well. The data, fitted to the Murnaghan equation of state, gave K o = 58.6 GPa, K o′ = 0.1 for kalsilite and K o = 45 GPa, K o′ = 5.7 for α-leucite. Apart from the above mentioned data on the properties of the individual phases, we have also obtained reaction-reversals on four equilibria in the system K2O-Al2O3-SiO2. The Bayesian method has been used simultaneously to process the properties of 13 phases and 15 reactions between them to derive an internally consistent thermodynamic dataset for the K2O-Al2O3-SiO2 ternary. The enthalpy of formation of K2Si4O9 wadeite is in perfect agreement with its revised calorimetric value, the standard entropy is 232.1 ± 10.4 J/K · mol, ∼15% higher than that implied by vibrational modeling. The phase diagram, generated from our internally consistent thermodynamic dataset, shows that for all probable P-T trajectories in the subduction regime, the stable pressure-induced decomposition of K-feldspar will produce coesite + kalsilite rather than coesite + kyanite + K2Si4O9 (cf. Urakawa et al. 1994).
