Entropies of kyanite, andalusite, and sillimanite: additional constraints on the pressure and temperature of the Al2SiO5 triple point

The low-temperature heat capacities of kyanite (Minas Gerais, Brazil), andalusite (Espirito Santo, Brazil), and sillimanite (Reinbolt Hills, Antarctica) were measured with an automatic, adiabatically shielded calorimeter between approximately l0 and 380 K. At 29E.15 K the entropies are E2.30-r0.13, 91.39-+0.14, and 95.79-ro.l4 J/(mol .K) for kyanite, andalusite, and sillimanite, respectively. our values are 1.8, 2.0 and0.4vo smaller than those of Todd (1950). Our calculated slope for the andalusite-sillimanite phase boundary is in significantly better agreement with the phase boundaries of Holdaway (1971), than with those of Richardson, Gilbert and Bell (1969) and strongly suggest that Al and Si are ordered in sillimanite to at least ll00 K. The thermal Debye temperatures, d$, calculated from our heat capacity data in the range ? < 18 K are 1lfi), E55, and 730 K for kyanite, andalusite, and sillimanite respectively. For andalusite and sillimanite our values for Ofi are in moderate agreement with those calculated from the room temperature adiabatic elastic stifness constants ofVaughan and Weidner (1978), 838 and 800 K, respectively.

[1]  Susan Werner Kieffer,et al.  Thermodynamics and lattice vibrations of minerals: 5. Applications to phase equilibria, isotopic fractionation, and high‐pressure thermodynamic properties , 1982 .

[2]  B. S. Hemingway,et al.  Thermodynamic tabulations for selected phases in the system CaO‐Al2O3‐ SiO2‐H2 at 101.325 kPa (1 atm) between 273.15 and 1800 K , 1981 .

[3]  Hillel Kumin,et al.  Thermodynamic analysis of the aluminum silicate triple point , 1980 .

[4]  E. Grew Sillimanite and Ilmenite from High-grade Metamorphic Rocks of Antarctica and Other Areas , 1980 .

[5]  H. Schneider Thermal Expansion of Andalusite , 1979 .

[6]  D. Weidner,et al.  The relationship of elasticity and crystal structure in andalusite and sillimanite , 1978 .

[7]  W. E. Cameron A mineral phase intermediate in composition between sillimanite and mullite , 1976 .

[8]  C. Hubbard,et al.  A silicon powder diffraction standard reference material , 1975 .

[9]  I. L. Barnes,et al.  Determination of the Avogadro Constant , 1974 .

[10]  O. J. Kleppa,et al.  Sillimanite—disordering enthalpy by calorimetry , 1973 .

[11]  W. Fyfe,et al.  Kyanite-andalusite equilibrium , 1971 .

[12]  M. J. Holdaway Stability of andalusite and the aluminum silicate phase diagram , 1971 .

[13]  O. J. Kleppa,et al.  The thermochemistry of the kyanite-sillimanite equilibrium , 1969 .

[14]  R. C. Newton Some high-pressure hydrothermal experiments on severely ground kyanite and sillimanite , 1969 .

[15]  R. A. Robie,et al.  Some Debye Temperatures from Single‐Crystal Elastic Constant Data , 1966 .

[16]  R. C. Newton Kyanite-Sillimanite Equilibrium at 750�C , 1966, Science.

[17]  D. Weill Stability relations in the Al2O3-SiO2 system calculated from solubilities in the Al2O3-Na3AlF6 system , 1966 .

[18]  B. W. Evans Application of a reaction-rate method to the breakdown equilibria of muscovite and muscovite plus quartz , 1965 .

[19]  C. Burnham Refinement of the crystal structure of kyanite , 1963 .

[20]  M. Buerger,et al.  Refinement of the crystal structure of andalusite , 1961 .

[21]  S. Todd Heat Capacities at Low Temperatures and Entropies at 298.16°K. of Andalusite, Kyanite, and Sillimanite , 1950 .