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The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2

January 1, 1986

The heat capacity of a natural monticellite (Ca1.00Mg.09Fe.91Mn.01Si0.99O3.99) measured between 9.6 and 343 K using intermittent-heating, adiabatic calorimetry yields Cp0(298) and S2980 of 123.64 ± 0.18 and 109.44 ± 0.16 J · mol−1K−1 respectively. Extrapolation of this entropy value to end-member monticellite results in an S0298 = 108.1 ± 0.2 J · mol−1K−1. High-temperature heat-capacity data were measured between 340–1000 K with a differential scanning calorimeter. The high-temperature data were combined with the 290–350 K adiabatic values, extrapolated to 1700 K, and integrated to yield the following entropy equation for end-member monticellite (298–1700 K): ST0(J · mol−1K−1) = S2980 + 164.79 In T + 15.337 · 10−3T + 22.791 · 105T−2 − 968.94. Phase equilibria in the CaO-MgO-SiO2 system were calculated from 973 to 1673 K and 0 to 12 kbar with these new data combined with existing data for akermanite (Ak), diopside (Di), forsterite (Fo), merwinite (Me) and wollastonite (Wo). The location of the calculated reactions involving the phases Mo and Fo is affected by their mutual solid solution. A best fit of the thermodynamically generated curves to all experiments is made when the S0298 of Me is 250.2 J · mol−1 K−1 less than the measured value of 253.2 J · mol−1 K−1.

A best fit to the reversals for the solid-solid and decarbonation reactions in the CaO-MgO-SiO2-CO2 system was obtained with the ΔG0298 (kJ · mole−1) for the phases Ak(−3667), Di(−3025), Fo(−2051), Me(−4317) and Mo(−2133). The two invariant points − Wo and −Fo for the solid-solid reactions are located at 1008 ± 5 K and 6.3 ± 0.1 kbar, and 1361 ± 10 K and 10.2 ± 0.2 kbar respectively. The location of the thermodynamically generated curves is in excellent agreement with most experimental data on decarbonation equilibria involving these phases.

Publication Year 1986
Title The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2
DOI 10.1016/0016-7037(86)90321-2
Authors Z.D. Sharp, E.J. Essene, Lawrence M. Anovitz, G.W. Metz, E.F. Westrum, B. S. Hemingway, J.W. Valley
Publication Type Article
Publication Subtype Journal Article
Series Title Geochimica et Cosmochimica Acta
Index ID 70015717
Record Source USGS Publications Warehouse