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Lawrence M. Anovitz

Publications and source records attributed to Lawrence M. Anovitz.

8 recordsLinked to original sources
USGS1993

Heat capacity and phase equilibria of almandine, Fe3Al2Si3O12

The heat capacity of a synthetic almandine, Fe 3 Al 2 Si 3 O 12 , was measured from 6 to 350 K using equilibrium, intermittent-heating quasi-adiabatic calorimetry and from 420 to 1000 K using differential scanning calorimetry. These measurements yield Cp 298 = 342.80 ± 1.4 J/mol · K and S 298 o = 342.60 J/mol · K. Mössbauer characterizations show the almandine to contain less than 2 ± 1% of the total iron as Fe 3+ . X-ray diffraction studies of this synthetic almandine yield a = 11.521 ± 0.001 Å and V 298 o = 115.11 +- 0.01 cm 3 /mol, somewhat smaller than previously reported. The low-temperature Cp data indicate a lambda transition at 8.7 K related to an antiferromagnetic-paramagnetic transition with T N = 7.5 K . Modeling of the lattice contribution to the total entropy suggests the presence of entropy in excess of that attributable to the effects of lattice vibrations and the magnetic transition. This probably arises from a low-temperature electronic transition (Schottky contribution). Combination of the Cp data with existing thermodynamic and phase equilibrium data on almandine yields ΔG f ,298 o = −4938.3 kJ/mol and ΔH f ,298 o = —5261.3 kJ/mol for almandine when calculated from the elements. The equilibrium almandine = hercynite + fayalite + quartz limits the upper T P "> TP for almandine and is metastably located at ca. 570°C at P = 1 bar, with a dP dT "> dPdT of +17 bars/°C. This agrees well with reversed experiments on almandine stability when they are corrected for magnetite and hercynite solid-solutions. In ‖ O 2- T space, almandine oxidizes near QFM by the reactions almandine + O 2 = magnetite + sillimanite + quartz and almandine + 02 = hercynite + magnetite + quartz . With suitable correction for reduced activities of solid phases, these equilibria provide useful oxygen barometers for medium- to high-grade metamorphic rocks.

Geochimica et Cosmochimica Acta↗
USGS1990

The thermodynamic properties of dumortierite Si 3 B[Al 6.75 [] 0.25 O 17.25 (OH) 0.75 ]

The heat capacities of dumortierite have been measured from 7 to 1000 K by quasiadiabatic low-temperature and differential scanning calorimetry. The corrected calorimetric entropy at 298.15 K calculated from the experimental data is 330.2 + 5.0 J/(mol.K) based upon the chemistry of the sample, average compositions proposed by Alexander et al. (1986), and correction to the structural formula given by Moore and Araki (1978). Moore and Araki (1978) have shown the Al(l) site to be disordered, and chemical analyses suggest that there is some Al substitution for Si. A minimum configurational entropy of 4.74 J/(mol'K) should be added to the corrected calorimetric entropy for third law calculations. The enthalpy and Gibbs free energy of formation of dumortierite from the elements have been estimated from synthesis and decomposition data and are -9109 + 20 and -8568 + 20 kJ/mol, respectively, at 298.15 K and I bar

American Mineralogist↗
USGS1987

Heat capacity measurements for cryolite (Na3AlF6) and reactions in the system NaFeAlSiOF

The heat capacity of cryolite (Na 3 AlF 6 ) has been measured from 7 to 1000 K by low-temperature adiabatic and high-temperature differential scanning calorimetry. Low-temperature data were obtained on material from the same hand specimen in the calorimetric laboratories of the University of Michigan and U.S. Geological Survey. The results obtained are in good agreement, and yield average values for the entropy of cryolite of: S 0 298 = 238.5 J / mol K "> S 0 298 = 238.5J/mol K S 0 T − S 0 298 = 145.114 ln T+ 193.009∗10 −3 T− 10.366∗ 10 5 T 2 − 872.89 J / mol K (273−836.5 K ) "> S 0 T −S 0 298 = 145.114lnT+ 193.009∗10 −3 T−10.366∗ 10 5 T 2 − 872.89J/mol K(273−836.5K) Δ S Trans = 9.9 J / mol K "> ΔS Trans = 9.9J/mol K S 0 T − S 0 298 =198.414 ln T+73.203∗ 10 −3 T−63.814∗ 10 5 T 2 −1113.11 J / mol K (836.5−1153 K ) "> S 0 T −S 0 298 =198.414 ln T+73.203∗ 10 −3 T−63.814∗10 5 T 2 −1113.11J/mol K(836.5−1153K) with the transition temperature between α- and β-cryolite taken at 836.5 K. These data have been combined with data in the literature to calculate phase equilibria for the system Na Fe Al Si O F. The resultant phase diagrams allow constraints to be placed on the f O 2 , f F 2 , a SiO 2 and T conditions of formation for assemblages in alkalic rocks. A sample application suggests that log f O 2 is approximately −19.2, log f F 2 is −31.9 to −33.2, and a SiO 2 is −1.06 at assumed P T "> PT conditions of 1000 K, 1 bar for the villiaumite-bearing Ilimaussaq intrusion in southwestern Greenland.

Geochimica et Cosmochimica Acta↗
USGS1986

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

The heat capacity of a natural monticellite (Ca 1.00 Mg .09 Fe .91 Mn .01 Si 0.99 O 3.99 ) measured between 9.6 and 343 K using intermittent-heating, adiabatic calorimetry yields C p 0 (298) and S 298 0 of 123.64 ± 0.18 and 109.44 ± 0.16 J · mol −1 K −1 respectively. Extrapolation of this entropy value to end-member monticellite results in an S 0 298 = 108.1 ± 0.2 J · mol −1 K −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): S T 0 ( J · mol −1 K −1 ) = S 298 0 + 164.79 In T + 15.337 · 10 −3 T + 22.791 · 10 5 T −2 − 968.94. Phase equilibria in the CaO-MgO-SiO 2 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 S 0 298 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-SiO 2 -CO 2 system was obtained with the ΔG 0 298 ( 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.

Geochimica et Cosmochimica Acta↗
USGS1985

The heat-capacity of ilmenite and phase equilibria in the system Fe-T-O

Low temperature adiabatic calorimetry and high temperature differential scanning calorimetry have been used to measure the heat-capacity of ilmenite (FeTiO 3 ) from 5 to 1000 K. These measurements yield S 298 0 = 108.9 J /( mol · K ). Calculations from published experimental data on the reduction of ilmenite yield Δ 298 0 ( I 1) = −1153.9 kJ /( mol · K ). These new data, combined with available experimental and thermodynamic data for other phases, have been used to calculate phase equilibria in the system Fe-Ti-O. Calculations for the subsystem Ti-O show that extremely low values of ƒO 2 ">ƒ ƒO2 are necessary to stabilize TiO, the mineral hongquiite reported from the Tao district in China. This mineral may not be TiO, and it should be re-examined for substitution of other elements such as N or C. Consideration of solid-solution models for phases in the system Fe-Ti-O allows derivation of a new thermometer/oxybarometer for assemblages of ferropseudobrookite-pseudobrookite ss and hematite-ilmenite ss . Preliminary application of this new thermometer/oxybarometer to lunar and terrestrial lavas gives reasonable estimates of oxygen fugacities, but generally yields subsolidus temperatures, suggesting re-equilibration of one or more phases during cooling.

Geochimica et Cosmochimica Acta↗