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B. S. Hemingway

Publications and source records attributed to B. S. Hemingway.

33 records · Page 2Linked to original sources
USGS1986

Akermanite: phase transitions in heat capacity and thermal expansion, and revised thermodynamic data.

A small but sharp anomaly in the heat capacity of akermanite at 357.9 K, and a discontinuity in its thermal expansion at 693 K, as determined by XRD, have been found. The enthalpy and entropy assigned to the heat-capacity anomaly, for the purpose of tabulation, are 679 J/mol and 1.9 J/(mol.K), respectively. They were determined from the difference between the measured values of the heat capacity in the T interval 320-365 K and that obtained from an equation which fits the heat-capacity and heat-content data for akermanite from 290 to 1731 K. Heat-capacity measurements are reported for the T range from 9 to 995 K. The entropy and enthalpy of formation of akermanite at 298.15 K and 1 bar are 212.5 + or - 0.4 J/(mol.K) and -3864.5 + or - 4.0 kJ/mol, respectively. Weak satellite reflections have been observed in hk0 single-crystal X-ray precession photographs and electron-diffraction patterns of this material at room T. With in situ heating by TEM, the satellite reflections decreased significantly in intensity above 358 K and disappeared at about 580 K and, on cooling, reappeared. These observations suggest that the anomalies in the thermal behaviour of akermanite are associated with local displacements of Ca ions from the mirror plane (space group P421m) and accompanying distortion of the MgSi2O7 framework.-L.C.C.

Canadian Mineralogist↗
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↗
USGS1985

Low-temperature molar heat capacities and entropies of MnO2 (pyrolusite), Mn3O4 (hausmanite), and Mn2O3 (bixbyite)

Pyrolusite (MnO2), hausmanite (Mn3O4), and bixbyite (Mn2O3), are important ore minerals of manganese and accurate values for their thermodynamic properties are desirable to understand better the {p(O2), T} conditions of their formation. To provide accurate values for the entropies of these important manganese minerals, we have measured their heat capacities between approximately 5 and 380 K using a fully automatic adiabatically-shielded calorimeter. All three minerals are paramagnetic above 100 K and become antiferromagnetic or ferrimagnetic at lower temperatures. This transition is expressed by a sharp ??-type anomaly in Cpmo for each compound with Ne??el temperatures TN of (92.2??0.2), (43.1??0.2), and (79.45??0.05) K for MnO2, Mn3O4, and Mn2O3, respectively. In addition, at T ??? 308 K, Mn2O3 undergoes a crystallographic transition, from orthorhombic (at low temperatures) to cubic. A significant thermal effect is associated with this change. Hausmanite is ferrimagnetic below TN and in addition to the normal ??-shape of the heat-capacity maxima in MnO2 and Mn2O3, it has a second rounded maximum at 40.5 K. The origin of this subsidiary bump in the heat capacity is unknown but may be related to a similar "anomalous bump" in the curve of magnetization against temperature at about 39 K observed by Dwight and Menyuk.(1) At 298.15 K the standard molar entropies of MnO2, Mn3O4, and Mn2O3, are (52.75??0.07), (164.1??0.2), and (113.7??0.2) J??K-1??mol-1, respectively. Our value for Mn3O4 is greater than that adopted in the National Bureau of Standards tables(2) by 14 per cent. ?? 1985.

Journal of Chemical Thermodynamics↗
USGS1985

Low-temperature heat capacity and entropy of chalcopyrite (CuFeS2): estimates of the standard molar enthalpy and Gibbs free energy of formation of chalcopyrite and bornite (Cu5FeS4)

The heat capacity of CuFeS2 (chalcopyrite) was measured between 6.3 and 303.5 K. At 298.15 K, Cp,mo and Smo(T) are (95.67??0.14) J??K-1??mol-1 and (124.9??0.2) J??K-1??mol-1, respectively. From a consideration of the results of two sets of equilibrium measurements we conclude that ??fHmo(CuFeS2, cr, 298.15 K) = -(193.6??1.6) kJ??mol-1 and that the recent bomb-calorimetric determination by Johnson and Steele (J. Chem. Thermodynamics 1981, 13, 991) is in error. The standard molar Gibbs free energy of formation of bornite (Cu5FeS4) is -(444.9??2.1) kJ??mol-1 at 748 K. ?? 1985.

Journal of Chemical Thermodynamics↗
USGS1984

Heat capacity and thermodynamic functions for gehlenite and staurolite: with comments on the Schootky anomaly in the heat capacity of staurolite.

The heat capacities of a synthetic gehlenite and a natural staurolite were measured from 12 and 5 K, respectively, to 370 K by adiabatic calorimetry, and the heat capacities of staurolite were measured to 900 K by differential scanning calorimetry. At 298.15 K and 1 bar the entropy of gehlenite is 210.1 + or - 0.6 J/(mol.K) and that of staurolite is 1019.6 + or - 12.0 for H2Al2Fe4Al16Si8O48 and 1101.0 + or - 12.0 for 103(H3Al1.15Fe2+0.60)- 324(Fe2+2.07Fe3+0.54 Ti0.08Mn0.02Al1.19)(Mg0.44Al15.26)Si8O48. -J.A.Z.

American Mineralogist↗
USGS1982

Thermodynamic properties of selected uranium compounds and aqueous species at 298.15 K and 1 bar and at higher temperatures; preliminary models for the origin of coffinite deposits

Thermodynamic values for 110 uranium-bearing phases and 28 aqueous uranium solution species (298.15 K and l bar) are tabulated based upon evaluated experimental data (largely from calorimetric experiments) and estimated values. Molar volume data are given for most of the solid phases. Thermodynamic values for 16 uranium-bearing phases are presented for higher temperatures in the form of and as a supplement to U.S. Geological Survey Bulletin 1452 (Robie et al., 1979). The internal consistency of the thermodynamic values reported herein is dependent upon the reliability of the experimental results for several uranium phases that have been used as secondary calorimetric reference phases. The data for the reference phases and for those phases evaluated with respect to the secondary reference phases are discussed. A preliminary model for coffinite formation has been proposed together with an estimate of the free energy of formation of coffinite. Free energy values are estimated for several other uranium-bearing silicate phases that have been reported as secondary uranium phases associated with uranium ore deposits and that could be expected to develop wherever uranium is leached by groundwaters.

Open-File Report↗
USGS1978

Revised values for the Gibbs free energy of formation of [Al(OH)4 aq-], diaspore, boehmite and bayerite at 298.15 K and 1 bar, the thermodynamic properties of kaolinite to 800 K and 1 bar, and the heats of solution of several gibbsite samples

Solution calorimetric measurements compared with solubility determinations from the literature for the same samples of gibbsite have provided a direct thermochemical cycle through which the Gibbs free energy of formation of [Al(OH) 4 aq − ] can be determined. The Gibbs free energy of formation of [Al(OH) 4 aq − ] at 298.15 K is −1305 ± 1 kJ/mol. These heat-of-solution results show no significant difference in the thermodynamic properties of gibbsite particles in the range from 50 to 0.05 μm. The Gibbs free energies of formation at 298.15 K and 1 bar pressure of diaspore, boehmite and bayerite are −9210 ± 5.0, −918.4 ± 2.1 and −1153 ± 2 kJ/mol based upon the Gibbs free energy of [A1(OH) 4 aq − ] calculated in this paper and the acceptance of −1582.2 ± 1.3 and −1154.9 ± 1.2 kJ/mol for the Gibbs free energy of formation of corundum and gibbsite, respectively. Values for the Gibbs free energy formation of [Al(OH) 2 aq + ] and [AlO 2 aq − ] were also calculated as −914.2 ± 2.1 and −830.9 ± 2.1 kJ/mol, respectively. The use of [AlC 2 aq − ] as a chemical species is discouraged. A revised Gibbs free energy of formation for [H 4 SiO 4aq 0 ] was recalculated from calorimetric data yielding a value of −1307.5 ± 1.7 kJ/mol which is in good agreement with the results obtained from several solubility studies. Smoothed values for the thermodynamic functions C P 0 , ( H T 0 - H 298 0 ) T "> HT0- H2980)T , ( G T 0 - H 298 0 ) T "> (GT0- H2980)T , S T 0 - S 0 0 , ΔH ƒ,298 0 ">ƒ ΔHƒ,2980 kaolinite are listed at integral temperatures between 298.15 and 800 K. The heat capacity of kaolinite at temperatures between 250 and 800 K may be calculated from the following equation: C P 0 = 1430.26 − 0.78850 T + 3.0340 × 10 −4 T 2 −1.85158 × 10 −4 T 2 1 2 + 8.3341 × 10 6 T −2 "> 12+ 8.3341 × 106T−2 . The thermodynamic properties of most of the geologically important Al-bearing phases have been referenced to the same reference state for Al, namely gibbsite.

Geochimica et Cosmochimica Acta↗
USGS1970

Specific heats of lunar surface materials from 90 to 350 degrees Kelvin

The specific heats of lunar samples 10057 and 10084 returned by the Apollo 11 mission have been measured between 90 and 350 degrees Kelvin by use of an adiabatic calorimeter. The samples are representative of type A vesicular basalt-like rocks and of finely divided lunar soil. The specific heat of these materials changes smoothly from about 0.06 calorie per gram per degree at 90 degrees Kelvin to about 0.2 calorie per gram per degree at 350 degrees Kelvin. The thermal parameter γ = (kρC) -½ for the lunar surface will accordingly vary by a factor of about 2 between lunar noon and midnight.

Science↗