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R. A. Robie

Publications and source records attributed to R. A. Robie.

At least 37 records · Page 2Linked to original sources
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↗
USGS1983

Calorimetric investigation of the excess entropy of mixing in analbite-sanidine solid solutions: lack of evidence for Na,K short- range order and implications for two-feldspar thermometry.

Heat capacities (5-380 K) have been measured by adiabatic calorimetry for five highly disordered alkali feldspars (Ab99Or1, Ab85Or15, Ab55Or45, Ab25Or75 and Ab1Or99). The thermodynamic and mineralogical implications of the results are discussed. The new data are also combined with recent data for plagioclases in order to derive a revised expression for the two-feldspar thermometer. T calculated from the revised expression tend to be higher than previous calculations.-J.A.Z.

American Mineralogist↗
USGS1979

A room-temperature phase transition in maximum microcline - Heat capacity measurements

The thermal hysteresis in heat capacity measurements recently reported (Openshaw et al., 1976) for a maximum microcline prepared from Amelia albite by fused-salt ion-exchange is described in detail. The hysteresis is characterized by two limiting and reproducible curves which differ by 1% of the measured heat capacities. The lower curve, denoted curve B, represents the values obtained before the sample had been cooled below 300 K. Measurements made immediately after cooling the sample below 250 K followed a second parallel curve, curve A, to at least 370 K. Values intermediate to the two limiting curves were also obtained. The transitions from the B to the A curve were rapid and observed to occur three times. The time required to complete the transition from the A to the B curve increased from 39 h to 102 h in the two times it was observed to occur. The hysteresis is interpreted as evidence of a phase change in microcline at 300??10 K The heat effect associated with the phase change has not been evaluated. ?? 1979 Springer-Verlag.

Physics and Chemistry of Minerals↗
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↗
USGS1977

The entropy and Gibbs free energy of formation of the aluminum ion

A reevaluation of the entropy and Gibbs free energy of formation of Al 3+ (aq) yields −308 ± 15 J/K·mol and 489.4 ± 1.4kj/mol for S 0 298 and ΔG 0 ƒ,298 "> ΔG 0 ƒ,298 respectively. The standard electrode potential for aluminum is 1.691 ± 0.005 volts.

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↗
USGS1966

Some Debye temperatures from single-crystal elastic constant data

The mean velocity of sound has been calculated for 14 crystalline solids by using the best recent values of their single‐crystal elastic stiffness constants. These mean sound velocities have been used to obtain the elastic Debye temperatures θ D e for these materials. Models of the three wave velocity surfaces for calcite are illustrated.

Journal of Applied Physics↗