Geology topics
Publications and source records attributed to B. S. Hemingway.
The heat capacities of phlogopite and paragonite were measured from 5-1000 and 800 K, respectively, by combined cryogenic- adiabatic and differential scanning calorimetry.-J.A.Z.
Modifications to an automated low-T, adiabatic calorimeter are described. Thermodynamic data obtained with this instrument are reported for minerals from metamorphic terrains. (U.S. Bureau of Mines Report of Investigations 8451)-J.A.Z.
The low-T 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 approx 10 and 380 K. -J.A.Z.
The heat capacity of Ni2SiO4-olivine has been measured between 5 and 387 K by cryogenic adiabatic-shield calorimetry and between 360 and 1000 K by differential scanning calorimetry. The heat capacity of Co2SiO4-olivine was measured between 360 and 1000 K by differential scanning calorimetry.-J.A.Z.
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.
The heat capacities of rhodochrosite, (Mn0.994Fe0.005Mg0.001)CO3, and siderite, 171(Fe0.956Mn0.042Mg0.002)CO3, were measured between 5 and 550 K by combined cryogenic-adiabatic and differential scanning calorimetry. These new data were used to reanalyse the thermodynamic properties of these phases.-J.A.Z.
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.
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.
At 298.15 K, 017Cop and So are 131.9 and 151.0 J/(mole.K). Also 045DELTA Hof,298 = -1478.17 and 045DELTA Gof,298 = -1378.98 kJ/mole. The temperature dependence of the equilibrium constant for the quartz - fayalite - magnetite buffer reaction is thus calculated.-K.A.R.
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.
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.
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.
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.