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R. A. Robie

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

At least 19 recordsLinked to original sources
USGS2002

Heat capacity from 12 to 305°K and entropy of talc and tremolite

The heat capacities of talc, Mg 3 Si 4 O 10 (OH) 2 , and tremolite, Ca 2 Mg 6 Si 8 O 22 (OH) 2 , have been measured between 12 and 305°K. Smoothed values of heat capacity, entropy, enthalpy, and free energy are tabulated. At 298.15° K. the values of the thermodynamic functions are: talc, C p °= 76.89 ± 0.23 cal. deg. -1 mole -1 , S° = 62.33 ± 0.19 cal. deg. -1 mole -1 , H° - H 0 ° = 11,206 ± 34 cal. mole -1 ; tremolite, Cp° = 156.7 ± 0.6 cal. deg. -1 mole -1 , S° = 131.2 ± 0.5 cal. deg. -1 mole -1 , H° - H 0 ° = 23,335 ± 90 cal. mole -1 . From the equilibrium data of Bowen and Tuttle and the entropy of talc, the heat of formation of talc from MgO, SiO 2 , and H 2 O (liq.) is calculated to be Δ H°f 298 = -43.6 ± 1 kcal.

Journal of Physical Chemistry↗
USGS1997

Molar heat capacity and entropy of calcium metal

The heat capacity of calcium has been measured at 85 mean temperatures between T ≈ 8 K and T ≈ 369 K using an adiabatically-shielded calorimeter in an intermittent heating mode. At T = 298.15 K, the recommended values for the molar heat capacity, molar entropy, and molar enthalpy increment referred to T = 0 are (25.77 ± 0.08) J·K −1 ·mol −1 , (42.90 ± 0.11) J·K −1 ·mol −1 , and (5811 ±12)J·mol −1 , respectively. The uncertainties are twice the standard deviation of the mean.

Journal of Chemical Thermodynamics↗
USGS1995

Heat capacities and thermodynamic properties of braunite (Mn7 SiO12) and rhodonite (MnSiO3)

The heat capacities, C0P, of synthetic rhodonite and braunite have been measured by adiabatic calorimetry from 6 to ~350 K. The heat capacity of braunite was also measured to ~900 K by differential scanning calorimetry. Brunite exhibits a ??-peak in C0P in the temperature region 93.4-94.2 K. Rhodonite did not show the expected peak in C0P characteristic of the co-operative ordering of the Mn2+ spins at temperatures above 6 K. A revised petrogenetic grid for the system Mn-Si-O-C at 2000 bars is presented and is consistent with both thermochemical values and occurrence of natural assemblages. -from Authors

American Mineralogist↗
USGS1991

Melting and thermodynamic properties of pyrope (Mg3Al2Si3O12)

The heat capacity of Mg 3 Al 2 Si 3 O 12 glass has been measured from 10 to 1000 K by adiabatic and differential scanning calorimetry. The heat capacity of crystalline pyrope has been determined from drop-calorimetry measurements between 820 and 1300 K. From these and previously published results a consistent set of thermodynamic data is presented for pyrope and Mg 3 Al 2 Si 3 O 12 glass and liquid for the interval 0–2000 K. The enthalpy of fusion at 1570 ± 30 "> 1570 ± 30 K, the metastable congruent 1-bar melting point, is 241 ± 12 kJ/mol "> 241 ± 12kJ/mol .

Geochimica et Cosmochimica Acta↗
USGS1991

Heat capacities and entropies of sillimanite, fibrolite, andalusite, kyanite, and quartz and the Al2SiO5 phase diagram

Low-temperature heat capacities for sillimanite, fibrolite, and both fine-grained and coarse-grained quartz have been measured. Superambient heat capacities have been measured for four sillimanite, two andalusite, one kyanite, and two fibrolite samples. Equations are recommended for the temperature dependence of the heat capacities of kyanite, andalusite, sillimanite, and fibrolite. The heat capacity functions have been combined with thermal expansion (fibrolite and sillimanite reported here), enthalpy of solution, and phase equilibrium data in order to construct a phase diagram for the Al2SiO5 polymorphs. -from Authors

American Mineralogist↗
USGS1990

Thermodynamics of open networks: Ordering and entropy in NaAlSiO4 glass, liquid, and polymorphs

The thermodynamic properties of carnegieite and NaAlSiO4 glass and liquid have been investigated through Cp determinations from 10 to 1800 K and solution-calorimetry measurements. The relative entropies S298-S0 of carnegieite and NaAlSiO4 glass are 118.7 and 124.8 J/mol K, respectively. The low-high carnegieite transition has been observed at 966 K with an enthalpy of transition of 8.1??0.3 kJ/mol, and the enthalpy of fusion of carnegieite at the congruent melting point of 1799 K is 21.7??3 kJ/mol. These results are consistent with the reported temperature of the nepheline-carnegieite transition and available thermodynamic data for nepheline. The entropy of quenched NaAlSiO4 glass at 0 K is 9.7??2 J/mol K and indicates considerable ordering among AlO4 and SiO4 tetrahedra. In the liquid state, progressive, temperature-induced Si, Al disordering could account for the high configurational heat capacity. Finally, the differences between the entropies and heat capacities of nepheline and carnegieite do not seem to conform to current polyhedral modeling of these properties ?? 1990 Springer-Verlag.

Physics and Chemistry of Minerals↗
USGS1990

Heat capacities and thermodynamic properties of annite (aluminous iron biotite)

The heat capacities have been measured between 7 and 650 K by quasi-adiabatic calorimetry and differential scanning calorimetry. At 298.15 K and 1 bar, the calorimetric entropy for our sample is 354.9??0.7 J/(mol.K). A minimum configurational entropy of 18.7 J/(mol.K) for full disorder of Al/Si in the tetrahedral sites should be added to the calorimetric entropy for third-law calculations. The heat capacity equation [Cp in units of J/mol.K)] Cp0 = 583.586 + 0.075246T - 3420.60T-0.5 - (4.4551 ?? 106)T-2 fits the experimental and estimated heat capacities for our sample (valid range 250 to 1000 K) with an average deviation of 0.37%. -from Authors

American Mineralogist↗
USGS1989

Heat capacities and entropies at 298.15 K of MgTiO3 (geikielite), ZnO (zincite), and ZnCO3 (smithsonite)

Heat capacities of synthetic MgTiO3 (geikielite), ZnO (zincite), and natural crystals of smithsonite (ZnCO3) were measured between 9 and 366 K using an automatic adiabatically shielded calorimeter. At 298.15 K the standard molar entropies Smo of MgTiO3, ZnO, and ZnCO3 are (74.64 ?? 0.15), (43.16 ?? 0.09), and (81.19 ?? 0.16) J??K-1??mol-1, respectively. Debye temperatures for MgTiO3 and ZnO calculated from our Cp, mo values below 20 K are (900 ?? 20) K and (440 ?? 25) K respectively. Heat capacities for MgTiO3 and ZnO were combined with enthalpy increments from the literature to derive heat-capacity equations for these phases from 260 to about 1800 K. The heat capacities of MgTiO3 between 260 and 1720 K were fitted with an average deviation of 0.3 per cent by the equation: C??p,m/(J??K-1??mol-1) = 222.5-0.05274(T/K)-6.092x105(T/K)-1-1874.6(T/K) -1/2+1.878x10-5(T/K)2 and for ZnO the equation: C??p,m/(J??K-1??mol-1) = 53.999+7.851x10-4(T/K)-5.868x105(T/K)-2 -127.50(T/K)-:1/2+1.9376x10-6(T/K)2 fits the heat capacities in the temperature interval of 250 to 1800 K with an average deviation of 0.7 per cent. ?? 1989.

Journal of Chemical Thermodynamics↗
USGS1988

Thermophysical properties of ilvaite CaFe22+Fe3+Si2O7O (OH); heat capacity from 7 to 920 K and thermal expansion between 298 and 856 K

The heat capacity of ilvaite from Seriphos, Greece was measured by adiabatic shield calorimetry (6.4 to 380.7 K) and by differential scanning calorimetry (340 to 950 K). The thermal expansion of ilvaite was also investigated, by X-ray methods, between 308 and 853 K. At 298.15 K the standard molar heat capacity and entropy for ilvaite are 298.9??0.6 and 292.3??0.6 J/(mol. K) respectively. Between 333 and 343 K ilvaite changes from monoclinic to orthorhombic. The antiferromagnetic transition is shown by a hump in Cp0with a Ne??el temperature of 121.9??0.5 K. A rounded hump in Cp0between 330 and 400 K may possibily arise from the thermally activated electron delocalization (hopping) known to take place in this temperature region. ?? 1988 Springer-Verlag.

Physics and Chemistry of Minerals↗
USGS1987

Heat capacities of synthetic hedenbergite, ferrobustamite and CaFeSi2O6 glass

Heat capacities have been measured for synthetic hedenbergite (9–647 K), ferrobustamite (5–746 K) and CaFeSi 2 O 6 glass (6–380 K) by low-temperature adiabatic and differential scanning calorimetry. The heat capacity of each of these structural forms of CaFeSiO 6 exhibits anomalous behavior at low temperatures. The X-peak in the hedenbergite heat-capacity curve at 34.5 K is due to antiferromagnetic ordering of the Fe 2+ ions. Ferrobustamite has a bump in its heat-capacity curve at temperatures less than 20 K, which could be due to weak cooperative magnetic ordering or to a Schottky anomaly. Surprisingly, a broad peak with a maximum at 68 K is present in the heat-capacity curve of the glass. If this maximum, which occurs at a higher temperature than in hedenbergite is caused by magnetic ordering, it could indicate that the range of distortions of the iron sites in the glass is quite small and that coupling between iron atoms is stronger in the glass than in the edge-shared octahedral chains of hedenbergite. The standard entropy change, S o 298.15 − S o 0 , is 174.2 ± 0.3, 180.5 ± 0.3 and 185.7 ± 0.4 J/mol·K for hedenbergite, ferrobustamite and CaFeSi 2 O 6 glass, respectively. Ferrobustamite is partially disordered in Ca-Fe distribution at high temperatures, but the dependence of the configuratonal entropy on temperature cannot be evaluated due to a lack of information. At high temperatures (298–1600 K), the heat capacity of hedenbergite may be represented by the equation C o p (J/mol·K) = 3 l 0.46 + 0.01257 T -2039.93 T −1 2 − 1.84604× l0 6 T −2 "> −12− 1.84604× 10 6 T −2 and the heat capacity of ferrobustamite may be represented by C o p (J/mol·K) = 403.83−0.04444T+ 1.597× 10 −5 T 2 −3757.3T −1 2 "> C o p (J/mol·K)= 403.83−0.04444T+ 1.597× 10 −5 T 2 −3757.3T −12 .

Geochimica et Cosmochimica Acta↗
USGS1986

Heat capacities and thermodynamic functions for beryl, Be3Al2Si6O18, phenakite, Be2SiO4, euclase, BeAlSiO4(OH), bertrandite, Be4Si2O7(OH)2, and chrysoberyl, BeAl2O4.

The heat capacities of beryl, phenakite, euclase and bertrandite have been measured between approx 5 and 800 K by combined quasi-adiabatic cryogenic calorimetry and differential scanning calorimetry. The heat capacities of chrysoberyl have been measured from 340 to 800 K. The resulting data have been combined with solution and phase-equilibrium experimental data and simultaneously adjusted using the programme PHAS20 to provide an internally consistent set of thermodynamic properties for several important beryllium phases. The experimental heat capacities and tables of derived thermodynamic properties are presented.-J.A.Z.

American Mineralogist↗
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

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↗