Thermochemistry and melting properties of basalt

The heat capacities of the liquid, glassy and crystalline phases of an alkali basalt have been determined from relative enthalpies measured between 400 and 1,800 K. Values given by available models of calculation generally agree to within 2% of these results. As derived from the new data and the enthalpy of vitrification measured at 973 K by oxide-melt drop solution calorimetry for the same sample, the enthalpy of fusion of this basalt increases from 15.4 kJ/mol at 1,000 K to 33.6 kJ/mol at 1,800 K. Comparisons between the enthalpies of fusion of basalt and model compositions confirm the small magnitude of the enthalpy of mixing between the molten mineral components of the liquids. Minor variations in the chemical composition have only a small effect in the heat capacity and the enthalpy of melting of basalt. The enthalpies of formation at 298 K from the oxides of the crystallized and glass phases of this alkali basalt are −112.2 and −98.5 kJ/mol, respectively, for a gram formula weight based on one mole of oxide components.     

Allochthonous and autochthonous organic matter in natural waters: Kinetic and thermodynamic patterns of transformation and quantitative and qualitative compositions

Using adsorption of organic matter (OM) on diethylaminoethyl cellulose (DEAE-cellulose) in the dynamic mode, OM is divided into autochthonous and allochthonous. Based on the experiments on BOD kinetics and OM division into components, the kinetic parameters of autochthonous and allochthonous OM transformation are established for the first time (k_aut = 0.013, k_all = 0.0013 day^–1 at t =20°C). The activation parameters of transformation for autochthonous OM (ΔH^# = 75.6 kJ/mol, ΔS^# =–116.5 J/(mol K), and ΔG^# = 108.3 J/mol) and allochthonous OM (ΔH^# = 66.1 kJ/mol, ΔS^# =–149.1 J/(mol K), and ΔG^# = 108.0 J/mol) are calculated by the Arrhenius equation.

     

Evaluation of thermochemical data on Fe-Mg olivine,orthopyroxene, spinel and Ca-Fe-Mg-Al garnet

Thermochemical data on Fe-Mg olivine, orthopyroxene, spinel and Ca-Fe-Mg garnet have been tested and reevaluated in reproducing experimental equilibrium data. All data (except of spinel) adjusted in this process lie within the error limits of original calorimetric experiments. For spinel, an enthalpy of −2307.2 kJ/mol and an entropy of 81.5 J/mol-K has been recommended. Recommended interaction parameters for the spinel-hercynite and forsterite-fayalite solutions are as follows:Spinel: W_{spinel-hercynite} = 9124.0 J/mol. W_{hercynite-spinel} = 0.0 J/molOlivine: W = 4500.0 J/mol for 1 cation.Excess entropies (on 1 cation basis) necessary to reproduce phase equilibria for the pyrope-almandine and almandine-grossular solutions are as follows:Mg-Fegarnet: W^s_{pyrope-almandine} = 11.760 − 0.00167 J/mol-K. W^s_{almandine-pyrope} = −10.146 +0.0037T J/mol-K.Fe-Ca garnet: W^s = −16.07 + 0.0126T J/mol-K.     

Thermodynamic properties and hydrogen speciation from vibrational spectra of dense hydrous magnesium silicates

Infrared absorption measurements were taken from 100 to 5000 cm^?1 of a natural chondrodite and three dense hydrous magnesium silicates: phase A, phase B, and superhydrous phase B (shy-B). Raman spectra were also acquired from phase B and the chondrodite. Roughly half of the lattice modes are represented and our data are the first report of the low frequency modes. Comparison of our new spectra to symmetry analyses suggests that multiple sites for hydrogen exist for all the phases. The shy-B we examined crystallizes in P2₁ nm with two OH sites. Models for the density of states are constructed based on band assignments for the lattice modes and for the OH stretching vibrations. Heat capacity C_P and entropy S calculated using Kieffer's formulation should be accurate within 3% from 200 to 800 K. Model values for C_P at 298 K are 299.6 J/mol-K for chondrodite, 421.5 J/mol-K for phase A, 529.4 J/mol-K for shy-B, and 618.9 J/mol-K for phase B. Model values for S₂₉₈ ⁰ are 234.2 J/mol-K for chondrodite, 303.5 J/ mol-K for phase A, 377.9 J/mol-K for shy-B, and 473.3 J/mol-K for phase B. Debye temperatures are near 1000 K.     

Synthesis, characterization, and thermochemistry of K-Na-H3O jarosites

The thermochemistry of well-characterized synthetic K-H₃O, Na-H₃O and K-Na-H₃O jarosites was investigated. These phases are solid solutions that obey Vegard’s law. Electron probe microanalyses indicated lower alkali and iron contents than predicted from the theoretical end-member compositions, in agreement with thermal analyses, suggesting the presence of hydronium and “additional” water. The standard enthalpies of formation (ΔH°_f) of K-H₃O, Na-H₃O and K-Na-H₃O jarosites were determined by high-temperature oxide melt solution calorimetry. These enthalpies vary linearly with the K/H₃O, Na/H₃O and K/Na ratio, respectively. The enthalpy of formation of pure hydronium jarosite was also determined experimentally (ΔH°_f = −3741.6 ± 8.3 kJ.mol⁻¹), and it was used to evaluate ΔH°_f for the end-members KFe₃(SO₄)₂(OH)₆ (ΔH°_f = −3829.6 ± 8.3 kJ.mol⁻¹) and NaFe₃(SO₄)₂(OH)₆ (ΔH°_f = −3783.4 ± 8.3 kJ.mol⁻¹). Finally, enthalpies of dehydration (loss of the “additional” water) of some jarosites were determined and found to be near the enthalpy of vaporization of water, suggesting that the “additional” water is weakly bonded in the structure.     

Stabilities of synthetic magnesian calcites in aqueous solution: Comparison with biogenic materials

Free-drift dissolution data and inverse time plots were used to evaluate the stabilities of synthetic and biogenic magnesian calcites in aqueous solutions at 25°C and 1 atm total pressure. Synthetic phases with MgCO₃ concentrations below 6 mole percent have stoichiometric ion activity products that are less than the value for calcite, whereas the values for phases with higher concentrations are greater than that of calcite. For synthetic phases, stability is a smooth function of composition and all phases (up to 15 mole percent MgCO₃) have values of ion activity products less than that for aragonite. These results agree with those of Mucci and Morse (1984) derived from precipitation of magnesian calcites in aqueous solutions. “Average” seawater at 25° and 1 atm total pressure is supersaturated with respect to all synthetic phases in the compositional range studied.Biogenic samples are less stable than synthetic phases of similar Mg concentrations and stability is not a smooth function of composition. Biogenic materials with compositions greater than 11–13 mole percent MgCO₃ have ion activity products greater than that for aragonite.The difference in stability between biogenic materials and synthetic phases is due to greater variation in chemical and physical heterogeneities found for the biogenic samples. If it is assumed that the results of the dissolution experiments reflect only differences in Gibbs free energies of formation between synthetic phases and biogenic materials of similar Mg concentration, the biogenic materials are 200–850 j/mol less stable than the synthetic phases. Only the results of synthetic dissolution experiments should be used to model the thermodynamic behavior of the magnesian calcite solid solution. The results for the synthetic phases, however, may not be appropriate to use for interpreting diagenetic reaction pathways for magnesian calcites in modern sediments, except as a basis of comparison with the behavior of natural materials.     

The aqueous solubility of trichloroethene (TCE) and tetrachloroethene (PCE) as a function of temperature

Using a flexible Au bag autoclave and a precision high-pressure liquid chromatography pump to control pressure, the liquid–liquid aqueous solubilities of TCE and PCE were measured as a function of temperature from 294 to 434 K (at constant pressure). The results were used to calculate the partial molal thermodynamic quantities of the organic liquid aqueous dissolution reactions: ΔḠ_soln, ΔH̄_soln, ΔS̄_soln and ΔC̄_{p soln}. Calculated values for these quantities at 298 K for TCE are: ΔḠ_soln=11.282 (±0.003) kJ/mol, ΔH̄_soln=−3.35 (±0.07) kJ/mol, ΔS̄_soln=−49.07 (±0.24) J/mol K, and ΔC̄_{p soln}=385.2 (±3.4) J/mol K. Calculated values for these quantities at 298 K for PCE are: ΔḠ_soln=15.80 (±0.04) kJ/mol, ΔH̄_soln=−1.79 (±0.58) kJ/mol, ΔS̄_soln=−59.00 (±1.96) J/mol K and ΔC̄_{p soln}=354.6 (±8.6) J/mol K. These thermodynamic quantities may be used to calculate the solubility of TCE and PCE at any temperature of interest. In the absence of direct measurements over this temperature range, the Henry's Law constants for TCE and PCE have been estimated using the measured aqueous solubilities and calculated vapor pressures.     

Calorimetric study of olivine solid solutions in the system Mg2SiO4-Fe2SiO4

Solution enthalpies of synthetic olivine solid solutions in the system Mg₂SiO₄-Fe₂SiO₄ have been measured in molten 2PbO·B₂O₃ at 979 K. The enthalpy data show that olivine solid solutions have a positive enthalpy of mixing and the deviation from ideality is approximated as symmetric with respect to composition, in contrast to the previous study. Applying the symmetric regular solution model to the present enthalpy data, the interaction parameter of ethalpy (W_H) is estimated to be 5.3±1.7 kJ/mol (one cation site basis). Using this W_h and the published data on excess free energy of mixing, the nonideal parameter of entropy (W_s) of olivine solid solutions is estimated as 0.6±1.5 J/mol·K.     

The accuracy of standard enthalpies and entropies for phases of petrological interest derived from density-functional calculations

The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO₃–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al₂SiO₅ polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.     

Modeling the thermodynamic parameters of six endmember garnets at ambient and high pressures from vibrational data

Raman and infrared spectroscopic data at ambient and high pressures were used to compute the lattice contribution to the heat capacities and entropies of six endmember garnets: pyrope, almandine, spessartine, grossular, andradite and uvarovite. Electronic, configurational and magnetic contributions are obtained from comparing available calorimetric data to the computed lattice contributions. For garnets with entropy in excess of the computed lattice contribution, the overwhelming majority is found in the subambient temperature regime. At room temperature, the non-lattice entropy is approximately 11.5 J/mol-K for pyrope, 49 J/mol-K for almandine, and 19 J/mol-K for andradite. The non-lattice entropy for pyrope and some for almandine cannot be accounted for by magnetic or electronic contributions and is likely to be configurational in nature. Estimates of low temperature non-lattice entropies for both spessartine and uvarovite are made in absence of calorimetric measurements and are based on low temperature calorimetry of other minerals containing the Mn²⁺ and Cr³⁺ cations as well as on solid solution garnets containing these cations. The estimate for uvarovite non-lattice entropy is approximately 18 J/mol-K, while for spessartine, approximately 45 J/mol-K. Neither of these cations is expected to provide electronic contributions to the entropy. For both iron-bearing garnets, a small electronic or magnetic entropy contribution continues above ambient temperatures. High pressure data on pyrope, grossular and andradite permit calculation of the thermodynamic parameters at high pressures, which are important for computation of processes in the Earth’s mantle. Thermal expansion coefficients of these materials were found to be 1.6, 1.5, 1.6×10⁻⁵ K⁻¹ at 298 K, respectively, using a Maxwell relation. These closely match the literature values at ambient conditions.     

Thermochemistry of yavapaiite KFe(SO4)2: Formation and decomposition

Yavapaiite, KFe(SO₄)₂, is a rare mineral in nature, but its structure is considered as a reference for many synthetic compounds in the alum supergroup. Several authors mention the formation of yavapaiite by heating potassium jarosite above ca. 400°C. To understand the thermal decomposition of jarosite, thermodynamic data for phases in the K-Fe-S-O-(H) system, including yavapaiite, are needed. A synthetic sample of yavapaiite was characterized in this work by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermal analysis. Based on X-ray diffraction pattern refinement, the unit cell dimensions for this sample were found to be a = 8.152 ± 0.001 Å, b = 5.151 ± 0.001 Å, c = 7.875 ± 0.001 Å, and β = 94.80°. Thermal decomposition indicates that the final breakdown of the yavapaiite structure takes place at 700°C (first major endothermic peak), but the decomposition starts earlier, around 500°C. The enthalpy of formation from the elements of yavapaiite, KFe(SO₄)₂, ΔH°_f = −2042.8 ± 6.2 kJ/mol, was determined by high-temperature oxide melt solution calorimetry. Using literature data for hematite, corundum, and Fe/Al sulfates, the standard entropy and Gibbs free energy of formation of yavapaiite at 25°C (298 K) were calculated as S°(yavapaiite) = 224.7 ± 2.0 J.mol⁻¹.K⁻¹ and ΔG°_f = −1818.8 ± 6.4 kJ/mol. The equilibrium decomposition curve for the reaction jarosite = yavapaiite + Fe₂O₃ + H₂O has been calculated, at pH₂O = 1 atm, the phase boundary lies at 219 ± 2°C.     

Premelting and high-temperature diffusion of Ca in synthetic diopside: An increase of the cation mobility

A study of Ca self-diffusion along the b axis in synthetic (iron free) diopside single crystal was performed at temperatures ranging from 1273 K to 1653 K. Diffusion profiles of ⁴⁴Ca were measured using α-particles Rutherford Backscattering (α-RBS) micro analysis. We unambiguously find two distinct diffusional regimes, characterized by activation enthalpies H = 280 ± 26 kJ/mol and H = 951 ± 87 kJ/mol at temperatures lower and upper than 1515 K, respectively. This change of diffusion regime takes place near the onset of premelting as detected in calorimetric measurements and can be interpreted in terms of enhanced formation of Frenkel point defects with an activation enthalpy of formation of 1524 ± 266 kJ/mol (H _f/2 = 762 kJ/mol), in accordance with our high-temperature diffusion data. If premelting of diopside is actually related to Ca-Frenkel point defect concentration, this concentration could reach up to few mole percents close to the melting temperature.     

Physical properties of calcium aluminates from vibrational spectroscopy

Heat capacity (C_V) and entropy (S) as a function of temperature were calculated for phases in the CaO-Al₂O₃ system from vibrational spectra using a quasi-harmonic model. Calculated values of C_V at 298 K for the calcium aluminates may have uncertainties as small as ±1%, based on comparison with published calorimetric data for CaO, Al₂O₃, and CaAl₂O₄. For hibonite (CaAl₁₂O₁₉), we predict C_P as 519.3 J/mol-K and S as 391.7 J/mol-K, at 298 K. For grossite (CaAl₄O₇), calculated values of C_P as 195.9 J/mol-K and of S as 172.0 J/mol-K are slightly smaller than the available calorimetric data at 298 K, consistent with calorimetric data having been obtained from samples containing ∼10 wt% hibonite impurities. Thermal conductivity at 298 K (k₀) is predicted from peak widths of the vibrational modes using the damped harmonic oscillator model of a phonon gas. Calculations of k₀ for CaO and Al₂O₃ differ from the measurements by 17% and 5%, respectively. The discrepancy for lime is larger due to uncertainties in its peak widths. This comparison suggests that our results for the calcium aluminates should be more accurate than conventional measurements of k₀ which are commonly uncertain by ∼25%.     

Partitioning of Fe and Mn between ilmenite and olivine at 1100 °C: constraints on the thermodynamic mixing properties of (Fe, Mn)TiO3 ilmenite solid solutions

The partitioning of Fe²⁺ and Mn²⁺ between (Fe, Mn)TiO₃ and (Fe, Mn)₂SiO₄ solid solutions in the system FeO-MnO-TiO₂-SiO₂ has been experimentally investigated at 1100 ^∘C and pressures of 1 bar and 25 kbar, over a wide range of Fe/Mn ratios, using electron microprobe analysis of quenched run products. The ilmenite solid solution in this system is within analytical uncertainty a simple binary between FeTiO₃ and MnTiO₃, but the olivine solid solution appears to contain up to 2.5 wt% TiO₂. The Fe-Mn partitioning results constrain precisely the difference in the thermodynamic mixing properties of the two solid solutions. If the mixing properties of (Fe, Mn)₂SiO₄ solid solutions are assumed to be ideal, as experimentally determined by Schwerdtfeger and Muan (1966), then the ilmenite is a regular, symmetric solution with W ^ilm _Fe-Mn=1.8±0.1 kJ mol⁻¹. The quoted uncertainty does not include the contribution from the uncertainty in the mixing properties of the olivine solution, which is estimated to be ±1.8 kJ mol⁻¹, and which therefore dominates the uncertainty in the present results. Nevertheless, this result is in good agreement with the previous experimental study of O'Neill et al. (1989), who obtained W ^ilm _Fe-Mn=2.2±0.3 kJ mol⁻¹ from an independent method. The results provide another item of empirical evidence supporting the proposition that solid solutions between isostructural end-members, in which order-disorder effects are not important, generally have simple thermodynamic mixing properties, with little asymmetry, modest excess entropies, and excess enthalpies approximately proportional to the difference in the molar volumes of the end-members. Received: 11 February 1998 / Accepted: 29 June 1998     

Thermochemistry of jarosite-alunite and natrojarosite-natroalunite solid solutions

The thermochemistry of jarosite-alunite and natrojarosite-natroalunite solid solutions was investigated. Members of these series were either coprecipitated or synthesized hydrothermally and were characterized by XRD, FTIR, electron microprobe analysis, ICP-MS, and thermal analysis. Partial alkali substitution and vacancies on the Fe/Al sites were observed in all cases, and the solids studied can be described by the general formula K_1-x-yNa_y(H₃O)_xFe_zAl_w(SO₄)₂(OH)_6-3(3-z-w)(H₂O)_3(3-z-w). A strong preferential incorporation of Fe over Al in the jarosite/alunite structure was observed. Heats of formation from the elements, ΔH°_f, were determined by high-temperature oxide melt solution calorimetry. The solid solutions deviate slightly from thermodynamic ideality by exhibiting positive enthalpies of mixing in the range 0 to +11 kJ/mol. The heats of formation of the end members of both solid solutions were derived. The values ΔH°_f = −3773.6 ± 9.4 kJ/mol, ΔH°_f = −4912.2 ± 24.2 kJ/mol, ΔH°_f = −3734.6 ± 9.7 kJ/mol and ΔH°_f = −4979.7 ± 7.5kJ/mol were found for K_0.85(H₃O)_0.15Fe_2.5(SO₄)₂(OH)_4.5(H₂O)_1.5, K_0.85(H₃O)_0.15Al_2.5(SO₄)₂(OH)_4.5(H₂O)_1.5, Na_0.7(H₃O)_0.3Fe_2.7(SO₄)₂(OH)_5.1(H₂O)_0.9, and Na_0.7(H₃O)_0.3Al_2.7(SO₄)₂(OH)_5.1(H₂O)_0.9 respectively. To our knowledge, this is the first experimentally-based report of ΔH°_f for such nonstoichiometric alunite and natroalunite samples. These thermodynamic data should prove helpful to study, under given conditions, the partitioning of Fe and Al between the solids and aqueous solution.     

Mechanistic evaluation of the sorption properties of endocrine disrupting chemicals in sewage sludge biomass

This study investigated the sorption behaviour of two endocrine disrupting chemicals; 17β-estradiol (E2) and 17β-ethinylestradiol and their thermodynamic properties in an activated sludge biomass. The partition coefficient values measured for E2 and EE2 at varying temperatures range from 245–604 L/kg ( log K_d 2.39–2.78) and 267–631 L/kg (Log K_d 2.43–2.80), respectively. The K_d values were inversely related to temperature. The average percentages of E2 and EE2 adsorbed to the solid phase at 4.3 % dry solid were 87.2 % and 92.5 %, respectively. Sorption of E2 and EE2 to the activated sludge biomass was found to be spontaneous and entropy retarded with ΔG values in the range of ?13 to ?16 KJ/mol and ΔS value of?105.2J/mol/K and 96.7 J/mol/k for E2 and EE2, respectively. The enthalpy changes for E2 and EE2 were ?45.7KJ/mol and ?43.4KJ/mol respectively, demonstrating that the sorption process is exothermic. The values of the enthalpy changes also show that the mechanism of sorption is physisorption with some element of chemisorption.     

Thermodynamic properties of Pd chloride complexes and the Pd2+(aq) ion in aqueous solutions

Based on the expert review of literature data on the thermodynamic properties of species in the Cl-Pd system, stepwise and overall stability constants are recommended for species of the composition [PdCl _n ]^{2 ? n} , and the standard electrode potential of the half-cell PdCl ₄ ^2? /Pd(c) is evaluated at E _298,15° = 0.646 ± 0.007 V, which corresponds to Δ _f G _298.15° = ?400.4 ± 1.4 kJ/mol for the ion PdCl ₄ ^2? (aq). Derived from calorimetric data, Δ _f H _298.15° PdCl ₄ ^2? (aq) = ?524.6 ± 1.6 kJ/mol and Δ _f H _298.15° Pd²⁺(aq) = 189.7 ± 2.6 kJ/mol. The assumed values of the overall stability constant of the PdCl ₄ ^2? ion and the standard electrode potential of the PdCl ₄ ^2? /Pd(c) half-cell correspond to Δ _f G _298.15° = 190.1 ± 1.4 kJ/mol and S _298.15° = ?94.2 ± 10 J/(mol K) for the Pd²⁺(aq) ion.     

Thermodynamic data from redox reactions at high temperatures. II. The MnO-0Mn3O4 oxygen buffer,and implications for the thermodynamic properties of MnO and Mn3O4

The \(\mu _{O_2 } \) defined by the reaction 6 MnO+O₂ =2 Mn₃O₄ has been determined from 917 to 1,433 K using electrochemical cells (with calcia-stabilized zirconta, CSZ) of the type: Steady emfs were achieved rapidly at all temperatures on both increasing and decreasing temperature, indicating that the MnO-Mn₃O₄ oxygen buffer equilibrates relatively easily. It therefore makes a useful alternative choice in experimental petrology to Fe₂O₃-Fe₃O₄ for buffering oxygen potentials at oxidized values. The results are (in J/mol, temperature in K, reference pressure 1 bar); \(\mu _{O_2 } \) (±200)=-563,241+1,761.758T-220.490T inT+0.101819T ² with an uncertainty of ±200 J/mol. Third law analysis of these data, including a correction for the deviations in stoichiometry of MnO, impliesS _298.15 for Mn₃O₄ of 166.6 J/K · mol, which is 2.5 J/K · mol higher than the calorimetric determination of Robie and Hemingway (1985). The low value of the calorimetric entropy may be due to incomplete ordering of the magnetic spins. The third law value of Δ _r H _298.15 ⁰ is-450.09 kJ/mol, which is significantly different from the calorimetric value of-457.5±3.4 kJ/mol, calculated from Δ _f H _298.15 ⁰ of MnO and Mn₃O₄, implying a small error in one or both of these latter.     

High temperature calorimetry of sulfide systems

Enthalpies of solution of synthetic pentlandite Fe_4.5Ni_4.5S₈, natural violarite (Fe_0.2941Ni_0.7059)₃S₄ from Vermillion mine, Sudbury, Ontario, synthetic pyrrhotite, FeS, synthetic high temperature NiS, synthetic vaesite, NiS₂, synthetic pyrite, FeS₂, Ni and Fe have been measured in a Ni_0.6S_0.4 melt at 1,100 K. Using these data and the standard enthalpies of formation of binary sulfides, given in literature, standard enthalpies of formation of pentlandite and violarite were calculated. The following values are reported: ΔH _f ^{o, Pent} =?837.37±14.59 kJ mol^?1 and ΔH _f ^{o, Viol} =?378.02±11.81 kJ mol^?1. While there are no thermo-chemical data for pentlandite with which our new value can be compared, an equilibrium investigation of stoichiometric violarite by Craig (1971) gives a significantly less negative enthalpy of formation. It is suggested that the difference may be due to the higher degree of order in the natural sample.     

The stability of annite+quartz: reversed experimental data for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite +2 H2O

Reversals for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite+2 H₂O have been experimentally determined in cold-seal pressure vessels at pressures of 2, 3, 4 and 5?kbar, limiting annite +quartz stability towards higher temperatures. The equilibrium passes through the temperature intervals 500–540°?C (2?kbar), 550–570°?C (3?kbar), 570–590°?C (4?kbar) and 590–610°?C (5?kbar). Starting materials for most experiments were mixtures of synthetic annite +fayalite+sanidine+quartz and in some runs annite+quartz alone. Microprobe analyses of the reacted mixtures showed that the annites deviate slightly from their ideal Si/Al ratio (Si per formula unit ranges between 2.85 and 2.92, Al^VI between 0.06 and 0.15). As determined by Mössbauer spectroscopy, the Fe³⁺ content of annite in the assemblage annite+fayalite +sanidine+quartz is around 5–7%. The experimental data were used to extract the thermodynamic standard state enthalpy and entropy of annite as follows: H ⁰ _f,?Ann =?5125.896±8.319 [kJ/mol] and S ⁰ _Ann=432.62±8.89 [J/mol/K] (consistent with the Holland and Powell 1990 data set), and H ⁰ _f,Ann =?5130.971±7.939 [kJ/mol] and S ⁰ _Ann=424.02±8.39 [J/mol/K] (consistent with the TWEEQ data base, Berman 1991). The preceeding values are close to the standard state properties derived from hydrogen sensor data of the redox reaction annite=sanidine+magnetite+H ₂ (Dachs 1994). The experimental half-reversal of Eugster and Wones (1962) on the annite +quartz breakdown reaction could not be reproduced experimentally (formation of annite from sanidine+fayalite+quartz at 540°?C/1.035?kbar/magnetite-iron buffer) and probable reasons for this discrepancy remain unclear. The extracted thermodynamic standard state properties of annite were used to calculate annite and annite+quartz stabilities for pressures between 2 and 5?kbar.