A thermochemical study of vaterite

Vaterite is shown to be unstable with respect to calcite at 25°C by measurements of the enthalpies of solution in 0·1 N HCl under 0·97 atm CO₂ and the solubilities in water under 0·97 atm CO₂ of the two polymorphs. For a pure, synthetic vaterite ΔH (tr) = ?1036 ±16 cal mol^?1 and ΔG(tr) = ?790 ± 25 cal mol^?1 for the transition to calcite. For other vaterites aged longer during preparation ΔH(tr) is smaller and shows a linear relationship with the X-ray line broadening which extrapolates to ΔH(tr) = ?545 ± 30 cal mo^?1 for zero broadening. The use of X-ray line broadening as a measure of crystal imperfection and stability is discussed for various synthetic and natural vaterites.     

The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4

Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe²⁺ which is a major constituent of the upper mantle. Previous calculations for Fe₂SiO₄ ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S _CFS). We have calculated free energy changes (ΔG _CFS) due to differences of crystal field splittings between Fe₂SiO₄ spinel and fayalite from: ΔG _CFS=?ΔCFSE?TΔS _CFS, as functions of P and T, for different energy splittings of t _2g orbital levels of Fe²⁺ in spinel. The results indicate that ΔG _CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe₂SiO₄, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg_1?x Fe _x )₂SiO₄ are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.     

Thermodynamic properties of copper carbonates — malachite Cu2(OH)2CO3 and azurite Cu3(OH)2(CO3)2

The thermodynamic properties of the copper carbonates malachite and azurite have been studied by adiabatic calorimetry, by heat-flux Calvet Calorimetry, by differential thermal analysis (DTA) and by thermogravimetrie (TGA) analysis. The heat capacities, C _p ⁰ of natural malachite and azurite have been measured between 3.8 and 300 K by low-temperature adiabatic calorimetry. The heat capacity of azurite exhibits anomalous behavior at low temperatures. At 298.15 K the molar heat capacities C _p ⁰ and the third law entropies S _298.15 ⁰ are 228.5±1.4 and 254.4±3.8 J mol^?1 K^?1 for azurite and 154.3±0.93 and 166.3±2.5 J mol^?1 K^?1 for malachite. Enthalpies of solution at 973 K in lead borate 2PbO·B₂O₃ have been measured for heat treated malachite and azurite. The enthalpies of decomposition are 105.1±5.8 for azurite and 66.1±5.0 kJ mol^? for malachite. The enthalpies of formation from oxides of azurite and malachite determined by oxide melt solution calorimetry, are ?84.7±7.4 and ?52.5±5.9 kJ mol^?1, respectively. On the basis of the thermodynamic data obtained, phase relations of azurite and malachite in the system Cu²⁺-H₂O-CO₂ at 25 and 75 °C have been studied.     

A thermochemical study of monohydrocalcite

The thermodynamic properties of monohydrocalcite, CaCO₃ · H₂O, have been obtained using a well-characterized natural specimen. Equilibration of the solid with water at 25°C under 0.97 atm CO₂ led to an activity product [Ca²⁺][CO₃^2?] = 10^?7.60±0.03 and a free energy of formation ΔG_f^o = ?325,430 ± 270 calmol^?. The enthalpy of solution of monohydrocalcite in 0.1 N HCl at 25°C led to a standard enthalpy of formation ΔH_f^o = ?358,100 ± 280 cal mol^?1. Estimates of the variation of ΔG_f with temperature and pressure showed monohydrocalcite to be metastable with respect to calcite and aragonite.     

The reaction forsterite+cordierite=aluminous orthopyroxene+spinel in the system MgO-Al2O3-SiO2

Reversal experiments at 1,150–1,300°C on the reaction forsterite+cordierite=aluminous orthopyroxene+spinel in the system MgO-Al₂O₃-SiO₂ show the equilibrium to have a negativedT/dP. The slope andT-P location of this equilibrium have been modelled using available heat capacity data and various structural models which explore the configurational entropy contributions to the totalΔS. The experimental data are consistent with the aluminous orthopyroxene model of Ganguly and Ghose (1979) where limited Al disorder occurs between theM1 andM2 sites, Al-Si mixing occurs on the tetrahedralB site with the ‘aluminum avoidance’ principle maintained, and Mg-Al disorder occurs in spinel with an interchange enthalpy of 9–12 kcal mol^?1. Additionally, Al-Si disordering which occurs in the indialite structure of cordierite is inconsistent with the experimental data and all pyroxene and spinel mixing models; consequently, Si and Al in anhydrous cordierites to 1,300°C in the system MgO-Al₂O₃-SiO₂ must be largely ordered.     

Standard Gibbs free energy of formation for Cu2O,NiO, CoO,and FexO: High resolution electrochemical measurements using zirconia solid electrolytes from 900–1400 K

Galvanic cells with oxygen-specific solid electrolytes made of calcia-stabilized zirconia have been used to make equilibrium measurements of the standard Gibbs free energy of formation, Δ_fG⁰_m,(T), for copper (I) oxide (Cu₂O), nickel (II) oxide (NiO), cobalt (II) oxide (CoO), and wüstite (Fe_xO) over the temperature range from 900–1400 K. The measured values of Δ_fG⁰_m at 1300 K are −73950, −123555, −142150, and −179459 J · mol⁻¹ for Cu₂O, NiO, CoO, and Fe_0.947O, respectively. The precision of these measurements is ± 30–60 J · mol⁻¹, and their absolute accuracy is estimated to be ± 100–200 J·mol⁻¹. Using values of –76.557, −94.895, −79.551, and −71.291 J · K⁻¹ · mol⁻¹ for the entropies of formation, Δ_fS_m⁰, (298.15 K), the calculated enthalpies of formation, Δ_fH_m⁰, (298.15 K), are −170508, −240110, −237390, and −266458 J · mol⁻¹ for Cu₂O, NiO, CoO, and Fe_0.947O, respectively. These values of Δ_fS_m⁰ (298.15 K) and Δ_fH_m⁰ (298.15 K) are in good agreement with the best available calorimetric measurements.     

Thermodynamics and crystal chemistry of the hematite–corundum solid solution and the FeAlO3 phase

High-temperature oxide-melt calorimetry and Rietveld refinement of powder X-ray diffraction patterns were used to investigate the energetics and structure of the hematite–corundum solid solution and ternary phase FeAlO₃ (with FeGaO₃ structure). The mixing enthalpies in the solid solution can be described by a polynomial ΔH_mix=WX _hem(1?X _hem) with W=116 ± 10 kJ mol^?1. The excess mixing enthalpies are too positive to reproduce the experimental phase diagram, and excess entropies in the solid solution should be considered. The hematite–corundum solvus can be approximately reproduced by a symmetric, regular-like solution model with ΔG _excess=(W _H ?TW _S )X _hem X _cor, where W _H= 116 ± 10 kJ mol^?1 and W _S =32 ± 4 J mol^?1 K^?1. In this model, short-range order (SRO) of Fe/Al is neglected because SRO probably becomes important only at intermediate compositions close to Fe:Al=1:1 but these compositions cannot be synthesized. The volume of mixing is positive for Al-hematite but almost ideal for Fe-corundum. Moreover, the degree of deviation from Vegard's law for Al-hematite depends on the history of the samples. Introduction of Al into the hematite structure causes varying distortion of the hexagonal network of oxygen ions while the position of the metal ions remains intact. Distortion of the hexagonal network of oxygen ions attains a minimum at the composition (Fe_0.95Al_0.05)₂O₃. The enthalpy of formation of FeAlO₃ from oxides at 298 K is 27.9 ± 1.8 kJ mol^?1. Its estimated standard entropy (including configurational entropy due to disorder of Fe/Al) is 98.9 J mol^?1 K^?1, giving the standard free energy of formation at 298 K from oxides and elements as +19.1 ± 1.8 and ?1144.2 ± 2.0 kJ mol^?1, respectively. The heat capacity of FeAlO₃ is approximated as C _p (T in K)= 175.8 ? 0.002472T ? (1.958 × 10⁶)/T ²? 917.3/T ^0.5+(7.546 × 10^?6) T ² between 298 and 1550 K, based on differential scanning calorimetric measurements. No ferrous iron was detected in FeAlO₃ by Mössbauer spectroscopy. The ternary phase is entropy stabilized and is predicted to be stable above about 1730 ± 70 K, in good agreement with the experiment. Static lattice calculations show that the LiNbO₃-, FeGaO₃-, FeTiO₃-, and disordered corundum-like FeAlO₃ structures are less stable (in the order in which they are listed) than a mechanical mixture of corundum and hematite. At high temperatures, the FeGaO₃-like structure is favored by its entropy, and its stability field appears on the phase diagram.     

Synthetic MgGa2O4-Mg2GeO4 spinel solid solution and β-Mg3Ga2GeO8: chemistry, crystal structures, cation ordering, and comparison to Mg2GeO4 olivine

 Structural parameters and cation ordering are determined for four compositions in the synthetic MgGa₂O₄-Mg₂GeO₄ spinel solid solution (0, 8, 15 and 23 mol% Mg₂GeO₄; 1400 °C, 1 bar) and for spinelloid β-Mg₃Ga₂GeO₈ (1350 °C, 1 bar), by Rietveld refinement of room-temperature neutron diffraction data. Sample chemistry is determined by XRF and EPMA. Addition of Mg₂GeO₄ causes the cation distribution of the MgGa₂O₄ component to change from a disordered inverse distribution in end member MgGa₂O₄, ^[4]Ga = x = 0.88(3), through the random distribution, toward a normal cation distribution, x = 0.37(3), at 23 mol% Mg₂GeO₄. An increase in a_o with increasing Mg₂GeO₄ component is correlated with an increase in the amount of Mg on the tetrahedral site, through substitution of 2 Ga³⁺⇄ Mg²⁺+Ge⁴⁺. The spinel exhibits high configurational entropy, reaching 20.2 J mol⁻¹ (four oxygen basis) near the compositional upper limit of the solid solution. This stabilizes the spinel in spite of positive enthalpy of disordering over the solid solution, where ΔH _D  = αx + βx ², α = 22(3), β = −21(3) kJ mol⁻¹. This model for the cation distribution across the join suggests that the empirically determined limit of the spinel solid solution is correlated with the limit of tetrahedral ordering of Mg, after which local charge-balanced substitution is no longer maintained. Spinelloid β-Mg₃Ga₂GeO₈ has cation distribution ^M1[Mg_0.50(2)Ga_0.50(2)] ^M2[Mg_0.96(2)Ga_0.04(2)] ^M3[Mg_0.77(2) Ga_0.23(2)]₂ (Ge_0.5Ga_0.5)₂O₈ (tetrahedral site occupancies are assumed). Octahedral site size is correlated to Mg distribution, where site volume, site distortion, and Mg content follow the relation M1<M3<M2. The disordered cation distribution provides local electrical neutrality in the structure, and stabilization through increased configurational entropy (27.6 J mol⁻¹; eight oxygen basis). Comparison of the crystal structures of Mg_{1+ N} Ga_{2−2 N} Ge _N O₄ spinel, β-Mg₃Ga₂GeO₈, and Mg₂GeO₄ olivine reveals β-Mg₃Ga₂GeO₈ to be a true structural intermediate. Phase transitions across the pseudobinary are necessary to accommodate an increasing divergence of cation size and valence, with addition of Mg₂GeO₄ component. Octahedral volume increases while tetrahedral volume decreases from spinel to β-Mg₃Ga₂GeO₈ to olivine, with addition of Mg and Ge, respectively. Furthermore, M-M distances increase regularly across the join, suggesting that changes in topology reduce cation-cation repulsion. Received: 9 November 1998 / Revised, accepted: 3 August 1999     

Comparison of the raman microprobe spectra of (Mg,Fe)2SiO4 and Mg2GeO4 with olivine and spinel structures

Raman microprobe (RMP) spectra were produced for each of the olivine and spinel structured phases of Mg₂GeO₄ and (Mg, Fe)₂SiO₄. The assembled data show that bands due to the tetrahedra in silicate and germanate olivines shift in a way that indicates a dominant mass effect. This correspondence is difficult to make in spinels due to differences in structural type. Differences in Fe/Mg content of olivine shift the tetrahedral vibration bands only slightly, but their linear shifts could be used to indicate the composition of the phase.     

Quantitative analysis of H2O and CO2 in cordierite using polarized FTIR spectroscopy

We report a FTIR (Fourier transform infrared) study of a set of cordierite samples from different occurrence and with different H₂O/CO₂ content. The specimens were fully characterized by a combination of techniques including optical microscopy, single-crystal X-ray diffraction, EMPA (electron microprobe analysis), SIMS (secondary ion mass spectrometry), and FTIR spectroscopy. All cordierites are orthorhombic Ccmm. According to the EMPA data, the Si/Al ratio is always close to 5:4; X _Mg ranges from 76.31 to 96.63, and additional octahedral constituents occur in very small amounts. Extraframework K and Ca are negligible, while Na reaches the values up to 0.84 apfu. SIMS shows H₂O up to 1.52 and CO₂ up to 1.11 wt%. Optically transparent single crystals were oriented using the spindle stage and examined by FTIR micro-spectroscopy under polarized light. On the basis of the polarizing behaviour, the observed bands were assigned to water molecules in two different orientations and to CO₂ molecules in the structural channels. The IR spectra also show the presence of small amounts of CO in the samples. Refined integrated molar absorption coefficients were calibrated for the quantitative microanalysis of both H₂O and CO₂ in cordierite based on single-crystal polarized-light FTIR spectroscopy. For H₂O the integrated molar coefficients for type I and type II water molecules (ν₃ modes) were calculated separately and are ^[I]ε?=?5,200?±?700?l?mol^?1?cm^?2 and ^[II]ε?=?13,000?±?3,000?l?mol^?1?cm^?2, respectively. For CO₂ the integrated coefficient is $ \varepsilon_{{{\text{CO}}_{ 2} }} $ ?=?19,000?±?2,000?l?mol^?1?cm^?2.     

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.     

A volume temperature relationship for liquid GeO2 and some geophysically relevant derived parameters for network liquids

The thermal expansivity of liquid GeO₂ at temperatures just above the glass transition has been obtained using a combination of scanning calorimetry and dilatometry. The calorimetric and dilatometric curves of c _p and dV/dT are normalized to the temperature derivative of fictive temperature versus temperature using the method of Webb et al. (1992). This normalization, based on the equivalence of relaxation parameters for volume and enthalpy, allows the completion of the dilatometric trace across the glass transition to yield liquid expansivity and volume. The values of liquid volume and expansivity obtained in this study are combined with high temperature densitometry determinations of the liquid volume of GeO₂ by Sekiya et al. (1980) to yield a temperature-volume relation for GeO₂ melt from 660 to 1400 °C. Liquid GeO₂ shows a strongly temperature-dependent liquid molar expansivity, decreasing from 20.27 × 10^?4 cm³ mol^?1°C^?1 to 1.97 × 10^?4cm³ mol^?1 °C^?1 with increasing temperature. The coefficient of volume thermal expansion (α _v ) decreases from 76.33 × 10^?6 °C^?1 to 2.46 × 10^?6 °C^?1 with increasing temperature. A qualitatively similar volume-temperature relationship, with α _v decreasing from 335 × 10^?6 °C^?1 to 33 × 10^?6 °C^?1 with increasing temperature, has been observed previously in liquid B₂O₃. The determination of the glass transition temperature, liquid volume, liquid and glassy expansivities and heat capacities in this study, combined with compressibility data for glassy and liquid GeO₂ from the literature (Soga 1969; Kurkjian et al. 1972; Scarfe et al. 1987) allows the calculation of the Prigogine-Defay ratio (Π), c _p -c _v and the thermal Grüneisen parameter (γ _th) for GeO₂. From available data on liquid SiO₂ it is concluded that liquid GeO₂ is not a good analog for the low pressure properties of liquid SiO₂.     

Thermodynamic calculation of peridotite phase relations in the system MgO-Al2O3-SiO2-Cr2O3, with some geological applications

The system MgO-Al₂O₃-SiO₂(MAS) comprises 88–90% of the bulk composition of an average peridotite. The MAS ternary is thus a suitable starting point for exploring peridotite phase relations in multicomponent natural systems. The basic MAS phase relations may be treated in terms of the reactions (see list of symbols etc).

1. py (in Gt)=en (in Opx)+mats (in Opx),
2. en (in Opx)+sp (in Sp)=mats (in Opx)+fo (in Ol), and
3. py (in Gt)+fo (in Ol)=en (in Opx)+sp (in Sp).

Extensive reversed phase equilibria data on these three reactions by Danckwerth and Newton (1978), Perkins et al. (1981), and Gasparik and Newton (1984) employing identical experimental methods in the same laboratory have been used by us to deduce the following internally consistent thermodynamic data applying the technique of linear programming:ΔH ₂₉₈₍₁₎ ⁰ = 2536 J, ΔS ₂₉₈₍₁₎ ⁰ =? 6.064 J/K;ΔH ₂₉₈₍₂₎ ⁰ = 29435 J, ΔS ₂₉₈₍₂₎ ⁰ = 8.323 J/K; andΔH ₂₉₈₍₃₎ ⁰ =?26899 J, ΔS ₂₉₈₍₃₎ ⁰ =?14.388 J/K.These data are also found to be consistent with results of calorimetry. Figure 2 shows the calculated phase relations based on our thermodynamic data; they are consistent with the phase equilibria experiments. Successful extension of the MAS phase relations to multicomponent peridotites pivots on the extent to which the effects of the “non-ternary” (i.e. other than MAS) components can be quantitatively handled. Particularly hazardous in this context is Cr₂O₃, although it barely makes up 0.2 to 0.5 wt% of such rocks. This is because Cr⁺³ fractionates extremely strongly into Sp. This study focuses on the peridotite phase relations in the MgO-Al₂O₃-SiO₂-Cr₂O₃ (MASCr) quaternary. Thermodynamic calculations of the MASCr phase relations have been accomplished by using ΔH ₂₉₈ ⁰ and ΔS ₂₉₈ ⁰ values for the reactions (1) through (3) indicated above, in conjunction with data on thermodynamic mixing properties of

1. binary Sp (sp-pc) crystalline solution (Oka et al. 1984),
2. ternary Opx (en-mats-mcts) crystalline solution (this study), and
3. binary Gt (py-kn) crystalline solution (this study).

The results are shown in P-T projections (Figs. 3a and b) and isobaric-isothermal sections of MASCr in a projection through the component fo onto the SiO₂-Al₂O₃-Cr₂O₃ ternary (Figs. 4a and b). The most important results of this work may be summarized as follows:

1. With increasing incorporation of Cr⁺³ into Sp and Gt, the X _mats isopleths of the reactions (1) and (2) are shifted to higher temperatures (Fig. 3a); simultaneously, the spinel-peridotite to garnet-peridotite phase transition is moved to higher pressures (Fig. 3b).
2. At identical P and T, the X _mats values of Opx coexisting in equilibrium with Ol and Sp is strongly dependent upon the X _pc value in the latter phase (Figs. 4a and b). Accurate correction for the composition of Sp is, therefore, a necessary precondition for geothermometry of the spinelperidotites.
3. The discrepant temperatures reported by Sachtleben und Seck (1981, Fig. 5) from the spinel-peridotites of the Eifel area (systematically too high temperatures as a function of X _pc in Sp) are demonstrated to be the result of ignoring the nonideality in the chromian spinels.

     

Thio complexes of gold and the transport of gold in hydrothermal ore solutions

The solubility of gold in aqueous sulphide solutions has been determined from pH_20°C ≈ 4 to pH_20°C ≈ 9.5 in the presence of a pyrite-pyrrhotite redox buffer at temperatures from 160 to 300°C and 1000 bar pressure. Maximum solubilities were obtained in the neutral region of pH as, for example, with m_NaHS = 0.15 m, pH_20°C = 5.96, T = 309°C, P = 1000 bar where a gold solubility of 225 mg/kg was obtained. It was concluded that three thio gold complexes contributed to the solubility. The complex Au₂(HS)₂S^2? predominated in alkaline solution, the Au(HS)₂^? complex occurred in the neutral pH region, and in the acid pH region, it was concluded with less certainty that the Au(HS)° complex was present. Formation constants calculated forAu₂(HS)₂S^2? and Au (HS)₂^? emphasize their high stability. In the temperature range from 175 to 250°C, values of pβ for Au₂(HS)₂S^2? vary from ?53.0 to 47.9 (±1.6) and from ?23.1 to ?19.5 ( ± 1.5) for Au(HS)₂^?. Equilibrium constante for the dissolution reactions, $\text{Au° + H}{}_2\text{S + HS}{}^{\mathrm{?}}\text{? Au(HS)}{}_2{}^{\mathrm{?}}\text{+}\text{1}\text{2}\text{H}{}_2$ and 2Au° + H₂S + 2H8^? ? Au(HS)₂^? + H₂ vary from pK_m = +2.4 to +2.55 (±0.10) for Au₂(HS)₂S^2? and from pK_n = + 1.29 to + 1.19 (±0.10) for Au(HS)₂^? over the temperature range 175 to 250°C. Enthalpies of these dissolution reactions were calculated to be ΔH_m° = ?5.2 ±2.0 kcal/mol and ΔH_n° = +1.7 ±2.0 kcal/mol respectively. It was concluded that gold is probably transported in hydrothermal ore solutions as both thio and chloro complexes and may be deposited in response to changes in temperature, pressure, pH, oxidation potential of the system and total sulphur concentration.     

Thermodynamic and magnetic properties of knorringite garnet (Mg3Cr2Si3O12) based on low-temperature calorimetry and magnetic susceptibility measurements

The low-temperature heat capacity of knorringite garnet (Mg₃Cr₂Si₃O₁₂) was measured between 2 and 300 K, and thermochemical functions were derived from the results. The measured heat capacity curves show a sharp lambda-shaped anomaly peaking at around 5.1 K. Magnetic susceptibility data show that the transition is caused by antiferromagnetic ordering. From the C _p data, we suggest a standard entropy (298.15 K) of 301 ± 2.5 J mol^?1 K^?1 for Mg₃Cr₂Si₃O₁₂. The new data are also used in conjunction with previous experimental results to constrain ?H _f ° for knorringite.     

Infrared spectra of olivine polymorphs: α, β phase and spinel

Infrared (IR) absorption spectra are presented for olivine (α) and spinel (γ) phases of A₂SiO₄ (A=Fe, Ni, Co) and Mg₂GeO₄. IR spectra of β phase (“modified spinel”) Co₂SiO₄ and of α Mg₂SiO₄ are also included. These results provide reference spectra for the identification of olivine high-pressure polymorphs. Isostructural and isochemical correlations are used to support a general interpretation of the spectra and to predict the spectrum of γ Mg₂SiO₄. A γ Mg₂GeO₄ sample equilibrated at 1,000° C shows evidence of partial inversion, but one equilibrated at 730° C does not. This suggests that partial inversion could occur in silicate spinels at elevated temperatures and pressures, however no evidence of inversion is seen in the ir spectra of the silicates in this study.     

The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2

The heat capacity of a natural monticellite (Ca_1.00Mg_.09Fe_.91Mn_.01Si_0.99O_3.99) measured between 9.6 and 343 K using intermittent-heating, adiabatic calorimetry yields C_p⁰(298) and S₂₉₈⁰ of 123.64 ± 0.18 and 109.44 ± 0.16 J · mol⁻¹K⁻¹ respectively. Extrapolation of this entropy value to end-member monticellite results in an S⁰₂₉₈ = 108.1 ± 0.2 J · mol⁻¹K⁻¹. High-temperature heat-capacity data were measured between 340–1000 K with a differential scanning calorimeter. The high-temperature data were combined with the 290–350 K adiabatic values, extrapolated to 1700 K, and integrated to yield the following entropy equation for end-member monticellite (298–1700 K): S_T⁰(J · mol⁻¹K⁻¹) = S₂₉₈⁰ + 164.79 In T + 15.337 · 10⁻³T + 22.791 · 10⁵T⁻² − 968.94. Phase equilibria in the CaO-MgO-SiO₂ system were calculated from 973 to 1673 K and 0 to 12 kbar with these new data combined with existing data for akermanite (Ak), diopside (Di), forsterite (Fo), merwinite (Me) and wollastonite (Wo). The location of the calculated reactions involving the phases Mo and Fo is affected by their mutual solid solution. A best fit of the thermodynamically generated curves to all experiments is made when the S⁰₂₉₈ of Me is 250.2 J · mol⁻¹ K⁻¹ less than the measured value of 253.2 J · mol⁻¹ K⁻¹.A best fit to the reversals for the solid-solid and decarbonation reactions in the CaO-MgO-SiO₂-CO₂ system was obtained with the ΔG⁰₂₉₈ (kJ · mole⁻¹) for the phases Ak(−3667), Di(−3025), Fo(−2051), Me(−4317) and Mo(−2133). The two invariant points − Wo and −Fo for the solid-solid reactions are located at 1008 ± 5 K and 6.3 ± 0.1 kbar, and 1361 ± 10 K and 10.2 ± 0.2 kbar respectively. The location of the thermodynamically generated curves is in excellent agreement with most experimental data on decarbonation equilibria involving these phases.     

Spinelloid phases in the system MgGa2O4-Mg2GeO4

Spinelloid phases have been observed and characterized by powder X-ray diffraction and high-resolution electron microscopy. Mg₃Ga₂GeO₃(III), with a narrow composition range of approximately 3 mole percent Mg₂GeO₄, is stable at atmospheric pressure up to about 1,420° C, and is isostructural with β-Mg₂SiO₄ and the spinelloid Phase III of the NiAl₂O₄-Ni₂SiO₄ system. This represents the first occurrence of a β-phase structure stable at 1 atm pressure. Above 1,420° C (1 atm) Mg₃Ga₂GeO₈ (III) decomposes reversibly into a mixture of spinel and olivine. At high pressure (around 30 kbar at 1,100° C) it transforms into another spinelloid phase, Mg₃Ga₂GeO₈ (IV), isostructural with Phase IV of the NiAl₂O₄-Ni₂SiO₄ system. In terms of crystal structures and phase relations therefore there exists a close analogy between the magnesium gallo-germanate and nickel alumino-silicate systems, the former being a lower-pressure analogue of the latter. Our investigation of a number of other pseudo-binary spinel-olivine oxide systems suggests that the formation of spinelloid phases can be associated with the inverse character of the spinel component.     

Heat capacity of ferrosilite, Fe2Si2O6

The heat capacity of synthetic ferrosilite, Fe₂Si₂O₆, was measured between 2 and 820 K. The physical properties measurement system (PPMS, Quantum Design^®) was used in the low-temperature region between 2 and 303 K. In the temperature region between 340 and 820 K measurements were performed using differential scanning calorimetry (DSC). The C _p data show two transitions, a sharp λ-type at 38.7 K and a small shoulder near 9 K. The λ-type transition can be related to collinear antiferromagnetic ordering of the Fe²⁺ spin moments and the shoulder at 10 K to a change from a collinear to a canted-spin structure or to a Schottky anomaly related to an electronic transition. The C _p data in the temperature region between 145 and 830 K are described by the polynomial $C_{p} {\left[ {\hbox{J\,mol}^{{ - 1}}\,{\hbox{K}}^{{ - 1}} } \right]} = 371.75 - 3219.2T^{{ - 1/2}} - 15.199 \times 10^{5} T^{{ - 2}} + 2.070 \times 10^{7} T^{{ - 3}} $ The heat content [H ₂₉₈ – H ₀] and the standard molar entropy [S ₂₉₈ – S ₀] are 28.6 ± 0.1 kJ mol^?1 and 186.5 ± 0.5 J mol^?1 K^?1, respectively. The vibrational part of the heat capacitiy was calculated using an elastic Debye temperature of 541 K. The results of the calculations are in good agreement with the maximum theoretical magnetic entropy of 26.8 J mol^?1 K^?1 as calculated from the relationship 2*Rln5.     

Thermodynamic properties of tellurite (β-TeO2), paratellurite (α-TeO2), TeO2 glass,and Te(IV) phases with stoichiometry M2Te3O8, MTe6O13, MTe2O5 (M2+ = Co,Cu, Mg,Mn, Ni,Zn)

Thermodynamic properties of several TeO₂ polymorphs and metal tellurites were measured by a combination of calorimetric techniques. The most stable TeO₂ polymorph is α-TeO₂, with its enthalpy of formation (Δ_fH^o) selected from literature data as ?322.0 ± 1.3 kJ·mol^?1. β-TeO₂ is metastable (in enthalpy) with respect to α-TeO₂ by +1.40 ± 0.07 kJ·mol^?1, TeO₂ glass by a larger amount of +14.09 ± 0.11 kJ·mol^?1. >200 experimental runs and post-synthesis treatments were performed in order to produce phase-pure samples of Co, Cu, Mg, Mn, Ni, Zn tellurites. The results of the hydrothermal and solid-state syntheses are described in detail and the products were characterized by powder X-ray diffraction. The standard thermodynamic data for the Te(IV) phases are (standard enthalpy of formation from the elements, Δ_fH^o in kJ·mol^?1, standard third-law entropy S^o in J·mol^?1·K^?1): Co₂Te₃O₈: Δ_fH^o = ?1514.2 ± 6.0, S^o = 319.2 ± 2.2; CoTe₆O₁₃: Δ_fH^o = ?2212.5 ± 8.1, S^o = 471.7 ± 3.3; MgTe₆O₁₃: Δ_fH^o = ?2525.8 ± 7.9, S^o = 509.2 ± 3.6; Ni₂Te₃O₈: Δ_fH^o not measured, S^o = 293.3 ± 2.1; NiTe₆O₁₃: Δ_fH^o = ?2198.7 ± 8.2, S^o = 466.5 (estimated); CuTe₂O₅: Δ_fH^o = ?820.2 ± 3.3, S^o = 187.2 ± 1.3; Zn₂Te₃O₈: Δ_fH^o = ?1722.5 ± 4.0, S^o = 299.3 ± 2.1. The solubility calculations show that the Te(IV) concentration in an aqueous phase, needed to produce such phases, must be at least 3–5 orders of magnitude higher than the natural Te background concentrations. The occurrence of these minerals, as expected, are restricted to hotspots of Te concentrations. In order to produce more reliable phase diagrams, more work needs to be done on the thermodynamics of potential competing phases in these systems, including Te(VI) phases.