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1.
The concentrations and behavior of oxygen and oxide ion were studied in silicate melts of composition CaO · MgO · xSiO2 (1.25 ≤ x ≤ 3) in the temperature range 1425 to 1575°C by cyclic voltammetry and chronopotentiometry. Electroreduction of oxygen is a reversible, 2 electron process involving dissociated oxygen atoms. The Henry's Law constant for O2 in molten diopside (CaO · MgO · 2SiO2) is 0.023 ± 0.004 mole/l atm at 1450°C. The diffusion coefficient for molecular oxygen in diopside melt is 4.5 ± .5 × 10?6 cm2/sec at 1450°C and the activation energy of diffusion is 80 ± 2 kcal/mole. Oxide ions produced by electroreduction of oxygen, rapidly dissociate silicate polymers, causing the concentration of free oxide ions in diopside melt to be buffered at a low level (4.7 ± .8 × 10?5 mole/l). The concentration of free oxide ion increases at higher proportions of metal oxides but remains at this value in more silicic melts. The rate of formation of oxide ions by polymerization in diopside melt is 0.021 ± .007 mole/l sec. Thermodynamic parameters (the standard free energy, enthalpy and entropy) for the oxidation of Ni, Co, and Zn in diopside melt in equilibrium with gaseous oxygen agree with those for solid oxide systems. The platinum reference electrode in molten diopside is a reversible, oxygen electrode.  相似文献   

2.
Wohl's model and Kohler's model are two empirical excess free energy of mixing models which have been formulated for ternary solutions. The two models are identical when the binary systems are regular solution model systems. When it is assumed that the binary systems are subregular model systems the two ternary models differ. This difference is examined using the subregular model parameter values suggested by Saxena to approximate the experimental work of Seck on coexisting feldspars in the system Anorthite-Albite-Orthoclase at 900° C and 0.5 Kb. For these conditions Wohl's model is closer to the experimental data than Kohler's model in generating the position of the solvus isotherm and is better in matching the shape of the albite partitioning curve. With regard to the slope of the tie-lines, Kohler's model provides a better fit to the experimental results than Wohl's model. Experimentally determined activities for this system are not yet available so that there is no absolute way of selecting the model which would provide the most realistic activities.A ternary solvus can be completely displayed on one diagram when two sets of contours are overlain on a ternary plot. One set of contours consists of isotherms while the other set consists of icophases which are usually at a reasonable angle to the isotherms. Not only are icophases a clear way of coding tie-line information, they also assist in the positioning of the consolute or critical line. The simple new activity matching algorithm that is used in the comparative calculations has the ability to produce icophases directly.Symbols N mole fraction - a activity - T temperature °K - R gas constant, 1.987 cals/mole - G x excess free energy of mixing - u i x excess chemical potential of mixing of component i - f activity coefficient - E AC , W AC characteristic parameter (cals/mole) for binary AC in a solution model  相似文献   

3.
A thermodynamic analysis of the intermediate solid solution (Iss) of near-cubanite composition has been attempted by considering an Fe–Zn exchange equilibrium between Iss and sphalerite. The interchange free-energy parameter of Fe–Zn mixing in Iss (WIss) and the free energy of the exchange equilibrium (G1,T ) have been deduced at 500, 600, 700 and 723° C using the compositional data of sphalerite and Iss from phase equilibrium experiments and by the standard method of linear regression analysis. For sphalerite, two independent activity-composition models have been chosen. The extracted values of G1,T and WIss, using both models, are compared. Although the values match, the errors in the extracted parameters are relatively larger when Hutcheon's model is used. Both G1,T and WIss show linear variations with temperature, as given by the following relations: G1,T = –35.41 + 0.033 T in kcal (SE=0.229)WISS= 48.451 – 0.041 T in kcal (SE=0.565) Activity-composition relations and different mixing parameters have been calculated for the Iss phase. A large positive deviation from ideality is observed in Iss on the join CuFe2S3–CuZn2S3. No geothermometric application has been attempted in this study, even though Iss of cubanite composition (isocubanite) in association with sphalerite, pyrite and pyrrhotite is reported from seafloor hydrothermal deposits. This is due to the fact that: (a) the temperatures of formation of these deposits are significantly lower than 500° C, the lower limit of appropriate experimental data base; (b) microprobe data of the coexisting isocubanite and sphalerite in the relevant natural assemblages are not available.Symbols a J i activity of component i in phase J - G1, T standard free energy change of reaction (cal) - GIM free energy of ideal mixing (cal) - GEM free energy of excess mixing (cal) - G M ex free energy of mixing (cal) - G i excess free energy of mixing at infinite dilution (cal) - i J activity coefficient of component i in phase J - i J, 0 standard chemical potential of component i in phase J (cal) - ; i J chemical potential of component i in phase J (cal) - R universal gas constant (1.98717 cal/K·mol) - T temperature in degree (K) - WJ interchange free energy of phase J in (cal) - X J i mole fraction of component i in phase J  相似文献   

4.
Four different solution models, the two-parameter Margules, the quasi-chemical (QC), the Wilson and the non-random two-liquid (NRTL) model, have been used for fitting the calorimetric excess enthalpy of solution for the following four binary silicate systems: anorthite-albite, pyrope-grossular, diopside-enstatite and diopside-Ca-Tschermak. All models except the Wilson model yield a satisfactory fit to the data but the NRTL model generally results in the lowest residuals. The use of NRTL and QC facilitates the study of the configurational and non-configurational parts of the excess entropy of mixing.Three different methods, namely those of Kohler, Wohl, and Hillert, have been used to combine binary solution properties to predict ternary solution properties. Comparison of computed excess free energy of mixing in a hypothetical solution shows that all the three methods are viable but the Kohler and Wohl methods are similar to each other and are significantly different from the Hillert method. The Kohler method with one or a combination of different binary models is recommended for predicting multicomponent solution properties.Abbreviations G ex excess free energy of mixing - H ex excess enthalpy of mixing - S ex total excess entropy of mixing - S ex c configurational excess entropy of mixing - W ij interaction energy parameter between speciesi andj - X i mole fraction of speciesi - QC quasi-chemical - NRTL non-random two-liquid - M Margules formulation - W Wohl's formulation - RK Redlich-Kister - K Bertrand-Kohler - H Hillert - Di diopside (CaMgSi2O6) - En enstatite (Mg2Si2O6) - Py pyrope (MgAl2/3SiO4) - Gr grossular (CaAl2/3SiO4) - CaTs Ca-Tschermak (CaAl2SiO6) - Ab albite (NaAlSi3O8) - An anorthite (CaAl2Si2O8)  相似文献   

5.
The thermodynamic properties of non-ideal binary solutions were investigated. By using reduced temperatures (T/T critical mixing) and comparing the width of the solvi in very different binary systems, a uniform relation for several systems is obtained for which the concept of corresponding solvi is introduced.A graphical method is developed to determine Margules parameters from two-phase regions in solid solutions. Graphs are presented for binodal — as well as spinodal solvi. The Margules parameters obtained with these graphs are comparable with the calculated ones.In well investigated systems from the literature constant ratios of Margules parameters (W a /W b ) were recognized so far. Combining this observation with the concept of corresponding solvi, a tentative solvus can be constructed with a minimum of data.List of Symbols Used in the Calculations x Mole fraction of component B in solid solution - x 1 Mole fraction of component B in phase 1 - x 2 Mole fraction of component B in phase 2 - A 0 Chemical potential of 1 mole pure component A - B 0 Chemical potential of 1 mole pure component B - A(x), A Chemical potential of component A in solid solution - B(x), B Chemical potential of component B in solid solution - G Total Gibbs energy of the system - ¯G m (x), ¯Gm Molar Gibbs energy of solid solution - ¯G m E (x) Excess function - W a , W b Margules parameters - T Absolute temperature in K - P Pressure  相似文献   

6.
A method for the prediction of Gibbs free energies of formation for minerals belonging to the alunite family is proposed, based on an empirical parameter ΔGO= Mz+(c) characterizing the oxygen affinity of the cation Mz+. The Gibbs free energy of formation from constituent oxides is considered as the sum of the products of the molar fraction of an oxygen atom bound to any two cations, multiplied by the difference of oxygen affinity ΔGO= Mz+(c) between any two consecutive cations. The ΔGO= Mz+(c) value, using a weighing scheme involving the electronegativity of a cation in a specific site (12-fold coordination site, octahedral and tetrahedral) is assumed to be constant. It can be calculated by minimizing the difference between experimental Gibbs free energies (determined from solubility measurements) and calculated Gibbs free energies of formation from constituent oxides. Results indicate that this prediction method gives values within 0.5% of the experimentally measured values. The relationships between ΔGO= Mz+(alunite) corresponding to the electronegativity of a cation in either dodecahedral sites, octahedral sites or tetrahedral sites and known as ΔGO= Mz+(aq) were determined, thereby allowing the prediction of the electronegativity of rare earth metal ions and trivalent ions in dodecahedral sites and highly charged ions in tetrahedral sites. This allows the prediction of Gibbs free energies of formation of any minerals of the alunite supergroup (bearing various ions located in the dodecahedral and tetrahedral sites). Examples are given for hydronium jarosite and hindsalite, and the results appear excellent when compared to experimental values.  相似文献   

7.
Compositional dependence of apparent partition coefficient of iron and magnesium between coexisting garnet and clinopyroxene from Mt. Higasiakaisi is studied by means of a multicomponent regular solution model. It is shown that garnet and clinopyroxene solid solutions are positively non-ideal, and the non-ideal parameters according to the symmetric regular solution model are 2.58 kcal and 2.39 kcal, respectively, assuming the equilibration temperature of the mass to be 550° C.Notations a i h activity of component i in phase h - ij interaction parameter of component i and j in a solid solution - i activity coefficient of component i - X i mole fraction of component i - K partition coefficient of Fe and Mg between coexisting garnet and clinopyroxene - K apparent partition coefficient of Fe and Mg between coexisting garnet and clinopyroxene - G 0 difference in free energy of the partition reaction - H 0 difference in enthalpy of the partition reaction - S 0 difference in entropy of the partition reaction - R gas constant - G garnet - Alm almandine component - Py pyrope component - Gr grossular component - Sp spessartine component - CPx clinopyroxene - Hd hedenbergite component - Di diopside component - Jd jadeite component - Ts Tschermac's molecule component Deceased on April 17, 1974.  相似文献   

8.
A parameter GO2– is defined as the difference between the Gibbs free energy of formation from the elements of a given oxide and its corresponding aqueous cation. The Gibbs free energies of formation of compounds such as sulfates, nitrates or carbonates, from their constituent oxides, are shown to be linear functions of GO2– values of their constituent cations.  相似文献   

9.
Reversed univariant hydrothermal phase-equilibrium reactions, in which a redox reaction occurs and is controlled by oxygen buffers, can be used to extract thermochemical data on minerals. The dominant gaseous species present, even for relatively oxidizing buffers such as the QFM buffer, are H2O and H2; the main problem is to calculate the chemical potentials of these components in a binary mixture. The mixing of these two species in the gas phase was assumed by Eugster and Wones (1962) to be ideal; this assumption allows calculation of the chemical potentials of the two components in a binary gas mixture, using data in the literature. A simple-mixture model of nonideal mixing, such as that proposed by Shaw (1967), can also be combined with the equations of state for oxygen buffers to permit derivation of the chemical potentials of the two components. The two mixing models yield closely comparable results for the more oxidizing buffers such as the QFM buffer. For reducing buffers such as IQF, the nonideal-mixing correction can be significant and the Shaw model is better.The procedure of calculation of mineralogical thermochemical data, in reactions where hydrogen and H2O simultaneously appear, is applied to the experimental data on annite, given by Wones et al. (1971), and on almandine, given by Hsu (1968). For annite the results are: Standard entropy of formation from the elements, S f 0 (298, 1)=–283.35±2.2 gb/gf, S 0 (298, 1) =+92.5 gb/gf. G f 0 (298, 1)=–1148.2±6 kcal, and H f 0 (298, 1)=–1232.7±7 kcal. For almandine, the calculation takes into account the mutual solution of FeAl2O4 (Hc) in magnetite and of Fe3O4 (Mt) in hercynite and the temperature dependence of this solid solution, as given by Turnock and Eugster (1962); the calculations assume a regular-solution model for this binary spinel system. The standard entropy of formation of almandine, S f,A 0 (298, 1) is –272.33±3 gb/gf. The third law entropy, S 0 (298, 1) is +68.3±3 gb/gf, a value much less than the oxide-sum estimate but the deviation is nearly the same as that of grossularite, referring to a comparable set of oxide standard states. The Gibbs free energy G f,A 0 (298, 1) is –1192.36±4 kcal, and the enthalpy H f,A 0 (298, 1) is –1273.56±5 kcal.Publication authorized by the Director, U. S. Geological Survey.  相似文献   

10.
Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔGr) in a continuously stirred flow-through reactor at 90 °C and pH90 °C = 5.05. The overall relation between r and ΔGr was determined over a free energy range of −130.9 < ΔGr < −47.0 kJ mo1−1. The data define a highly non-linear, sigmoidal relation between r and ΔGr. At far-from-equilibrium conditions (ΔGr ? −76.2 kJ mo1−1), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔGr. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔGr region defined by −76.2 < ΔGr ? −61.5 kJ mo1−1. Dissolution closer to equilibrium (ΔGr > −61.5 kJ mo1−1) is characterised by a much weaker inverse dependence of the rates on ΔGr. Modeling the experimental r-ΔGr data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔGr relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO2 over long time spans. In order to take into account the actual experimental r-ΔGr relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO2 interactions performed with classical geochemical codes should be evaluated with great caution.  相似文献   

11.
In the present study, the modified Sverjensky–Molling equation, derived from a linear-free energy relationship, is used to predict the Gibbs free energies of formation of crystalline phases of α-MOOH (with a goethite structure) and α-M2O3 (with a hematite structure) from the known thermodynamic properties of the corresponding aqueous trivalent cations (M3+). The modified equation is expressed as ΔG0f,MVX=aMVXΔG0n,M3++bMVX+βMVXγM3+, where the coefficients aMVX, bMVX, and βMVX characterize a particular structural family of MvX (M is a trivalent cation [M3+] and X represents the remainder of the composition of solid); γ3+ is the ionic radius of trivalent cations (M3+); ΔG0f,MVX is the standard Gibbs free energy of formation of MvX; and ΔG0n,M3+ is the non-solvation energy of trivalent cations (M3+). By fitting the equation to the known experimental thermodynamic data, the coefficients for the goethite family (α-MOOH) are aMVX=0.8838, bMVX=?424.4431 (kcal/mol), and βMVX=115 (kcal/mol.?), while the coefficients for the hematite family (α-M2O3) are aMVX=1.7468, bMVX=?814.9573 (kcal/mol), and βMVX=278 (kcal/mol.?). The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases (i.e. phases that are thermodynamically unstable and do not occur at standard conditions) within the isostructural families of goethite (α-MOOH) and hematite (α-M2O3) if the standard Gibbs free energies of formation of the trivalent cations are known.  相似文献   

12.
An asymmetric, Margules-type, solid solution model was used to model the mixing behavior of Fe-Zn sphalerites. The model is based on an analysis of experimental results from fifteen independent data sources. After a careful, stepwise, analysis of the available runs, the solid solution model was constrained using a refined experimental database of 279 experiments which were simultaneously regressed to obtain the excess parameters and a general geobarometric equation. The model indicates that, when pressures are low, the value of γFeSSph, which is always greater than one, is higher at low FeS contents and an increase in temperature causes it to decline. However, for certain compositions γFeSSph values might be slightly less at low T than at high T. This behavior is corrected when pressure increases, regardless of the composition. The excess Gibbs free energy has positive values at any P&T while it is asymmetric. Pressure increases the value of the excess free energy. On the other hand, the Gibbs free energy of mixing is always negative, with a single minimum that tends to move towards Fe-poorer compositions as the pressure goes up. An increase in temperature leads to a more negative Gibbs free energy mixing function suggesting that increasingly Fe-poorer sphalerite would be expected at high temperatures and pressures. The application of the solid solution model to a selection of case-studies provided results which are consistent with independent pressure estimates. However, the pressure determinations for sphalerite + pyrite + pyrrhotite and sphalerite + pyrrhotite assemblages are very sensitive to uncertainties in the composition of the phases involved and, to a lesser extent, to temperature. The results of the application of the model to a field case (scheelite-mineralized Hercynian veins from the Central Pyrenees) were also consistent when compared with independent pressure-constraining silicate assemblages. Thus, the solid solution model described in this paper provides a workable framework with which to compute the pressures of the formation of rocks over a wide range of geological conditions.  相似文献   

13.
The P–T partition function in statistical thermodynamics can be used to derive semi-empirical formulations of the Gibbs free energy G for minerals and fluids. Parameterization of these equations includes simultaneous regression of experimental heat capacity and molar volume data, allowing fitting, appraisal and optimization of various data sources, as required in the construction of internally consistent petrological data bases. This approach can also be extended to minerals with -transitions and to fluids by considering the Gibbs free energy as a function of pressure P, temperature T and an ordering parameter X, so that accurate modelled representation and extrapolation of the thermodynamic properties of large numbers of petrologically significant minerals and coexisting fluids can be attained. The ordering parameter is chosen to denote the equilibrium mole fraction (thermodynamic probability) of ordered clusters (structural units) in a substance when G(T,P, X)=min. The procedure is tested on existing experimental data for the system MgO–SiO2–H2O. The proposed Gibbs free energy formulation permits thermodynamic properties of minerals, fluids and phase equilibria to be described and extrapolated over a wide range of pressure (0–800 kbar) and temperature (20–3000 K), thus allowing effective use in thermodynamic data bases of petrological interest.  相似文献   

14.
Steady-state dissolution rates of diopside are measured as a function of solution saturation state using a titanium flow-through reactor at pH 7.5 and temperature ranging from 125 to 175°C. Diopside dissolved stoichiometrically under all experimental conditions and rates were not dependent on sample history. At each temperature, rates continuously decreased by two orders of magnitude as equilibrium was approached and did not exhibit a dissolution plateau of constant rates at high degrees of undersaturation. The variation of diopside dissolution rates with solution saturation can be described equally well with a ion exchange model based on transition state theory or pit nucleation model based on crystal growth/dissolution theory from 125 to 175°C. At 175°C, both models over predict dissolution rates by two orders of magnitude indicating that a secondary phase precipitated in the experiments. The ion exchange model assumes the formation of a Si-rich, Mg-deficient precursor complex. Lack of dependence of rates on steady-state aqueous calcium concentration supports the formation of such a complex, which is formed by exchange of protons for magnesium ions at the surface. Fit to the experimental data yields where the Mg-H exchange coefficient, n = 1.39, the apparent activation energy, E a = 332 kJ mol-1, and the apparent rate constant, k = 1041.2 mol diopside cm-2 s-1. Fits to the data with the pit nucleation model suggest that diopside dissolution proceeds through retreat of steps developed by nucleation of pits created homogeneously at the mineral surface or at defect sites, where homogeneous nucleation occurs at lower degrees of saturation than defect-assisted nucleation. Rate expressions for each mechanism (i) were fit to where the step edge energy (α) for homogeneously nucleated pits were higher (275 to 65 mJ m-2) than the pits nucleated at defects (39 to 65 mJ m-2) and the activation energy associated with the temperature dependence of site density and the kinetic coefficient for homogeneously nucleated pits (Eb-homogeneous = 2.59 × 10-16 mJ K-1) were lower than the pits nucleated at defects (Eb-defect assisted = 8.44 × 10-16 mJ K-1).  相似文献   

15.
A new set of reversal experiments for coexisting ortho- and clinopyroxenes in the system CMAS at conditions between 1,000–1,570° C and 30 to 50 kb is presented and combined with literature data. Pyroxene behaviour, particularly that of clinopyroxene, is very complicated and different styles of Al incorporation into the pyroxene structure for low and high concentrations of Al are indicated, strongly influencing the exchange of the enstatite component between ortho- and clinopyroxene. Thermodynamic modelling of this exchange is problematic because of the large number of unknown coefficients compared to the number of experiments. Thermometry based on such models becomes very dependent on accuracy of experimental data and analyses of small quantities of elements. Despite this complexity very simple empirical thermometric equations are capable of reproducing experimental conditions in the systems CMS and CMAS over a wide range of P, T conditions. We derived the equation which gives a mean error of estimate of 25° C when applied to CMS and CMAS data.Abbreviations Used in the Text cpx clinopyroxene - di diopside, CaMgSi2O6 - en enstatite, Mg2Si2O6 - opx orthopyroxene - px Pyroxene - py pyrope - a i j activity of component i in phase j - activity coefficient - G P,T (A) molar Gibbs free energy difference of reaction (A) at P, T - X i j mole fraction of component i in phase j  相似文献   

16.
A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe3O4–FeCr2O4 spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe1-x2+ Fex3+)[Fex2+Fe2-2y-x3+Cr2y]O4, and their thermodynamic properties depend strongly on Fe2+–Cr3+ cation mixing. Mixing of Fe2+–Fe3+ and Fe3+–Cr3+ can be accepted as ideal. If Fe2+, Fe3+ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x2/((1–x)(2–2y–x)))= G13* + (1–2x)W13+y(W14–W13–W34) where G13* is the difference between the Gibbs energy of inverse and normal magnetite, Wij is a Margules parameter of cation mixing and G13*, J/mol =–23,000+13.4 T, W14=36 kJ/mol, W13=W34=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe3O4–FeCr2O4 spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.  相似文献   

17.
The heat capacity of praseodymium orthophosphate PrPO4 was measured by adiabatic and relaxation calorimetric techniques at 5.12–345.54 K, and these data were utilized to calculate thermodynamic functions of PrPO4 at 6–350 K. The Gibbs free energy of PrPO4 formation ΔfG0(298.15 K) is evaluated at 1851.8 ± 4.7 kJ mol–1.  相似文献   

18.
Existing data on the temperature and composition dependence of the Fe2+-Mg2+ distribution between Fe-Mg olivine and orthopyroxene, the intra-crystalline distribution of Fe2+ and Mg2+ between M1 and M2 sites in orthopyroxene, and macroscopic activity-composition relations in olivine and orthopyroxene are shown to be inconsistent with generally accepted thermodynamic formulations which assume that the non-configurational Gibbs energy of orthopyroxene is independent of the degree of long-range ordering of Fe2+ and Mg+ between M1 and M2 sites. These data are interpreted in terms of the constraints they provide on the size of Bragg-Williams type energy, entropy, and volume terms for olivine and orthopyroxene. The apparent equilibrium constant for Fe-Mg exchange between olivine and orthopyroxene is shown to be a potentially useful ‘geothermometer’ for olivine-orthopyroxene assemblages with olivines with mole fraction of Fe2SiO4 component less than 0.2 or greater than 0.6. A provisional calibration of this ‘geothermometer’ is presented.  相似文献   

19.
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.  相似文献   

20.
Heats of mixing of synthetic C2/m fluortremolite-fluoredenite amphiboles measured at 985 K show a systematic deviation from ideal mixing consistent with a subregular solution model. The deviations from ideal mixing are interpreted in terms of Na ordering in the A-site and Na-Al interactions in edenite-poor compositions. Enthalpies of edenite substitution reactions in amphiboles and in SiO2-NaAlO2 glasses and framework silicates are comparable. Gibbs free energies of formation of fluortremolite and fluoredenite at 298K are -2,821.07±3.34 kcal mol–1 and -2,889.59±2.40 kcal mol–1 respectively. The former value is in good agreement with values calculated from both F-OH exchange experiments and from a natural fluortremolite-bearing metamorphic rock. Least-squares fitted sub-regular heat-of-mixing parameters are poorly constrained and unrealistically high, but estimated subregular mixing parameters consistent with 95% confidence interval uncertainties in the calorimetric data and with TEM constraints give activity-composition relations in good agreement with the A-site compositions of natural metamorphic and igneous hornblendes. These relations predict unmixing in edenite-rich compositions over a wide range of temperature, but lend no support to the existence of a hornblende-actinolite miscibility gap. Calibration of the reaction tremolite+ albite=edenite+4 quartz as a function ofP,T andX ed amph indicates negativedP/dT slopes and a limited range of X ed amph (0.3 to 0.5) in equilibrium with plagioclase and quartz over a wide range of pressure and temperature, consistent with metamorphic hornblende-plagioclase assemblages. The energetics of this reaction suggest, however, that amphibole-plagioclase disequilibrium may be common.  相似文献   

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