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1.
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.  相似文献   

2.
The results of thermochemical studies are reported for nontronite samples from the Pinares-de-Majari (Eastern Cuba) (Sample I) and Kempirsai serpentine massif (South Urals, Kazakhstan) (Sample II). The enthalpies of formation of dehydrated hydroxyl-bearing nontronites from elements were determined by melt dissolution calorimetry using high-temperature heat-flux Tiana-Calvet microcalorimeter: Δ f H el o (298.15 K): ?4958 ± 13 kJ/mol for Mg0.4(Fe 1.5 3+ Mg0.4Ni0.1)[Si3.7Al0.3O10](OH)2 (I) and ?5003.6 ± 8.0 kJ/mol for Mg0.3Na0.1Ca0.1(Fe 1.4 3+ Mg0.5Ni0.1)[Si3.7Al0.3O10](OH)2 (II). It was determined experimentally that the enthalpy of dehydration (removal of molecular adsorption and interlayer water) of the studied nontronites is 6 ± 2 kJ per 1 mole H2O. The enthalpy of formation of nontronite of theoretical composition Mg0.15Fe 2 3+ [Si3.7Al0.3]O10(OH)2 was estimated at ?4750 kJ/mol. The Gibbs free energies of formation of the nontronites were calculated.  相似文献   

3.
Forty-six reversed determinations of the Al2O3content of enstatite in equilibrium with garnet were made in the P/T range 15–40 kbar/900–1,600° C in the MgO-Al2O3-SiO2 system. Starting materials were mixtures of synthetic pyrope+Al-free enstatite and pyrope+enstatite (5–12% Al2O3). Al2O3 contents in reversal run pairs closely approached common values from both the high- and low-Al sides. Most experiments were done in a piston-cylinder device using a NaCl medium; some runs at very high temperatures were made in pyrex/NaCl or pyrex/talc assemblies. The measured enstatite compositions, expressed as mole fractions of Mg2(MgAl)(AlSi3)O12(X Opy En ) were fitted by a Monte-Carlo method to the equilibrium condition: $$\begin{gathered} \Delta H_{970}^0 - 970\Delta S_{970}^0 \hfill \\ + \mathop \smallint \limits_1^P \Delta V_{970}^0 dP - \mathop \smallint \limits_{970}^T \Delta S_T^0 dT + RT\ln X_{Opy}^{En} = 0 \hfill \\ \end{gathered}$$ where the best fit parameters of ΔH, ΔS and ΔV (1 bar, 970 K) for the reaction pyrope=opy are 2,040 cal/mol, 2.12 eu and 9.55 cc/mol. In addition to the determination of Al2O3 contents of enstatite, the univariant reaction pyrope+forsterite=enstatite+spinel was reversibly located in the range 1,100–1,400°C. A “best-fit” line passes through 22, 22.5 and 25 kbar at 1,040, 1,255 and 1,415°C, respectively. Our results for the univariant reaction are in agreement with previous studies of MacGregor (1974) and Haselton (1979). However, comparison of the experimentally determined curve with thermochemical calculations suggests that there may be a small error in the tabulated ΔH f(970,1) 0 value for enstatite. A value of?8.32 rather than?8.81 kcal/mole (Charlu et al. 1975) is consistent with the present data. Application of garnet-enstatite-spinel-forsterite equilibria to natural materials is fraught with difficulties. The effects of nonternary components are poorly understood, and the low solubilities of Al2O3 in enstatite under most geologically reasonable conditions make barometric or thermometric calculations highly sensitive. More detailed studies, including reversed determinations in low-friction assemblies, are sorely needed before the effects of important diluents such as Fe, Ca and Cr can be fully understood.  相似文献   

4.
With increasing pressure, MnSiO3 rhodonite stable at atmospheric pressure transforms to pyroxmangite, then to clinopyroxene and further to tetragonal garnet, which finally decomposes into MnO (rocksalt) plus SiO2 (stishovite). High temperature solution calorimetry of synthetic rhodonite, clinopyroxene and garnet forms of MnSiO3 was used to measure the enthalpies of these transitions. ΔH 974 0 for the rhodonite-clinopyroxene and ΔH 298 0 for the clinopyroxene-garnet transition are 520±490 and 8,270±590 cal/mol, respectively. The published data on the enthalpy of the rhodonite-pyroxmangite transition, phase equilibrium boundaries, compressibility and thermal expansion data are used to calculate entropy changes for the transitions. The enthalpy, entropy and volume changes are very small for all the transitions among rhodonite, pyroxmangite and clinopyroxene. The calculated boundary for the clinopyroxene-garnet transition is consistent with the published experimental results. The pyroxene-garnet transition in several materials, including MnSiO3, is characterized by a relatively small negative entropy change and large volume decrease, resulting in a small positiveP – T slope. The disproportionation of MnSiO3 garnet to MnO plus stishovite and of Mn2SiO4 olivine to garnet plus MnO are calculated to occur at about 17–18 and 14–15 GPa, respectively, at 1,000–1,500 K.  相似文献   

5.
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.  相似文献   

6.
Experiments reproducing the development of bimetasomatic zoning in the CaO-MgO-SiO2-H2O-CO2 system were conducted at elevated P-T parameters with the use of samples of naturally occurring quartzdolomite and calcite-serpentinite rocks. In order to maintain mass transfer exclusively via the diffusion-controlled mechanism, we used the method of the ensured compaction of the cylindrical sample surface with a thin-walled gold tube. In the course of the experiments, a single diopside zone ～2.5 × 10?5 m thick was obtained at the quartz-dolomite interface at T = 600°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.5 for 25–40 days and a succession of metasomatic zones at T = 750°C, $P_{H_2 O + CO_2 } $ = 300 MPa, and $X_{CO_2 } $ = 0.4 for 48 days. The metasomatic zones were as follows (listed in order from quartz to dolomite): wollastonite ‖ diopside ‖ tremolite ‖ calcite + forsterite; with the average width of the diopside zone equal to ～1.3 × 10?5 m and the analogous part of the wollastonite zone equal to ～2.6 × 10?5 m. Two zones (listed in order from calcite to serpentine) diopside and diopside-forsterite (the average widths of these zones were ～6 × 10?4 and ～8 × 10?4 m, respectively) were determined to develop at contact between serpentine and calcite during experiments that lasted 124 days at T = 500°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.2–0.4. In the former and latter situations, the growth rate of the zoning ranged between 3.1 × 10?12 and 1.2 × 10?11 m/s and between 5.6 × 10?11 and 7.5 × 10?11 m/s, respectively. The higher growth rate in the latter case can be explained by the higher water mole fraction in the fluid, with this water released during serpentinite decomposition in the experiments. The development of the only diopside zone in the experiments modeling the interaction of quartz and dolomite at T = 600–650°C and $P_{H_2 O + CO_2 } $ = 200 MPa is in conflict with theoretical considerations underlain by the Korzhinskii-Fisher-Joesten model. The interaction of quartz and dolomite in the CaO-MgO-SiO2-CO2-H2O system at the P-T- $X_{CO_2 } $ parameters specified above should be attended by the origin of a number of reaction zones consisting of various proportions of talc, forsterite, tremolite, diopside, and calcite. The saturation of the fluid with respect to these minerals was likely not reached, and this resulted in the degeneration of the respective stability fields in the succession of zones. Conceivably, this was related to the insufficient rates of quartz and dolomite dissolution and the relatively low diffusion rates of the dissolved species in the low-permeable medium. In the experiments with interacting calcite and serpentine, the zoning calcite ‖ diopside ‖ diopside + forsterite ‖ serpentine developed in its complete form, in agreement with the theory. Equilibrium was likely achieved in these experiments due to the higher diffusion coefficients.  相似文献   

7.
Enthalpies of solution of synthetic pentlandite Fe4.5Ni4.5S8, natural violarite (Fe0.2941Ni0.7059)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 Ni0.6S0.4 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.  相似文献   

8.
The paper reports results of an experimental thermochemical study (in a heat-flux Tian-Calvet microcalorimeter) of montmorillonite from (I) the Taganskoe and (II) Askanskoe deposits and (III) from the caldera of Uzon volcano, Kamchatka. The enthalpy of formation Δ f H el 0 (298.15 K) of dehydrated hydroxyl-bearing montmorillonite was determined by melt solution calorimetry: ?5677.6 ± 7.6 kJ/mol for Na0.3Ca0.1(Mg0.4Al1.6)[Si3.9Al0.1O10](OH)2 (I), ?5614.3 ± 7.0 kJ/mol for Na0.4K0.1(Ca0.1Mg0.3Al1.5Fe 0.1 3+ )[Si3.9Al0.1O10](OH)2 (II), ?5719 ± 11 kJ/mol for K0.1Ca0.2Mg0.2(Mg0.6Al1.3Fe 0.1 3+ ) [Si3.7Al0.3O10](OH)2 (III), and ?6454 ± 11 kJ/mol for water-bearing montmorillonite (I) Na0.3Ca0.1(Mg0.4Al1.6)[Si3.9Al0.1O10](OH)2 · 2.6H2O. The paper reports estimated enthalpy of formation for the smectite end members of the theoretical composition of K-, Na-, Mg-, and Ca-montmorillonite and experimental data on the enthalpy of dehydration (14 ± 2 kJ per mole of H2O) and dehydroxylation (166 ± 10 kJ per mole of H2O) for Na-montmorillonite.  相似文献   

9.
The paper reports data obtained in the course of a comprehensive physicochemical study of Li-tosudite, a mixed-layer mineral from hydrothermally altered rocks in western Chukotka, Russia, whose formula was reliably established. The enthalpy of formation of Li-tosudite from Chukotka, Ca0.15(Li0.9Mg0.2Al6.0)[Si6.4Al1.6O20](OH)10 · 3.3H2O, from elements was experimentally determined by melt solution calorimetry in a high-temperature Calvet microcalorimeter: ΔfH el o (298.15 К) =–15087 ± 26 kJ/mol. The standard entropy and Gibbs free energy of formation of this mineral were evaluated.  相似文献   

10.
Internally consistent thermodynamic data, including their uncertainties and correlations, are reported for 22 phases of the quaternary system CaO-Al2O3-SiO2-H2O. These data have been derived by simultaneous evaluation of the appropriate phase properties (PP) and reaction properties (RP) by the novel technique of Bayes estimation (BE). The thermodynamic model used and the theory of BE was expounded in Part I of this paper. Part II is the follow-up study illustrating an application of BE. The input for BE comprised, among others, the a priori values for standard enthalpy of formation of the i-th phase, Δf H i 0 , and its standard entropy, S i 0 , in addition to the reaction reversal constraints for 33 equilibria involving the relevant phases. A total of 269 RP restrictions have been processed, of which 107 turned out to be non-redundant. The refined values for Δf H i 0 and S i 0 obtained by BE, including their 2σ-uncertainties, appear in Table 4; the Appendix reproduces the corresponding correlation matrix. These data permit generation of computed phase diagrams with 2σ-uncertainty envelopes based on conventional error propagation; Fig. 3 depicts such a phase diagram for the system CaO-Al2O3-SiO2. It shows that the refined dataset is capable of yielding phase diagrams with uncertainty envelopes narrow enough to be geologically useful. The results in Table 4 demonstrate that the uncertainties of the prior values for Δf H i Emphasis>0 , given in Table 1, have decreased by up to an order of magnitude, while those for S i 0 improved by a factor of up to two. For comparison, Table 4 also lists the refined Δf H i 0 and S i 0 data obtained by mathematical programming (MAP), minimizing a quadratic objective function used earlier by Berman (1988). Examples of calculated phase diagrams are given to demonstrate the advantages of BE for deriving internally consistent thermodynamic data. Although P-T curves generated from both MAP and BE databases will pass through the reversal restrictions, BE datasets appear to be better suited for extrapolations beyond the P-T range explored experimentally and for predicting equilibria not constrained by reversals.  相似文献   

11.
L. Ya. Aranovich 《Petrology》2013,21(6):539-549
The paper presents a review of an experimental method to quantitatively constrain thermodynamic mixing properties of fluid systems at high temperature T and pressure P. The method is based on bracketing equilibrium parameters of simple fluid-mineral reactions. Experimental data obtained with this technique for the H2O-CO2, H2O-N2, and H2O-H2 binary systems were utilized to calculate mixing parameters corresponding to the simplified van Laar model W 12 VL , according to which the equation for the integral excess Gibbs free energy of a binary mixture G ex is G ex =X 1 X 2 W 12 VL /(X 1 V 1 0 + X 2 V 2 0 ), where X i is the mole fractions of the components, and V i 0 are pure species molar volumes at given P and T (in cm3). The W 12 VL for the three mixtures correspond to 202, 219, and 331 kJ cm3/mol. The empirical correlation $W_{H_2 O - X}^{VL}$ (kJ cm3/mol) = 887.012 Q X ? 16.674, where Q = P c (critical pressure, bar)/T c (critical temperature, K) for gas X (where X = CH4, CO, H2S, O2, Ar, and NH3) is used to evaluate the van Laar parameters for a number of petrologically important water-gas mixtures. The H2O-H2 system is characterized by the greatest positive deviation from the ideal mixing and can thus decompose into two immiscible fluid phases under the P-T parameters typical of deep lithospheric zones. The exsolution of the H2O-CO2 and H2O-N2 systems is expected to occur only under high pressure and low temperature. This combination of parameters may be expected only in the environments of cold subduction. Salts (highly soluble simple salts and/or silicates) should significantly expand the exsolution regions in petrologically important fluids.  相似文献   

12.
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.
  相似文献   

13.
The non-ideal regular Mg-Fe binary in cordierite has been derived through multivariate linear regression of the expressionRT InKD +(P- 1)ΔVK 1 0 , 298 along with updated subfegular mixing parameter of almandine-pyrope solution (Hackler and Wood 1989; Berman 1990). The data base used for multivariate analyses consists of published experimental data (n = 177) on Mg-Fe partitioning between garnet and cordierite in theP-T range 650–1050°C and 4–12 K bar. The non-ideality can be approximated by temperature-dependent Margules parameters. The retrieved values of ΔH<T> o and ΔH<T> o of exchange reaction between garnet and cordierite and enthalpy and entropy of mixing of Mg-Fe cordierite were combined with recent quaternary (Fe-Mg-Ca-Mn) mixing data in garnet to obtain the geothermometric expressions to determine temperature (T Kelvin): $$\begin{gathered} T(WH) = 6832 + 0.031(P - 1) - \{ 166(X_{Mg}^{Gt} )^2 - 506(X_{Fe}^{Gt} )^2 + 680X_{Fe}^{Gt} X_{Mg}^{Gt} + 336(X_{Ca} + X_{Mn} ) \hfill \\ (X_{Mg} - X_{Fe} )^{Gt} - 3300X_{Ca}^{Gt} - 358X_{Mn}^{Gt} \} + 954(X_{Fe} - X_{Mg} )^{Crd} /1.987\ln K_D + 3.41 + 1.5X_{Ca}^{Gt} \hfill \\ + 1.23(X_{Fe} - X_{Mg} )^{Crd} \hfill \\ \end{gathered} $$ $$\begin{gathered} T(Br) = 6920 + 0.031(p - 1) - \{ 18(X_{Mg}^{Gt} )^2 - 296(X_{Fe}^{Gt} )^2 + 556X_{Fe}^{Gt} X_{Mg}^{Gt} - 6339X_{Ca}^{Gt} X_{Mg}^{Gt} \hfill \\ - 99(X_{Ca}^{Gt} )^2 + 4687X_{Ca}^{Gt} (X_{Mg} - X_{Fe}^{Gt} ) - 4269X_{Ca}^{Gt} X_{Fe}^{Gt} - 358X_{Mn}^{Gt} \} + 640(X_{Fe} - X_{Mg} )^{Crd} \hfill \\ + 1.90X_{Ca}^{Gt} (X_{Mg} - X_{Ca} )^{Gt} . \hfill \\ \end{gathered} $$   相似文献   

14.
In the lattice energy expression of forsterite, based on a Born-Mayer (electrostatic+repulsive+dispersive) potential, the oxygen charge z o, the hardness parameter ρ and the repulsive radii r Mg and r Si appear as unknown parameters. These were determined by calculating the first and second partial derivatives of the energy with respect to the cell edges, and equalizing them to quantities related to the crystal elastic constants; the overdetermined system of equations was solved numerically, minimizing the root-mean-square deviation. To test the results obtained, the SiO 4 4? ion was assumed to move in the unit-cell, and the least-energy configuration was sought and compared with the experimental one. By combining the two methods, the optimum set of parameters was: z o=?1.34, ρ=0.27 Å, r Mg=0.72 Å, r Si=0.64 Å. The values ?8565.12 and ?8927.28 kJ mol?1 were obtained, respectively, for the lattice energy E Land for its ionic component E L 0 ,which accounts for interactions between Mg2+ and SiO 4 4? ions only. The charge distribution calculated on the SiO 4 4? ion was discussed and compared with other results. Using appropriate thermochemical cycles, the formation enthalpy and the binding energy of SiO 4 4? were estimated to be: ΔH f(SiO 4 4? )=2117.6 and E(SiO 4 4? )=708.6 kJ mol?1, respectively.  相似文献   

15.
Boron-bearing kornerupine was synthesized in the simplest possible model system at fluid pressures and temperatures both within and outside the stability field of boron-free kornerupine. Best conditions for synthesis of single-phase products are 7 kb and 830 °C. Microprobe and wet chemical analyses as well as X-ray studies indicate compositional variations of kornerupines regarding all five constituent components: Increasing B-contents (from 0.37 to 3.32 wt% B2O3) are correlated with decreasing OH? values largely according to the Eq. B3+?3 H+; the ratio MgO∶Al2O3∶SiO2 varies from 4∶3∶4 in the direction towards 1∶1∶1. Thus kornerupine exhibits an at least ternary range of solid solution in the system studied. Crystallochemically speaking it is significant that, although the Mg∶Al∶Si ratio of kornerupine may remain constant with increasing boron contents, the total number of cations per formula unit increases beyond the ideal number of 14.0 as given by Moore and Bennett (1968). Considering the presence of an additional structural site at (000) it is suggested that the introduction of boron initiates a sequence of substitutions such as $$B^{[4]} \to Si^{[4] } \to A1^{[4]} \to Mg^{[6]} \to \square$$ . The filling of this site, empty in boron-free kornerupine, by Mg is connected with a loss of hydrogen located near this site. Petrologically speaking an exchange reaction relation exists between kornerupine and its coexisting fluid according to the equation Boron-free kornerupine+B2O3=boron-kornerupine+H2O. The molar fractions $$X_{B_2 O_3 } = B_2 O_3 /\left( {B_2 O_3 + H_2 O} \right)$$ of kornerupines exceed those of their coexisting fluids by about one order of magnitude. Fluids with relatively low XB 2 O 3 lead to the coexistence of kornerupine with boron-free minerals such as enstatite and sapphirine, fluids with relatively high XB 2 O 3 produce the boron-minerals grandidierite, sinhalite, and tourmaline (in the present system without Na!) in addition to kornerupine.  相似文献   

16.
The system Fe-Si-O: Oxygen buffer calibrations to 1,500K   总被引：1，自引：0，他引：1  
The five solid-phase oxygen buffers of the system Fe-Si-O, iron-wuestite (IW), wuestite-magnetite (WM), magnetite-hematite (MH), quartz-iron-fayalite (QIF) and fayalite-magnetite-quartz (FMQ) have been recalibrated at 1 atm pressure and temperatures from 800°–1,300° C, using a thermogravimetric gas mixing furnace. The oxygen fugacity, \(f_{{\text{O}}_{\text{2}} }\) was measured with a CaO-doped ZrO2 electrode. Measurements were made also for wuestite solid solutions in order to determine the redox behavior of wuestites with O/Fe ratios varying from 1.05 to 1.17. For FMQ, additional determinations were carried out at 1 kb over a temperature range of 600° to 800° C, using a modified Shaw membrane. Results agree reasonably well with published data and extrapolations. The reaction parameters K, ΔG r o , ΔH r o , and ΔS r o were calculated from the following log \(f_{{\text{O}}_{\text{2}} }\) /T relations (T in K): $$\begin{gathered} {\text{IW }}\log f_{{\text{O}}_{\text{2}} } = - 26,834.7/T + 6.471\left( { \pm 0.058} \right) \hfill \\ {\text{ }}\left( {{\text{800}} - 1,260{\text{ C}}} \right), \hfill \\ {\text{WM }}\log f_{{\text{O}}_{\text{2}} } = - 36,951.3/T + 16.092\left( { \pm 0.045} \right) \hfill \\ {\text{ }}\left( {{\text{1,000}} - 1,300{\text{ C}}} \right), \hfill \\ {\text{MH }}\log f_{{\text{O}}_{\text{2}} } = - 23,847.6/T + 13.480\left( { \pm 0.055} \right) \hfill \\ {\text{ }}\left( {{\text{1,040}} - 1,270{\text{ C}}} \right), \hfill \\ {\text{QIF }}\log f_{{\text{O}}_{\text{2}} } = - 27,517.5/T + 6.396\left( { \pm 0.049} \right) \hfill \\ {\text{ }}\left( {{\text{960}} - 1,140{\text{ C}}} \right), \hfill \\ {\text{FMQ }}\log f_{{\text{O}}_{\text{2}} } = - 24,441.9/T + 8.290\left( { \pm 0.167} \right) \hfill \\ {\text{ }}\left( {{\text{600}} - 1,140{\text{ C}}} \right). \hfill \\ \end{gathered}$$ These experimentally determined reaction parameters were combined with published 298 K data to determine the parameters Gf, Hf, and Sf for the phases wuestite, magnetite, hematite, and fayalite from 298 K to the temperatures of the experiments. The T? \(f_{{\text{O}}_{\text{2}} }\) data for wuestite solid solutions were used to obtain activities, excess free energies and Margules mixing parameters. The new data provide a more reliable, consistent and complete reference set for the interpretation of redox reactions at elevated temperatures in experiments and field settings encompassing the crust, mantle and core as well as extraterrestrial environments.  相似文献   

17.
Various members of the KAlSi3O8-BaAl2Si2O8 feldspar series are hydrothermally synthesized. Cellparameters of these are calculated from diffractometer patterns and found to be similar to those of Gay and Roy. A variation diagram is constructed correlating Cn-content and values of ΔFeKα(2θ(111)CaF2—2θ(004)Fsss), which gives $${\text{Mol}}\% {\text{ Cn = 229}}{\text{.83}}\Delta {\text{2}}\theta ---{\text{190}}{\text{.81}}$$ by a least square regression fitting. Phase equilibria relation in the solidus-liquidus-region for the KAlSi3O8-BaAl2Si2O8-H2O system at 1000 kg/cm2 are investigated. It is found to be a case of simple solid solution in a binary system, with reservations at the potassium-rich side of the system. Goranson (1938) gives a temperature of about 1000°C at 1000 kg/cm2 \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) for the incongruent melting of sanidine, but the authors prefer a value around 930°C at the same \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) . Reaction products of starting materials on the join KAlSi2O6-BaAl2Si2O8 and KAlSiO4-BaAl2Si2O8 gave no experimental hint for replacement of K+ by Ba++.  相似文献   

18.
Experiments at high pressure and temperature indicate that excess Ca may be dissolved in diopside. If the (Ca, Mg)2Si2O6 clinopyroxene solution extends to more Ca-rich compositions than CaMgSi2O6, macroscopic regular solution models cannot strictly be applied to this system. A nonconvergent site-disorder model, such as that proposed by Thompson (1969, 1970), may be more appropriate. We have modified Thompson's model to include asymmetric excess parameters and have used a linear least-squares technique to fit the available experimental data for Ca-Mg orthopyroxene-clinopyroxene equilibria and Fe-free pigeonite stability to this model. The model expressions for equilibrium conditions \(\mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction A) and \(\mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction B) are given by: 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Mg}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ W_{21} [2(X_{{\text{Ca}}}^{{\text{M2}}} )^3 - (X_{{\text{Ca}}}^{{\text{M2}}} ] \hfill \\ {\text{ + 2W}}_{{\text{22}}} [X_{{\text{Ca}}}^{{\text{M2}}} )^2 - (X_{{\text{Ca}}}^{{\text{M2}}} )^3 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{Wo}}}^{{\text{opx}}} )^2 \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Ca}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ 2W_{21} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^2 - (X_{{\text{Mg}}}^{{\text{M2}}} )^3 ] \hfill \\ {\text{ + W}}_{{\text{22}}} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^3 - (X_{{\text{Mg}}}^{{\text{M2}}} )^2 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{En}}}^{{\text{opx}}} )^2 \hfill \\ \hfill \\ \end{gathered} $$ where 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = 2.953 + 0.0602{\text{P}} - 0.00179{\text{T}} \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = 24.64 + 0.958{\text{P}} - (0.0286){\text{T}} \hfill \\ {\text{W}}_{{\text{21}}} = 47.12 + 0.273{\text{P}} \hfill \\ {\text{W}}_{{\text{22}}} = 66.11 + ( - 0.249){\text{P}} \hfill \\ {\text{W}}^{{\text{opx}}} = 40 \hfill \\ \Delta {\text{G}}_*^0 = 155{\text{ (all values are in kJ/gfw)}}{\text{.}} \hfill \\ \end{gathered} $$ . Site occupancies in clinopyroxene were determined from the internal equilibrium condition 1 $$\begin{gathered} \Delta G_{\text{E}}^{\text{O}} = - {\text{RT 1n}}\left[ {\frac{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}{{X_{{\text{Ca}}}^{{\text{M2}}} \cdot X_{{\text{Mg}}}^{{\text{M1}}} }}} \right] + \tfrac{1}{2}[(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} )(2{\text{X}}_{{\text{Ca}}}^{{\text{M2}}} - 1) \hfill \\ {\text{ + }}\Delta G_*^0 (X_{{\text{Ca}}}^{{\text{M1}}} - X_{{\text{Ca}}}^{{\text{M2}}} ) + \tfrac{3}{2}(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} ) \hfill \\ {\text{ (1}} - 2X_{{\text{Ca}}}^{{\text{M1}}} )(X_{{\text{Ca}}}^{{\text{M1}}} + \tfrac{1}{2})] \hfill \\ \end{gathered} $$ where δG E 0 =153+0.023T+1.2P. The predicted concentrations of Ca on the clinopyroxene Ml site are low enough to be compatible with crystallographic studies. Temperatures calculated from the model for coexisting ortho- and clinopyroxene pairs fit the experimental data to within 10° in most cases; the worst discrepancy is 30°. Phase relations for clinopyroxene, orthopyroxene and pigeonite are successfully described by this model at temperatures up to 1,600° C and pressures from 0.001 to 40 kbar. Predicted enthalpies of solution agree well with the calorimetric measurements of Newton et al. (1979). The nonconvergent site disorder model affords good approximations to both the free energy and enthalpy of clinopyroxenes, and, therefore, the configurational entropy as well. This approach may provide an example for Febearing pyroxenes in which cation site exchange has an even more profound effect on the thermodynamic properties.  相似文献   

19.
Subsolidus phase relations on the join CaMgSi2O6-CaFe3+ AlSiO6-CaTiAl2O6 were studied by the ordinary quenching method at \(f_{O_2 } = 10^{ - 11} \) atm and 1,100°C. Crystalline phases encountered are clinopyroxeness (ss:solid solution) (Cpxss), melilite (Mel), perovskite (Pv), spinelss (Spss), magnetitess (Mtss) and anorthite (An). There is no Cpxss single phase field, and the following assemblages were found; Cpxss+Mel, Cpxss+Mel+Spss, Cpxss+Mel+Pv, Cpxss+Mel+Spss+Pv, Cpxss+Pv+Spss+An, Spss+Pv+Mel+An+Cpxss, Mel+Mtss+An+Spss+Cpxss+liquid and Mel+Mtss+An+Spss+Cpxss+Pv. Mössbauer spectral study revealed that Cpxss contains both Fe2+ and Fe3+ in the octahedral site, and it was confirmed that the CaFe3+ AlSiO6 content in the Cpxss at low \(f_{O_2 } \) is considerably less than that in the Cpxss crystallized in air, whereas the CaFe2+Si2O6 component increases. The maximum solubility of CaTlAl2O6 component in the Cpxss at low \(f_{O_2 } \) is higher than that in air. The decrease of CaFe3+ AlSiO6 in the Cpxss at low \(f_{O_2 } \) may cause increase of CaTial2O6 in the Cpxss.  相似文献   

20.
The solubility of Gd2Ti2O7 ceramic in acidic solutions (HCl and HClO4) was studied at 250°C and saturation vapor pressure within pH 2.5–5.2. The dissolution process occurs mainly via two reactions: 0.5 Gd2Ti2O7(cr) + 3H+ = Gd3+ + TiO2(cr) + 1.5 H2O at pH < 3 and 0.5Gd2Ti2O7(cr) + H+ + 0.5H2O = Gd(OH) 2 + TiO2(cr) at pH 3–5. The thermodynamic equilibrium constants were calculated at the 0.95 confidence level as log K (1) o = 4.12 ± 0.47; = ?0.97 ± 0.16 at 250°C. It was shown that Gd3+ undergoes hydrolysis in solutions with pH > 3, and the species Gd(OH) 2 + dominates up to at least pH 5. At pH < 3, Gd occurs in solutions as Gd3+. The second constant of Gd3+ hydrolysis was determined at 250°C as K o = ?5.09 ± 0.5, and the thermodynamic characteristics of the initial Gd2Ti2O7 solid phase were determined: S 298.15 o = 251.4 J/(mol K) and ΔfG 298.15 o = ?3630 ± 10 kJ/mol.  相似文献   

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