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1.
Phase relations in the system KAlSi3O8-NaAlSi 3O8 have been examined at pressures of 5–23 GPa and temperatures of 700–1200° C. KAlSi3O8 sanidine first dissociates into a mixture of wadeite-type K2Si4O9, kyanite and coesite at 6–7 GPa, which further recombines into KAlSi3O8 hollandite at 9–10 GPa. In contrast, NaAlSi3O8 hollandite is not stable at 800–1200° C near 23 GPa, where the mixture of jadeite plus stishovite directly changes into the assemblage of calcium ferrite-type NaAlSiO4 plus stishovite. Phase relations in the system KAlSi3O8-NaAlSi3O8 at 1000° C show that NaAlSi3O8 component gradually dissolves into hollandite with increasing pressure. The maximum solubility of NaAlSi3O8 in hollandite at 1000° C was about 40 mol% at 22.5 GPa, above which it decreases with pressure. Unit cell volume of the hollandite solid solution decreases with increasing NaAlSi3O8 component. The hollandite solid solution in this system may be an important candidate as a host mineral of K and Na in the uppermost lower mantle  相似文献   

2.
The low-temperature heat capacity (C p ) of KAlSi3O8 with a hollandite structure was measured over the range of 5–303 K with a physical properties measurement system. The standard entropy of KAlSi3O8 hollandite is 166.2±0.2 J mol−1 K−1, including an 18.7 J mol−1 K−1 contribution from the configurational entropy due to disorder of Al and Si in the octahedral sites. The entropy of K2Si4O9 with a wadeite structure (Si-wadeite) was also estimated to facilitate calculation of phase equilibria in the system K2O–Al2O3–SiO2. The calculated phase equilibria obtained using Perple_x are in general agreement with experimental studies. Calculated phase relations in the system K2O–Al2O3–SiO2 confirm a substantial stability field for kyanite–stishovite/coesite–Si-wadeite intervening between KAlSi3O8 hollandite and sanidine. The upper stability of kyanite is bounded by the reaction kyanite (Al2SiO5) = corundum (Al2O3) + stishovite (SiO2), which is located at 13–14 GPa for 1,100–1,400 K. The entropy and enthalpy of formation for K-cymrite (KAlSi3O8·H2O) were modified to better fit global best-fit compilations of thermodynamic data and experimental studies. Thermodynamic calculations were undertaken on the reaction of K-cymrite to KAlSi3O8 hollandite + H2O, which is located at 8.3–10.0 GPa for the temperature range 800–1,600 K, well inside the stability field of stishovite. The reaction of muscovite to KAlSi3O8 hollandite + corundum + H2O is placed at 10.0–10.6 GPa for the temperature range 900–1,500 K, in reasonable agreement with some but not all experiments on this reaction.  相似文献   

3.
Recent hydrofluoric acid solution calorimetric data are used to derive standard enthalpies and Gibbs free energies of formation of low-albite, high-albite, NaAlSi3O8 glass, microcline, sanidine, and KAlSi3O8 glass. The data are presented as high-temperature functions from 298.15 to 1400° K.  相似文献   

4.
High temperature solution calorimetry of glasses in the system CaMgSi2O6 (Di)-CaAl2SiO6 (CaTs) show them to have negative enthalpies of mixing with a regular enthalpy parameter, WH, of -11.4 ± 0.7 kcal. Negative heats of mixing between alumina-rich and alumina-poor glasses seem to be a general phenomenon in aluminosilicates and are not confined only to glassy systems containing anorthite as a component. The thermodynamic behavior of glasses in the system SiO2-Ca0.5;AlO2-CaMgO2 appears to vary in a smooth fashion, with small positive heats of mixing near SiO2 and substantial negative heats of mixing for other compositions. The exothermic behavior with increasing A1(Al + Si) may be related to local charge balance of M2+ and Al3+. The negative heats of mixing in MgCaSi2O6-CaAl2SiO6, MgCaSi2O6-CaAl2Si2O8 and NaAlSi3O8-CaAl2Si2O8 glasses are in contrast to the positive heats of mixing found in MgCaSi2O6-CaAl2SiO6 (pyroxene) and NaAlSi3O8-CaAl2Si2O8 (high plagioclase) crystalline solid solutions.  相似文献   

5.
For a pure phase at equilibrium with a polycomponent melt, two sets of expressions can be derived; one expressing its activity as a function of enthalpy, entropy, heat capacity and temperature, and the other by coupling a Flory-Huggins' polymerisation model with the van Laar heat of mixing term. Interaction parameters for binary and ternary systems have been computed at 1 bar by equating these two expressions. Assuming the interaction parameter to be independent of temperature, equilibrium temperatures at higher pressures can be calculated by an iterative procedure. Such retrieval calculations were carried out in simple eutectic, volatile-free systems like CaAl2Si2O8-CaMgSi2O6, Mg2SiO4-TiO2, MgSiO3-TiO2, Mg2SiO4-CaMgSi2O6, NaAlSi3O8-SiO2 and CaAl2Si2O8-CaMgSi2O6-Mg2SiO4. The close agreement between the theoretically retrieved and the experimentally determined equilibrium temperatures testifies to the validity of the model at higher pressures. The successful application of the model to simple eutectic, binary and ternary systems involving vastly dissimilar phases without imposing added constraints implies that it can be possibly extended to hitherto unknown systems provided the thermodynamic parameters of the phases involved are known.  相似文献   

6.
KAlSi3O8 sanidine dissociates into a mixture of K2Si4O9 wadeite, Al2SiO5 kyanite and SiO2 coesite, which further recombine into KAlSi3O8 hollandite with increasing pressure. Enthalpies of KAlSi3O8 sanidine and hollandite, K2Si4O9 wadeite and Al2SiO5 kyanite were measured by high-temperature solution calorimetry. Using the data, enthalpies of transitions at 298 K were obtained as 65.1 ± 7.4 kJ mol–1 for sanidine wadeite + kyanite + coesite and 99.3 ± 3.6 kJ mol–1 for wadeite + kyanite + coesite hollandite. The isobaric heat capacity of KAlSi3O8 hollandite was measured at 160–700 K by differential scanning calorimetry, and was also calculated using the Kieffer model. Combination of both the results yielded a heat-capacity equation of KAlSi3O8 hollandite above 298 K as Cp=3.896 × 102–1.823 × 103T–0.5–1.293 × 107T–2+1.631 × 109T–3 (Cp in J mol–1 K–1, T in K). The equilibrium transition boundaries were calculated using these new data on the transition enthalpies and heat capacity. The calculated transition boundaries are in general agreement with the phase relations experimentally determined previously. The calculated boundary for wadeite + kyanite + coesite hollandite intersects with the coesite–stishovite transition boundary, resulting in a stability field of the assemblage of wadeite + kyanite + stishovite below about 1273 K at about 8 GPa. Some phase–equilibrium experiments in the present study confirmed that sanidine transforms directly to wadeite + kyanite + coesite at 1373 K at about 6.3 GPa, without an intervening stability field of KAlSiO4 kalsilite + coesite which was previously suggested. The transition boundaries in KAlSi3O8 determined in this study put some constraints on the stability range of KAlSi3O8 hollandite in the mantle and that of sanidine inclusions in kimberlitic diamonds.  相似文献   

7.
Nepheline-alkali feldspar equilibria with alkali chloride aqueoussolutions have been determined for the temperature range 400to 700 °C at 1000 bars pressure. Nepheline-alkali feldsparequilibria with alkali chloride melts have been determined forthe temperature range 800 to 1100 °C at approximately 6bars pressure. (1) NaAlSiO4 + KCl(aq) = NaCl(aq) + KAlSiO4 (2) NaAlSiO4 + KCl(melt) = NaCl(melt) + KAlSiO4 (3) NaAlSi3O8(high) + KCl(aq) = NaCl(aq) + KAlSi3O8(San) (4) NaAlSi3O8(low) + KCl(aq) = NaCl(aq) + KAlSi3O8(Mic) (5) NaAlSi3O8(high) + KCl(melt) = NaCl(melt) + KAlSi3O4(San) (6) NaAlSi3O8(low) + KCl(melt) = NaCl(melt) + KAlSi3O8(Mic) From these, two diagrams of phase relationships were derivedfor the following exchange equilibria: (7) NaAlSiO4 + KAlSi3O8(San) = NaAlSi3O8(high) + KAlSiO4; (8) NaAlSiO4 + KAlSi3O8(Mic) = NaAlSi3O8(low) + KAlSiO4. The effect of pressure on these equilibria has been determinedby comparing the experimental data for 1000 and 5000 bars (t= 500 °C) and thermodynamic calculations. It has also beenshown that the effect of excess silica in nepheline solid solutionon the K—Na distribution between nepheline and alkalifeldspar is substantial and opposite to that of temperature.In the high temperature region an increase in silica contentin nepheline of 2 wt. per cent eliminates the effect on theredistribution of a temperature increase of 100 °C. Thesecation exchange data and unit cell data for the crystal phasesare used to calculate thermodynamic mixing properties of nephelinesolid solution and alkali feldspar solid solution for a widerange of temperature and pressure.  相似文献   

8.
We report relative enthalpy measurements on quartz, cristobalite and amorphous SiO2 between 1000 and 1800 K. We have observed a glass transition around 1480 K for amorphous SiO2. From our results and available Cp, relative enthalpy, and enthalpy of solution data we have derived a consistent set of thermodynamic data for these phases. Our calculated enthalpies of fusion are 8.9 ± 1.0 kJ mole?1 for cristobalite at 1999 K and 9.4 ± 1.0 kJ mole?1 at 1700 K for quartz.  相似文献   

9.
Enthalpies of solution in 2PbO · B2O3 at 981 K have been measured for glasses in the system albite-orthoclase-silica and along the join Na1.6Al1.6Si2.4O8-K1.6Al1.6Si2.4O8. The join KAlSi3O8-Si4O8 shows zero heat of mixing similar to that found previously for NaAlSi3O8-Si4O8 glasses. Albite-orthoclase glasses show negative heats of mixing symmetric about Ab50Or50 (Wn = ? 2.4 ± 0.8 kcal). Negative heats of (Na, K) mixing are also found at Si(Si + Al) = 0.6. Ternary excess enthalpies of mixing in the glassy system Ab-Or-4Q are positive but rarely exceed 1 kcal mol?1.Using earlier studies of the thermodynamic properties of the crystals, the present calorimetric data and the “two-lattice” entropy model, the albite-orthoclase phase diagram is calculated in good agreement with experimental data. Attempts to calculate albite-silica and orthoclase-silica phase diagrams reveal complexities probably related to significant (but unknown) mutual solid solubility between cristobalite and alkali feldspar and to the very small heat and entropy of fusion of SiO2.  相似文献   

10.
Enthalpies and heat capacities of glasses and of stable liquids in the system NaAlSi3O8-CaAl2Si2O8 have been measured by drop and differential scanning calorimetry. Within experimental error, values of C p and of H T 300 of three intermediate compositions fall on straight line interpolations between the end members for both liquids and glasses, indicating that excesses in true and in mean heat capacities [(H T –H 300)/(T–300)] are small or absent. A value for the heat capacity of the An100 liquid component can therefore be derived, and is probably a better estimate than that based on measurements on the pure substance alone. On the assumption of zero excess heat capacity in this system, heats of mixing in the stable liquids are equal to those measured in the glasses by solution calorimetry, and can be as negative as -2 kcal mol–1.Heat capacities of solids and glasses in the Ab-An system are similar and do not vary greatly with composition. The C P's of the liquids, however, increase strongly with An content, suggesting major structural changes take place across the binary.  相似文献   

11.
The electrical conductivities of alkali feldspar solid solutions ranging in chemical composition from albite (NaAlSi3O8) to K-feldspar (KAlSi3O8) were measured at 1.0 GPa and temperatures of 873–1,173 K in a multi-anvil apparatus. The complex impedance was determined by the AC impedance spectroscopy technique in the frequency range of 0.1–106 Hz. Our experimental results revealed that the electrical conductivities of alkali feldspar solid solutions increase with increasing temperature, and the linear relationship between electrical conductivity and temperature fits the Arrhenius formula. The electrical conductivities of solid solutions increase with the increasing Na content at constant temperature. At 1.0 GPa, the activation enthalpy of solid solution series shows strong dependency on the composition, and there is an abrupt increase from the composition of Or40Ab60 to Or60Ab40, where it reaches a value of 0.96 eV. According to these results in this study, it is proposed that the dominant conduction mechanism in alkali feldspar solid solutions under high temperature and high pressure is ionic conduction. Furthermore, since the activation enthalpy is less than 1.0 eV for the alkali feldspar solid solutions, it is suggested to be a model where Na+ and K+ transport involves an interstitial mechanism for electrical conduction. The change of main charge carriers can be responsible for the abrupt increase in the activation energy for Or60Ab40. All electrical conductivity data were fitted by a general formula in order to show the dependence of activation enthalpy and pre-exponential factor on chemical composition. Combining our experimental results with the effective medium theory, we theoretically calculated the electrical conductivity of alkali feldspar granite, alkali feldspar quartz syenite, and alkali feldspar syenite with different mineral content and variable chemical composition of alkali feldspar at high temperatures at 1.0 GPa, and the calculated results are almost in agreement with previous experimental studies on silicate rocks.  相似文献   

12.
Experiments carried out in the system granite-H2O-HF at 0.1 GPa show that the crystal-liquid equilibrium temperature of quartz rises and that of alkali-feldspar goes down with increasing F content. The calculated results of quartz and alkali feldspar crystal-liquid equilibrium show that the activity of SiO2 in melt increases and the activities of NaAlSi3O8(Ab) and KAlSi3O8(Or) decrease, with a greater decreasing extent for a Ab L than a Or L . These systematic changes are believed to be caused by F complexing with Al, Na, K, but not Si in the melt, and are consistent with F decomposing AlO 2 ? tetrahedra and more preferentially forming complexes with Na than K. The comparison between effects of F and H2O on phase equilibrium suggests that the maximum difference affecting melt structure between F and OH is F complexing without Si and OH complexing with Si in granitic melt.  相似文献   

13.
In situ X-ray diffraction study on KAlSi3O8 has been performed using the cubic type high pressure apparatus, MAX90, combined with synchrotron radiation. We determined the phase relations of sanidine, the wadeite-type K2Si4O9+kyanite (Al2SiO5)+coesite (SiO2) assemblage, and hollandite-type KAlSi3O8, including melting temperatures of potassic phases, up to 11 GPa. Our data on subsolidus phase boundaries are close to the recent data of Yagi and Akaogi (1991). Melting relations of sanidine are consistent with the low pressure data of Lindsley (1966). The breakdown of sanidine into three phases reduces melting temperature, and wadeite-type K2Si4O9 melts first around 1500° C in three phase coexisting region. Melting point of hollandite-type KAlSi3O8 is between 1700° C and 1800° C at 11 GPa. If these potassic phases host potassium in the earth's mantle, the true mantle solidus temperature will be much lower than the reported dry solidus temperature of peridotite.  相似文献   

14.
Solution enthalpies of synthetic olivine solid solutions in the system Mg2SiO4-Fe2SiO4 have been measured in molten 2PbO·B2O3 at 979 K. The enthalpy data show that olivine solid solutions have a positive enthalpy of mixing and the deviation from ideality is approximated as symmetric with respect to composition, in contrast to the previous study. Applying the symmetric regular solution model to the present enthalpy data, the interaction parameter of ethalpy (WH) is estimated to be 5.3±1.7 kJ/mol (one cation site basis). Using this Wh and the published data on excess free energy of mixing, the nonideal parameter of entropy (Ws) of olivine solid solutions is estimated as 0.6±1.5 J/mol·K.  相似文献   

15.
We have measured in-situ Raman spectra of aluminosilicate glasses and liquids with albite (NaAlSi3 O8) and anorthite (CaAl2Si2O8) compositions at high temperatures, through their glass transition range up to 1700 and 2000 K, respectively. For these experiments, we have used a wire-loop heating device coupled with micro-Raman spectroscopy, in order to achieve effective spatial filtering of the extraneous thermal radiation. A major concern in this work is the development of methodology for reliably extracting the first and second order contributions to the Raman scattering spectra of aluminosilicate glasses and liquids from the high temperature experimental data, and analyzing these in terms of vibrational (anharmonic) and configurational changes. The changes in the first order Raman spectra with temperature are subtle. The principal low frequency band remains nearly constant with increasing temperature, indicating little change in the T-O-T angle, and that the angle bending vibration is quite harmonic. This is in contrast to vitreous SiO2, studied previously. Above Tg, intensity changes in the 560–590 cm?1 regions of both sets of spectra indicate configurational changes in the supercooled liquids, associated with formation of additional Al-O-Al linkages, or 3-membered (Al, Si)-containing rings. Additional intensity at 800 cm?1 reflects also some rearrangement of the Si-O-Al network.  相似文献   

16.
Isobaric (200 MPa) experiments have been performed to investigate the effects of H2O alone or in combination with P, S, F or Cl on liquid-phase separation in melts in the systems Fe2SiO4–Fe3O4–KAlSi2O6–SiO2, Fe3O4–KAlSi2O6–SiO2 and Fe3O4–Fe2O3–KAlSi2O6–SiO2 with or without plagioclase (An50). Experiments were heated in a rapid-quench internally heated pressure vessel at 1,075, 1,150 or 1,200 °C for 2 h. Experimental fO2 was maintained at QFM, NNO or MH oxygen buffers. H2O alone or in combination with P, S or F increases the temperature and composition range of two-liquid fields at fO2 = NNO and MH buffers. P, S, F and Cl partition preferentially into the Fe-rich immiscible liquid. Two-liquid partition coefficients for Fe, Si, P and S correlate well with the degree of polymerization of the SiO2-rich liquid and plot on similar but distinct power-law curves compared with equivalent anhydrous or basaltic melts. The addition of 2 wt% S to the system Fe3O4–Fe2O3–KAlSi2O6–SiO2 stabilizes three immiscible melts with Fe-, FeS- and Si-rich compositions. H2O-induced suppression of liquidus temperatures in the experimental systems, considered with the effects of pressure on the temperature and composition ranges of two-liquid fields in silicate melts, suggests that liquid-phase separation may be stable in some H2O-rich silicate magmas at pressures in excess of 200 MPa.  相似文献   

17.
Viscosity measurements are reported for amorphous silica and liquids belonging to the systems SiO2-M, SiO2-Al2O3-M, where M is an alkali-earth metal oxide, MnO, or alumina, and the systems SiO2-“FeO”, SiO2-FeO-Fe2O3-CaO, and SiO2-Al2O3-N, where N = Na2O or K2O. The implications of these measurements concerning the coordination of Al and the structure of these liquids are briefly discussed. Stable liquids in the systems SiO2-Al2O2-M show a non-Arrhenian temperature dependence of their viscosity, in general. Results obtained with empirical methods to calculate the viscosity of silicate liquids are compared with our observations.  相似文献   

18.
Direct measurements of liquid heat capacity, using a Setaram HT1500 calorimeter in step-scanning mode, have been made in air on six compositions in the Na2O-FeO-Fe2O3-SiO2 system, two in the CaO-FeO-Fe2O3-SiO2 system and four of natural composition (basanite, andesite, dacite, and peralkaline rhyolite). The fitted standard deviations on our heat capacity measurements range from 0.6 to 3.6%. Step-scanning calorimetry is particularly useful when applied to iron-bearing silicate liquids because: (1) measurements are made over a small temperature interval (10K) through which the ferric-ferrous ratio of the liquid remains essentially constant during a single measurement; (2) the sample is held in equilibrium with an atmosphere that can be controlled; (3) heat capacity is measured directly and not derived from the slope of enthalpy measurements with temperature. Liquid compositions in the sodic and calcic systems were chosen because they contain large concentrations of Fe2O3 (up to 19 mol%), and their equilibrium ferric-ferrous ratios were known at every temperature of measurement. These measurement have been combined with heat capacity (Cp) data in the literature on iron-free silicate liquids to fit Cp as a function of composition. A model assuming no excess heat capacity (linear combination of partial molar heat capacities of oxide components) reproduces the liquid data within error (±2.2% on average). The derived partial molar heat capacity of the Fe2O3 component is 240.9 ±7.9 J/g.f.w.-K, with a standard error reduced by more than a factor of two from that in earlier studies. The model equation, based primarily on simple, synthetic compositions, predicts the heat capacity of the four magmatic liquids within 1.8% on average.  相似文献   

19.
Atomistic model was proposed to describe the thermodynamics of mixing in the diopside-K-jadeite solid solution (CaMgSi2O6-KAlSi2O6). The simulations were based on minimization of the lattice energies of 800 structures within a 2 × 2 × 4 supercell of C2/c diopside with the compositions between CaMgSi2O6 and KAlSi2O6 and with variable degrees of order/disorder in the arrangement of Ca/K cations in M2 site and Mg/Al in Ml site. The energy minimization was performed with the help of a force-field model. The results of the calculations were used to define a generalized Ising model, which included 37 pair interaction parameters. Isotherms of the enthalpy of mixing within the range of 273–2023 K were calculated with a Monte Carlo algorithm, while the Gibbs free energies of mixing were obtained by thermodynamic integration of the enthalpies of mixing. The calculated T-X diagram for the system CaMgSi2O6-KAlSi2O6 at temperatures below 1000 K shows several miscibility gaps, which are separated by intervals of stability of intermediate ordered compounds. At temperatures above 1000 K a homogeneous solid solution is formed. The standard thermodynamic properties of K-jadeite (KAlSi2O6) evaluated from quantum mechanical calculations were used to determine location of several mineral reactions with the participation of the diopside-K-jadeite solid solution. The results of the simulations suggest that the low content of KalSi2O6 in natural clinopyroxenes is not related to crystal chemical factors preventing isomorphism, but is determined by relatively high standard enthalpy of this end member.  相似文献   

20.
花岗岩—H2O—HF体系相关系及氟对花岗质熔体结构的影响   总被引:4,自引:0,他引:4  
通过在0.1GPa压力下钠长花岗岩-H2O-HF体系相关系实验获得,随体系F含量的增加,石英的温度稳定域上限升高,长石的温度稳定域上限降低;石英、碱性长石的晶-液平衡热力学计算表明,F导致花岗质熔体中组分SiO2的活度增加,组分NaAlSi3O8和KAlSi3O8的活度减小,且NaAlSi3O8活度较KAlSi3O8活度减小幅度大。这些结果显示了F在花岗质熔体中与Si以外的阳离子Al、Na、K等产生了结合,且F与Na结合的优先性大于K,破坏了具有电荷平衡离子Na、K的AlO2-四面体,使熔体架状网格中Si/(Si+Al)和K/Na比值增大。通过F与H2O对花岗岩体系相平衡的影响比较,作者认为F不与Si结合是它与OH-在干扰熔体结构方面的最大区别。  相似文献   

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