首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
A thermodynamic solution model is developed for minerals whose compositions lie in the two binary systems Mg2SiO4-Fe2SiO4 and Mg2Si2O6-Fe2Si2O6. The formulation makes explicit provision for nonconvergent ordering of Fe2+ and Mg2+ between M1 and M2 sites in orthopyroxenes and non-zero Gibbs energies of reciprocal ordering reactions in both olivine and orthopyroxene. The calibration is consistent with (1) constraints provided by available experimental and natural data on the Fe-Mg exchange reaction between olivine and orthopyroxene ± quartz, (2) site occupancy data on orthopyroxenes including both crystallographic refinements and Mössbauer spectroscopy, (3) enthalpy of solution data on olivines and orthopyroxenes and enthalpy of disordering data on orthopyroxene, (4) available data on the temperature and ordering dependence of the excess volume of orthopyroxene solid solutions, and (5) direct activity-composition determinations of orthopyroxene and olivine solid solutions at elevated temperatures. Our analysis suggests that the entropies of the exchange [Mg(M2)Fe(M1)Fe(M2)Mg(M1)] and reciprocal ordering reactions [Mg(M2)Mg(M1)+ Fe(M2)Fe(M1)Fe(M2)Mg(M1)+Mg(M2)Fe(M1)] cannot differ significantly (± 1 cal/K) from zero over the temperature range of calibration (400°–1300° C). Consideration of the mixing properties of olivine-orthopyroxene solid solutions places tight constraints on the standard state thermodynamic quantities describing Fe-Mg exchange reactions involving olivine, orthopyroxene, pyralspite garnets, aluminate spinels, ferrite spinels and biotite. These constraints are entirely consistent with the standard state properties for the phases-quartz,-quartz, orthoenstatite, clinoenstatite, protoenstatite, fayalite, ferrosilite and forsterite which were deduced by Berman (1988) from an independent analysis of phase equilibria and calorimetric data. In conjunction with these standard state properties, the solution model presented in this paper provides a means of evaluating an internally consistent set of Gibbs energies of mineral solid solutions in the system Mg2SiO4-Fe2SiO4-SiO2 over the temperature range 0–1300° C and pressure interval 0.001–50 kbars. As a consequence of our analysis, we find that the excess Gibbs energies associated with mixing of Fe and Mg in (Fe, Mg)2SiO4 olivines, (Fe, Mg)3Al2Si3O12 garnets, (Fe, Mg)Al2O4 and (Fe, Mg)Fe2O4 spinels, and K(Mg, Fe)3AlSi3O10(OH)2 biotites may be satisfactory described, on a macroscopic basis, with symmetric regular solution type parameters having values of 4.86±0.12 (olivine), 3.85±0.09 (garnet), 1.96±0.13 (spinel), and 3.21±0.29 kcals/gfw (biotite). Applications of the proposed solution model demonstrate the sensitivity of petrologic modeling to activity-composition relations of olivine-orthopyroxene solutions. We explore the consequences of estimating the activity of silica in melts forming in the mantle and we develop a graphical geothermometer/geobarometer for metamorphic assemblages of olivine+orthopyroxene+quartz. Quantitative evaluation of these results suggests that accurate and realistic estimates of silica activity in melts derived from mantle source regions,P-T paths of metamorphism and other intensive variables of petrologic interest await further refinements involving the addition of trace elements (Al3+ and Fe3+) to the thermodynamic formulation for orthopyroxenes.  相似文献   

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

3.
Enthalpies of solution in molten 2 PbO · B2O3 at 974 K were measured for four spinelloids, phases I (0.75 NiAl2O4 · 0.25 Ni2SiO4), II (0.60 NiAl2O4 · 0.40 Ni2SiO4), III and IV (0.50 NiAl2O4 · 0.50 Ni2SiO4) in the system NiAl2O4 · Ni2SiO4. The enthalpies (in cal per 4-oxygen mol) of formation from NiAl2O4 and Ni2SiO4 spinels are: phase I, 945±366; phase II, 1072±360; phase III, 2253±390; phase IV, 3565±544. Using these enthalpy data in combination with phase relations at high pressure at 1373 K, positive entropies of formation of the spinelloids from NiAl2O4 and Ni2SiO4 spinels were estimated (in cal mol?1 K?1): phase I, 1.2; phase II, 1.5; phase III, 2.0–2.3; phase IV, 3.0–3.1. The thermochemical data obtained above suggest that the spinelloids are “entropy-stabilized” phases with partially disordered cation distributions. The configurational entropies of the spinelloids were calculated based on the observed cation distribution in each spinelloid phase. The positive entropies of formation of the spinelloids from the spinel endmembers are due primarily to the configurational entropies although small positive vibrational entropy changes may also exist.  相似文献   

4.
The enthalpies of solution of synthetic Mg2SiO4-Fe2SiO4 olivine solid solutions have been measured in Pb2B2O5 melt at 970 K. The heat of solution of forsterite was found to be 15.62 ± 0.3 kcal mol?1 and that of fayalite 9.39 ± 0.14 kcal mol?1. Solid solutions between these end-members exhibit small positive deviations from mixing ideality, asymmetric towards the Fe end-member. In terms of the sub-regular solution model, excess enthalpies of intermediate olivine are adequately represented by the equation Hxs = 2(1000 + 1000XFe) XFeXMgThe enthalpies of solution at 970 K are consistent with high temperature phase equilibrium measurements of activity-composition relationships in the olivine series. Excess entropy terms are not needed to relate the phase equilibrium data to the calorimetric data presented here.The enthalpy of solution of FeSiO3 ferrosilite at 970 K was found to be 4.36 ± 0.10 kcal mol?1. This value, when taken together with calorimetric measurements on fayalite and quartz, is consistent with phase equilibrium investigations of the reaction: 2FeSiO3 = Fe2SiO4 + SiO2 Ferrosilite Fayalite QuartzThese provide a check on the internal consistency of the calorimetric data presented here.  相似文献   

5.
A high temperature calorimetric solution method involving the use of a sodium and lithium metaborate (NaBO2+LiBO2) molten bath at 1,180 K, has been developed in order to measure the enthalpy of formation of the forsterite-fayalite (Mg2SiO4-Fe2SiO4) system. The samples used for these measurements have been obtained by synthesis. They have been carefully controlled by chemical and X-ray analysis and Mössbauer spectroscopy. The results obtained for forsterite and fayalite agree closely with the data commonly found in the literature. Owing to the uncertainty of the experimental results, it is not possible to determine conclusively whether an enthalpy of mixing exists in this system.  相似文献   

6.
Calorimetric measurements of fusion enthalpies for Ni2SiO4 and Co2SiO4 olivines were carried out using a high-temperature calorimeter, and Ni and Co partitioning between olivine and silicate liquid was analyzed using the measured heats of fusion. The fusion enthalpy of Co2SiO4 olivine measured by transposed-temperature drop calorimetry was 103 ± 15 kJ/mol at melting point (1688 K). The fusion enthalpy of Ni2SiO4 olivine was calculated based on the enthalpies of liquids in the system An50Di50-Ni2SiO4 measured by transposed-temperature drop calorimetry at 1773 K, and was 221 ± 26 kJ/mol at its metastable melting point (1923 K). The fusion enthalpy of Ni2SiO4 is the largest among those of olivine group, this is caused by the large crystal field stabilization energy of six-coordinated Ni2+ in olivine. The larger fusion enthalpy of Ni2SiO4 can account for the large and variable partition coefficient of Ni between olivine and silicate liquid. Based on the comparison between partition coefficients calculated from thermodynamic data and those observed in partition experiments, it is considered that the magnitude of partition coefficients is primarily dependent on the heats of fusion of the components. Furthermore, the activity coefficients for Ni-, Co- and Mn-bearing components in magmatic liquid are nearly of the same magnitude.  相似文献   

7.
《Chemical Geology》2006,225(3-4):256-265
SeO42− ions can substitute for sulphate in the gypsum structure. In this work crystals of different Ca(SO4,SeO4)·2H2O solid solutions were precipitated by mixing a CaCl2 solution with solutions containing different ratios of Na2SO4 and Na2SeO4. The compositions of the precipitates were analysed by EDS and the cell parameters were determined by X-ray powder diffraction. Moreover, a comparative study on dehydration behaviour of selenate rich and sulfate rich Ca(SO4,SeO4)·2H2O solid solutions was carried out by thermogravimetry.The experimental results show that the Ca(SO4,SeO4)·2H2O solid solution presents a symmetric miscibility gap for compositions ranging from XCaSO4·2H2O = 0.23 to XCaSO4·2H2O = 0.77. By considering a regular solution model a Guggenheim parameter a0 = 2.238 was calculated. The solid phase activity coefficients obtained with this parameter were used to calculate a Lippmann diagram for the system Ca(SO4,SeO4)·2H2O–H2O.  相似文献   

8.
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   

9.
Raman spectra of γ-Mg2SiO4 taken to 200 kbar were used to calculate entropy and heat capacity at various P-T conditions. These new thermodynamic data on γ-MgSiO4, similar data on MgSiO3 perovskite (pv), previous data on β-MgSiO4 and MgO (mw), and previous volumetric data of all phases were used to calculate the phase boundaries in the Mg2SiO4 phase diagram. Our resulting slope for the β→γ transition (50±4 bar K-1) is in excellent agreement with recent multi-anvil studies. The slopes for the β→pv+MgO and γ→pv+MgO are-7±3 and -25±4 bar K-1, respectively, and are consistent with our CO2 laser heated diamond anvil studies. These slopes result in a β-γ-MgO+pv triple point at approximately 229 kbar and 2260 K for the iron free system.  相似文献   

10.
Infrared absorption spectra of the high-pressure polymorphs β-Mg2SiO4 and β-Co2SiO4 have been measured between 0 and 27 GPa at room temperature. Grüneisen parameters determined for 11 modes of β-Mg2SiO4 (frequencies of 300 to 1,050 cm?1) and 5 modes of β-Co2SiO4 (490 to 1,050 cm?1) range between 0.8 and 1.9. Averaging the mid-infrared spectroscopic data for β-Mg2SiO4 yields an average Grüneisen parameter of 1.3 (±0.1), in good agreement with the high-temperature thermodynamic value of 1.35. Similarly, we find a value of 1.05 (±0.2) for the average spectroscopic Grüneisen parameter of β-Co2SiO4.  相似文献   

11.
A multi-anvil device was used to synthesize 24 mg of pure γ-Fe2SiO4 crystals at 8.5 GPa and 1,273 K. The low-temperature heat capacity (C p) of γ-Fe2SiO4 was measured between 5 and 303 K using the heat capacity option of a physical properties measurement system. The measured heat capacity data show a broad λ-transition at 11.8 K. The difference in the C p between fayalite and γ-Fe2SiO4 is reduced as the temperature increases in the range of 50–300 K. The gap in C p data between 300 and 350 K of γ-Fe2SiO4 is an impediment to calculation of a precise C p equation above 298 K that can be used for phase equilibrium calculations at high temperatures and high pressures. The C p and entropy of γ-Fe2SiO4 at standard temperature and pressure (S°298) are 131.1 ± 0.6 and 140.2 ± 0.4 J mol−1 K−1, respectively. The Gibbs free energy at standard pressure and temperature (ΔG° f,298) is calculated to be −1,369.3 ± 2.7 J mol−1 based on the new entropy data. The phase boundary for the fayalite–γ-Fe2SiO4 transition at 298 K based on current thermodynamic data is located at 2.4 ± 0.6 GPa with a slope of 25.4 bars/K, consistent with extrapolated results of previous experimental studies.  相似文献   

12.
Enthalpies of solution in 2PbO · B2O3 at 974 K have been measured for glasses along the joins Ca2Si2O6 (Wo)-Mg2Si2O6 (En) and Mg2Si2O6-MgAl2SiO6 (MgTs). Heats of mixing are symmetric and negative for Wo-En with WH = ?31.0 ± 3.6 kJ mol?. Negative heats of mixing were also found for the En-MgTs glasses (WH = ?33.4 ± 3.7 kJ mol?).Enthalpies of vitrification of pyroxenes and pyroxenoids generally increase with decreasing alumina content and with decreasing basicity of the divalent cation.Heats of mixing along several glassy joins show systematic trends. When only non-tetrahedral cations mix (outside the aluminosilicate framework), small exothermic heats of mixing are seen. When both nontetrahedral and framework cations mix (on separate sublattices, presumably), the enthalpies of mixing are substantially more negative. Maximum enthalpy stabilization near compositions with Al/Si ≈ 1 is suggested.  相似文献   

13.
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   

14.
Based on the available experimental data on phase equilibria in the FeO -MgO -SiO2 system the mixing properties of the solid solutions (olivine, β- and γ-spinel, pyroxene, majorite, ilmenite and perovskite and magnesiowustite), the enthalpies of FeO and fictive FeSiO3 phases with ilmenite and majorite structures have been assessed. The entropies, temperature dependance of heat capacities for fictive FeSiO3 end-members were estimated from structural analogies. The calculated phase diagrams for Mg2SiO4-Fe2SiO4 and MgSiO3 — FeSiO3 systems at pressures up to 30 GPa and temperatures between 1000 and 2100 K are quite consistent with the available experimental determinations except for the fine features of the phase diagram at 2073 K.  相似文献   

15.
We use a lattice vibrational technique to derive thermophysical and thermochemical properties of fayalite, Fe2SiO4. This semi-empirical technique is based on an extension of Kieffer’s model to incorporate details of the phonon spectrum. It includes treatment of intrinsic anharmonicity and electronic effects based on crystal field theory. We extend it to predict thermodynamic mixing properties of olivine (Mg,Fe)2SiO4 solid solutions by using results of our previous work on the system MgO–SiO2. Achieving this requires a relation between phonon frequency and composition and a composition relation for the energy of the static lattice. Directed by experimental Raman spectroscopic data for specific optic modes in magnesium–iron solid solutions of olivine and pyroxene we use an empirical relation for the composition dependence for phonon frequencies. We show that lattice vibrations have a large effect on the excess entropy and that the static lattice contribution and lattice vibrations have a large impact on excess enthalpy and excess Gibbs energy. Our model indicates that compositional effects in electronic and magnetic properties are negligible. The compositional variation the Néel temperature has a large impact on excess heat capacity for temperatures below 100 K.  相似文献   

16.
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 (Mg1?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.  相似文献   

17.
 The spinel solid solution was found to exist in the whole range between Fe3O4 and γ-Fe2SiO4 at over 10 GPa. The resistivity of Fe3− x Si x O4 (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe3+ and Fe2+ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy of the electron hopping becomes larger with increasing γ-Fe2SiO4 component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe3+–Fe2+ electron hopping with increasing the total Si content. This is probably because a large number of Si4+ ions occupies the octahedral site and the adjacent Fe2+ keeping the local electric neutrality around Si4+ makes a cluster, which generates a local deformation by Si substitution. The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases from 124(±2) K at x=0 (Fe3O4) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si4+ substitution. Received: 15 March 2000 / Accepted: 4 September 2000  相似文献   

18.
This paper reports measurements of electrical conductivity in Co2SiO4 as a function of temperature in the range from 780 to 1540 K and oxygen fugacity in the range from 5 × 10–8 to 2.6 × 10–5 MPa at 1540 K. From the present data and available literature data on defect concentrations in Co2SiO4, the mobility of the defect responsible for conduction is determined to be 8.6 × 10–7 m2/V-s at 1373 K. On the basis of these data and the observed dependence of conduction on oxygen fugacity, it is concluded that small polarons associated with oxidized cobalt ions is the likely mechanism controlling conduction. The mobility of small polarons in iron-bearing olivine under similar conditions is likely to be of the same order of magnitude.  相似文献   

19.
A drop calorimetric study, between 900 and 1800 K, of amorphous SiO2, NaAlSi3O8, NaAlSi2O6, NaAlSiO4 and KAlSi3O8 shows the increase in heat capacity which results from glass transitions. For these glasses, the fictive temperature has a negligible effect on the heat capacity above room temperature, but it has an important influence on the enthalpy of formation as obtained from solution calorimetry. From these results and published Cp and enthalpy of solution data, several properties have been calculated: the enthalpies of fusion of high albite, nepheline, Jadeite and high sanidine, the thermodynamic functions of amorphous NaAlSi3O8 and KAlSi3O8 between 0 and 2000 K, and some mixing properties of liquids along the join SiO2-NaAlSi3O8. The latter data suggest that these liquids behave more closely as athermal solutions than as regular solutions.  相似文献   

20.
Samples of microcrystalline silica varieties containing variable amounts of the new silica polymorph moganite (up to R~82 wt.%) have been studied by a combination of high temperature solution calorimetry using lead borate (2 PbO · B2O3) solvent and transposed temperature drop calorimetry near 977 K, in order to investigate the thermochemical stability of this new silica mineral. The enthalpy of solution at 977 K and the heat content (H977 — H298) of “pure” moganite phase were estimated to be -7.16 ± 0.35 kJ/mol and 43.62 ± 0.50 kJ/mol, respectively. The standard molar enthalpy of formation is-907.3 ± 1.2 kJ/mol. Thus, calorimetry strongly supports results of previous X-ray and Raman spectroscopic studies that moganite is a distinct silica polymorph. Its thermochemical instability relative to quartz at 298 K of 3.4 ± 0.7 kJ/mol is marginally higher than those of cristobalite and tridymite. Structurally, this instability may be related to the presence of distorted 4-membered rings of SiO4 tetrahedra, which are not found in the quartz structure. The metastability relative to quartz may also explain the apparent scarcity of moganite in altered rocks and in rocks that are older than 130 my.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号