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 46 毫秒
1.
Structural parameters and thermodynamic properties of strontianite — witherite solid solutions have been studied by X-ray powder diffraction, heat flux Calvet calorimetry and cation-exchange equilibria technique. X-ray study of the synthetic samples have shown linear and quadratic (for c-parameter) composition dependencies of the lattice constants in the carbonate solid solution. The thermodynamic energy parameters demonstrate the non-ideal character of strontianite — witherite solid solutions. Enthalpies of solution of the samples have been measured in 2PbO*B2O3 at 973 K. The new data on the enthalpy of formation H f,298.15 0 of SrCO3 and BaCO3 were obtained: -1231.4±3.2 and -1209.9±5.8 kJ*mol-1 respectively. The enthalpy of mixing of the solid solution was found to be positive and asymmetric with maximum at XBa (carbonate)=0.35. The composition dependence of the enthalpy of mixing may be described by two — parametric Margules model equation: H mix=X BaX Sr[(4.40±3.91)X Ba+(28.13±3.91)X Sr] kJmol–1 Cation-exchange reactions between carbonates and aqueous SrCl2-BaCl2 supercritical solutions (fluids) were carried out at 973 and 1073 K and 2 kbar. Calculated Margules model parameters of the excess free energy are: for orthorhombic carbonate solid solutions W Sr=W Ba=11.51±0.40 kJmol–1 (973 K) and W Sr=W Ba=12.09±0.95 kJmol– (1073 K) for trigonal carbonate solid solutions W Sr=W Ba=13.55±0.40 kJmol– (1073 K).  相似文献   

2.
The heat of mixing for the binary solid solution diopside–Ca-Tschermak was investigated at T = 980 K by lead borate solution calorimetry. A new statistical technique was applied to overcome the problem of using experimental data of various precisions. A two-parameter Margules model was fitted to the calorimetric data leading to W CaTs–DiH = 31.3 ± 3.4 kJ mol−1 and W H Di–CaTs = 2.4 ± 4.3 kJ mol−1. The results are in good agreement with calorimetric data given in the literature. They agree also with enthalpy data that were extracted from phase equilibrium experiments. With configurational entropy values taken from the literature, the volume and the vibrational entropy, presented in Part I of this work, and the enthalpy data of this study, the activity–composition relationships of the diopside–Ca-Tschermak binary were calculated.  相似文献   

3.
We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K d (X Fe carb X Mg ol /X Fe ol X Mg carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W FeMg ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO3 a W FeMg carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K d substantially enabling us to calculate W CaMg carb -W CaFe carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO2(CMS)–CO2 system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO2. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.  相似文献   

4.
Local structural heterogeneities in crystals of the binary grossular–spessartine solid solution have been analyzed using powder IR absorption spectroscopy. Wavenumber shifts of the highest energy Si–O stretching mode in spectra collected at room temperature are consistent with variations in Si–O bond length from structural data. They show a smaller positive deviation from linearity across the join than is seen for the grossular–pyrope and grossular–almandine binaries. The effective line widths, corr, of three selected wavenumber regions all deviate positively from linear behaviour. An empirical calibration of this excess spectroscopic property, obtained by comparison with calorimetric enthalpy of mixing data, gives an estimate for the symmetric Margules parameter of WHspec = 14.4(7) kJ mol–1 in Hmix = WHspecXGrXSp. WHspec values derived on the same basis for four aluminosilicate garnet solid solutions analyzed by IR spectroscopy vary with V2, where V represents the difference in molar volume between the end members of each binary system. Measurements of lattice parameters and IR spectra were made over a range of temperatures for seven samples with different compositions. Positive excess molar volumes of mixing at low temperature (30 K) may be larger than the excess molar volumes at room temperature. The saturation temperatures of the molar volumes show no correlation with composition, however, in contrast with what had been expected on the basis of data for the grossular–pyrope binary. Saturation temperatures for spectroscopic parameters and lattice parameters of samples with compositions Gr15Sp85 and Gr60Sp40 seem to be outliers in all experiments. It is concluded that the data hint at systematic changes in saturation temperatures across the solid solution, with implications for both the excess entropy of mixing and the excess volume of mixing, but more precise data or further sample characterization are needed to prove that this composition dependence is real in garnet solid solutions.  相似文献   

5.
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   

6.
The univariant reaction governing the upper stability of heulandite (CaAl2Si7O18·6H2O), heulandite=laumontite+3 quartz+2H2O (1), has been bracketed through reversal experiments at: 155±6° C, 1000 bar; 175±6° C, 1500 bar; and 180±8° C, 2000 bar. Reversals were established by determining the growth of one assemblage at the expense of the other, using both XRD and SEM studies. The standard molal entropy of heulandite is estimated to be 783.7±16 J mol–1 K–1 from the experimental brackets. Predicted standard molal Gibbs free energy and enthalpy of formation of heulandite are –9722.3±6.3 kJ mol–1 and –10524.3±9.6 kJ mol–1, respectively. The reaction (1), together with the reaction, stilbite=laumontite+3 quartz+3 H2O, defines an invariant point at which a third reaction, stilbite=heulandite+ H2O, meets. By combining the present experimental data with past work, this invariant point is located at approximately 600 bar and 140° C. Heulandite, which is stable between the stability fields of stilbite and laumontite, can occur only at pressures higher than that of the invariant point, for = P total.These results are consistent with natural parageneses in low-grade metamorphic rocks recrystallized in equilibrium with an aqueous phase in which is very close to unity.  相似文献   

7.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

8.
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   

9.
High temperature oxide melt solution calorimetry was used to study the energy associated with dislocations in quartz by comparing undeformed and deformed single crystals of synthetic quartz. Samples were deformed at 698 K, 1000–1500 MPa at a strain rate of 10–5 sec–1. Two sets of calorimetric measurements were made: (i) using a Pt capsule as a container for powdered sample, and (ii) using pellets made from sample powder without any container. For the first set of measurements, the undeformed sample with a dislocation density of enthalpy is sum of heat content H 973-H 295 and enthalpy of solution in molten lead borate at 973 K of 39.22 ± 1.00 kJ mol–1, while the sample deformed in the dislocation creep regime with a dislocation density of 6 × 1010 to 1 × 1011 cm–2 gave an enthalpy of 38.59 ± 0.78 kJ mol–1. For the second set of measurements the measured enthalpy of the undeformed sample was 38.87 ± 0.31 kJ mol–1, and that of a deformed sample with a dislocation density of 3 × 1010 to 1 × 1011 cm–2 was 38.24 ± 0.58 kJ mol–1.The present study and previous theoretical calculations and estimates are consistent and suggest that the energy associated with dislocations in quartz is 0.6 ± 0.6 kJ mol–1 for a dislocation density of 1011 cm–2; a precise value is difficult to determine because of the overlapping errors. These results indicate that for geologically realistic dislocation densities, the maximum excess energy due to dislocations would be 0.5 kJ mol–1 for most minerals; the exact value would depend on the Burgers vector as well as the shear modulus.  相似文献   

10.
The activity of FeTiO3 in the binary ilmenitepyrophanite (FeTiO3-MnTiO3) solid solution has been determined for the temperature range 1050–1300 K by displacement of the reaction: 2 FeTiO3=2 Fe+2 TiO2+O2 in T-O2 space, using an electrochemical technique with calcia- and yttria-stabilized zirconia solid electrolytes. The activities show small positive deviations from ideality, which, although the data are unusually precise, may be perfectly described by the simple regular solution model, with an interaction parameter, W Fe-Mn ilm , of 2.2±0.3 kJ g-atom–1, which is independent of temperature. This value, together with the experimental data on the partitioning of Fe and Mn between ilmenite and garnet (Pownceby et al. 1987), gives W Fe-Mn gt =1.2±0.5 kJ g-atom–1 for the almandine-spessartine (Fe3Al2Si3O12-Mn3Al2Si3O12) solid solution.  相似文献   

11.
We have measured the mixing properties of Mn-Mg olivine and Mn-Mg garnet at 1300° C from a combination of interphase partitioning experiments involving these phases, Pt-Mn alloys and Mn-Mg oxide solid solutions. Activity coefficients of Mn dilute in Pt-Mn alloys at 1300° C/1 atm were measured by equilibrating the alloy with MnO at known f O 2. Assuming that the log f O 2 of the Mn-MnO equilibrium under these conditions is-17.80 (Robie et al. 1978), we obtain for Mn: logMn = –5.25 + 3.67 XMn + 11.41X2 Mn Mixing properties of (Mn,Mg)O were determined by reversing the Mn contents of the alloys in equilibrium with oxide at known f O 2. Additional constraints were obtained by measuring the maximum extent of immiscibility in (Mn,Mg)O at 800 and 750° C. The data are adequately described by an asymmetric (Mn,Mg)O solution with the following upper and lower limits on nonideality: (a) WMn = 19.9kj/Mol; WMg = 13.7kj/Mol; (b) WMn = 19.9kj/Mol; WMg = 8.2kj/Mol; Olivine-oxide partitioning was tightly bracketed at 1300° C and oxide properties used to obtain activity-composition relations for Mn-Mg olivine. Despite strong M2 ordering of Mn in olivine, the macroscopic properties are adequately described by a symmetric model with: Wol = 5.5 ± 2.5 kj/mol (1-site basis) Using these values for olivine, garnet-olivine partitioning at 27 kbar/1300° C leads to an Mn-Mg interaction parameter in garnet given by: Wgt = 1.5 ± 2.5kJ/mol (1-site basis) Garnet-olivine partitioning at 9 kbar/1000° C is consistent with the same extent of garnet nonideality and the apparent absence of excess volume on the pyrope-spessartine join indicates that any pressure-dependence of WGt must be small. If olivine and garnet properties are both treated as unknown and the garnet-olivine partitioning data alone used to derive WOl and WGt, by multiple linear regression, best-fit values of 6.16 and 1.44 kJ/mol. are obtained. These are in excellent agreement with the values derived from metal-oxide, oxide-olivine and olivine-garnet equilibria.  相似文献   

12.
In contrast to Ferry (1980) (X Ca)-values in garnet even lower than 0.1 have a significant effect on the calculated equilibrium temperature using the experimental calibration of the Fe and Mg paritioning between garnet and biotite. Garnet compositions and Mg/Fe — distribution coefficients from samples of the Eoalpine staurolite — in zone in the southern Ötztal are related by the quadratic regression equation: InK D= -1.7500 (±0.0226) + 2.978 (±0.5317)X Ca Gt -5.906(±2.359)(X Ca Gt )2 Temperatures derived by the Ferry and Spear (1978) calibration using chemistry — correctedK D values are petrologically realistic.Analysis of our data supports non ideal mixing of grossular with almandine — pyrope solid solution. The derived excess mixing energies are quite small for the almandine — pyrope solution (W FeMg= –133 cal/mole) and about +2775 cal/mole for the difference between pyrope-grossular and almandine-grossular solutions (W MgCa —W FeCa) at metamorphic conditions of 570° C and 5,000 bar. The mixing parameters proposed by Ganguly and Saxena (1984) are not confirmed by our data as they would result in significantly lower temperatures.  相似文献   

13.
Fluoride-hydroxyl exchange equilibria between phlogopite-pargasite and phlogopite-tremolite mineral pairs were experimentally determined at 1,173K, 500 bars and 1,073–1,173 K, 500 bars respectively. The distribution of fluorine between phlogopite and pargasite was found to favor phlogopite slightly, G ex . (1,173 K)=–1.71 kJ anion–1, while in the case of phlogopite-tremolite, fluorine was preferentially incorporated in the mica, G ex . (1,073)=– 5.67 kJ anion–1 and G ex . (1,173K)=–5.84 kJ anion–1. These results have yielded new values of entropy and Gibbs energy of formation for fluortremolite, S f =–2,293.4±16.0JK–1 mol–1 and G f = –11,779.3±25.0 kJ mol–1, respectively. In addition, F-OH mineral exchange equilibria support a recent molten oxide calorimetric value for the Gibbs energy of fluorphlogopite, G f =–6,014.0±7.0 kJ mol–1, which is approximately 40 kJ mol–1 more exothermic than the tabulated value.This work performed in part at Sandia National Laboratories supported by the U.S. Department of Energy, DOE, under contract number DE-AC04-76DP00789  相似文献   

14.
The dehydration rate of hydrous rhyolitic glasses at 475–875 °C was measured by in situ infrared (IR) spectroscopy in order to determine the diffusion coefficient of water in rhyolitic glasses. The IR spectra of glass thin sections were obtained at 90-s intervals during 90 min at high temperatures, and the change in absorbance at 3550 cm–1 corresponding to total water was monitored. The diffusion coefficients obtained from dehydration rates of the rhyolitic glasses are considered to be averaged value over the water-concentration profile in the sample. The averaged apparent diffusion coefficients increase with the initial total water content from 0.20 m2 s–1 for 0.7 wt% to 0.37 m2 s–1 for 2.8 wt% at 700 °C. The apparent activation energy for the diffusion of total water decreases with increasing initial water content from 112 ± 6 kJ mol–1 for 0.7 wt% to 60 ± 17 kJ mol–1 for 4.1 wt%. Assuming a linear relation between the diffusion coefficient of total water and the total water content, the diffusion coefficients at each initial total water content were also determined. The diffusion coefficients of total water at the water contents of 0.7 and 1.9 wt% and at 0.1 MPa were best fitted by ln D=[(12.9 ± 0.8) – (111 500 ± 6400)/RT] and ln D=[(10.6 ± 0.4) – (86 800 ± 2800)/RT], respectively, and are in agreement with previous data (D in m2 s–1, T in K). The present in situ IR dehydration experiment is a rapid and effective method for the determination of water diffusivity at high temperatures.  相似文献   

15.
Activity-composition relationships for pyrope-grossular garnet   总被引：1，自引：0，他引：1  
Activity coefficients () for grossular in pyrope-grossular garnet have been determined experimentally using the divariant assemblage garnet-anorthite-sillimanite (kyanite)-quartz. Values of for garnets with 10–12 mole % grossular have been obtained at 1000 °, 1100 °, 1200 ° and 1300 ° C at pressures between 15 and 21 Kb. The data are consistent with a symmetrical regular solid model for grossular-pyrope solid solutions. The interaction parameter (W) increases linearly with decreasing temperature and is given by W = 7460-4.3 T cals (T in °K). A solvus in the pyrope-grossular solid solution is predicted with a temperature of critical mixing of 629°C±90 ° C.  相似文献   

16.
The kinetics of cation disordering in a natural ordered (P2/n) omphacite have been followed at P=18 and 30 kb, T= 750–1,260° C, for times of between 1.5 min and 16 days in a piston-cylinder apparatus. Time-temperature-transformation (TTT) analysis of the experimental data, using the presence or absence of the 11¯1 reflection in single crystal X-ray precession photographs to indicate the extent of reaction, yields an equilibrium order/disorder temperature (T ord) of 865±10° C, an activation enthalpy (1 bar) of 71±6 kcal mole–1 and an activation volume of 9±4 cm3 mole–1 (plus and minus figures represent the precision of a best fit between experimental data and TTT theory rather than absolute errors). The activation volume is consistent with a vacancy mechanism of cation diffusion. H2O, added in the form of oxalic acid, appears to speed the process up slightly. The overall transformation mechanism is continuous, involving neither the nucleation of a disordered phase nor a change in antiphase-domain distribution. This is consistent with both first- and non-first-order character for the C2/cP2/n transformation, though a range of ordered states below T ord is indicated by the weakening of h+k=odd reflections. A simple extrapolation of the disordering rates to geological conditions leads to the first estimate of how long disordered omphacites would take to order in nature, ranging from less than one year at T800° C to more than 107 years at T<350° C.  相似文献   

17.
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   

18.
Chemical diffusion of Pb has been measured in K-feldspar (Or93) and plagioclase of 4 compositions ranging from An23 to An93 under anhydrous, 0.101 MPa conditions. The source of diffusant for the experiments was a mixture of PbS powder and ground feldspar of the same composition as the sample. Rutherford Backscattering (RBS) was used to measure Pb diffusion profiles. Over the temperature range 700–1050°C, the following Arrhenius relations were obtained (diffusivities in m2s-1):Oligoclase (An23): Diffusion normal to (001): log D = ( – 6.84 ± 0.59) – [(261 ± 13 kJ mol –1)/2.303RT]Diffusion normal to (010): log D = ( – 3.40 ± 0.50) – [(335 ± 11 kJ mol –1)/2.303RT]Andesine (An43): Diffusion normal to (001): log D = ( – 6.73 ± 0.54) – [(266 ± 12 kJ mol –1)/2.303RT] Diffusion normal to (010) appears to be only slightly slower than diffusion normal to (001) in andesine.Labradorite (An67): Diffusion normal to (001): log D = ( – 7.16 ± 0.61) – [(267 ± 13 kJ mol –1)/2.303RT] Diffusion normal to (010) is slower by 0.7 log units on average.Anorthite Diffusion normal to (010): log D = ( – 5.43 ± 0.48) – [(327 ± 11 kJ mol –1)/2.303RT]K-feldspar (Or93): Diffusion normal to (001): log D = ( – 4.74 ± 0.52) – [(309 ± 16 kJ mol –1)/2.303RT] Diffusion normal to (010): log D = ( – 5.99 ± 0.51) – [(302 ± 11 kJ mol –1)/2.303RT]In calcic plagioclase, Pb uptake is correlated with a reduction of Ca, indicating the involvement of PbCa exchange in chemical diffusion. Decreases of Na and K concentrations in sodic plagioclase and K-feldspar, respectively, are correlated with Pb uptake and increase in Al concentration (measured by resonant nuclear reaction analysis), suggesting a coupled process for Pb exchange in these feldspars. These results have important implications for common Pb corrections and Pb isotope systematics. Pb diffusion in apatite is faster than in the investigated feldspar compositions, and Pb diffusion rates in titanite are comparable to both K-feldspar and labradorite. Given these diffusion data and typical effective diffusion radii for feldspars and accessory minerals, we may conclude that feldspars used in common Pb corrections are in general less inclined to experience diffusion-controlled Pb isotope exchange than minerals used in U-Pb dating that require a common Pb correction.  相似文献   

19.
A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe 2+ s Ti 4+ 1–s ) A (Fe 2+ 1–s Ti 4+ s ) B O3]-geikielite [(Mg 2+ t Ti 4+ 1–t ) A (Mg 2+ 1–t Ti 4+ t ) B O3]-hematite [(Fe3+) A (Fe3+) B O3]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0s, t1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of the transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg–Fe2+ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe2+–Fe3+ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (–1488.5 and –822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe–Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility gap across much of the ternary system. The predicted shape of the miscibility gap, and the orientation of tie-lines relating the compositions of coexisting phases, display the effects of coupling between the excess enthalpy of solution and the degree of long-range order. One limb of the miscibility gap follows the composititiontemperature surface corresponding to the ternary second-order transition.  相似文献   

20.
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   

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