Thermochemistry of glasses and liquids in the systems CaMgSi₂O₆-CaAl₂Si₂O₈-NaAlSi₃O₈, SiO₂-CaAl₂Si₂O₈-NaAlSi₃O₈ and SiO₂-Al₂O₃-CaO-Na₂O     

A. Navrotsky  R. Hon  D.F. Weill  D.J. Henry 《Geochimica et cosmochimica acta》1980,44(10):1409-1423

Enthalpies of solution in 2PbO· B₂O₃ at 712°C have been measured for glasses in the systems albite anorthite diopside, NaAlO₂-SiO₂, Ca_0.5AlO₂-SiO₂ and albite-anorthite-quartz. The systems albite-anorthite and diopside-anorthite show substantial negative enthalpies of mixing, albite-diopside shows significant positive heats of mixing. For compositions up to NaAlO₂ = 0.42 (which includes the subsystem albite-silica) the system NaAlO₂-SiO₂ shows essentially zero heats of mixing. A negative ternary excess heat of mixing is found in the plagioclase-rich portion of the albite-anorthite-diopside system. The join Si₄O₈-CaAl₂Si₂O₈ shows small but significant heats of mixing. In albite-anorthite-quartz. ternary glasses, the ternary excess enthalpy of mixing is positive.Based on available heat capacity data and appropriate consideration of the glass transition, the enthalpy of the crystal-glass transition (vitrification) is a serious underestimate of the enthalpy of the crystal-liquid transition (fusion) especially when the melting point, T_f, is many hundreds of degrees higher than the glass transition temperature, T_g. On the other hand, the same heat capacity data suggest that the enthalpies of mixing in albite-anorthite-diopside liquids are calculated to be quite similar to those in the glasses. The enthalpies of mixing observed in general support the structural models proposed by Taylor and Brown (1979a, b) and others for the structure of aluminosilicate glasses.  相似文献   

Thermochemistry of glasses along joins of pyroxene stoichiometry in the system Ca₂Si₂O₆-Mg₂Si₂O₆-Al₄O₆     

Richard L. Hervig  Derry Scott  Alexandra Navrotsky 《Geochimica et cosmochimica acta》1985,49(7):1497-1501

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 W_H = ?31.0 ± 3.6 kJ mol^?. Negative heats of mixing were also found for the En-MgTs glasses (W_H = ?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   

Thermochemistry of synthetic clinopyroxenes on the join CaMgSi₂O₆-Mg₂Si₂O₆     

R.C. Newton  T.V. Charlu  P.A.M. Anderson  O.J. Kleppa 《Geochimica et cosmochimica acta》1979,43(1):55-60

Enthalpies of solution of synthetic clinopyroxenes on the join CaMgSi₂O₆-Mg₂Si₂O₆ have been measured in a melt of composition Pb₂B₂O₅ at 970 K. Most of the measurements were made on samples crystallized at 1600°–1700°C and 30 kbar pressure, which covered the range 0–78 mole per cent Mg₂Si₂O₆, and whose X-ray patterns could be satisfactorily indexed on the diopside (C2/c) structure. For the reaction: Mg₂Si₂O₆→-Mg₂Si₂O₆ enstatite diopside the present data, in conjunction with previous and new measurements on Mg₂Si₂O₆ enstatite, determine ΔH° ~ 2 kcal and W_H (regular solution parameter) ~ 7 kcal. These values are in good agreement with those deduced by Saxena and Nehru (1975) from a study of high temperature, high pressure phase equilibrium data under the assumption that the excess entropy of mixing is small, but, in light of the recent theoretical treatment of Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), the meanings of these parameters may be ambiguous.Heat of solution measurements on Ca-rich binary diopsides made by annealing glasses at 1358°C in air gave slighter higher values than the higher temperature high pressure samples. This may be evidence for some (Ca, Mg) disorder of the sort postulated by Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), although no differences in heat of solution dependent on synthesis temperature in the range 1350°–1700°C could be found in stoichiometric CaMgSi₂O₆.  相似文献   

Thermochemical study of glasses in the system CaMgSi2O6-CaAl2SiO6     

Alexandra Navrotsky  Hans D Zimmermann  Richard L Hervig 《Geochimica et cosmochimica acta》1983,47(8):1535-1538

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, W_H, 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-Ca_0.5;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 $\text{A1}\text{(Al + Si)}$ 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   

A hydrofluoric acid solution calorimetric investigation of glasses in the systems NaAlSi₃O₈-KAlSi₃O₈ and NaAlSi₃O₈-Si₄O₈     

Guy L. Hovis 《Geochimica et cosmochimica acta》1984,48(3):523-525

Glasses in the systems NaAlSi₃O₈-KAlSi₃O₈ and NaAlSi₃O₈-Si₄O₈ have been studied by means of hydrofluoric acid solution calorimetry at 50°C. Results indicate small negative enthalpies of mixing in the former system and small positive departures from ideality in the latter.  相似文献   

Thermochemistry of high pressure garnets and clinopyroxenes in the system CaO-MgO-Al₂O₃-SiO₂     

R.C. Newton  T.V. Charlu  O.J. Kleppa 《Geochimica et cosmochimica acta》1977,41(3):369-377

The enthalpies of solution of several synthetic garnets on the join Mg₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ (pyrope-grossular) and of several synthetic clinopyroxenes on the join CaMgSi₂O₆-CaAl₂SiO₆ (diopside-Ca-Tschermak's molecule) were measured in a melt of composition 2PbO · B₂O₃ at 970 K. The determinations were made with sufficient precision so that thermochemical characterizations of the solid solutions could be achieved.The pyrope-grossular solutions show positive enthalpies of mixing. The non-ideality in the range 0–30 mole % grossular is relatively the largest and is in good agreement with the predictions of Ganguly and Kennedy (1974) based largely on cation partitioning of natural high grade metamorphic garnets with biotite, and with the deductions of Hensenet al. (1975) based on measurement of the compositions of synthetic pyrope-rich garnets equilibrated with anorthite, Al₂SiO₅ and quartz. However, the garnets show smaller excess enthalpies at higher grossular contents. This would lead to an asymmetric solvus with a critical temperature lower than predicted by the symmetrical regular solution model of Ganguly and Kennedy (1974). The composition-dependent non-ideality can be understood by simple ionic size considerations in solid substitution and is analogous to the situations for the calcite-dolomite and enstatite-diopside solvi.The heats of solution of pyropes crystallized in the range 1000–1500°C were all the same, within the precision of measurement, and thus we have found no evidence for temperature-dependent cation disordering as a possible explanation of the high entropy of pyrope, as suggested by Charluet al. (1975). Positional disorder of dodecahedral Mg is a more probable reason.The diopside-CaTs join is also non-ideal, with the larger positive enthalpy deviations near the diopside end. The calorimetric data in the magnesian range are consistemt with the model for completely disordered tetrahedral Si and Al which results from the free energy derivations of wood (1975) based on syntheses of diopside-rich aluminous pyroxenes in the presence of anorthite and quartz. At higher Al concentrations the calorimetric data seem more consistent with the ‘local charge-balance’ model of Wood (1975).No evidence for temperature-dependent disorder was found for either the diopside or CaTs end-members.  相似文献   

Structure of mineral glasses—I. The feldspar glasses NaAlSi₃O₈, KAlSi₃O₈, CaAl₂Si₂O₈     

Mark Taylor  Gordon E. Brown 《Geochimica et cosmochimica acta》1979,43(1):61-75

The short range distribution of interatomic distances in three feldspar glasses has been determined by X-ray radial distribution analysis. The resulting radial distribution functions (RDF's) are interpreted by comparison with RDF's calculated for various quasi-crystalline models of the glass structure.The experimental RDF's of the alkali feldspar glasses were found to be inconsistent with the four-membered rings of tetrahedra associated with crystalline feldspars; the structures of these glasses are probably based on interconnected six-membered rings of the type found in tridymite, nepheline, or kalsilite. In contrast, the RDF of calcic feldspar glass is consistent with a four-membered ring structure of the type found in crystalline anorthite. T-O bond lengths (T = Si,Al) increase from 1.60 Å in SiO₂ glass [J. H. Konnert and J. Karle (1973) Acta Cryst.A29, 702–710] to 1.63 Å in the alkali feldspar glasses to 1.66 Å in the calcic feldspar glass due to the substitution of Al for Si in the tetrahedra] sites. The T-O-T bond angles inferred from the RDF peak positions are 151° in SiO₂ glass (see reference above), 146° in the alkali feldspar glasses, and 143° in the calcic feldspar glass. Detail in the RDF at distances greater than 5 Å suggests that the alkali feldspar glasses have a higher degree of long range order than the calcic feldspar glasses.Assuming that the structural details of our feldspar glasses are similar to those of the melts, the observed structural differences between the alkali feldspar and calcic feldspar glasses helps explain the differences in crystallization kinetics of anhydrous feldspar composition melts. Structural interpretations of some thermodynamic and rheologic phenomena associated with feldspar melts are also presented based on these results.  相似文献   

Alkali-free tourmaline in the system MgO-Al₂O₃-B₂O₃-SiO₂-H₂O     

Günter Werding  Werner Schreyer 《Geochimica et cosmochimica acta》1984,48(6):1331-1344

An end member of the tourmaline series with a structural formula □(Mg₂Al)Al₆(BO₃)₃[Si₆O₁₈](OH)₄ has been synthesized in the system MgO-Al₂O₃-B₂O₃-SiO₂-H₂O where it represents the only phase with a tourmaline structure. Our experiments provide no evidence for the substitutions Al → Mg + H, Mg → 2H, B + H → Si, and AlAl → MgSi and we were not able to synthesize a phase “Mg-aluminobuergerite” characterized by Mg in the (3a)-site and a strong (OH)-deficiency reported by Rosenberg and Foit (1975). The alkali-free tourmaline has a vacant (3a)-site and is related to dravite by the □ + Al for Na + Mg substitution. It is stable from at least 300°C to about 800°C at low fluid pressures and 100% excess B₂O₃, and can be synthesized up to a pressure of 20 kbars. At higher temperatures the tourmaline decomposes into grandidierite or a boron-bearing phase possibly related to mullite (“B-mullite”), quartz, and unidentified solid phases, or the tourmaline melts incongruently into corundum + liquid, depending on pressure. In the absence of excess B₂O₃ tourmaline stability is lowered by about 60°C. Tourmaline may coexist with the other MgO-Al₂O₃-B₂O₃-SiO₂-H₂O phases forsterite, enstatite, chlorite, talc, quartz, grandidierite, corundum, spinel, “B-mullite,” cordierite, and sinhalite depending on the prevailing PTX-conditions.The (3a)-vacant tourmaline has the space group R3m with $\text{a =15.90}\text{A}\text{?}$, $\text{c = 7.115}\text{A}\text{?}$, and $\text{V = 1557.0}\text{A}\text{?}{}^3$. However, these values vary at room temperature with the pressure-temperature conditions of synthesis by $\text{±0.015}\text{A}\text{?}\text{in a}$, $\text{±0.010}\text{A}\text{?}\text{in c}$, and $\text{±4.0}\text{A}\text{?}{}^3\text{in V}$, probably as a result of MgAl order/disorder relations in the octahedral positions. Despite these variations intensity calculations support the assumed structural formula. Refractive indices are n_o = 1.631(2), n_E = 1.610(2), Δn = 0.021. The infrared spectrum is intermediate between those of dravite and elbaite. The common alkali and calcium deficiencies of natural tourmalines may at least partly be explained by miscibilities towards (3a)-vacant end members. The apparent absence of (3a)-vacant tourmaline in nature is probably due to the lack of fluids that carry boron but no Na or Ca.  相似文献   

Pyroxene geothermometry and geobarometry: experimental and thermodynamic evaluation of some subsolidus phase relations involving pyroxenes in the system CaO-MgO-Al₂O₃-SiO₂     

Claude T. Herzberg 《Geochimica et cosmochimica acta》1978,42(7):945-957

One petrogenetic grid for plagioclase-, spinel- and garnet-lherzolite analogues in the system CaO-MgO-Al₂O₃-SiO₂ is presented from 1 bar to 30 kbar and 400 to 1500°C. Another grid for olivine-gabbro, spinel-gabbro and garnet-pyroxenite analogues in the same system is presented from 1 bar to 25 kbar and 500 to 1500°C. Both grids show the distribution of the mineral assemblages and the variations in the composition of clinopyroxene with temperature and pressure. They were developed by applying simple thermodynamic mixing models of clinopyroxene to experimentally determined clino-pyroxene compositions.Calcium tschermak's pyroxene (CaAl₂SiO₆) in complex CaMgSi₂O₆-CaAl₂SiO₆-Mg₂Si₂O₆ clinopyroxenes is best represented by a local charge balance mixing model where Enthalpy and entropy changes of subsolidus reactions involving variations in the CaAl₂SiO₆ and Mg₂Si₂O₆ content of clinopyroxene are interdependent due to nonideal mixing of these two end-members. CaAl₂SiO₆ can strongly reduce the mutual solubility of clinopyroxene and orthopyroxene at moderate pressures and high temperatures. Failure to take this into account can result in temperature underestimates (up to 150°C) of spinel-lherzolites, garnet-pyroxenites, low pressure garnet-lherzolites, spinel-gabbros, and high pressure plagioclase-lherzolites and olivine-gabbros. However, at temperatures and pressures where the Al₂O₃ content of clinopyroxene is low (e.g. garnet-lherzolite nodules in kimberlite), the mutual solubility is adequantely represented by experimental results in the system CaO-MgO-SiO₂.  相似文献   

The mixing properties of melts and glasses in the system NaAlSi₃O₈-KAlSi₃O₈: Comparison of experimental data obtained by knudsen cell mass spectrometry and solution calorimetry     

Donald G. Fraser  Yan Bottinga 《Geochimica et cosmochimica acta》1985,49(6):1377-1381

The apparent differences between heats of mixing determined by solution calorimetric measurements on quenched samples in the system NaAlSi₃O₈-KAlSi₃O₈ and heats of mixing determined at high temperatures by Knudsen cell mass spectrometry are caused by thermal effects related to the glass transition. When these effects are allowed for, the calorimetric data and Knudsen cell measurements are in good agreement.  相似文献   

A high pressure-high temperature study of TiO₂ solubility in Mg-rich phlogopite: implications to phlogopite chemistry     

R.G Tronnes  A.D Edgar  M Arima 《Geochimica et cosmochimica acta》1985,49(11):2323-2329

The solubility of Tio₂ in phlogopites has been experimentally determined in the system K₂Mg₆Al₂Si₆O₂₀(OH)₄-K₂Mg₄TiAl₂Si₆O₂₀(OH)₄-K₂Mg₅TiAl₄Si₄O₂₀(OH)₄ between 825–1300°C and 10–30 kbar under vapour absent conditions. Starting compositions lie along the join K₂Mg₆Al₂Si₆O₂₀(OH)₄-K₂Mg_4.5TiAl₃Si₅O₂₀(OH)₄ which represents a combination of the Mg^[VI]2Si^[IV] = Ti^[VI]2Al^[VI] and $\text{2Mg}{}^{\mathrm{[VI]}}\text{=}\text{Ti}{}^{\mathrm{[VI]}}\text{□}{}^{\mathrm{[VI]}}$ substitution mechanisms for Ti in phlogopites. The results of the experiments indicate a systematic increase in solubility of Ti with increasing temperature and decreasing pressure for given bulk Tio₂ content. Under isobaric conditions high temperature Ti-saturated phlogopite breaks down to Ti-deficient phlogopite + rutile + vapour. Mass balance calculations suggest that the vapour phase may contain K₂O dissolved in H₂O and that the reaction is controlled by the vapour phase. Analyses of phlogopites coexisting with rutile and vapour can be represented in terms of the end-member components phlogopite [K₂Mg₆Al₂Si₆O₂₀(OH)₄], eastonite [K₂Mg₅Al₄Si₅O₂₀(OH)₄], an octahedral site deficient Ti-phlogopite (Ti-OSD) of composition K₂(Mg₄Ti□)Al₂Si₆)O₂₀(OH)₄, and Ti-eastonite [K₂Mg₅TiAl₄Si₄O₂₀(OH)₄]. With decreasing amounts of Ti in these phlogopites there is a decrease in the Ti-eastonite component and increase in the eastonite component.The general equation for the breakdown of Ti-phlogopite solid solution to Ti-free phlogopite + rutile + vapour is: 14 Ti-eastonite + 7 Ti-OSD ? 16 eastonite + 3 phlogopite + 21 rutile + 4 H₂O + 2 K₂O. Lack of knowledge of H₂O and K₂O activities in the vapour phase does not permit evaluation of thermodynamic constants for this reaction. The Ti solubility in phlogopites and hence its potential as a geothermobarometer under lower crustal to upper mantle conditions is likely controlled by common mantle minerals such as forsterite.  相似文献   

PbO-SiO₂ melts: structure and thermodynamics of mixing     

Paul C Hess 《Geochimica et cosmochimica acta》1975,39(5):671-687

Thermodynamic properties of PbO-SiO₂ melts, obtained from published data and calculated from freezing point depressions, reflect the gradual polymerization of silicate anions in the melt as the $\text{SiO}{}_2\text{PbO}$ ratio is increased. The free energy of mixing curve at 1000°C has a minimum at 40 mole % SiO₂ and is convex-upward between 72 and 98 mole % SiO₂. The latter is an indication of metastable liquid immiscibility. The free energy minimum is correlated with the maximum in the distribution of nonbridging oxygens in the melt. In SiO₂-poor melts, the activities of PbO and SiO₂ (pure liquid standard states) show sharp negative deviations from ideality. The PbO activity reflects the paucity of free oxygen species in the melt whereas the SiO₂ activity reflects the depolymerized state of the silicate anions. In more SiO₂-rich melts, the activity of SiO₂ shows a positive deviation from ideality which is qualitatively correlated to a polymerization parameter. The heat of mixing term has a minimum of ?2000 cal at 35 mole % SiO₂ and a maximum of +200 cal at 90 mole % SiO₂. The minimum is associated with the exothermic heat effect obtained during the reaction (O⁰) + (O^2?) = 2(O^?), whereas the maximum corresponds to the endothermic heat effect obtained when coordination polyhedra of oxygens form around the Pb cation. The entropy of mixing curve has the same form but is systematically smaller than a theoretical curve calculated on the assumption of random mixing of oxygen species. The discrepancy is due to the entropy loss obtained by the clustering of oxygen species to form complex silicate species.  相似文献   

Structure, thermodynamics, and diffusion in CaAl₂Si₂O₈ liquid from first-principles molecular dynamics     

Nico de Koker 《Geochimica et cosmochimica acta》2010,74(19):5657-470

We have performed first-principles molecular dynamics simulations of CaAl₂Si₂O₈ (anorthite) liquid at pressures up to 120 GPa and temperatures of 3000, 4000 and 6000 K. At the lowest degrees of compression the liquid is seen to accommodate changes in density through decreasing the abundance of 3- and 4-membered rings, while increases in coordination of network forming cations take effect at somewhat higher degrees of compression. Results are fit to a fundamental thermodynamic relation with 4th order finite strain and 1st order thermal variable expansions. Upon compression by a factor of two, the Grüneisen parameter (γ) is found to increase continuously from 0.35 to 1.10. Weak temperature dependence in γ is thermodynamically consistent with a slight decrease in isochoric heat capacity (C_V), for which values of between 4.4 and 5.2 Nk_B are obtained, depending on the temperature. Pressure and temperature dependence of self-diffusivities is found to be well represented by an Arrhenius relation, except at 3000 K and pressures lower than 5 GPa, where self-diffusivities of Si, Al, and O increase with pressure. Analysis of the lifetimes of individual coordination species reveals that this phenomenon arises due to the disproportionately high stability of 4-fold coordinated Si, and to a lesser extent 4-fold coordinated Al. Our results represent a marked improvement in accuracy and reliability in describing the physics of CaAl₂Si₂O₈ liquid at deep mantle pressures, pointing the way to a general thermodynamic model of melts at extreme pressures and temperatures relevant to planetary-scale magma oceans and deep mantle partial melting.  相似文献   

Enthalpies of formation at 970 K of compounds in the system MgO-Al₂O₃-SiO₂ from high temperature solution calorimetry     

T.V Charlu  R.C Newton  O.J Kleppa 《Geochimica et cosmochimica acta》1975,39(11):1487-1497

The enthalpies of solution of petrologically important phases in the system MgO-Al₂O₃-SiO ₂ were measured in a melt of composition 2PbO · B₂O₃ at 970 ± 2K. The substances investigated included synthetic and natural (meteoritic) enstatite (MgSiO₃), synthetic aluminous enstatite (MgSiO_30.9Al₂O_30.1), synthetic and natural cordierite (Mg₂Al₄Si₅O₁₈), synthetic and natural sapphirine (approx. 7MgO·9Al₂O₃ · 3SiO₂), synthetic spinel (MgAl₂O₄), natural sillimanite (Al₂SiO₅), synthetic forsterite (Mg₂SiO₄), synthetic pyrope (Mg₃Al₂Si₃O₁₂), natural quartz (SiO₂), synthetic periclase (MgO) and corundum (Al₂O₃). Improvement in standardization of the calorimeter solvent made possible greater precision in this study than obtainable in former work in this laboratory on some of the same substances.The enthalpies of formation of enstatite, synthetic cordierite, forsterite and spinel are in reasonable agreement with values previously determined by solution calorimetry. The enthalpy of formation of enstatite is about 0.7 kcal less negative than the value for clinoenstatite resulting from the HF calorimetry of Torgesen and Sahama (J. Amer. Chem. Soc.70. 2156–2160, 1948), and is in accord with predictions based on analysis of published pyroxene equilibrium work. Aluminous enstatite with 10 wt.% Al₂O₃ shows an enthalpy of solution markedly lower than pure MgSiO₃: the measurements lead to an estimate of the enthalpy of formation at 970 K for MgAl₂SiO₆ (Mg-Tschermak) orthopyroxene of + 9.4 ± 1.5 kcal/mole from MgSiO₃ and Al₂O₃.Comparison of the enthalpies of formation of synthetic cordierite and anhydrous natural low-iron cordierite shows that they are energetically quite similar and that the synthetic cordierite is not likely to have large amounts of (Al, Si) tetrahedral disorder. Comparison of the enthalpies of formation of synthetic sapphirine and natural low-iron sapphirine shows, on the other hand, that the former is not a good stability model for the latter. The lower enthalpy of formation of the high-temperature synthetic sample is undoubtedly a consequence of cation disordering.The enthalpy of formation of natural sillimanite is considerably less negative than given by the tables of Robie andWaldbaum (U.S. Geol. Surv. Bull.1259 1968).The measured enthalpy of formation of synthetic pyrope is consistent with that deduced from published equilibrium diagrams in conjunction with the present measured enthalpy of formation of aluminous enstatite. Calculation of the entropy of synthetic pyrope from the present data yields surprisingly high values and suggests that synthetic pyrope is not a good stability model for natural pyrope-rich garnets. Hence, considerable doubt exists about the direct quantitative application of experimental diagrams involving pyropic garnet to discussions of the garnet stability field in the Earth's outer regions.  相似文献   

Thermochemistry of the high structural state plagioclases     

R.C. Newton  T.V. Charlu  O.J. Kleppa 《Geochimica et cosmochimica acta》1980,44(7):933-941

The enthalpies of solution of a suite of 19 high-structural state synthetic plagioclases were measured in a Pb₂B₂O₅ melt at 970 K. The samples were crystallized from analyzed glasses at 1200°C and 20 kbar pressure in a piston-cylinder apparatus. A number of runs were also made on Amelia albite and Amelia albite synthetically disordered at 1050–1080°C and one bar for one month and at 1200°C and 20 kbar for 10 hr. The component oxides of anorthite, CaO, Al₂O₃ and SiO₂, were remeasured.The ΔH of disorder of albite inferred in the present study from albite crystallized from glass is 3.23 kcal, which agrees with the 3.4 found by Holm and Kleppa (1968). It is not certain whether this value includes the ΔH of a reversible displacive transition to monoclinic symmetry, as suggested by Helgesonet al. (1978) for the Holm-Kleppa results. The enthalpy of solution value for albite accepted for the solid solution series is based on the heat-treated Amelia albite and is 2.86 kcal less than for untreated Amelia albite.The enthalpy of formation from the oxides at 970 K of synthetic anorthite is ?24.06 ± 0.31 kcal, significantly higher than the ?23.16 kcal found by Charluet al. (1978), and in good agreement with the value of ?23.89 ± 0.82 given by Robieet al. (1979), based on acid calorimetry.The excess enthalpy of mixing in high plagioclase can be represented by the expression, valid at 970 K: ΔH^ex(±0.16 kcal) = 6.7461 X_abX²_An + 2.0247 X_AnX²_Ab where X_Ab and X_An are, respectively, the mole fractions of NaAlSi₃O₈ and CaAl₂Si₂O₈. This ΔH^ex, together with the mixing entropy of Kerrick and Darken's (1975) Al-avoidance model, reproduces almost perfectly the free energy of mixing found by Orville (1972) in aqueous cation-exchange experiments at 700°C. It is likely that Al-avoidance is the significant stabilizing factor in the high plagioclase series, at least for X_An≥ 0.3. At high temperatures the plagioclases have nearly the free energies of ideal one-site solid solutions. The Al-avoidance model leads to the following Gibbs energy of mixing for the high plagioclase series: $\text{ΔG}{}^{\mathrm{mix}}\text{= ΔH}{}^{\mathrm{ex}}\text{+ RT X}{}_{\mathrm{Ab}}\text{ln[X}{}^2{}_{\mathrm{Ab}}\text{(2 ? X}{}_{\mathrm{Ab}}\text{)]+ X}{}_{\mathrm{An}}\text{ln}\text{[X}{}_{\mathrm{An}}\text{(1+X}{}_{\mathrm{An}}\text{)}{}^2\text{]}\text{4}$. The entropy and enthalpy of mixing should be very nearly independent of temperature because of the unlikelihood of excess heat capacity in the albite-anorthite join.  相似文献   

La sénégalite,Al₂ (PO₄) (OH)₃ · H₂O,un nouveau minéral     

Zdenek Johan 《Lithos》1976,9(2):165-171

Senegalite is orthorhombic, mm2, a:b:c:=1.296:1:1.007; $\text{a}{}_0\text{=9.673,}\text{b}{}_0\text{=7.596,}\text{c}{}_0\text{=7.668}\text{A}\text{?}$, Z=4, G_calc=2551; space group Pna2. The strongest lines in the powder pattern are: 5.41(7); 4.089(9); 3.834(10); 3.610(8); 2.990(9); 2.348(8); 2.070(7) 1.929(7); 1.505(7) Å. The chemical analysis: Al₂O₃ ? 46.23; Fe₂O₃ ? 0.28; P₂O₅ ? 31.85 H₂O ? 21.00; sum 99.34, gives a formula Al₂(PO₄)(OH)₃ · H₂O. Colourless optically biaxial positive, n_S: α=1.562, β=1.566, γ=1.587, plane of optical axies (001), Z=a, Y=c; 2V=53°, weak dispersion r > v. Measured density 2.552. The DTA curve shows endothermic reactions at 250, 370 and 440°C corresponding to the dehydration of mineral. Infrared spectrum indicates the presence of OH and H₂O groups. Found in oxidation zone of Kouroudiako iron deposit, Senegal, associated with turquoise, augelite, wavellite and crandallite.  相似文献   

High temperature heat contents and heat capacities of liquids and glasses in the system NaAlSi3O8-CaAl2Si2O8     

J. F. Stebbins  D. F. Weill  I. S. E. Carmichael  L. K. Moret 《Contributions to Mineralogy and Petrology》1982,80(3):276-284

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   

Molecular H₂O in armenite, BaCa₂Al₆Si₉O₃₀·2H₂O, and epididymite, Na₂Be₂Si₆O₁₅·H₂O: Heat capacity, entropy and local-bonding behavior of confined H₂O in microporous silicates     

Charles A. Geiger  Edgar Dachs  Gilberto Artioli 《Geochimica et cosmochimica acta》2010,74(18):5202-5215

Armenite, ideal formula BaCa₂Al₆Si₉O₃₀·2H₂O, and its dehydrated analog BaCa₂Al₆Si₉O₃₀ and epididymite, ideal formula Na₂Be₂Si₆O₁₅·H₂O, and its dehydrated analog Na₂Be₂Si₆O₁₅ were studied by low-temperature relaxation calorimetry between 5 and 300 K to determine the heat capacity, C_p, behavior of their confined H₂O. Differential thermal analysis and thermogravimetry measurements, FTIR spectroscopy, electron microprobe analysis and powder Rietveld refinements were undertaken to characterize the phases and the local environment around the H₂O molecule.The determined structural formula for armenite is Ba_0.88(0.01)Ca_1.99(0.02)Na_0.04(0.01)Al_5.89(0.03)Si_9.12(0.02)O₃₀·2H₂O and for epididymite Na_1.88(0.03)K_0.05(0.004)Na_0.01(0.004)Be_2.02(0.008)Si_6.00(0.01)O₁₅·H₂O. The infrared (IR) spectra give information on the nature of the H₂O molecules in the natural phases via their H₂O stretching and bending vibrations, which in the case of epididymite only could be assigned. The powder X-ray diffraction data show that armenite and its dehydrated analog have similar structures, whereas in the case of epididymite there are structural differences between the natural and dehydrated phases. This is also reflected in the lattice IR mode behavior, as observed for the natural phases and the H₂O-free phases. The standard entropy at 298 K for armenite is S° = 795.7 ± 6.2 J/mol K and its dehydrated analog is S° = 737.0 ± 6.2 J/mol K. For epididymite S° = 425.7 ± 4.1 J/mol K was obtained and its dehydrated analog has S° = 372.5 ± 5.0 J/mol K. The heat capacity and entropy of dehydration at 298 K are Δ = 3.4 J/mol K and ΔS^rxn = 319.1 J/mol K and Δ = −14.3 J/mol K and ΔS^rxn = 135.7 J/mol K for armenite and epididymite, respectively. The H₂O molecules in both phases appear to be ordered. They are held in place via an ion-dipole interaction between the H₂O molecule and a Ca cation in the case of armenite and a Na cation in epididymite and through hydrogen-bonding between the H₂O molecule and oxygen atoms of the respective silicate frameworks. Of the three different H₂O phases ice, liquid water and steam, the C_p behavior of confined H₂O in both armenite and epididymite is most similar to that of ice, but there are differences between the two silicates and from the C_p behavior of ice. Hydrogen-bonding behavior and its relation to the entropy of confined H₂O at 298 K is analyzed for various microporous silicates.The entropy of confined H₂O at 298 K in various silicates increases approximately linearly with increasing average wavenumber of the OH-stretching vibrations. The interpretation is that decreased hydrogen-bonding strength between a H₂O molecule and the silicate framework, as well as weak ion-dipole interactions, results in increased entropy of H₂O. This results in increased amplitudes of external H₂O vibrations, especially translations of the molecule, and they contribute strongly to the entropy of confined H₂O at T < 298 K.  相似文献   

Solubility of grossular, Ca₃Al₂Si₃O₁₂, in H₂O-NaCl solutions at 800 °C and 10 kbar, and the stability of garnet in the system CaSiO₃-Al₂O₃-H₂O-NaCl     

Robert C. Newton 《Geochimica et cosmochimica acta》2007,71(21):5191-5202

The solubility and stability of synthetic grossular were determined at 800 °C and 10 kbar in NaCl-H₂O solutions over a large range of salinity. The measurements were made by evaluating the weight losses of grossular, corundum, and wollastonite crystals equilibrated with fluid for up to one week in Pt capsules and a piston-cylinder apparatus. Grossular dissolves congruently over the entire salinity range and displays a large solubility increase of 0.0053 to 0.132 molal Ca₃Al₂Si₃O₁₂ with increasing NaCl mole fraction (X_NaCl) from 0 to 0.4. There is thus a solubility enhancement 25 times the pure H₂O value over the investigated range, indicating strong solute interaction with NaCl. The Ca₃Al₂Si₃O₁₂ mole fraction versus NaCl mole fraction curve has a broad plateau between X_NaCl = 0.2 and 0.4, indicating that the solute products are hydrous; the enhancement effect of NaCl interaction is eventually overtaken by the destabilizing effect of lowering H₂O activity. In this respect, the solubility behavior of grossular in NaCl solutions is similar to that of corundum and wollastonite. There is a substantial field of stability of grossular at 800 °C and 10 kbar in the system CaSiO₃-Al₂O₃-H₂O-NaCl. At high Al₂O₃/CaSiO₃ bulk compositions the grossular + fluid field is limited by the appearance of corundum. Zoisite appears metastably with corundum in initially pure H₂O, but disappears once grossular is nucleated. At X_NaCl = 0.3, however, zoisite is stable with corundum and fluid; this is the only departure from the quaternary system encountered in this study. Corundum solubility is very high in solutions containing both NaCl and CaSiO₃: Al₂O₃ molality increases from 0.0013 in initially pure H₂O to near 0.15 at X_NaCl = 0.4 in CaSiO₃-saturated solutions, a >100-fold enhancement. In contrast, addition of Al₂O₃ to wollastonite-saturated NaCl solutions increases CaSiO₃ molality by only 12%. This suggests that at high pH (quench pH is 11-12), the stability of solute Ca chloride and Na-Al ± Si complexes account for high Al₂O₃ solubility, and that Ca-Al ± Si complexes are minor. The high solubility and basic dissolution reaction of grossular suggest that Al may be a very mobile component in calcareous rocks in the deep crust and upper mantle when migrating saline solutions are present.  相似文献   

Structure of mineral glasses—II. The SiO₂NaAlSiO₄ join     

Mark Taylor  Gordon E Brown 《Geochimica et cosmochimica acta》1979,43(9):1467-1473

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