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1.
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 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) + (O2?) = 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
2.
The partitioning of germanium between forsterite (Fo) and liquids in the diopside-anorthiteforsterite join was investigated by electron microprobe analysis of Ge-doped samples equilibrated at 1300°–1450°C. Germanium is somewhat incompatible in Fo relative to the haplobasaltic melts, with a grand mean for all simple partition coefficients (DFo-lGe) of 0.68 ± 0.06. For the melt composition range studied, DFo-lGe is virtually constant in isothermal series of experiments, and shows only minor overall temperature dependence. The exchange reaction partition coefficient ] is near unity in all cases, with a grand mean of 0.93 ± 0.11. One exploratory run at 20 kbar yielded a distinctly lower partition coefficient (DFo-lGe = 0.54 ± 0.04), which confirms the negative pressure dependence predicted by the thermodynamics of Ge ai Si exchange.These new data indicate that absolute Ge enrichment must occur in terrestrial magmas undergoing olivine fractionation, while remains nearly constant. 相似文献
3.
Diopside-melt and forsterite-melt rare earth (REE) and Ni partition coefficients have been determined as a function of bulk compositions of the melt. Available Raman spectroscopic data have been used to determine the structures of the melts coexisting with diopside and forsterite. The compositional dependence of the partition coefficients is then related to the structural changes of the melt.The melts in all experiments have a ratio of nonbridging oxygens to tetrahedral cations () between 1 and 0. The quenched melts consist of structural units that have, on the average, 2 (chain), 1 (sheet) and 0 (three-dimensional network) nonbridging oxygens per tetrahedral cation. The proportions of these structural units in the melts, as well as the overall , change as a function of the bulk composition of the melt.It has been found that Ce, Sm, Tm and Ni crystal-liquid partition coefficients () decrease linearly with increasing . The values of the individual REE crystal-liquid trace element partition coefficients have different functional relations to , so that the degree of light REE enrichment of the melts would depend on their .The solution mechanisms of minor oxides such as CO2, H2O, TiO2, P2O5 and Fe2O3 in silicate melts are known. These data have been recast as changes of of the melts with regard to the type of oxide and its concentration in the melt. From such data the dependence of crystal-liquid partition coefficients on concentration and type of minor oxide in melt solution has been calculated. 相似文献
4.
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: ΔHex(±0.16 kcal) = 6.7461 XabX2An + 2.0247 XAnX2Ab where XAb and XAn are, respectively, the mole fractions of NaAlSi3O8 and CaAl2Si2O8. This ΔHex, 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 XAn≥ 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: . 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
5.
To better understand the process of crustal contamination/assimilation, 23 Pb isotopic compositions and 12 concentrations have been measured on lavas and basement rocks from the Edgecumbe volcanic field, SE Alaska. Measured isotopic ratios have the following ranges: ; ; . While the data form well-constrained linear arrays on Pb-Pb diagrams, no simple correlation exists with major element composition. Basaltic lavas (≤ 51 wt% SiO2) are characterized by two isotopic groups. The olivine basalt (≤ 48% SiO2) is more radiogenic than the plagioclase basalt (48–51%) which also shows more heterogeneity. In the silica range 52–55%, Pb isotopic ratios increase significantly but remain fairly constant in the range 55–70% SiO2. Lead concentrations vary from 1 ppm in the basalts to 7 ppm in the rhyodacites. Analyzed basement rocks are more radiogenic than any of the lavas ; ; . The Pb isotopic data are qualitatively consistent with the contamination process described by Myerset al. (1984). However, because of fundamental differences in the mixing relations between the Sr system studied earlier and the Pb system, the new Pb data have revealed details of the process not apparent from the Sr data alone. In particular, it has been shown that the parent magma was more primitive than originally assumed, and that two contamination events are recorded in the lavas. The first event, involving a mafic parent and different crustal contaminants, produced the intermediate and siliceous hybrids in cupolas located above the main basaltic chamber. The types of country rock intruded as well as the degree of partial fusion achieved in individual cupolas controlled the range of hybrid compositions produced while the eruption sequence was determined by the order in which the cupolas were tapped. The second contamination event produced the plagioclase basalt, the most voluminous basaltic unit, by mixing the mafic parent with the olivine basalt, an independent, primary magma. Our results suggest crustal contamination models that assume bulk assimilation of crustal end members may be too simplistic. 相似文献
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7.
A differential rate equation for silica-water reactions from 0–300°C has been derived based on stoichiometry and activities of the reactants in the reaction SiO2(s) + 2H2O(l) = H4SiO4(aq) where () = (the relative interfacial area between the solid and aqueous phases/the relative mass of water in the system), and k+ and k? are the rate constants for, respectively, dissolution and precipitation. The rate constant for precipitation of all silica phases is and Eact for this reaction is 49.8 kJ mol?1. Corresponding equilibrium constants for this reaction with quartz, cristobalite, or amorphous silica were expressed as . Using , k was expressed as and a corresponding activation energy calculated:
a | b | c | Eact(kJ mol -1) | |
Quarts | 1.174 | -2.028 x 103 | -4158 | 67.4–76.6 |
α-Cristobalite | -0.739 | 0 | -3586 | 68.7 |
β-Cristobalite | -0.936 | 0 | -3392 | 65.0 |
Amorphous silica | -0.369 | -7.890 x 10-4 | 3438 | 60.9–64.9 |