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1.
The thermochemical study of a natural basic copper phosphate, pseudomalachite Cu5(PO4)2(OH)4 (Virneberg deposit, Germany), was carried out using high-temperature melt solution calorimetry method with a Tian–Calvet microcalorimeter. The enthalpy of formation of the mineral from elements was obtained to be Δ f Hel(298.15 K) =–3214 ± 13 kJ/mol. The value of the Gibbs energy of pseudomalachite formation calculated using literature data on its standard entropy is Δ f Hel°(298.15 K) =–2812 ± 13 kJ/mol.  相似文献   

2.
The thermochemical study of natural hydrous calcium and iron phosphate, anapaite Ca2Fe(PO4)2 · 4H2O (Kerch iron ore deposit, Crimea, Russia), was carried out using high-temperature melt solution calorimetry with a Tian-Kalvet microcalorimeter. The enthalpy of formation of the mineral from elements was obtained to be Δ f Hel°(298.15 K) =–4812 ± 16 kJ/mol. The values of the standard entropy and the Gibbs energy of anapaite formation are S°(298.15 K) = 404.2 J/K mol and Δ f Gel°(298.15 K) =–4352 ± 16 kJ/mol, respectively.  相似文献   

3.
Using the method of direct synthesis calorimetry, we determined the standard enthalpy of formation of PtSb (stumpflite), Δ f H°298.15 (PtSb, cr) =–105.16 ± 0.84 kJ/mol and PdSb2 (geversite), Δ f H°298.15 (PtSb2,cr) =–160.92 ± 0.84 kJ/mol. Isothermal (298.15 K, p = 1 bar) phase diagrams were computed for the Pt–Sb–S and Pt–Sb–O ternary systems in the coordinates composition of the Pt–Sb binary system versus fugacity of a gaseous volatile component (O2, S2).  相似文献   

4.
The paper presents the results of a thermochemical and thermal study of cancrinite, (Na6.93Ca0.545K0.01)Σ7.485[(Si6.47Al5.48Fe0.05)Σ12O24](CO3)1.25 · 2.30 H2O, and cancrisilite, (Na7.17 Ca0.01)Σ7.18[(Si7.26Al4.70Fe0.04)Σ12O24][(CO3)1.05(OH)0.21(PO4)0.04(SO4)0.01] · 2.635 H2O, from the Khibina-Lovozero Complex, Kola Peninsula, Russia. Stages of the thermal decomposition of these minerals were studied using IR spectroscopy. The enthalpies of formation of the minerals from elements were determined by melt drop solution calorimetry: Δ f H el 0 (298.15 K) = ?14 490 ± 16 kJ/mol for cancrinite and ?14302 ± 17 kJ/mol for cancrisilite. The values of Δ f H el 0 (298.15 K), S o(298.15 K), and Δ f H el 0 (298.15 K) are determined for cancrinite and cancrisilite of theoretical composition.  相似文献   

5.
The heat capacity of praseodymium orthophosphate PrPO4 was measured by adiabatic and relaxation calorimetric techniques at 5.12–345.54 K, and these data were utilized to calculate thermodynamic functions of PrPO4 at 6–350 K. The Gibbs free energy of PrPO4 formation ΔfG0(298.15 K) is evaluated at 1851.8 ± 4.7 kJ mol–1.  相似文献   

6.
The paper reports data obtained in the course of a comprehensive physicochemical study of Li-tosudite, a mixed-layer mineral from hydrothermally altered rocks in western Chukotka, Russia, whose formula was reliably established. The enthalpy of formation of Li-tosudite from Chukotka, Ca0.15(Li0.9Mg0.2Al6.0)[Si6.4Al1.6O20](OH)10 · 3.3H2O, from elements was experimentally determined by melt solution calorimetry in a high-temperature Calvet microcalorimeter: ΔfH el o (298.15 К) =–15087 ± 26 kJ/mol. The standard entropy and Gibbs free energy of formation of this mineral were evaluated.  相似文献   

7.
Absorption of the synchrotron emission of the quasar 3C 345 in the continuum and H(93–95)α and H(78–79)α radio recombination lines is studied. The upper limit for absorption in the H(93–95)α lines is Tal/Tac < 0.7%; absorption in the H(78–79)α lines with antenna temperature Tal = 25 mK, linewidth Δf = 5.3 ± 0.08 MHz, and Tal/Tac ≥ 0.3% has been detected. A correction to the redshift Δz = 0.00135 ± 0.00008 (z = 0.59365) has been determined.  相似文献   

8.
AIA/SDO data in the 193 Å channel preceding a coronal mass ejection observed at the solar limb on June 13, 2010 are used to simultaneously identify and examine two different shock fronts. The angular size of each front relative to the CME center was about 20°, and their propagation directions differed by ≈25° (≈4° in position angle). The faster front, called the blast shock, advanced the other front, called the piston shock, by R ≈ (0.02-0.03)R⊙ (R⊙ is the solar radius) and had a maximum initial speed of VB ≈ 850 km/s (with VP ≈ 700 km/s for the piston shock). The appearance and motion of these shocks were accompanied by a Type II radio burst observed at the fundamental frequency F and second harmonic H. Each frequency was split into two close frequencies f1 and f2 separated by Δf = f2 - f1 ? F, H. It is concluded that the observed frequency splitting Δf of the F and H components of the Type II burst could result from the simultaneous propagation of piston and blast shocks moving with different speeds in somewhat different directions displaying different coronal-plasma densities.  相似文献   

9.
The behavior of the 0.1 mNaCl + 0.002 mHCl + 1.9 × 10?5 mUO2(NO3)2 solution was studied at pH from 2.7 to 11.0, 25°C, and 1 bar in an argon atmosphere. The curve of variations in U concentration exhibits two minima at pH = 6.6 ± 0.7 and 10.0 ± 0.5. These minima are related to the precipitation of schoepite and clarkeite, respectively. The experimental data were used to refine the stability constants of U(VI) (hydroxo) complexes. For the polymer species of U(VI) with charges from +2 to ?1, the method of additivity of thermochemical increments was used, and increments of the linear relation were determined for the calculation of the Gibbs free energies of formation (ΔfG 298.15 0 ) of respective homologue series. The proposed method was applied to calculate the ΔfG 298.15 0 of formation of U(VI) (hydroxo)complexes containing from one to five uranium atoms.  相似文献   

10.
The standard thermodynamic properties (Δf G°, S°, Δf H°) of the following synthetic minerals and compounds in the Ag-Au-Se and Ag-Au-Te systems were determined by the EMF method: β-Ag2Se (low-temperature naumannite), α-Ag2Se (high-temperature naumannite), Ag3AuSe2 (fischesserite), AuSe, Ag5Te3 (stützite), Ag2 Te (hessite), and Ag3AuTe2 (petzite). All minerals and compounds were produced by solid-phase synthesis from elements or electrum of the given composition in evacuated ampoules made of quartz glass. The phases were verified by X-ray diffraction analysis, microscopically in reflected light, and with an electron microprobe. The absence of the ternary compound AgAuSe in the Ag-Au-Se system was confirmed by solid-phase annealing. On the basis of experimental data on the electromotive force E versus temperature, the equations E(T) were calculated, from which the temperature-dependent relationships of the Gibbs energy in the relevant reactions and the standard thermodynamic functions of compounds within the range 300–502 K were obtained.  相似文献   

11.
This paper investigates, using the random field theory and Monte Carlo simulation, the effects of random field discretization on failure probability, p f, and failure mechanism of cohesive soil slope stability. The spatial sizes of the discretized elements in random field Δx, Δy in horizontal and vertical directions, respectively, are assigned a series of combinational values in order to model the discretization accuracy. The p f of deterministic critical slip surface (DCSS) and that of the slope system both are analyzed. The numerical simulation results have demonstrated that both the ratios of Δy/λ y (λ y  = scale of fluctuation in vertical direction) and Δx/λ x (λ x  = scale of fluctuation in horizontal direction) contribute in a similar manner to the accuracy of p f of DCSS. The effect of random field discretization on the p f can be negligible if both the ratios of Δx/λ x and Δy/λ y are no greater than 0.1. The normalized discrepancy tends to increase at a linear rate with Δy/λ y when Δx/λ x is larger than 0.1, and vice versa for p f of DCSS. The random field discretization tends to have more considerable influence on the p f of DCSS than on that of the slope system. The variation of p f versus λ x and λ y may exhibit opposite trends for the cases where the limit state functions of slope failure are defined on DCSS and on the slope system as well. Finally, the p f of slope system converges in a more rapid manner to that of DCSS than the failure mechanism does to DCSS as the spatial variability of soil property grows from significant to negligible.  相似文献   

12.
The structure of the ejector region in the active star-forming region Orion KL has been studied over a broad dynamic range with a high angular resolution of 0.1 milliarcsec, or 0.05 AU. The line profile of the H2O supermaser emission has broad wings and can be represented as a superposition of two Gaussians with frequency widths Δf1=31 kHz and Δf2=163 kHz. The line intensities are I1≈3×105 Jy/beam and I2≈400 Jy/beam, and the brightness temperatures, Tb1≈5×1016 K and Tb2≈6×1014 K. The broadband ejector emission is determined by a rotating bipolar outflow with a rotational period of 5 months. The ejector emission in the 31-kHz component at a velocity of 7.64 km/s is amplified by more than two orders of magnitude by the surrounding envelope. The maser amplification regime is partially saturated.  相似文献   

13.
Based on the expert review of literature data on the thermodynamic properties of species in the Cl-Pd system, stepwise and overall stability constants are recommended for species of the composition [PdCl n ]2 ? n , and the standard electrode potential of the half-cell PdCl 4 2? /Pd(c) is evaluated at E 298,15° = 0.646 ± 0.007 V, which corresponds to Δ f G 298.15° = ?400.4 ± 1.4 kJ/mol for the ion PdCl 4 2? (aq). Derived from calorimetric data, Δ f H 298.15° PdCl 4 2? (aq) = ?524.6 ± 1.6 kJ/mol and Δ f H 298.15° Pd2+(aq) = 189.7 ± 2.6 kJ/mol. The assumed values of the overall stability constant of the PdCl 4 2? ion and the standard electrode potential of the PdCl 4 2? /Pd(c) half-cell correspond to Δ f G 298.15° = 190.1 ± 1.4 kJ/mol and S 298.15° = ?94.2 ± 10 J/(mol K) for the Pd2+(aq) ion.  相似文献   

14.
The thermal evolution of 10-Å phase Mg3Si4O10(OH)2·H2O, a phyllosilicate which may have an important role in the storage/release of water in subducting slabs, was studied by X-ray single-crystal diffraction in the temperature range 116–293 K. The lattice parameters were measured at several intervals both on cooling and heating. The structural model was refined with intensity data collected at 116 K and compared to the model refined at room temperature. As expected for a layer silicate on cooling in this temperature range, the a and b lattice parameters undergo a small linear decrease, α a  = 1.7(4) 10?6 K?1 and α b  = 1.9(4) 10?6 K?1, where α is the linear thermal expansion coefficient. The greater variation is along the c axis and can be modeled with the second order polynomial c T  = c 293(1 + 6.7(4)10?5 K?1ΔT + 9.5(2.5)10?8 K?2(ΔT)2) where ΔT = T ? 293 K; the monoclinic angle β slightly increased. The cell volume thermal expansion can be modeled with the polynomial V T  = V 293 (1 + 8.0 10?5 K?1 ΔT + 1.4 10?7 K?2 (ΔT)2) where ΔT = T ? 293 is in K and V in Å3. These variations were similar to those expected for a pressure increase, indicating that T and P effects are approximately inverse. The least-squares refinement with intensity data measured at 116 K shows that the volume of the SiO4 tetrahedra does not change significantly, whereas the volume of the Mg octahedra slightly decreases. To adjust for the increased misfit between the tetrahedral and octahedral sheets, the tetrahedral rotation angle α changes from 0.58° to 1.38°, increasing the ditrigonalization of the silicate sheet. This deformation has implications on the H-bonds between the water molecule and the basal oxygen atoms. Furthermore, the highly anisotropic thermal ellipsoid of the H2O oxygen indicates positional disorder, similar to the disorder observed at room temperature. The low-temperature results support the hypothesis that the disorder is static. It can be modeled with a splitting of the interlayer oxygen site with a statistical distribution of the H2O molecules into two positions, 0.6 Å apart. The resulting shortest Obas–OW distances are 2.97 Å, with a significant shortening with respect to the value at room temperature. The low-temperature behavior of the H-bond system is consistent with that hypothesized at high pressure on the basis of the Raman spectra evolution with P.  相似文献   

15.
The solubility of Gd2Ti2O7 ceramic in acidic solutions (HCl and HClO4) was studied at 250°C and saturation vapor pressure within pH 2.5–5.2. The dissolution process occurs mainly via two reactions: 0.5 Gd2Ti2O7(cr) + 3H+ = Gd3+ + TiO2(cr) + 1.5 H2O at pH < 3 and 0.5Gd2Ti2O7(cr) + H+ + 0.5H2O = Gd(OH) 2 + TiO2(cr) at pH 3–5. The thermodynamic equilibrium constants were calculated at the 0.95 confidence level as log K (1) o = 4.12 ± 0.47; = ?0.97 ± 0.16 at 250°C. It was shown that Gd3+ undergoes hydrolysis in solutions with pH > 3, and the species Gd(OH) 2 + dominates up to at least pH 5. At pH < 3, Gd occurs in solutions as Gd3+. The second constant of Gd3+ hydrolysis was determined at 250°C as K o = ?5.09 ± 0.5, and the thermodynamic characteristics of the initial Gd2Ti2O7 solid phase were determined: S 298.15 o = 251.4 J/(mol K) and ΔfG 298.15 o = ?3630 ± 10 kJ/mol.  相似文献   

16.
The influence of oxygen fugacity (fO2) and temperature on the valence and structural state of iron was experimentally studied in glasses quenched from natural aluminosilicate melts of granite and pantellerite compositions exposed to various T-fO2 conditions (1100–1420°C and 10?12–10?0.68 bar) at a total pressure of 1 atm. The quenched glasses were investigated by Mössbauer spectroscopy. It was shown that the effect of oxygen fugacity on the redox state of iron at 1320–1420°C can be described by the equation log(Fe3+/Fe2+) = k log(fO2) + q, where k and q are constants depending on melt composition and temperature. The Fe3+/Fe2+ ratio decreases with decreasing fO2 (T = const) and increasing temperature (fO2 = const). The structural state of Fe3+ depends on the degree of iron oxidation. With increasing Fe3+/Fe2+ ≥ 1, the dominant coordination of Fe3+ changes from octahedral to tetrahedral. Ferrous iron ions occur in octahedral (and/or five-coordinated) sites independent of Fe3+/Fe2+.  相似文献   

17.
We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO2 contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1–3 GPa, 1375–1550?°C, and fO2 of FMQ ?3.2 to FMQ ?2.3 and the resulting experimental glasses were analyzed for CO2 and H2O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO2 content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO2 as molecular CO2: ln(K 0) = ?21.79?±?0.04, ΔV 0?=?32.91?±?0.65 cm3mol?1, ΔH 0?=?107?±?21 kJ mol?1, and dissolution of CO2 as CO3 2?: ln(K 0 ) = ?21.38?±?0.08, ΔV 0?=?30.66?±?1.33 cm3 mol?1, ΔH 0?=?42?±?37 kJ mol?1, where K 0 is the equilibrium constant at some reference pressure and temperature, ΔV 0 is the volume change of reaction, and ΔH 0 is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO2 contents and CO2/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO2 contents and CO2/Nb ratios of CO2-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO2-enriched basalts, and suggests that fO2 measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO2-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.  相似文献   

18.
To test a recently developed oxybarometer for silicic magmas based on partitioning of vanadium between magnetite and silicate melt, a comprehensive oxybarometry and thermometry study on 22 natural rhyolites to dacites was conducted. Investigated samples were either vitrophyres or holocrystalline rocks in which part of the mineral and melt assemblage was preserved only as inclusions within phenocrysts. Utilized methods include vanadium magnetite–melt oxybarometry, Fe–Ti oxide thermometry and -oxybarometry, zircon saturation thermometry, and two-feldspar thermometry, with all analyses conducted by laser-ablation ICP–MS. Based on the number of analyses, the reproducibility of the results and the certainty of contemporaneity of the analyzed minerals and silicate melts the samples were grouped into three classes of reliability. In the most reliable (n = 5) and medium reliable (n = 10) samples, all fO2 values determined via vanadium magnetite–melt oxybarometry agree within 0.5 log units with the fO2 values determined via Fe–Ti oxide oxybarometry, except for two samples of the medium reliable group. In the least reliable samples (n = 7), most of which show evidence for magma mixing, calculated fO2 values agree within 0.75 log units. Comparison of three different thermometers reveals that temperatures obtained via zircon saturation thermometry agree within the limits of uncertainty with those obtained via two-feldspar thermometry in most cases, whereas temperatures obtained via Fe–Ti oxide thermometry commonly deviate by ≥50 °C due to large uncertainties associated with the Fe–Ti oxide model at T-fO2 conditions typical of most silicic magmas. Another outcome of this study is that magma mixing is a common but easily overlooked phenomenon in silicic volcanic rocks, which means that great care has to be taken in the application and interpretation of thermometers and oxybarometers.  相似文献   

19.
It is attempted to determineT, P values for the lowgrade metamorphic facies. From geologic-petrographic observations and from experiments mineralreactions are outlined which characterize the zeolitic-, the glaucophane- and the greenschistfacies, respectively. Only such reactions are considered which are univariant if Pf=Ps; thus aP-T grid can be arrived at. Experimental data on the equilibria of the relevant reactions is taken from the literature and from own experiments. Experimental results are always checked against known field-observations. Contrary to current opinium, we arrive at rather higher temperatures for the beginning of the lowgrade metamorphic facies: Diagenesis. From sedimentation up to slightly below 300° C. Zeolitic facies. From slightly below 300° C up to about 400° C. Greenschistfacies. From about 400° C up to about 550° C. Glaucophaneschistfacies. Under pressures of at least 6–7 kb this facies begins somewhat above 300° C, probably at about 330° C, grading into high-pressure greenschistfacies.  相似文献   

20.
Experimental studies in the Fe3C–SiO2–MgO system (P = 6.3 GPa, T = 1100–1500°C, t = 20–40 h) have been carried out. It has been established that carbide-oxide interaction resulted in the formation of Fe-orthopyroxene, graphite, wustite, and cohenite (1100 and 1200°C), as well as a Fe–C–O melt (1300–1500°C). The main processes occurring in the system at 1100 and 1200°C are the oxidation of cohenite, the extraction of carbon from carbide, and the crystallization of metastable graphite, as well as the formation of ferrosilicates. At T ≥ 1300°C, graphite crystallization and diamond growth occur as a result of the redox interaction of a predominantly metallic melt (Fe–C–O) with oxides and silicates. The carbide–oxide interaction studied can be considered as the basis for modeling a number of carbon-producing processes in the lithospheric mantle at fO2 values near the iron–wustite buffer.  相似文献   

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