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1.
Solubility of senarmontite (Sb2O3, cubic) in pure water and NaCl-HCl aqueous solutions, and local atomic structure around antimony in these fluids were characterized using in situ X-ray absorption fine structure (XAFS) spectroscopy at temperatures to 450 °C and pressures to 600 bars. These experiments were performed using a new X-ray cell which allows simultaneous measurement of the absolute concentration of the absorbing element in the fluid, and atomic environment around the absorber. Results show that aqueous Sb(III) speciation is dominated by the complex in pure water, mixed Sb-hydroxide-chloride complexes in acidic NaCl-HCl solutions (2 m NaCl-0.1 m HCl), and by Sb-chloride species in concentrated HCl solutions (3.5 m HCl). Interatomic Sb-O and Sb-Cl distances in these complexes range from 1.96 to 1.97 Å and from 2.37 to 2.47 Å, respectively. These structural data, together with senarmontite solubility determined from XAFS spectra, were complemented by batch-reactor measurements of senarmontite and stibnite (Sb2S3, rhombic) solubilities over a wide range of HCl and NaCl concentrations from 300 to 400 °C. Analysis of the whole dataset shows that Sb(III) speciation in high-temperature moderately acid (pH > 2-3) Cl-rich fluids is dominated by mixed hydroxy-chloride species like Sb(OH)2Cl° and Sb(OH)3Cl−, but other species containing two or three Cl atoms appear at higher acidities and moderate temperatures (?300 °C). Calculations using stability constants retrieved in this study indicate that mixed hydroxy-chloride complexes control antimony transport in saline high-temperature ore fluids at acidic conditions. Such species allow for a more effective Sb partitioning into the vapor phase during boiling and vapor-brine separation processes occurring in magmatic-hydrothermal systems. Antimony hydroxy-chloride complexes are however minor in the neutral low- to moderate-temperature solutions (?250-300 °C) typical of Sb deposits formation; the antimony speciation in these systems is dominated by Sb(OH)3 and potentially Sb-sulfide species.  相似文献   

2.
The solubility of the albite-paragonite-quartz mineral assemblage was measured as a function of NaCl and fluorine concentration at 400°C, 500 bars and at 450°C, 500 and 1000 bars. Decreasing Al concentrations with increasing NaCl molality in F-free fluids of low salinity (mNaCl < 0.01) demonstrates that Al(OH)4− dominates Al speciation and is formed according to the reaction 0.5 NaAl3Si3O12H2(cr)+2 H2O = 0.5 NaAlSi3O8(cr)+Al(OH)4−+H+. Log K results for this reaction are −11.28 ± 0.10 and −10.59 ± 0.10 at 400°C, 500 bars and 450°C, 1000 bars, respectively. Upon further salinity increase, Al concentration becomes constant (at 400°C, 500 bars) or even rises (at 450°C, 1000 bars). The observed Al behavior can be explained by the formation of NaAl(OH)40(aq) or NaAl(OH)3Cl(aq)0. The calculated constant for the reaction Al(OH)4−+Na+=NaAl(OH)40(aq) expressed in log units is equal to 2.46 and 2.04 at 400°C, 500 bars and 450°C, 1000 bars, respectively. These values are in good agreement with the predictions given in Diakonov et al. (1996). Addition of fluoride at m(NaCl) = const = 0.5 caused a sharp increase in Al concentration in equilibrium with the albite-paragonite-quartz mineral assemblage. As fluid pH was also constant, this solubility increase indicates strong aluminum-fluoride complexation with the formation of NaAl(OH)3F(aq)0 and NaAl(OH)2F20(aq), according to 0.5 NaAl3Si3O12H2(cr)+Na++HF(aq)0+H2O = 0.5 NaAlSi3O8(cr)+ NaAl(OH)3F(aq)0+H+, log K = −5.17 and −5.23 at 400°C and 450°C, 500 bars, respectively, and 0.5 NaAl3Si3O12H2(cr)+Na++2 HF(aq)0 = 0.5 NaAlSi3O8(cr)+NaAl(OH)2F20(aq)+H+, log K = −2.19 and −1.64 at the same P-T conditions. It was found that temperature increase and pressure decrease promote the formation of Na-Al-OH-F species. Stability of NaAl(OH)2F20(aq) in low-density fluids also increases relative to NaAl(OH)3F(aq)0. These complexes, together with Al(OH)2F(aq)0 and AlOHF20(aq), whose stability constants were calculated from the corundum solubility measured by Soboleva and Zaraisky (1990) and Zaraisky (1994), are likely to dominate Al speciation in metamorphic fluids containing several ppm of fluorine.  相似文献   

3.
The solubility of baddeleyite (ZrO2) and the speciation of zirconium have been investigated in HF-bearing aqueous solutions at temperatures up to 400 °C and pressures up to 700 bar. The data obtained suggest that in HF-bearing solutions zirconium is transported mainly in the form of the hydroxyfluoride species ZrF(OH)3° and ZrF2(OH)2°. Formation constants determined for these species (Zr4+ + nF− + mOH− = ZrFn(OH)m°) range from 43.7 at 100 °C to 46.41 at 400 °C for ZrF(OH)3°, and from 37.25 at 100 °C to 43.88 at 400 °C for ZrF2(OH)2°.Although the solubility of ZrO2 is retrograde with respect to temperature, the measured concentrations of Zr are orders of magnitude higher than those predicted from theoretical extrapolations based on simple fluoride species (ZrF3+-ZrF62−). Model calculations performed for zircon show that zirconium can be transported by aqueous fluids in concentrations sufficient to account for the concentration of this metal at conditions commonly encountered in fluoride-rich natural hydrothermal systems.  相似文献   

4.
Stability and solubility of arsenopyrite, FeAsS, in crustal fluids   总被引：3，自引：0，他引：3  
The stability and solubility of natural arsenopyrite (FeAsS) in pure water and moderately acid to slightly basic aqueous solutions buffered or not with H2 and/or H2S were studied at temperatures from 300 to 450°C and pressures from 100 to 1000 bar. The solubilities of FeAsS in pure water and dilute HCl/NaOH solutions without buffering are consistent with the formation of the As(OH)30(aq) species and precipitation of magnetite. At more acid pH (pH ≤2), arsenopyrite dissolves either stoichiometrically or with formation of the As-FeAsS assemblage. In H2S-rich and H2-rich aqueous solutions, arsenopyrite dissolution results in the formation of pyrrhotite (±pyrite) and iron arsenide(s), respectively, which form stable assemblages with arsenopyrite.Arsenic concentrations measured in equilibrium with FeAsS in slightly acid to neutral aqueous solutions with H2 and H2S fugacities buffered by the pyrite-pyrrhotite-magnetite assemblage are 0.0006 ± 0.0002, 0.0055 ± 0.0010, 0.07 ± 0.01, and 0.32 ± 0.03 mol/kg H2O at 300°C/400 bar, 350°C/500 bar, 400°C/500 bar, and 450°C/500 bar, respectively. These values were combined with the available thermodynamic data on As(OH)30(aq) (Pokrovski et al., 1996) to derive the Gibbs free energy of FeAsS at each corresponding temperature and pressure. Extrapolation of these values to 25°C and 1 bar, using the available heat capacity and entropy data for FeAsS (Pashinkin et al., 1989), yields a value of −141.6 ± 6.0 kJ/mol for the standard Gibbs free energy of formation of arsenopyrite. This value implies a higher stability of FeAsS in hydrothermal environments than was widely assumed.Calculations carried out using the new thermodynamic properties of FeAsS demonstrate that this mineral controls As transport and deposition by high-temperature (>∼300°C) crustal fluids during the formation of magmatic-hydrothermal Sn-W-Cu-(Au) deposits. The equilibrium between As-bearing pyrite and the fluid is likely to account for the As concentrations measured in modern high- and moderate-temperature (150 ≤ T ≤ 350°C) hydrothermal systems. Calculations indicate that the local dissolution of arsenopyrite creates more reducing conditions than in the bulk fluid, which is likely to be an effective mechanism for precipitating gold from hydrothermal solutions. This could be a possible explanation for the gold-arsenopyrite association commonly observed in many hydrothermal gold deposits.  相似文献   

5.
Available experimental data on the solubility of Nb2O5 and the stability constants for particles of an aqueous solution in the Nb–O–H–F system were processed. As a result, a set of thermodynamic properties for 25°C and 1 bar was obtained, in addition to the equation parameters for the HKF model (Helgeson–Kirkham–Flowers) for hydroxo and hydroxofluoride niobium complexes. F– ion is the most important factor governing the concentration of dissolved Nb: neutral hydroxo complex Nb(OH)5(aq) is formed at a low HF concentration, whereas an increase in HF results in an increase in the first Nb(OH)4F(aq) and second Nb(OH)3F2(aq) fluoride complexes. The Nb(OH)5F– oxofluoride anion determines oxide solubility in alkali F-bearing fluids. Neutralization of acidic fluoride solution can be the main factor leading to niobium deposition.  相似文献   

6.
A modified commercial (Setaram C80) calorimeter has been used to measure the isobaric volumetric heat capacities of concentrated alkaline sodium aluminate solutions at ionic strengths from 1 to 6 mol kg−1, with up to 40 mol.% substitution of hydroxide by aluminate, at temperatures from 50 to 300 °C and a pressure of 10 MPa. Apparent molar heat capacities for the mixtures, Cp?, derived from these data were found to depend linearly on the aluminate substitution level, i.e., they followed Young’s rule. These quantities were used to estimate the apparent molar heat capacities of pure, hypothetical sodium aluminate solutions, Cp? (‘NaAl(OH)4’(aq)). Slopes of the Young’s rule plots were invariant with ionic strength at a given temperature but depended linearly on temperature. The heat capacities of ternary aqueous sodium hydroxide/aluminate mixtures could therefore be modelled using only two parameters in addition to those needed for the correlation of Cp? (NaOH(aq)) reported previously from these laboratories. An assessment of the standard thermodynamic quantities for boehmite, gibbsite and the aluminate ion yielded a set of recommended values that, together with the present heat capacity data, accurately predicts the solubility of gibbsite and boehmite at temperatures up to 300 °C.  相似文献   

7.
The speciation and thermodynamic properties of ferric chloride complexes in hydrothermal solutions and hypersaline brines are still poorly understood, despite the importance of this element as a micronutrient and ore-component. Available experimental data are limited to room temperature and relatively low chloride concentrations. This paper reports results of UV-Vis spectrophotometric and synchrotron XAFS experiments of ferric chloride complexes in chloride concentrations up to 15 m and at temperatures of 25-90 °C. Qualitative interpretation of the UV-Vis spectra shows that FeCl2+, FeCl2+, FeCl3(aq) and FeCl4− were present in the experimental solutions. As chloride concentrations increase, higher ligand number complexes become important with FeCl4− predominating in solutions containing more than 10 m at 25 °C. The predominance fields of FeCl3(aq) and FeCl4− expand to lower Cl concentrations with increasing T. Both XANES and UV-Vis spectra reveal a major change in the geometry of the complex between FeCl2+ and FeCl3(aq). EXAFS data confirm that the number of chloride ligands increases with increasing chloride concentration and show that Fe3+, FeCl2+ and FeCl2+ share an octahedral geometry. FeCl3(aq) could be either tetrahedral or trigonal dipyramidal, while FeCl4− is expected to be tetrahedral. EXAFS data support a tetrahedral geometry for FeCl4−, especially at 90 °C, but do not allow to distinguish between a tetrahedral or trigonal dipyramidal geometry for FeCl3(aq) because of similar Fe-Cl distances. At room temperature, EXAFS data suggest that FeCl3(aq) may be a mixture of octahedral and tetrahedral or trigonal dipyramidal forms.The room temperature formation constants for three ferric chloride complexes (FeCl2+, FeCl3(aq) and FeCl4−) determined from the UV data are generally in good agreement with previous studies. Calculations based on the properties extrapolated to 300 °C show that hematite solubility is much higher than previously estimated, and that the high orders complexes FeCl3(aq) and FeCl4− are important at high temperatures even in solutions with low chloride concentrations. The accuracy of these properties is limited by a poor understanding of activity-composition relationships in concentrated electrolytes, and by limitations in the available experimental techniques and extrapolation algorithms; however, the inclusion of higher order complexes in numerical models of ore transport and deposition allows for a more accurate qualitative prediction of Fe behaviour in hydrothermal and hypersaline systems.  相似文献   

8.
The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10−7 to 1.30 × 10−4 mol kg−1 (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg−1 and pHT,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag2S(s) + 0.5H2S(aq) = AgHS(aq) Ks,1110.5Ag2S(s) + 0.5H2S(aq) + HS− = Ag(HS)2− Ks,122Ag2S(s) + 2HS− = Ag2S(HS)22− Ks,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag2S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H2S(aq). Consequently, Ag2S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logKs,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logKs,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logKs,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag+ and HS− at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag+ and AgClOH− are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.  相似文献   

9.
Formation of aqueous aluminate-borate complexes was characterized at 25°C using 27Al NMR spectroscopy, and at 50-200°C via measurements of gibbsite and boehmite solubility in the presence of boric acid. 27Al spectra performed at pH = 9 in Al-B solution with m(B) = 0.02 show the presence of two peaks at 80.5 and 74.5 ppm which correspond to Al(OH)4− and a single Al-substituted Q1Al dimer, Al(OH)3OB(OH)2−, respectively. In 0.08 m and 0.2 m borate solution, a third peak appears at 68.5 ppm which can be assigned to the Q2Al trimer Al(OH)2O2(B(OH)2)2−. These chemical shifts are close to those measured for Al(OH)3OSi(OH)3− and Al(OH)2O2(Si(OH)3)2− (74 and 69.5 ppm, respectively; Pokrovski et al., Min. Mag.62a (1998), 1194) which demonstrates the similar structure of Al-B and Al-Si complexes formed in alkaline solutions. Gibbsite and boehmite solubility were measured in weakly basic solutions as a function of boric acid concentration at 50°C and 78 to 200°C, respectively. Equilibrium was reached within several days at m(B) = 0.01-0.1, but more slowly at higher boron concentrations, and at 50°C and m(B) = 0.2, Al concentration increased continuously during at least 3 months as a result of the sluggish formation of Al-polyborates. The equilibrium constant of the reaction Al(OH)4− + B(OH)30(aq) = Al(OH)3OB(OH)2− + H2O decreases very slowly with increasing temperature to 200°C. The log K values are 1.58 ± 0.10, 1.46 ± 0.10, 1.52 ± 0.15, and 1.25 ± 0.15 at 50, 78, 150 and 200°C, respectively, which result in the following values of the standard thermodynamic properties for this reaction: ΔrG0 = −9.22 ± 3.25 kJ/mol, ΔrH0 = −4.6 ± 2.5 kJ/mol, ΔrS0 = 15.5 ± 6.9 J/mol K. The thermodynamic data generated in this study indicate that Al-B complexes can dominate aqueous aluminum speciation in solutions containing ≥0.7 g/L of boron at temperature to at least 400°C.  相似文献   

10.
The Pitzer’s interaction parameters, λN–M, involving the Mth cationic Al species Al3+ or AlOH2+ or AlO+ and the Nth neutral species SiO2(aq) (at temperatures of 25–300 °C) or CO2(aq) (at temperatures of 25–150 °C), have been evaluated through empirical linear relationships between λN–M and the surface electrostatic field of the ionic species of interest. These relationships have been obtained starting from the known λN–M for both SiO2(aq) and CO2(aq) with the main dissolved cations. The Pitzer’s interaction parameter thus estimated for the pair CO2(aq)–Al3+ at 25 °C, 0.327, is 20–40% higher than the corresponding values obtained from CO2 solubilities in concentrated solutions of AlCl3, 0.272 ± 0.010 (2σ), and Al2(SO4)3, 0.232 ± 0.002 (2σ), partly corroborating the empirical approach adopted in this study. To test the Pitzer’s interaction coefficients for cationic Al species with aqueous SiO2, the log K values of the kaolinite dissolution reaction have been computed starting from available experimental data at 23–25 °C and ionic strengths of 0.0001–0.12 mol/kg adopting, alternatively, the Pitzer’s equations and the Debye–Hückel equation. A satisfactory agreement has been found between the log K values obtained through these two approaches, with maximum deviations of 0.11–0.12 log units. This good convergence of results is encouraging as it represents a necessary condition to prove the reliability of the Pitzer’s interaction coefficients estimated in this work. These results are a first step to take into account specific interactions among solutes in concentrated electrolyte solutions, such as those hosted in sedimentary basins or geothermal waters, for instance through the Pitzer’s equations. However, experimental or field data at higher ionic strengths are absolutely necessary to validate the reliability of the Pitzer’s interaction coefficients determined in this study.  相似文献   

11.
The solubility of gold has been measured in aqueous solutions at temperatures between 300 and 600°C and pressures from 500 to 1500 bar to determine the stability and stoichiometry of the hydroxy complexes of gold(I) in hydrothermal solutions. The experiments were carried out using a flow-through autoclave system. The solubilities, measured as total dissolved gold, were in the range 1.2 × 10−8 to 2.0 × 10−6 mol kg−1 (0.002 to 0.40 mg kg−1), in solutions of total dissolved sodium between 0.0 and 0.5 mol kg−1, and total dissolved hydrogen between 4.0 × 10−6 and 4.0 × 10−4 mol kg−1. At constant hydrogen molality, the solubility of gold increases with increasing temperature and decreases with increasing pressure. The solubilities were found to be independent of pH but increased with decreasing hydrogen molality at constant temperature and pressure. Consequently, gold dissolves in aqueous solutions of acidic to alkaline pH according to the reactionAu(s)+H2O(l)=AuOH(aq)+0.5H2(g) Ks,1The solubility constant, logKs,1, increases with increasing temperature from a minimum of −8.76 (±0.18) at 300°C and 500 bar to a maximum of −7.50 (±0.11) at 500°C and 1500 bar and decreases to −7.61 (±0.08) at 600°C and 1500 bar. From the equilibrium solubility constant and the redox potential of gold, the formation constant to form AuOH(aq) was calculated. At 25°C the complex formation is characterised by an exothermic enthalpy and a positive entropy. With increasing temperature and decreasing pressure, the formation reaction becomes endothermic and is accompanied by a large positive entropy, indicating a greater electrostatic interaction between Au+ and OH−.  相似文献   

12.
The solubility of chalcocite has been measured over the temperature range 35-95°C at pH 6.5-7.5 in aqueous hydrosulfide solutions in order to determine the stability constants of the Cu(HS)2− complex. A heated flow-through system was used in which solutions are collected at temperature to avoid the problem of copper precipitation due to quenching. The quality of the data was sufficient to resolve a 0.1 log unit increase of the dissolution/complexation equilibrium constant with each 10°C increase in temperature. The equilibrium constants were fit using previously published methods to obtain the values of thermodynamic parameters for the Cu(HS)2− complexation reaction. To compare results with predictive techniques, one-term and two-term isocoulombic extrapolation methods were applied to the stability constants measured below 100°C. The two-term extrapolation to 350°C showed excellent agreement with the derived constants proving its applicability to soft metal-soft ligand interactions. The one-term method gave a reasonable agreement but deviated about one logarithmic unit at 350°C. This is attributed to differences in energetic, volumetric, and structural properties of the reactants and products. Speciation calculations show that at low temperatures (<150°C), the hydrosulfide complexes of copper will dominate over chloride complexes at low salinites (<0.1 mol kg−1) while at higher temperatures, chloride complexes will be dominant under most geological conditions. Only in solutions with high reduced sulfur content and alkaline pH values will hydrosulfide complexes predominate and may play a role in the generation of economic copper mineralization.  相似文献   

13.
Chloride and hydrosulfide are the principal ligands assumed to govern transport of copper in hydrothermal fluids. Existing solubility experiments suggest that Cu(I)-hydrosulfide complexes are dominant compared to chloride complexes at low salinities in alkaline solutions (H2S(aq)/HS− pH buffer), and may be important in transporting Cu in low density magmatic vapors, potentially controlling the liquid-vapor partitioning of Cu. This study provides the first in situ evidence of the solubility of copper sulfides and the nature and structure of the predominant Cu species in sulfur-containing fluids at temperatures up to 592 °C and pressures of 180-600 bar. XANES and EXAFS data show that at elevated T (?200 °C), Cu solubility occurs via a linear Cu complex. At 428 °C in alkaline solutions, Cu is coordinated by two sulfur atoms in a distorted linear coordination (angle ∼150-160°). This geometry is consistent with the species predicted by earlier solubility studies. In addition, in situ measurements of the solubility of chalcocite in 2 m NaHS solutions performed in this study are in remarkably good agreement with the solubilities calculated using available thermodynamic data for Cu(I)-hydrosulfide complexes, also supporting the interpretation of speciation in these studies and validating the extrapolation of low-T thermodynamic properties for to high P-T. Data on phase separation for the 2 m NaHS solution show that while significant amounts of copper can be partitioned into the vapor phase, there is no indication for preferential partitioning of Cu into the vapor. This is consistent with recent partitioning experiments conducted in autoclaves by Pokrovski et al. (2008a) and Simon et al. (2006). XANES data suggest that the species present in the low density phase is very similar to that present in the high density liquid, i.e., , although Cu(HS)(H2S)0 cannot be excluded on the basis of XAS data.  相似文献   

14.
The dissolution and growth of uranophane [Ca(UO2)2(SiO3OH)2·5H2O] have been examined in Ca- and Si-rich test solutions at low temperatures (20.5 ± 2.0 °C) and near-neutral pH (∼6.0). Uranium-bearing experimental solutions undersaturated and supersaturated with uranophane were prepared in matrices of ∼10−2 M CaCl2 and ∼10−3 M SiO2(aq). The experimental solutions were reacted with synthetic uranophane and analyzed periodically over 10 weeks. Interpretation of the aqueous solution data permitted extraction of a solubility constant for the uranophane dissolution reaction and standard state Gibbs free energy of formation for uranophane ( kJ mol−1).  相似文献   

15.
Corundum (α-Al2O3) solubility was measured in 0.1-molal CaCl2 solutions from 400 to 600°C between 0.6 and 2.0 kbar. The Al molality at 2 kbar increases from 3.1 × 10−4 at 400°C to 12.7 × 10−4 at 600°C. At 1 kbar, the solubility increases from 1.5 × 10−4m at 400°C to 3.4 × 10−4m at 600°C. These molalities are somewhat less than corundum solubility in pure H2O (Walther, 1997) at 400°C but somewhat greater at 600°C. The distribution of species was computed considering the Al species Al(OH)30 and Al(OH)4−, consistent with the solubility of corundum in pure H2O of Walther (1997) and association constants reported in the literature. The calculated solubility was greater than that measured except at 600°C and 2.0 kbar, indicating that neutral-charged species interactions are probably important.A Setchénow model for neutral species resulted in poor fitting of the measured values at 1.0 kbar. This suggests that Al(OH)30 has a greater stability relative to Al(OH)4− than given by the models of Pokrovskii and Helgeson (1995) or Diakonov et al. (1996). The significantly lower Al molalities in CaCl2 relative to those in NaCl solutions at the same concentration confirm the suggestions of Walther (2001) and others that NaAl(OH)40 rather than an Al-Cl complex must be significant in supercritical NaCl solutions to give the observed increase in corundum solubility with increasing NaCl concentrations.  相似文献   

16.
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17.
Neptunium is one of the few radioactive elements that are of great concern in the disposal of nuclear wastes in the geological repository, due to its hazards and the long half-life of the isotope, 237Np (t1/2 = 2.14 × 106 years). To understand and predict the migration behavior of neptunium in the geological media, it is of importance to study its hydrolysis at elevated temperatures, because the temperature in the waste package and the vicinity of the repository could be high. Moreover, the chemical analogy between neptunium(V) and plutonium(V) adds even greater value to this investigation, because the latter could exist at tracer levels in neutral and slightly oxidizing waters but is difficult to study due to its rather labile redox behavior.In this work, the hydrolysis of neptunium(V) was studied at variable temperatures (10 to 85°C) in tetramethylammonium chloride (1.12 mol kg−1). Two hydrolyzed species of neptunium(V), NpO2OH(aq) and NpO2(OH)2−, were identified by potentiometry and Near-IR absorption spectroscopy. The hydrolysis constants (*βn) and enthalpy of hydrolysis (ΔHn) for the reaction NpO2+ + nH2O = NpO2(OH)n(1−n)+ + nH+ (n = 1 and 2) were determined by titration potentiometry and microcalorimetry. The hydrolysis constants, *β1 and *β2, increased by 0.8 and 3.4 orders of magnitude, respectively, as the temperature was increased from 10 to 85°C. The enhancement of hydrolysis at elevated temperatures is mainly due to the significant increase of the degree of ionization of water as the temperature is increased. The hydrolysis reactions are endothermic but become less endothermic as the temperature is increased. The heat capacities of hydrolysis, ΔCp1 and ΔCp2, are calculated to be −(71 ± 17) J K−1 mol−1 and −(127 ± 17) J K−1 mol−1, respectively. Approximation approaches to predict the effect of temperature, including the constant enthalpy approach, the constant heat capacity approach and the DQUANT equation, have been tested with the data.  相似文献   

18.
Zusammenfassung Erzpetrographische Untersuchungen von Ni-reichen Erzproben der Ni–Co–Bi–(Ag)-Lagerstätte Zinkwand (Schladminger Tauern, Steiermark) führten zum Nachweis einer Paragenese von Gersdorffit, Nickelin, Pararammelsbergit, ged. Wismut, Wismutglanz und Parkerit. Gersdorffit tritt in zwei deutlich voneinander verschiedenen (Reflexionsvermögen, Mikrohärte) Komponenten M und I auf. Mikrosondenanalysen zeigen einheitlichen Chemismus der Komponente M, hingegen unterschiedlichen der Komponente I, hervorgerufen durch starken Zonarbau. Gersdorffit I repräsentiert vermutlich Gersdorffit mit ungeordneter Struktur und RaumgruppePa3, Gersdorffit M hingegen vertritt Gersdorffit mit RaumgruppeP213. Gersdorffit, Nickelin und Parkerit weisen Gehalte von±2Gew.% Sb auf. Antimon-hältiger Parkerit ist von den bis heute nachgewiesenen vier Fundpunkten des Minerals nicht bekannt. Vorsichtige Abschätzung der Bildungstemperatur ergibt für die Gersdorffit-Nickelin-Pararammelsbergit-Assoziation sicher <450°C, für jene von Parkerit-ged. Wismut-Wismutglanz<273°C.
Gersdorffite (in two structure varieties) and antimonian-parkerite, Ni3 (Bi, Sb)2S2 of the Zinkwand, Cchladminger Tauern, Austria
Summary Ore petrologic investigations of a Ni-rich assemblage from the Ni–Co–Bi–(Ag)-deposit Zinkwand (Schladminger Tauern, Styria, Austria) resulted in the identification of gersdorffite, nickeline, pararammelsbergite, native bismuth, bismuthinite and the rate ore mineral parkerite, so far not recorded from that locality. Gersdorffite occurs as two distinctly different varieties M and I (reflectance, microhardness). Microprobe analyses show uniform composition of phase M, but compositional variations of phase I caused by strong zonal texture. Gersdorffite I probably represents gersdorffite with disordered structure with space groupPa3; gersdorffite M corresponds to the gersdorffite with space groupP213. Gersdorffite, nickeline and parkerite contain about 2 wt.% Sb. Sb-containing parkerite has not been reported from the four known occurrences of that mineral. Temperature of formation for the Ni-minerals has been estimated to be (considerably?) below 450°C, for the Bi-bearing minerals below 273°C.

Mit 3 Abbildungen

Herrn Univ. Prof. Dr.H. Meixner zum 70. Geburtstag gewidmet.  相似文献   

19.
In this study, the solubility constant of magnesium chloride hydroxide hydrate, Mg3Cl(OH)5·4H2O, termed as phase 5, is determined from a series of solubility experiments in MgCl2-NaCl solutions. The solubility constant in logarithmic units at 25 °C for the following reaction,
Mg3Cl(OH)5·4H2O+5H+=3Mg2++9H2O(l)+Cl-  相似文献   

20.
Published solubility data for amorphous ferric arsenate and scorodite have been reevaluated using the geochemical code PHREEQC with a modified thermodynamic database for the arsenic species. Solubility product calculations have emphasized measurements obtained under conditions of congruent dissolution of ferric arsenate (pH < 3), and have taken into account ion activity coefficients, and ferric hydroxide, ferric sulfate, and ferric arsenate complexes which have association constants of 104.04 (FeH2AsO42+), 109.86 (FeHAsO4+), and 1018.9 (FeAsO4). Derived solubility products of amorphous ferric arsenate and crystalline scorodite (as log Ksp) are −23.0 ± 0.3 and −25.83 ± 0.07, respectively, at 25 °C and 1 bar pressure. In an application of the solubility results, acid raffinate solutions (molar Fe/As = 3.6) from the JEB uranium mill at McClean Lake in northern Saskatchewan were neutralized with lime to pH 2-8. Poorly crystalline scorodite precipitated below pH 3, removing perhaps 98% of the As(V) from solution, with ferric oxyhydroxide (FO) phases precipitated starting between pH 2 and 3. Between pH 2.18 and 7.37, the apparent log Ksp of ferric arsenate decreased from −22.80 to −24.67, while that of FO (as Fe(OH)3) increased from −39.49 to −33.5. Adsorption of As(V) by FO can also explain the decrease in the small amounts of As(V)(aq) that remain in solution above pH 2-3. The same general As(V) behavior is observed in the pore waters of neutralized tailings buried for 5 yr at depths of up to 32 m in the JEB tailings management facility (TMF), where arsenic in the pore water decreases to 1-2 mg/L with increasing age and depth. In the TMF, average apparent log Ksp values for ferric arsenate and ferric hydroxide are −25.74 ± 0.88 and −37.03 ± 0.58, respectively. In the laboratory tests and in the TMF, the increasing crystallinity of scorodite and the amorphous character of the coexisting FO phase increases the stability field of scorodite relative to that of the FO to near-neutral pH values. The kinetic inability of amorphous FO to crystallize probably results from the presence of high concentrations of sulfate and arsenate.  相似文献   

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