首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 717 毫秒
1.
The stoichiometric dissociation constant, pK1 of TRISH+ has been determined in NaCl, KCl, MgCl2 and CaCl2 solutions to an ionic strength of 6 molal. The results have been used to derive Pitzer coefficients for the interactions of TRIS with Na+, K+, Mg2+ and Ca2+ ions. These results can be used to determine the pK1 of TRISH+ in mixed brines which can be used to calibrate pH electrodes. Measurements of pK1 of TRISH+ in mixtures of NaCl-MgCl2, NaCl-CaCl2, NaCl-Na2SO4, KCl-MgCl2 and KCl-CaCl2, artificial seawater and Dead Sea waters were made to determine the reliability of the Pitzer coefficients. The estimated values were found to be in good agreement with the measured values provided corrections were made for the interactions of H+ with SO2−4. It now is possible to use dilute solutions of TRIS and TRISH+ to make buffers that can be used to make reproducible pH measurements in brines.  相似文献   

2.
Dissolution of CO2 into deep subsurface brines for carbon sequestration is regarded as one of the few viable means of reducing the amount of CO2 entering the atmosphere. Ions in solution partially control the amount of CO2 that dissolves, but the mechanisms of the ion's influence are not clearly understood and thus CO2 solubility is difficult to predict. In this study, CO2 solubility was experimentally determined in water, NaCl, CaCl2, Na2SO4, and NaHCO3 solutions and a mixed brine similar to the Bravo Dome natural CO2 reservoir; ionic strengths ranged up to 3.4 molal, temperatures to 140 °C, and CO2 pressures to 35.5 MPa. Increasing ionic strength decreased CO2 solubility for all solutions when the salt type remained unchanged, but ionic strength was a poor predictor of CO2 solubility in solutions with different salts. A new equation was developed to use ion hydration number to calculate the concentration of electrostricted water molecules in solution. Dissolved CO2 was strongly correlated (R2 = 0.96) to electrostricted water concentration. Strong correlations were also identified between CO2 solubility and hydration enthalpy and hydration entropy. These linear correlation equations predicted CO2 solubility within 1% of the Bravo Dome brine and within 10% of two mixed brines from literature (a 10 wt % NaCl + KCl + CaCl2 brine and a natural Na+, Ca2+, Cl− type brine with minor amounts of Mg2+, K+, Sr2+ and Br−).  相似文献   

3.
The solubility of calcite in NaCl-H2O and in HCl-H2O fluids was measured using an extraction-quench hydrothermal apparatus. Experiments were conducted at 2 kbar, between 400° C and 600° C. Measurements in NaCl-H2O were conducted in two ways: 1) at constant pressure and NaCl concentration, as a function of temperature; and 2) at constant pressure and temperature, as a function of NaCl concentration. In both the NaCl-H2O and the HCl-H2O systems, the solubility of calcite increases with increasing chlorine concentrations. For example, the log calcium molality in equilibrium with calcite increases from –3.75 at 2 kbar and 500° C, in pure H2O to –3.10 at 2 kbar and 500° C at log NaCl molality=–1.67. At fixed pressure and NaCl molality, the solubility of calcite is almost constant from 400° C to 550° C, but increases somewhat at higher temperatures. The results can be used to determine the dominant calcium species in the experimental solutions as a function of NaCl concentration and to obtain values for the second dissociation constant of CaCl2(aq). At 2 kbar, 400° C, 500° C, and 600° C, we calculate values for the log of the dissociation constant of CaCl+ of –2.1, –3.2, and –4.3, respectively. The 400° C and 500° C values are consistent with those obtained by Frantz and Marshall (1982) using electrical conductance techniques. However, our 600° C value is 0.8 log units higher than that reported by Frantz and Marshall. The calcite solubilities in the NaCl-H2O and HCl-H2O systems are inconsistent with the solubilities of calcite in pure H2O reported by Walther and Long (1986). They are, however, consistent with the measurements of calcite solubilities in pure H2O presented in this study. These results allow for the calculation of the solubilities of calcium silicates and carbonates in fluids that contain CO2 and NaCl.  相似文献   

4.
A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H2O-CO2-NaCl-CaCO3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H+, Na+, Ca2+, , Ca(OH)+, OH−, Cl−, , , CO2(aq) and CaCO3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T-P-m range, hence calcite solubility, CO2 gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data.One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO2 can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility.The functionality of pH value, alkalinity, CO2 gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl(aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.  相似文献   

5.
复杂卤水组分对于石盐流体包裹体均一温度的影响尚不明确,文章基于NaCl-X-H_2O(X=KCl, MgCl_2,CaCl_2, Na_2SO_4)三元卤水体系,尝试探讨K~+、Mg~(2+)、Ca~(2+)、SO_4~(2-)对石盐流体包裹体均一温度测试结果的影响。不同卤水体系最大均一温度分析结果表明,K~+、Mg~(2+)、Ca~(2+)的存在总体上会导致石盐流体包裹体均一温度偏大,SO_4~(2-)的存在对均一温度的影响很小。以NaCl-H_2O体系为参照,NaCl-Na_2SO_4-H_2O体系平均均一温度较之要低,而NaCl-KCl-H_2O、NaCl-MgCl_2-H_2O和NaCl-CaCl_2-H_2O体系与其相反。NaCl-KCl-H_2O体系中的KCl浓度与平均均一温度呈现负相关关系,NaCl-MgCl_2-H_2O、NaCl-CaCl_2-H_2O、NaCl-Na_2SO_4-H_2O体系中的w(MgCl_2)、w(CaCl_2)和w(Na_2SO_4)与平均均一温度则呈现正相关关系。平均和最大均一温度分析结果都显示出复杂卤水体系中不同离子及其浓度对石盐流体包裹体均一温度会产生影响。本研究对于具有复杂化学组分卤水结晶析出石盐均一温度的研究具有重要的参考价值。  相似文献   

6.
The solubility of amorphous silica was measured at 25°C in ten separate sets of aqueous salt solutions—potassium chloride, potassium nitrate, sodium chloride, lithium chloride, lithium nitrate, magnesium chloride, calcium chloride, magnesium sulfate, sodium bicarbonate and sodium sulfate. The concentrations of the salts were varied from zero to saturation with both salt and amorphous silica. With increasing concentration of salt, the solubility of amorphous silica always decreased as expected from an average value of 0.00218 m in water. Nevertheless, the extent of decrease differed greatly from a 6% decrease in a solution saturated with NaHCO3 to a 95.7% decrease in a solution saturated with CaCl2. A striking correlation was observed: In the 1-1 and 2-1 electrolyte salt solutions at a given molality the effect on the solubility of silica depended upon the cation in the order Mg2+, Ca2+ > Li+ > Na+ > K +.  相似文献   

7.
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   

8.
Fluorine-bearing minerals are uncommon in submarine exhalative ores, exhalites and associated alteration zones, probably because of the low solubility of CaF2. The Broken Hill (Australia) deposit contains fluorapatite and fluorite with one lens containing 1.35% F and greater than 3 volume % F-bearing minerals. The calcite-fluorite-fluorapatite assemblage at Broken Hill indicates that ore deposition was probably from hypersaline fluorine-bearing fluids which decreased in pH by base leaching reactions which released Ca2+ and mixing with seawater promoting the rapid and simultaneous precipitation of calcite, fluorite and fluorapatite as a result of temperature and salinity decrease and pH and [Ca2+] increase. The abundance of fluorine minerals in the Broken Hill ore and the association of F and B minerals with stratigraphically equivalent W- and Sn-bearing exhalites suggest that F complexes are important for ore transport in some exhalative systems. The Fe/Mn ratio decreases and the F/Cl ratio increases in fluorapatite in exhalites with increasing proximity to the Broken Hill deposit.  相似文献   

9.
Long-term intake of high-fluoride groundwater causes endemic fluorosis. This study, for the first time, discovered that the salt lake water intrusion into neighboring shallow aquifers might result in elevation of fluoride content of the groundwater. Two cross-sections along the groundwater flow paths were selected to study the geochemical processes controlling fluoride concentration in Yuncheng basin, northern China. There are two major reasons for the observed elevation of fluoride content: one is the direct contribution of the saline water; the other is the undersaturation of the groundwater with respect to fluorite due to salt water intrusion, which appears to be more important reason. The processes of the fluorine activity reduction and the change of Na/Ca ratio in groundwater induced by the intrusion of saline water favor further dissolution of fluorine-bearing mineral, and it was modeled using PHREEQC. With the increase in Na concentration (by adding NaCl or Na2SO4 as Na source, calcium content kept invariable), the increase of NaF concentration was rapid at first and then became slower; and the concentrations of HF, HF2−, CaF+, and MgF+ were continuously decreasing. The geochemical conditions in the study area are advantageous to the complexation of F− with Na+ and the decline of saturation index of CaF2, regardless of the water type (Cl–Na or SO4–Na type water).  相似文献   

10.
A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H2O-CO2-NaCl-CaCO3-CaSO4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca2+, , , and CaSO4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results.Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.  相似文献   

11.
The Fengjia barite–fluorite deposit in southeast Sichuan is a stratabound ore deposit which occurs mainly in Lower Ordovician carbonate rocks. Here we present results from fluid inclusion and oxygen and hydrogen isotope studies to determine the nature and origin of the hydrothermal fluids that generated the deposit. The temperature of the ore‐forming fluid shows a range of 86 to 302 °C. Our detailed microthermometric data show that the temperature during mineralization of the fluorite and barite in the early ore‐forming stage was higher than that during the formation of the calcite in the late ore‐forming stage. The salinity varied substantially from 0.18% to 21.19% NaCl eqv., whereas the density was around 1.00 g/cm3. The fluid composition was mainly H2O (>91.33%), followed by CO2, CH4 and traces of C2H6, CO, Ar, and H2S. The dominant cation was Na+ and the dominant anion Cl‐, followed by Ca2+, SO42‐, K+, and Mg2+, indicating a mid–low‐temperature, mid‐low‐salinity, low‐density NaCl–H2O system. Our results demonstrate that the temperature decreased during the ore‐forming process and the fluid system changed from a closed reducing environment to an open oxidizing environment. The hydrogen and oxygen isotope data demonstrate that the hydrothermal fluids in the study area had multiple sources, primarily formation water, as well as meteoric water and metamorphic water. Combined with the geological setting and mineralization features we infer that the stratabound barite–fluorite deposits originated from mid–low‐temperature hydrothermal fluids and formed vein filling in the fault zone.  相似文献   

12.
In the design of hydrothermal solubility studies it is important that the system be completely defined chemically. If the solubilities of minerals containing m metallic elements are to be determined in hydrothermal NaCl solutions, the phase rule requires that a total of m + 6 independent intensive parameters be controlled or measured in order to determine completely the system.In this study the solubility of the univariant assemblage pyrite + pyrrhotite + magnetite has been determined in vapor saturated hydrothermal solutions from 200 to 350°C for NaCl concentrations ranging from 0.0 to 5.0 molal. At any temperature, oxygen and sulfur fugacities were buffered by the chosen assemblage. System pH was determined from excess CO2 partial pressures and computed ionic equilibria. Equilibrium constants were calculated by regression analysis of solubility data. The results show that more than 10 ppm of each mineral can dissolve in typical hydrothermal solutions under geologically realistic conditions. Solubilities were best represented by the species Fe2+ and FeCl+ at 200 and 250°C; Fe2+, FeCl+ and FeCl20 at 300°C; and Fe2+ and FeCl20 at 350°C. Ore deposition would occur by lowering temperature, diluting chloride concentration, or by raising pH through wall rock alteration reactions.  相似文献   

13.
《Chemical Geology》2006,225(1-2):40-60
Fluorite is the most common fluoride mineral in magmatic silicic systems and its crystallization can moderate or buffer fluorine concentrations in these settings. We have experimentally determined fluorite solubility and speciation mechanisms in haplogranitic melts at 800–950 °C, 100 MPa and aqueous-fluid saturation. The starting haplogranite compositions: peraluminous (alumina saturation index, ASI = 1.2), subaluminous (ASI = 1.0) and peralkaline (ASI = 0.8) were variably doped with CaO or F2O−1 in the form of stoichiometric mineral or glass mixtures. The solubility of fluorite along the fluorite–hydrous haplogranite binaries is low: 1.054 ± 0.085 wt.% CaF2 (peralkaline), 0.822 ± 0.076 wt.% (subaluminous) and 1.92 ± 0.15 wt.% (peraluminous) at 800 °C, 100 MPa and 10 wt.% H2O, and exhibits a minimum at ASI ∼ 1. Fluorite saturation isotherms are strongly hyperbolic in the CaO–F2O−1 space, suggesting that fluorite saturation is controlled by the activity product of CaO and F2O−1, i.e., these components are partially decoupled in the melt structure. The form of fluorite liquidus isotherms implies distinct roles of fluorite crystallization: in Ca-dominant systems, fluorite crystallization is controlled by the fluorine concentration in the melt only and remains nearly independent of calcium contents; in F-rich systems, the crystallization of fluorite is determined by CaO contents and it does not buffer fluorine concentration in the melt. The apparent equilibrium constant, K, for the equilibrium CaO + cF2O−1 = CaF2 (+ associates) is log K= − (2.449 ± 0.085)·Al2O3exc + (4.902 ± 0.066); the reaction-stoichiometry parameter varies as follows: c= − (0.92 ± 0.11)·Al2O3exc + (1.042 ± 0.084) at 800 °C, 100 MPa and fluid saturation where Al2O3exc are molar percent alumina in excess over alkali oxides. The reaction stoichiometry, c, changes at subaluminous composition: in peralkaline melts, competition of other network modifiers for excess fluorine anions leads to the preferential alkali–F short-range order, whereas in peraluminous compositions, excess alumina associates with calcium cations to form calcioaluminate tetrahedra. The temperature dependence of fluorite solubility is described by the binary symmetric Margules parameter, W = 36.0 ± 1.4 kJ (peralkaline), 39.7 ± 0.5 kJ (subaluminous) and 32.8 ± 0.7 kJ (peraluminous). The strong positive deviations from ideal mixing imply the occurrence of CaF2–granite liquid–liquid immiscibility at temperatures above 1258 °C, which is consistent with previous experimental data. These experimental results suggest very low solubilities of fluorite in Ca-rich melts, consistent with the lack of fluorine enrichment in peralkaline rhyolites and calc-alkaline batholiths. On the other hand, high CaO concentrations necessary to crystallize fluorite in F-rich peraluminous melts are not observed in nature and thus magmatic crystallization of fluorite in topaz-bearing silicic suites is suppressed. A procedure for calculating fluorite solubility and the liquidus isotherms for a whole-rock composition and temperature of interest is provided.  相似文献   

14.
Fluorite solubility equilibria in selected geothermal waters   总被引：2，自引：0，他引：2  
Calculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF2, provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions.Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the pK (10,96), ΔGof (?280.08 kcal/mole), ΔHof (?292.59 kcal/mole), S° (16.39 cal/deg/mole) and CoP (16.16 cal/deg/mole) for CaF2 at 25°C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised pK suggests that the chemistry of geothermal waters may also be a guide to evaluating mineral solubility data where major discrepancies are evident.  相似文献   

15.
Celestite solubility measurements have been conducted in pure water at temperatures from 10 to 90°C. Equilibrium was achieved with respect to a crystalline solid phase from both undersaturated and supersaturated solutions. The measurements show that the solubility undergoes a maximum near 20°C. LogK values for the solubility reaction are adequately described by the following expression over the temperature range 283.15 to 363.15 K: −logK= −35.3106+0.00422837T+318312/T2+14.99586 logT.The following thennodynamic values for the dissolution reaction of SrSO4(s), at 25°C have been derived: ΔGR0 = 37852 ± 30 Jmol−1ΔHR0 = −1668±920Jmol−1ΔSR0= −132.6±3.2JK−1mol−1Celestite solubility measurements were also determined in NaCl solutions up to 5 m concentration and from 10 to 40°C. These data are in good agreement with the work of StrÜbel (1966), who reports solubility measurements to temperatures of 100°C.The application of the Pitzer relations and the solubility constants determined in this study to calculate celestite solubility in NaCl solutions yields excellent agreement between predicted values and experimental measurements over the entire range of temperature and NaCl concentration conditions. For the limited number of solubility measurements in seawater-type solutions and mixed-salt brines, the agreement using the Pitzer relations is within three percent of the measured solubility.  相似文献   

16.
《Geochimica et cosmochimica acta》1999,63(11-12):1751-1765
Solubility methods were employed to determine conditional equilibrium constants for the formation of hydroxide and mixed hydroxy–chloride complexes of Pd(II). Measurements were made over a temperature range of 25–85°C, a pH range from 0 to 12, and ionic strengths of 0.1, 0.2, 0.5 and 1.0 molal in both KCl and NaClO4 media. Several speciation models were fit to the data using nonlinear regression, and the model yielding the best fit with the fewest number of species was accepted for each temperature and ionic strength. The conditional equilibrium constants were then fit to a function of ionic strength and temperature (including a Debye–Hückel term) to facilitate interpolation and extrapolation to infinite dilution. The following species were found to be important in KCl solutions: PdCl42−, PdCl3(OH)2−, and Pd(OH)20. The relative proportions of the species are dependent on pH and ionic strength (chloride concentration). In perchlorate media the predominant species were Pd(OH)3−, Pd(OH)20, PdOH+ and Pd2+, depending on pH. Conditional stability constants determined in this study agree well with those reported in previous work for the simple chloride and hydroxide complexes, but our results suggest that mixed complexes may be more important than previously thought, and that PdCl3(OH)2− may be the dominant species in seawater, followed by Pd(OH)20.  相似文献   

17.
Fluorite solubility in HCl and HF solutions with varied concentrations of boric acid was studied at 81, 155, and 208°C and saturated vapor pressure. Our experimental results demonstrate that fluorite solubility increases with increasing B(OH)3 concentration, and this was interpreted as the formation of the BF3OH–complex (Ryss, 1956). The experimental data were used to determine, using the OptimA software, the free energies of formation of HF°(aq) and, which were then used to calculate the constants of the reactions HF = H+ + F– (1) and B(OH)3(aq) + 2H+ + 3 F– (2). The pK 1 values are 3.71 ± 0.013, 4.28 ± 0.015, and 4.89 ± 0.017 and pK 2 13.60 ± 0.02, 13.99 ± 0.02, and 14.95 ± 0.03 at saturated vapor pressure and 81, 155, and 208°C, respectively.  相似文献   

18.
The solubility of all possible Zn and Pb species in aqueous chloride fluids was evaluated by means of thermodynamic simulations in systems ZnO(PbO)-aqueous solution of NaCl (KCl, NaCl + HCl) within broad ranges of temperature (600–900°C), pressure (0.7–5 kbar), and chloride concentrations, under parameters corresponding to the crystallization and degassing of granitoid magmas in the Earth’s crust. Our simulation results demonstrate that the addition of Cl to the fluid phase in the form of Na(K)Cl and HCl significantly increases the concentrations of Cl-bearing Zn and Pb complexes and the total concentration of the metals in the solutions in equilibrium with the solid oxides. In Zn-bearing fluids, the Zn(OH) 2 0 , ZnOH+, and Zn(OH) 3 ? —hydroxyl complexes and the ZnCl 2 0 , and ZnCl+ chlorocomplexes, which are predominant at low Cl concentrations (CCl < 0.05–0.1 m) give way to ZnCl 4 2? with increasing CCl, which becomes the predominant Zn species of the fluid at CCl > 0.1–0.5 m throughout the whole temperature range in question and pressures higher than 1 kbar. For Pb-bearing fluids, the T-P-X region dominated by the Pb(OH) 2 0 , and Pb(OH) 3 ? hydroxyl complexes is remarkably wider than the analogous region for Zn, particularly at elevated temperatures (≥700°C) in alkaline solutions. An increase in CCl is associated with an increase in the concentration and changes in the speciation of Pb chlorocomplexes: PbCl 2 0 → PbCl 3 ? → PbCl 4 2? . The concentrations of Zn and Pb chlorocomplexes increase with increasing pressure, decreasing temperature, and decrease pH with the addition of HCl to the system. It is demonstrated that the solubility of ZnO at any given T-P-X in alkaline solutions with low chloride concentrations are lower than the solubility of PbO. The Zn concentration increases more significantly than with the Pb concentration with increasing CCl and decreasing pH, so that the Zn concentration in acidic solutions is higher than the Pb concentration over broad ranges of temperature, pressure, and Cl concentration. Chloride complexes of Zn (ZnCl 2 0 , and ZnCl 4 2? ) and Pb (PbCl 2 0 , and PbCl 3 ? are proved to be predominant within broad T-P-X-pH ranges corresponding to the parameters under which magmatic fluid are generated. Our simulation results confirm the hypothesis that chlorocomplexes play a leading role in Zn and Pb distribution between aqueous chloride fluids and granitic melts. These simulation results are consistent with experimental data on the Zn and Pb distribution coefficients (D(Zn)f/m and D(Pb)f/m, respectively) between aqueous chloride fluids and granitic melts that demonstrated that (1) D(Zn)f/m and D(Pb)f/m increase with increasing Na and K chloride concentrations in the aqueous fluid, (2) both D(Zn)f/m and D(Pb)f/m drastically increase when HCl is added to the fluid, and (3) (D(Zn)f/m is higher than D(Pb)f/m at any given T-P-X parameters. The experimentally established decrease in D(Zn)f/m and D(Pb)f/m with increasing pressure (at unchanging temperature and Cl concentration) is likely explained by an increase in the alkalinity of the aqueous chloride fluid in equilibrium with granite melt and, correspondingly, a decrease in the Zn and Pb solubility in this fluid.  相似文献   

19.
The aqueous silica species that form when quartz dissolves in water or saline solutions are hydrated. Therefore, the amount of quartz that will dissolve at a given temperature is influenced by the prevailing activity of water. Using a standard state in which there are 1,000 g of water (55.51 moles) per 1,000 cm3 of solution allows activity of water in a NaCl solution at high temperature to be closely approximated by the effective density of water, pe, in that solution, i.e. the product of the density of the NaCl solution times the weight fraction of water in the solution, corrected for the amount of water strongly bound to aqueous silica and Na+ as water of hydration. Generally, the hydration of water correction is negligible.The solubility of quartz in pure water is well known over a large temperature-pressure range. An empirical formula expresses that solubility in terms of temperature and density of water and thus takes care of activity coefficient and pressure-effect terms. Solubilities of quartz in NaCl solutions can be calculated by using that equation and substituting pe, for the density of pure water. Calculated and experimentally determined quartz solubilities in NaCl solutions show excellent agreement when the experiments were carried out in non-reactive platinum, gold, or gold plus titanium containers. Reactive metal containers generally yield dissolved silica concentrations higher than calculated, probably because of the formation of metal chlorides plus NaOH and H2. In the absence of NaOH there appears to be no detectable silica complexing in NaCl solutions, and the variation in quartz solubility with NaCl concentration at constant temperature can be accounted for entirely by variations in the activity of water.The average hydration number per molecule of dissolved SiO2 in liquid water and NaCl solutions decreases from about 2.4 at 200°C to about 2.1 at 350°C. This suggests that H4SiO4 may be the dominant aqueous silica species at 350°C, but other polymeric forms become important at lower temperatures.  相似文献   

20.
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   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号