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1.
《Geochimica et cosmochimica acta》1999,63(13-14):1969-1980
The solubility of ettringite (Ca6[Al(OH)6]2(SO4)3 · 26H2O) was measured in a series of dissolution and precipitation experiments at 5–75°C and at pH between 10.5 and 13.0 using synthesized material. Equilibrium was established within 4 to 6 days, with samples collected between 10 and 36 days. The log KSP for the reaction Ca6[Al(OH)6]2(SO4)3 · 26H2O ⇌ 6Ca2+ + 2Al(OH)4− + 3SO42− + 4OH− + 26H2O at 25°C calculated for dissolution experiments (−45.0 ± 0.2) is not significantly different from the log KSP calculated for precipitation experiments (−44.8 ± 0.4) at the 95% confidence level. There is no apparent trend in log KSP with pH and the mean log KSP,298 is −44.9 ± 0.3. The solubility product decreased linearly with the inverse of temperature indicating a constant enthalpy of reaction from 5 to 75°C. The enthalpy and entropy of reaction ΔH°r and ΔS°r, were determined from the linear regression to be 204.6 ± 0.6 kJ mol−1 and 170 ± 38 J mol−1 K−1. Using our values for log KSP, ΔH°r, and ΔS°r and published partial molal quantities for the constituent ions, we calculated the free energy of formation ΔG°f,298, the enthalpy of formation ΔH°f,298, and the entropy of formation ΔS°f,298 to be −15211 ± 20, −17550 ± 16 kJ mol−1, and 1867 ± 59 J mol−1 K−1. Assuming ΔCP,r is zero, the heat capacity of ettringite is 590 ± 140 J mol−1 K−1.  相似文献   

2.
《Applied Geochemistry》2000,15(8):1203-1218
Ca6[Al(OH)6]2(CrO4)3·26H2O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca6[Al(OH)6]2(CrO4)3·26H2O⇌6Ca2++2Al(OH)−4+3CrO2−4+4OH−+26H2O varies with pH unless a CaCrO4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca2++CrO2−4=CaCrO4(aq) was obtained by minimizing the variance in the IAP for Ca6[Al(OH)6]2(CrO4)3·26H2O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log KSP) of Ca6[Al(OH)6]2(CrO4)3·26H2O at 25°C is −41.46±0.30. The temperature dependence of the log KSP is log KSP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG0r,298 and ΔH0r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol−1. the values of ΔC0P,r,298 and ΔS0r,298 are −1506±140 and −534±83 J mol−1 K−1. Using these values and published standard state partial molal quantities for constituent ions, ΔG0f,298=−15,131±19 kJ mol−1, ΔH0f,298=−17,330±8.6 kJ mol−1, ΔS0298=2.19±0.10 kJ mol−1 K−1, and ΔC0Pf,298=2.12±0.53 kJ mol−1 K−1, were calculated.  相似文献   

3.
《Geochimica et cosmochimica acta》1999,63(19-20):3487-3497
The solubility of iron(III) hydroxide as a function of pH was investigated in NaCl solutions at different temperatures (5–50°C) and ionic strengths (0–5 M). Our results at 25°C and 0.7 M in the acidic range are similar to the solubility in seawater. The results between 7.5 to 9 are constant (close to 10−11 M) and are lower than those found in seawater (>10−10) in this pH range. The solubility subsequently increases as the pH increases from 9 to 12. The solubility between 6 and 7.5 has a change of slope that cannot be accounted for by changes in the speciation of Fe(III). This effect has been attributed to a solid-state transformation of Fe(OH)3 to FeOOH. The effect of ionic strength from 0.1 to 5 M at a pH near 8 was quite small. The solubility at 5°C is considerably higher than at 25°C at neutral pH range. The effects of temperature and ionic strength on the solubility at low and high pH have been attributed to the effects on the solubility product and the formation of FeOH2+ and Fe(OH)4−. The results have been used to determine the solubility products of Fe(OH)3, K1Fe(OH)3 and hydrolysis constants, β11, β12, β13, and β14 as a function of temperature (T, K) and ionic strength (I):log K1Fe(OH)3 = −13.486 − 0.1856 I0.5 + 0.3073 I + 5254/T (σ = 0.08)log β11 = 2.517 − 0.8885 I0.5 + 0.2139 I − 1320/T (σ = 0.03)log β12 = 0.4511 − 0.3305 I0.5 − 1996/T (σ = 0.1)log β13 = −0.2965 − 0.7881 I0.5 − 4086/T (σ = 0.6)log β14 = 4.4466 − 0.8505 I0.5 − 7980/T. (σ = 0.2)Both strong ethylenediaminetetraacetic acid and weak (HA) organic ligands greatly affect iron solubility. The additions of ethylenediaminetetraacetic acid and humic material were shown to increase the solubility near pH 8. The higher solubility of Fe(III) in seawater compared to 0.7 M NaCl may be caused by natural organic ligands.  相似文献   

4.
From conductance measurements, the negative logarithm of the dissociation constant of the CaHCO3+ ion pair, pK(CaHCO3+), is 0.7, 1.0 and 1.35 within ±0.05 units at 0, 25 and 60°C, respectively. A revaluation of published and unpublished data yields pK(CaCO30) ≈ 3.2 at 25°C. Use of these pK's to compute the dissociation constant of calcite (Kc) from published calcite solubility measurements in pure water gives pKc values which increase markedly with ionic strength. However, if the ion pairs are ignored, computed pKc values are nearly constant with ionic strength. All reasonable attempts to eliminate the trend in pKc by adjusting ion activity coefficients, and/or values of K(CaCO30) failed, so the dilemma remains. Kc values computed from the most reliable published calcite solubility data are in good agreement with such values based on solubility data measured in this study at 5, 15, 35 and 50°C. Study results ignoring ion pairs are accurately represented by the equation log Kc = 13.870 — (3059/T) ?0.04035T, and correspond to ?8.35, ?8.42, and ?8.635 at 0, 25 and 50°C, respectively. The logarithmic expression leads to ΔHro = ?2420 ± 300 cal/mol, ΔCp = ?110 ± 2 cal/deg mol, and ΔSro = ?46.6 ± 1.0 cal/deg mol for the calcite dissociation reaction at 25°C. The dependence of Kc on temperature when CaCO30 and CaHCO3+ are assumed, is described by log Kc = 13.543 ? (3000/T) ? 0.0401T which yields ?8.39, ?8.47, and -8.70 at 0, 25 and 50°C. This gives ΔHro = ?2585 ± 300 cal/mol, ΔCp = ?109 ± 2 cal/deg mol, and ΔSr0 = ?47.4 ± 1.0 cal/deg mol at 25°C.  相似文献   

5.
Solubilities of silver chloride in aqueous hydrochloric acid solutions have been determined from 100 up to 350°C. From these measurements, the ionisation constant of HC1 has been evaluated up to 225°C. Evidence is presented to show that a protonated silver species, HAgCl20, exists at 275°C and above. Available experimental data up to 200°C have been firted to Pitzer's equation to generate an algorithm to calculate stoichiometric activity and osmotic coefficients of HCl up to 350°C and concentrations up to at least 3.0 m. Using the present results and those of Wrightet al. (1961), Pearsonet al. (1963) and Lukashowet al. (1976), the dissociation constant (Kd) of HCl as a function of temperature is described by the equation log10K = 2136.898 + 1.020349T−4.5045 × 10−4T2−50396.40/T−901.770 10g10T (Tin °K) which is valid in the range 25–350°C. Calculated enthalpy (ΔH0), entropy (ΔS0) and heat capacity change (ΔCp0) functions for HCl dissociation have been rationalized in terms of changing solute and solvent characteristics as temperature is raised.  相似文献   

6.
《Geochimica et cosmochimica acta》1999,63(19-20):3417-3427
In order to verify Fe control by solution - mineral equilibria, soil solutions were sampled in hydromorphic soils on granites and shales, where the occurrence of Green Rusts had been demonstrated by Mössbauer and Raman spectroscopies. Eh and pH were measured in situ, and Fe(II) analyzed by colorimetry. Ionic Activity Products were computed from aqueous Fe(II) rather than total Fe in an attempt to avoid overestimation by including colloidal particles. Solid phases considered are Fe(II) and Fe(III) hydroxides and oxides, and the Green Rusts whose general formula is [FeII1−xFeIIIx(OH)2]+x· [x/z A−z]−x, where compensating interlayer anions, A−, can be Cl−, SO42−, CO32− or OH−, and where x ranges a priori from 0 to 1. In large ranges of variation of pH, pe and Fe(II) concentration, soil solutions are (i) oversaturated with respect to Fe(III) oxides; (ii) undersaturated with respect to Fe(II) oxides, chloride-, sulphate- and carbonate-Green Rusts; (iii) in equilibrium with hydroxy-Green Rusts, i.e., Fe(II)-Fe(III) mixed hydroxides. The ratios, x = Fe(III)/Fet, derived from the best fits for equilibrium between minerals and soil solutions are 1/3, 1/2 and 2/3, depending on the sampling site, and are in every case identical to the same ratios directly measured by Mössbauer spectroscopy. This implies reversible equilibrium between Green Rust and solution. Solubility products are proposed for the various hydroxy-Green Rusts as follows: log Ksp = 28.2 ± 0.8 for the reaction Fe3(OH)7 + e− + 7 H+ = 3 Fe2+ + 7 H2O; log Ksp = 25.4 ± 0.7 for the reaction Fe2(OH)5 + e− + 5 H+ = 2 Fe2+ + 5 H2O; log Ksp = 45.8 ± 0.9 for the reaction Fe3(OH)8 + 2e− + 8 H+ = 3 Fe2+ + 8 H2O at an average temperature of 9 ± 1°C, and 1 atm. pressure. Tentative values for the Gibbs free energies of formation of hydroxy-Green Rusts obtained are: ΔfG° (Fe3(OH)7, cr, 282.15 K) = −1799.7 ± 6 kJ mol−1, ΔfG° (Fe2(OH)5, cr, 282.15 K) = −1244.1 ± 6 kJ mol−1 and ΔfG° (Fe3(OH)8, cr, 282.15 K) = −1944.3 ± 6 kJ mol−1.  相似文献   

7.
The conversion of secondary lead orthophosphate [PbHPO4] into chloropyromorphite [Pb5(PO4)3Cl] in ca. 10?1 M NaCl solutions has been investigated at 25°C. From the composition of the supernatant solutions, the solubility product constant for Pb5(PO4)3Cl has been calculated to be 10?84.4±0.1, corresponding to ΔG?° of ?906.2 kcal mol?1. The solution equilibria and phase relationships in the system PbCl2-PbO-P2O8-H2O are discussed along with the geological implications.  相似文献   

8.
《Geochimica et cosmochimica acta》1999,63(19-20):3105-3119
A comprehensive low-temperature thermodynamic model for the geochemically important Na2CO3−MgCO3−CaCO3−H2O system is presented. The model is based on calorimetrically determined ΔfH°298 values, S°298 values and C°p(T) functions taken from the literature as well as on μ°298 values of solids derived in this work from solubility measurements obtained in our laboratories or by others. When these thermodynamic quantities were combined with temperature-dependent Pitzer parameters taken from the literature, solubilities calculated for a wide range of conditions agree well with experimental data. The results for several subsystems were summarized by depicting the respective phase diagrams. For the MgO−CO2−H2O subsystem, it was found that the commonly believed stability relations must be revised, i.e., in the temperature range covered, nesquehonite never becomes more stable than hydromagnesite at pCO2 ≤ 1 atm. Although the recommended set of thermodynamic data on sparingly soluble solids was derived from experimental results on mainly NaClO4 systems, it can be incorporated in databanks containing additional Pitzer parameters for modeling more complex fresh- or seawater systems.  相似文献   

9.
The solubility product of rhodochrosite (MnCO3) was measured in seawater, deionized water and dilute NaCl solutions. The solubility product extrapolated to infinite dilution at 25.0 C was (2.60 ± 0.07)× 10?11. The stoichiometric solubility product measured in seawater of 34.27%. salinity was (3.24 ± 0.23) × 10?9 at 25.0 C and (2.28 ± 0.24) × 10?9 at 3.3 C. The stoichiometric solubility product is in good agreement with the value calculated from an ion association model. The enthalpy of the reaction is in fair agreement with the estimated value.  相似文献   

10.
Methods have been developed for solution calorimetry of hydrous phases in molten lead borate near 700°C. These involve thermochemical cycles using dissolution and decomposition reactions of hydrous silicates and hydroxides. Preliminary results suggest that H2O derived from the decomposition of hydroxides dissolves in molten 2PbO-B2O3 with an exothermic enthalpy of solution of −5.7 ±0.7 kcal mol−1. Hydroxyphologopite persists metastably at 714°C and its heat of solution in 2PbO·B2O3 has been measured. From these new data, the standard enthalpy of formation of phlogopite from the elements at 25°C is −1485.5 ±1.5 kcal mol−1. The standard free energy of formation is -1394.6 ±1.5 kcal mol−1, assuming complete tetrahedral Al-Si disorder.Two structural features complicate the thermodynamics of synthetic and natural micas. The first is a varying degree of tetrahedral Al-Si disorder. Raman spectroscopic study of phlogopite synthesized above 600°C suggests a disordered Al-Si distribution. Calculations of the P-T locus of the geologically important equilibrium: Phl + 3Qtz = 3En + Sa + H2O, using our thermochemical data, agree within experimental error with the results of calculations based on the best available phase equilibrium data only if a tetrahedrally disordered phlogopite is assumed. Such calculations are very sensitive to uncertainties in ΔH° and ΔG°, and reversed phase equilibrium experiments remain essential to obtaining reliable estimates of thermodynamic properties. In contrast to these Al-Si disordered phlogopites, some biotites of low temperature parageneses (<600°C) may have substantial Al-Si order. A variable Al-Si distribution has a substantial effect on the configurational entropy and therefore on the free energy of the mica in question. Because of these and other questions, applications of biotite equilibria to determining volatile fugacities in igneous and metamorphic petrogenesis are subject to large uncertainties.The second structural complication is stacking disorder, which is present in phlogopite synthesized at 650°C but not in the 850°C sample. The enthalpy difference between these two samples, determined by solution calorimetry, is smaller than the experimental uncertainty of ±1.0 kcal mol−1. Thus there appears to be little driving force for ordering, and micas with disordered stacking sequences may persist in many geologic environments. The effect of stacking disorder on thermodynamic properties is probably very small.  相似文献   

11.
Vaterite is shown to be unstable with respect to calcite at 25°C by measurements of the enthalpies of solution in 0·1 N HCl under 0·97 atm CO2 and the solubilities in water under 0·97 atm CO2 of the two polymorphs. For a pure, synthetic vaterite ΔH (tr) = ?1036 ±16 cal mol?1 and ΔG(tr) = ?790 ± 25 cal mol?1 for the transition to calcite. For other vaterites aged longer during preparation ΔH(tr) is smaller and shows a linear relationship with the X-ray line broadening which extrapolates to ΔH(tr) = ?545 ± 30 cal mo?1 for zero broadening. The use of X-ray line broadening as a measure of crystal imperfection and stability is discussed for various synthetic and natural vaterites.  相似文献   

12.
《Chemical Geology》2004,203(1-2):139-151
Aragonite is precipitated by a new CO2-diffusion technique from a Ca2+–Mg2+–Cl− solution between 10 and 50 °C. Crystallisation of aragonite instead of calcite occurs by maintaining a [Mg2+]/[Ca2+] ratio of 2 in the fluid. The dissolved inorganic carbon (DIC) is received by diffusion of CO2 through a polyethylene membrane (diffusion coefficient: DCO2=10−6.4 cm2 s−1 at 19 °C). It is suggested that significant amounts of DIC may be transferred by diffusion of CO2 in natural systems if the CO2 gradient is high. The CO2-diffusion technique is used as a kind of simple mixed flow reactor for the co-precipitation of barium and strontium with aragonite. The distribution coefficients of Ba2+ and Sr2+ decrease from 10 to 50 °C according to DBa,a*=2.42−0.03595T (°C) and DSr,a*=1.32−0.005091T (°C). At 25 °C, the distribution coefficients are DBa,a*=1.5±0.1 and DSr,a*=1.19±0.03. The effect of temperature on DBa,a* is about one order of magnitude higher versus that on DSr,a*. Thus, Ba2+ may be a potential paleotemperature indicator if the composition of the solution is known.  相似文献   

13.
The heat capacity of synthetic andradite garnet (Ca3Fe2Si3O12) was measured between 9.6 and 365.5 K by cryogenic adiabatic calorimetry and from 340 to 990 K by differential scanning calorimetry. At 298.15 K Cop,m and Som are 351.9 ± 0.7 and 316.4 ± 2.0 J/(mol·K), respectively.Andradite has a λ-peak in Cop,m with a maximum at 11.7 ± 0.2 K which is presumably associated with the antiferromagnetic ordering of the magnetic moments of the Fe3+ ions. The Gibbs free energy of formation, ΔfGom (298.15 K) of andradite is −5414.8 ± 5.5 kJ/mol and was obtained by combining our entropy and heat capacity data with the known breakdown of andradite to pseudowollastonite and hematite at ≈ 1410 to 1438 K. From a reexamination of the calcite + quartz = wollastonite equilibrium data we obtained ΔfHom (298.15 K) = − 1634.5 ± 1.8 kJ/mol for wollastonite.Between 300 and 1000 K the molar heat capacity of andradite can be represented by the equation Cop,m = 809.24 - 7.025 × 10−2T− 7.403 × 103T−0.5 − 6.789 × 105T−2. We have also used our thermochemical data for andradite to estimate the Gibbs free energy of formation of hedenbergite (CaFeSi2O6) for which we obtained ΔfGom (298.15 K) = −2674.3 ± 5.8 kJ/mol.  相似文献   

14.
The solubility of CaCO3 (calcite), SiCO3 (strontianite), and BaCO3 (witherite) has been determined in NaCl solutions from 0.1 to 6 m at 25°C. Activity coefficients estimated from Pitzer's equations with higher order interaction terms (θ and Ψ) were used to extrapolate the results to infinite dilution. Thermodynamic values of pKsp = 8.46 ± 0.03,9.13 ± 0.03 and 8.56 ± 0.04 were found, respectively, for CaCO3, SrCO3 and BaCO3 at 25°C. These results are in reasonable agreement with literature data. Since Pitzer parameters for the interactions of CO32? with Ca2+, Sr2+ and Ba2+ were not used, our results indicate that they are not necessary at low values of Pco2.  相似文献   

15.
《Applied Geochemistry》2001,16(5):559-570
Fe(II)–Fe(III) layered double hydroxysalt green rusts, GRs, are very reactive compounds with the general formula, [FeII(1−x) FeIIIx (OH)2]x+·[(x/n) An−·(m/n) H2O]x−, where x is the ratio FeIII/Fetot, and reflects the structure in which brucite-like layers alternate with interlayers of anions An− and water molecules. Two types of crystal structure for GRs, GR1 and GR2, represented by the hydroxychloride GR1(Cl−) and the hydroxysulphate GR2(SO42−) are distinguished by X-ray diffraction due to different stacking. By analogy with GR1(Cl−) the structure of the fougerite GR mineral, [FeII(1−x) FeIIIx (OH)2]x+·[x OH−·(1−x) H2O]x-  Fe(OH)(2+x)·(1−x) H2O, is proposed displaying interlayers made of OH− ions and water molecules (in situ deprotonation of water molecules is necessary for explaining the flexibility of its composition). The space group of mineral GR1(OH−) would be R3̄m, with lattice parameters a≅0.32 and c≅2.25 nm. Stability conditions and the Eh-pH diagram of Fe(OH)(2+x) (the water molecules are omitted) are determined from hydromorphic soil solution equilibria with GR mineral in Brittany (France). Computed Gibbs free energies of formation from soil solution/mineral equilibrium fit well with a regular solid solution model: μ°[Fe(OH)(2+x)]=(1−x) μ°[Fe(OH)2]+x μ°[Fe(OH)3]+RT [(1−x) ln (1−x)+x ln x]+A0 x (1−x), where μ°[Fe(OH)2]=−492.5 kJ mol−1, μ°[Fe(OH)3]=−641 kJ mol−1 and A0=−243.9 kJ mol−1 at the average temperature of 9±1°C. The upper limit of occurrence of GR mineral at x=2/3, i.e. Fe3(OH)8, is explained by its unstability vs. α-FeOOH and/or magnetite; Fe(OH)3 is thus a hypothetical compound with a GR structure which cannot be observed. These thermodynamic data and Eh-pH diagrams of Fe(OH)(2+x) can be used most importantly to predict the possibility that GR minerals reduce some anions in contaminated soils. The cases of NO3−, Se(VI) or Cr(VI) are fully illustrated.  相似文献   

16.
The thermodynamic properties of monohydrocalcite, CaCO3 · H2O, have been obtained using a well-characterized natural specimen. Equilibration of the solid with water at 25°C under 0.97 atm CO2 led to an activity product [Ca2+][CO32?] = 10?7.60±0.03 and a free energy of formation ΔGfo = ?325,430 ± 270 calmol?. The enthalpy of solution of monohydrocalcite in 0.1 N HCl at 25°C led to a standard enthalpy of formation ΔHfo = ?358,100 ± 280 cal mol?1. Estimates of the variation of ΔGf with temperature and pressure showed monohydrocalcite to be metastable with respect to calcite and aragonite.  相似文献   

17.
The speciation of CO2 in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO2 into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO2 re-appeared. Infrared extinction coefficients of both carbonate and molecular CO2 decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO2 + O2? = CO3 2? in the melt shifts toward CO2 with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 103 T ?1 for dacite melt (ΔH = ?42 kJ mol?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 103 T ?1 for phonolite melt (ΔH = ?65 kJ mol?1), where K is the molar ratio of carbonate over molecular CO2 and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO2 speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO2, and therefore, the diffusion coefficient of CO2 is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO2 solubility and speciation on melt composition, in accordance with available solubility data.  相似文献   

18.
Pore waters of natural clays, which are investigated as potential host rock formations for high-level nuclear waste, are known to contain large amounts of low-molecular weight organic compounds. These small organic ligands might impact the aqueous geochemistry of the stored radionuclides and, thus, their migration behavior. In the present work, the complexation of Cm(III) with formate in aqueous NaCl solution is investigated by time-resolved laser fluorescence spectroscopy (TRLFS) as a function of the ionic strength (0.5–3.0 mol/kg), the ligand concentration (0–0.2 mol/kg) and the temperature (20–90 °C). The Cm(III) speciation is determined by deconvolution of the emission spectra. The obtained distribution of Cm(III) species is used to calculate the conditional stability constants (log K′(T)) at a given temperature and ionic strength which are extrapolated to zero ionic strength by using the specific ion interaction theory (SIT). Thus, the thermodynamic log K0n(T) values for the formation of [Cm(Form)n](3−n)+ (n = 1, 2) and the ion interaction coefficients (ε(i,k)) for [Cm(Form)n](3−n)+ (n = 1, 2) with Cl− are obtained. The log K01(T) (2.11 (20 °C)–2.49 (90 °C)) and log K02(T) values (1.17 (30 °C–2.01 (90 °C)) increase continuously with increasing temperature. The log K0n(T) values are used to derive the standard reaction enthalpies and entropies (ΔrH0m, ΔrS0m) of the respective complexation reactions according to the Van’t Hoff equation. In all cases, positive ΔrH0m and ΔrS0m values are obtained. Thus, both complexation steps are endothermic and entropy-driven.  相似文献   

19.
The Sivrikaya Fe-skarn mineralization is hosted by dolomitic limestone layers of Late Cretaceous volcano-sedimentary unit, comprised of andesite, basalt and their pyroclastites, including, sandstone, shale and dolomitic limestone layers. Intrusion of the Late Cretaceous–Eocene İkizdere Granitoid in the volcano–sedimentary unit resulted in skarn mineralization along the granitoid–dolomitic limestone contact. The ore is associated with exoskarns, and mineralization is characterized by early anhydrous garnet and pyroxene with late hydrous minerals, such as epidote, tremolite, actinolite and chlorite. The ore minerals are mainly magnetite and hematite, with minor amounts of pyrite and chalcopyrite. The composition of garnet and pyroxene in the exoskarn is Adr79.45−99.03Grs0−17.9Prs0.97−2.65 and Di69.1−77.1Hd22.2−29.8Jhn0.6−1.4, respectively, and abundances of magnetite in the ore suggest that the Fe-skarn mineralization formed under relatively oxidized conditions.Homogenization temperatures (Th) of all fluid inclusions and calculated salinity content are in the range of 166 °C–462 °C and 0.35–14.3 wt% NaCl equ., respectively. Well-defined positive correlation between Th and salinity values indicates that meteoric water was involved in the hydrothermal solutions. Eutectic temperatures (Te) between −40.8 °C and −53.6 °C correspond to the presence of CaCl2 in the early stage of fluid inclusions. On the other hand, the Te temperatures of later-stage fluid inclusions, in the range of −38 °C and −21.2 °C, correspond to the presence of MgCl2, FeCl2, KCl and NaCl type salt combinations. None of the fluid inclusions were found to contain separated gas phases in microscopy observations. However, a limited amount of dissolved CH4 was identified in the early stage, high temperature fluid inclusions using Raman spectroscopic studies.Δ18O values in both dolomitic limestone (10.8–12.5‰) and skarn calcite (7.6–9.8‰) were highly depleted compared to the typical δ18O values of marine limestones. Decreases in δ18O values are accepted as an indication of dilution by meteoric water because retrograde brecciation of garnet, magnetite and breccia filling epidote and quartz in volcanic host rocks are an indication of increasing permeability, allowing infiltration of meteoric water. Highly depleted δ13C isotopes (up to −6.5‰) of dolomitic limestone, indicate that organic matter in carbonates had an effect on the decreasing isotopic ratios. The presence of CH4 and CH2 in fluid inclusions can be explained by the thermal degradation of these organic materials.  相似文献   

20.
《Applied Geochemistry》2005,20(1):23-39
Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (Tmi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (Th)  = 325 ± 5 °C. The boiling zone shows Th = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO2. Positive clathrate melting temperatures (fusion) with Th = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO2 (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ18O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ18O is due to the rock–water interaction at relatively high temperatures. δ13C stable isotope data show a magmatic source with a minor meteoric contribution for CO2. The initial isotopic value δ34SRES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ34S (FeS2) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ18O.  相似文献   

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