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1.
Abstract. This study examined the effect of CO2 on NaCl solubility in hydrothermal fluid, with the synthetic fluid inclusion technique. Fluid inclusions of 30–40 wt% NaCl and 5 mol % CO2 were synthesized, and their halite dissolution temperatures, Tm (halite), were measured. The solubilities of NaCl in CO2 -bearing aqueous fluid were obtained at 160–320C under vapor-saturated pressures. The Tm (halite) value in aqueous fluid with 5 mol % CO2 obtained in this study agrees with that of Schmidt et al. (1995), showing that 5 mol % CO2 reduces the solubility of NaCl by about 1 wt%.
Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2-free solution. Therefore, an increase of CO2 content in ore-forming solutions may cause deposition of iron minerals and produce ore deposits. 相似文献
Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2-free solution. Therefore, an increase of CO2 content in ore-forming solutions may cause deposition of iron minerals and produce ore deposits. 相似文献
2.
该文将段振豪及合作者建立的单气体溶解度模型推广到混合气体系,建立了能够计算CO2-CH4-N2-C2H6-H2S混合气
体在电解质水溶液中溶解度的热力学模型。本模型将DMW92方程扩展到上述多组分混合气体系并使用其计算气体组分的
逸度系数,采用Pitzer活度系数模型描述液相并沿用段振豪及合作者以前确定的纯CO2、CH4、C2H6和H2S的溶解度模型参
数,而纯N2的溶解度模型参数由本研究确定。由于本模型不包含依赖混合气体溶解度实验数据确定的参数,因此对混合气
体溶解度的计算是预测性的。通过与实验数据的对比,证实了本模型能够在宽广的温度、压力范围内准确预测
CO2-CH4-N2-C2H6-H2S混合气体在水溶液中的溶解度（对于CO2和CH4的摩尔百分数超过90%的混合气体,本模型适用于
273~523 K和0~2000×105 Pa的温压范围）。本模型的计算表明,相对于纯CO2气相,少量CH4、N2或H2S的加入会降低CO2的溶解度。对于CO2-H2O-NaCl型流体包裹体,少量CH4的加入会增大流体包裹体的均一压力。相关的计算程序可从通讯作者
处获得。 相似文献
3.
《Chemical Geology》2003,193(3-4):257-271
A thermodynamic model for the solubility of carbon dioxide (CO2) in pure water and in aqueous NaCl solutions for temperatures from 273 to 533 K, for pressures from 0 to 2000 bar, and for ionic strength from 0 to 4.3 m is presented. The model is based on a specific particle interaction theory for the liquid phase and a highly accurate equation of state for the vapor phase. With this specific interaction approach, this model is able to predict CO2 solubility in other systems, such as CO2–H2O–CaCl2 and CO2–seawater, without fitting experimental data from these systems. Comparison of the model predictions with experimental data indicates that the model is within or close to experimental uncertainty, which is about 7% in CO2 solubility. 相似文献
4.
Jun Li 《Geochimica et cosmochimica acta》2011,75(15):4351-4376
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
5.
A thermodynamic model is presented to calculate methane solubility, liquid phase density and gas phase composition of the H2O-CH4 and H2O-CH4-NaCl systems from 273 to 523 K (possibly up to 573 K), from 1 to 2000 bar and from 0 to 6 mol kg−1 of NaCl with experimental accuracy. By a more strict theoretical approach and using updated experimental data, this model made substantial improvements over previous models: (1) the accuracy of methane solubility in pure water in the temperature range between 273 and 283 K is increased from about 10% to about 5%, but confirms the accuracy of the Duan model [Duan Z., Moller N., Weare J.H., 1992a. Prediction of methane solubilities in natural waters to high ionic strength from 0 to 250 °C and from 0 to 1600 bar. Geochim. Cosmochim. Acta56, 1451-1460] above 283 K up to 2000 bar; (2) the accuracy of methane solubility in the NaCl aqueous solutions is increased from >12% to about 6% on average from 273 K and 1 bar to 523 K and 2000 bar; (3) this model is able to calculate water content in the gas phase and liquid phase density, which cannot be calculated by previous models; and (4) it covers a wider range of temperature and pressure space. With a simple approach, this model is extended to predict CH4 solubility in other aqueous salt solutions containing Na+, K+, Mg2+, Ca2+, Cl− and , such as seawater and geothermal brines, with excellent accuracy. This model is also able to calculate homogenization pressure of fluid inclusions (CH4-H2O-NaCl) and CH4 solubility in water at gas-liquid-hydrate phase equilibrium. A computer code is developed for this model and can be downloaded from the website: www.geochem-model.org/programs.htm. 相似文献
6.
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
7.
热水溶液地球化学 总被引：8，自引：0，他引：8
概述了热水溶液地球化学的主要研究内容和近年来在实验和理论研究方面的进展，包括高温高压下水的热力学性质、状态方程式、介电常数、电导率和电离平衡；ＮａＣｌ－ＣＯ２－Ｈ２Ｏ体系及其边界体系（ＮａＣｌ－Ｈ２Ｏ和ＣＯ２－Ｈ２Ｏ）的相关系、热力学性质和状态方程式，特别是利用人工流体包裹体技术和分子动力学模拟取得的新成果；高温高压电解质稀水溶液的电导测定；以ＨＫＦ模型为基础，热水溶液中不同物种的标准偏摩尔热力学性质和高温高压有关物理化学参数的估算；热水溶液中的物种形成（热液流体中的矿物溶解度测定、电势测量和谱学研究）；水和热水溶液结构的红外和拉曼谱学研究；水和热水溶液的传输性质（粘度和导热系数）。 相似文献
8.
J. V. WALTHER 《Journal of Metamorphic Geology》1992,10(6):789-797
The equilibrium constant, K a , of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H2 O and CO2 at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H2 O–CO2 mixtures can be obtained and the change in log K a with addition of CO2 in aqueous solutions evaluated. These changes in log K a with addition of CO2 are consistent with measured changes of log K a with addition of Ar in supercritical H2 O–Ar solutions.
Log Ka of KCl and NaCl increase to an increasing extent as the mole fraction of CO2 increases in H2 O–CO2 solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO2 mole fraction increases from 0.0 to 0.35. Such changes in log K a will have dramatic effects on the solubility of minerals in CO2 -rich environments. 相似文献
Log K
9.
10.
《Chemical Geology》1999,153(1-4):187-209
This paper describes a model for barite and celestite solubilities in the Na–K–Ca–Mg–Ba–Sr–Cl–SO4–H2O system to 200°C and to 1 kbar. It is based on Pitzer's ion interaction model for the thermodynamic properties of the aqueous phase and on values of the solubility products of the solids revised in this work. It is shown how barite and celestite solubilities in electrolyte solutions can be accurately predicted as a function of temperature and pressure from previously determined Pitzer's parameters. The equilibrium constant for the BaSO4(aq) ion pair dissociation reaction is calculated from recently reported barite solubility in Na2SO4 solutions from 0 to 80°C. Pressure corrections are evaluated through partial molal volume calculations and are partially validated by comparing model predictions to measured barite and celestite solubilities in pure water to 1 kbar and in NaCl solutions to 500 bars. The model is then used to investigate the tendency of ion pairing of Ca, Sr and Ba with sulfate in seawater. Finally, the activity coefficient of aqueous barium sulfate in seawater is calculated for temperature, pressure and salinity values found in the ocean and compared to published values. 相似文献
11.
Correlations presented by Spycher et al. (2003) to compute the mutual solubilities of CO2 and H2O are extended to include the effect of chloride salts in the aqueous phase. This is accomplished by including, in the original formulation, activity coefficients for aqueous CO2 derived from several literature sources, primarily for NaCl solutions. Best results are obtained when combining the solubility correlations of Spycher et al. (2003) with the activity coefficient formulation of Rumpf et al. (1994) and Duan and Sun (2003), which can be extended to chloride solutions other than NaCl. This approach allows computing mutual solubilities in a noniterative manner with an accuracy typically within experimental uncertainty for solutions up to 6 molal NaCl and 4 molal CaCl2. 相似文献
12.
石英在热水溶液中的溶解度对地球化学和岩石学的研究都极为重要.我们提出一个能够适用于H2O-CO2-NaCl 复杂流体成分,高温高压(0～ 1000℃,0～ 1.5GPa)条件下的石英溶解度计算模型,形式如下:logmSiO2=A(T)+B(T)·logMH2O/V*H2O+C(t)? logxH2O 其中A(T)、B(T)、C(t)均为温度T(K)和t(℃)的多项式.xH2O和V*H2O分别代表流体中水的摩尔分数和有效偏摩尔体积.V*H2O值由公式Vmix=xHOV*H2O+∑xsVs计算得到.其中,Vmix代表流体混合物的摩尔体积,由Mao et al.(2010)的最新模型计算得到,xs和Vs分别代表溶质的摩尔分数和本征体积.具体采用VCO2=29.9cm3/mol、VNaCl=30.8cm3/mol.本模型精度较前人模型有所提高,并且适用深达下地壳的温度-压力-成分环境,如:巴罗式变质带、板块俯冲带等.另外,本模型可被用于建立石英地质温度计,加深人们对于石英脉及有关矿床成因的认识,并且可用来指导实验及工程.本模型的在线计算程序可通过以下网站获得:www.geochem-mode1.org. 相似文献
13.
温度及CO2对方解石、白云石溶解度影响特征分析 总被引：7，自引：1，他引：6
借助水文地球化学模拟软件--PHREEQC对不同Pco2(0～100bar)和不同温度条件下(0～100℃)方解石、白云石在纯水中的溶解度进行模拟和分析.结果表明,Pco2和温度对方解石和白云石溶解度的影响均很大:无Pco2时其溶解度随着温度的升高而逐渐增大,这是因为对于方解石、白云石晶格破坏及溶解高温能提供的能量较大所致;当Pco2较大时(Pco2≥10-3.5bar)其溶解度随温度的升高而降低,原因主要是CO2在高温下形成碳酸的能力较差;当Pco2很小(0 相似文献
14.
The phase behavior of CO2–CH4–H2S–brine systems is of importance for geological storage of greenhouse gases, sour gas disposal and enhanced oil recovery (EOR). In such projects, reservoir simulations play a major role in assisting decision makings, while modeling the phase behavior of the relevant CO2–CH4–H2S–brine system is a key part of the simulation. There is a need for an equation of state (EOS) for such system which is accurate, with wide application range (pressure, temperature and aqueous salinity), computationally efficient and easy for implementation in a reservoir simulator.In this study, an improved cubic EOS model of the system CO2–CH4–H2S–brine is developed based on the modifications of the binary interaction parameters in Peng–Robinson EOS, which is widely implemented in reservoir simulators. Thus the new model is suited for numerical implementation in reservoir simulators.The available experimental data of pure gas brine equilibrium and gas mixture solubility in water/brine are carefully reviewed and compared with the new model. From the comparison, the new model can accurately reproduce (1) the CO2–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 1000 bar and NaCl molality (mole number in 1 kg water, molal is used for short) from 0 to 6 molal, (2) CH4–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 2000 bar and NaCl molality from 0 to 6 molal, (3) H2S–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 200 bar and NaCl molality from 0 to 6 molal, and (4) has good accuracy for gas mixture solubility in brine. 相似文献
15.
L. Ya. Aranovich I. V. Zakirov N. G. Sretenskaya T. V. Gerya 《Geochemistry International》2010,48(5):446-455
New experimental data on the solubility of NaCl in gaseous CO2 were obtained at pressures (P) of 30–70 MPa and temperatures of 623 and 673 K on experimental equipment making possible to sample a portion of the gas
in the course of the experiment. The new measures have demonstrated that the NaCl solubility increases with increasing temperature
(T) and pressure and is approximately four to five orders of magnitude higher than the saturated vapor pressure of NaCl at the
corresponding temperature. The paper also reports newly obtained experimental data on the equilibrium conditions of the reaction
of talc decomposition into enstatite and quartz at a variable H2O/NaCl ratio in the fluid. The results of the experiments validate the empirical equations previously suggested for H2O and NaCl activities in concentrated aqueous salt solutions that can be used in describing silica-saturated fluids at high
T-P parameters. A new empirical equation is suggested for the Gibbs free mixing energy in the H2O-CO2-NaCl ternary system, with the parameters of the equation calibrated against experimental data on phase equilibria in marginal
binary systems and on the location of the boundary of the region of homogeneous three-component fluid according to data on
synthetic fluid inclusions in quartz. 相似文献
16.
Robert O. Fournier Robert J. Rosenbauer James L. Bischoff 《Geochimica et cosmochimica acta》1982,46(10):1975-1978
The solubility of quartz in 2, 3, and 4 molal NaCl was measured at 350°C and pressures ranging from 180 to 500 bars. The molal solubility in each of the salt solutions is greater than that in pure water throughout the measured pressure range, with the ratio of solubility in NaCl solution to solubility in pure water decreasing as pressure is increased. The measured solubilities are significantly higher than solubilities calculated using a simple model in which the water activity in NaCl solutions decreases either in proportion to decreasing vapor pressure of the solution as salinity is increased or in proportion to decreasing mole fraction of water in the solvent. 相似文献
17.
An equation of state (EOS) based on thermodynamic perturbation theory is presented for the NaCl-H2O-CH4 system. This equation consistently reproduces PvTX properties and phase equilibria with an accuracy close to that of data in the temperature, pressure and concentration ranges from 648 K to 873 K, 0 to 2500 bar and up to 2.37 mol % NaCl. Good agreement with recent ternary immiscibility data from 673 K to 873 K suggests that the EOS may provide accurate predictions for NaCl concentrations as high as 40 mol %. We could not find any experimental data above 873 K that can be used to validate the predictions of the EOS inside the ternary. However, parameters for the mixed ternary system were established from parameters evaluated for pure and binary systems and accurate combination rules. Therefore, predictions in the ternary should be reliable to the high temperatures and pressures where the EOS for the lower order systems are valid (about 1300 K and 5000 bar). Using the same combining approach, an EOS for the quaternary NaCl-H2O-CO2-CH4 is constructed on the basis of parameters from our earlier model for the NaCl-H2O-CO2 system and the present NaCl-H2O-CH4 model. This suggests that predictions of the quaternary EOS are reliable also to about 1300 K and 5000 bar. 相似文献
18.
Robert O. Fournier 《Geochimica et cosmochimica acta》1983,47(3):579-586
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
19.
Experimental Study of Gold and Platinum Solubility in a Complex Fluid under Hydrothermal Conditions 总被引：2，自引：0，他引：2
Abstract: The solubility of gold was studied in water and aqueous NaCl (1– 5 m) solutions under oxygen and sulfur buffered conditions between 300–500C at a constant pressure 1 kb. Two buffer assemblages HMP and PPM were used. Analysis of the scatter in measured values in log mAu–mNaCl–T frame fixed linear dependence between log mAu and T at any studied iso‐pleth (mNaCl) in the form of log mAu = a. T(C) + b. Coefficients of the equation were calculated for water and NaCl (1, 3, 5 m) solutions. The maximum solubility characterizes the NaCl‐free system in the presence of HMP. In the case, Au solubility increases from (log mAu) –6. 72 to –5. 04 at 300 and 500C, respectively. In the presence of PPM, maximum of Au solubility was obtained for the 5 mNaCl solution. In a similar manner solubility rises from –6. 54 to –5. 77 at 300 and 500C, accordingly. In studied fO2/fS2 area the behavior of Au solubility testified that: (i) – a composite interaction between chloride and hydrosulfide speciation of gold affects its total solubility; (ii) – in addition of NaCl up to about 1. 5 m the solubility decreases, more pronounced in the presence of HMP; (iii) – the contribution of chloride in total Au solubility is more for PPM despite of lower fO2value, than for HMP. The solubility of platinum was studied in the Pt–Cl–S–H2O system between 300 and 500C, 1 kb. PPM solid buffer controlled oxidation state, pH and sulfur activity of solutions (H2O, 1 mNaCl and 0. 1 mHCl). Under the conditions, PtS precipitated from the solutions with increasing temperature and acidity. The PtS solubility in the 0. 1 mHCl solutions lowers slightly in the range of 300–500C from –5. 30 to –5. 60 (in log mPt) that is typical to the hydrosulfide species. It was deduced that reducing media, regulated by the PPM assemblage, suppress activity of chloride species of Pt. More oxidizing conditions were modeled in runs using mixtures of Mn(II), Mn(III) and Mn(IV) oxides to buffer the aqueous‐chloride solutions between 300 and 500C, 1 kb. It was found that MnO tends to oxidize at T below 400C forming intermediate Mn‐hydroxides (β–MnOOH, Mn (OH)2 and Mn2(OH)3Cl). These phases are metastable and transfer to Mn3O4 with increasing duration. Generation of the Mn‐hydroxides leads to a change of physical‐chemical parameters of the solutions, such as water activity, pH and Eh. The last results in abrupt increase in the noble metals dissolution. At stable existence of only Mn3O4, the solubility of both Pt and Au lowers to equilibrium values. Essential catalysis effect of Pt on intensity and rate of Mn(II) oxidation was found. The dominant role of chloride of Pt and Au was defined under most oxidized conditions, specified by Mn2O3–MnO2 buffer. So at 400C, dissolved Au (log mAu) increases from –4. 40 in water to –1. 00 in 0. 1 mHCl, and ones of Pt (log mPt) from –4. 80 to –2. 90 accordingly. Thus, mixing of hydrosulfide and chloride solutions, as well as transformation of the systems to the stable state act upon total solubility of the noble metals. 相似文献
20.
Simulation results of the equilibrium state of systems water-carbonaceous chondrite material, water-primary mantle material,
water-ultramafic rock material, and water-mafic rock material open with respect to carbon dioxide and methane at 25°C, 1 bar
indicate that highly alkaline reduced aqueous solutions with K/Na > 1 can be formed only if water is in equilibrium with compositions
close to those of continental crust and primitive mantle. Yu.V. Natochin’s hypothesis that the living cell can be formed only
in an aqueous environment with K/Na > 1 leads to the conclusion that terrestrial life could arise and further evolve on the
Earth during the differentiation of primary chondritic material into the Earth’s core and mantle (during the first few million
years of the planet’s lifetime) in an alkaline (pH 9–10) reduced (Eh = −400–500 mV) aqueous solution at a temperature of 50–60°C,
in equilibrium with an N2-bearing atmosphere, which also contained CH4 (partial pressure from 10−2 to 10−8 bar), CO2 (partial pressure from 10−5 to 10−8 bar), NH3, H2, H2S, CO, and other gases. 相似文献