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1.
采用等温溶解平衡法研究了288K时Li+, Mg2+//SO2-4, B4O2-7- H2O四元体系的固液相平衡关系,测定了该四元体系在288K时平衡液相的溶解度和密度.依据实验测定的平衡溶解度数据及对应的平衡固相,绘制了该四元体系的平衡相图及密度组成图.研究结果表明:交互四元体系Li+, Mg2+//SO2-4, B4O2-7- H2O 288K时平衡相图中有2个共饱点,5条单变量曲线,4个结晶区对应的平衡固相分别为Li2B4O7·3H2O,Li2SO4·H2O,MgB4O7·9H2O和MgSO4·7H2O.  相似文献   

2.
桑世华  李明  李恒  孙明亮 《地质学报》2010,84(11):1704-1707
采用等温溶解平衡法研究了288K时Li+, Mg2+//SO2-4, B4O2-7- H2O四元体系的固液相平衡关系,测定了该四元体系在288K时平衡液相的溶解度和密度。依据实验测定的平衡溶解度数据及对应的平衡固相,绘制了该四元体系的平衡相图及密度组成图。研究结果表明:交互四元体系Li+, Mg2+//SO2-4, B4O2-7- H2O 288K时平衡相图中有2个共饱点,5条单变量曲线,4个结晶区对应的平衡固相分别为Li2B4O7·3H2O,Li2SO4·H2O,MgB4O7·9H2O和MgSO4·7H2O。  相似文献   

3.
彭芸  曾英  于旭东  张龙钦  吴祎  冯珊 《地质学报》2010,84(11):1697-1703
针对西藏扎布耶盐湖卤水组成,采用等温蒸发法分别研究了含钾四元体系Na+,K+//Cl-,B4O27--H2O308.15K、五元体系K+//Cl-,CO23-,SO42-,B4O72--H2O273.15K下的介稳相关系。分别测定了上述体系308.15K、273.15K时介稳平衡液相组成及密度、pH值。根据实验数据绘制了相应的介稳相图、水图。结果表明,本文研究的两个体系均为简单共饱型,无复盐和固溶体生成。其中,四元体系介稳相图由2个共饱点,5条单变量曲线,4个结晶区组成。平衡固相分别为Na2B4O7.10H2O、K2B4O7.4H2O、NaCl和KCl。对比四元体系308.15K和273.15K下的介稳相图发现,平衡固相盐的种类及结晶形式均没有发生变化,但结晶区大小产生变化:在308.15K下,Na2B4O7.10H2O结晶区变小,K2B4O7.4H2O结晶区变大。五元体系投影图中有1个共饱点、3条单变量曲线和3个结晶相区。结晶相区分别为K2CO3.3/2H2O、K2SO4和KCl。K2CO3.3/2H2O结晶区面积最小,K2SO4结晶区面积最大。K2CO3对KCl有较强的盐析作用。  相似文献   

4.
采用等温蒸发法研究简单四元体系Na ∥Cl-,CO32-,B4O72--H2O273K时的介稳相平衡,并测定该体系273K平衡液相中各组分的溶解度及密度,该体系的介稳相图和密度组成图显示:该四元体系在273K时的相图由3条溶解度单变量线、3个结晶区及1个共饱和点组成。体系属简单共饱型,无复盐或固溶体形成,3个结晶区分别对应单盐Na2CO3·10H2O,NaCl和Na2B4O7·10H2O。共饱点E处于Na2CO3·10H2O,NaCl及Na2B4O7·10H2O3盐共饱和,所对应的平衡液相组成为w(Na2CO3)=6.81%,w(NaCl)=21.69%,w(Na2B4O7)=0.65%,w(H2O)=70.85%。研究体系在273K下,Na2CO3·10H2O是碳酸钠盐的唯一析出形式,且硼酸钠对碳酸钠有盐析作用。  相似文献   

5.
采用等温溶解平衡法开展了三元体系K+,Mg2+∥B4O72--H2O 348K的稳定相平衡研究,获得溶解度数据及平衡液相的密度,折光率,pH值。根据溶解度数据绘制了三元体系稳定相图。该三元体系在348K时的稳定相图含有一个共饱点E、两条单变量曲线AE,BE和两个结晶相区MgB4O7.9H2O(AECA)和K2B4O7·4H2O(BEDB)。共饱点的平衡固相组成为MgB4O7·9H2O和K2B4O7·4H2O,对应的平衡液相组成为w(K2B4O7)=42.28%、w(MgB4O7)=8.11%。研究结果表明,该三元体系属于简单共饱和型,无复盐和固溶体形成。K2B4O7·4H2O和MgB4O7·9H2O互相存在盐溶作用,使得这两种盐的溶解度明显增大。平衡液相的密度、折光率均随溶液中K2B4O7质量分数的增大而增大。  相似文献   

6.
采用等温蒸发法研究简单四元体系Na+//CI-,CO32-,B4O72---H2O 273 K时的介稳相平衡,并测定该体系273 K平衡液相中各组分的溶解度及密度,该体系的介稳相图和密度组成图显示:该四元体系在273 K时的相图由3条溶解度单变量线、3个结晶区及1个共饱和点组成.体系属简单共饱型,无复盐或固溶体形成,3个结晶区分别对应单盐Na2CO3?10H2O,NaCI和Na2B4O7?10H2O.共饱点E处于Na2CO3?10H2O,NaCI及Na2B4O,?10H2O3盐共饱和,所对应的平衡液相组成为ω(Na2CO3)=6.81%,ω(NaCl)=21.69%,ω(Na2B4O7)=0.65%.ω(H20)=70.85%.研究体系在273 K下,Na2CO3?10H2O是碳酸钠盐的唯一析出形式,且硼酸钠对碳酸钠有盐析作用.  相似文献   

7.
西藏扎北盐湖秋季卤水(硫酸钠亚型)5℃等温蒸发实验研究   总被引:2,自引:0,他引:2  
西藏扎北盐湖硫酸钠亚型卤水中富含元素Li、B、K和微量元素Rb、Cs等.为了更好地了解卤水在自然条件下的蒸发结晶规律,需对相应卤水进行低温室内等温蒸发实验研究.本文对该盐湖卤水进行了5℃等温蒸发试验,并利用Na+、K+、Mg2+//Cl-、SO42--H2O五元水盐体系0℃相图,构筑了从干基立体图Na2SO4角顶的放射...  相似文献   

8.
四元体系K_2SO_4-K_2B_4O_7-K_2CO_3-H_2O 273K时介稳相平衡研究   总被引:1,自引:1,他引:0  
采用等温蒸发法研究K2SO4-K2B4O7-K2CO3-H2O四元体系在低温273K时的介稳固液相平衡关系,测定了介稳平衡液相的溶解度和密度。研究发现,该四元体系273K时的介稳平衡相图有3个固相结晶相区分别为K2SO4,K2B4O7.4H2O和K2CO3.3/2H2O;3条单变量曲线E1E,E2E和E3E;一个共饱点E,在共饱点E处的液相中各盐的溶解度分别为K2CO3(43.46%),K2SO4(2.52%)和K2B4O7(3.10%);研究结果表明K2CO3对K2B4O7和K2SO4有强烈的盐析作用。实验证明在富含硼钾的扎布耶盐湖卤水中,低温平衡条件下硫酸钾和硼酸钾极易从溶液中结晶析出,而碳酸钾则由于溶解度大,介稳性强,即使在低温条件下也难以从溶液中析出。  相似文献   

9.
采用等温蒸发法研究简单四元体系Na+//Cl-,CO3^2-,B4O7^2--H2O273K时的介稳相平衡,并测定该体系273K平衡液相中各组分的溶解度及密度,该体系的介稳相图和密度组成图显示:该四元体系在273K时的相图由3条溶解度单变量线、3个结晶区及1个共饱和点组成。体系属简单共饱型,无复盐或固溶体形成,3个结晶区分别对应单盐Na2CO3·10H2O,NaCl和Na2B4O7·10H2O。共饱点E处于Na2CO3·10H2O,NaCl及NaB4O7·10H2O3盐共饱和,所对应的平衡液相组成为w(Na2CO3)=6.81%,w(NaCl)=21.69%,w(Na2B4O7)=0.65%,w(H2O)=70.85%。研究体系在273K下,Na2CO3·10H2O是碳酸钠盐的唯一析出形式,且硼酸钠对碳酸钠有盐析作用。  相似文献   

10.
根据对西藏扎布耶盐湖四元子体系L i /C l-,CO32-,B4O72--H2O 298 K介稳平衡实验数据,绘制出的介稳平衡相图及物化性质(密度、pH值、电导率、折光率)组成图的研究结果表明:该四元体系属简单共饱型,无复盐或固溶体形成;其溶解度等温图含有一个共饱点、3条单变量曲线和3个结晶相区;3个结晶相区分别对应为L i2B4O7.3H2O,L i2CO3和L iC lH2O。  相似文献   

11.
Based on the requirement of the new technology for producing potassium sulfate and N-Mg compound fertilizer,boussingaultite,by the reaction of the mineral shoenite from Kunteyi Salt Lake,Qinghai province,and the industrial byproduct ammonium sulfate,the solubilities of the quaternary system (NH_4)_2SO_4-Mg SO_4-K_2SO_4-H_2O at 25.0oC in the isothermal evaporation and crystallization process were measured using the isothermal evaporation method,and the corresponding phase diagrams were plotted.According to the diagram,this system contains six saturation points and six solid phase fields of crystallization,which correspond to (K_(1-m),(NH_4)_m)_2SO_4,(NH_4)_2SO_4·Mg SO_4·6H_2O,K_2SO_4·Mg SO_4·6H_2O,Mg SO_4·6H_2O,(K_(1-n),(NH_4)_n)_2SO_4·Mg SO_4·6H_2O and Mg SO_4·7H_2O,respectively.By analyzing and calculating the isothermal evaporation and dissolution phase diagram of this quaternary system at 25.0oC,K_2SO_4 and (NH_4)_2SO_4·Mg SO_4·6H_2O can be separated via K_2SO_4·Mg SO_4·6H_2O and (NH_4)_2SO_4 as raw materials.Theoretical calculations about the proposed process were carried out and verified by experiment,which indicated that the yield of potassium sulfate was improved and the magnesium resources were fully utilized.  相似文献   

12.
彭芸  曾英  周琳  李元波 《矿物岩石》2005,25(2):118-120
采用等温平衡溶解平衡法测定了三元体系NaVO3-H2NCONH2-H2O 298K下的溶解度及平衡液相物化性质(密度、电导率、pH值),绘制出了相应的溶解度等温图和物化性质一组成图。此三元体系等温溶解度图属简单共饱型,未产生新的复盐和固溶体。2个结晶区分别对应为盐NaVO3和H2NCONH2,无变量点平衡液相组成为:ω(NaVO3)3.99%,ω(H2NCONH2)40.17%,对应的平衡固相盐为NaVO3和H2NCONH2。  相似文献   

13.
We report new measurements of equilibrium relative humidities for stable and metastable hydration-dehydration equilibria involving several magnesium sulfates in the MgSO4·nH2O series. We also report a comprehensive thermodynamic treatment of the system including solution properties and experimental data from the published literature, i.e. solubilities, heat capacities and additional decomposition humidities. While for some magnesium sulfate hydrates solubility data in the binary system MgSO4-H2O are sparse, there is a reasonable database of solubility measurements of these hydrates in the ternary MgCl2-MgSO4-H2O and the quaternary reciprocal Na+-Mg2+-Cl-SO42-H2O systems. To make these data suitable for the determination of solubility products, we parameterized a Pitzer ion interaction model for the calculation of activity coefficients and water activities in mixed solutions of these systems and report the ion interaction parameters for the Na+-Mg2+-Cl-SO42-H2O system. The model predicted solubilities in the reciprocal system are in very good agreement with experimental data. Using all available experimental data and the solution model an updated phase diagram of the MgSO4-H2O system covering the whole temperature range from about 170 to 473 K is established. This treatment includes MgSO4·H2O (kieserite), MgSO4·4H2O (starkeyite), MgSO4·5H2O (pentahydrite), MgSO4·6H2O (hexahydrite), MgSO4·7H2O (epsomite) and MgSO4·11H2O (meridianiite). It is shown that only kieserite, hexahydrite, epsomite and meridianiite show fields of stable existence while starkeyite and pentahydrite are always metastable. Due to sluggish kinetics of kieserite formation, however, there is a rather extended field of metastable existence of starkeyite which makes this solid a major product in dehydration reactions. The model predicted behavior of the magnesium sulfates is in excellent agreement with observations reported in the literature under terrestrial temperature and relative humidity conditions. We also discuss the implications of the new phase diagram for sulfates on Mars.  相似文献   

14.
This paper presents the results of experiments on the physicochemical conditions for the formation of picromerite in the five-component brine system K-Na-Mg-Cl-SO4-H2O and the process of isothermal evaporation-crystallization of picromerite from brines. The metastable phase fields of picromerite at 15.10 and 5°C and its stable equilibrium phase field at -5°C have been established. In addition. the phase equilibrium relationships have also been established for other salt minerals. The lower limit of formation temperature of picromerite has been deduced on the basis of experimental results. The isothermal evaporation crystallization path of the invariant assemblage (point D) of picromerite, epsomite. sylvite and halite at 25, 15, 10 and 5°C has been revealed. Furthermore, some controversial problems are approached concerning the 25°C “solar” diagram and the 25°C metastable phase diagram of this system.  相似文献   

15.
The low-temperature heat capacity (C p) of Si-wadeite (K2Si4O9) synthesized with a piston cylinder device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system. The entropy of Si-wadeite at standard temperature and pressure calculated from the measured heat capacity data is 253.8 ± 0.6 J mol−1 K−1, which is considerably larger than some of the previous estimated values. The calculated phase transition boundaries in the system K2O–Al2O3–SiO2 are generally consistent with previous experimental results. Together with our calculated phase boundaries, seven multi-anvil experiments at 1,400 K and 6.0–7.7 GPa suggest that no equilibrium stability field of kalsilite + coesite intervenes between the stability field of sanidine and that of coesite + kyanite + Si-wadeite, in contrast to previous predictions. First-order approximations were undertaken to calculate the phase diagram in the system K2Si4O9 at lower pressure and temperature. Large discrepancies were shown between the calculated diagram compared with previously published versions, suggesting that further experimental or/and calorimetric work is needed to better constrain the low-pressure phase relations of the K2Si4O9 polymorphs. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

16.
Phase relations in the 6-component system Na-K-Mg-Ca-SO4-Cl-H2O have been calculated for halite saturation, 25°C and 1 atm pressure. Using a Jänecke projection with the apices Ca-Mg-K2-SO4, 27 stable invariant points have been located which are connected by 69 univariant curves. Polyhalite is the only quaternary solid, but anhydrite occupies the bulk of the interior tetrahedral space. Consequently, 24 of the invariant points lie very close to the Ca-free base, Mg-K2-SO4. The remaining three points involve tachyhydrite and/or antarcticite. All points but two (20,27) represent peritectic conditions. Metastable equilibria have been calculated for the Ca-free system and yield relations corresponding to the solar diagram.Seawater lies in the subspace anhydrite-halite-carnallite-kieserite-bischofite (point 20) and its evaporation has been discussed for conditions of equilibrium and fractional crystallization. After gypsum is converted to anhydrite, halite precipitates. The next phase, under equilibrium conditions, is glauberite, crystallizing at the expense of anhydrite. Continued evaporation leads to glauberite resorption and eventual replacement by polyhalite. Then follow the magnesium sulfates epsomite, hexahydrite and kieserite, which are joined by carnallite. Polyhalite is replaced by anhydrite and bischoflte is added at the final invariant condition. Kainite does not appear as a primary phase under equilibrium conditions, but it is an important phase during fractional crystallization, where Ca-phases are not allowed to back-react with the brine.Up to the appearance of glauberite, thickness ratios of halite: anhydrite couplets (equilibrium or fractionation) can vary from 0 to 7, the relative amount of halite increasing with more intense evaporation. During evaporation, the activity of H2O decreases from 0.98 (seawater) to 0.34 (final invariant brine). The data provided can be used to evaluate the effects of mineral precipitation, evaporation and brine mixing for a wide variety of natural brines.  相似文献   

17.
This work reports the application of thermodynamic models, including equations of state, to binary (salt-free) CH4-H2O fluid inclusions. A general method is presented to calculate the compositions of CH4-H2O inclusions using the phase volume fractions and dissolution temperatures of CH4 hydrate. To calculate the homogenization pressures and isolines of the CH4-H2O inclusions, an improved activity-fugacity model is developed to predict the vapor-liquid phase equilibrium. The phase equilibrium model can predict methane solubility in the liquid phase and water content in the vapor phase from 273 to 623 K and from 1 to 1000 bar (up to 2000 bar for the liquid phase), within or close to experimental uncertainties. Compared to reliable experimental phase equilibrium data, the average deviation of the water content in the vapor phase and methane solubility in the liquid phase is 4.29% and 3.63%, respectively. In the near-critical region, the predicted composition deviations increase to over 10%. The vapor-liquid phase equilibrium model together with the updated volumetric model of homogenous (single-phase) CH4-H2O fluid mixtures (Mao S., Duan Z., Hu J. and Zhang D. (2010) A model for single-phase PVTx properties of CO2-CH4-C2H6-N2-H2O-NaCl fluid mixtures from 273 to 1273 K and from 1 to 5000 bar. Chem. Geol.275, 148-160), is applied to calculate the isolines, homogenization pressures, homogenization volumes, and isochores at specified homogenization temperatures and compositions. Online calculation is on the website: http://www.geochem-model.org/.  相似文献   

18.
According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide (KBr) and potassium tetraborate tetrahydrate (K2B4O7·4H2O),and those in the ternary system KCl-K2B4O7-H2O are potassium chloride (KCl) and potassium tetraborate tetrahydrate (K2B4O7·4H2O).Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller.  相似文献   

19.
Liquidus phase equilibria have been determined in the system CaAl2Si2O8-NaAlSi3O8-KAlSi3O8-NaAlSiO4-KAlSiO4 (An-Ab-Or-Ne-Ks) at a pressure of water of 5 kb, for low anorthite contents. The main effects of increasing anorthite content on phase relationships in the system Ab-Or-Ne-Ks include the expansion of the plagioclase stability field towards the potassium-rich part of the system, and an accompanying contraction of the alkali feldspar, leucite, nepheline and kalsilite stability fields; and an increase in liquidus temperatures throughout most of the compositional range. Two quaternary invariant points have been identified in the system, one a reaction point between the fields of alkali feldspar, plagioclase, nepheline and kalsilite at approximately An4, and the other probably a quaternary eutectic between the fields of alkali feldspar, plagioclase, leucite and kalsilite at approximately An6. A shallow minimum trough in liquidus temperatures occurs on the two-feldspar surface, and this would be expected to control the paths of liquids cooling under equilibrium conditions. Phase relationships in this quaternary system have been applied to the interpretation of the histories of the potassium-rich rocks of the Roman Volcanic Region, Italy. Differentiation of the phonolitic series in this region may have occurred by two-feldspar fractionation.  相似文献   

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