四元体系Na~ ∥Cl~-,CO_3~(2-),B_4O_7~(2-)-H_2O 273K介稳相平衡研究

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。     

四元体系Na+//Cl-,CO32-,B4O72--H2O273 K介稳相平衡研究

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.     

四元体系Na＋／／Cl-，CO3^2-，B4O7^2——H2O273K介稳相平衡研究

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。     

含钾水盐体系介稳相关系研究

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。     

交互四元体系Li+,Mg2+//SO2-4,B4O2-7-H2O 288 K时相平衡研究

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.     

Li+/Cl-,CO32-,B4O72--H2O四元体系 298 K介稳相平衡的研究

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。     

交互四元体系Li~+,Mg~(2+)//SO_4~(2-),B_4O_7~(2-)-H_2O 288K时相平衡研究

采用等温溶解平衡法研究了288K时Li+,Mg2+//SO42-,B4O72--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+//SO42-,B4O27--H2O288K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。     

三元体系K+,Mg2+∥B4O72--H2O 348K稳定相平衡研究

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。     

交互四元体系Li+, Mg2+//SO2-4, B4O2-7H2O 288 K

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。     

西藏扎布耶盐湖秋季卤水25℃等温蒸发研究

本文对西藏扎布耶盐湖秋季卤水进行了25℃等温蒸发试验,并参考Na 、K //CO32-、SO24-、Cl-—H2O五元水盐体系介稳相图和Li 、Na //Cl-、SO24-、CO32-、B4O27-—H2O六元(赝)体系(25℃,对NaCl及Li2CO3饱和)溶解度相图,研究了该季卤水25℃等温蒸发过程中盐类结晶路线和析出规律,为该盐湖卤水的综合开发利用提供重要的依据。     

高锰酸钾—过硫酸钾消化氢化物发生-原子荧光光谱法测定水中汞

为了寻找一种灵敏准确测定有机污染物水样中微量汞的方法,通过高锰酸钾—过硫酸钾消化氢化物发生原子荧光光谱法测定,发现汞含量在0.100 0～1.000 0ug/L范围内呈线形关系,相关系数为0.999 6,检出线为0.006 6ug/L,相对标准偏差在0.7％ ～ 2.3％,样品加标回收率在93.1％～102.9％之间.该方法检出线低,灵敏度高,精密度好,准确度好,适合于有机物较多体系水样中汞的测定.     

Phase Equilibria in the Ternary Systems KBr–K2B4O7–H2O and KCl–K2B4O7–H2O at 373 K

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.     

Heat capacity and phase equilibria of wadeite-type K2Si4O9

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.     

298K时三元体系K^＋／CO3^2—,B4O7^2——H2O和Li^＋／CO3^2—,B4O7^2——H2O相关系

研究了二个三元体系Ｌｉ＋／ＣＯ２－３,Ｂ４Ｏ２－７Ｈ２Ｏ（１）和Ｋ＋／ＣＯ２－３,Ｂ４Ｏ２－７Ｈ２０（２）２９８Ｋ时的相平衡关系和平衡液相的物化性质（密度、折光密、粘度、电导率、ｐＨ值）。研究表明：这二个三元体系均属简单共饱型,无复盐或固溶体形成。体系（１）的两段溶解度曲线对应于无水Ｌｉ２ＣＯ３和Ｌｉ２Ｂ４Ｏ７·３Ｈ２Ｏ结晶区,体系（２）的两段溶解度曲线对应于Ｋ２ＣＯ３·３／２Ｈ２Ｏ和Ｋ２Ｂ４Ｏ７·４Ｈ２Ｏ结晶区。     

Die Kristallstruktur des Polyhalits,K2Ca2Mg[SO4]4.2H2O

Zusammenfassung Die Kristallstruktur des triklin-pinakoidalen Polyhalits, K₂Ca₂Mg[SO₄]₄. 2H₂O wurde aus photographischen Daten mit Hilfe der 3-dimensionalen Patterson-Funktion ermittelt. Die Verfeinerung mit der Methode der kleinsten Quadrate führte mit individuellen, isotropen Temperaturfaktoren für die beobachteten Reflexe auf R=0,09.In der Atomanordnung sind Sulfatgruppen durch oktaedrisch koordinierte Mg²⁺, 8-koordinierte Ca²⁺ und 11-koordinierte K⁺ miteinander verknüpft. Die H₂O-Moleküle sind jeweils an ein Mg²⁺ und ein K⁺ koordiniert. Die wahrscheinliche Lage der H-Atome wird aus den interatomaren Abständen erschlossen.

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The crystal structure of polyhalite, K₂Ca₂Mg[SO₄]₄.2H₂O

Summary The crystal structure of the triclinic-pinacoidal mineral polyhalite, K₂Ca₂Mg[SO₄].2H₂O, is derived from photographic data by means of the 3-dimensional Patterson-function. The least squares-refinement resulted for the observed reflections and individual, isotropic temperature factors in R=0.09.In the atomic arrangement the sulfate groups are linked by octahedrally coordinated Mg²⁺, 8-coordinated Ca²⁺, and 11-coordinated K⁺. Each H₂O-molecule is coordinated to one Mg²⁺ and one K⁺. The probable positions of the H-atoms are derived from the interatomic distances.

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Mit 2 Abbildungen     

Elasticity of single-crystal MgAl2O4 spinel up to 1273 K by Brillouin spectroscopy

The adiabatic single-crystal elastic constants, C _ij , of stoichiometric magnesium aluminate spinel (MgAl₂O₄) have been measured up to 1273 K by highresolution Brillouin spectroscopy, using a 6-pass tandem Fabry-Pérot interferometer and an argon ion laser (514.5 nm). Two platelet samples were employed for probing the acoustic phonons along [100] and [110] directions by platelet and backscattering geometries. The measured temperature dependences of the elastic moduli show a distinct anomaly at 923 K in the shear modulus C _s = (C₁₁-C₁₂)/2 (along [110] direction) and the longitudinal modulus C₁₁ (along [100] direction). This anomaly is consistent with the order-disorder phase transition, resulting from the atomic exchange between Mg at the tetrahedral site and Al at the octahedral site, which has been well documented recently (Peterson et al. 1991; Millard et al. 1992) by neutron powder diffraction and ²⁷Al magic-angle spinning NMR. The values of the temperature derivatives of v _p , v _s , and K _s , in the temperature range 300–923 K, calculated by the Voigt-Reuss-Hill approximation are -0.40ms^?1 K^?1, -0.26ms^?1 K^?1, and -1.89 x 10^?2GPaK^?1.     

Heat capacity of liquid silicates: new measurements on NaAlSi3O8 and K2Si4O9

Drop calorimetric measurements of H_T-H₂₇₃ are reported for glassy and liquid albite and potassium tetrasilicate for the temperature interval 600–1500 K. Analysis of these observations as well as data for 13 other stable and supercooled silicate liquids suggests strongly that the isobaric heat capacities of stable and supercooled liquids are equal and thus temperature independent. Available evidence indicates that the isochoric heat capacities of liquid alkali silicates are also temperature independent within present experimental uncertainties.     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.