K2B4O7-Na2B4O7-Li2B4O7-H2O四元体系273 K介稳相平衡

采用等温蒸发平衡法研究了四元体系K2B4O7-Na2B4O7-Li2B4O7-H2O在273 K时的介稳相平衡及平衡液相的密度. 研究发现该四元体系为简单共饱和型, 无复盐及固溶体形成, 根据溶解度数据绘制了相图, 相图中有一个共饱点E, 三条单变度曲线E3E, E2E, E1E; 三个平衡固相分别为K2B4O7·4H2O、Na2B4O7·10H2O 和LiBO2·8H2O. 并简要讨论了实验结果.     

Mg^2＋，K^＋//Cl^-，B4O7^2——H2O四元体系288K固液相平衡

采用等温溶解平衡法研究了288K时Mg^2＋,K^＋//Cl^-,B4O7^2--H2O四元体系的相平衡关系,测定该体系在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以及其密度一组成图．研究结果表明,四元体系Mg^2＋,K^＋//Cl^-,B4O7^2--H2O288K时的固液相平衡实验中,有复盐KCl·MgCl2·6H2O生成,平衡相图中有3个共饱点,7条单变量曲线,5个结晶区,对应的平衡固相分别为MgB4O7·9H2O,K2B4O7·4H2O,KCl,MgCl2·6H2O,KCl·MgCl2·6H2O．简要讨论了实验结果．     

Li~ ,Na~ //SO_4~(2-),B_4O_7~(2-)-H_2O交互四元体系288K介稳相平衡研究

采用等温蒸发法研究了四元体系Li ,Na //SO42-,B4O72--H2O288K介稳相平衡及平衡液相物化性质(密度、电导率、折光率、粘度和pH值),测定了该四元体系288K条件下介稳平衡溶液溶解度及物化性质。根据实验数据绘制了相应的介稳相图及物化性质组成图。研究发现:该体系介稳平衡中有复盐Li2SO·4Na2SO4形成。其介稳相图中有3个共饱和点,7条单变量曲线,平衡固相为:Li2SO·4H2O,Na2SO4,Li2SO·4Na2SO4,Li2B4O7·3H2O,Na2B4O·710H2O。复盐Li2SO·4Na2SO4和一水硫酸锂(Li2SO·4H2O)有较小的结晶区,而Li2B4O7·3H2O和Na2B4O7·10H2O有较大的结晶区;该四元体系介稳平衡条件下未发现Na2SO·410H2O的结晶区。     

Na+, K+//Cl-, B4O2-7-H2O四元体系273 K介稳相平衡

采用等温蒸发法研究了四元体系Na+, K+//Cl-, B4O2-7-H2O 273 K时的介稳相平衡与相图. 测定了该体系273 K平衡液相中各组分的溶解度及平衡液相的密度; 绘制了该体系的介稳相图. 该四元体系273 K相图由5条溶解度单变量线、4个结晶区及2个共饱和点组成. 体系无复盐或固溶体形成. 四个结晶区分别对应单盐NaCl、KCl、K2B4O7·4H2O 和Na2B4O7·10H2O. 共饱点E1处KCl、NaCl及Na2B4O7·10H2O三盐共饱和,所对应的平衡液相组成为w(Cl-)=29.15%, w(B4O2-7)=0.64%, w(K+)=5.97%, w(Na+)=15.55%; 共饱和点E2处盐KCl、Na2B4O7·10H2O和K2B4O7·4H2O的三盐共饱和, 所对应的平衡液相组成为w(Cl-)=22.84%, w(B4O2-7)=10.98%, w(K+)=28.01%, w(Na+)=1.53%. 同体系298 K时的稳定相图相比, 273 K时硼酸钠的结晶区变大, 而硼酸钾、氯化钠结晶区变小.     

Mg2+, K+//Cl-, B4O2-7-H2O四元体系288 K固液相平衡

采用等温溶解平衡法研究了288 K时Mg2+, K+//Cl-, B4O2-7-H2O四元体系的相平衡关系, 测定该体系在288 K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以及其密度-组成图. 研究结果表明, 四元体系Mg2+, K+//Cl-, B4O2-7-H2O 288 K时的固液相平衡实验中, 有复盐KCl·MgCl2·6H2O生成, 平衡相图中有3个共饱点, 7条单变量曲线, 5个结晶区, 对应的平衡固相分别为MgB4O7·9H2O, K2B4O7·4H2O, KCl, MgCl2·6H2O, KCl·MgCl2·6H2O. 简要讨论了实验结果.     

Mg2+,K+//Cl-,B4O2-7-H2O四元体系288 K固液相平衡

采用等温溶解平衡法研究了288 K时Mg2+,K+//Cl-,B4O2-7-H2O四元体系的相平衡关系,测定该体系在288 K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以及其密度-组成图.研究结果表明,四元体系Mg2+,K+//Cl-,B4O2-7-H2O 288 K时的固液相平衡实验中,有复盐KCI·MgCl2·6H2O生成,平衡相图中有3个共饱点,7条单变量曲线,5个结晶区,对应的平衡固相分别为MgB4O7·9H2O,K2B4O7·4H2O,KCl,MgCl2·6H2O,KCl·Mgcl2·6H2O.简要讨论了实验结果.     

Li＋,Na＋∥,CO32－,B4O72－-H2O 四元交互体系288 K的相平衡

采用等温溶解平衡法对Li＋,Na＋∥,CO32－,B4O72－-H2O四元体系进行288 K相平衡研究.结果表明,该体系属简单共饱型，在288 K等温溶解度相图中有二个共饱点，五条单变量曲线，平衡固相为Na2CO3•10H2O， Li2B4O7•3H2O，Na2B4O7•10H2O, Li2CO3.     

Li^+, Mg^2^+/Cl^-, SO4^2^——H2O四元体系(25℃)的介稳平衡

本文用等温蒸发的方法, 研究了Li^+, Mg^2^+//Cl^-,SO4^2^--H2O体系(25℃)介稳相平衡, 绘制了介稳相图, 测定了密度、粘度、折光率、电导率和某些液相点的蒸汽压。该介稳相图由六个结晶区构成, 即LiCl·H2O、LiCl·MgCl2·7H2O、MgCl2·6H2O、Li2SO4·H2O、MgSO4·7H2O和MgSO4·6H2O相区。该体系的25℃介稳相图和稳定相图的差异是, 新结晶区MgSO4·6H2O的出现, 使LiSO4·H2O相区扩大, 其它相区缩小。根据Pitzer电解质溶液理论, 用单纯形法在M68000计算机上进行了体系溶解度关系的计算,并获得了计算的溶解度数据, 绘 制了计算的相     

Na2B4O7-Na2CO3-NaHCO3-NaBO2-H2O四元体系的等温溶度

测定了四元体系Na2B4O7 Na2CO3 NaHCO3 NaBO2 H2O在25 、 35及45 ℃时的等温溶度和饱和溶液的折光率,绘制了相应的溶度图和组成 折光率图.体系在35和45 ℃时有异成分化合物－天然碱（Na2CO3•NaHCO3•2H2O）生成.这些结果有助于揭示含硼碱湖的固体盐矿成因,对有关盐卤存在的反应2Na2CO3＋Na2B4O7＋H2O=4NaBO2＋2NaHCO3,揭示了相化学规律.     

Li+,Na+∥CO2-3,B4O2-7-H2O四元交互体系288K的相平衡

采用等温溶解平衡法对Li+,Na+∥CO2-3,B4O2-7-H2O四元体系进行288K相平衡研究.结果表明,该体系属简单共饱型,在288K等温溶解度相图中有二个共饱点,五条单变量曲线,平衡固相为Na2CO3@10H2O,Li2B4O7@3H2O,Na2B4O7@10H2O,Li2CO3.     

(Solid+Liquid) Equilibria in the Quaternary System Na2B4O7-MgB4O7-K2B4O7-H2O at 288 K

(Solid+Liquid) phase equilibria in the quaternary system Na₂B₄O₇‐MgB₄O₇‐K₂B₄O₇‐H₂O at 288 K were studied experimentally using the method of isothermal solution saturation. Solubility of any single salt in the solution of the quaternary system was determined experimentally. Based on the experimental data achieved, the phase diagram and water content diagram of the quaternary system were constructed, respectively. In the phase equilibrium diagram of the quaternary system Na₂B₄O₇‐MgB₄O₇‐K₂B₄O₇‐H₂O at 288 K, there are one invariant point E, three univariant curves E1E, E2E and E3E, and three fields of crystallization corresponding to Na₂B₄O₇·10H₂O, K₂B₄O₇·4H₂O and MgB₄O₇·9H₂O. The experimental results show that potassium borate (K₂B₄O₇·4H₂O) have higher solubilities than the magnesium borate and sodium borate in the quaternary system Na₂B₄O₇‐MgB₄O₇‐K₂B₄O₇‐H₂O at 288 K.     

(Solid + liquid) metastable equilibria in quaternary system (Li2SO4 + K2SO4 + Li2B4O7 + K2B4O7 + H2O) at T = 288 K

Metastable equilibrium solubilities and properties such as densities, conductivity, pH, refractive index, and viscosity of the solution were determined experimentally. According to the experimental data, the metastable equilibrium phase diagram was plotted. In the phase diagram, there are three invariant points, seven univariant curves, five fields of crystallization: Li₂SO₄ · H₂O, K₂SO₄, Li₂B₄O₇ · 3H₂O, K₂B₄O₇ · 4H₂O, and K₂SO₄ · Li₂SO₄. The double salt K₂SO₄ · Li₂SO₄ was found in the quaternary system metastable equilibria. Lithium sulfate (Li₂SO₄) has the highest concentration and strong salting-out effects on other salts.Also, the relationship diagram between the properties and the ion concentration of solution was constructed. It can be seen from the relationship diagram that the equilibrium solution density values, viscosity values, and refractive index values are increased apparently with the rise of sulfate ion concentration, reaching the maximum values at eutonic point F3. Electrical conductivity values and pH values, however, fall down with the rise of ion concentration on the whole.     

Metastable phase equilibria in the systems K2SO4 + K2B4O7 + H2O and KCl + K2B4O7 + H2O at 308.15 K

Experimental studies on the metastable solubilities and physicochemical properties (density and refractive index) in the ternary systems K₂SO₄ + K₂B₄O₇ + H₂O and KCl + K₂B₄O₇ + H₂O at 308.15 K were determined with the method of isothermal evaporation. According to the experimental results, the phase diagrams of the two ternary systems were plotted. In the phase diagrams, there are both two isotherm evaporation curves, one eutectic point corresponding to K₂SO₄ + K₂B₄O₇ · 4H₂O, and KCl + K₂B₄O₇ · 4H₂O, respectively. Both of the ternary systems belong to a simple eutectic type, and neither double salts nor solid solutions formed in the ternary systems. A comparison of the stable and metastable phase diagrams of the ternary systems K₂SO₄ + K₂B₄O₇ + H₂O and KCl + K₂B₄O₇ + H₂O shows that the supersaturated phenomenon of potassium borate tetrahydrate is significant and easier to appear the metastable behavior.     

(Liquid + solid) metastable equilibria in quinary system Li2CO3 + Na2CO3 + K2CO3 + Li2B4O7 + Na2B4O7 + K2B4O7 + H2O at T=288 K for Zhabuye salt lake

An experimental study on metastable equilibria at T=288 K in the quinary system Li₂CO₃ + Na₂CO₃ + K₂CO₃ + Li₂B₄O₇ + Na₂B₄O₇ + K₂B₄O₇ + H₂O was done by isothermal evaporation method. Metastable equilibrium solubilities and densities of the solution were determined experimentally. According to the experimental data, the metastable equilibrium phase diagram under the condition saturated with Li₂CO₃ was plotted, in which there are four invariant points; nine univariant curves; six fields of crystallization: K₂CO₃ · 3/2H₂O, K₂B₄O₇ · 5H₂O, Li₂B₂O₄ · 16H₂O, Na₂B₂O₄ · 8H₂O, Na₂CO₃ · 10H₂O, NaKCO₃ · 6H₂O. Some differences were found between the stable phase diagram at T=298 K and the metastable one at T=288 K.     

Phase diagrams and physicochemical properties of Li<Superscript>+</Superscript>,K<Superscript>+</Superscript>(Rb<Superscript>+</Superscript>)//borate–H<Subscript>2</Subscript>O systems at 323 K

The phase and physicochemical properties diagrams of Li⁺,K⁺(Rb⁺)//borate–H₂O systems at 323 K were constructed using the experimentally measured solubilities, densities, and refractive indices. The Schreinemakers’ wet residue method and the X-ray diffraction were used for the determination of the compositions of solid phase. Results show that these two systems belong to the hydrate I type, with no solid solution or double salt formation. The borate phases formed in our experiments are RbB₅O₆(OH)₄ · 2H₂O, Li₂B₄O₅(OH)₄ · H₂O, and K₂B₄O₅(OH)₄ · 2H₂O. Comparison between the stable phase diagrams of the studied system at 288, 323, and 348 K show that in this temperature range, the crystallization form of salts do not changed. With the increase in temperature, the crystallization field of Li₂B₄O₅(OH)₄ · H₂O salt at 348 K is obviously larger than that at 288 K. In the Li⁺,K⁺(Rb⁺)//borate–H₂O systems, the densities and refractive indices of the solutions (at equilibrium) increase along with the mass fraction of K₂B₄O₇ (Rb₂B₄O₇), and reach the maximum values at invariant point E.     

Solid‐Liquid Equilibria in the Quinary Na+, K+//Cl−, SO2−4, B4O2−7‐H2O System at 298 K

The solid‐liquid equilibria in the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K had been studied experimentally using the method of isothermal solution saturation. Solubilities and densities of the solution of the quinary system were measured experimentally. Based on the experimental data, the dry‐salt phase diagram and water content diagram of the quinary system were constructed, respectively. In the equilibrium diagram of the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K, there are five invariant points F1, F2, F3, F4 and F5; eleven univariant curves E1F1, E2F2, E3F3, E4F5, E5F2, E6F4, E7F5, F1F4, F2F4 F1F3 and F3F5, and seven fields of crystallization saturated with Na₂B₄O₇ corresponding to Na₂SO₄, Na₂SO₄·10H₂O, Na₂SO₄·3K₂SO₄ (Gla), K₂SO₄, K₂B₄O₇·4H₂O, NaCl and KCl. The experimental results show that Na₂SO₄·3K₂SO₄ (Gla), K₂SO₄ and K₂B₄O₇·4H₂O have bigger crystallization fields than other salts in the quinary system Na⁺, K⁺//Cl^?, SO^2?₄, B₄O^2?₇‐H₂O at 298 K.     

五元体系Li＋, K＋//, CO32- ,SO42- , B4O72- -H2O在288 K时的介稳相平衡研究

采用等温蒸发法研究了五元体系Li^＋, K^＋//, , -H₂O 在288 K时的介稳相平衡关系, 测定了该五元体系在288 K条件下的介稳平衡的溶解度和溶液密度, 根据实验数据绘制了相应的介稳平衡相图和水图. 相平衡研究结果表明该五元体系介稳相平衡中有复盐K₂SO₄•Li₂SO₄生成, 其介稳相图(Li₂CO₃饱和)有4个共饱和点, 9条单变量曲线, 6个Li₂CO₃饱和的结晶区分别为LiBO₂•8H₂O, K₂B₄O₇•4H₂O, K₂CO₃•3/2H₂O, K₂SO₄, Li₂SO₄•H₂O和复盐 K₂SO₄•Li₂SO₄.     

Synthesis and Thermodynamic Properties of MgO·B_2O_3·4H_2O

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｒｅａｒｅｍａｎｙｋｉｎｄｓｏｆｍａｇｎｅｓｉｕｍｂｏｒａｔｅｓ ,ｂｏｔｈｎａｔｕｒａｌａｎｄｓｙｎｔｈｅｔｉｃ .Ａｂｏｒａｔｅｄｏｕｂｌｅｓａｌｔ (2ＭｇＯ·2Ｂ2 Ｏ3 ·ＭｇＣｌ2 · 14Ｈ2 Ｏ)ｎａｍｅｄｃｈｌｏｒｏｐｉｎｎｏｉｔｅｗａｓｏｂ ｔａｉｎｅｄｆｒｏｍｔｈｅｎａｔｕｒａｌｃｏｎｃｅｎｔｒａｔｅｄｓａｌｔｌａｋｅｂｒｉｎｅ .1Ｉｎｏｒｄｅｒｔｏｆｉｎｄｔｈｅｆｏｒｍｉｎｇｒｅｌａｔｉｏｎｂｅｔｗｅｅｎｔｈｅｄｏｕｂｌｅｓａｌｔａｎｄｍａｇｎｅｓｉｕｍ ｂｏｒａ…     

白硼钙石的合成新方法及其热化学研究(英)

0IntroductionTherearemanykindsofhydratedcalciumbo-rates,bothnaturalandsynthetic.Someofthemarematerialsusedinglass,potteryandporcelainenamelindustry,especiallyinunalkaliglassindustry.4CaO·5B2O3·7H2O,calledpriceite,isacalciumboratemin-eral,notfoundinCaO-B…     

Metastable phase equilibria for the ternary aqueous system of lithium sulfate and potassium sulfate at <Emphasis Type="Italic">T</Emphasis> = 308.15 K: Experimental data and prediction using Pitzer model

The metastable solubilities and the physicochemical properties including density, refractive index, pH and conductivity in the ternary system (Li₂SO₄ + K₂SO₄ + H₂O) at T = 308.15 K were determined experimentally using the isothermal evaporation method, and the metastable phase diagram and the physicochemical properties versus composition diagram were plotted. In the metastable phase diagram, there are two invariant points, three univariant curves and three crystallization regions corresponding to lithium sulfate monohydrate (Li₂SO₄ · H₂O), double salt (K₂SO₄ · Li₂SO₄) and arcanite (K₂SO₄). It was found that the double salt of K₂SO₄·Li₂SO₄ belongs to the incongruent double salt, and the hydrate of Li₂SO₄ · H₂O belongs to hydrate type I. On the basis of Pitzer model of the electrolyte solution theory, the mixing-ion parameter of θ_Li,K, \({\Psi _{Li,K,S{O_4}}}\) and the metastable equilibrium constants of the solid phases K₂SO₄, Li₂SO₄ · K2SO4 and Li₂-SO₄ · H₂O at 308.15 K were obtained for the first time. The calculated metastable solubility data for this ternary system at 308.15 K agree well with the experimental values, and this result indicates that the mixing-ion parameters and the metastable equilibrium constants obtained in this work are reliable.