An investigation of the polythermal diagram of the H2ONa2HPO4Na2SO4 system

The polythermal diagram of the ternary system H₂ONa₂HPO₄Na₂SO₄ has been established, setting up nine isotherms obtained between 0 and 25°C by conductimetric analysis. The solubility domains of the various solid phases have been determined. One eutectic, three stable and one metastable transitional transformations have been observed. Temperature and composition of the eutectic point have been obtained by thermal analysis at constant flow.     

Interaction of salts in ionic melts of the ternary reciprocal systems Na,K‖BO2,MoO4 and Na,K‖BO2,WO4

The phase diagrams of the ternary reciprocal systems Na,K‖BO₂,MoO₄ and Na,K‖BO₂,WO₄ were studied for the first time by a calculation-experimental method and differential thermal analysis. The coordinates were determined for binary eutectics of the diagonal stable sections NaBO₂-K₂MoO₄(K₂WO₄) and the ternary invariant points e(55 mol % NaBO₂, 45 mol % K₂MoO₄, 740°C), e(55 mol % NaBO₂, 45 mol % K₂WO₄, 730°C), E(4.5 mol % NaBO₂, 78 mol % Na₂MoO₄, 17.5 mol % K₂MoO₄, 652°C), E(4.5 mol % NaBO₂, 78 mol % Na₂WO₄, 17.5 mol % K₂WO₄, 643°C), P₂(5 mol % NaBO₂, 56 mol % Na₂MoO₄, 39 mol % K₂MoO₄, 673°C), P₂(5 mol % NaBO₂, 56 mol % Na₂WO₄, 39 mol % K₂WO₄, 671°C). Binary solid solutions based on sodium and potassium metaborates were shown to be stable. Analytical models of phase equilibrium states of the ternary reciprocal systems Na,K‖BO₂,MoO₄(WO₄) were obtained, which enable one to calculate melting (crystallization) points and construct isotherms at any given composition. The specific heats of melting of samples of invariant compositions were found by quantitative differential thermal analysis.     

Phase complex of the Na,K‖Br,MoO4 system

The Na,K‖Br,MoO₄ system was studied by differential thermal analysis and X-ray powder diffraction. It was established that the liquidus surface consists of the crystallization fields of the initial components and the incongruently melting compound NaKMoO₄. The coordinates of three nonvariant points were determined, which represent one eutectic, E ^Δ, and two peritectics, P ₁ ^Δ , and P ₂ ^Δ , with the melting points 472, 512, and 538°C, respectively, and the specific enthalpies of melting Δ_melt H = 177, 230, and 184 kJ/kg, respectively.     

复盐K3Na(SO4)2的热化学研究

钾芒硝是一种成因复杂的复盐[1～ 3 ] ,并且由于钾芒硝Ｋ3 Ｎａ(ＳＯ4 ) 2 与硫酸钾石 [Ｋ3 Ｎａ(ＳＯ4 ) 2 或Ｎａ2 ＳＯ4 ·3Ｋ2 ＳＯ4 ]的化学组成相同 ,未能确定二者是否属于同一种复盐[4 ,5] 。我们合成了复盐Ｋ3 Ｎａ(ＳＯ4 )2[3 ] ,用溶解量热法测定了Ｋ3 Ｎａ(ＳＯ4 )2 和反应物 [Ｎａ2 ＳＯ4 (ｓ) +Ｋ2 ＳＯ4 (ｓ) ]的溶解焓 ,通过设计热化学循环计算出复盐的标准生成焓 ,为我们了解钾芒硝和硫酸钾石是否为同一复盐 ,并为进一步研究其成因和组成提供参考。1　实验部分1 1　试剂与仪器Ｋ2 ＳＯ4 (ｓ)和Ｎａ2 ＳＯ4 (ｓ)为Ａ .Ｒ .…     

Sodium ion-conducting solid electrolytes in the system Na3PO4Na2SO4

In the system Na₃PO₄Na₂SO₄, the high-temperature, cubic γ form of Na₃PO₄ forms an extensive range of solid solutions: Na_3−x(P_1−xS_x)O₄, 0 < x < (0.57 to 0.70, depending on temperature). For compositions in the range x = ca. 0.33 to 0.57, these γ solid solutions are thermodynamically stable at all temperatures. The conductivity of the γ solid solutions increases with increasing x and reaches a maximum at x = 0.5 to 0.6, with values of 2 × 10⁻⁵ ohm⁻¹ cm⁻¹ at 100°C, rising to 1.3 × 10⁻² ohm⁻¹ cm⁻¹ by 300°C; this conductivity increase with x is attributed to an increase in the sodium ion vacancy concentration, associated with the solid solution mechanism Na + PS. The phase diagram for the system Na₃PO₄Na₂SO₄ is given together with lattice parameters of the γ solid solutions.     

Phase equilibria in the Na,K,Mg,Ca‖SO4,Cl-H2O system at 50°C in the halite crystallization field

Phase equilibria of the Na,K,Mg,Ca‖SO₄,Cl-H₂O system at 50°C in the halite (NaCl) crystallization field were studied using the translation method. Halite, which is an equilibrium phase of the title system at 50°C, was found to be involved in 25 invariant points, 59 monovariant curves, and 43 divariant fields. A fragment of the equilibrium phase diagram of the title system in the halite crystallization field was constructed.     

Phase equilibria in the Na,K,Mg,Ca‖SO4,Cl-H2O system at 50°C in the astrakhanite crystallization region

Phase equilibria of the Na,K,Mg,Ca‖SO₄,Cl-H₂O system at 50°C in the astrakhanite (Na₂SO₄ · MgSO₄ · 4H₂O) crystallization region were studied using the translation method. Astrakhanite was found to be involved, as an equilibrium phase of the title system, in 35 divariant fields, 39 monovariant curves, and 22 invariant points. The data gained were used to construct a fragment of a schematic equilibrium phase diagram of the title system in the astrakhanite crystallization region.     

Osmotic and activity coefficients of {yNaH2PO4+(1−y)Na2SO4}(aq) at the temperature 298.15 K

The osmotic coefficients of the mixed electrolyte solution {yNaH₂PO₄+(1−y)Na₂SO₄}(aq) have been measured by the isopiestic method, at the temperature T=298.15 K. The activity coefficients of NaH₂PO₄ and Na₂SO₄ were calculated by Scatchard's neutral-electrolyte method and by Pitzer and Kim's treatment for mixed-electrolyte solutions. The Scatchard interaction parameters are used for calculation of the excess Gibbs energy as a function of ionic strength and ionic-strength fraction of NaH₂PO₄. Also, the Zdanovskii's rule of linearity is tested.     

Measurements of the Solid–Liquid Equilibria in the Quaternary System NaCl–NaBr–Na2SO4–H2O at 323 K

Phase equilibria of the quaternary NaCl–NaBr–Na₂SO₄–H₂O system at 323 K were studied by the isothermal dissolution equilibrium method. The solubilities of salts and densities of saturated solutions were determined. Solid solutions [Na(Cl, Br)] were found in the experiments. The phase diagram of the quaternary system has no invariant point, but has one univariant curve at the boundary of Na(Cl, Br) and Na₂SO₄ crystallization fields. The experimental results show that an increase of the NaBr concentration is accompanied by an obvious increase of the solution density and the decrease of the solubilities of NaCl and Na₂SO₄.     

电解合成Na2FeO4制备K2FeO4

复分解;电解合成Na2FeO4制备K2FeO4     

Thermochemical investigations of the systems KCl−KBr−H2O,K2SO4−(NH4)2SO4−H2O and KNO3−NH4NO3−H2O at 298.15 K

For the equilibrium solid phases occurring in the systems: KCl?KBr?H₂O, K₂SO₄?(NH₄)₂SO₄?H₂O and KNO₃?NH₄NO₃?H₂O, the concentration dependencies of differential solution enthalpies, Δ_sol H ₂ for several crystallization paths, were measured. The limiting differential solution enthalpies, Δ_sol H ₂ ⁰ , were determined by extrapolation of the above dependencies to the ionic strength,I _m ⁰ , corresponding to the appropriate binary solutions. For KCl?KBr?H₂O system only, the clear dependence between Δ_sol H ₂ ⁰ andI _m ⁰ values was found and discussed.     

Phase equilibria in the Na,Ca‖SO4,CO3,F-H2O at 0°C

Phase equilibria in the Na,Ca‖SO₄,CO₃,F-H₂O system at 0°C were studied using the translation method. Seven invariant points, 18 monovariant curves, and 17 divariant fields were found to exist. A looped phase diagram (phase complex) of the title system was constructed.     

25 ℃下Na+, K+, Mg2+//Cl-, SO2-4, NO-3, H2O体系液固相平衡

本文应用等温溶解平衡法,研究了Na+, K+, Mg2+//Cl-, SO42-, NO3-, H2O六元体系在25℃、氯化钠饱和时的相平衡关系,测定了溶解度数据,并绘制出相应的相图. 研究表明： 25℃时,该体系在氯化钠饱和的区域里存在8种复盐,有15个两盐结晶区,25个零变量点;零变量点中只有一个共结点,为Mg(NO3)2?6H2O、NaCl、MgCl2?6H2O、MgSO4?(1～6)H2O、KCl?MgCl2?6H2O五盐共饱点,其余为反应点. 在此基础上,研究了新疆硝酸盐卤水矿蒸发析盐规律.     

Differentiation of the Na,K,Ca,Ba‖F,WO4 multicomponent system and phase equilibria in its stable secant complex NaF-K2WO4-CaF2-BaF2

The Na,K,Ca,Ba‖F,WO₄ quinary mutual system was differentiated based on graph theory with consideration of identified internal secant elements using a program complex. For the first time, by a combination of physicochemical analysis methods (differential thermal, visual polythermal, X-ray diffraction and projection-thermal-analytical), the NaF-K₂WO₄-CaF₂-BaF₂ quaternary system was studied, which is a stable secant complex of the quinary mutual system. The coordinates of invariant points were determined.     

Synthesis,Crystal Structures,Spectroscopic Characterization,and Thermal Analyses of the New Bismuth Sulfates NaBi(SO4)2·H2O and ABi(SO4)2 (A = K,Rb, Cs)

Four alkali metal bismuth sulfates, NaBi(SO₄)₂ · H₂O ( 1 ) and ABi(SO₄)₂ [A = K ( 2 ), Rb ( 3 ), Cs ( 4 )], were successfully synthesized by hydrothermal methods. The crystal structure of 1 features a three-dimensional tunnel framework constructed by BiO₉ tri-capped trigonal prisms and SO₄ tetrahedra interconnected via common corners and edges. Compound 2 exhibits a two-dimensional ²_∞[Bi(SO₄)₂]^– double-layered structure, assembled by one-dimensional ¹_∞[BiS(1)O₄]⁺ chains which are linked via S(2)O₄^2– tetrahedra. The isostructural compounds 3 and 4 possess a two-dimensional layered structure, and the layers being composed by BiO₈ square antiprism and SO₄ tetrahedra. The alkali metal cations are located between the layers or in the tunnels of the structures, respectively. The differences in the crystal structures of the title compounds can mainly be attributed to the different sizes of the alkali metal cations and their different coordination environments. Thermogravimetric analysis evidence that compound 1 losses one equivalent of water at 120 °C whereas the anhydrous compounds 2 – 4 are stable up to about 450, 575, and 578 °C, respectively. The solid-state UV/Vis/NIR diffuse reflectance spectra indicate bandgaps of approximately 4.48, 4.43, 3.98, and 3.96 eV for compounds 1 – 4 , respectively.     

Na+, K+, Mg2+∥Cl-, SO2-4-H2O五元体系35 ℃介稳相图研究

研究得出（Na+, K+, Mg2+∥Cl-, SO2-4-H2O）五元体系35 ℃时的介稳溶解度数据,绘制了该体系35 ℃的介稳相图,共有9个为氯化钠所饱和的结晶区域：氯化钾、钾芒硝（3K2SO4*Na2SO4）、钾镁矾（K2SO4*MgSO4*4H2O）、钾盐镁矾（KCl*MgSO4*2.75H2O）、光卤石（KCl*MgCl2*6H2O）、白钠镁矾（Na2SO4*MgSO4*4H2O）、硫酸钠、六水硫酸镁（MgSO4*6H2O）和水氯镁石（MgCl2*6H2O）. 所得35 ℃介稳相图与Vant Hoff 25 ℃稳定相图比较有较大区别：软钾镁矾（K2SO4*MgSO4*6H2O）、七水硫酸镁、五水硫酸镁及四水硫酸镁结晶区域消失,钾镁矾和钾盐镁矾结晶区域显著扩大. 所得35 ℃介稳相图与25 ℃介稳相图区别很大：软钾镁矾和七水硫酸镁结晶区域消失,同时出现了钾镁矾和钾盐镁矾的结晶区域. 在该五元体系35 ℃介稳相平衡研究中发现析出的是钾盐镁矾的低水化合物（KCl*MgSO4*2.75H2O）.     

Solid-liquid Metastable Equilibria in Quaternary System （NaCl＋Na2CO3＋Na2SO4＋H2O） at 273.15 K

The metastable phase equilibria of the quaternary system NaCl+Na2CO3+Na2SO4+H2O were studied at 273.15 K. The salts' solubilities, densities and pH values of the equilibrated solution in this system were determined. According to the experimental data, the metastable equilibrium phase diagram, the diagram of density vs. composition and pH vs. composition diagram were plotted. The phase diagram consists of five univariant curves, four crystallization fields and two invariant points. The four crystallization fields correspond to sodium carbonate decahydrate (Na2CO3·10H2O), sodium sulfate decahydrate(Na2SO4·10H2O), sodium chloride(NaCl) and burkeite(2Na2SO4· Na2CO3), respectively. The crystallization field of sodium sulfate decahydrate(Na2SO4·10H2O) is the largest, which indicates that sodium sulfate is easy to saturate and crystallize from solution at 273.15 K.     

Na+, K+, Mg2+∥Cl-, SO2-4-H2O五元体系15 ℃介稳相图研究

得到Na+, K+, Mg2+∥Cl-, SO2-4-H2O五元体系15 ℃时的介稳溶解度数据, 绘制了该体系15 ℃的介稳相图, 共有9个为氯化钠所饱和的结晶区域 氯化钾、硫酸钠、钾钠芒硝、软钾镁矾、白钠镁矾、光卤石、七水硫酸镁、六水硫酸镁和水氯镁石. 所得15 ℃介稳相图和Vant Hoff稳定相图比较有较大区别; 在15 ℃介稳相图中钾镁矾、钾盐镁矾以及五水硫酸镁和四水硫酸镁结晶区域消失, 而软钾镁矾结晶区域显著扩大. 比较作者所作该五元体系15 ℃, 25 ℃及35 ℃介稳相图, 发现软钾镁矾(包括钾镁矾)相区以25 ℃时最大, 35 ℃时最小; 随温度升高, 钾钠芒硝结晶相区依次向KCl相区平行移动, 导致KCl相区缩小, Na2SO4相区扩大; 随温度升高相应点的钠含量和水含量依次减小.