Stable tetrahedron LiF-KCl-KBr-K2MoO4 of the quinary reciprocal system Li,K‖F,Cl,Br,MoO4

The stable tetrahedron LiF-KCl-KBr-K₂MoO₄ of the quinary reciprocal system Li,K‖F,Cl,Br,MoO₄ was studied by differential thermal analysis, and phase equilibria were determined.     

Phase equilibria in the quaternary systems Li‖F,Cl,Br,CrO4 and Li‖F,Cl,Br,WO4

Phase equilibria in the quaternary systems Li‖F,Cl,Br,CrO₄ and Li‖F,Cl,Br,WO₄ were studied by differential thermal analysis. In these systems, the stability of continuous series of solid solutions based on lithium chloride and bromide is preserved. The number and compositions of crystallizing phases in the systems Li‖F,Cl,Br,CrO₄ and Li‖F,Cl,Br,WO₄ were confirmed by X-ray powder diffraction analysis.     

Li,K‖Cl,MoO4 ternary mutual system

Phase equilibria in the Li,K‖Cl,MoO₄ ternary mutual system were studied by differential thermal analysis (DTA). The characteristics of the following three ternary eutectics were determined: E ₁: 348°C, 41 mol % KCl, 7.75 mol % Li₂MoO₄, and 51.25 mol % LiCl; E ₂: 475°C, 44 mol % KCl, 17.25 mol % Li₂MoO₄, and 38.75 mol % LiCl; and E ₂: 477°C, 35 mol % KCl, 47 mol % Li₂MoO₄, and 18 mol % LiCl.     

Investigation of the United stable tetrahedron LiF-KBr-K2MoO4-KF of the quaternary reciprocal system Li,K‖F,Br,MoO4

The united stable tetrahedron LiF-KBr-K₂MoO₄-KF of the quaternary reciprocal system Li,K‖F,Br,MoO₄ was studied by differential thermal analysis. The melting points and ternary eutectic and peritectic compositions in the secant triangle LiF-KBr-K₃FMoO₄ were identified. The melting points of the samples corresponding to the quaternary invariant equilibrium points (eutectic and peritectic points) and their compositions in the stable tetrahedron LiF-KBr-K₃FMoO₄-KF were determined. The volumes of crystallizing phases in the united stable tetrahedron were determined; the phase equilibria at invariant points were described.     

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.     

Li,K∥F,NO3 and Li,K∥Cl,NO3 three-component reciprocal systems

Phase equilibria in Li,K∥F,NO₃ and Li,K∥Cl,NO₃ three-component reciprocal systems were studied by differential scanning calorimetry (DSC). Eutectic compositions (mol %) in the Li,K∥F,NO₃ system were determined to be as follows: 5.0 LiF, 10.0 KF, and 85.0 KNO₃ with T _m = 281°C and 48.5 KNO₃, 44.0 LiNO₃, and 7.5 LiF with T _m = 105°C. Eutectic compositions (mol %) in the Li,K∥Cl,NO₃ system were determined to be as follows: 10.0 LiCl, 32.1 KCl, and 57.9 LiNO₃ with T _m = 147°C and 44.5 KNO₃, 45.0 LiNO₃, and 10.5 KCl with T _m = 97°C.     

Phase complex of the Li,K,Ba‖F,Br quaternary reciprocal system

The partition of the Li,K,Ba??F,Br quaternary reciprocal system into simplexes was performed and confirmed by X-ray powder diffraction. Internal partitioning elements, LiF-2KBr · BaBr₂ and KBr-LiF · BaF₂, were identified; the tree of phases forms two cycles. Simplexes involving phase separation were determined. The stable partitioning triangles LiF-KBr-BaBr₂ and LiF-KBr-BaF₂ · BaBr₂ were experimentally studied by differential thermal and X-ray powder diffraction analyses. The T-x diagrams of explored sections and the liquidi of the systems were constructed. Phase separation regions within the systems under investigations were delimited. The characteristics of alloys corresponding to invariant compositions were determined.     

Li, K‖Br, VO3 ternary mutual system

Phase equilibria in the Li, K‖Br, VO₃ ternary mutual system were studied by differential thermal analysis. The composition square of the ternary mutual system is divided into two phase triangles, LiVO₃-KBr-KVO₃ and LiBr-LiVO₃-KBr. The ternary eutectics E ₁ at 331°C and E ₂ at 330°C have the compositions 40.0 mol % LiVO₃, 6.0 mol % KBr, 54.0 mol % KVO₃ and 58.0 mol % LiBr, 3.2 mol % LiVO₃, 38.8 mol % KBr, respectively. The fields of phases crystallizing in the system were delimited.     

Phase equilibria in the ternary reciprocal system Li,Rb‖F,CrO4

The ternary reciprocal system of fluorides and chromates of lithium and rubidium was studied for the first time. The stable pair of salts LiF and Rb₂CrO₄ and also binary compounds on the bordering sides partition the system into five simplexes. Studying a number of polythermal sections allowed us to determine the melting points and compositions of two peritectics and three eutectics. The crystallization fields of phases in the system were demarcated, and phase equilibria were described.     

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.     

Partition of the Li,K‖F,Cl,Br quaternary reciprocal system into simplexes and investigation of components of the LiF-KCl-KBr stable triangle

A quaternary reciprocal system of fluorides, chlorides, and bromides of lithium and potassium was partitioned into simplexes by a geometric method and by a graph method. Phase transformations and chemical reactions in the boundary ternary reciprocal systems were described. A conversion line was experimentally studied, and information on crystallizing phases within the composition prism of the Li,K‖F,Cl,Br system was obtained and confirmed by X-ray powder diffraction data. An immiscibility region in the LiF-KCl-KBr stable triangle was outlined.     

Quaternary reciprocal system Li,K‖F,Br,NO<Subscript>3</Subscript>

The quaternary reciprocal system Li,K‖F,Br,NO₃ was described and studied for the first time. The system was partitioned into simplexes by writing an adjacency matrix and solving a logical expression. The partition was confirmed by the results of differential scanning calorimetry of two partitioning triangles (LiF-KBr-KNO₃ and LiF-KBr-LiNO₃) and three stable triangles (LiBr-LiF-KBr-LiNO₃, LiNO₃-LiF-KNO₃-KBr, and KF-LiF-KNO₃-KBr). The compositions (mol %) and melting points of quaternary eutectics of the system Li,K‖F,Br,NO₃ were determined: E ₁ ^□ (4.0% LiF, 48.0% LiNO₃, 17.28% KBr, 30.7% LiBr, T _melt = 186°C), E ₂ ^□ (7.35% LiF, 47.53% KNO₃, 2.0% KBr, 43.12% LiNO₃, T _melt = 102°C), and E ₃ ^□ (2.0% LiF, 84.28% KNO₃, 0.98% KBr, 12.74% KF, T _melt = 280°C).     

Na,Rb‖F,Br three-component reciprocal system and analysis of the Na,M‖F,Br (M = K,Rb, and Cs) series

Solid-phase reactions were studied by differential thermal analysis and X-ray powder diffraction in a sample whose composition corresponds to the complete conversion point K of the Na,Rb‖F,Br three-component reciprocal system. A stable diagonal and a metastable diagonal were studied, and the parameters of two ternary eutectics were determined.     

Rules on intrapair and interpair correlation energy for Cl, Cl−and MCl (M=H, Li, Na, K)

According to the calculation results of the intrapair and interpair correlation energy for the title systems, it has been found that the intrapair correlation energy of K shell of Cl is almost a constant and both the intrashell and intershell correlation energy of K and L shell changes little. It has also been found that in MCl series compounds the value of Cl correlation energy contribution depends on the ionicity of MCl compounds, i.e., the Cl correlation energy contribution increases with the increase of the ionic bond strength of the compound and this value is always less than the correlation energy of Cl^- anion but always larger than that of Cl atom. These rules are helpful for the estimation of the correlation energy of ionic compounds and the energy changes of chemical reactions.     

F Cl_2→ClF Cl和Cl′F Cl→Cl′ ClF的反应机理

用密度泛函理论(DFT)B3LYP方法,取6-311G基组,计算研究了F＋Cl2→ClF＋Cl的反应机理.求得1个线形和2个三角形过渡态,反应能垒分别为1.24、46.37和105.09kJ·mol－1;同时发现F以∠FClCl为10～20°（或120～160°）进攻Cl2时,反应无能垒.此外,求得对称反应Cl′F＋Cl→Cl′＋ClF的能垒为40.57kJ·mol－1的1个过渡态.     

用NH4Cl氯化Li2CO3的研究

近年来利用熔盐电解法制备Al-Li合金已开始受到重视。但由于LiCl具有强烈的吸水性给工艺及其电解质溶液物化性质的研究带来很大的困难。因此本文利用热分析手段研究了NH_4Cl氯化Li_2CO_3的反应,为今后在电解工艺及其基础研究中用NH_4Cl定量氯化Li_2CO_3取代直接使用LiCl提供依据。     

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.     

Cl,Cl~-和MCl(M=H,Li,Na,K)对内对间相关能的规律性

通过对内对间相关能的计算,发现Ｃｌ,Ｃｌ－及其化合物中的Ｋ电子层的对内相关能基本上是一常数,而且Ｃｌ的Ｋ,Ｌ层电子层内相关能和它们之间的层间相关能也变化很小．另外,所研究的ＭＣｌ系列化合物中Ｃｌ价电子对相关能的贡献是跟ＭＣｌ的离子性有关,即随着化合物离子性的增加而增加,但其相关能最大不大于Ｃｌ离子的,最小不小于Ｃｌ原子的．这些规律对人们考虑一些化合物的相关能,以至化学反应能量很有参考意义．     

在小硅化物SiX^m4（X=H,He,Li,Be,O,F,Ne,Na,Mg,S,Cl,Ar;m=0,…

用从头算方法，在ＨＦ／ＳＴＯ－３Ｇ、ＨＦ／３－２１Ｇ和ＨＦ／６－３１Ｇ水平上研究了小硅化物ＳｉＸ＾ｍ４的成键倾向性。计算结果表明，所研究的分子势能曲线均有稳定的极小值（ＳｉＬｉ４除外）。与已知的稳定分子ＳｉＨ１、ＳｉＦ４和ＳｉＣｌ４比较，含惰性元素的未知分子ＳｉＨｅ＾４＋４、ＳｉＮｅ＾４＋４和ＳｉＡｒ＾４＋４比含碱金属和碱土金属的未知分子ＳｉＬＩ４、ＳｉＮａ４、ＳｉＢｅ＾４＋４和ＳｉＭｇ＾４＋４有     

Structure and Crystal Growth of Li2Zn2（MoO4）3

Single crystal of Li2Zn2(MoO4)3 has been grown from a flux of Li2MoO4 by the top-seeded solution-growth method,and its structure was refined by the Rietveld method. It belongs to the orthorhombic system,space group Pnma with a=5.1114,b=10.4906 and c=17.6172. Good agreement between the experimental and calculated profile(Rp=6.69%,Rwp=9.73% and Rexp= 6.58%) was reached.