MeX—REX3系相图的模式识别分析

用化学键参数－模式识别或人工神经网络方法研究ＭｅＸ－ＲＥＸ３型熔盐相图，总结中间化合物的形成、配比和Ｍｅ３ＲＥＸ６型化合物同分或异分熔化规律，并对其熔点或分解点进行预报。     

含MoFe3Se4类立方烷核芯簇合物的合成与结构表征

室温下［Ｅｔ_４Ｎ］_２ＭｏＳｅ_４, ＦｅＣｌ_２和 Ｒ_２ＮＣＳ_２Ｎａ在 ＤＭＦ和 ＣＨ_３ＣＮ混合溶剂中反应,得到含ＭｏＦｅ_３Ｓｅ_４核芯的Ｍｏ－Ｆｅ－Ｓｅ簇合物ＭｏＦｅ_３Ｓｅ_４（μ－Ｒ_２ＮＣＳ_２）_２（Ｒ_２ＮＣＳ_２）_４（Ｒ２＝Ｍｅ_２（１）,Ｅｔ_２（２）,Ｃ_４Ｈ_８（３））．化合物２的单晶Ｘ射线衍射分析表明,其分子结构为２个桥式和４个螫合Ｅｔ_２ＮＣＳ_２~－配体包围的一个扭曲类立方烷Ｍ_４Ｓｅ_４簇核对３个化合物的ＣＶ进行了表征,它们在ＤＭＳＯ溶液中的电化学行为表现出了多电子可逆的传递过程．     

线型异核三金属M－E－M（M＝Mo，W；E＝Hg，Zn）化合物的研究──［η~5－RC_5H_4（CO）_3M］_2Zn（M＝Mo，W；R＝CO_2Me，CO_2Et）的合成、性质及结构

研究了含汞三金属化合物［η_５－ＲＣ_５Ｈ_４（ＣＯ）_３Ｍ］_２Ｈｇ（Ｍ＝Ｍｏ，Ｗ；Ｒ＝Ｍｅ，Ｅｔ，ＣＯ_２Ｍｅ，ＣＯ_２Ｅｔ）与锌粉的置换反应，发现当取代基Ｒ为给电子的Ｍｅ和Ｅｔ时底物不发生反应，而取代基Ｒ为拉电子的ＣＯ_２Ｍｅ和ＣＯ_２Ｅｔ时，则底物中的汞可被锌置换，生成带有机官能团的三金属化合物［η_５－ＲＣ_５Ｈ_４（ＣＯ）_３Ｍ］_２Ｚｎ；另外，还发现Ｒ为ＣＯ_２Ｅｔ，Ｍ为Ｍｏ的产物［η_５－ＲＣ_５Ｈ_４（ＣＯ）_３Ｍ］_２Ｚｎ可在室温下被分解为相应的氯代物η_５－ＥｔＯ_２ＣＣ_５Ｈ_４ＭｏＣｌ．     

Eu_（0．5）RE_（0．5）Fe_（0．5）Mn_（0．5）O_3的~（57）Fe Msosbauer谱研究

利用固相反应合成了Ｅｕ_（０．５）ＲＥ_（０．５）Ｆｅ_（０．５）Ｍｎ_（０．５）Ｏ_３（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｙ）等化合物。测量了其ＸＲＤ谱及~（５７）ＦｅＭｓｓｂａｕｅｒ谱．实验发现，随着ＲＥ原子序数的增加，样品的晶胞体积减小，Ｆｅ在化合物中处于Ｆｅ~（３＋）的高自旋状态，~（５７）Ｆｅ的四极裂矩与样品的畸变参数Ｄ成线性关系。     

A NOVEL REACTION BETWEEN Ge－Ge AND Fe－Fe BONDS IN COMPLEX （Me_2GeGeMe_2）［（η~5－C_5H_4）Fe（CO）］_2（μ－CO）_2 AND CRYSTAL STRUCTURE OF THE PRODUCT

ＡＮＯＶＥＬＲＥＡＣＴＩＯＮＢＥＴＷＥＥＮＧｅ－ＧｅＡＮＤＦｅ－ＦｅＢＯＮＤＳＩＮＣＯＭＰＬＥＸ（Ｍｅ_２ＧｅＧｅＭｅ_２）［（η~５－Ｃ_５Ｈ_４）Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２ＡＮＤＣＲＹＳＴＡＬＳＴＲＵＣＴＵＲＥＯＦＴＨＥＰＲＯＤＵＣＴ￥ＸｉｕＴ?..     

稀土取代的复合氧化物Eu_（0．5）RE_（0．5）Fe_（0．5）Mn_（0．

利用固相反应合成了稀土取代的复合氧化物Ｅｕ_（０．５）ＲＥ_（０．５）Ｆｅ_（０．５）Ｍｎ_（０．５）Ｏ_３（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ）．测量了这些化合物的ＸＲＤ和ＸＰＳ谱。在ＸＰＳ研究中发现，稀土取代而使稀土元素本身的结合能相对于其倍半氧化物中的有所降低；在取代的复合氧化物中，随着ＲＥ离子半径的减小，Ｆｅ、Ｍｎ的结合能随之增加。     

硫醇（酚）及其盐与羰基铁反应研究进展──蝶状阴离子［（μ－CO）（μ－RS）Fe_2（CO）_6］~－的合成、结构及反应

对一类新型阴离子络盐Ｍ~＋［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ_２（ＣＯ）_６］~－（Ｍ~＋＝Ｅｔ＋３ＮＨ~＋，Ｌｉ~＋，Ｎａ~＋，ＭｇＸ~＋）的合成、结构和反应进行了综述。该类络盐可由硫醇或硫酚盐ＲＳ~－Ｍ~＋与Ｆｅ_３（ＣＯ）_（１２）在ＴＨＦ中合成并于原位（ｉｎｓｉｔｕ）反应。经单晶Ｘ射线衍射分析证实其阴离子中的Ｆｅ_２ＳＣ骨架具蝶状结构，它显示高度的亲核反应活性，能同多种亲电底物反应。典型的底物包括卤代不饱和烃、酰氯、炔烃、磷、砷卤代物、二硫化碳、二氯化二硫、单质硫或硒及烃基卤化汞等。该类络盐业已成为一种有效试剂，它在新颖金属有机和原子簇化合物的合成中具有广泛的应用价值。     

A NOVEL SYNTHETIC METHOD FOR THE CLUSTERS FeCo_2（CO）_9－（RCCR）（R＝MeO_2C，EtO_2C）．X－RAY CRYSTAL STRUCTURE ANALYSES OF THE CLUSTERS FeCo_2（CO）_9（MeO_2CCCCO_2Me）andCo_4（CO）_（10）－（EtO_2CCCCO_2Et）

ＡＮＯＶＥＬＳＹＮＴＨＥＴＩＣＭＥＴＨＯＤＦＯＲＴＨＥＣＬＵＳＴＥＲＳＦｅＣｏ_２（ＣＯ）_９－（ＲＣＣＲ）（Ｒ＝ＭｅＯ_２Ｃ，ＥｔＯ_２Ｃ）．Ｘ－ＲＡＹＣＲＹＳＴＡＬ　ＳＴＲＵＣＴＵＲＥ　ＡＮＡＬＹＳＥＳ　ＯＦ　ＴＨＥ　ＣＬＵＳＴＥＲＳ　ＦｅＣｏ_２（?..     

ELECTRON TRANSFER BETWEEN Eu~(3+) AND Ce~(3+) IN SrMgF_4 MATRIX

ＥＬＥＣＴＲＯＮ　ＴＲＡＮＳＦＥＲ　ＢＥＴＷＥＥＮ　Ｅｕ~（３＋）　ＡＮＤ　Ｃｅ~（３＋）　ＩＮ　ＳｒＭｇＦ_４　ＭＡＴＲＩＸＥＬＥＣＴＲＯＮＴＲＡＮＳＦＥＲＢＥＴＷＥＥＮＥｕ~（３＋）ＡＮＤＣｅ~（３＋）ＩＮＳｒＭｇＦ_４ＭＡＴＲＩＸ￥ＹｉｎｇＷＵ；Ｃｈ...     

ELECTRON－TRANSFER IN POLYNUCLEAR CYANO－BRIDGED COMPLEX OF THE TYPE［Co（Ⅲ）L_3－μ－Nc－Fe（Ⅱ）（CN）_5］~－（L＝en

ＥＬＥＣＴＲＯＮ－ＴＲＡＮＳＦＥＲＩＮＰＯＬＹＮＵＣＬＥＡＲＣＹＡＮＯ－ＢＲＩＤＧＥＤＣＯＭＰＬＥＸＯＦＴＨＥＴＹＰＥ［Ｃｏ（Ⅲ）Ｌ_３－μ－Ｎｃ－ＦｅⅡ）（ＣＮ）_５］~－（Ｌ＝ｅｎ）ＳｈｕＺｈｏｎｇＺＨＡＮ；ＸｉａｏＹｕａｎＣＨＥＮ；ＱｉｎｇＪｉｎ?..     

Topology of melting diagrams of ternary reciprocal systems without continuous solid solutions

The topological properties were considered for melting diagrams of ternary reciprocal systems with constant-composition phases or with isomorphic diagrams with limited solid solutions. An algorithm for constructing the diagrams was described, and an example was given for a melting diagram with one binary peritectic compound and two ternary stoichiometric compounds, all melting without decomposition. A problem of enumeration of all the phase diagrams with such a set of compounds was solved.     

金属卤化物熔盐系相图的规律及计算机预报

Rules of molten salt phase diagrams of binary system MeX-Me’X4 (Me is monovalent metal, Me’ quadrivalent metal, X halides) were investigated using chemical bond parameter and pattern recognition-artificial neural networks method. Formability of intermediate compounds, chemical stiochiometry, melting type (congruent or incongruent) of intermediate compounds Me2Me’X6 and MeMe’X5 were summarized and predicted, the results were of good reliability.     

Correlation of the volumes and heat capacities of solutions with their solid-liquid phase diagrams

Liquid systems which have strong non-idealities, as seen from their thermodynamic properties, often show evidence of these interactions in the solid-liquid phase diagrams. This suggests that some of the structures present in the solid state can persist in the solution state, on a time average, up to temperatures much higher than the melting point. Volumes and heat capacities of typical systems were either taken from the literature or measured to illustrate this correlation with the phase diagrams. With mixtures of aprotic solvents which show nearly-ideal simple eutectic phase diagrams, the properties of the solutions are also nearly ideal. Examples of systems investigated which show strong non-idealities are ionic surfactant solutions, alcohol-water mixtures, chloroform-triethylamine mixtures and lithium salts in aprotic solvents.Paper written in the honor of Loren Hepler on the occasion of his retirement.     

A view and a review of the melting of alkali metal halide crystals

Summary A representational model, proposed to account for the physical changes that accompany the melting of alkali halides, was described in Part 1 [1]. The liquid is portrayed as undergoing continual dynamic structural reorganization of its constituent ions between individual small domains, zones of various regular, crystal-type arrays. These alternative arrangements are stabilized by the enthalpy of melting, which, in liquids, relaxes the restriction for solids that only the single, most stable, crystal structure can be present. The dynamic character of the melt accounts for its fluid character and the loss of long-range order [1, 2]. This model is extended here to consider the phase diagrams of binary, common ion, alkali halide mixtures comprehensively reviewed in [3]. Factors determining whether each of these yields a eutectic, or a solid solution, on cooling are discussed and several trends in the 70-phase diagrams are identified. Eutectic formation, involving maintenance of the liquid state below the melting points of the pure components, is ascribed to the participation, in an extended dynamic equilibrium, of additional domains having the regular structures characteristic of double salts. The known crystalline double binary halides [3], Li/Cs or Rb/F, Cl, Br or I, melt at temperatures well below those of the simpler pure component salts. It is concluded that the set/liq model for melting, proposed in [1, 2], accounts for some important properties of the phase diagrams presented in [3].     

Physicochemical analysis in materials science

The concepts of a substance, phase, component, and directed synthesis strategy are discussed. Attention is paid to nonstoichiometry and defect composition. The following features of P-T-x phase diagrams are considered: highest melting point of a nonstoichiometric compound (T _{m, AB}^max); noncoincidence between the solid-, liquid-, and vapor-phase compositions at this temperature; factors determining the nonstoichiometry range; and congruent and incongruent phases and phase processes. Principles of directed synthesis of chemical compounds and homogeneity criteria for the synthesized products are discussed.     

Phase-Separation Phenomena of Copolymer Solutions and Fractionation of Copolymers by Chemical Composition

Precipitation temperature-total polymer concentration diagrams for toluene solutions of two styrene-acrylonitrile copolymers different in chemical composition and their mixtures were determined and then triangular phase diagrams of this system were constructed from these diagrams. It is speculated from the triangular phase diagrams and experimentally shown that the copolymer may be effectively fractionated by chemical composition in this system.     

Chemical equilibrium in a heterogeneous fluid phase system: thermodynamic regularities and topology of phase diagrams

Singularities of the systems with simultaneous phase and chemical equilibria were examined. The thermodynamic regularities were revealed and topology of phase diagrams was presented for multicomponent heterogeneous systems including two or several equilibrium liquid phases (solution layering). The thermodynamic conditions for displacement of phase and chemical equilibrium are considered.     

Phase diagrams of metal systems with highly volatile components: Simulation and experiments

A critical analysis is performed of existing literature data on the melting diagrams of systems whose components are a low-volatile metal and a high-volatile component. Models for the р–Т phase diagrams of binary systems are developed, and characteristic isobaric sections (partial state diagrams) are presented that correspond to the experimental data for real systems.     

Thermodynamic modeling of mineralogical phases formed by continuous casting powders

A great amount of mineralogical phases were predicted and represented in stability phase diagrams, which were obtained by the use of the thermodynamic software FACTSage considering both the chemical composition and the melting temperature of the mould flux. Melting-solidification tests on commercial mould flux glasses for thin slab casting of steel revealed the existence of cuspidine (Ca₄Si₂O₇F₂) as the main mineralogical phase formed during the flux solidification by X-ray powder diffraction (XRD). This phase directly influences the heat transfer phenomena from the strand to the mould and it is obtained with higher fluorite content (22% CaF₂). Cuspidine is desirable only in fluxes to produce medium carbon (included peritectic grade) steels, because it reduces the heat flux from the strand to the mould, thus controlling the shrinkage rate during the flux solidification. The experimental results are in agreement with those obtained by the thermodynamic software. The stability phase diagrams could be used as an important tool in the flux design for continuous casting process.     

Phase diagrams of diastereomeric pairs in inclusion resolution

In the development and understanding of the resolution of diastereomeric salts, phase diagrams are of great importance. This study constitutes the first example of phase diagrams of diastereomeric complexes formed from simple chiral compounds, as used in inclusion resolutions. Simple melting diagrams and DSC thermograms could not be used, because of the decomposition of the complex caused by the escape of the guest from the inclusion complex upon heating. A ternary solution phase diagram was constructed from the diastereomeric inclusion complexes of phenethylamine with a taddol. Solid solution behavior was found and confirmed by powder diffraction and X-ray studies. The limited scope of inclusion resolutions, as already indicated by our earlier studies, was confirmed by these results.