四元体系MCl-GdCl~3-HCl-H~2O(M=K,Rb, Cs; 20℃)的研究

本文研究了四元体系MCl-GdCl~3-HCl-H~2O(M=K, Rb, Cs; 20℃)在不同酸浓度下的溶度, 绘制了相应的溶度图, 当M=K, HCl wt%=14~23%的平行截面时, 体系中无化合物形成; 当M=Rb, HCl wt%=13%时, 体系中无化合物形成, 但在HCl wt%=22的平行截面时, 体系中形成固液异组成的化合物RbCl.GdCl~3.4H~2O(1); 当M=Cs, 在HCl wt%分别为13%5和20%的条件下, 体系均形成4CsCl.GdCl~3.H~2O(2)和2CsCl.GdCl~3.7H~2O(3)两种化合物, 2在两种酸浓度下都是固液异组成的化合物, 3随酸浓度由低到高的变化, 从固液同组成化合物转变为固液异组成化合物。化合物1, 2未见文献报道。本文的研究结果为Meyer的合成反应提供了热力学相平衡基础和新的机理解释, 并可以更好地应用和指导Meyer合成反应。同时, 首次提出了合成RbGd~2Cl~7、Cs~3Gd~2Cl~9两个化合物的可能性。     

三元体系MCl-SbCl~3-HOAc (M=Li,Na; 25℃)的研究

测定了三元体系MCl-SbCl~3-HOAc(M=Li,Na;25℃)的溶度数据和饱和溶液的折光指数,并绘制了相应的溶度图及其折光指数曲线。M=Li时,体系的溶度曲线和折光指数曲线均由三支组成,分别与LiCl.0.5HOAc,LiCl,SbCl~3相对应。M=Na时,体系属于简单共饱型,无任何新相形成。研究结果表明,当M分别是Li,Na或K,NH~4,Rb,Cs时,体系的物理化学行为有着极为显著的不同,说明MCl-SbCl~3-HOAc(M=Li,Na,K,NH~4,Rb,Cs)体系可以作为区分碱金属系列阳离子性质差别的典型体系。     

三元体系RbCl-SbCl3-HOAc(25℃)的研究

本文测定了三元体系RbCl-SbCl3-HOAc在25℃时的溶度及饱和溶液折光指数,并绘制了相应的溶度图,体系中有8种固相:RbCl,SbCl3两种原始盐;3RbCl.SbCl3,7RbCl.3SbCl3,3RbCl.2SbCl3,RbCl.SbCl3四种二元复盐和2RbCl.3SbCl3.4HOAc,2RbCl.3SbCl3.1.5HOAc两种三元复盐,两种三元复盐在以往的文献中未见报道.文中初步描述了以上六种复盐的一些物理化学性质,并给出了RbCl.SbCl3复盐的X射线衍射数据,本文提供了一种制备3RbCl.SbCl3的新方法.该体系的研究可能为改进从光卤石提取RbCl,CsCl的工艺提供相     

三元体系C_sCl-SbCl_3-HOAc(25℃)的研究

本文测定了三元体系CsCl-SbCl_3-HOAc在25℃时的稳定平衡态的溶度及饱和溶液折光指数,绘制了相应的溶度图。稳定平衡态时体系中有五种固相:CsCl,SbCl_3两种原始盐;3CsCl·SbCl_3,3CsCl·2SbCl_3两种二元复盐和CsCl·5SbCl_3·4HOAc三元复盐。3CsCl·2SbCl_3相区极大,该复盐是固液同组成的。3CsCl·SbCl_3与CsCl·5SbCl3·4HOAc是固液异组成的。三元复盐在以往的文献中未见报道。3CsCl·SbCl_3,3CsCl·2SbCl_3在空气中稳定,不吸潮水解。三元复盐仅能在溶液中稳定存在,移出母液后易转变为3CsCl·2SbCl_3。测定了该体系25℃时一根甚长的介稳溶度曲线及饱和溶液折光指数。介稳溶度曲线所对应的固相为5CsCl·2SbCl_3。向该体系中的饱和溶液加入晶种,长时间搅拌,5CsCl·2SbCl_3转变为稳定态的3CsCl·2SbCl_3,溶液的组成亦降到3CsCl·2SbCl_3的溶度曲线上。在本实验条件下没有发现7CsCl·5SbCI_3复盐形成。除了文献报道过的从液态SO_2中制取3CsCl·8bCl_3的方法之外,本文提供了又一种制取该复盐的方法。本文为从铯榴石中提取CsCl的工艺及铯的定量分析,提供了相图上的根据.     

三元体系NH4Cl-SbCl3-HOAc(25℃)的研究

本文测定了三元体系NH4Cl-SbCl3-HOAc在25℃时平衡态和介稳态的溶度及部分饱和溶液的折光指数, 并绘制了相应的溶度图. 体系在稳定平衡态时有五种固相: NH4Cl、SbCl3(原始盐), 5NH4Cl-SbCl3(1)、2NH4Cl-SbCl3.5HOAc(2)和5NH4Cl-3SbCl3.2.5HOAc(3)(复盐). 一支介稳溶度曲线所对应的固相是3NH4Cl.SbCl3(4). 本文初步描述了以上四种复盐的一些物理化学性质. 体系中合成的二元复盐1和溶剂合复盐2与3文献中均未见报道. 本文提供了一种制备3NH4Cl.SbCl3的新方法.     

121,123Sb NQR study of solid phases formed in systems (MF)1−x −(M′F) x −SbF3−H2O (M, M′=Na, K, Rb, Cs, and NH4)

Crystalline substances formed in the (MF)_1−x −(M′F) _x −SbF₃−H₂O systems (M, M′=Na, K, Rb, Cs, and NH₄;x=0 to 1) were investigated by^121,123Sb NQR spectroscopy at 77 K. The formation of individual Sb^III complexes NaCs₃Sb₄F₁₆·H₂O and NaKSbF₅·1.5H₂O, and statistically disordered mixed crystals M_1−x −M′ _x −SbF₄ (M, M′=K, Rb, Cs, and NH₄) was established. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 109–112, January, 1999.     

碱金属硒化物MHgSbSe~3(M=K,Rb, Cs)的晶体结构及其半导体性 质的研究

用有机溶剂热生长技术(SolvothermalTechnique)制备碱金属硒化物MHgSbSe~3(M=K,Rb,Cs),用单晶X射线衍射技术对其进行晶体结构分析,热分析结果表明,在常温(<200℃)下均为稳定的化合物。光学性质测试表明它们是半导体材料,KHgSbSe~3,RbHgSbSe~3,CsHgSbSe~3的禁带宽度依次为1.85eV,1.75eV,1.65eV。     

Preparation and photoluminescent properties of Eu(III) containing M-layered silicates (M = Li,Na, K,Rb, Cs)

Eu(III) containing M-layered silicates (M = Li, Na, K, Rb, Cs) were prepared using the layered silicates, such as ilerite, magadiite, and kenyaite, as a host matrix and the luminescence properties were investigated. The results from the luminescence measurements indicated that the luminescence properties in the EuM-layered silicate system depended strongly on the types of host matrices and alkali cations. Among the EuM-layered silicates, EuM-ilerite exhibited the strongest luminescence intensity for all alkali cations, whereas EuM-kenyaite exhibited relatively weak luminescence intensity. The luminescence intensity was significantly increased by heat treatment at high temperature, mainly due to the phase change of host matrices and the presence of alkali cations in the host matrices. Particularly, the luminescence intensity of EuM-layered silicate calcined at 1,000 °C increased with the increase of the ion size of alkali cations.     

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.     

三元体系LaCl3-Am(Am=Gly,Glu,Ser)-H2O(25℃)的研究

测定了3个三元体系LaCl₃-Am-H₂O(Am=Gly,Glu,Ser)在25℃时的溶度和饱和溶液的折光指数。报道了三元体系中生成的三元配合物La(Gly)Cl₃·2H₂O(A₁)、La(Gly)₃Cl₃·3H₂O(A₂)、La₂(Glu)₃Cl₆·8H₂O(C)、La(Ser)Cl₃·3H₂O(E)。用摩尔电导、红外光谱、X射线衍射、热分析及偏光显微镜鉴测定了各配合物的一些物理化学性质。     

三元体系KCl-SbCl_3-HOAc(35℃)的研究

KCl-SbCl_3熔盐体系以及KCl,SbCl_3在盐酸溶液和在液态SO_2中的化学行为均已有文献报道,而对在非水有机溶剂冰醋酸中的化学行为的研究报道则尚未见.本文报道对三元体系KCl-SbCl_3-HOAc(35℃)的研究结果.     

ABeF_3(A=Na,K,Rb,Cs)体系中Eu~(2+)的f→f跃迁发射

合成了一系列Eu~(2+)激活的碱金属氟化物一氟化铍复合氟化物(ABeF_3∶Eu~(2+))磷光体。观察到了f→f跃迁引起的Eu~(2+)很强的锐线发射,尖峰位于360nm附近。随碱金属原子电负性减小,峰值向短波方向稍有移动。得到了与A.S.T.M一致的结晶学数据。穆斯堡尔谱和电子能谱结果表明,体系中有少许Eu~(3+)与Eu~(2+)共存。     

三元体系KCl-SrCl_2-H_2O 25℃相平衡研究

Phase equilibria in the ternary system KCl-SrCl2-H2O at 25 ℃ was studied by using the isothermal method. Density and refractive index of the solution were also determined. The phase diagram was plotted according to the experimental data. In the equilibrium phase diagram of KCl-SrCl2-H2O, there is one invariant point, two univariant curves and two regions of crystallization: KCl and SrCl2·6H2O. In the invariant point, the composition of the liquid phase (mass fraction, wB) was wKCl 7.22%, wSrCl232.31%, the solid phase was KCl and SrCl2·6H2O. Neither double salts nor solid solutions between KCl and SrCl2·6H2O were found, and dehydration of SrCl2·6H2O didn′t occur in the system. The system is a simple eutectic type.     

298.15和308.15 K时1,2-丙二醇+MCl (M=Na,K, Rb,Cs)+H2O三元体系的溶解度、密度和折光率

系统研究了1,2-丙二醇+MCl (M=Na, K, Rb, Cs)+H₂O三元体系在298.15 和308.15 K时的等温相平衡. 采用硝酸汞滴定法测定了体系中无机盐的含量, 采用安东帕RXA170 折光率仪及DMA4500 密度计测定了所有体系的折光率和密度数值. 报道了1,2-丙二醇质量分数从0增加到0.9过程中饱和及不饱和三元溶液体系的等温溶解度、密度和折光率数据. 实验结果发现, 随着1,2-丙二醇的不断加入, 饱和溶液的溶解度和密度均呈现出减小的趋势, 而折光率的变化则呈现出相反的趋势. 采用经验方程关联了不同醇水比条件下不饱和溶液的密度和折光率实验数据, 获得了较为理想的拟合结果. 本研究的开展充实了碱金属盐在混合溶剂中的热力学数据, 为相关溶液化学研究奠定了基础.     

三元体系KCI-SrCl_2-H_2O 25℃相平衡研究

我国的无机盐液体矿床资源主要有海水、井卤、盐湖卤水和油田卤水.其中盐湖数量多、种类齐全,主要分布在青藏高原、内蒙古高原和新疆广大地区~([1]).盐湖中的卤水资源,现已大量开发利用.     

三元体系CsCl-SbCl3-HOAc(25 C)的研究

The system CsCl-SbCl3-HOAc (25`C) has been studied. Solubilities of this system were measured at 25 +/- 0.05`C(Table 1 in Chinese Text) and the corresponding equilibrium diagram was constructed There are 5 solid phases in the system: two original salts (CsCl, SbCl3), two double salts (3CsCl.SbCl3, 3CsCl.2SbCl3) and a ternary compound (CsCl.5SbCl3.4HOAc) which was shown to be present for the first time. The region of 3CsCl.2SbCl3 is predominantly large in the phase diagram. 3CsCl.2SbCl3 is soluble congruently, while 3CsCl.SbCl3 and CsCl.5SbCl3.4HOAc are soluble incongruently in HOAc. In air, the double salts are stable, but the solvate compound decomposes easily with the formation of 3CsCl.2SbCl3. A metastable phase 5CsCl.2SbCl3 was found, and its solubilities were determined at the same temperature (Table 2). It is stable in air, but under certain conditions it changes into 3CsCl.2SbCl3. No 7CsCl.5SbCl3 was found. This work presents a new method for preparing 3CsCl.SbCl3 in addition to that reported by G. Jander and E.Martineau. The results of this work present a profitable basis of the phase diagram for extracting CsCl from pollucite and analysing Cs with SbCl3.     

Synthesis and Properties of Uranosilicates M[HSiUO6] · nH2O (M = NH4+, Li,Na, K,Rb, Cs)

A complete set of uranosilicates M[HSiUO₆] · nH₂O of alkali metals and ammonium was obtained under hydrothermal conditions. The functional and phase similarity of the compounds was proved by X-ray phase analysis and IR spectroscopy. The effect of water molecules on the structures of hydrated and anhydrous uranosilicates and the nature of water in these compounds were elucidated by studying hydration-dehydration processes. The dependence of the X-ray and thermal properties of the compounds on the nature of interlayer atoms was considered.     

Synthesis of Tetrahedranes Containing the Unique Bridging Hetero-Dipnictogen Ligand EE′ (E ≠ E′=P,As, Sb,Bi)

In order to improve and extend the rare class of tetrahedral mixed main group transition metal compounds, a new synthetic route for the complexes [{CpMo(CO)₂}₂(μ,η²:η²- PE )] (E=As ( 1 ), Sb ( 2 )) is described leading to higher yields and a decrease in reaction steps. Via this route, also the so far unknown heavier analogues containing AsSb ( 3 a ), AsBi ( 4 ) and SbBi ( 5 ) ligands, respectively, are accessible. Single crystal X-ray diffraction experiments and DFT calculations reveal that they represent very rare examples of compounds comprising covalent bonds between two different heavy pnictogen atoms, which show multiple bond character and are stabilised without any organic substituents. A simple one-pot reaction of [CpMo(CO)₂]₂ with ME(SiMe₃)₂ (M=Li, K; E=P, As, Sb, Bi) and the subsequent addition of PCl₃, AsCl₃, SbCl₃ or BiCl₃, respectively, give the complexes 1–5 . This synthesis is also transferable to the already known homo-dipnictogen complexes [{CpMo(CO)₂}₂(μ,η²:η²- E₂ )] (E=P, As, Sb, Bi) resulting in higher yields comparable to those in the literature reported procedures and allows the introduction of the bulkier and better soluble Cp′ (Cp′=tert butylcyclopentadienyl) ligand.     

Aqueous sol–gel synthesis,thermoanalytical study and luminescent properties of M0.05Eu0.05Ca0.9MoO4 (M=Li,Na, K,Rb, Cs) nanocrystallites

Nano-sized M_0.05Eu_0.05Ca_0.9MoO₄ (M=Li, Na, K, Rb, Cs) ceramics have been successfully synthesized by an aqueous sol–gel synthesis method using a tartaric acid as a ligand. In order to reveal the influence of the peculiarities of the nature of dopants effect into the crystallization of CaMoO₄ double oxide, the thermal analysis of the as-prepared gels was performed. In addition, infrared spectroscopy was used in order to identify the functional groups from the characteristic stretching vibrations in the M–Eu–Ca–Mo–O tartrate gel precursors. Besides, to confirm the dynamics of growing crystallites in the final ceramics and to reveal the morphological changes on the surface, the x-ray diffraction and scanning electron microscopy were applied. Finally, photoluminescence measurements were used to estimate the optical properties of europium oxide as a dopant in the samples according to the nature of alkali metal. Therefore, according to the obtained results, it was estimated that luminescence intensity of Eu³⁺ ions is mainly affected by the chemical reaction, which takes place at about 973 K of temperature. This effect was partly confirmed from the results of the thermal decomposition of M–Eu–Ca–Mo–O tartrate gel precursors with an endothermic behaviour in the DSC curve, which indicates the crystallization mechanism of the CaMoO₄ double oxide.