The bonding in second row transition metal dihydrides,difluorides and dichlorides

Summary The dihydrides, the difluorides and the dichlorides of the second row transition metal atoms from yttrium to palladium have been studied with methods including electron correlation of all valence electrons. Comparisons are made to the previously studied corresponding diatomic systems. It is found that the general trends of the binding energies of the second hydride and halide remain the same as in the diatomic hydrides and halides. The second ligand binding energies for the dihalides thus vary much more than for the dihydrides. This is due to important attractive effects between the halide lone-pairs and empty 4d-orbitals to the left and strong repulsions towards occupied 4d-orbitals to the right. For some systems the second ligand binds much more than the first ligand, as for RuF₂ where the difference is 34.3 kcal/mol, whereas for other systems the reverse is true, as for PdCl₂ where the first ligand binds more than the second with 20.4 kcal/mol. The results can be explained by strong ligand field effects and differences in the atomic spectra.     

阳极氧化膜WO3（Ⅱ）：电显色的介质效应

用循环计时电量法、循环伏安法、电化学现场(in-situ)紫外可见反射光谱技术和光电流谱技术研究了溶剂和阳离子(H~+,Li~+)对阳极氧化膜WO_3电显色稳定性和过程的影响。从循环计时电量图可以测定表征膜稳定性的氢或锂的累积量和暂态周期数。实验发现W/WO_3/LiCLO_4乙腈溶液体系具有高的电显色稳定性。引起WO_3膜可逆电显色的H~+和Li~+离子的嵌-脱过程的界面电化学机理不同。着色态WO_3膜的色心是自由电子,其密度超过10~(21)/cm~3,生色机理是等离子体振荡。     

XRD法研究CrO3与NaY、NaM分子筛的表面相互作用

负载于多孔性、高比表面载体上的三氧化铝是重要的工业催化剂，多年来人们对催化剂中Croa的存在状态以及与载体的相互作用进行了广泛的研究［‘－4］，发现CrO。能在载体表gn散成非晶相的表面化合物，非晶相Cr（VI）具有较高的催化活性．我们曾经对MoO。／NaY，MoO。／NaM体系进行过系统的研究，发现MOO。与分子筛载体间存在强表面相互作用［’］．在此研究基础上，选择了CrO3／NaY、CrO。／NaM体系，采用XRD法对上述体系进行了研究．结果表明170oC下晶相CrO。能在NaY、NaM分子筛上自发分散成非晶相Cr（VI），且分散量大．C…     

有机溶剂对镧和钇ICP光谱信号的增敏机理研究

本文考察了有机溶剂（乙酸丁酯）及有机试剂（PMBP）引入ICP－AES对稀土元素镧和钇光谱信号的影响。实验结果表明，有机溶剂的引入明显增大了待测物的传质效率，从而导致分析灵敏度的改善。与水相相比，有机相的引入对ICP激发温度未产生明显影响，但使线对强度比（LogI^ /I)增强，有利于待测物的电离。     

钇提高YT14硬质合金耐磨性的机制

研究了不同Ｙ添加量对ＹＴ１４硬质合金显微组织、结构和耐磨性的影响。结果表明，在ＹＴ１４硬质合金中添加微量Ｙ，可显著提高合金的耐磨性。Ｙ的主要作用是均匀细化碳化物相和Ｃｏ相；提高Ｃｏ粘结相中Ｗ、Ｔｉ元素的固溶量及αＣｏ相所占的体积分数，从而提高Ｃｏ粘结相的强韧性；Ｙ在合金中形成Ｙ２ＷＯ６，表明Ｙ还可还原和清除碳化钨表面氧化膜，增强Ｃｏ粘结相与硬质相之间的结合强度     

Electrochromic and structural characteristics of mesoporous WO<Subscript>3</Subscript> films prepared by a sol-gel method

The preparation of electrochromic films of mesoporous tungsten trioxide from tungstic acid and tungstic hexaethoxide precursors with the addition of an organic stabiliser via a sol-gel method is reported. These films have been structurally characterised and both the film morphology and crystalline composition of the films were found to be significantly dependent on the temperature at which the films were annealed and upon the choice of precursor. Films annealed at lower temperatures consisted of amorphous and hexagonal tungsten trioxide, whereas films annealed above 500 °C comprised solely of monoclinic WO₃. The electrochromic activity of the films was found to be equally dependent on method of preparation, and both the composition and the structure of the WO₃ films were shown to clearly influence the colouration efficiency of the films.Dedicated to Zbigniew Galus on the occasion of his 70^th birthday.     

Complex formation constants and thermodynamic parameters for La(III) and Y(III)L-serine complexes

Summary The stoichiometric stability constants for La(III) and Y(III)L-serine complexes were determined by potentiometric methods at different ionic strengths adjusted with NaClO₄ and at different temperatures. The overall changes in free energy (G ^o), enthalpy (H ^o), and entropy (S ^o) during the protonation ofL-serine and that accompanying the complex formation with the metal ions have been evaluated.

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Komplexbildungskonstanten und thermodynamische Parameter für La(III)- und Y(III)-L-Serin-Komplexe

Zusammenfassung Die stöchiometrischen Komplexbildungskonstanten für La(III)- und Y(III)-L-Serin-Komplexe wurden mittels potentiometrischer Methoden bei verschiedenen Ionenstärken (mit NaClO₄ adjustiert) und bei verschiedenen Temperaturen bestimmt. Die Änderungen in der freien Energie (G ^o), Enthalpie (H ^o) und Entropie (S ^o) während der Protonierung und der Komplexbildung mit den Metallionen wurden ermittelt.

     

钇(Ⅲ)-莫西沙星配合物的荧光性质及分析应用

钇(Y3+)与莫西沙星(MoxifloxacinMXFX)形成的配合物能显著地增敏莫西沙星的荧光强度,据此,建立了测定莫西沙星的新方法。该方法的检出限为8.5×10-10mol/L;莫西沙星的浓度在1.0×10-8～1.0×10-6mol/L范围内与配合物体系的荧光强度呈良好的线性关系。对1.0×10-6mol/L莫西沙星平行测定12次,RSD为1.1%。该法可用于测定尿样中的莫西沙星。对荧光增强机理作了简要的探讨。     

Synthesis and electrochemical properties of yttrium-doped LiMn<Subscript>0.98</Subscript>Y<Subscript>0.02</Subscript>O<Subscript>2</Subscript> for lithium secondary batteries

Yttrium-doped lithium manganese oxide (LiMn_0.98Y_0.02O₂) was prepared by ion exchange of lithium for sodium in NaMn_0.98Y_0.02O₂ precursors obtained by using rheological phase reaction method. This material had small particle size, which was composed of grain size of about 100 nm. Especially, LiMn_0.98Y_0.02O₂ delivered the initial discharge capacity of about 191 mA h g⁻¹ at room temperature when cycled between 2.0 and 4.4 V vs Li/Li⁺. Moreover, it showed an excellent cycling behavior, its specific capacity remained above 173 mA h g⁻¹ after 20 cycles, and the material did not transform into spinel structure during the electrochemical cycling according to the cyclic voltammograms and X-ray powder diffraction. The electrochemical results revealed that the doping of Y³⁺ improved the performance of LiMnO₂ considerably.     

钙与 DBC-偶氮氯膦显色反应的研究及其在高纯氧化钇中钙的测定的应用

在PH8.5-9的液中,钙可与DBC-偶氮氯膦形成一种紫色的稳定配合物。该配合物在625nm处有最大吸收,表观摩尔吸光系数为2.6×10~4L.mol~(-1).cm~(-1),配合物组成为Ca:DBC-偶氮氯膦=1:1。在Zn-DTPA和乙二胺的存在下,较大量的Y~(3+)、Fe~(3+)及Cu~(2+)、Mo(Ⅵ)、Cr~(3+)等三十余种离子不干扰钙的测定。方法的选择性较好,利用本方法,并经简单萃取分离基体后,测定了高纯氧化钇和易切削钢中的微量钙,结果令人满意。标准加入试验回收率好。方法简便实用。