The phase diagram and tetragonal superstructures of the rare earth cobaltate phases Ln1−xSrxCoO3-δ (Ln=La, Pr, Nd, Sm, Gd, Y, Ho, Dy, Er, Tm and Yb)

Single phase perovskite-based rare earth cobaltates (Ln_1−xSr_xCoO_3−δ) (Ln=La³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Gd³⁺, Dy³⁺, Y³⁺, Ho³⁺, Er³⁺, Tm³⁺ and Yb³⁺; 0.67?x?0.9) have been synthesized at 1100°C under 1 atmosphere of oxygen. X-ray diffraction of phases containing the larger rare earth ions La³⁺, Pr³⁺ and Nd³⁺ reveals simple cubic structures; however electron diffraction shows orientational twinning of a local, tetragonal (I4/mmm; a_p×a_p×2a_p) superstructure phase. Orientational twinning is also present for Ln_1−xSr_xCoO_3−δ compounds containing rare earth ions smaller than Nd³⁺. These compounds show a modulated intermediate parent with a tetragonal superstructure (I4/mmm; 2a_p×2a_p×4a_p). Thermogravimetric measurements have determined the overall oxygen content, and these phases show mixed valence (3⁺/4⁺) cobalt oxidation states with up to 50% Co(IV). X-ray diffraction data and Rietveld techniques have been used to refine the structures of each of these tetragonal superstructure phases (Ln=Sm³⁺-Yb³⁺). Coupled Ln/Sr and oxygen/vacancy ordering and associated structural relaxation are shown to be responsible for the observed superstructure.     

B-site substitutions in LaNb1−xMxO4−δ materials in the search for potential proton conductors (M=Ga, Ge, Si, B, Ti, Zr, P, Al)

The solid solubilities of potential B-site dopants in LaNb_1-xM_xO_4−δ, materials, M=Ga, Ge, Si, Al, B, P, Zr or Ti, have been investigated in the search for possible novel proton conductors. In general, the solubility levels of these cations were found to be very low (x≤0.03). At the maximum value x=0.03, only compositions containing Ti, Ge, Ga and Si appeared pure at the limit of resolution of XRD. The literature phase diagram, La₂O₃-Nb₂O₅-ZrO₂, has been re-analysed for compositions of low Zr-content around the composition LaNbO₄. The electrical properties of phase pure Ti-doped compositions have been studied. Higher bulk and total conductivities were observed in wet than dry conditions, suggesting a significant protonic contribution to total conductivity. In wet conditions, the activation energy for bulk conductivity of LaNb_0.98Ti_0.02O_4-δ was found to be much higher than that of an A-site, Sr-doped material, Sr_0.02La_0.98NbO_4-δ, of similar acceptor dopant concentration. The Sr-doped composition offered higher conductivities than the Ti-doped composition up to approximately 900°C.     

SO2, HCl, CO2, HS und S?urechloride

Ohne Zusammenfassung     

Degree of order and redox balance in B-site ordered double-perovskite oxides, Sr2MMoO6−δ (M=Mg, Mn, Fe, Co, Ni, Zn)

We have investigated a series of double-perovskite oxides Sr₂MMoO_6−δ (M=Mg, Mn, Fe, Co, Ni, Zn) for redox stability, oxygen content and crystal structure. Phases with M=Co, Ni and Zn were found to be oxygen-stoichiometric and stable under oxidizing conditions, whereas those with M=Mn and Fe were oxygen-deficient and stable under reducing conditions. The M=Mg phase is stable both under reducing and oxidizing conditions, showing variable oxygen contents within 0.00≤δ≤0.04 depending on the annealing conditions. Structural data indicate somewhat depressed values for the degree of M/Mo cation order and also evidence of electron transfer from M^II to Mo^VI for M=Mn, Fe and Co.     

Zum schnellen Nachweis der Kationen Cu++, Ni++, Co++, Fe++ und Mn++, der AnionenSCN?,OCN?,CN?,S2O82?,J?und Br? sowie tert.aliphatischer Amine und Pyridine

Ohne Zusammenfassung     

Vibrational spectra of N,N-dimethyl/diethylaniline,N,N,N′,N′-tetramethyl/tetraethyl-p-phenylenediamine and N,N,N′,N′-tetramethyl/tetraethylbenzidine derivatives

The ground state and protonated state (quaternized salt) vibrational spectra (200–1800 cm⁻¹) of the title amines are reported for various ring and/or methyl deuterated derivatives. Complete assignments are proposed and compared to those established for the parent hydrocarbons, benzene and biphenyl, and for the parent primary amines, aniline, p-phenylenediamine and benzidine. The electronic distribution, N(n)→ring(π) charge-transfer character and inductive effects are characterized from a vibrational point of view. Finally changes in the vibrational and electronic conformation upon protonation of the nitrogen atom are discussed. These results provide a fundamental basis for the vibrational investigation of excited states and reactive transients of aromatic amines.     

Сrystal structure and physical properties of the new ternary antimonides Ln3Pd8Sb4 (Ln=Y, Gd, Tb, Dy, Ho, Er, Tm)

The ternary antimonides Ln₃Pd₈Sb₄ (Ln=Y, Gd, Tb, Dy, Ho, Er, Tm) have been synthesized for the first time. The crystal structure of Er₃Pd₈Sb₄ has been solved from the X-ray single crystal data: own type structure, space group Fm3¯m, a=1.3050(1) nm, R_F=0.0484, R_W=0.0524 for 17 free parameters and 401 reflections with F(hkl)>4σ(F). The structure of Er₃Pd₈Sb₄ can be viewed as a ternary ordered version of the Sc₁₁Ir₄-type. The lattice parameters of the isotypic compounds Ln₃Pd₈Sb₄ (Ln=Y, Gd, Tb, Dy, Ho, Tm) have been refined from the X-ray powder diffraction data. The magnetic and electrical properties of the compounds Ln₃Pd₈Sb₄ (Ln=Tb, Ho, Er) have been studied down to 1.75 K. The Ho- and Er-based phases have been found to order antiferromagnetically at 2.5 and 2.0 K, respectively. For all three compounds, the magnetic susceptibility follows in the paramagnetic region the Curie-Weiss behavior with the effective magnetic moments close to the respective free trivalent ion values. All three antimonides studied exhibit metallic character of the electrical conductivity.     

低温下Na //Cl-,SO42-,NO3-,H2O体系相平衡研究

采用等温溶解平衡法研究了四元体系Na+//Cl-,SO42-,NO-3-H2O在5、0、-5与-15℃下的相平衡关系。结果表明,4个温度下体系无复盐形成,平衡相图的构型基本一致;平衡相图均由3个结晶区(Na2SO4·10H2O、Na Cl和Na NO3)、3条单变量曲线(Na Cl-Na2SO4·10H2O、Na Cl-Na NO3、Na NO3-Na2SO4·10H2O)及1个共饱点(Na Cl-Na NO3-Na2SO4·10H2O)组成;4个温度下的平衡相图相比,随着温度的下降Na2SO4·10H2O结晶区不断扩大,Na Cl和Na NO3结晶区相对缩小;与该体系常温下的平衡相图相比,由于无复盐形成,低温下的相图大为简化。     

Single crystal studies on Co-containing τ-borides Co23−xMxB6 (M=Al, Ga, Sn, Ti, V, Ir) and the boron-rich τ-boride Co12.3Ir8.9B10.5

Single crystals of the cubic τ-Borides Co_23-xM_xB₆ (M=Al, Ga, Sn) were synthesised from the elements at temperatures between 1200 and 1500 °C. According to the structure refinements one (Ga, Sn: 8c) or two (Al: 4a and 8c) of the four independent metal sites show a mixed occupation Co/M resulting in the compositions Co_20.9Al_2.1B₆, Co_21.9Ga_1.1B₆, and Co_21.4Sn_1.6B₆, respectively. Melts with Indium gave access to Co₂₃B₆ as the first binary τ-boride (a=10.4618(13) Å, 104 refl., 14 param., R₁(F)=0.0132, wR₂(F²)=0.0210). With M=Ir mixed occupations occur for all sites and the boron content varies. The composition for the boron-poor single crystal was Co_16.2Ir_6.8B₆. A higher Ir-content enables the uptake of additional boron resulting in a composition Co_12.3Ir_8.9B_10.5. This can be explained be the substitution of metal atoms on the 8c-site by B₄-tetrahedra. A boron-rich phase was observed for the first time for a τ-boride of cobalt. All compositions were confirmed by EDX measurements.     

298.16 K时Na+, Mg2+//Cl-, SO42-, NO3-, H2O体系中NaCl饱和区域相平衡

采用等温溶解平衡法研究了五元体系Na+, Mg2+//Cl-, SO42-, NO3-, H2O在298.16 K下氯化钠饱和平衡体系的溶解度, 获得了相应的投影干盐图、氯图和水图. 研究结果表明, 在298.16 K下氯化钠饱和时, 该五元体系投影干盐图由8个二盐共饱和的双变面、13条三盐共饱的单变线和6个四盐共饱的零变点构成, 存在两种复盐, 8个二盐共饱双变面分别对应于NaCl+NaNO3, NaCl+Na2SO4, NaCl+MgCl2·6H2O, NaCl+MgSO4·Na2SO4·4H2O, NaCl+Mg(NO3)2·6H2O, NaCl+NaNO3·Na2SO4·2H2O, NaCl+MgSO4·7H2O 和NaCl+MgSO4·(1—6)H2O. 讨论了该相图在新疆硝酸盐矿开发利用过程中的应用.     

Solid–liquid equilibria of acenaphthene with o-, m-, or p-dichlorobenzene

A differential scanning calorimetry (DSC) was used to determine binary solid–liquid equilibria (SLE) for acenaphthene  + o-dichlorobenzene, +m-dichlorobenzene, and +p-dichlorobenzene over the whole concentration range. It was found that all systems are simple eutectic systems. The eutectic point of the (acenaphthene + o-dichlorobenzene) system is at 254.95 K and 0.0334 mole fraction of acenaphthene, that of the (acenaphthene + m-dichlorobenzene) system at 246.15 K and 0.0460 mole fraction of acenaphthene and that of the (acenaphthene + p-dichlorobenzene) system at 307.75 K and 0.2940 mole fraction of acenaphthene. Furthermore, the activity coefficients of the components in the binary mixtures have been correlated by the Scatchard–Hildebrand expression with one adjustable parameter. This approach offers a useful procedure for estimating with good accuracy.     

Interplay between Cu and Fe Valences in BaR(Cu0.5Fe0.5)2O5+δ Double Perovskites with R=Lu, Yb, Y, Eu, Sm, Nd, and Pr

We have conducted a systematic ⁵⁷Fe Mössbauer study on BaR(Cu_0.5Fe_0.5)₂O_5+δ double perovskites with various oxygen contents and rare-earth elements (R=Lu, Yb, Y, Eu, Sm, Nd, and Pr). In samples based on R=Lu, Yb, Y, Eu, Sm the oxygen content remained at δ≈0, upon reductive or oxidative heat treatments under normal pressure. The larger rare-earth elements, i.e. Nd or Pr, readily allowed for continuous oxygen content tuning up to δ≈0.3. By employing high-pressure heat treatments higher oxygen contents were achieved for all samples. The Néel temperature of the samples was found to decrease with increasing amounts of oxygen entering the lattice. In high-pressure oxygenated samples the decrease was less severe indicating that despite the incorporation of oxygen a large amount of Fe still remains in the high-spin trivalent state. By using charge-neutrality arguments together with the relative intensities of the Mössbauer spectral components the average valences of Fe and Cu were obtained. Oxygenation under normal pressure led to a corresponding increase of the valence of Fe, while Cu remained divalent. Upon high-pressure heat treatment equal amounts of Fe³⁺ and Cu²⁺ were found to be oxidized to Fe⁵⁺ and Cu³⁺, respectively.     

Electron diffraction evidence for continuously variable, composition-dependent O/F ordering in the ReO3 type, Nb1−xNbxO2−xF1+x, 0?x?0.48, solid solution

A spread of compositions within the Nb^V_1−xNb^IV_xO_2−xF_1+x solid solution have been successfully synthesized in the range 0?x?0.48. In each case electron diffraction has revealed the presence of strong planar diffuse scattering perpendicular to each of the three 〈001〉 directions at the G±〈hkq〉^* regions of reciprocal space, where G represents a Bragg reflection of the ReO₃ type average structure, h and k are continuously variable and q is a fixed (at any one particular composition), composition-dependent parameter in the range from 1/3 to 1/2. Careful electron probe microanalysis indicates that the value of q is directly related to composition via the equation q=(x+1)/3 and hence acts as a “chemical ruler” for the composition. A plausible model for the implied one-dimensional O/F ordering as well as for the observed shift in the position of the diffuse versus composition is provided via a crenel type occupational atomic modulation function.     

Mg0.9Ti0.1Ni1－xCox (x＝0.05, 0.1, 0.15, 0.2)合金的合成及电化学性能研究

采用机械合金化法合成了Mg_0.9Ti_0.1Ni_1－xCo_x (x＝0.05, 0.1, 0.15, 0.2)系列四元合金, 并对该系列合金的结构和电化学性能等方面进行了研究. 球磨100 h的该系列合金, XRD结果表明, X射线衍射峰均呈现宽化趋势, 基本呈非晶态. 充放电结果表明, 该系列合金具有较好的活化性能, 它们的循环稳定性明显好于MgNi合金, 其中Mg_0.9Ti_0.1Ni_0.8Co_0.2最大放电容量最高, 为427.5 mAh•g^－1. 在充放电循环过程中, Mg在合金表面形成了Mg(OH)₂是合金电极衰减的主要原因. 腐蚀曲线的测试结果表明, Co的添加可以提高合金电极在碱液中的抗腐蚀能力, 从而提高了电极的循环稳定性.     

CH3SOx (x＝0, 1)与三线态Oy (y＝1, 2, 3)反应机理的理论研究

采用B3LYP方法和6-311G(d, p)基组对CH₃S及其氧化后继物CH₃SO与O_y (y＝1, 2, 3)反应形成酸雨的微观机理进行了理论研究. 对反应势能面上的各驻点进行几何构型全优化. 振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系. 找到了7条生成SO₂的反应途径, 其中CH₃S与O直接反应得到产物CH₃和SO最容易进行; CH₃S先与O₃反应, 其产物再与O₃反应得到CH₃SO₂, CH₃SO₂最后分解得到CH₃S和SO₂较容易进行, 其它的反应较难进行.     

Synthesis, structure, and properties of M[VO2(XO4)(H2O)2] · H2O (X = S, M = K, Rb, NH4, Tl; X = Se, M = K, Rb, NH4)

Keeping of MVO(XO₄)₂ under saturated vapor pressure at room temperature resulted in the synthesis of a number of isostructural complexes M[VO₂(XO₄)(H₂O)₂] · H₂O, where X = S, M = K, Rb, NH₄, Tl and X = Se, M = K, Rb, NH₄. The conclusion about the isostructural nature of the synthesized sulfate and selenate compounds was based on X-ray diffraction and vibrational spectroscopy data. Characteristic features of the thermal decomposition of M[VO₂(XO₄)(H₂O)₂] · H₂O on heating in air were identified. It was shown that K[VO₂(SeO₄)(H₂O)₂] · H₂O tends to undergo spontaneous dehydration under ambient conditions to give the monohydrate K[VO₂(SeO₄)(H₂O)].     

Syntheses, structures and properties of five chiral quaternary sulfides, AlxLn3(SiyAl1?y)S7 (Ln = Y, Gd, Dy) and In0.33Sm3SiS7

Five new quaternary isostructural rare-earth sulfides, Al_0.57Gd₃(Si_0.27Al_0.73)S₇ (1), Al_0.55Dy₃(Si_0.34Al_0.66)S₇ (2), Al_0.50Y₃(Si_0.50Al_0.50)S₇ (3), Al_0.44Gd₃(Si_0.70Al_0.30)S₇ (4) and In_0.33Sm₃SiS₇ (5), have been synthesized by facile solid-state reactions. They crystallize in the 3-D ALn₃EQ₇ structure type in the hexagonal chiral space group P6₃. The structures feature a 3-D host framework constructed by Ln-S bicapped trigonal prisms, in which the octahedral and tetrahedral interspaces are occupied by A and E atoms, respectively. The investigation of optical and magnetic properties of 4 indicates that it is a semiconductor and behaves antiferromagnetic-like interaction.     

Die halbquantitative Bestimmung von Cl?, Br?, J?, SCN?, AsO43?, Cr2O72? und [Fe(CN)6]3?

Ohne Zusammenfassung     

273.15K下Na , K //Cl-, SO42-, NO3--H2O五元体系的相平衡研究

新疆盐湖资源丰富,冬季寒冷漫长,已有研究表明利用冬季冷能可以实现卤水浓淡分离。本文采用等温溶解平衡法针对新疆含硝酸盐卤水开发过程中涉及的Na~+,K~+//Cl~-,SO_4~(2-),NO_3~-H_2O及Na~+,K~+//Cl~-,NO_3~-H_2O体系273.15K下的相平衡关系进行了研究。通过查找文献及实验获得两个体系各盐的溶解度及溶液密度,并绘制相图。研究表明,上述四元体系的干盐相图有2个零变量点、5条单变量溶解度曲线、4个单盐结晶区分别对应于NaNO_3、NaCl、KNO_3和KCl,与该体系在298.15K下的相图相比,硝酸钾结晶区扩大很多;上述五元体系干盐相图(NaCl饱和)有2个零变量点、5条单变量溶解度曲线、4个两盐结晶区分别对应于NaCl+NaNO_3,NaCl+Na_2SO_4·10H_2O,NaCl+KNO_3,NaCl+KCl,与该体系298.15K下的相图相比,复盐钾芒硝和钠硝矾结晶区消失,芒硝结晶区扩大,相图大为简化。