Diagramme polythermique du systeme ternaire H2O—Al(NO3)3—Mg(NO3)2

The solid—liquid equilibria of the ternary system H₂O—Al(NO₃)₃—Mg(NO₃)₂ were studied at –30, –20, –10 and 0°C by using a synthetic method which allows to detemine all the characteristic points of isothermal sections. The stable solid phases which appear are respectively: ice, Al(NO₃)₃·9H₂O, Mg(NO₃)₂·9H₂O and Mg(NO₃)₂·6H₂O. Neither double salts nor mixed crystals are observed in the temperature and composition field studied. Polytherm diagram layout show two invariant transformations correspond with an eutectic point and a peritectic point.This revised version was published online in November 2005 with corrections to the Cover Date.     

(A19N7)[In4]2 (A = Ca,Sr) and (Ca4N)[In2]: Synthesis,Crystal Structures,Physical Properties,and Chemical Bonding

Single phase powders of (A₁₉N₇)[In₄]₂ (A = Ca, Sr) and (Ca₄N)[In₂] were prepared by reaction of melt beads of the metallic components with nitrogen. The crystal structure of (Ca₁₉N₇)[In₄]₂ was refined based on neutron and X‐ray powder diffraction data. The crystal structure of (Sr₁₉N₇)[In₄]₂ was solved from the X‐ray powder pattern. The structure refinements in combination with results from chemical analyses ascertain the compositions. The compounds (A₁₉N₇)[In₄]₂ (A = Ca, Sr) are isotypes of (Ca₁₉N₇)[Ag₄]₂; (Ca₁₉N₇)[In₄]₂ is probably identical to the earlier reported (Ca_18.5N₇)[In₄]₂. The crystal structure of the isotypes (A₁₉N₇)[In₄]₂ (A = Ca, Sr; cubic, , Ca: a = 1471.65(3) pm; Sr: a = 1561.0(1) pm) contains isolated [In₄] tetrahedra embedded in a framework of edge‐ and vertex‐sharing (A₆N) octahedra. Six of these octahedra are condensed by edge‐sharing around one central A²⁺ ion to form “superoctahedra” (A₁₉N₆) which are connected three‐dimensionally via further octahedra by corner‐sharing. The crystal structure of (Ca₄N)[In₂] (tetragonal, I4₁/amd, a = 491.14(4) pm, c = 2907.7(3) pm) consists of alternating layers of perovskite type slabs of vertex‐sharing octahedra (Ca₂Ca_4/2N) and parallel arranged infinite zigzag chains equation/tex2gif-stack-1.gif[In₂]. In the sense of Zintl‐type counting the compounds (A²⁺)₁₉(N^3?)₇[(In^2.125?)₄]₂ present an electron excess, (Ca²⁺)₄(N^3?)[(In^2.5?)₂] is electron deficient. Metallic properties are supported by electrical resistivity and magnetic susceptibility measurements. The analysis of the electronic structures gives evidence for the existence of homoatomic interactions In–In and significant heteroatomic metal–metal interactions Ca–In which favor the deviations of the title compounds from the (8 – N) rule.     

Densities and Excess Molar Volumes of Binary and Ternary Mixtures of Aqueous Solutions of 2,2,2-Trifluoroethanol with Acetone and Alcohols at the Temperature of 298.15 K and Pressure of 101 kPa

Excess molar volumes V_m^E of the binary mixtures of (trifluoroethanol + 1-propanol), (trifluoroethanol + 2-propanol), (acetone + water), (methanol + water), (ethanol + water), (1-propanol + water), (2-propanol + water), and the ternary mixtures of (trifluoroethanol + methanol + water), (trifluoroethanol + ethanol + water), (trifluoroethanol~+ 1-propanol + water), (trifluoroethanol + 2-propanol + water) and (trifluoroethanol + acetone + water) were measured with a vibrating tube densimeter at the temperature of 298.15 K and the pressure 101 kPa. The extrema in V_m^E of trifluoroethanol mixtures occur at –0.690 cm³-mol^–1 for (trifluoroethanol + 1-propanol), at –0.990~cm³-mol^–1 for (trifluoroethanol + 2-propanol); at 0.562 and –0.973 cm³-mol^–1 for (trifluoroethanol + methanol + water), at 0.629 and –0.973 cm³-mol^–1 for (trifluoroethanol + ethanol + water), at 1.082 and –0.659 cm³-mol^–1 for (trifluoroethanol~+ 1-propanol + water), at 0.998 and –0.991 cm³-mol^–1 for (trifluoroethanol~+ 2-propanol + water), and at 0.515 and –1.472 cm³-mol^–1 for (trifluoroethanol + acetone + water). The experimental ternary V_m^E values were predicted by empirical expressions using binary solution data.     

铕(Ⅲ)水杨酸邻菲咯啉三元配合物性质研究

合成了Eu3+的水杨酸和邻菲咯啉三元配合物,其组成为Eu(Hsal)3phen,用IR,UV,XPS研究配合物的性质和成键特征.结果表明,Hsal-的羧基、phen的两个氮原子均与Eu3+离子呈双齿配位,形成配合物后芳香环上的共轭性减小.用循环伏安法研究了配合物在玻碳电极上的电化学行为,发现配合物的电化学可逆性比游离Eu3+离子差,不同底液对配合物的电化学行为有影响.     

钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用

用pH-电位滴定法测定了Pd(L)(Aa)⁺三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO₃)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。     

Adsorption of the Ternary Liquid Mixture Ethanol/n-Octane/n-Hexadecane onto Activated Carbon: I. The Adsorption Excess of the Ternary Mixture and of Its Binary Combinations

The adsorption isotherms of the binary mixtures of ethanol/n-Octane, ethanol/n-hexadecane and n-octane/n-hexadecane onto the activated carbon TA 95 were measured at 278 K, 288 K, 298 K and 308 K and described with mathematical functions. About 300 experimental values of the adsorption excess of the ternary mixture ethanol/n-octane/n-hexadecane onto activated carbon TA 95 at 298 K were measured by gas chromatography inside the ternary triangle. The ternary miscibility gap was determined at three temperatures. A good representation of the ternary data and the calculated activity coefficients (using the UNIFAC model) in three-dimensional space was possible with the help of transformation of coordinates. It was possible, too, by utilization of the conception of the quasi two-component representation of the mole fractions with and without miscibility gap. Several influencing factors on ternary adsorption isotherms were discussed for the system ethanol/n-octane/n-hexadecane/TA 95.     

Crystal Structure of Ternary Molybdate Rb5FeHf(MoO4)6 — a New Phase in the Rb2MoO4-Fe2(MoO4)3-Hf(MoO4)2 System

Physicochemical analysis (XRPA, DTA) was used to study phase equilibria in a ternary salt system Rb₂MoO₄-Fe₂(MoO₄)₃-Hf(MoO₄)₂ in the subsolidus region. Ternary molybdates with compositions 5:1:3, 5:1:2, and 1:1:1 have been found and synthesized. Crystal and thermal characteristics have been determined. Single crystals of the ternary molybdate Rb₅FeHf(MoO₄)₆ with a composition of 5:1:2 were grown. The crystal structure of the compound was solved using X-ray diffractometry (CAD-4 automatic diffractometer, MoK _α radiation, 1766 F(hkl), R = 0.0298). Hexagonal crystals with unit cell dimensions: a = b = 10.124(1) Å, c =15.135(3) Å, V = 1343.4(4) ų, Z = 2, ρ_calc = 4.008 g/cm³, space group P6₃. The mixed three-dimensional framework of the structure is formed from two sorts of MoO₄ tetrahedra and Fe and Hf octahedra linked through their common O-vertices. Rubidium atoms of three varieties occupy the large voids of the framework.Original Russian Text Copyright © 2004 by B. G. Bazarov, R. F. Klevtsova, A. D. Tsyrendorzhieva, L. A. Glinaskaya, and Zh. G. Bazarova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1038–1043, November–December, 2004.     

Binary and Ternary Copper(II) Complexes with NIPAAm/IA Copolymers and Aminoacids: Interpretation of UV‐Visible Spectra and Cyclic Voltammograms

The complex formations of homopolymers and copolymers of poly(N‐isopropyl acrylamide) (PNIPAAm), polyacrylamide (PAAm) and poly(itaconic acid) (PIA) with Cu(II) ions in aqueous solutions were studied by using UV‐visible spectra in the region of 200–1100 nm and cyclic voltammograms between ?0.800 V and 0.600 V. According to the optical and electrochemical spectra of the polymer‐ and copolymer‐Cu(II) complexes and their ternary complexes with alanine, i.e., absorptions and the shifts in the wavelength of the maximum absorptions, currents and potentials of the peaks in the pH range of 3–12, the intensities of anodic and cathodic peak currents of polymers containing IA groups decrease with increasing pH and they show maximum absorptions at lower wavelengths than do the homopolymers used in this work. The peak point of the visible band shifts from 800 to 650 nm, with increasing pH, while the intensity of the third anodic peak observed after pH=4 increases in the case of both Ala‐Cu(II) and its ternary solution with P(NIPAAm‐co‐IA, 9.8 mol%). Both the pH‐dependent shifts of maximum absorptions and the appearence of the third anodic peaks as the pH raised were interpreted as a presence of tetracoordinated Cu(II) complexes in the solution and on the electrode surface, involving combined carboxyl, amide and amine interaction.     

CF4 decomposition over solid ternary mixture NaF-Si-MO（MO=La2O3,CeO2,Pr6O-（11）,Nd2O3,Y2O3）

A solid ternary mixture consisting of NaF,silicon and one metal oxide such as La2O3,CeO2,Pr6O11,Nd2O3,and Y2O3 was prepared and usedas de-fluorinated reagent for CF4 decomposition.The results show that 90% conversion of CF4 can be reached initially over NaF-Si-La2O3,NaF-Si-CeO2,NaF-Si-Nd2O3,and NaF-Si-Y2O3 at 850 C.The fresh and used reagents were characterized using XRD and XPS techniques.It was found that the active components of NaF and metal oxides in NaF-Si-CeO2,NaF-Si-Pr6O11,NaF-Si-Nd2O3,and NaF-Si-Y2O3 weretransformed into inert phases of mixed metal fluorides and silicates,respectively,resulting in an ineffective utilization of these de-fluorinatedreagents,whereas no inert phases from NaF and La2O3 can be observed in the used NaF-Si-La2O3,indicating the NaF-Si-La2O3 reagent couldbe utilized more efficiently than the other reagents in CF4 decomposition.     

Etude du Systeme Ternaire H2O-Al(NO3)3-Mg(NO3)2 I - Isothermes 15, 25, 30, 40 et 50°C

The solid-liquid equilibria of the ternary system H₂ O-Al(NO₃ )₃ -Mg(NO₃ )₂ were studied at 15, 25, 30, 40 and 50°C by using a synthetic method which allows to determine all the characteristic points of isothermal sections. In all isotherms the liquidus exhibit two curves corresponding to the saturation in Mg(NO₃ )₂ ⋅6H₂ O and Al(NO₃ )₃ ⋅9H₂ O. Neither double salts nor mixed crystals are observed in the temperature and composition field studied. This revised version was published online in July 2006 with corrections to the Cover Date.