Strukturen von neuenSE-Verbindungen, 1. Mitt.

Zusammenfassung Die Phasen GdZn₁₂, TbZn₁₂, DyZn₁₂ und YbZn₁₁ werden aus den metallischen Komponenten hergestellt und kristallchemisch untersucht. GdZn₁₂, TbZn₁₂ und DyZn₁₂ kristallisieren im ThMn₁₂-Typ, YbZn₁₁ ist isotyp mit BaCd₁₁.

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The phases GdZn₁₂, TbZn₁₂, DyZn₁₂ and YbZn₁₁ have been prepared from the metallic components and examined by X-rays. GdZn₁₂, TbZn₁₂ and DyZn₁₂ are crystallising with the ThMn₁₂-type, YbZn₁₁ is isotypic with BaCd₁₁.

     

Die Kristallstrukturen von YAg2, YAu2 und YZn12

Zusammenfassung Die Phasen YAg₂, YAu₂ und YZn₁₂ werden aus den metallischen Komponenten hergestellt und kristallchemisch untersucht. YAg₂ und YAu₂ gehören zum MoSi₂-Typ und YZn₁₂ zum ThMn₁₂-Typ.

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The phases YAg₂, YAu₂ and YZn₁₂ have been prepared from the components and examined by X-rays. YAg₂ and YAu₂ are crystallizing with the MoSi₂-type and YZn₁₂ with the ThMn₁₂-type. *** DIRECT SUPPORT *** A3615111 00005

     

The influence of Yb, B, and Ga-doped Er3+:Y3Al5O12 on solar light photocatalytic activity of TiO2 in degradation of organic dyes

Five up-conversion luminescence agents (Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb _n Y_{3 ? n} Al₅O₁₂, Er³⁺:Y₃B _a Al_{5 ? a} O₁₂, Er³⁺:Y₃Ga _b Al_{5 ? b} O₁₂, and Er³⁺:Yb _n Y_{3 ? n} B _a Ga _b Al_{5 ? a ? b} O₁₂) were synthesized using sol-gel method and then the corresponding coated composites (Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb _n Y_3?n Al₅O₁₂/TiO₂, Er³⁺:Y₃B _a Al_{5 ? a} O₁₂/TiO₂, Er³⁺:Y₃Ga _b Al_{5 ? b} O₁₂/TiO₂, and Er³⁺:Yb _n Y_{3 ? n} B _a Ga _b Al_{5 ? a ? b} O₁₂/TiO₂) as photocatalysts were prepared by sol-gel coating process. The XRD and SEM were used to confirm the crystalline phase and surface morphology. The UV-vis absorption and fluorescence-emission spectra were used to research the effect of doping category and amount on the up-conversion emission ability. The photocatalytic activities were detected through the degradation of Acid Red B dye in aqueous solution. Some key parameters of catalyst amount and initial concentration of organic dye on solar light photocatalytic degradation were also examined. The extensive feasibility of prepared photocatalysts in solar light degradation was detected by other organic dyes. The results suggest that the photocatalysts can be widely used in sewage treatment.     

Physico-chemical studies on the chelation behaviour of biologically active 2-hydroxy-1-naphthaldehyde semicarbazone (HNAS) with some lanthanons

Summary The chelation behaviour of the complexes of La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Y³⁺, Tb³⁺, Dy³⁺, Ho³⁺ with biologically active 2-Hydroxy-1-naphthaldehyde semicarbazone (HNAS) has been studied potentiometrically in 75% (v/v) dioxane-water medium at various ionic strengths. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of n andpL. The formation constants of metal chelates and the values ofS _min have been calculated. The order of formation constants of chelates was found to be: La³⁺3+3+3+3+3+3+3+3+3+3+.

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Physikochemische Untersuchungen zur Komplexierung von biologisch aktivem 2-Hydroxy-1-naphthaldehyd-Semicarbazon (HNAS) mit Lanthanoiden

Zusammenfassung Das Chelierungsverhalten von La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Y³⁺, Tb³⁺, Dy³⁺ und Ho³⁺ mit 2-Hydroxy-1-naphthaldehydsemicarbazon (HNAS) wurde potentiometrisch in 75% (v/v) Dioxan-Wasser bei verschiedenen Ionenstärken untersucht. Die Werte für n undpL wurden nach der Methode von Bjerrum und Calvin in der Modifikation von Irving und Rossotti bestimmt. Die Komplexbildungskonstanten der Metallchelate und die WerteS _min wurden ermittelt. Die Reihung der Komplexbildungskonstanten war La³⁺3+3+3+3+3+3+3+3+33+.

     

Vacuum ultraviolet and near-infrared excited luminescence properties of Ca3(PO4)2:RE, Na (RE=Tb, Yb, Er, Tm, and Ho)

Tb³⁺, Yb³⁺, Tm³⁺, Er³⁺, and Ho³⁺ doped Ca₃(PO₄)₂ were synthesized by solid-state reaction, and their luminescence properties were studied by spectra techniques. Tb³⁺-doped samples can exhibit intense green emission under VUV excitation, and the brightness for the optimal Tb³⁺ content is comparable with that of the commercial Zn₂SiO₄:Mn²⁺ green phosphor. Under near-infrared laser excitation, the upconversion luminescence spectra of Yb³⁺, Tm³⁺, Er³⁺, and Ho³⁺ doped samples demonstrate that the red, green, and blue tricolored fluorescence could be obtained by codoping Yb³⁺-Ho³⁺, Yb³⁺-Er³⁺, and Yb³⁺-Tm³⁺ in Ca₃(PO₄)₂, respectively. Good white upconversion emission with CIE chromaticity coordinates (0.358, 0.362) is achieved by quadri-doping Yb³⁺-Tm³⁺-Er³⁺-Ho³⁺ in Ca₃(PO₄)₂, in which the cross-relaxation process between Er³⁺ and Tm³⁺, producing the ¹D₂-³F₄ transition of Tm³⁺, is found. The upconversion mechanisms are elucidated through the laser power dependence of the upconverted emissions and the energy level diagrams.     

Die durch Blei(II) und Kupfer(II) katalysierte Zersetzung von Wasserstoffperoxid als Endpunktindikation chelatometrischer Titrationen

Zusammenfassung Die Anwendung der durch Blei(II) und Kupfer(II) katalysierten Zersetzung von Wasserstoffperoxid als exotherme Indikatorreaktion bei katalytisch-thermometrischer Endpunktindikation chelatometrischer Bestimmungen wird gezeigt. Die katalytische Wirkung von Blei(II) wird in ammoniak-ammoniumtartrathaltiger Lösung (p_H 12) und die Wirkung von Kupfer(II) in ammoniumcarbonathaltigem (p_H 8,8), natriumhydroxid-natriumcarbonathaltigem (p_H 10) und in ammoniakalischem Medium herangezogen. Die direkte Titration von ÄDTA, DCTA und NTA mit Kupfer(II) und Blei(II), die inverse Titration dieser Metalle, wie auch die Bestimmung einiger Metallionen (Zn²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Pb²⁺, Bi³⁺, In³⁺, Th⁴⁺) durch Rücktitration wird beschrieben. Die genannten Ionen können im Milligramm- und Mikrogrammbereich mit befriedigender Genauigkeit bestimmt werden.

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The end-point indication of chelatometric titrations by the decomposition of hydrogen peroxide catalyzed by lead(II) and copper(II)

Summary The application of the decomposition of hydrogen peroxide as exothermic indicator reaction catalyzed by lead(II) and copper(II), to catalytic thermometric endpoint detection of chelatometric titrations is described. The catalytic action of lead(II) is applied in ammonia-ammonium tartrate solution (p_H 12), the action of copper(II) in ammonium carbonate (p_H 8.8), sodium hydroxide-sodium carbonate (p_H 10) and in ammoniacal medium (p_H 12). The direct titration of EDTA, DCTA and NTA with copper(II) and lead(II), the invers titration of this metals, as well as the determination of several ions (Zn²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Pb²⁺, Bi³⁺, In³⁺, Th⁴⁺) by backtitration has been developed. The ions mentioned can be determined in the milligram and in the microgram range with reasonable accuracy.

     

Anion-exchange separation of thorium and protactinium from uranium matrix

Summary The distribution behaviour of Th⁴⁺, Pa⁵⁺, and UO₂ ²⁺ ions between the anion-exchanger Amberlite IRA-400 and acetic acid-hydrochloric acid mixtures, has been investigated. It was found that the general behaviour of Th⁴⁺ ions is similar to that of UO₂ ²⁺ ions though the latter are much more highly adsorbed by the resin than Th⁴⁺. Protactinium exhibited a different behaviour from both Th⁴⁺ and UO₂ ²⁺ ions. The separation factors were calculated, and a Chromatographic procedure for sequential isolation of each element was developed.

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Zusammenfassung Das Verteilungsverhalten von Th⁴⁺, Pa⁵⁺ und UO₂ ²⁺ zwischen dem Anionenaustauscher Amberlit IRA-400 und Gemischen aus Essigsäure und Salzsäure wurde untersucht. Das allgemeine Verhalten von Th⁴⁺ ist ähnlich dem von Uranylionen, wenngleich letztere von dem Harz viel stärker adsorbiert werden als Th⁴⁺. Protactinium zeigt ein abweichendes Verhalten im Vergleich zu Th⁴⁺ und UO₂ ²⁺. Die Trennfaktoren wurden berechnet und ein chromatographisches Verfahren zur Isolierung der angeführten Ionen entwickelt.

     

Anion Transport in BaR2F8 Crystals at Elevated Temperatures

Electroconduction of BaR₂F₈ crystals (R = Y_0.9Er_0.1, Y_0.5Yb_0.5, Er_0.945Tm_0.05Ho_0.005) with the structure -BaTm₂F₈ (monoclinic syngony, spatial group C2/m) is studied at 323–1073 K. Effect of partial pyrohydrolysis on the conduction of Ba(Y, Er)₂F₈ single crystals is investigated. Anion conductivity of crystals of Ba(Y, Yb)₂F₈ and Ba(Er, Tm, Ho)₂F₈ is measured at high temperatures. To a first approximation, there is no change in the ion transport mechanism in these crystals at elevated temperatures. Charge carriers in BaR₂F₈ crystals are, most probably, fluorine vacancies, and the anion conductivity reaches 1–2 mS cm^–1 at 1073 K.     

Intense Upconversion Luminescence of CaSc2O4:Ho3+/Yb3+ from Large Absorption Cross Section and Energy‐Transfer Rate of Yb3+

Concentration‐optimized CaSc₂O₄:0.2 % Ho³⁺/10 % Yb³⁺ shows stronger upconversion luminescence (UCL) than a typical concentration‐optimized upconverting phosphor Y₂O₃:0.2 % Ho³⁺/10 % Yb³⁺ upon excitation with a 980 nm laser diode pump. The ⁵F₄+⁵S₂→⁵I₈ green UCL around 545 nm and ⁵F₅→⁵I₈ red UCL around 660 nm of Ho³⁺ are enhanced by factors of 2.6 and 1.6, respectively. On analyzing the emission spectra and decay curves of Yb³⁺: ²F_5/2→²F_7/2 and Ho³⁺: ⁵I₆→⁵I₈, respectively, in the two hosts, we reveal that Yb³⁺ in CaSc₂O₄ exhibits a larger absorption cross section at 980 nm and subsequent larger Yb³⁺: ²F_5/2→Ho³⁺: ⁵I₆ energy‐transfer coefficient (8.55×10^?17 cm³ s^?1) compared to that (4.63×10^?17 cm³ s^?1) in Y₂O₃, indicating that CaSc₂O₄:Ho³⁺/Yb³⁺ is an excellent oxide upconverting material for achieving intense UCL.     

Easy and General Synthesis of Large‐Sized Mesoporous Rare‐Earth Oxide Thin Films by ′Micelle Assembly′

Large‐sized (ca. 40 nm) mesoporous Er₂O₃ thin films are synthesized by using a triblock copolymer poly(styrene‐b‐2‐vinyl pyridine‐b‐ethylene oxide) (PS‐b‐P2VP‐b‐PEO) as a pore directing agent. Each block makes different contributions and the molar ratio of PVP/Er³⁺ is crucial to guide the resultant mesoporous structure. An easy and general method is proposed and used to prepare a series of mesoporous rare‐earth oxide (Sm₂O₃, Dy₂O₃, Tb₂O₃, Ho₂O₃, Yb₂O₃, and Lu₂O₃) thin films with potential uses in electronics and optical devices.     

Tb2Mn17C3−x with filled Th2Ni17-type structure and some structural and magnetic properties of related compounds

The new compounds R₂Mn₁₇C_3−x (R = Y, Gd, Tb, Dy, Ho, Er, Tm, Lu) were prepared by reacting the elemental components in an arc-melting furnace with subsequent annealing at temperatures between 400 and 900°C. Their crystal structures were determined from single-crystal X-ray diffractometer data of Tb₂Mn₁₇C_3−x and refined to a residual of R = 0.035 for 27 variable parameters and 588 structure factors. It is hexagonal, space group P6₃/mmc with the lattice constants a = 873.8(1) pm, C = 851.1(1) pm and Z = 2 formula units per cell. The positions of the metal atoms correspond to those of Th₂Ni₁₇. The carbon atoms are situated in approximately octahedral voids formed by two Tb and a rectangle of Mn atoms. Of these carbon positions 81 (4)% are occupied in the crystal investigated; this corresponds to the composition Tb₂Mn₁₇C_2.43. The new carbides CeMn₁₁C_2−x, NdMn₁₁C_2−x, and ThMn₁₁C_2−x crystallize with LaMn₁₁C_2−x (filled BaCd₁₁) structure; Th₂Mn₁₇C_3−x has Pr₂Mn₁₇C_3−x (filled Th₂Zn₁₇) structure. The crystal chemistry of these and other interstitial carbides is discussed. The compounds LaMn₁₁C_2−x, CeMn₁₁C_2−x, Pr₂Mn₁₇C_3−x, and Tb₂Mn₁₇C_3−x are paramagnetic with Curie-Weiss behavior at high temperature and no magnetic order at least above about 100 K. The Mn atoms carry magnetic moments in all four compounds. Down to 1.9 K no transition to a superconducting state could be observed for LaMn₁₁C_2−x, La₂Mn₁₇C_3−x, Y₂Mn₁₇C_3−x, or Lu₂Mn₁₇C_3−x.     

Yttrium(III) bonding to organic ligands: A comparison with the lanthanoid(III) cations

Summary The yttrium(III) bonding to organic substrates (oximes, -diketonates and (poly)amino-(poly)carboxylates) has been compared with that of the lanthanoid(III) cations. The complexation constants of Y³⁺ with the examined organic ligands are similar to those of some cations of the first half of the lanthanoid series, in contrast with the fact that the Y³⁺ ionic dimensions are similar to those of Ho³⁺. This has been explained by correlating the formation constants of the Y³⁺ and the lanthanoids(III) complexes by the equation logK ₁=C _AC_B+E _AE_B, where the parametersC andE indicate the tendency of each Lewis acidA and Lewis baseB to undergo covalent or ionic bonding, and where the ratioH=E/C indicates the charge control on the bond formation tendency of each speciesA orB. The results are commented in terms of the utility of Y³⁺ in assisting organic reactions.

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Bindung von Yttrium(III) an organische Liganden: Vergleich mit Lanthanoid(III)-Kationen

Zusammenfassung Es wurde die Bindung von Yttrium(III) an organische Substanzen [Oxime, -Diketonate und (Poly)Amino(poly)carboxylate] im Vergleich mit Lanthanoid(III)-Kationen behandelt. Die Komplexierungskonstanten von Y³⁺ sind ähnlich denen einiger Kationen der ersten Hälfte der Lanthanoidenserie; dies steht im Gegensatz zur Tatsache, daß die Dimensionen des Y³⁺-Ions denen des Ho³⁺ entsprechen. Die Erklärung wurde mittels der für die Bildungskonstanten der Y³⁺- und Lanthanoid(III)-Komplexe gültigen Gleichung logK ₁=C _AC_B+E _AE_B gefunden, wobeiC undE Parameter sind, die die Tendenz der Lewis-SäurenA und der Lewis-BasenB zum Eingehen von kovalenten oder ionischen Bindungen charakterisieren und wo das VerhältnisH=E/C den Steuerungseffekt der Ladung auf die Bindungstendenz der SpeziesA oderB beschreibt. Die Ergebnisse werden im Hinblick auf den Nutzen von Y³⁺ zur Unterstützung organischer Reaktionen diskutiert.

     

Anion Transport in Superionic Conductors Na0.5 – x R0.5 + x F2 + 2x (R Are Cations of Rare-Earth Elements) at Elevated Temperatures

Anion conduction in solid solutions Na_{0.5 – x} R_{0.5 + x} F_{2 + 2x} (R = Dy; Ho; Tm; Y; combinations Y_0.9Nd_0.1, Y_0.5Yb_0.5, Lu_0.998Ho_0.002, Lu_0.9Ho_0.1, Lu_0.9Nd_0.1) with a fluorite structure is studied at 251–1073 K. The ion transport mechanism alters at T _c 723–773 K. Below T _c the mechanism involves migration of interstitial fluorine atoms and depends mainly on the defect-containing (clustered) structure of the solid solutions. Above T _c the mechanism probably involves the dissociation of interstitial fluorine atoms from structural clusters, and the anion conductivity reaches 1 S cm^–1. The fluorite solid solution in the Na_0.4Ho_0.6F_2.2 crystals partly decomposes, yielding NaHoF₄ compounds with a gagarinite (NaCaYF₆) structure.     

Stability constants of thorium(IV) complexes with aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl) methane ligands

Summary Stability constants of complexes of aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl) methane [ArBPyM] derivatives with thorium(IV) ions were determined by the potentiometric method at 30°C and an ionic strength of 0.1 mol·dm^–3 (KNO₃) in 75% (v/v) dioxane-water. The evaluation of the titration data indicated that four kinds of complexes ([ThL]²⁺, [ThLOH]⁺, [ThL ₂], and [ThL(OH)₂]^2–) were formed. The formation constants for all [ThL]²⁺ and [ThL ₂] complexes have been calculated to compare these values with those previously reported [1, 2] with Ln³⁺ and UO ₂ ²⁺ metal ions [2, 3]. The probable ligand-bonding sites of the complexes are proposed. In addition, the applicability of theHammett equation for the correlation of the stability constants of [Th(IV)-ArBPyM] complexes are discussed.

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Stabilitätskonstanten von Thorium(IV)-Komplexen mit Aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)-methan-Liganden

Zusammenfassung Stabilitätskonstanten von Komplexen von Aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)-methan — Derivaten [ArBPyM] mit Thorium(IV) — Ionen wurden bei 30°C und einer Ionenstärke von 0.1 mol-dm^–3 (KNO₃) in 75% (v/v) Dioxan-Wasser potentiometrisch bestimmt. Die Auswertung der Titrationskurven zeigte, daß vier verschiedene Komplexe vorlagen ([ThL]²⁺, [ThLOH]⁺, [ThL ₂] und [ThL(OH)₂]²⁺). Die Bildungskonstanten aller [ThL]²⁺- und [ThL ₂]-Komplexe wurden berechnet, um sie mit den früher für Ln³⁺- und UO ₂ ²⁺ -Ionen publizierten zu vergleichen. Potentielle Bindungsstellen der Komplexe für Liganden werden vorgeschlagen. Zusätzlich wird die Anwendbarkeit derHammet-Beziehung auf die Korrelation der Stabilitätskonstanten von [Th(IV)-ArBPyM] — Komplexen diskutiert.

     

Zur spektralphotometrischen Bestimmung von Uran(VI) in Gegenwart einiger Fremdelemente mit Hilfe von Halogenderivaten der Essigs?ure

Zusammenfassung Die Pufferlösungen CH₂ClCOOH + CH₂ClCOONa (I), CH₂BrCOOH + CH₂BrCOONa (II) und CH₂JCOOH + CH₂JCOONa (III) wurden als Reagentien für die Uranbestimmung vorgeschlagen.Das Beersche Gesetz wird für den Konzentrationsbereich von 0,11903 bis 2,85684 mg/ml Uran mit 0,1 m Reagenslösungen befolgt. Y³⁺, Ce³⁺ und Th⁴⁺ sind ohne Einfluß.Für den Konzentrationsbereich von 0,11903–3,80912 mg/ml Uran werden 1 m Reagenslösungen angewendet. Bei Verwendung von (I) oder (II) stören Y³⁺, Ce³⁺ und Th⁴⁺ nicht. Wird (III) benutzt, muß man zur Vermeidung der Störung durch Thorium, Uran mit Essigester extrahieren.

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Summary The buffer solutions CH₂ClCOOH + CH₂ClCOONa (I), CH₂BrCOOH + CH₂BrCOONa (II) and CH₂ICOOH + CH₂ICOONa (III) are shown to provide new reagents for the spectrophotometric determination of uranium.The method can be used for the direct determination of 0.11903 to 2.85684 mg of uranium with. 0.1 M reagents, when Y³⁺ or Ce³⁺ or Th⁴⁺ are present. With 1 M concentrations, 0.11903 to 3.80912 mg of uranium can be directly determined in presence of Y³⁺ and Ce³⁺; with (I) or (II), thorium has no effect on the absorbance, too; with. (III) uranium must be previously extracted into ethyl acetate.

     

Crystal chemistry of some Th2Zn17-type rare-earth-zinc phases

Full single-crystal determinations of several Th₂Zn₁₇-type rare-earth-zinc phases were carried out (graphite monochromatized Mo Kα radiation, 2θ up to 80°, absorption correction with Gauss method, typical residual R = 4.5%). In this structure type, the lattice constants as well as the atomic positions were observed to depend linearly on the radius of the rare-earth atom. The zinc framework, although rather rigid, allows internal readjustments to accommodate the chemical pressure generated by the different sizes of the inserted rareearth atoms. The shortest rare-earth-rare-earth distance varies only slightly and can be considered to be nearly constant. The overall variations in this series are quite uniform except for Yb₂Zn₁₇, where ytterbium is in the divalent state, in contrast with the trivalent state of the rare-earth atom in the other compounds.     

Microdetermination of uranium (VI)

Summary A new method has been evolved for the separation and estimation of UO₂ ²⁺ from Cu²⁺, Zn²⁺, Ag⁺, Pb²⁺, Ga³⁺, In³⁺, Tl³⁺, La³⁺, Ti⁴⁺, Zr⁴⁺ and Th⁴⁺ with the sodium salt of benzilic acid as precipitating and chelating agent andn-butanol as solvent for solvent extraction. All these cations except UO₂ ²⁺ are precipitated by benzilic acid; UO₂ ²⁺ forms a deep yellow complex extractable byn-butanol. The uranium can be determined in the organic phase spectrophotometrically at 430 nm. The pH range over which the separation can be carried out is 2.6–4.0. Few anions and cations interfere.

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Zusammenfassung Eine neue Methode der Trennung und Bestimmung von UO₂ ²⁺ neben Cu²⁺, Zn²⁺, Ag⁺, Pb²⁺, Ga³⁺, In³⁺, Tl²⁺, La³⁺, Ti⁴⁺, Zr⁴⁺ und Th⁴⁺ wurde ausgearbeitet. Das Natriumsalz der Benzilsäure dient als Färbungs- und Komplexbildungsmittel und n-Butanol zur Extraktion. Alle angeführten Kationen mit Ausnahme von UO₂ ²⁺ werden von Benzilsäure gefällt; UO^{2 2+} bildet einen tiefgelben, mit n-Butanol extrahierbaren Komplex und kann in der organischen Phase spektrophotometrisch bei 430 nm bestimmt werden. Die Trennung kann bei pH 2,6 bis 4,0 durchgeführt werden. Nur wenige Anionen und Kationen stören.

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Résumé On développe une nouvelle méthode pour la séparation et l'évaluation de UO₂ ²⁺ dans Cu²⁺, Zn²⁺, Ag⁺, Pb²⁺, Ga³⁺, In³⁺, Tl³⁺, La³⁺, Ti⁴⁺, Zr⁴⁺ et Th⁴⁺, par le sel de sodium de l'acide benzilique comme agent précipitant et chélatant et le N-butanol comme solvant pour l'extraction par solvant. Tous ces cations, sauf UO₂ ²⁺, précipitent par l'acide benzilique; UO₂ ²⁺ forme un complexe jaune intense que l'on peut extraire par le N-butanol. On peut doser l'uranium en phase organique par spectrophotométrie à 430 nm. La séparation peut s'effectuer dans le domaine de pH de 2,6 à 4,0. Peu d'anions et de cations interfèrent.

     

Polarographische Untersuchung der Methoxy-äthylthioglykolatkomplexe von Zink

Zusammenfassung Wir untersuchten polarographisch die Komplexierung von Zink mit Methoxyäthylthioglykolat (MET). Es zeigte sich, daß die Reduktion von Zn²⁺ reversibel und diffusionskontrolliert verläuft, und daß es sich dabei um einen Zwei-Elektronen-Übertragungsprozeß handelt. Wir legten der Interpretation der Daten, die sich beim Auftragen von Potential gegen Konzentration bei konstanter Ionenstärke ergaben, die Vorstellung zugrunde, daß sich drei komplexe Species (ZnA ⁺, ZnA ₂ und ZnA _3–) bilden. Die Auswertung erfolgte mit Hilfe der Methode vonDe Ford undHume. Die Bestimmung der Logarithmen der Stabilitätskonstanten bei 25°C führte zu Werten von 3.95, 6.95 bzw. 10.04.

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Polarographic study of methoxy ethylthioglycolate complexes of zinc

Complexation of zinc by methoxyethylthioglycolate (MET) has been studied polarographically. The reduction of Zn²⁺ inMET solution has been found to be reversible and diffusion controlled involving a two-electron transfer process. Potential vs. concentration data at constant ionic strength (-0.5M) have been interpreted on the basis of the formation of three complex species ZnA ⁺, ZnA ₂, and ZnA _3– employingDeFord andHume's method. The logarithms of their stability constants at 25°C were determined and found to be 3.95, 6.95, and 10.04, resp.

     

ErxYb1-x(TPB)3Bath(x=0,0.218,0.799,0.896,0.987,1)配合物的近红外发光性能

采用4,4,4-三氟-1-苯基-1,3-丁二酮（TPB）为第一配体,4,7-二苯基-1,10-菲咯啉（Bath）为第二配体,分别制备了配合物Er（TPB）₃Bath和Yb（TPB）₃Bath,以及它们的混合配合物Er_xYb_1-x（TPB）₃Bath（x=0.218,0.799,0.896,0.987）,并对所制得配合物的发光性能进行了系统研究。研究结果表明,所有配合物均能发射所含稀土离子的近红外特征光,并且可以通过调节混合配合物中的n_Er/n_Yb来调控Yb³⁺/Er³⁺之间的能量传递,进而提高Er³⁺离子在1530 nm处的发光。     

Die Seltenerdmetallpolyselenide Gd8Se15, Tb8Se15−x,Dy8Se15−x,Ho8Se15−x,Er8Se15−x und Y8Se15−x (0 < x ≤ 0.3) – Zunehmende Fehlordnung in ausgedünnten,planaren Selenschichten

The Rare Earth Metal Polyselenides Gd₈Se₁₅, Tb₈Se_15?x, Dy₈Se_15?x, Ho₈Se_15?x, Er₈Se_15?x, and Y₈Se_15?x – Increasing Disorder in Defective Planar Selenium Layers Single crystals of the rare earth metal polyselenides Gd₈Se₁₅, Tb₈Se_15?x, Dy₈Se_15?x, Ho₈Se_15?x, Er₈Se_15?x, and Y₈Se_15?x (0 < x ≤ 0.3) have been prepared by chemical transport reactions (1120 K→ 970 K, 14 days, I₂ as carrier) starting from pre‐annealed powders of nominal compositions between LnSe₂ and LnSe_1.9. The isostructural title compounds adopt a 3 × 4 × 2 superstructure of the ZrSSi type and can be described in space group Amm2 with lattice parameters of a = 12.161(1) Å, b = 16.212(2) Å and c = 16.631(2) Å (Gd₈Se₁₅), a = 12.094(2) Å, b = 16.123(2) Å and c = 16.550(2) Å (Tb₈Se_15?x), a = 12.036(2) Å, b = 16.060(2) Å and c = 16.475(2) Å (Dy₈Se_15?x), a = 11.993(2) Å, b = 15.999(2) Å and c = 16.471(2) Å (Ho₈Se_15?x), a = 11.908(2) Å, b = 15.921(2) Å and c = 16.428(2) Å (Er₈Se_15?x), and a = 12.045(2) Å, b = 16.072(3) Å and c = 16.626(3) Å (Y₈Se_15?x), respectively. The structure consists of puckered [LnSe] double slabs and planar Se layers alternating along [001]. The planar Se layers contain a disordered arrangement of dimers, Se^2? and vacancies. All compounds are semiconducting and contain trivalent rare earth metals (Ln³⁺).