Über Silicid- und Germanidchalkogenide des Thoriums

On Thorium Silicide and Germanide Chalcogenides The compounds ThSiS, ThSiSe, ThSiTe, ThGeS, ThGeSe, and ThGeTe were synthetized from the elements at temperatures ranging from 800 to 1050°C. For structural X-ray investigation single crystals of the compound ThGeS were grown. ThGeS is tetragonal, space group I4/mmm with a = 3.9411(7), c = 17.1395(40) Å, and Z = 4. In order to refine the structure parameters intensity measurements were carried out by means of a four-circle single crystal diffractometer. By indexing the Debye-Scherrer diagrams the remaining ternary thorium chalcogenides were proved to be isostructural with ThGeS. This structure type is identical with the anti-Ti₂Bi-type structure and closely related to the PbFCl structure in the sense of a transposition structure. The interatomic distances, the relations to comparable structures and possible reasons for the formation of the anti-Ti₂Bi-type structure by ternary chalcogenides of the actinides are discussed.     

Beiträge zur Chemie des Phosphors. 167 [1, 2]. Konstitutions- und Konfigurationsisomere von Pentaphosphan(7), P5H7

Contributions to the Chemistry of Phosphorus. 167. Constitutional and Configurational Isomers of Pentaphosphane(7), P₅H₇ Phosphane mixtures containing 10—15 P-% of pentaphosphane(7), P₅H₇, are obtained by thermolysis of diphosphane, P₂H₄, or as residue from distillation of crude diphosphane [3]. According to the complete analysis of the ³¹P{¹H}-NMR spectrum on the basis of selective population transfer experiments, P₅H₇ exists as a mixture of three diastereomers of n-P₅H₇ — 1a (erythro, erythro), 1b (erythro, threo), 1c (threo, threo) — and of the constitutional isomer 2-phosphinotetraphosphane 2 (iso-P₅H₇, largest relative isomeric abundance). The correlation between the diastereomers and the observed spin systems results from the preferred gauche orientation of neighboring free electron pairs, the dependence of ¹J(PP) on dihedral angles, and the ³J(PP) long range couplings. From the ³¹P-NMR data of the phosphane molecules P_nH_n+2 with n = 1—5 general relationships for the δ(³¹P) values and the ¹J(PP) coupling constants of chain-type phosphorus hydrides as a function of their structural parameters are derived.     

R?ntgenspektrometrische Goldbestimmung in sulfidischen Erzen nach chemischer Anreicherung

Zusammenfassung Es wird eine Goldbestimmung an sulfidischen Erzen für den Bereich von 0,05–5 ppm bei 20 g Einwaage beschrieben. Das Gold wird durch Salpetersäurebehandlung von den übrigen Metallen getrennt, mit Salzsäure/ Salpetersäure gelöst und mit Selen als innerem Standard und Tellur als Spurenfänger mittels Zinn(II)-chlorid gefällt. Der Niederschlag wird auf ein Membranfilter aufgezogen. Die Goldbestimmung erfolgt über den Impulsratenquotienten der Gold L- und Selen K-Linien. Die störende Molybdän K-Strahlung und die Comptonstreuung werden durch ein Zirkoniumblech auf dem Röhrenfenster unterdrückt. Der Variationskoeffizient beträgt 20% für 0,2–5 ppm und 53,6% für 0,05 ppm.

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Summary A method is described for the determination of gold in sulphide ores within the concentration range of 0.05–5 ppm with sample weights of 20 g. Gold is separated from the other metals by treatment with nitric acid, dissolved by hydrochloric acid, containing some nitric acid, and is finally precipitated by stannous chloride applying selenium as internal standard and tellurium as collecting agent. The precipitate is mounted on a diaphragm filter and the determination of gold is carried out by X-ray analysis suppressing the disturbing Mo _K radiation and compton scattering by a zirconium sheet-metal on the X-ray tube. The pulse rate quotient of the lines Au _L /Se _K is a function of the concentration of gold. The variation coefficient is 20% for 0.2–5 ppm and 53.6% for 0.05 ppm.

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Herrn Prof. Dr.-Ing. habil. J. Hesemann zum 65. Geburtstag gewidmet.     

Perfluororganocadmium-verbindungen als sehr wirksame perfluoralkylierungs- und perfluorphenylierungsmittel zur darstellung von perfluororganozinn- und -blei-verbindungen [1]

Perfluoroorgano tin and lead compounds can be prepared in high yields from the reactions of (CH₃)₃SnOCOCF₃ and (CH₃)₃Pb(OCOCF₃) with perfluoroorgano cadmium complexes. (CH₃)₃SiOCOCF₃ reacts with (CF₃)₂Cd complexes — probably via the intermediate (CH₃)₃SiCF₃ and CF₂ elimination — to form (CH₃)₃SiF and CF₃CdOCOCF₃ complexes. While the reaction of (CF₃)₂Cd·D with (CH₃)₃SnONO₂ yields CF₃NO as the only volatile product, (R_f)₂Cd·D (R_f  C₂F₅, iC₃F₇) forms R_fCdONO₂·D and (CH₃)₃SnR_f. The preparations and properties of the partly new compounds as well as the n.m.r. spectra are described.     

Equational partiality

A special kind of partiality of heterogeneous algebraic structures is introduced. Every operator of a heterogeneous operator domain is associated with a set of term equations as necessary and sufficient domain condition.It is shown that some kind of hierarchy condition for the system of domain equations is equivalent to the condition that every injective weak homomorphism is a strong homomorphism which is equivalent to the statement that every bijective weak homomorphism is an isomorphism.On the base of this result the notions of a quasi-variety and of a variety of equationally partial heterogeneous algebras are suggested. The class of all small categories becomes a standard example of a variety of equational partial heterogeneous algebras.Presented by V. Trnková.     

Potentiometric titration of milligram quantities of uranium in the presence of iron

A method is described for the potentiometric titration of milligram quantities of the uranium(IV) ion in the presence of iron. This is accomplished by complexing the iron with 1.10-phcnanthroline. The uranium can then be titrated with standard ceric sulfate without interference from the iron.     

Beiträge zur Chemie des Phosphors. 143. Li4P26 und Na4P26, die ersten Salze mit Hexacosaphosphid(4−)-Ionen

Contributions to the Chemistry of Phosphorus. 143. Li₄P₂₆ and Na₄P₂₆, the First Salts with Hexacosaphosphid(4?) Ions The hexacosaphosphides Li₄P₂₆ ( 1 ) and Na₄P₂₆ ( 2 ) are formed besides other polyphosphides in the reaction of white phosphorus with lithium dihydrogenphosphide or sodium. 1 also results from the decomposition of Li₂HP₇ in tetrahydrofuran at room temperature and can be obtained pure as a crystalline solvent adduct Li₄P₂₆ · 16 THF. According to 2D?³¹P-NMR spectroscopic investigations the P₂₆^4? ion is a conjucto-phosphane of two P₇(5)^?-and two P₉(3)^?-unit groups with structures analogous to norbornane and deltacyclane, respectively.     

Duplex Stabilization of DNA: Oligonucleotides containing 7-substituted 7-deazaadenines

The oligonucleotide building blocks 4b–d derived from 7-bromo-, 7-chloro-, and 7-methyl-substituted 7-deaza-2′-deoxyadenosines 3b–d were prepared. They were employed in the solid-phase synthesis of the oligonucleotides 7–25 . The dA residues of the homomer d(A₁₂), the alternating d[(A-T)₆], and the palindromic d(G-T-A-G-A-A-T-T-C-T-A-C) were replaced by 3b–d as well as by the parent 7-deaza-2′-deoxyadenosine ( 3a ). The melting profiles and CD spectra of oligonucleotide duplexes, showing this major groove modification, were measured, and the T_m values as well as the thermodynamic data were determined. It was found that small substituents such as Br, Cl, or Me introduced in the 7-position of a 7-deazaadenine residue increase the duplex stability compared to oligonucleotides containing adenine.     

Nachweis der Keimwirkung bei der katalytischen Goldreaktion

Zusammenfassung Eisen(II)sulfat reduziert in saurer Lösung Silbernitrat zu metallischem Silber; diese Reaktion wird durch Goldspuren katalysiert. Bei Abwesenheit von Trägerkeimen liegt die molare Grenzkonzentration für Gold bei etwa 10^–8, bei Gegenwart von Keimen dagegen bei 10^–11 bis 10^–12. Eine geregelte Keimzahl wird durch Zusatz kleinster Bariummengen erhalten, die eine an sich kaum wahrnehmbare Bariumsulfattrübung bilden. Zur praktischen Anwendung geeignet dürfte eine Abänderung der Reaktion sein, bei der als Reduktor Hydrazin in alkalischer, Tartrat und Ammoniak enthaltender Lösung benutzt wird.

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Summary In acid solution, iron(II) sulfate reduces silver nitrate to metallic silver. This reaction is catalyzed by traces of gold. In the absence of carrier nuclei, the molar limiting concentration for gold is about 10^–8, but in the presence of nuclei this limit is 10^–11 to 10^–12. A controlled number of nuclei is obtained by adding very small amounts of barium, which produce a barely visible turbidity of barium sulfate. — For practical application, it may be possible to use a modified form of the reaction, in which the reductant is hydrazine acting in an alcaline solution containing tartrate and ammonia.

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Résumé En solution acide le sulfate de fer (II) réduit le nitrate d'argent à l'état d'argent métallique; cette réaction est catalysée par des traces d'or. En l'absence des germes, la concentration limite pour l'or est environ 10^–8, mais en présence des germes cette limite est 10^–11 à 10^–12. On peut obtenir un nombre connu de germes par addition d'une très petite quantité de baryum qui produira un trouble àpeine visible dû au sulfate de baryum formé. En pratique on peut employer une forme de réaction différente, l'agent réducteur étant l'hydrazine agissant en milieu alcalin en présence de tartrate et d'ammoniaque.