Studium des gegenseitigen Einflusses der Bindungen in Thiocyanat-Kupfer(II)-Komplexen mit Methyl- und Dimethylpyridinen mittels Infrarotspektroskopie

The infrared spectra of thiocyanato-copper(II) complexes of the type Cu(NCS)₂ L ₂ with all isomeric picolines and lutidines (L) as well as those of the type Cu(NCS)₂ L ₃ withL=3- and 4-picoline, 3,4- and 3,5-lutidine were measured. The behaviour of the (CN) stretching vibrations of the Cu(NCS)₂ L ₂ complexes led to conclusions on the different kind of coordination of the NCS groups in dependence on the ligandL. The mutually conditioned strength of the Cu–NCS and Cu–N(L) bonds in the equatorial plane, especially in the presence of ligandsL with the steric effect, was determined from the frequency shift of the Cu–NCS and Cu–N(L) stretching vibrations with regard to the vibrations for Cu(NCS)₂(pyridine)₂.

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Mit 1 Abbildung     

Synthesen in der Pyridazin-Reihe, 26. Mitt.:

Zusammenfassung Es wird über die Synthese von verschiedenen methylsubstituiertens-Triazolo[4,3—b]pyridazinen berichtet. Außerdem wurdens-Triazolo[4,3—b]pyridazin und seine 7-Methyl- und 6-Chlor-Derivate der homolytischen Methylierung unterworfen, die Reaktionsgemische gaschromatographisch auf einzelne Methyl-s-triazolo[4,3—b]pyridazine aufgetrennt und die Verbindungen identifiziert.

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Syntheses of pyridazines, XXVI: Synthesis and homolytic methylation of s-triazolo[4.3—b]pyridazines

The syntheses of some methyl substituteds-triazolo[4,3—b]-pyridazines are reported.s-Triazolo[4.3—b]pyridazine and its 7-methyl and 6-chloro analogs were submitted to homolytic methylations and the obtained reaction mixtures were separated by gas chromatography into particular components which were then identified.

     

Spektroskopische Untersuchungen der Metallkomplexe des 2,5-Dibenzoyl-3,4-dihydroxyselenophens

Zusammenfassung Eine Reihe von Metallkomplexen des 2,5-Dibenzoyl-3,4-dihydroxy-selenophens wurden spektroskopisch untersucht. Das Verhalten des Wismutkomplexes und die Möglichkeiten einer spektrophotometrischen Wismutbestimmung auf diesem Wege wurden eingehend studiert.

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Summary A spectroscopic examination was made of a series of metal complexes of 2,5-dibenzoyl-3,4-dihydroxyselenophen. The behavior of the bismuth complex and the possibilities of a spectrophotometric method of determining bismuth in this manner were studied thoroughly.

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Herrn Univ.-Prof. Dr.Hans Lieb zum 80. Geburtstag gewidmet.     

Analytische Aspekte der Oxydation organischer Stickstoffverbindungen mit Chromsäure. XXIII

Zusammenfassung Die früher beschriebene Halbmikromethode zur Bestimmung von Isonitrosogruppen in organischen Verbindungen wurde in den Mikromaßstab übergeführt. Sie beruht auf der Reaktion der Substanz mit Eisen(III)-sulfat in verd. Schwefelsäure. Dabei wird der Oximstickstoff als Distickstoffoxid frei, das mit Kupfer zu elementarem Stickstoff reduziert und im Mikroazotometer gemessen wird. Für die Berechnung des Oximstickstoffgehaltes aus den abgelesenen Gasvolumina wurden Werte für die konstante und proportionale Volumenkorrektur mit Hilfe der Methode der Regressionsgeraden experimentell festgestellt. Beide Werte sind den bei der N-N-Gruppenbestimmung benützten Volumenkorrekturen fast gleich. Die Bestimmung von Oximgruppen ist durch die Anwesenheit von Nitro- oder Aminogruppen nicht gestört. Diese Gruppen können aus derselben Einwaage durch nachfolgende Oxydation mit Chromsäure bestimmt werden.

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Analytical aspects of the oxidation of organic nitrogen compounds with chromic acid. XXIII

Summary The semimicro method previously described for the determination of isonitroso groups in organic compounds has been converted to the microscale. It is based on the reaction of the material with iron(III)-sulfate in dilute sulfuric acid. The oxime nitrogen is thus liberated as dinitrogen oxide, which is reduced to elementary nitrogen by copper and measured in the mieroazotometer. To calculate the oxime nitrogen content from the read-off gas volume, values for the constant and proportional volume correction with the aid of the regression lines were established experimentally. Both values are almost equal in the case of the determination of the volume corrections employed in the determination of the N-N-groups. The presence of nitro-or amino groups does not interfere with the determination of oxime groups. These groups may be determined from the same sample by subsequent oxidation with chromic acid.

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XXII. Mitteilung s.¹.     

Membrane extraction of pertechnetate with quaternary ammonium salts comparison with solvent extraction

The liquid membrane extraction (MX) and the solvent extraction (SX) of pertechnetate with Aliquat 336 as a carrier has been studied. From the results of SX the percentage of pertechnetate in the inner solution in experiment with LM was proposed. It has been found that the pertraction of pertechnetate depends on the inner solution used and the most effective solutions were those with ClO ₄ ^– and SCN^–. Effects of the carrier concentration in membranes and outer phase composition have been studied too. The results of these experiments were kinetic curves with a minimum, which may be interpreted as a result of competing processes in the systems.     

A simple laboratory generator for low concentrations of sulphur dioxide

The generator is based on permeation of sulphur dioxide through silicone rubber tubes immersed in a buffered, thermostated solution of sodium hydrogensulphite. The generator contains three (or more) permeation tubes of different lengths immersed simultaneously in the generation solution. The tubes can be connected stepwise to the carrier gas source, so that three (or more) different concentrations of SO₂ in the carrier gas can be obtained from a single solution. The tested generator produced 1.25–25.4 ng s^?1 SO₂, depending on the hydrogensulphite concentration in the solution. Long-term stability was tested for the production of 10.49 ng s^?1 over 50 h; the relative standard deviation was 1.57%. The experimental conditions affecting the production of SO₂ are discussed. An equation is derived for estimating the SO₂ production for various solution compositions and surface areas of the permeation tubes.     

Effects of genesis and ionizing radiation on the kinetics of reduction of NiO-CeO2 mixed oxides with hydrogen

The reduction of mixed oxides NiO-CeO₂ of various composition with hydrogen was studied at 290–470° by means of thermogravimetry. Some physicochemical properties of the system were also investigated and compared with earlier studied analogous samples of different “origin”. The degree of mutual interaction of the two components, the reduction kinetics and the sensitivity to the different sorts of radiation (gamma-rays, fast neutrons and electrons), applied in different doses, are strongly affected by the “pre-history” and by the composition in both compared series of mixed oxides.     

Beitrag zur mikroskopischen Identifizierung organischer Stoffe nach L. Kofler. V

Zusammenfassung In Fortsetzung früherer Untersuchungen zum Zweck der Ergänzung und Erweiterung der Identifizierungs-Tabelle nachKofler werden für 62 Substanzen die thermomikroskopischen Konstanten mitgeteilt und die gegebenenfalls notwendigen Zusatzreaktionen beschrieben. Bei Nicotinamid, das auf Grund seiner Fähigkeit, mit vielen Stoffen wie organischen Säuren, Säureestern, Phenolen u. a. Komplexverbindungen zu bilden, häufig als Reagens in Betracht kommt, wird das polymorphe Verhalten erläutert und das Auftreten von sieben Modifikationen beschrieben.

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Contribution to the microscopic identification of organic materials after L. Kofler. V

Summary In continuation of earlier investigations for the purpose of supplementing and extending the identification tables ofKofler, the thermomicroscopic constants are given for 62 substances and when necessary the supplementary reactions are described. In the case of nicotinamide, which because of its ability to yield among other things complex compounds with organic acids, acid esters, phenols, is frequently considered as reagent, the complex behavior is illustrated and the occurrence of 7 modifications is described.

     

Tritium volume activity in natural waters of the NPP Temelín region

With the use of the tritium monitoring network the samples of river water, air humidity and precipitation are collected and analysed for HTO in the vicinity of Temelín nuclear power plant.     

Gold(III) complexes with imidazole,benzoxazole, purine and pyrimidine derivatives

Summary The synthesis and characterization of Au^III complexes with several heterocyclic ligands are reported. The compounds have general formula [AuX₃(L)], where L =N-methylimidazole (N-MeIz),N-ethylimidazole (N-EtIz),N-propylimidazole (N-PrIz), benzoxazole (BO), 2-methylbenzoxazole (2-MeBO), 2,5-dimethylbenzoxazole (2,5-diMeBO), 2-amino-pyrimidine (2-APm), 4(6) -hydroxy-pyrimidine [4(6)-hydrPm] or hypoxanthine (Hypox) and X = Cl or Br. Elemental analysis, conductivity measurements and spectral studies were used for the characterization of the complexes. A square-planar geometry withN-bonded heterocyclic ligands is suggested.