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.     

Accroissement de la reactivite des phosphorines en tant que dienes et philodienes par complexation du phosphore

The 2-Phenyl-4,5-dimethylphosphorin P-W(CO)₅ complex reacts easily as a dienophile with 2,3-dimethylbutadiene through its 1,6-positions and as a diene with N-phenylmaleimide, dimethyl acetylenedicarboxylate and cyclopentadiene, through its 1,4-positions.     

Ein weiterer Beitrag zum Scandiumdicarbidproblem

Zusammenfassung Die bei 1850, 2000 bzw. 2300°C durch die Reduktion von Scandiumoxid mittels Kohlenstoff in dem der Scandiumdicarbidbildung entsprechenden Molverhältnis hergestellten Produkte wurden mit Wasser zersetzt und mit Hilfe der gleichzeitigen gaschromatographischen und massenspektrometrischen Analyse untersucht. Aus den Ergebnissen geht hervor, daß bei der Scandiumdicarbidbildung gleichzeitig ein weiteres Scandiumcarbid, höchstwahrscheinlich ein Sesquicarbid, entsteht.

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Scandium(III) dicarbide problem. Further experimental results

Products obtained by the reduction of Sc₂O₃ with carbon at 1850, 2000 and 2300°C, resp., in the molar ratio corresponding to the scandium dicarbide were hydrolysed with water. Gaseous reaction products were analysed using gas chromatography combined with mass spectrometry. Results show, that during dicarbide formation another scandium carbide, probably sesquicarbide, is also formed.

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Herrn Prof. Dr.H. Nowotny gewidmet.

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7. Mitt.: Coll. Czech. Chem. Commun., im Druck.     

Relationships for determining the rate constant of the polymerization growth reaction by means of the emulsion polymerization method

Some simple equations for the emulsion polymerization system were derived on the basis of the Smith-Ewart theory. These are used in calculating the molar monomer concentration and rate of polymerization in units of moles per liter per second for the zero-order region with respect to the monomer as well as in calculating the rate constant of the growth reaction.     

Study of the drying zirconia gel-precipitates using thermal analysis

Thermoanalytical techniques (TG, DTG, DTA and EGA) can be helpful in studying gel compositions and relating the chemical history and the role of the precipitant to the chemical properties of gels. The objective of our work was to determine the influence of the initial conditions in the reaction mixture on the product characteristics. Zirconia gels were prepared by the gelprecipitation method by the hydrolysis of zirconium tetrachloride dissolved in methanol. The substitution of water by methanol was chosen in order to obtain a reaction medium in which better control of the hydrolysis and condensation reactions of the zirconium precursor were achieved and thus also better control of the final properties of the dried zirconia gel-precipitates could be obtained. The nature of the hydrated zirconia gels obtained during the gelation process is strongly influenced by the conditions of the reaction mixture, e.g. concentration of the zirconium precursor, the mixing rate and particularly by the amount of water added. To distinguish between various types of water in the gel-precipitates, the furnace atmosphere and the partial water pressure were altered appropriately. It was shown that initial zirconium to water molar ratio has a significant effect on the properties of the final products. It was assumed that, according to the preparation conditions, three different types of water are present in the formed zirconia gel-precipitates. Modification of the dehydration processes of zirconia gel-precipitates enables control of the final microstructural and surface properties of the dried gels which are suitable for further catalysts support as well as mixed oxide preparation.     

Analysis of90Sr in environmental and biological samples by extraction chromatography using a crown ether

The use of crown ethers is a simple and rapid method for the separation and determination of strontium in various samples. After sample dissolution oxalate precipitation was carried out to remove K. Chromatographic separation of strontium from most inactive and radioactive interference was done with a crown ether. The chemical recovery was determined gravimetrically. Radiostrontium was then determined by liquid scintillation counting.     

Analytische Aspekte der Oxydation organischer Stickstoffverbindungen mit Chromsäure. II

Zusammenfassung Eine Halbmikromethode zur Bestimmung der an Kohlenstoff oder Sauerstoff gebundenen Nitro- und Nitrosogruppen in organischen Verbindungen wurde ausgearbeitet. Die Methode beruht auf dem oxydativen Aufschluß der Substanz mit einem Chromsäure—Schwefelsäure-Gemisch, wobei die Nitro- und Nitrosogruppen quantitativ in Salpetersäure übergehen. Diese wird mit Devarda-Legierung in alkalischem Medium zu Ammoniak reduziert, das dann im Stickstoffstrom abdestilliert und acidimetrisch titriert wird.

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Summary A semimicro method for determining nitro- and nitroso groups attached to carbon or oxygen in organic compounds has been worked out. The method is based on the oxidative decomposition of the sample with a chromic acid-sulfuric acid mixture, the nitro and the nitroso groups being quantitatively transformed into nitric acid. The latter is reduced to ammonia by means of Devarda alloy in alkaline medium, and is then distilled off in a stream of nitrogen and titrated with a standard acid solution.

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Résumé On a mis au point une méthode à l'échelle semimicro pour le dosage dans les substances organiques de groupes nitro et nitroso liés au carbone ou à l'oxygène. La méthode repose sur l'attaque oxydante de la substance par un mélange acide chromique-acide sulfurique, ce qui transforme quantitativement les groupes nitro et nitroso en acide nitrique. Au moyen de l'alliage de Devarda en milieu alcalin, on réduit celui-ci en ammoniac que l'on chasse par distillation dans un courant d'azote et que l'on titre par acidimétrie.

     

Stability of tin etiopurpurin

Formulations of the tin etiopurpurin (SnET2) have been observed to undergo a spectral change on storage in dimethylformamide solution. This results in an alteration in the action spectrum, with enhanced photodynamic activity at lower wavelengths and decreased activity at 660 nm. On the basis of structural considerations, a reduced analog of SnET2 was prepared with an absorbance maximum at 640 nm. Formation of this product, termed SnET2H(2) relieves steric strain inherent in the parent molecule. Nuclear magnetic resonance, spectral and photodynamic data are consistent with the formation of SnET2H(2) during SnET2 storage. Slight modifications in the original synthesis are also reported, resulting in improved yields of intermediate products.     

Corpuscular diagnostics of a hollow-cathode discharge-III. The metal-ions-regime evolution

The variations in time of mass spectra of ions, extracted from the hollow-cathode discharge in the regime of the intensive sputtering of the cathode material were measured. The mass spectrum changes in time conspicuously. From the results of measurements a distinct anisotropy of ion beam is inferred. The discharge turns into a metal-ions regime.The helpful discussions with Dr. J. Musil are gratefully acknowledged.