Mikrobestimmung von Kohlenstoff und Wasserstoff, sowie von 14C, Tritium und Deuterium im Stickstoffstrom

Zusammenfassung Eine mikroanalytische Kohlenstoff-Wasserstoffbestimmung wird beschrieben, bei der die organische Substanz im Stickstoffstrom verbrannt und deren Crackprodukte mit Sauerstoff oxydiert werden. Halogene und Schwefel werden vom Verbrennungskatalysator (nach Körbl) absorbiert, während eventuell entstandene Stickoxide an einer Kupferschicht zur Reduktion gelangen. Die entstandenen Verbrennungsprodukte CO₂ und H₂O können gravimetrisch erfaßt oder bei radioaktiven Proben durch entsprechende Absorptionsmöglichkeiten in einem Flüssigkeits-Szintillationszähler zur Zählung gebracht werden.Stark quenchende einfache, sowie doppelt markierte Proben, die man auch durch Modifikationen des Zählgeräts nicht mehr genau auszählen kann, können mit gleich hoher Zählausbeute wie nichtquenchende erfaßt werden (75% für ¹⁴C und 30% für ³H), da keine störenden Fremdgase die Zählung beeinflussen.Deuterium wird durch Ausmessen der OD-Bande bei 2500 cm^–1 mit einem Infrarot-Spektrometer quantitativ bestimmt.

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Microanalytical determination of carbon and hydrogen, ¹⁴C, tritium and deuterium in a stream of nitrogen

A microanalytical method for the determination of carbon and hydrogen is described. The procedure involves the combustion of the organic substance in a stream of nitrogen and the oxidation of the decomposition products with oxygen. Halogens and sulphur are absorbed by the combustion catalyst (according to Körbl), whereas nitrogen oxides are reduced on a copper surface. The combustion products, CO₂ and H₂O are determined gravimetrically; in the case of radioactive samples they are appropriately absorbed and counted in a liquid scintillation counter. Strongly quenching singly and doubly labelled samples, which cannot be accurately counted even by modification of the counting device, give equally high radioactive yields (75% for ¹⁴C, 30% for ³H), since counting is not influenced by other gaseous impurities. Deuterium is quantitatively determined by measuring the intensity of the OD-signal at 2500 cm^–1 with an infrared spectrometer.

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Herrn Prof. Dr. H. Schmid bin ich für das wohlwollende Verständnis meinen Arbeiten gegenüber zu bestem Dank verpflichtet. Sämtliche Glas- und Quarzgeräte wurden in der Glasbläserei unserer Institute von Herrn B. Thueler angefertigt, wofür ich auch ihm an dieser Stelle danken möchte.     

Autoxydationsprodukte des Guaiazulens

Zusammenfassung Guaiazulen wird bei Luftzutritt durch Autoxydation verändert. Die dabei auftretenden Produkte wurden chromatographisch aufgetrennt und die drei als Hauptmenge auftretenden Verbindungen charakterisiert: 3.3-Diguaiazulenyl, 1.4-Dimethyl-3-(3-guaiazulenyl)-6-isopropyl-5H-inden-5-on, 1.4-Dimethyl-3-(3-guaiazulenyl)-5-oxo-6-isopropyl-5H-inden-7-aldehyd.

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Autoxidation products of guaiazulene

Guaiazulene exposed to air undergoes autoxidation. The products were separated by chromatography, and the three major products characterized: 3.3-diguaiazulenyl, 1.4-dimethyl-3-(3-guaiazulenyl)-6-isopropyl-5H-inden-5-one, and 1.4-Dimethyl-3-(3-guaiazulenyl)-5-oxo-6-isopropyl-5H-inden-7-aldehyd.

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Herrn Prof. Dr.H. Nowotny gewidmet.     

Binding energy of lithium halide molecules

A semi-empirical open shell model of sigma bonded systems has been employed to calculate the binding energies for diatomic lithium halides. The repulsion between the atomic cores is taken as the Coulomb repulsion term $\text{1}\text{R}{}_{12}$ modified by the presence of electronic cores. This modification has been estimated from the repulsion term in the Rittner potential function. The agreement with the experimental values is quite satisfactory but the extension of the same method to alkali hydrides results in gross discrepancies. The results are discussed in the light of other results.     

Carbon suboxide and some of its reactions

The reaction of carbon suboxide with a number of 2-amino-1,3,4-thiadiazoles has given the corresponding pyrimido[1,2-b]-1,3,4-thiadiazoles     

Neutronenaktivierungsanalytische Bestimmung von Osmium in Geologischen Proben

A neutron activation analysis procedure was developed for the determination of osmium in geological materials. The method consists in the measurement of the 129.4 keV γ-rays of¹⁹¹Os after radiochemical separation of osmium. The sample decomposition, the chemical separation process and the optimal measuring conditions are described and discussed.      

Distribution of polymer deposition in plasma polymerization. III. Effect of discharge power

Distribution of polymer deposition in an inductively coupled rf discharge system is studied as a function of level of discharge power with acetylene and styrene as monomers. When a fixed flow rate is used, the discharge power has a relatively small effect on the pattern of distribution of polymer deposition as long as values of W/FM, where W is discharge wattage, F is flow rate, and M is molecular weight of monomer, are maintained above a critical level to maintain full glow in the reaction tube. It has been shown that plasma polymerization of two monomers which have different molecular weights can be compared in a fair manner by selecting conditions to yield similar value of W/FM.     

Rearrangement thermique des α-ceto, α-cyano epoxydes en dioxoles : Etude du mecanisme de la reaction

The thermolysis of α-cyano α-keto epoxides to give dioxoles is a new rearrangement. The reactivity of the epoxides is dependent upon the nature of the substituents on the epoxide ring, and solvent polarity. When the reaction is carried in the presence of benzaldehyde, a 1,3 cycloadduct is obtained. These results are in good agreement with a carbonyl ylide intermediate.     

Nitro compounds as alkylating reagents in friedel-crafts conditions : Reaction of 2-nitropropane with benzene

Friedel-Crafts reaction of benzylic or tertiary nitro compounds with benzene gave normal alkylation products. Similarly, 2-nitropropane (2-NP) gave cumene (1) which underwent further transformation affording a mixture whose behaviour with time was investigated : results were consistent with oxidative formation of the cumyl carbonium ion (7').