Rapid chemical separation procedures

Fast, discontinuous separation procedures are described for zirconium, niobium, technetium and antimony from fission products. Other rapid separation methods from aqueous solutions are summarized. The combination of a gas jet recoil transport system with a continuous solvent extraction technique and with a thermochromatographic separation method is presented. The application of such procedures to the investigation of new and already known short-lived nuclides is illustrated by some examples.     

Comparative analysis of local spin definitions

This work provides a survey of the definition of electron spin as a local property and its dependence on several parameters in actual calculations. We analyze one-determinant wave functions constructed from Hartree-Fock and, in particular, from Kohn-Sham orbitals within the collinear approach to electron spin. The scalar total spin operators S2 and Sz are partitioned by projection operators, as introduced by Clark and Davidson, in order to obtain local spin operators SASB and SzA, respectively. To complement the work of Davidson and co-workers, we analyze some features of local spins which have not yet been discussed in sufficient depth. The dependence of local spin on the choice of basis set, density functional, and projector is studied. We also discuss the results of Sz partitioning and show that SzA values depend less on these parameters than SASB values. Furthermore, we demonstrate that for small organic test molecules, a partitioning of Sz with preorthogonalized Lowdin projectors yields nearly the same results as one obtains using atoms-in-molecules projectors. In addition, the physical significance of nonzero SASB values for closed-shell molecules is investigated. It is shown that due to this problem, SASB values are useful for calculations of relative spin values, but not for absolute local spins, where SzA values appear to be better suited.     

Jod-spezifischer Detektor für einen Gas-Chromatographen

The In-flame detector earlier applied to the specific chlorine (359.9 nm) and bromine (372.7 nm) analysis has now been employed for the iodine determination at 409.9 nm. It is shown that the resolution power of a GC column can be improved by such a specific detector. After calibration quantitative measurements of the iodine contents of the GC fractions are possible. The detection limits are 0.01–1.4 μg of iodine.     

Application of a micro carbon rod atomizer as Br-spezific gas-chromatographic detector

Summary A micro carbon rod atomizer has been employed for specific and quantitative bromine determinations. This Br-specific gas-chromatographic detector works by help of InBr-bands and measurement at 372.7 nm. The performance of this flame band emission detector (FBD) is demonstrated by calibration curves and the detection limits of 2 examples (ethyl bromide, ethylene dibromide), the latter being 5 and 36 ng of bromine, respectively. The reproducibility has been found to be 4.3%. An example of this detector in comparison with a thermoconductivity detector (TCD) is presented.

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Verwendung einer Mikro-Graphitküvette als Br-spezifischer Detektor für die Gas-Chromatographie

Zusammenfassung Eine Mikro-Graphit-Küvette wird für spezifische quantitative Brombestimmungen nach der Indium-Methode bei 372,7 nm benützt und in Verbindung mit einem Gas-Chromatographen als Br-spezifischer Detektor eingesetzt. Die Leistungsfähigkeit dieses Detektors wird an 2 Beispielen (Äthylbromid, Dibromäthan) mit Hilfe von Eichkurven, Bestimmung von Nachweisgrenzen u. ä. demonstriert. Die Nachweisgrenzen liegen bei 5 bzw. 36 ng Brom für die 2 genannten Substanzen. Die Reproduzierbarkeit der Messungen liegt bei 4,3%. Ein Beispiel für die Registrierung eines Gemisches verschiedener Substanzen, gemessen mit dem GC + Flammen-Banden-emissions-Detektor (FBD) und zum Vergleich mit einem Wärmeleitfähigkeitsdetektor (TCD), wird dargestellt.

This research work was supported by financial help of the Bundesminister für Forschung und Technologie in Bonn (GFR).     

Determination of picogram amounts of lipoxin A4 and lipoxin B4 by high-performance liquid chromatography with electrochemical detection

A new method for the determination of lipoxins with electrochemical detection after high-performance liquid chromatography is described. The half-wave potentials of lipoxin A4 and lipoxin B4 at a glassy carbon electrode and a mobile phase of methanol-water (65:35 v/v) and 1 mM trifluoroacetic acid was found to be +1.14 V versus an Ag/AgCl reference electrode. The use of trifluoroacetic acid instead of sulphuric acid and lithium perchlorate led to a background current of 6-8 nA at +1.20 V. The detection limits for both lipoxins, based on a signal-to-noise ratio of 3:1 were found to be 5-10 pg (15-30 fmol). The new method was applied to an extract of human polymorphonuclear granulocytes, preincubated with 15-hydroxyeicosatetraenoic acid and stimulated with Ca2+ ionophore A23187.     

Neuere Entwicklungen der flammenphotometrischen Analysenverfahren

Zusammenfassung Es wird gezeigt, daß man durch Einsatz von reduzierenden Flammen, durch Einsatz von Chemiluminescenzvorgängen in Flammen, durch Atomabsorptionsverfahren, durch Modulations- und Differentiations-operationen eine Reihe von weiteren Elementen mit den schnellen und spezifischen Flammenmethoden analytisch gut erfassen kann. Hierbei wird insbesondere auf die Bestimmung von Spurenelementen in Mikroproben mit möglichst einfachen Mitteln eingegangen.

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Summary It is demonstrated that one can grasp analytically well a series of further elements with the quick and specific flame methods by use of chemiluminescence processes in flames, by atomic absorption methods, by operations of modulation and differentiation. Hereby the determination of trace elements is specifically treated in microprobes with the most possible simple means.

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Unterstützt mit Mitteln der Deutschen Forschungsgemeinschaft.

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Herrn Prof. Dr. Bohnstedt zum 65. Geburtstag gewidmet.

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Meinen Mitarbeitern, insbesondere Herrn Dipl. Phys. W. Lang und Frau B. Gutsche, die an den zuletzt besprochenen Ergebnissen einen maßgeblichen Anteil hatten, als auch der Deutschen Forschungsgemeinschaft sei an dieser Stelle herzlichst gedankt.     

Identification of iodoorganic compounds in kerosene from nuclear fuel reprocessing

In kerosene samples from nuclear fuel reprocessing, iodoalkanes with chain-lengths from C₄ to C₁₃ have been identified. The kerosene samples were purified by means of solid-phase extraction. By this method other fission products like¹²⁵Sb and¹⁰⁶Ru were quantitatively removed from the solution. The only remaining radioactive nuclide was thus¹²⁹I. The iodoorganic compounds in the kerosene from the solvent were enriched from 6000 Bq/L to 100 000 Bq/L¹²⁹I by vacuum distillation. Chromatographic separation by HPLC, fractionation, and -measurement of the fractions showed that at least one polar and one nonpolar iodoorganic compound were present. Derivatisation of the iodoorganic compounds with, 1,4-diazabicyclo-2,2,2-octane to quatermary ammonium salts and²⁵²Cf plasma desorption mass spectrometry of the products revealed that the main iodoorganic constituents in the kerosene were iodobutane as polar and iodododecane as nonpolar compound in approximately equal concentrations.