Simultaneous determination of metal ion concentrations in binary mixtures with a multi-LED photometer

 A compact photometer is based on up to seven different light-emitting diodes whose light is guided into a photometric cell by means of a fibre-optic coupler. The wavelength is selected by switching on the appropriate light source. The application of this multi-wavelength photometer to the determination of binary metal ion samples is demonstrated using model mixtures. Solutions of Fe, Co, Cu, Ni, Cr and Mn were used in combination with several photometric reagents. It was found that the instrument yielded concentration measurements which were usually within a few percent of the correct concentration. These results are comparable to reported data obtained with conventional instruments for similar measurements. The application of the instrument for simultaneous determination in flow-injection analysis employing rapid computer controlled switching of the light-emitting diodes is also demonstrated. A limitation in the use of light-emitting diodes for the simultaneous determination was found to arise from the fact that in some instances non-linear calibration curves are obtained when employing light-emitting diodes as light sources. This occurs when the absorptivity of the measured compound changes over the emission band of the diodes. Multiple regression analysis is then not easily possible. Received: 16 September 1996/Revised: 14 October 1996/Accepted: 16 October 1996     

Regio- and stereoselective oxetane formation via paterno-buchi photocycloaddition

Carbonyl 2 + 2 photoaddition occurs selectively to the alkene moiety of 3-(4-methyl-3-pentenoxy)pyridine. Photolysis of alkene containing pyridines in acetophenone gives rise to an oxetane which is obtained with extremely high diastereoselectivity as shown by analysis of the major 2 + 2 photoproduct. A second photoproduct, 2,3-dihydroxy-2,3-diphenylbutane, is obtained as a result of acetophenone coupling.     

Bis{2-[dimethylamino)methyl]phenyl}silverlithium,a tetranuclear organometallic compound with bridging aryl groups between silver and lithium

Bis{2-[(dimethylamino)methyl]phenyl}silverlithium has been prepared and characterized. Molecular weight determinations, and ¹³C NMR and ¹H NMR spectra reveal that the compound exists (in benzene) as a tetranuclear mixed metal cluster containing aryl groups bridging the silver and lithium atoms. Silver-proton, silver-carbon and lithium-carbon couplings have been observed in the NMR spectra of this compound.     

Die Methanolyseprodukte von 14-Brom-codeinon-dimethylacetal: (14S)-14-Methoxy-codeinon

Zusammenfassung Beim Erhitzen von 14-Brom-codeinon-dimethylacetal (1) in absol. Methanol mit einer äquivalenten Menge Na₂CO₃ entstehen die drei isomeren Methoxycodeinon-acetale3, 4 und5 sowie die beiden Indolino-codeinonderivate6 und7. Die Strukturen und Konfigurationen der Verbindungen3–6 werden auf Grund der NMR- und IR-Spektren sowie durch Umwandlung in bekannte Verbindungen bewiesen.

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The methanolysis of 14-bromo-codeinone dimethyl acetal

14-Bromocodeinone dimethyl acetal (1) reacts in methanol containing sodium carbonate (0.5 moles) to give the three isomeric methoxycodeinone acetals3, 4, and5 besides the indolino-codeinones6 and7. The structures and configurations of3–6 were established on the basis of NMR- and IR-spectroscopy and by conversion to known compounds.

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Herrn Prof.E. Ziegler mit den besten Wünschen zum 60. Geburtstag gewidmet.     

Analysis of aerosols at the bosporus bridge of Istanbul

Air samples collected at the second Bosporus bridge of Istanbul which carries a heavy traffic load between Asia and Europe, were analyzed for 22 elements by the INAA method. Pb, Cd and Fe concentrations in the samples were determined by AAS. Iron concentrations were used as a cross check between the two methods. In order to define the enrichment factors for the elements in the bridge area, a sample collected from our university campus which can be considered as a rural site, was also analyzed. Differences were observed especially for Br, Al, Mg, Ti, Cu and Na between the two sites. Based on the results of the samples from the bridge, we got a value of 0.58(16) for the Br/Pb-ratio.     

Automatic coulometric micro-determination of unsaturation with kinetic proof of real equivalence-point

Summary A fully automatic coulometric method has been applied successfully to the determination of unsaturated compounds on the micro-scale. Results are quoted which show a reproducibility of ± 0.3% for monoolefinic hydrocarbons. It is possible to control by means of a simple operation whether the addition reaction is complete and unaccompanied by side reactions. It has been shown that the concentrations of olefines in a mixture can be determined when their bromination speeds differ sufficiently from each other.

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Zusammenfassung Eine für kinetische Zwecke entwickelte vollautomatische, coulometrische Methode wurde mit Erfolg auf die Bromtitration ungesättigter Verbindungen im Mikromaßstab angewandt. Die angeführten Testuntersuchungen zeigen, daß bei monoolefinischen Kohlenwasserstoffen und ähnlichen Verbindungen die erreichbare Reproduzierbarkeit besser ist als ± 0,3%. Die Anordnung ermöglicht auf einfache Weise die Feststellung, ob die Addition vollständig abgelaufen ist und ob der Titrationswert nicht durch eine Nebenreaktion verfälscht wird. An Beispielen wird gezeigt, wie bei Gemischen olefinischer Verbindungen, die Bestandteile ausreichend verschiedener Reaktivität enthalten, die einzelnen Anteile nebeneinander bestimmt werden können.

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Résumé Les auteurs ont appliqué avec succès une méthode coulométrique entièrement automatique pour le dosage des composés non saturés à l'échelle microanalytique. Les résultats obtenus sont reproductibles à ± 0,3% près pour les hydrocarbures mono-oléfiniques. Une opération simple permet de contrôler que la réaction d'addition est complète et qu'elle n'est pas accompagnée par des réactions secondaires. Les auteurs ont montré également qu'il était possible de déterminer les concentrations de diverses oléfines dans un mélange lorsque leurs vitesses de fixation du brome diffèrent suffisamment les unes des autres.

     

Chemical autocatalysis in the NO + CO reaction on Pt(100)

It is shown that the reaction between NO and CO on Pt(100) is autocatalytic and probably involves a surface species which accelerates the reaction. Temperature-programmed desorption (TPD) of co-adsorbed NO and CO yields complete reaction, with N₂ and CO₂ desorbing simultaneously in sharp peaks at ≈410 K. Isothermal desorption also yields rates characteristic of chemical autocatalysis.     

Atomabsorptionsspektroskopische Bestimmung von Edelmetallen

Zusammenfassung Die atomabsorptionsspektroskopische Palladiumbestimmung wird vom Platin nicht und vom Rhodium nur wenig beeinflußt. Berücksichtigt man, daß ein Zusatz von Uran die Palladiumbestimmung neben Rhodium desaktiviert, so liegen allgemein die günstigsten Bedingungen für die Palladiumbestimmung vor, wenn Lanthan als spektroskopischer Puffer zugesetzt wird. Korrekturgleichungen werden gegeben.

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Determination of noble metals by atomic absorption spectroscopy3. Effect of platinum and rhodium on the determination of palladium

The atomic-absorption determination of Pd is not affected by Pt, but there is a small influence by Rh. The aim of this investigation is to determine these effects quantitatively, furthermore under the releasing effects of uranium and lanthanum. Equations to correct the results are given.

     

Röntgenographische,thermoelektrische, und IR-spektroskopische Untersuchung des Spinellsystems LixMn1−xV2O4

The spinels of the system Li_xMn_1?xV₂O₄ (0 ? x ? 1) have been prepared at 700–750°C from LiV₂O₄ and MnV₂O₄. The lattice constants decrease linearly with increasing x. In the region x>0.75, the d-electrons of V should be delocalized as the VV distances are lower than the critical VV separation of 2.94 Å. Experimentally, the samples with x>0.6 show no IR absorption bands and the Seebeck coefficient is near zero. The Seebeck coefficient can be described with a model of intermediate polarons and can be expressed by the equation $\text{Θ = 198}\text{log}\text{[1 +}\text{(1 ? x)}{}^5\text{x}\text{]}$.     

Chromatographie von Carbamat- und Phenylharnstoff-Pesticiden auf Dünnschichten von basischem Zinkcarbonat

Thin layers of basic zinc carbonate can be used with good results for separation and multiple identification of carbamate and phenylurea pesticides. Five important substances could be separated by one-dimension TLC. The best results were obtained by the following developing solvents: a) benzene, b) a mixture of benzene/petroleum ether/chloroform (6∶1∶1). The substances are either recognisable in short-wave UV-light, when a fluorescence indicator (F 254 nm) is added, or in day-light, after spraying a solution of 0.1 N AgNO₃ in 3 N HNO₃, followed by an UV-exposure for about 4 min.