Die Oxydation des Germaniums (2) an der Quecksilbertropfelektrode und ihre analytische Anwendung

Zusammenfassung Das durch Reduktion von vierwertigem Germanium mit Natriumhypophosphit erhaltene zweiwertige Germanium gibt in saurer Lösung eine Anodenstufe, die der Konzentration vollkommen proportional ist. Die Messung der Stufenhöhe wird durch einen Überschuß von Chlorionen gestört. Um dieser Tatsache zu begegnen, werden cadmiumhaltige Grundlösungen vorgeschlagen. Die quantitative Bestimmung kann bereits bei Konzentrationen von 1.10^–6 Mol/l vorgenommen werden, ohne daß bei Einhaltung bestimmter Bedingungen die gewöhnlich vorkommenden Metalle stören.

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Summary The bivalent germanium obtained by reduction of quadrivalent germanium by means of sodium hypophosphite, gives, in acid solution, an anode stage, which is completely proportional to the concentration. The measurement of the height of the stage is interfered by an excess of chloride ions. To overcome this difficulty, it is advised that cadmium-bearing solutions be used. The quantitative determination can be made even at concentrations of 1 × 10^–6 mol/liter with no interference by the metals usually present, provided certain conditions are mainteined.

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Résumé Le germanium bivalent obtenu par réduction du germanium tétravalent avec l'hypophosphite de sodium donne, en solution acide, une vague anodique qui est rigoureusement proportionelle à la concentration. La mesure de la hauteur du palier est troublée par un excès d'ions chlore. Pour prévenir ce fait, on préconise l'emploi de solutions de base contenant du cadmium. La mesure quantitative peut déjà être effectuée pour des concentrations de 1 10^–6 Mol/l sans que les métaux habituellement rencontrés ne gênent, à condition d'observer des conditions précises.

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Mit 4 Abbildungen.     

A general stereoselective enamine mediated alkylation of α-substituted aldehydes

We herein present a general enamine-mediated α-alkylation of α-substituted aldehydes with carbenium ions for the stereoselective construction of quaternary stereogenic centers.     

1,3-dipolar cycloaddition reactions of azomethine ylides on enantiomerically pure (E)-γ-alkoxy-α,β-unsaturated esters.

Enantiomerically pure (E)-γ-alkoxy-α,β-unsaturated esters were reacted with azomethine ylides obtained from glycine imines in the presence of LiBr and diazabicycloundecene (DBU), to afford tetrasubstituted pyrrolidines with complete regiocontrol and fair to excellent diastereoselectivity (only two diastereoisomers formed in up to 96: 4 diastereoisomeric ratio). The results are compared with those of other 1,3-dipolar cycloadditions, and the origin of stereocontrol is discussed.     

Organocatalytic synthesis of dipyrromethanes by the addition of N-methylpyrrole to aldehydes

The reaction of aldehydes with N-methylpyrrole carried out in the presence of catalytic pyrrolidinium tetrafluoroborate at room temperature affords the corresponding dipyrromethanes and minor amounts of tripyrranes. This new, mild, and convenient process represents the first organocatalytic synthesis of dipyrromethanes. The products are obtained in chemical yields similar to those obtained with existing methods, which, however, require either a much larger excess of heterocycle (when aldehydes are employed as starting materials), or more drastic reaction conditions (when aldehyde equivalents are used as starting materials) than those employed here. A mechanism is proposed to explain the course of this reaction.     

Sulla determinazione polarografica delle impurezze metalliche nello zinco iperpuro

Résumé (W) On précise les conditions expérimentales les plus favorables pour l'exécution d'analyses polarographiques de zine extrêmement pur, en vue d'endéceler les impuretés, soit les éléments Cu, Bi, Pb, Cd, Tl et Fe. La méthode, très sensible, permet le dosage de ces divers métaux quand la concentration, dans le zinc, est de 0,0001% pour Pb, Bi et Tl, et de 0,00005% pour Cd, Cu et Fe.

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Zusammenfassung Es wurden die günstigsten experimentellen Bedingungen für die polarographische Bestimmung der in äußerst reinem Zink als Verunreinigungen vorkommenden Elemente Cu, Bi, Pb, Cd, Tl und Fe ermittelt.Das sehr empfindliche Verfahren gestattet die Bestimmung dieser Metalle, selbst wenn die betreffenden Konzentrationen im Zink bloß 0,0001% Pb, Bi oder Tl und 0,00005% Cd, Cu oder Fe betragen.

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Riassuno Vengono precisate le condizioni sperimentali più favorevoli per l'esecuzione dell'analisi polarografica dello zinco iperpuro per la determinazione delle impurezze di Cu, Bi, Pb, Cd, Tl, Fe.Il metodo, molto sensibile, permette il dosaggio dei varii metalli anche quando la concentrazione nello zinco è di 0,0001% per Pb, Bi, Tl e di 0,00005% per Cd, Cu, Fe.

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A 3 figure     

Sediment metal contamination in a creek flowing from a pristine to an industrial area of Trieste Province (Italy)

The following metals: Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined by inductively coupled plasma - atomic emission spectroscopy (ICP-AES) in fluvial sediments of Rosandra Creek, using two different, strong and mild sediment decomposition methods. The purpose was to obtain information about the contamination by metals and distribution paths of pollutants in the area crossed by Rosandra Creek: this little river is the unique epigeous watercourse in the Italian Karst and very few data can be found in literature. In this area, we can find a natural park, but also agricultural activities and an industrial district that was recently defined as "polluted site of national interest". By comparing the results of the strong and mild extraction we have obtained the percentage of extraction and enrichment factors for each metal in the different sediments of the sites R2 and R3 exposed to pollution, while the site R1 was considered as a pristine one because situated in the natural park. The computed enrichment factors are generally not very high, but copper, lead and zinc have factors that require attention. The principal component analysis (PCA) shows that the typically anthropogenic metals (as Cr, Pb, Cu and Zn) constitute the first factor, while the lithogenic metals, as Fe and Ni, constitute the second one; moreover the score plots permit to classify and distinguish the 3 sites: site R3, possibly the more exposed to contamination, has high scores both for anthropogenic and lithogenic metals.