Zur colorimetrischen Bestimmung von Rheniumspuren

Zusammenfassung Es wird gezeigt, daß mit Hilfe von Fuchsin eine colorimetrische Bestimmung von Rhenium in Mengen von 1–10 g mit einer Standardabweichung von 0,1 g möglich ist. Ein Abtrennungsverfahren, bestehend aus Sublimation des Rheniums und dessen Extraktion mit Tetraphenylarsoniumchlorid gestattet die Anwendung der colorimetrischen Methode zur Erfassung von Rheniumgehalten von 10^–1 bis 10^–4% in Mineralien und technischen Produkten.Herrn Prof. Geilmann und Herrn Prof. Bock danke ich für anregende Diskussionen. Herrn Prof. Strassmann und Herrn Dr. Herrmann bin ich für die Erlaubnis zur Benutzung der Hilfsmittel der radiochemischen Abteilung und für gegebene Ratschläge zu Dank verpflichtet.     

Substituent control of hydrogen bonding in palladium(II)-pyrazole complexes

Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions.     

Characterisation of humic substances using atmospheric pressure chemical ionisation and electrospray ionisation mass spectrometry combined with size-exclusion chromatography

Humic substances were analysed by atmospheric pressure chemical ionisation (APCI) and electrospray ionisation (ESI) mass spectrometry in positive and negative modes. Using APCI the average m/z range of humic substances was reduced 5-fold compared to ESI. High-resolution time-of-flight mass spectrometry revealed the formation of multiply charged molecules in the ESI mode. Moreover, it was possible to obtain daughter ion mass spectra of humic substances by nanospray tandem mass spectrometry. The size-exclusion chromatography elution profile of humic substances was highly influenced by the pH of the analyte solution. By contrast, the pH had no significant influence on the observed mass spectra of humic substances.     

Longitudinal nuclear relaxation measurements in hcp H2

Measurements of T₁ in the hep phase of H₂, over the temperature range 2°–12°K and the ortho concentration range between 0.5 and 0.97 are presented. At temperatures below 10°K, the thermally activated self-diffusion is negligible and the mechanism for nuclear relaxation is that attributed by Moryia and Motizuki and by Harris to intramolecular dipolar interaction, modulated by intennolecular electric quadrupole-quadrupole (EQQ) interaction. The gaussian approximation for the correlation function was used by these authors to predict T₁. From the comparison between experiment and theory, we determine the EQQ parameter Γ/k_B to be 0.67°K. Above 10°K the effect of diffusion influences T₁, and the experimental results for an 88 per cent ortho H₂ sample up to the melting point suggest that the relaxation mechanisms resulting from EQQ interaction and diffusion are not independent of one another.     

Cyclotomic units over finite fields

Let ζ be a primitivesp-th root of unity for a primep>2, and consider the group Ω(ζ) of cyclotomic units in the ringR(ζ)=ℒ[ζ+ζ^-1]. This paper deals with the image of Ω(ζ) in the unit group ofR(ζ)/qR(ζ), whereq is a prime ≠p. In particular, it obtains criteria for this image to be essentially everything, and a lower bound on the density of primesp (withq fixed) for which it cannot be. These results have a direct bearing on previous work about units in integral group rings for cyclic groups of orderpq. Work supported in part by an operating grant from NSERC (Canada).     

Almost block independence and bernoullicity of ℤ d -actions by automorphisms of compact abelian groups

Summary We prove that a ^d -action by automorphisms of a compact, abelian group is Bernoulli if and only if it has completely positive entropy. The key ingredients of the proof are the extension of certain notions of asymptotic block independence from -actions to ^d -action and their equivalence with Bernoullicity, and a surprisingly close link between one of these asymptotic block independence properties for ^d -actions by automorphisms of compact, abelian groups and the product formula for valuations on global fields.Oblatum 20-X-1994