Cyclic chronopotentiometry of nickel(II) at mercury electrodes in acidic perchlorate solutions: Case of higher order nonregenerative reactions following electron transfer

The reduction of Ni²⁺ ions at mercury electrodes in acidic perchlorate solutions, at perchlorate concentrations below 0.2 M, is characterized by absence of kinetic control in the preceding step, and by a complex reaction mechanism following the electron transfer. This reaction sequence is known to involve intermetallic compound formation between Ni and Hg and is best described, as shown here, by a parallel second and third order kinetic scheme. Apparent rate coefficients for this kinetic scheme were determined using cyclic chronopotentiometric data and fitting by digital simulation. A linearization test of computed kinetic rate coefficients versus the number of transitions permits quantitative tests of validity of assumptions made.     

Zwei neue pentacyclische dimere des cycloheptatriens

Titanium - catalyzed dimerization of cycloheptatriene affords pentacyclo[7.5.0.0^2,8.0^5,14.0^7,11]tetradeca-3,12-diene, $\text{3}$, and pentacyclo[8.4.0.0^3,7.0^4,14.0^6,11]tetradeca-8,12-diene, $\text{4}$. By heating, $\text{3}$ is converted quantitatively into $\text{4}$.     

Zur entmischung der Lösungsmittel bei der chromatographischen trennung—v: Sorption von fliessmitteldämpfen an cellulose

The sorption of solvent vapours onto dried cellulose has been investigated. The time-dependence and the effect of the solvent-water ratio is discussed. The studies concerned the properties of methanol, ethanol, propanol and butanol.     

Flow injection analysis for calcium in serum,water and waste waters by spectrophotometry and by ion-selective electrode

The Flow Injection technique is shown to provide fast, reliable and sensitive methods for the determination of calcium in various aqueous as well as serum samples; spectrophotometric or potentiometric detection can be used. At sampling rates of 100–110 samples per hour, with 30-μl sample injections, high reproducibility of measurement and low reagent consumption are achieved in both methods. In the spectrophotometric method, the analytical readout is available within 12 s after sample injection at a total reagent consumption of 0.75 ml per analysis. The potentiometric measurement of the calcium activity in serum is placed on a reliable basis by alternating measurements of serum samples and aqueous standards without incurring any non-reproducible changes in potential between aqueous and serum solutions. This permits the simultaneous determination of pH and pCa, the analytical readout being available within XXX s of sample injection. The good agreement between the results obtained with the Flow Injection method and those attained by atomic absorption and EDTA titrations as well as pCa stat-measurements show that the new methods are potentially suitable for routine analysis.     

Hybridization in some macrocyclic polyacetylenes

The hybridization in several cyclic polyacetylene compounds has been calculated by the maximum overlap method, assuming planar and non-planar geometries of the molecules. In the planar configuration the hybrids describing the molecular skeleton deviate from the corresponding bond directions. We have a few “bent” bonds, but in contrast to the situation in small rings, here the deviation angles are negative, i.e., the hybrids point toward the inside of the ring. Non-planar structures in which acetylene groups are kept in a plane and CCH₂ or CH₂ groups are displaced out of the plane show less deviation from the bond directions of bent bonds. Furthermore, the deviation angles decrease with an increase in the out-of-plane displacement of methylene groups. Finally, when the angle of bending of the molecules approaches 50°, the deviation vanishes, predicting a puckered conformation for the molecules. Correlation between CC stretching vibration frequencies and the corresponding CC bond overlap is discussed.     

Papierchromatographische Trennung und Identifizierung der Polyäthylenglykole und ihrer Monoäther

Zusammenfassung Es wurde eine chromatographische Methode zur Auftrennung und Identifizierung der Polyäthylenglykole und ihrer Monoäther nach Über-führung in die Ester der 3,5-Dinitrobenzoesäure ausgearbeitet. Es wurden entweder Lösungsmittelsysteme mit Dimethylformamid oder Formamid als stationäre und Hexan, Cyklohexan, Benzol, Chloroform und ihre Gemische als mobile Phase oder mit Paraffinöl imprägnierte Papiere und das Gemisch Dimethylformamid—Methylalkohol—Wasser als mobile Phase angewendet.

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Summary A Chromatographic method has been developed for the separation and identification of the polyethylene glycols and their mono-ethers after conversion into the esters of 3,5-dinitrobenzoic acid. The solvent systems employed consisted of dimethylformamide or formamide as stationary phase and hexane, cyclohexane, benzene, chloroform and their mixtures as mobile phase, or papers impregnated with paraffin oil and the mixture of dimethyl-formamide-methyl alcohol were used as the mobile phase.

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Résumé On a élaboré une méthode chromatographique de séparation et d'identification des polyéthylèneglycols et de leurs monoéthers après leur transformation en ester de l'acide dinitro-3,5 benzoïque. On a employé soit les systèmes de solvants avec le diméthylformamide ou le formamide comme phase stationnaire, et l'hexane, le cyclohexane, le benzène, le chloroforme et leurs mélanges comme phase mobile, ou des papiers imprégnés d'huile de paraffine et le mélange diméthylformamide-alcool méthylique-eau comme phase mobile.

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Herrn Dipl.-Ing.J. Kami aus unserem Institut danken wir für die Darstellung und Reinigung einiger angewandter Verbindungen.     

Secondary kinetic isotope effects: Deuterium abstraction by chlorine atoms from the CD3 group in CD3CH2Cl,CD3CHDCl,and CD3CD2Cl

The occurrence and magnitude of secondary kinetic isotope effects in the gas phase has been determined for deuterium abstraction from the CD₃ group in CD₃CH₂Cl, CD₃CHDCl, and CD₃CD₂Cl by photochemically generated ground-state chlorine atoms. Over the temperature range 10–94°C a discernible “inverse” kinetic isotope effect is observed. Both the pre-exponential factors and activation energies decrease with deuterium substitution in the vicinal chloromethyl group. The opposing trends result in a net effect close to unity.     

Über Reaktionen von Nitrosophenolen, 4. Mitt.: Reaktion von Nitrosonaphtholen mit Naphtholen

Zusammenfassung Die Reaktion von 1-Nitroso-2-naphthol mit 1-und 2-Naphthol sowie die Reaktion von 2-Nitroso-1-naphthol mit 2-Naphthol in Äthanol und in Äther bei Anwesenheit von HNO₃ gibt 5H-Dibenzo[a,j]phenoxazon-(5) (I), 5H-Dibenzo[a,j]phenoxazon-(5)-14-oxid (II), 5H-Dibenzo[a,h]phenoxazon-(5) (III) sowie 5H-Dibenzo[a,h]phenoxazon-(5)-14-oxid (IV). Es wurde ein Reaktionsmechanismus vorgeschlagen und die Konstitution der hergestellten Verbindungen spektrophotometrisch und potentiometrisch bestimmt.

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The reaction of 1-nitroso-2-naphthol with 2-and 2-naphthol and the reaction of 2-nitroso-1-naphthol with 2-naphthol in ethanol or ether in the presence of nitric acid have been studied. The main reaction products isolated were the dibenzophenoxazones I–IV. The reaction mechanism for their formation is proposed.

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Mit 4 Abbildungen     

The effect of mechanical activation on the thermal decomposition of chalcopyrite

Experimental results on the influence of preliminary mechanical activation on the thermal decomposition of chalcopyrite are presented and discussed. The following experimental facts were found:

Peroxides of higher aliphatic ethers

The oxidation of higher aliphatic ethers with oxygen at 50° yields two peroxides as the main oxidation products for each ether, namely a dihydroperoxy-dialkyl ether and a dihydroperoxy-dialkyl peroxide. The mass spectra of these compounds are recorded and the main fragmentation pattern is discussed.