Fast formation of aromatic cations in cyclohexane observed by pulse radiolysis

The fast formation of cations of benzophenone, biphenyl, naphthalene, anthracene and phenanthrene in liquid cyclohexane was studied by nanosecond pulse radiolysis. Rate constants between 2.3 × 10¹⁰ M^?1 s^?1 (for naphthalene) and not below 2.5 × 10¹² M^?1 s^?1 (for benzophenone) were derived and compared with the corresponding rate constants for anion formation.     

Template synthesis in the nickel(II)–thiocarbohydrazide–propanone triple system

The complexing process proceeding in the Ni^II–thiocarbohydrazide (H₂N–H–NC(=S)–NH–NH₂)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of Ni^II with (N,N,S,S)-donor tetradentate ligands having NiL¹, NiL² and NiL³compositions where L¹ is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L² is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L³ is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur.     

Beiträge zur quantitativen Dünnschichtchromatographie. V

Zusammenfassung Eine dünnschichtchromatographische Trennung des Wismuts von einem Überschuß an Metallen der Schwefelwasserstoffgruppe wurde beschrieben. Als Laufmittel dient ein Gemisch von tert.-Butanol, Salzsäure und Wasser. Nach Absaugen der Sorptionsschicht wird das Wismut mit MDCM spektralphotometrisch bestimmt. Standardabweichung und Varianz des Verfahrens werden angegeben.

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Summary A thin layer Chromatographic separation of the bismuth from an excess of metal ions of the hydrogen sulfide group is described. A mixture of tert. butanol, hydrochloric acid and water serves as mobile phase. After sucking off the sorption layer, the bismuth is determined spectrophotometrically with MDCM. The standard deviation and the variance of the procedure is given.

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Résumé On décrit une séparation par Chromatographie en couche mince du bismuth de métaux en excès du groupe de l'hydrogène sulfuré. On utilise comme éluant un mélange de butanol tert., d'acide chlorhydrique et d'eau. Après aspiration de la couche de sorption, on dose par spectrophotométrie le bismuth par le MDCM. On communique l'écart-type et le coefficient de variation du procédé.

     

Untersuchungen an oxidischen Katalysatoren. XXIX. Spektroskopische und katalytische Untersuchungen an Ni2+-, Co2+-, Cr3+- und Cu2+-ausgetauschten Mordeniten

Studies on Oxide Catalysts. XXIX. Spectroscopic and Catalytic Investigations on Ni²⁺-, Co²⁺-, Cr³⁺-, and Cu²⁺-exchanged Mordenites NiNaM, CoNaM, CrNaM und CuNaM (M = Mordenite) have been characterized by UV-VIS, EPR and i.r. spectroscopy and the results were compared with the catalytic activity and the activity-time-dependence in the cracking of n-octane and with the shape selectivity in the cracking of a n-octane and isooctane mixture. Water molecules acting as ligands of the exchanged cations are able to dissociate yielding Brönsted acidity. Brönsted sites may be regarded as catalytic active centers in the cracking reaction. Unreduced transition metal cations facilitate the “coking” of the mordenite. The unreduced chromium and cobalt cations for which a position within the main channel is expected, affect the diffusion of the branched paraffin molecule thus increasing shape selectivity.     

Zur Bestimmung von β-Aminocrotonsäureester nach Migration in Lebensmittel

β-Aminocrotonic esters are of great importance as stabilizers for the production of clearly transparent food packaging of PVC. For the purpose of studying the migration into foods a thin-layer Chromatographic and a polarographic method were elaborated. The TLC method consists of the visual comparison of the intensity of the spots after treatment with Fast Blue B salt. The polarographic determination is carried out after nitrosation of the stabilizer. By the TLC method 10^?7 g of ester per spot are still detectable; the concentration which is still determinable by cathode-ray polarography is 5×10^?7 g of ester and by conventional d.c. polarography 5×10^?6g of ester per ml of final solution. After extraction with acetonitrile traces of the stabilizer which are migrated into edible oil are still determinable down to 2 ppm by the methods described.     

A hydrodynamic voltammetric study of the ferricyanide/ferrocyanide system with convective electrodes of platinum,gold, glassy carbon,carbon film,and boron carbide

Hydrodynamic voltammetry employing empirically determined mass transport coefficients is used to determine heterogeneous rate constants and transport coefficients for the ferricyanide/ferrocyanide system in 0.1 M phosphate buffer and other supporting electrolytes with turbulent tubular and rotated disk electrodes of platinum, gold, glassy carbon, carbon film, and boron carbide. Different kinetic parameters are obtained at the various electrode materials. For the platinum, gold, and boron carbide electrodes, the magnitudes of the rate parameters depend on scan direction. The nature of this hysteresis varies with the electrode material and is explained in terms of adsorbed oxide and ionic layers or other phenomena not described by simple double layer theory.     

Optimization of simulated moving bed plants with low efficient stationary phases: separation of fructose and glucose

An optimization procedure for simulated moving bed (SMB) plants with low efficient stationary phases is presented. The new aspect is that the desorbent consumption can be cut by 70% by running the plant with lower internal liquid flows and a corresponding larger switch time while the productivity is kept constant. This concept was validated by the separation of fructose and glucose in water on a calcium resin with an eight-column SMB plant. The separation can be predicted well by a true moving bed (TMB) and a simulated moving bed simulation. Adsorption isotherms were determined up to 300 kg/m3 for glucose and 500 kg/m3 for fructose from 25 to 80 degrees C. Experimental SMB runs were performed over a wide range of feed concentrations (10-350 kg/m3) and temperatures (25-80 degrees C). The strong influence of the delay volume is pointed out. For an experimental run with high feed concentration a complete set of data is presented. To reduce biological growth separation at 80 degrees C is recommended.     

Darstellung und thermische Zersetzung von Lithiumcyanuraten Eine einfache Methode zur Gewinnung von wasserfreiem Lithiumcyanat

Zusammenfassung Die Darstellung von Mono-, Di- und Tri-Lithiumcyanurat durch Umsetzung von Cyanursäure mit LiOH bzw. Li₂CO₃ in hochsiedenden Alkoholen und durch lösungsmittelfreie Festkörperreaktion wird beschrieben. Die Festkörperreaktionen werden mit Hilfe thermoanalytischer Methoden untersucht. Die Reaktion mit LiOH erfolgt in zwei Schritten und ergibt bei 400°C. Trilithium-cyanurat. Unter denselben Bedingungen wird mit Li₂CO₃ nur Dilithium-cyanurat gebildet. Die Thermolyse von Trilithium-cyanurat bei 550°C liefert in hoher Ausbeute Lithiumcyanat und stellt somit eine einfache Methode zur Darstellung dieser Verbindung in wasserfreier Form dar.

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Formation and thermolysis of lithium cyanurates (a simple preparation of anhydrous lithium cyanate)

The formation of mono-, di- and tri-lithium cyanurate by reaction of LiOH or Li₂CO₃ with cyanuric acid has been investigated as a solid state reaction and by using high boiling alcohols as reaction medium. For investigating the solid state reactions thermoanalytical methods were used. The reaction with LiOH proceeds in two steps yielding trilithium cyanurate at 400°C. Under the same conditions only dilithium cyanurate is formed by reaction with Li₂CO₃. Lithium cyanate is obtained in high yields by thermolysis of trilithium cyanurate at 550°C. This procedure is therefore a simple method in synthesizing pure anhydrous lithium cyanate.

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Mit 3 Abbildungen

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Herrn Univ.-Prof. Dr.O. Kratky zum 70. Geburtstag gewidmet.     

Determination of copper impurities in nickel and cobalt salts by atomic absorption spectroscopy

Summary A method is described for the rapid determination of traces of copper in the ppm range in cobalt and nickel salts. The % standard deviation for the analysis is reported as 3.4 to 3.7 for aequous solutions and 4.8 to 5.0 for carbon tetrachloride sprayed directly into the flame after extraction.

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Zusammenfassung Ein Verfahren zur raschen Bestimmung von Kupferspuren im ppm-Bereich in Kobalt- und Nickelsalzen wurde beschrieben. Die Standardabweichung in wäßrigen Lösungen beträgt 3,4 bis 3,7%, bei unmittelbarem Versprühen der Tetrachlorkohlenstoffextrakte in die Flamme 4,8 bis 5,0%.