Investigations of alkali doped Fe2O3--V2O5 catalysts by transmission and conversion electron Mössbauer spectroscopy

Fe₂O₃--V₂O₅ catalysts doped with Cs₂SO₄ (molar ratio: V:Fe:Cs=1:0.74:0.06) were found to be a rather inhomogeneous mixture of various crystalline and amorphous iron vanadate phases. After calcination in air the catalyst was divided into three different parts which were analyzed separately revealing the formation of FeVO₄ in the top and bottom fraction of the crucible and Fe₂V₄O₁₃ in the middle fraction. As compared to the well crystallized FeVO₄ reference sample, the quadrupole splittings of FeVO₄ in the Cs-doped catalysts were larger pointing to more distorted iron sites which were assumed to be responsible for high catalytic selectivities. In contrast, the quadrupole splittings of FeVO₄ in the less selective K- and Rb-doped Fe₂O₃--V₂O₅ catalysts were smaller. Additional components in the bottom fraction were also α-Fe₂O₃ and Fe_1-xS. As indicated by the CEMS spectra the latter is located preferentially on the surface of the catalyst particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

A study of thin surface layers by multilayer Mössbauer spectroscopy /MMS/

A stacking Mössbauer technique, MMS has been applied for studying thin surface layers. The surface layers formed on the⁵⁷Fe film in aqueous solutions of corrosion inhibitors, such as zinc phosphate and barium metaborate, and in distilled water was studied by this method. It has been found that the corrosion is much slower in the presence of zinc phosphate and barium metaborate. XPS analysis suggests the formation of a mixed iron zinc phosphate on the surface of the⁵⁷Fe film after corrosion in a zinc phosphate solution.     

Untersuchung der thermischen Eigenschaften von Alkalibenzolsulfonaten

Zusammenfassung Der Einfluß von Atmosphäre, Aufheizungsgeschwindigkeit und Spülgasgeschwindigkeit auf die thermische Zersetzung von Alkalibenzolsulfonaten wurde untersucht. Kristallwassergehalt, Dehydratations-temperatur und -wärme, gegebenenfalls die Zusammensetzung, Art, Temperatur und Wärme der Modifikationsänderungen, Schmelzpunkte und Schmelzwärmen der Verbindungen wurden bestimmt. Die Zersetzung verläuft in zwei Abschnitten. In dem ersten Hauptteil entstehen in Inertgasatmosphäre Diphenyloxid, Diphenyl, Diphenylsulfon, Benzol, Phenol, Thiophenol, Diphenylsulfid, Thiantren, Diphenylenoxid und wahrscheinlich Diphenylensulfid, weiterhin Koks, Schwefeldioxid, Natriumsulfit und wenig Natriumsulfat, Natriumsulfid, Acetylen und Wasser. Im zweiten Hauptzersetzungsvorgang entstehen Natriumsulfid und Kohlenoxid. Die Produkte wurden isoliert und analysiert. Dazu wurden Derivatographie, Differentialthermoanalyse, Gaschromatographie, Infrarotspektroskopie, kontinuierliche thermische Titration und chemische Methoden gemeinsam angewandt.

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Summary An investigation was made of the influence of the atmosphere, rate of temperature rise, and velocity of the purging gas on the thermal decomposition of alkali benzene sulfonates. The crystal water content, the dehydration temperature and heat, and if need be the composition, the kind, temperature, and heat of the modification changes, melting points and heats of fusion of the compounds, were determined. The decomposition proceeds in two stages. In the first main stage (in an inert atmosphere) the resulting compounds include diphenyl oxide, diphenyl, diphenylsulfone, benzene, phenol, thiophenol, diphenyl sulfide, thianthrene, diphenylene oxide and probably diphenylene sulfide; also coke, sulfur dioxide, sodium sulfite and a little sodium sulfate, sodium sulfide, acetylene, water. Sodium sulfide and carbon monoxide are formed in the second main decomposition. The products were isolated and analyzed. Furthermore, use was made of derivatography, differential thermal analysis, gas chromatography, infra red spectroscopy, continuous thermal titration, and chemical methods.

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Résumé On a étudié l'influence de l'atmosphère, de la vitesse d'échauffement et de balayage du gaz, sur la décomposition thermique des benzène-sulfonates alcalins. On a déterminé la teneur en eau de cristallisation, la température et la chaleur de déshydratation, éventuellement la composition, la nature, la température et la chaleur des changements d'état, les points de fusion et les chaleurs de fusion des composés. La décomposition s'effectue en deux temps. Tout d'abord, en atmosphère inerte, il se forme de l'oxyde de diphényle, du diphényle, de la diphénylsulfone, du benzène, du phénol, du thiophénol, du sulfure de diphényle, du thianthrène, de l'oxyde de diphénylène et probablement du sulfure de diphénylène, et aussi du coke, de l'anhydride sulfureux, du sulfite de sodium et, en moins grande quantité, du sulfate de sodium, du sulfure de sodium, de l'acétylène et de l'eau. Dans une deuxième étape de la décomposition principale, du sulfure de sodium et de l'oxyde de carbone prennent naissance. On a isolé et analysé ces produits. Pour cela, on a utilisé simultanément la dérivatographie, l'analyse thermique différentielle, la chromatographie en phase gazeuse, la spectroscopie infrarouge, le titrage thermique en continu et les méthodes chimiques.

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Vorgetragen beim Symposium für analytische Chemie in Graz, 29. September bis 1. Oktober 1965.     

Magnetism of metal cyanide networks assembled at interfaces

Studies of metal cyanide thin films prepared directly at interfaces are reviewed. The systems range from monolayers, single-layer analogs of Prussian blue-like networks, to bulk powders prepared as thin films. Monolayer networks are prepared at the air/water interface and transferred to solid supports using Langmuir-Blodgett film methods. Films of bulk materials are prepared directly on solid surfaces using a templated sequential deposition procedure. The magnetic properties of the films have been explored, and in some cases, these monolayers and surface films give rise to new behavior that is only possible because of the fabrication method or thin film architecture. The methods of synthesis can generate oriented samples, even when the materials are poorly crystalline. Furthermore, the interface-assembled networks are inherently anisotropic, leading to phenomena not present in the solid-state analogs, such as anisotropic photomagnetism in a thin film of Rb_jCo_k[Fe(CN)₆]_l·nH₂O.     

Salze von Halogennophosphorsäuren. VII Darstellung und Eigenschaften von Siliciumdichlorphosphaten

Salts of Halogenophosphoric Acids. VII. Preparation and Properties of Silicon Dichlorophosphates By reaction of SiCl₄ or SiHCl₃ with dichlorophosphoric acid the compounds H[Si(PO₂Cl₂)₅] · C₂H₅OC₂H₅, H[Si(PO₂Cl₂)₅] or Si(PO₂Cl₂)₄ have been prepared, the composition of which depends on the solvents used. Some properties of these compounds are described and possible Constitutions are discussed.     

Thermal properties of tetrahydroperparine derivatives

The thermal behaviour of tetrahydroperparine (THP) and its derivatives with various acids has been investigated. The acid is liberated from the formate derivative basically in two steps, while the other aliphatic acids are released quantitatively before the thermal decomposition of the THP molecule. The thermoanalytical curves, electrical conductivity data measured in the molten phase, and infrared spectra prove that while part of the formic acid is hydrogen-bonded the other part is bound ionically in the molecule. It may be assumed that the marked biological activity of the compound can be explained by this difference in the nature of the bonds.     

Zur Darstellung von Imidazolidin-thionen-(4) und Imidazolin-(3)-thionen-(5)

Zusammenfassung 2,2,5-Trisubstituierte Imidazolidin-thione-(4) lassen sich mittels Schwefels mit guten Ausbeuten zu Imidazolin-(3)-thionen-(5) dehydrieren. Hierüber sowie über einige Verbesserungen der bisher bekannten Synthesen für insbesondere 2,2,5-trisubstituierte Imidazolidin-thione-(4) wird berichtet.

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Dehydration of 2.2.5-trisubstituted imidazolidine-(4)-thiones with elementary sulfur gives in good yields 3-imidazoline-(5)-thiones. This reaction and improved methods of the well known syntheses of especially 2.2.5-trisubstituted imidazolidine-(4)-thiones are described.

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Mitt.:F. Asinger, W. Schäfer undH. Triem, Mh. Chem.97, 1510 (1966).

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Teil der Dissertation vonH. Meisel, Techn. Hochschule Aachen, 1963.

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Teil der Dipl.-Arbeit vonHilde Kersten, Techn. Hochschule Aachen, 1963, und Teil der Dissertation vonHilde Kersten, Techn. Hochschule Aachen, 1965.