X-ray studies of ZSM-5 zeolites with framework cations of various sizes

From a comparison of the X-ray difractograms for various ZSM-5 zeolites the isomorphous substitution of framework Si⁴⁺ by large cations (Al³⁺, Ga³⁺, Fe³⁺) is suggested to be ordered as contrasted to the statistical substitution by small ones (B³⁺).

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ZSM-5 , Si⁴⁺ (Al³⁺, Ga³⁺, Fe³⁺) , (B³⁺).

     

Action des molecules organiques sur les composes d'insertion de metaux alcalins dans le graphite

Resume Les bases de Lewis (Tétrahydrofuranne, Diméthyl-2,5 tétrahydrofuranne, Diméthoxyéthane, Diméthyl éther du triéthylène glycol, Dioxanne, Triéthylamine, N,N,N,N tétraméthyl éthylène diamine) pénètrent dans les composés d'insertion de métaux alcalins dans le graphite (LiC₁₂, KC₃₆).Des changements de stades et de nouvelles distances interplanaires sont observées par diffraction des rayons X. En général, les nouveaux composés lamellaires obtenus comportent plusieurs phases, et sont comparables aux composés ternaires obtenus par synthèse directe.Ces solvates peuvent contenir jusqu'à deux molécules de solvant par cation, leurs stabilités thermiques peuvent donner des informations sur les pouvoirs complexants des solvants basiques.

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Lewis bases (tetrahydrofuran, 2,5-dimethyltetrahydrofuran, dimethoxyethane, triethyleneglycol dimethyl ether, dioxane, triethylamine, N,N,N,N-tetramethylethylenediamine) penetrate into graphite inclusion compounds of alkali metals (LiC₁₂, KC₃₆).Stage changes and new interlayer distances are inferred from the X-ray diffraction data. Generally these lamellar compounds have several phases. They are similar to those made by direct synthesis.These solvates can contain up to two solvent molecules for one cation and the complexing powers of the solvents can be inferred from their thermal stabilities.

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Zusammenfassung Die Lewis-schen Basen (Tetrahydrofuran, Dimethyl-2,5-Tetrahydrofuran, Dimethoxyäthan, Triäthylenglykol Dimethyläther, Dioxan, Triäthylamin, N,N,N,,N-Tetramethyl-Á thylendiamin) dringen in die Insertionsverbindungen der Alkalimetalle des Graphits ein (LiC₁₂, KC₃₆).Phasenveränderungen und neue interplanare Entfernungen wurden mittels Röntgendiffraktion beobachtet. Im allgemeinen bestehen die erhaltenen neuen lamellaren Verbindungen aus verschiedenen Phasen und können mit den durch direkte Synthese erhaltenen Ternärverbindungen verglichen werden.Diese Solvate können je Kation bis zu zwei Molekülen Lösungsmittel enthalten, ihre Thermostabilitäten können Informationen über das Komplexierungsvermögen der basischen Lösungsmittel geben.

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( , 2,5- , , , , , N,N,N,N ) - (LiC₁₂, KC₃₆). - . , , . . .

     

State of the structural hydroxyl groups in minerals of the kaolinite group according to infrared spectroscopic data

An interpretation of the IR spectra of kaolinite, dickite, and nacrite is proposed, based on the concept of resonance interaction of two intrasurface hydroxyl groups, and their manifestation in the spectrum as a split doublet 30 cm^–1 and by the individual vibration of a third intrasurface OH-group. The structural identification of each band in the IR spectra of the kaolinite minerals is given. It was demonstrated that thermal dehydroxylation under vacuum of kaolinite occurred in two stages with activation energies of 43 and 84 kJ/mole. The activation energy of proton delocalization of the structural hydroxyl groups of kaolinite has been evaluated (E 13 kJ/mole). The contribution of the energy of the interlayer hydrogen bonds (AH 28 kJ/mole) to the total cohesion energy of adjoining layers of kaolinite (E_c 165 kJ/mole) was calculated.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 1, pp. 73–81, January–February, 1985.     

Acio-Base properties and actvity of complex oxide catalysts for m-xylene ammoxidation

Introduction of small quantities of alkaline and alkalineearth metal oxides into supported Sb–Bi–V oxide catalysts increasses the concentration of surface basic centers and increases significantly its activity in m-xylene ammoxidation. Promoting effect is suggested to be due to the heterolytic type of the primary activation of hydrocarbon.

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- -. .

     

After-effect of light in the photocatalytic oxidation of isobutene on immobilized vanadium oxide catalysts

A photocatalytic after-effect of visible and UV light in isobutene oxidation to acetone on immobilized vanadium oxide catalysts has been established. It is ascribed to the formation of labile active sites from coordinatively unsaturated V(V) compounds upon irradiation.

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. - - .

     

Chemical oscillatory reaction in a hydrodynamic oscillator

The periodic mixing of the reactants (bromate-thiocyanate or bromate-hydroxylamine) by the hydrodynamic oscillator gives rise to both periodic and aperiodic chemical oscillations.

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(- -) , .

     

Structural and substructural parameters of carbon supports sibunit and altunit

Two carbon material — sibunit and altunit have been studied using X-ray phase analysis methods. Coherent scattering region of Sibunit is a globule with a diameter of 35 Å, which preserves a stratified structure of graphite with the azimutal disorientation of graphite networks. Altunit has a diamond structure and consists of small particles with the average size of 20 Å, having no microstrains and characterized by a narrow size distribution of particles.

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— . , 35 Å, . , 20 Å, .

     

Effect of thermal treatment on the properties of Pd/Al2O3 catalysts having various dispersity

This effect of reduction temperature (293–673 K) on the properties of monodisperse Pd/Al₂O₃ catalysts with 9, 15, 25 and 75 Å particles has been studied. It is shown that the selectivity of catalysts in DMEC hydrogenation rises with growing the size of Pd particles.

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(293–673 ) Pd/Al₂O₃-- (9, 15, 25, 75Å). , - Pd.

     

Structural peculiarities of orthorhombic MoO3 prepared at low temperatures

Upon drying the solution prepared via the ion exchange of sodium molybdate on KU-2-8 cationite, MoO₃ is formed with water molecules in the interlayer space.

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, KU-2-8, , .

     

14 MeV neutron activation analysis of ternary copper ilver selenide by X-ray and gamma-ray spectrometry

14 MeV neutron activation of ternary copper silver selenide gives rise to a predominant activity from the 0.511 MeV annihilation peak from the three elements when -ray spectrometry is used. To overcome the interference problems, X-ray spectrometry was applied to the simultaneous nondestructive determination of silver and selenium, after which copper can be determined by -ray spectrometry. The results of analysis show a relative error not higher than ±5%, when the samples were diluted with H₃BO₃ /90%/ to minimize the interelement effects.     

Hydrogenolysis of ethane over Ni/Al2O3 catalysts of high nickel dispersity

The effect of nickel dispersity on the rate of ethane hydrogenolysis and the number of B₅ centers has been studied. A maximum in the rate of ethane hydrogenolysis is observed in the range of nickel dispersity of 2–3.5 nm. There is a minimum of the apparent activation energy of ethane hydrogenolysis in this range of metal crystallite size.

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₅. 2–3,5 . .

     

Catalytic properties of phosphorus and sodium promoted VMo catalysts in acrolein oxidation

The change in the ratio of stepwise and concerted routes of acrolein conversion to complete oxidation products upon promotion of a V-Mo catalyst by phosphorus and sodium dopants is ascribed to modification of surface acid-base properties.

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V-Mo - .

     

Die Phase La2U2N5

In the system U–La–N a new phase of composition La₂U₂N₅ was observed. The differaction pattern of this phase can be indexed with a tetragonal unit cell:a=8.43 Å,c=8.50 Å andc/a=1.008. The pseudocubic sub-cell withaca/2 is closely related to the CsCl-type.

Auszug aus der von der Technisch-Naturwissenschaftlichen Fakuktät der TU Wien approbierten Diplomarbait des Herrn Dipl.-Ing.J. Waldhart.     

Sintering of supported palladium

Sintering results of Pd supported on carbon black at 723–973 K, in water vapor, in H₂ and under high vacuum are reported. They are compared with sintering data of Pd on other supports. The observed sequences are: SiO₂C>sepioliteAl₂O₃>AlPO₄ and H₂O>high vacuum>H₂.

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Pd 723–973 , , H₂ . Pd . : SiO₂Al₂O₃>AlPO₄ H₂O> >H₂.

     

Vacuum ultraviolet spectroscopic analysis of nitrogen in iron and steel with low-voltage condensed-spark discharge

Summary The determination of nitrogen in steels was investigated by low voltage condensed spark discharge and far ultraviolet vacuum spectroscopy. The excitation conditions were 1,000V, 193, 63 F and 50H in helium atmosphere of 700 mm Hg. Nitrogen contents from 20 ppm to 100 ppm in steel could be determined with the line pair of N I 1,745 Å/Fe I 1,876 Å or N I 1,742 Å/Fe I 1,876 Å.

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Zusammenfassung Zur Bestimmung von Stickstoff (20–100 ppm) in Stählen wurde eine UV-vakuumspektrometrische Methode mit Niederspannungs-Funkenentladung benutzt. Die Entladungsbedingungen waren: 1000 V, 193 , 63 F und 50 H, unter Heliumatmosphäre von 700 mm Hg; verwendet wurden die Linienpaare N I 1,745 Å/Fe I 1,876 Å oder N I 1,742 Å/ Fe I 1,876 Å.

     

Separation of fatty acid esters and fatty acid ester derivatives using preparative scale sequential gas-liquid chromatographic equipment

Summary A sequential continuous chromatographic refiner (SCCR-2) for preparative-scale GLC up to 200°C is described. The separating capabilities and other characteristics of the SCCR-2 unit have been investigated using fatty acid ester mixtures of different separation difficulty and volatility. The feed mixtures selected had separation factors () between 1.1 and 1.5 and required operating temperatures between 110 and 200°C, while using FFAP (free fatty acid phase) on Chromosorb W or OV-275 (a cyanosilicone) on Chromosorb P. Initially the separation of a 50/50 v/v mixture of methyl chloroacetate/ethyl lactate (1.5) was studied and the ability of the SCCR-2 unit to separate the mixture into two products with purities in excess of 99.8% has been demonstrated at feedrates up to 80 cm³h^–1 and temperatures between 110 and 130°C. For the more difficult system ethyl chloroacetate/ethyl lactate (1.2) the column was too short for successful separation, although purities of about 95% for one product stream were obtained at feedrates of 33 cm³ h^–1 at 125°C. Preliminary studies on the recovery of -linolenic acid from fungal oil, at temperatures of 200°C are reported. Although this equipment has been demonstrated on the laboratory scale it is amenable to scale up to production levels. Partition coefficient data for several fatty acid solutes were determined using a comerical analytical scale GLC and some of the most favoured stationary phases for the GLC of fatty acids.     

Kinetics and mechanism of substitution reactions of complexes,XX

Thermal decomposition of 21 complexes of the type [Co(DH)₂(amine)₂]NCS has been studied under the conditions of thermogravimetric analysis, by using different heating rates. From the thermogravimetric curves apparent kinetic parameters of the pyrolysis reaction have been derived by means of the modified Doyle method. Apparent reaction order increases and apparent activation energy decreases with increasing heating rate. Thus, the obtained kinetic parameters do not characterize the purely chemical reaction, but the complex heterogeneous process as a whole. The explanation of the observed effect is discussed. Results are compared with those obtained with other analogous complexes.

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Zusammenfassung Die thermische Zersetzung von 21 Komplexen des Typs [Co(DH)₂(Amin)₂]NCS wurde thermogravimetrisch bei verschiedenen Aufheizungsgeschwindigkeiten untersucht. Aus den TG-Kurven wurden die scheinbaren kinetischen Parameter der Reaktion mit Hilfe der Doyleschen Methode ermittelt. Bei zunehmender Aufheizungsgeschwindigkeit wächst die scheinbare Reaktionsordnung während die scheinbare Aktivierungsenergie abnimmt. Die erhaltenen chemischen Parameter kennzeichnen nicht die eigentliche chemische Reaktion, sondern den ganzen komplexen heterogenen Vorgang. Die beobachteten Effekte wurden diskutiert und die Ergebnisse verglichen mit Resultaten von Untersuchungen anderer analoger Komplexe.

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Résumé On a étudié par thermogravimétrie, avec différentes vitesses d'échauffement, la décomposition thermique de 21 complexes du type [Co(DH)₂(amine)₂SCN. On a calculé suivant la méthode deDoyle les paramètres cinétiques apparents déduits des courbes d'ATG. L'ordre apparent de la réaction augmente si la vitesse d'échauffement croît, alors que l'énergie d'activation apparente décroît. Les paramètres cinétiques obtenus ne caractérisent que le processus hétérogène complexe et non la réaction chimique proprement dite. Les effets observés ont été discutés et comparés avec les résultats obtenus avec d'autres complexes analogues.

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21 [(D)₂()₂]NS , . . . , , . . , .

     

Magnetische Eigenschaften von Fe3Al und FeAl und spezifische Wärmen bei tiefen Temperaturen

Zusammenfassung Wir berechneten die magnetischen Momente, die in Verbindung mit Fe-Atomen in Fe–Al-Legierungen auftreten, für Umgebungen mit verschiedenen nächsten Nachbarn. Dazu analysierten wir die Ergebnisse aus früheren Neutronenbeugungsexperimenten und aus neuen Messungen der Magnetisierung an Fe₃Al-Proben mit bekannten Fernordnungsparametern. Die einander augenscheinlich widersprechenden Ergebnisse von Untersuchungen der magnetischen Eigenschaften können miteinander und mit dem Modell der atomaren Umgebung von nächsten Nachbarn in Einklang gebracht werden, wenn man die Ergebnisse eingehender magnetischer Messungen und Untersuchungen der spezifischen Wärme bei tiefen Temperaturen mit folgenden Vorstellungen zu erklären versucht: magnetische Cluster ( 21 _B), individuelle Momente des Fe ( 2,2 _B) und keine Momente, aber verstärkter Paramagnetismus der meisten Fe-Atome, je nach der lokalen atomaren Umgebung.

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Magnetic properties and low temperature specific heat of Fe₃Al and FeAl

The moments associated with Fe atoms in Fe–Al alloys, with various nearest neighbor atomic environments, have been evaluated by analyzing earlier neutron diffraction results together with new magnetization data for a Fe₃Al specimen with known long range order parameters. The apparently contradictory reports on the magnetic properties of FeAl can be reconciled with one another and with the nearest neighbor atomic environment model by interpreting the results of detailed magnetic measurements and of a study of the low temperature specific heat in terms of magnetic clusters ( 21 _B), of individual Fe moments ( 2,2 _B) and of no moments, but enhanced paramagnetism for most Fe atoms, depending on the local atomic environment.

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Mit 5 Abbildungen

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Herrn Prof. Dr.H. Nowotny gewidmet.

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Diese Arbeit entstand mit Unterstützung der U.S. National Science Foundation.     

Investigation of the self-heating phenomenon in the bulk polymerization of acrylonitrile

The temperature of the polymerizing system was measured with a thermistor during the bulk polymerization of acrylonitrile initiated by azoisobutyronitrile. The temperature of self-heating suddenly rises at a conversion of about 2%. This jump of temperature is presumably caused by the formation of a gel structure and, consequently, the outfall of thermal convection within the system.

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, -- . , - . - , .

     

Determination of basic sites on the surface of metal oxide catalysts by desorption of benzoic acid

A method has been developed for the determination of the concentration of basic sites on white and deeply colored solid porous materials, which is based on the displacement of adsorbed benzoic acid by acetic acid. The determination is rapid and gives results comparable with those obrained by the titration with benzoic acid using thymolphthalein as indicator.

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. . , , , .