PMR study of the lifetime of complexes with a strong hydrogen bond at low temperatures

The kinetics of formation and cleavage of hydrogen bonds in complexes of carboxylic acids with proton acceptors have been studied by PMR spectroscopy over the range –100 to 150°C. The activation parameters of the processes have been measured.

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¹H –100° ÷–155°C . .

     

ESR studies on stabilized cool flame of propylene

In the oxidation of propylene a sharp change in the concentration of radicals, observed when passing from the slow reaction region to cool flames, indicates the chain character of the cool flame. Unlike propane and butane, the temperature dependence of the radical concentration and the maximum self-heating are practically unchanged within 603–663 K.

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. , . , 603–663 , .

     

Quantum chemical study of the physical characteristics of the hydroxy groups of zeolites, III

The CNDO/2 method was applied to calculate the electronic structure of HY zeolite using cluster models Si₃AlO₁₂H ₈ ^– and Si₃AlO₁₂H₉. It has been shown that the probability of occurrence of H on a particular type of oxygen as well as the other physical characteristics of zeolite depend on both the type of oxygen and the position of the Al atom.

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/2 , Si₃AlO₁₂H₈ Si₃AlO₁₂H₉. , , , Al.

     

Investigations on the compatibility of milk fat fractions and lauric fats

The compatibility of a lauric fat with several milk fat fractions (MF) was investigated. The enthalpy of crystallization was measured by differential scanning calorimetry (DSC). These values were related to the corresponding values calculated for an Ideal Blend. The different compatibility of the milk fat fractions with the lauric fat could be shown by this method very clearly.

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Untersuchungen zur Mischbarkeit/Verträglichkeit von Milchfettfraktionen mit laurischen Fetten

Zusammenfassung Die Mischbarkeit/Verträglichkeit von Milchfettfraktionen mit einem laurischen Fett wurde differenzkalorimetrisch untersucht. Die Auswertung der Befunde bezieht sich auf die entsprechenden Rechnungswerte einer Idealen Mischung. Es wurde nachgewiesen, da sich diese Milchfette deutlich in ihrer Mischbarkeit unterscheiden.

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. $ . , $ - . $ .

     

Construction of a thermoanalyzer for DTA-TD-TMAG-T measurements on metals up to 1100 °C

A thermoanalyzer is described for the simultaneous testing of metals and alloys by three methods: differential thermal analysis (DTA), thermal dilatometry (TD) and thermomagnetometry (TMAG). One reference specimen is used as a standard for each of the above kinds of analysis. Measurements can be performed in vacuum or in a static or dynamic atmosphere of gases at any pressure between normal and 5× 10^–5 Torr. The temperature of the sample can be changed linearly in the range 20–1100 °C. DTA and TD are performed classically, whereas TMAG is based on the temperature and magnetic field-dependences of the reversible magnetic susceptibility of the sample. Some analysis results are presented.

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Zusammenfassung Es wird ein Thermoanalysator zur simultanen Untersuchung von Metallen und Legierungen durch drei Methoden beschrieben: Differentialthermoanalyse (DTA), Thermodilatometrie (TD) und Thermomagnetometrie (TMAG). Für alle drei Verfahren wurde die gleiche Referenzsubstanz als Standard benutzt. Messungen können im Vakuum oder is statischer bzw. bewegter Atmosphäre von Gasen beliebigen Druckes zwischen Normaldruck und 5·10^–5 Torr durchgeführt werden. Die Temperatur der Probe kann zwischen 20 und 1100 °C linear variiert werden. Während DTA und TG die herkömmlichen Verfahren zu Grunde liegen, basiert TMAG auf der Temperatur- und Magnetfeldabhängigkeit der reversiblen magnetischen Suszeptibilität der Probe. Einige Analysenergebnisse wurden dargestellt.

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: (), () (). . , 5·10^–5 . 20–1100°. , . .

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Presented at the 4th European Symposium on Thermal Analysis and Calorimetry, Jena, GDR, August 1987.     

Mechanism of hydrogenolysis and isomerization of oxacyloalkanes on metals, V. Selectivities of metal catalysts in ring-opening reactions of oxiranes

The deoxygenation of methyloxirane to propene and its isomerization to oxo compounds on a Ni/SiO₂ catalyst were studied in a pulse microreactor, in the presence of H₂ as carrier gas, at 473 K. It was found that the deoxigenation leads to the creation of new types of active centers (Lewis acid site-basic site), which cause a change in the direction of ring opening. The differences in regioselectivity observed between Ni and Cu, and Pt and Pd, can be explained by the different affinities of the metals for oxygen. This finding can be generalized to other oxygen-containing compounds.

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=qa Ni/SiO₂ 473 . , - - , . Ni Cu, Pt Pd . .

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Part IV: J. Catal. (to be published)     

Preparation and properties of high dispersity palladium catalysts

Preparation methods for monodisperse sols of palladium with 9, 15, 30 and 75 Å particles are suggested. It has been revealed that with decreasing size of palladium particles (d25 Å), the dissolved hydrogen species disappear. As a result, their behavior in dimethyl ethynyl carbinol hydrogenation is close to the platinum properties.

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9, 15, 30, 75 Å. , (d25 Å) , .

     

Hydrogenation of ethylene on gadolinium X, Y and L-type zeolites

It is shown that Gd-zeolites have a catalytic activity towards ethylene hydrogenation at 1 atm. This activity decreases with an increase in the SiO₂/Al₂O₃ ratio from 2.2 to 6.1 and 4.1, i.e. upon going from an X type zeolite to Y and L. For these types of zeolite the activity grows with an increase in Gd³⁺ content from 50 to 80%. Oxygen addition to the reaction mixture stabilizes the catalytic activity of zeolites.

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, qv 1 . , SiO₂/Al₂O₃ 2,2 6,1 4,1, .. X Y L. , 50 80%. .

     

Effect of the roughness factor on the surface oxidation of ruthenium catalysts

The surface oxidation of ruthenium catalysts with different roughness factor values has been analyzed. It is shown that electro formation of oxidized species on the exposed surface of ruthenium is strongly affected by the rougher characteristics of the surface. This effect has been explained through the addition and removal of protons to and from the oxidized species.

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. , . .

     

Determination thermogravimetrique des energies d'activation I

Résumé Après une revue critique de divers procédés d'obtention thermogravimétrique des énergies d'activation, on sélectionne certains d'entre eux en vue de les appliquer d'une part à la déshydratation thermique de divers borates et acides boriques, d'autre part à l'oxydation du nickel à température élevée. On compare les résultats qu'ils fournissent respectivement.

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After a critical survey of various methods available for the determination of activation energies by thermogravimetry, certain methods are applied to the thermal dehydration of various borates and boric acids and to the oxidation of nickel at high temperature. The results are compared.

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Zusammenfassung Nach einer kritischen Übersicht verschiedener Verfahren zur Bestimmung von Aktivierungsenergien mittels Thermogravimetrie werden einige Ausgewählte auf die thermische Dehydratierung verschiedener Borate und Borsäuren, so wie auf die Oxydation des Nickels bei erhöhter Temperatur angewendet. Die verschiedenen Ergebnisse wurden verglichen.

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, . .

     

Kinetic isotope effect in trans-alkylation with ethylbenezene

Kinetic isotope effect (KIE) measurements in the trans-alkylation of toluene and benzene with ethylbenzene in hexane in the presence of AlBr₃ at 313 K indicate that deuterium in the toluene methyl group causes a small inverse KIE characteristic for a -complex transiton state. The small direct KIE found for the reaction with C₂D₅C₆H₅ does not agree with a mechanism involving alkyl-and -phenylalkyl cations.

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() - AlBr₃ 313 . , , - C₂D₅C₆H₅ , - -.

     

Thermal and other studies on bivalent metal selenltes

BaSeO₃·2·5H₂O(I), PbSeO₃· 2H₂O(II) and CdSeO₃·3.5H₂O(III) were prepared and analysed. Their hygroscopicity and solubility was investigated. These compounds have high thermal Stability, as shown by their TG and DTA data. IR spectra show multi-dentate coordination of selenite to cations, due to considerable splitting of the asymmetric v₃ and v₄ bands of SeO ₃ ^{2 –} in the 780-730 cm^–1 and 420-325 cm^–1 region.Tentative structures have been proposed involving bridging oxygen atoms.

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Zusammenfassung BaSeO₃-2.5H₂O(I), PbSeO₃ · 2H₂O(II) und CdSeO₃· 3.5H₂O(III) wurden hergestellt, analysiert sowie deren Hygroskopizität und Löslichkeit untersucht. TG- und DTA-Untersuchungen erweisen die hohe thermische Stabilität dieser Verbindungen. Die IR-Spektren zeigen mehrzählige Koordination von Selenit zu Kationen, was aus einer beträchtlichen Aufspaltung der antisymmetrischenv ₃ undv ₄ Banden von SeO ₃ ^{2 –} im Bereich 780-730cm^–1 bzw. 420-325 cm^–1 hervorgeht. Es wurden versuchsweise Strukturen mit überbrückenden Sauerstoffatomen vorgeschlagen.

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BaSeO₃· 2,5H₂O, PbSeO₃ · 2H₂O CdSeO₃ · 3,5H₂O . . - , v ₃ v ₄ SeO ₃ ² }- 780-730 420-325 ^–1. , .

     

Thermal investigation of active carbons in presence of air

Thermal analysis data on the oxidation reaction between air and active carbons obtained during activation by carbon dioxide are presented. The correlation between the modified DTA curves and the TG curves leads to the conclusion that the oxidation of active carbons in the temperature range from 20 to 1000° is a two-step process. It is pointed out that the oxidation reactions in the low-temperature region (450–550°) are governed by the oxygen content of the samples, whereas the reactions in the higher temperature region (550–850°) are controlled by the diffusion process.

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Zusammenfassung Die thermoanalytischen Ergebnisse über die während der Aktivierung durch Kohlendioxid stattfindende Oxidationsreaktion zwischen Luft und Aktivkohlen werden vorgestellt. Die Korrelation zwischen den modifizierten DTA-Kurven und den TG-Kurven führte zur Schlußfolgerung, daß die Oxidation der Aktivkohlen im Temperaturbereich von 20 bis 1000° ein Zweistufen-Vorgang ist. Es wird betont, daß die Oxidationsreaktion im niedrigen Temperaturbereich (450 bis 550°) durch den Sauerstoffgehalt der Proben gesteuert wird, während er im Bereich der höheren Temperaturen (550 bis 850°) durch Diffusionsvorgänge geregelt wird.

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Résumé On présente les résultats de l'étude par analyse thermique de la réaction d'oxydation des charbons actifs par l'air qui a lieu lors de l'activation par l'anhydride carbonique. La corrélation entre les courbes ATD modifiées et les courbes TG conduit à la conclusion que l'oxydation des charbons actifs s'effectue entre 20 et 1000°, suivant un processus en deux étapes. Dans l'intervalle des températures faibles (450 à 550°) les réactions d'oxydation sont gouvernées par la teneur en oxygène des échantillons tandis qu aux températures plus élevées (550 à 850°) elles le sont par le processus de diffusion.

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, . , 20 1000° . , (450–550°) , (550–850°) .

     

Kinetics and mechanism of oxidation of triphenylphosphine by hydrogen peroxide

Kinetics of oxidation of triphenylphosphine (TPP) by hydrogen peroside has been investigated in 95 vol. % aqueous ethanol. The reaction is first-order each in TPP and hydrogen peroxide. A mechanism involving a bimolecular nucleophilic displacement of TPP on the peroxide molecule in the rate-determining step is proposed.

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() 95 .% . , H₂O₂. , , , H₂O₂ .

     

Liquid phase CO+H2 reactions in presence of ruthenium catalysts

Several effects on the hydrogenation of carbon monoxide in propanol in presence of ruthenium catalysts are examined. The homologation reaction is not observed, only propyl formate and propyl acetate are produced with any ruthenium catalyst. The pH-value is an important parameter: in acid media, the yield of propyl formate is noticeably increased indicating different catalytic active species. The addition of cesium salts is also benefitial for formate formation. This is not the case when water is associated with propanol as solvent. Finally, no ethylene glycol is detected. The process is found to be homogeneous and methanol seems to be the precursor of methyl formate.

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, . , . : , . . , . . , -, .

     

Measurement of the dispersity of supported ruthenium catalysts by oxygen chemisorption

A highly dispersed (Ø (Ru)<10 Å, from electron microscopy) Al₂O₃-supported catalyst and not so well dispersed silica supported Pt, Ru, Pt, Ru-alloy catalysts were investigated. Oxygen coverage of Ru is found to be close to 2 at 20 °C over the monometallic Ru catalysts as well as over the Pt, Ru-alloy catalysts.

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(Ø (Ru)<10 Å ) Al₂O₃ Pt Ru Pt Ru . Ru 2 20°C Ru, Pt Ru.

     

Study of hydrogen adsorption on iridium catalysts

The influence of dispersity on hydrogen adsorption on Ir black and Ir/C catalysts has been studied. It is shown that supported iridium reduces the heat of hydrogen adsorption as compared to Ir black. With decreasing catalyst dispersity, the amount of weakly bound hydrogen increases, while its adsorption heat decreases on all Ir catalysts.

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Ir- Ir/C-. , Ir-. C , Ir-.

     

Photochemical reactions of anthraquinone with hydrocarbons in the presence and absence of oxygen: Trapping of radical intermediates

Radical intermediates formed at 25°C in the presence and absence of oxygen during the photolysis of anthraquinone in aromatic, cyclic and aliphatic hydrocarbon solvents were trapped by 2,6-dichloronitrosobenzene, 2,6-dibromonitrosobenzene and 2,4,6-tribromonitrosobenzene. The resulting nitroxide radicals have been characterized in situ by ESR spectra.

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: 2,6-, 2,6- 2,4,6-— , , 25°C. .