Microscopic cross section for ion-molecule reactions with polar molecules

Using Kapitsa's method of separating rapidly varying processes from slower translational motions, a microscopic capture cross section for gas phase ion-molecule reactions is derived (centrifugal barrier approximation), leading to rate coefficients lying between the values of Langevin's theory and those of the locked dipole approximation (LD).

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, , - ( ), , , , LD-.

     

Oxygen solubility in the superconducting compound YBa2Cu3O x (6⩽x⩽7), studied by TG and barometric measurements

Thermogravimetry in controlled oxygen atmospheres and barometric measurements between 300 and 1200 K were performed on the YBa₂Cu₃O _x superconducting phase. The complete reversibility of the exchange of a certain part of the oxygen, as found even at 250 °C, and the observed relationship between oxygen partial pressure, oxygen content and temperature, can be explained by the dissolution of oxygen in YBa₂Cu₃O _x . It is concluded that samples with highx values (), as necessary for good superconducting properties, can be obtained at high temperatures only at high oxygen pressures, but they were obtained by annealing at normal pressure between 250 and 350 °C.

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Zusammenfassung Die supraleitende Phase YBa₂Cu₃O _x wurde mit Hilfe von Thermogrametrie und barometrischen Messungen im Bereich 300 bis 1200 K untersucht. Die sogar bei 250 °C beobachtete Reversibilität des Austausches von einem Teil des Sauerstoffs sowie die gefundenen Beziehungen zwischen Sauerstoffaktivität (Partialdruck), Sauerstoffgehalt und Temperatur können durch eine Lösung von Sauerstoff in YBa₂Cu₃O _x erklärt werden. Aus den Ergebnissen kann gefolgert werden, daß Proben mit hohemx (7), die gute Supraleitungseigenschaften zeigen, bei hohen Temperaturen nr unter hohem Sauerstoffdruck hergestellt werden können. Sie werden jedoch auch durch Tempern bei Normaldruck bei 250 bis 350 °C erhalten.

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YBa₂Cu₃O_x 300–1200 . , 250°, , , YBa₂Cu₃O_x. , ( 7), , . , 250 350°.

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The authors thank Mrs. W. Höppner, Mrs. B. Thaut and Mr. F. Hansch for careful experimental assistance.     

Anomalous effect of nitrogen on side-chain alkylation of toluene with methanol over solid bases

The alkylation of toluene with methanol was carried out at 500°C over various base catalysts. The activity of MgO was found to be highest when treated specially with nitrogen. The effect of nitrogen was anomalously large, 8, 8% ethylbenzene and 2.3% styrene being formed.

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500°C . MgO, . : 8,8% 2,3% .

     

Mechanism of o-xylene conversion on magnesium modifications of Y zeolite

o-Xylene conversions has been investigated in the presence of MgNaY zeolites with different Si/Al ratios and degrees of exchange. Disproportionation proceeds to a higher degree than does isomerization. The distribution of reaction products is attributed to geometric factors. The results are in agreement with a monomolecular mechanism of isomerization.

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- MgNaY Si/Al . , , . . .

     

Enhancement of catalytic activity by effect of graphite on Ru?Pt/C catalysts

Surface composition and catalytic activity of Ru–Pt/C catalysts were determined. A surface enrichment in Pt was found over the entire composition range. Catalytic activity showed a maximum value (140) on 66% Ru bimetallic catalyst. These results are correlated with the nature of the impregnating salts and with the conductive properties of graphite.

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Ru–Pt/C. Pt . (140) 66% Ru . .

     

Reduction profiles of supported Ru, Au and Ru?Au

The reduction with hydrogen of Ru, Au and Ru–Au supported catalysts was followed by Differential Scanning Calorimetry (DSC). The supports used were MgO, SiO₂ and Al₂O₃. The differences in the reduction behavior of both metals on each carrier are correlated with the surface composition of the bimetallic clusters.

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Ru, Au Ru–Au . MgO, SiO₂ Al₂O₃. .

     

On the sub-Tg annealing of uniaxially oriented and unoriented atactic polystyrene

DSC analysis was performed on uniaxially oriented and unoriented atactic polystyrene samples prior to and after annealing at 80 °C. With increasing annealing times, an endothermic peak appeared, whose area increased with the duration of the annealing period. No difference was found between the endotherm areas for the oriented and the unoriented polymer.The DSC curve of the unannealed oriented polystyrene exhibited a relaxation exotherm. DSC and relaxation studies indicated that this relaxation exotherm was independent of the main chain orientation; it may rather be due to sample densification.

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Zusammenfassung Uniaxial orientierte und unorientierte ataktische Polystyrenproben wurden vor und nach dem Tempern bei 80° mittels DSC untersucht. Mit länger werdender Temperungszeit erscheint in endothermer Peak, dessen Fläche mit der Dauer der Temperungsperiode ansteigt. Die Flächen der endothermen Peaks von orientierten und unorientierten Polymeren unterscheiden sich nicht. Die DSC-Kurve von ungetempertem orientiertem Polystyren zeigt einen exothermen Relaxationseffekt. DSC und Relaxationsuntersuchungen ergaben, daß dieser exotherme Relaxationseffekt unabhängig von der Orientierung der Hauptkette ist und eher einer Probeverdichtung zuzuschreiben ist.

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80°. , . . , , . , , .

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We are grateful to Prof. B. Wunderlich of the Rensselaer Polytechnic Institute, New York, for useful discussions.

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The financial support of C.N.R. (progetto finalizzato chimica fine e secondaria) is gratefully acknowledged.     

The thermal decomposition of alkaline earth metal salicylates

The thermal decompositions of the salicylates of magnesium, calcium, strontium and barium were investigated using thermogravimetry and differential thermal analysis, together with the analysis of intermediate products formed during the decomposition processes. One intermediate product was isolated and identified during the decomposition of the magnesium salt, and two for each of the remaining metal salts.

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Zusammenfassung Die thermische Zersetzung der Salicylate von Magnesium, Calcium, Strontium und Barium sowie die Analyse der während des Vorganges gebildeten Zwischenprodukte wurden durch die thermogravimetrische und Differential-Thermal-Analyse untersucht. Im Verlaufe der Zersetzung des Magnesiumsalzes wurde ein Zwischenprodukt isoliert und identifiziert, bei den übrigen Metallsalzen je zwei.

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Résumé On a étudié par thermogravimétrie et analyse thermique différentielle la décomposition thermique des salicylates de magnésium, calcium, strontium et baryum et l'on a analysé les produits intermédiaires qui se forment pendant la décomposition. C'est ainsi que l'on a isolé et identifié un produit intermédiaire au cours de la décomposition du sel de magnésium et deux pour chacun des autres sels.

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, , , , , . , - .

     

Propane aromatization over Pt?Sn/ZSM-5 catalysts

Addition of Sn modifies the catalytic performance of Pt/ZSM-5. Total conversions decrease with increasing Sn/Pt ratio. Selectivity to aromatics is higher on the Pt–Sn samples. A Pt–Sn interaction has been confirmed by H₂ chemisorption and TPR experiments.

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Sn Pt/ZSM5. Sn/Pt . Pt–Sn. Pt–Sn H₂ .

     

Carbon monoxide adsorption and hydrogen-oxygen titration on Ru/Al2O3

Hydrogen-oxygen titration and carbon monoxide adsorption on Ru/Al₂O₃ samples were employed to determine metal dispersity values. To avoid Ru–CO polycarbonyl formation, before CO adsorption, the ruthenium surface was precovered with hydrogen. By this procedure, good agreement between H₂–O₂ titration, CO adsorption and electron microscopy is obtained.

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Ru/Al₂O₃ H₂–O₂ CO. Ru–CO, . H₂–O₂, CO .

     

Sulfuration of Pt/Al2O3, Pt?Re/Al2O3 and Pt?Ir/Al2O3 catalysts

Three reforming catalysts Pt/Al₂O₃, Pt–Ir/Al₂O₃ and Pt–Re/Al₂O₃ have been sulfurated by H₂S and tested by their activities in benzene hydrogenation. By treatment at 500°C under hydrogen flow only a part of the initial activity of the non-sulfurated catalyst is retained. So only a part of the adsorbed sulfur is easily removed in these conditions. The remaining sulfur for each of the catalysts (Pt/Al₂O₃, Pt–Ir/Al₂O₃ and Pt–Re/Al₂O₃) gives the same atomic ratio of 0.5 sulfur atom per accessible metallic atom.

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Pt/Al₂O₃, Pt–Ir/Al₂O₃ Pt–Pe/Al₂O₃ . 500°C H₂ . . ., . (Pt/Al₂O₃, Pt–Ir/Al₂O₃ Pt–Pe/Al₂O₃) 0,5.

     

On acrylonitrile polymerization in the presence of zinc salts

Acrylonitrile polymerization photoinitiated at 365 nm by pyrene and/or azobisisobutyronitrile in the presence of zinc salts in N,N-dimethylformamide solution has been studied by the rotating sector method. It was found that the ratio of the rate constants for propagation and termination (k_p/k_t) increases on addition of zinc salts (chloride, nitrate, acetate). This increase was more pronounced for the azobisisobutyronitrile photoinitiated polymerization of acrylonitrile then for its pyrene photoinitiated polymerization. The results confirm the previously expressed view concerning the dual role of zinc chloride in initiation as well as in propagation steps of acrylonitrile polymerization photoinitiated by aromatic hydrocarbons.

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, 365 / N,N- . , (k_p/k_t) ( , , ). , . , , , .

     

IR-spectroscopic study of the mechanism of pyridine protomation on the surface of HNaY zeolite

The interaction of pyridine with the surface of Y-type decationized zeolite has been studied by IR spectroscopy over a wide temperature range. It has been shown that the first step of the transfer of a hydroxyl proton to a base is the formation of a strong hydrogen bond. The protonated pyridine exists in free and hydrogen-bonded forms.

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. , . .

     

Liquid phase oxidation of allyl alcohol by air oxygen in acetic acid medium

Studies of the oxidation of allyl alcohol by air oxygen in acetic acid medium indicate that one of the intermediates is allyl epoxide transforming in 90% to polyglycerol esters of acetic and formic acids.

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. , , 90% .

     

Radiochromatographic studies of isobutylene oxidation over SnO2

Radiochromatographic studies of isobutylene oxidation over SnO₂ confirm the formation of carbon dioxide from the products of oxidative olefin condensation.

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.

     

Oxidation of o-xylene on tin-antimony oxides

Arcolein adsorption on - and -polymorphous modifications of CoMoO₄ has been studied by the thermal desorption technique. The effect of molybdenum coordination on the bond strength of surface acrolein compounds has been treated in terms of the interaction between frontier molecular orbitals of the active center and acrolein.

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- CoMoO₄ .

     

On the most significant processes of thermooxidative PVC degradation

In the thermooxidative degradation of PVC two processes are of decisive importance: the elimination of HCl in allyl-activated steps producing polyene sequences in the polymer backbone, and the radical chain oxidation of these polyenes. The two processes are closely interrelated as the carrier radicals of the oxidation chain initiate also sequential HCl elimination. This results in an enhanced rate of HCl elimination and a low steady-state concentration of polyenes.

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

     

Thermogravimetric and EPR study of the vacuum thermal decomposition of some zinc and copper(II) chromates

The thermal decompositions in vacuum of the compounds ZnCrO₄, ZnCrO₄·3.5 Zn(OH)₂·H₂O and CuCrO₄ have been investigated using a combination of various techniques: TG, EPR, IR and X-ray.While the TG and X-ray data confirm the final formation of Cu(I) and Zn chromites with the spinel structure resulting from the spontaneous thermal reduction of the Cr(VI) ions, EPR reveals the progressive formation and decay of the following intermediate paramagnetic species: Cr(V) ions and Cr(III) species either dispersed in theM(II) oxide bulk and/or clustered in a Cr₂O₃-like phase, or finally ordered in the chromite phase formed at high temperature.The paramagnetic species which appear, as well as their temperature ranges of stability, are strongly dependent on the nature of theM(II) ion and the Cr(III)/M(II) ratio.The successive detection of these intermediates by EPR yields some detailed information about the decomposition mechanisms of the chromates.

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Zusammenfassung Die thermische Zersetzung der Verbindungen: ZnCrO₄, ZnCrO₄·3.5 Zn(OH)₂ · H₂O und CuCrO₄ in Vakuum wurde unter Anwendung der Kombination verschiedener Techniken, wie TG, EPR, IR und Röntgen, untersucht.Während die TG- und Röntgen-Daten die schließlich erfolgende Bildung der Chromite von Cu (I) Zn mit der aus der spontanen thermischen Reduktion der Cr (VI)-Ionen hervorgehenden Spinellstruktur bestätigen, zeigt EPR die progressive Bildung sowie den Zerfall der folgenden intermediären paramagnetischen Species: Cr(V)-Ionen und Cr(III)-Species entweder in der Masse desM (II)-Oxids dispergiert und/oder in einer Cr₂O₃ ähnlichen Phase eingeschlossen oder aber endlich in der bei hoher Temperatur gebildeten Chromitphase geordnet.Sowohl die auftretenden paramagnetischen Species als auch der Temperaturbereich, in welchem sie stabil sind, hängen stark von der Beschaffenheit desM (II)-Ions und des Verhältnisses Cr(III) (M/II) ab.Der schrittweise Nachweis dieser Zwischenprodukte durch EPR erbringt einige eingehende Informationen über die Zersetzungsmechanismen der Chromate.

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ZnCrO₄₄, ZnCrO₄. 3.5 Zn(OH)₂·H₂O CuCrO₄, , , , , . , Cr(VI). : Cr(V) Cr(III), , Cr₂O₃, , . (II) Cr(III)/()II). .

     

Benzene activation over high-silica zeolites

The effect of treatment conditions of high-silica zeolites on their oxidation-reduction properties in benzene adsorption has been studied.

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- - .

     

Oxidation of carbon monoxide with nitrous oxide over CeO2

With the help of the transient response method and fluorescence spectroscopy, it has been revealed that the title reaction proceeds by the catalyst redox transformation Ce(III)Ce(IV) over CeO₂ in great contrast to previous observations over MgO. , Ce(III)Ce(IV) CeO₂ MgO.