Acid strength distributions in the Mo?Al?Si and the Ni?Mo?Al oxide systems determined by ammonia adsorption

Acid strength distributions of Mo–Al–Si and Ni–Mo–Al oxide systems have been found by means of a relationship that gives pK_a values from amounts of ammonia adsorption. Molybdenum is suggested to cause a homogenization in the acid strength distribution of alumina but a heterogenization in silicaalumina, whereas nickel is found to neutralize strong acid sites inherent to molybdenum.

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Mo–Al–Si Ni–Mo–Al , . , , .

     

Phase composition of a selective V2O5?Fe2O3 catalyst of methanol oxidation to formaldehyde

Redispersion of Re/SiO₂ catalysts during air-aging at ambient temperature has been confirmed by TEM analysis. The splitting of large primary crystallites (>10 nm) under the influence of the strain energy of the oxide layer formed on the Re surface has been proposed to explain the observed phenomenon.

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Re/SiO₂ . , Re(>10 nm), , .

     

Measurement of thermal constants of calcium chromite by Laser Flash method

Calcium chromite, CaCr₂O₄, was prepared and its purity and stoichiometry were ascertained by chemical analysis and X-ray diffraction methods. The thermal diffusivity, specific heat capacity and thermal conductivity of calcium chromite were measured by Laser Flash method using an Ulvac-Sinku Riko TC-3000 series instrument in the temperature range of 298 to 1100 K. The heat capacity data were utilised to calculate the thermodynamic parametersenthalpy increments, entropy increments and free energy increments—in the above temperature range.

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Zusammenfassung Kalziumchromit, CaCr₂O₄, wurde hergestellt und seine Reinheit und stöchiometrische Zusammensetzung mit Hilfe chemischer Analyse und Röntgendiffraktionsmethoden ermittelt. Anhand eines Ulyac-Sinku Riko TC-3000 Gerätes wurde mit Laser Flash Verfahren die Temperaturleitfähigkeit, die spezifische Wärmekapazität und die Wärmeleitfähigkeit von Kalziumchromit im Temperaturbereich 298–1100 K bestimmt. Die Wärmekapazitätsdaten wurden zur Berechnung der thermodynamischen Größen (Enthalpie-, Entropie-, Freie Energieänderung) in obigem Temperaturbereich benutzt.

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CaCr₂O₄, . , - TC-3000, 298–1100K , . , , .

     

Kinetics of oxidation of glycine by aqueous chlorine

The kinetics of oxidation of glycine with aqueous chlorine has been investigated. The reaction is first order with respect to both molecular chlorine and glycine and inverse first order with respect to H⁺. The effect of various factors on the initial rate has also been studied. The kinetic parameters have been calculated and a possible mechanism is proposed.

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. , H⁺. , . .

     

Исследование роли фосфиновых комплексов никеля различных степеней окисления в каталитической димеризации олефинов

Ni(II), Ni(I) Ni(O) . , , , Ni(O) Ni(I) - Ni(I) Ni(II) Ni(O).

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The interaction of organoaluminium compounds with phosphine complexes of Ni(II), Ni(I) and Ni(0) has been studied under the conditions of catalytic propylene dimerization. The active complexes are formed from Ni(II) compounds, the regeneration of the latter is ensured by repeated reduction, oxidation of Ni(0) to Ni(I), and by disproportionation of Ni(I) into Ni(II) and Ni(0).

     

Kinetics and mechanism of TI(III) oxidation of cellobiose in acidic medium

TI(III) oxidation of cellobiose in the presence of H₂SO₄ in aqueous acetic acid is first order in each reactant and is acid catalyzed. TI(OAc) ₂ ⁺ is the active species. Products identified are gluconic acid and glucose. A mechanism consistent with the temperature, solvent, acidity and salt effects is been proposed.

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TI(III) H₂SO₄ . TI(OAc) ₂ ⁺ . . , , , .

     

The use of thermal analysis to predict the thermal life of organic electrical insulating materials

Three different thermoanalytical methods are introduced as significant time-saving techniques in conventional life tests of some organic electrical insulating materials. DTA in cyclically alternated atmospheres of nitrogen and oxygen according to Randino and Andreotti, and TG analysis methods at different heating rates according to Flynn and Wall and to Broido were applied to two electrical insulations based on aromatic poly-imide and epoxy resin. The activation energies obtained are compared with those derived from the slopes of the life-lines produced via conventional life tests. The assumptions necessary for applying the thermal analyses in these cases are discussed.

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Zusammenfassung Drei verschiedene thermoanalytische Methoden werden als wesentlich zeitsparende Techniken bei der üblichen Prüfung der Lebensdauer einiger organischer elektrischer Isoliermaterialien beschrieben. DTA in zyklisch wechselnden Atmosphären von Stickstoff und Sauerstoff nach Randino und Andreotti und Methoden der TG-Analyse bei verschiedenen Aufheizgeschwindigkeiten nach Flynn und Wall und Broido wurden bei zwei elektrischen Isolierstoffen auf aromatischer Polyimid und Epoxyd-Harz Basis eingesetzt. Die erhaltenen Aktivierungsenergien werden mit den aus der Neigung der an Hand konventioneller Lebensdauertests erhaltenen Lebenslinien verglichen. Die nötigen Voraussetzungen zur Anwendung der Thermoanalyse in diesen Fällen werden erörtert.

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Résumé On présente trois méthodes thermoanalytiques différentes qui permettent de réaliser un gain de temps important lors de l'examen conventionnel de la durée de vie de quelques isolants électriques organiques. L'analyse termique différentielle en atmosphères cycliquement alternées d'azote et d'oxygène, suivant Randino et Andreotti, et la thermogravimétrie avec différentes vitesses de chauffage, suivant Flynn et Wall et Broido, ont été appliquées à deux isolants électriques à base de polyimide aromatique et de résine époxy. Les énergies d'activation obtenues sont comparées à celles déduites de la pente des lignes de vie, obtenues par des examens conventionnels de durée de vie. Les approximations nécessaires pour appliquer l'analyse thermique à ces différents cas sont discutées.

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. , , , , , , . , . .

     

Study of thermal behaviour of some derivatives of triphenylamine,with a view to obtaining new stationary phases for gas chromatography

A study was carried out upon the thermal behaviour of eight derivatives of triphen-y l amine, i. e. trinitrotriphenylamine; triaminotriphenylamine; triaminotriphenylamine chlorhydrate, tetraphenylborate and picrate; and a trisazo derivative and its compound with Be(II) and U(VI). The aim of this study was to find compounds with satisfactory thermal stability for use as stationary phases in gas chromatography.

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Zusammenfassung Eine umfassende Untersuchung zum thermischen Verhalten von acht Triphenylaminderivaten, d. h. Trinitrotriphenylamin, Triaminotriphenylamin, Triaminotriphenylamin Chlorhydrat, Tetraphenylborat und Pikrat, sowie ein Trisazoderivat und seine Verbindungen mit Be(II) und U(VI) wurde durchgeführt. Der Zweck dieser Studie war Verbindungen befriedigender Thermostabilität zum Einsatz als stationäre Phasen in der Gaschromatographie zu finden.

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: , , -, , () U(VI). .

     

Reactions in the combustion of hydrocarbons

Combustion of LPG produces carbon dioxide directly up to a temperature of 525°C. In addition, the formation of unsaturates is observed at temperatures above 550°C as a result of oxidative dehydrogenation and subsequent combustion of unsaturates to carbon dioxide at temperatures higher than 575°C.

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525°C. , 550°C . 575°C .

     

Characteristics and surface morphology change of modified PtRh 10 gauze of HCN synthesis

The modification of PtRh10 gauze catalysts by coating their surfaces with a thin film of PtRh/Al₂O₃ is reported. The investigation of the activity, selectivity and morphological change of the surface of the catalyst for standard gauzes and those covered with a thin film, applied in the HCN synthesis is deseribed.

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PtRh 10 PtRh–Al₂O₃. , HCN.