Polymorphic modifications of barium metagermanate

Polymorphic transformations of BaGeO₃ were investigated by DTA and X-ray diffraction methods and the data obtained were compared with those previously published. BaGeO₃ undergoes a reversible phase transformation at 1100° from a low-temperature hexagonal polymorph to a medium-temperature polymorph having an unknown crystal structure, which undergoes a further reversible transformation at 1200° to a high-temperature orthorhombic polymorph found to be stable up to the melting temperature of 1287°. On cooling from the melt, the high-temperature form can be retained metastably at room temperature, but transforms to the low-temperature form at 900°.

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Zusammenfassung Polymorphe Umwandlungen von BaGeO₃ wurden unter Anwendung der DTA- und Röntgendiffraktionsmethoden untersucht und die erhaltenen Angaben mit den früher veröffentlichten verglichen. Bei 1100° vollzieht sich eine reversible Phasentransformation der BaGeO₃ von der hexagonalen Struktur bei niedrigen Temperaturen in eine Verbindung unbekannter Kristallstruktur bei mittleren Temperaturen, welche wiederum bei 1200° eine weitere reversible Umwandlung in eine orthorhombische Struktur erfuhr und sich bis zur Schmelztemperatur von 1287° als stabil erwies. Beim Abkühlen der Schmelze kann die Form bei hohen Temperaturen bei Zimmertemperatur in metastabilem Zustand erhalten bleiben, wird jedoch bei 900° in die Form bei niedrigen Temperaturen umgewandelt.

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Résumé On a étudié les transformations polymorphiques de BaGeO₃ par ATD et diffraction des rayons X et comparé les résultats avec ceux obtenus antérieurement. A 1100° C BaGeO₃ subit une transformation de phase réversible de la forme hexagonale stable à basse température à la forme stable à moyenne température, de structure cristalline inconnue, qui se transforme réversiblement à 1200° C en une phase orthorhombique qui reste stable jusqu'à 1287° C. Au refroidissement, la forme stable à haute température peut être maintenue à l'état métastable à la température ambiante, mais elle se transforme à 900° C en la forme stable à basse température.

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BaGeO₃ . BaGeO₃ 1100° - - 1200° , 1287°. - , - 900°.

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This investigation was supported by the Boris Kidri Foundation for Scientific Research     

Kinetics of partly diffusion controlled reactions

We propose a simple kinetic model in which two types of processes between two reactants occur: diffusional processes for distances greater than , the reaction distance, and static quenching for distances smaller than . This model might be useful in the studies of diffusion in membrane systems.

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, , : , , , . .

     

Thermal decompositions of kaolinite intercalation compounds

Through a combination of X-ray diffraction and thermal analysis (simultaneous TG-DTG-DTA and quasi-isothermal TG), it was shown that the molar ratio intercalation agent/kaolinite in all intercalation compounds is approximately 1. In a saturated atmosphere of the corresponding intercalation agent, the intercalation compounds are stable up to more than 150 °C.Decomposition of the potassium acetate intercalation compound proceeds simultaneously with the dehydroxylation of kaolinite at an extrapolated onset temperature of 360 °C. The high-temperature reactions (dehydroxylation and transformation) of kaolinite obtained through the decomposition of intercalation compounds with volatile intercalation agents depend on the conditions applied during decomposition.

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Zusammenfassung Mittels Röntgenbeugung und thermischer Analyse (simultane TG-DTG-DTA und quasi-isotherme-quasi-isobare TG) konnte gezeigt werden, daß das molare Verhältnis Einlagerungsmedium/Kaolinit in allen Einlagerungsverbindungen etwa 1 ist. In gesättigter Atmosphäre des jeweiligen Einlagerungsmediums ist die Einlagerungsverbindung stabil bis über 150 °C. Die Zersetzung der Kaliumacetat-Einlagerungsverbindung läuft zusammen mit der Dehydroxylation des Kaolinits bei einer extrapolierten onset-Temperatur von 360 °C ab. Die Hochtemperaturreaktionen (Dehydroxylation, Phasenneubildung) von Kaolinit, der aus der Zersetzung von Einlagerungsverbindungen mit flüchtigen Einlagerungsmedien erhalten würde, werden von den Zersetzungsbedingungen beeinflußt.

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- ( , , ) , - 1. , , 150°. — ** 360°, ** . , , .

     

Kinetics and mechanism of redox reactions of U(III) ions with 2-chloro and 2-bromopropanoic acids

The kinetics and mechanism of redox reactions of U³⁺ ions with 2-chloro and 2-bromopropanoic acids were studied. The influence of pH led to the determination of the rate constants corresponding to two parallel steps. The influence of binary mixtures on the reaction rate was followed. The kinetic results for halogen-substituted carboxylic acids forming an isokinetic series have been compared.

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U⁺³ 2-- 2- . pH . . , .

     

XPS studies of Cu-Cr catalyst deactivation in catalytic heat generators

Changes in the valence state of transition metal cations on the CuCr₂O₄/–Al₂O₃ catalyst under its deactivation in catalytic heat generators have been studied by the XPS method. Partial reduction of the catalyst active component has been revealed. It has been established that a freshly prepared catalyst contains Cr(VI) that is most likely responsible for its high initial activity.

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CuCr₂O₄/–Al₂O₃ (). , . , Cr(VI), .

     

Fossil age determination by thermal analysis

Subsequent to a comparative examination of recent bone material the author has recently completed the paleobiogeochemical evaluation of classical Quaternary and Pliocene terrestrial fossils of vertebrata from Hungary. A derivatograph (MOM) has been used to determine two thermoanalytical parameters which are closely associated with the passage of geological time: the total bound organic-matter content of the fossil and the fossilization cofficient.Derivatographic measurement of the organic matter in the bones is supplemented by fine-structure analysis of bone-tissue slides.Sample material of unknown age from several provenances was evaluated with the new dating method. The importance of the procedure is even greater in cases when only indefinite sporadic finds can be obtained from the sediments.

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Zusammenfassung Nach einer vergleichenden Untersuchung an neuzeitlichem Knochenmaterial hat der Autor kürzlich die paleobiogeochemische Auswertung der klassischen Quaternären und Pliocenen terrestren Fossilien von Vertebraten aus Ungarn ergänzt.Ein Derivatograph (MOM) wurde zur Bestimmung zweier thermoanalytischer Parameter eingesetzt, die eng mit dem Fortschreiten der geologischen Zeit verbunden waren: dem Gesamtgehalt an gebundenem organischem Material und dem Fossilisationskoeffizienten.Die derivatographische Messung der organischen Substanz in den Knochen wurde durch die Feinstrukturanalyse von Knochengewebeschnitten ergänzt.Probenmaterial unbekannten Alters verschiedener Herkunft wurde mit der neuen Methode ausgewertet. Die Bedeutung des Verfahrens ist in den Fällen noch grösser, wenn aus den Sedimenten nur unbestimmte sporadische Funde erhalten werden können.

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, . (MOM) , : . - . . , .

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The author wishes to thank the staff of the Department of Experimental Physics of L. Kossuth University for the neutron activation measurements and the Computer Center of the University for the calculation work.     

Kinetics of the thermal decomposition of alkaline earth metal hydrofluorides

The thermal stability of alkaline earth metal hydrofluorides was studied by means of a Derivatograph. The values of the activation energy, reaction order and rate constant were determined. The comparison of the kinetic parameters of the decomposition process for the complete series of hydrofluorides studied led to a certain regularity in the differences in their thermal stabilities and its correlation with the strength of the hydrogen bond in their structure.

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Zusammenfassung Die thermische Stabilität von Erdalkalihydrofluoriden wurde mit Hilfe eines Derivatographen untersucht, die Werte der Aktivierungsenergien, der Reaktionsordnung und der Geschwindigkeitskonstanten bestimmt. Der Vergleich der kinetischen Parameter des Zersetzungsvorganges wies auf eine gewisse Regelmäßigkeit in ihrer verschiedenen thermischen Stabilität, die in Zusammenhang mit der Stärke ihrer strukturalen Wasserstoffbindung steht.

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Résumé On a étudié la stabilité thermique des hydrogénofluorures des métáux alcalinoterreux et déterminé les valeurs des énergies d'activation, des ordres de réaction et des constantes de vitesse de réaction à l'aide d'un Dérivatographe. Après comparaison des paramètres cinétiques on a pu établir une certaine régularité dans le changement de la stabilité thermique en corrélation avec la force de liaison de l'hydrogène dans la structure.

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. , . .

     

Reduction of CuO-containing catalysts, CuO: I: TPR and TGA

For CuO/ZnO reduction has been shown [M. S. W. Vong et al., Catal. Lett.,4, 15 (1990)] to be faster and more extensive with CO than by H₂ and here this is shown to be the case for CuO itself, this being so then it may be preferable to characterize CuO-containing catalysts by temperature-programmed reduction with CO than with H₂. The activation energies of reduction (57–82 kJ/mol) are those expected for chemical reduction, but it is an important finding that the order with respect to hydrogen partial pressure (0.04) is extremely low and far removed from the value of unity often assumed. Different samples of CuO exhibit different reduction characteristics.

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CuO/ZnO, (Vong, M. S. W. et al., Catal. Lett. (in press)), CO, H₂. , CuO. CO , CuO, . Cu₂O , . . . (57–82 /) , . ,

     

Influence of Cr loading on the catalytic properties of CrO3/SiO2 catalysts in 2-propanol conversion

Catalytic activity of CrO₃/SiO₂ samples for 2-propanol conversion is governed by only a small amount of active centers (estimated to be around 10¹⁷ per gram of catalyst), whereas excess chromium neither develops catalytic activity nor inhibits the reaction on the active sites. Only when the chromium loading is high enough to allow formation of bulk-like agglomerates (5 wt.% Cr) is 2-propanol converted also on this CrO_x surface phase, but with a significant higher activation energy.

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CrO₃/SiO₂ 2- ( 10¹⁷ ), . , - (5 .% Cr), 2- CrO_x , .

     

Catalytic activity of perovskite-type oxides LaMeO3

Catalytic activities for CO oxidation of a series of LaMeO₃(Me³⁺=V³⁺, Cr³⁺, Mn³⁺, Fe³⁺, Co³⁺, Ni³⁺) perovskite-type oxides were measured. Maxima for Mn³⁺ and Co³⁺ were found. The relation between local symmetry of solid surfaces and chemisorption and catalysis is discussed.

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, LaMeO₃ (Me⁺³=V⁺³, Cr⁺³, Mn⁺³, Fe⁺³, Co⁺³, Ni⁺³) CO. Mn⁺³ Co⁺³. , .

     

Thermal decomposition of zirconyl oxalates

Conditions for the preparation of stoichiometric barium zirconyl oxalate heptahydrate (BZO) have been standardized. The thermal decomposition of BZO has been investigated employing TG, DTG and DTA techniques and chemical and gas analysis. The decomposition proceeds through four steps and is not affected much by the surrounding gas atmosphere. Both dehydration and oxalate decomposition take place in two steps. The formation of a transient intermediate containing both oxalate and carbonate groups is inferred. The decomposition of oxalate groups results in a carbonate of composition Ba₂Zr₂O₅CO₃, which decomposes between 600 and 800° and yields barium zirconate. Chemical analysis, IR spectra and X-ray powder diffraction data support the identity of the intermediate as a separate entity.

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Zusammenfassung Die Bedingungen für die Herstellung von stöchiometrischem Barium-zirconyl-oxalat Heptahydrat (BZO) wurden standardisiert. Die thermische Zersetzung von BZO wurde unter Einsatz der TG-, DTG- und DTA, sowie der chemischen und Gasanalyse untersucht. Die Zersetzung verläuft über vier Stufen und wird von der umgebenden Gasathmosphäre nicht besonders beeinflusst. Sowohl die Dehydratisierung als auch die Oxalatzersetzung erfolgt in zwei Stufen. Die Bildung einer intermediären Übergangsverbindung mit sowohl Oxalat- als auch Carbonatgruppen wirken hierbei mit. Die Zersetzung der Oxalatgruppen ergibt ein Carbonat der Zusammensetzung Ba₂Zr₂O₅CO₃, das zwischen 600 und 800° zersetzt wird und Bariumzirconat ergibt. Die Angaben der chemischen Analyse, der IR-Spekren und der Röntgen-Pulver-Diffraktion unterstützen die Identität der Intermediärverbindung als eine separate Einheit.

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Résumé On a standardisé les conditions de préparation de l'oxalate heptahydraté de zirconyle et de baryum (BZO) stoechiométrique. On a étudié la décomposition thermique de BZO par TG, TGD et ATD ainsi que par analyses chimiques et analyses des gaz. La décomposition a lieu en quatre étapes et n'est pas trop influencée par l'atmosphère ambiante. La déshydratation et la décomposition de l'oxalate ont lieu en deux étapes. Il se forme un composé intermédiaire de transition contenant à la fois les groupes oxalate et carbonate. La décomposition des groupes oxalate fournit un carbonate de composition Ba₂Zr₂O₅CO₃ qui se décompose entre 600 et 800° pour fournir du zirconate de baryum. L'analyse chimique, les spectres IR et la diffraction des rayons X sur poudre, apportent les preuves de l'existence d'un composé intermédiaire comme entité séparée.

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() . , , . . . , . Ba₂Zr₂O₅CO₃, 600–800 c . , .

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The authors express their sincere thanks to Professor A. R. Vasudevamurthy for his keen interest and constant encouragement. One of us (TG) is grateful to the Council of Scientific and Industrial Research, India, for the award of a research fellowship.     

Non quasi-stationary state pyrolysis. Induction period of neopentane pyrolysis

The principle of an apparatus using an isothermal continuous flow stirred tank reactor to study homogeneous gas phase reactions at space times of the order of 1 sec is given. With this apparatus, the induction period of neopentane pyrolysis (as an example) has been clearly shown.

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, , 1 . , , .

     

Thermal decomposition of ammonium nitrate dispersed in a multicomponent nitrate system

To obtain the kinetic curves of thermal decomposition of ammonium nitrate occurring together with decomposition of metal nitrates contained in a mixture, the ammonia contents evolved from samples heated under thermoanalytical conditions were determined by the Kjeldahl method.

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Zusammenfassung Der aus unter thermoanalytischen -Bedingungen erhitzten Proben freigesetzte Ammoniakgehalt wird durch das Kjeldahlverfahren bestimmt, um die kinetischen Kurven der thermischen Zersetzung von Ammoniumnitrat zusammen mit der Zersetzung von Metallnitraten in Gemischen zu erhalten.

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, , , .

     

Influence of carbon dioxide on the position of oxygen adsorption equilibrium on silver

Due to interaction with carbon dioxide, when some adsorbed oxygen atoms on silver surfaces are converted into carbonate groups, the binding energy diminishes and the volatility of adsorbed oxygen rises.

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, , .

     

Kinetics of partly diffusion controlled reactions, IX. Cage effect in the photolysis of benzyl chloride in the liquid phase. First results

The cage recombination of free benzyl and chloride radicals after their formation via photolysis of benzyl chloride is interpreted using a model for partly diffusion controlled reactions. A new kinetic model is presented which takes into account the noncontact of the interacting species at the moment of their formation. There is good agreement between the results observed and the model presented.

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, , , . , . .

     

Cracking of cumene on vanadium doped silica-alumina

The influence of small admixtures of vanadium on the activity of a silica-alumina catalyst in cumene cracking has been investigated. A correlation has been established between the catalytic and acidic properties of the vanadium doped catalyst.

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. .

     

M?ssbauer spectroscopic studies of passivated layers of iron-containing catalysts for ammonia synthesis

Combined conversion electron (CEMS) and transmission -ray (MS) Mössbauer spectroscopy was used to study the structure of passivated layers of promoted and unpromoted iron-containing catalysts. In both catalysts the oxide-coated films were found to consist of small paramagnetic (at 300 K) clusters of ferric oxide.

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. , ( 300 ) .

     

Decomposition of isopropanol on V2O5 of different grain morphology and its relation to o-xylene oxidation catalysts

Decompositon of isopropanol has been studied on V₂O₅ samples of different morphology. It has been shown that the selectivity to acetone increases with the increase in the fraction of (010) plane of V₂O₅ on the sample surface, whereas the selectivity to propene decreases. The results are compared with previous data of o-xylene oxidation on the same samples and discussed in terms of the model of V₂O₅ surface [7].

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V₂O₅ . , (010) V₂O₅ , . - V₂O₅.

     

Role of tellurium in the oxidation of 1-butene on Te-doped CdMoO4

New active and selective catalysts were prepared by adding different quantities of Te to CdMoO₄. These were already selective at low Te levels, but the one with a Cd/Te/Mo ratio of 1/1/1 was specific for butadiene. The catalytic behavior of the Cd–Te–Mo–O system has been correlated mainly with the CdTeMoO₆ phase in the region rich in Te and with the CdMoO₄ phase with Te as dopant in the region poor in Te.

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Te CdMoO₄. Te, CdTeMo=111 . Cd–Te–Mo–O CdTeMoO₆ Te, CdMoO₄ Te , Te.