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.     

Induction period of the conversion of methanol to hydrocarbons on a nickel loaded faujasite: Evidence for a suppression of the autocatalytic step

The conversion of methanol to hydrocarbons on nickel loaded faujasites can be retarded for many hours time-on-stream. The induction period is interpreted to be due to a suppression of the autocatalytic step of the reaction. An autocatalytic mechanism is proposed based on the -scission of branched carbenium ion intermediates.

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. . , - .

     

Studies of vanadium catalysts for sulfur dioxide oxidation by51V-NMR

Studies of the⁵¹V-NMR spectra of a series of industrial catalysts and systems modelling the active catalyst component indicate that the catalyst composition depends on the preparation method and during thermal treatment the support interacts with the active component. The local environment of vanadium is being formed in the process of catalytic reactions.

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⁵¹V , -I-4, , : KVO₃, KVO₃–SiO₂, KVO₃–K₂SO₄ , , . .

     

Changes in the catalytic properties of a multicomponent molybdenum catalyst under vibro-fluidized catalyst bed conditions

Activation effect of oxidative dehydrogenation of butene-l on a multicomponent molybdenum catalyst at various temperatures has been studied by pulse and flow techniques. It is shown that under vibrofluidization not only reactive but also adsorption properties of the catalyst surface change. Oxygen consumption in the reaction process has been examined.

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-1 . , , . .

     

Poisoning effect of carbon monoxide on the desorption process of hydrogen from palladium

The desorption of H₂ from clean and CO-poisoned Pd wires was studied by a temperature programmed desorption technique. Poisoning effect of CO on H₂ desorption process can be accounted for in terms of blockage of the surface sites for the recombination of H atoms.

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H₂ , CO, - . CO H₂ , , , .

     

New autooscillation chemiluminescence reaction of 4-oxyquinoline oxidation by bromate ions

A new autooscillation chemiluminescence reaction of 4-oxyquinoline oxidation by bromate ions, catalyzed by cerium ions and tris-(2,2-dipyridine) ruthenium complexes, has been discovered.

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4- , , -2,2- .

     

Studies on water retention and water release from some protein systems

The hydrogen-bond properties (WBI index), water retention and water release from the protein-water systems gluten-water, soya protein- water and casein-water, have been investigated using differential scanning calorimetry in the temperature range 223–423 K. The proteins were characterized by their isoelectric point, contents of carboxyl groups and sulfur-containing groups, and readiness of undergo chloromethylation. It was concluded that the marked difference in water-release behaviour is chiefly explained by conformational differences and charge effects.

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Zusammenfassung Wasserstoffbrückenbindugseigenschaften (WBI-Index), Wasserretention und Wasserabgabe von Protein-Masser-Systemen — Gluten-Wasser, Sojaprotein-Wasser und Casein-Wasser — wurden im Temperaturbereich von 233–423 K mit einem Scanning-Kalorimeter untersucht. Die Proteine wurden durch ihren isoelektrischen Punkt, den Gehalt an Carbonylgruppen und Schwefel enthaltenden Gruppen und durch ihre Reaktivität in der Chlormethylierung charakterisiert. Es wurde gefolgert, dass der ausgesprochene Unterschied im Wasserabgabeverhalten in erster Linie auf strukturelle Unterschiede und Ladungseffekte zurückzuführen ist.

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223–423 K , , — , — — . , , . , .

     

Investigation of complete oxidation of organic materials with thermal analytical measurements

The complete oxidation of styrene-divinylbenzene has been examined with complex thermoanalytical methods by derivatograph and thermogastitrimeter. With the combined application of combustion catalyst and postcatalytic method the oxidation of the styrene-divinylbenzene is complete.

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Zusammenfassung Die vollständige Oxydation von Styrol-Divinylbenzol wurde mittels einer komplexen thermoanalytischen Methode unter Verwendung eines mit einem Gastitrimeter kombinierten Derivatographen untersucht. Eine vollständige Oxydation wird bei Anwendung eines Verbrennungskatalysators und der postkatalytischen Methode erreicht.

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- . .

     

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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. , . .

     

Thermal decomposition of Cu(I) phosphine complexes

The thermal decomposition of Cu(I) phosphine complexes of the general types (CuXPPh₃)₄, [CuX(PPh₃)₂] and [CuX(PPh₃)₃] was investigated.The thermal decomposition of (CuXPPh₃)₄, where X denotes Cl^–, Br^–, I^–, NO ₃ ^– and PPh₃=P(C₆H₅)₃, occurs with formation of a phosphine oxide intermediate. For the remaining complexes this intermediate was not proved in the thermal decomposition.

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Zusammenfassung Die thermische Zersetzung der Cu(I)-Phosphinkomplexe vom allgemeinen Typ (CuXPPh₃)₄ und [CuX(PPh₃)₂], wie auch [CuX(PPh₃)₃] wurde untersucht. Die thermische Zersetzung von (CuXPPh₃)₄, wobei X=Cl^–, Br^–, I^– und NO ₃ ^– bedeutet und PPh₃=P(C₆H₅)₃, verläuft unter Bildung eines Phosphinoxid Zwischenproduktes, bei den übrigen Komplexen konnte dieses im Laufe der thermischen Zersetzung nicht nachgewiesen werden.

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Résumé On a étudié la décomposition thermique des complexes phosphine-Cu(I) de formule générale (CuXPPh₃)₄, [CuX(PPh₃)₂], [CuX(PPh₃)₃]. La décomposition thermique de (CuXPPh₃)₄, où X désigne Cl^–, Br^–, I^– et NO ₃ ^– , et PPh₃=P(C₆H₅)₃, s'effectue avec formation d'un oxyde de phosphine intermédiaire; avec les autres complexes, cet intermédiaire n'a pas été mis en évidence au cours de la décomposition thermique.

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(CuXPPb₃)₄ [CuX(PPh₃)₂] [CuX(PPh₃)₃]. (CuXPPh₃)₄, X=Cl^–, Br^–, I^–, NO ₃ ^– , PPh₃=(₆₅)₃ . .

     

Improvement of the zeolite catalyst for olefin synthesis from methanol by regulating the shape factor with the aid of seed crystals

By the use of seed crystals in the initial stage of preparation of a new type of zeolite for olefin synthesis, shape and size distribution of the zeolite could be regulated uniformly, and the catalyst performance was improved markedly especially with respect to olefin selectivity and the catalyst life.

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, . , , .

     

Stopped-flow study of the oxidation of ascorbic acid by the oxo-bridged trinuclear ruthenium complex [(NH3)5RuORu(NH3)4 ORu(NH3)5]7+

The kinetics of the oxidation of ascorbic acid by [(NH₃)₅RuORu(NH₃)₄ORu(NH₃)₅]⁷⁺ has been studied by the stopped-flow method. The activation parameters have been calculated and a possible mechanism is suggested.

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[(NH₃)₅RuORu(NH₃)₄ORu·(NH₃)₅]⁷⁺ . .

     

Investigation of the pore structure of Raney nickel catalysts

Ar and N₂ adsorption and capillary condensation studies at 77.4 and 84K on Raney nickel catalysts modified by Ti, V, Cr, Mn, Zr, Mo, Ta, W, Re and on BAU char coal show that at 77.4K, in pores with d_eff>100Å, argon exists in the solid state.

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Ar N₂ 77,4 84°K - , Ti, V, Cr, Mn, Zr, Mo, Ta, W, Re , d>100 Å 77,4 °K .

     

Catalysts for metathesis of olefins, prepared by anchoring of MoO2(acac)2 to Al2O3

New highly active catalysts for metathesis of olefins were obtained through the interaction of bis(acetylacetonato)dioxymolybdenum(VI) with surface OH groups of -Al₂O₃ and subsequent reduction in H₂ or CO.

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()(VI) OH -Al₂O₃ H₂ CO .

     

Role of high temperature hydrogen treatment in n-hexane aromatization over Pt/Al2O3 catalyst. Temperature programmed reaction study

Ultrazet zeolites (Polish counterparts of the ZSM-5 zeolite) with SiO₂/Al₂O₃ ratios ranging from 40 to 186, have been studied to elucidate the correlation of SiO₂/Al₂O₃ ratio with transformation of the orthorhombic into monoclinic symmetry in the zeolite (during preparation), cracking reaction of n-hexane and 3-methylpentane and zeolite acidity.

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( ZSM-5) SiO₂/Al₂O₃ 40 186 SiO₂/Al₂O₃ ( ), - - .

     

Redistribution kinetics of isotope molecules due to reversible bimolecular reactions with several atomic channels

Isotope kinetic equations for reversible bimolecular reactions describe the rearrangement of atoms in activated complexes. It has been established from the model reaction CH₄+HCH₃+H₂ that the isotopic homoexchange of methane via two atomic channels is given by one set of equations with different sets of parameters.

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- . CH₄+HCH₃+H₂ , .

     

Electronic influence of water adsorbed on ZnO in H2 and Co oxidation

In this paper we calculate the effect of surface OH/OH^– on the simultaneous adsorption of H₂ and O₂ on ZnO. A quantitative comparison between H₂ and CO oxidation rates shows that the two mechanisms are similar for the same water recovery on ZnO.

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OH/OH^– H₂ O₂ ZnO. H₂ CO , ZnO.

     

Thermal decomposition of Cr(III) complexes with urea and thiourea

The thermal decompositions of Cr(III) complexes with urea and thiourea were investigated. The courses of the decompositions were found to be anion- and ligand-dependent. Suggestions for a mechanism of decomposition of these complexes are presented. The final product of decomposition of the complexes investigated was chromium(III) oxide (Cr₂O₃).

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Zusammenfassung Die thermische Zersetzung der Komplexe von Cr(III) mit Karbamid und Thiokarbamid wurde untersucht. Der Verlauf der Zersetzung wurde für Anionen- und Liganden-abhängig gefunden. Vorstellungen über eine mechanische Zersetzung dieser Komplexe werden gegeben. Das Endprodukt der Zersetzung der untersuchten Komplexe war jeweils Chrom(III)oxid (Cr₂O₃).

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Résumé On a étudié la décomposition thermique des complexes du chrome(III) avec l'urée et la thiourée. On a trouvé que le processus de la décomposition dépend de l'anion et du ligand. On propose un mode de décomposition mécanique pour ces complexes. Le produit final de la décomposition des complexes étudiés est l'oxyde de chrome(III), Cr₂O₃.

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Cr (111) . , . . (111) (Cr₂O₃).

     

Reactivity of allyl (o-halophenyl) ethers with organonickel (0) complexes

The reactivity of allyl (o-halophenyl) ethers with zerovalent nickel complexes, with triphenylphosphine and pyridine as ligands, leading to benzo[b]furan derivatives has been checked. Cyclization products were not isolated, but deallylation, substitution, reduction and rearrangement products were obtained in low to moderate yields. Mechanisms are proposed to explain the formation of these side products.

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-(o-) , , [b] . , , , , . .

     

Thermal properties of elastin-fatty acid complexes

Differential scanning calorimetry has been applied to study the interaction of fibrous or of soluble elastin with fatty acids and their trialanine derivatives. The DSC curves of elastin-fatty acid preparations exhibited an endothermic transition in the temperature range - 10° to + 50°. The peak temperatures and the enthalpy changes were independent of the chain length and of the saturation of the fatty acid. The interaction with the trialanine derivatives was similar to that with the fatty acids.Such interactions between elastin and lipids might take place in vivo as well, resutling in the loss of elasticity of elastin fibres and consequently in the development of arteriosclerotic lesions.

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Zusammenfassung Zur Untersuchung der Wechselwirkung zwischen dem fibrösen oder lösbaren Elastin, und den Fettsäuren und ihren Trialanin-Derivaten wurde die DSC-Methode angewandt. Die DSC-Kurven der Elastin-Fettsäure-Präparate zeigten in dem Temperaturbereich von - 10° bis + 50° einen endothermischen Übergang. Die Peak-Temperaturen und die Änderungen der Enthalpie waren von der Kettenlänge und der Sättigung der Fettsäure unabhängig. Die Wechselwirkung mit den Trialanin-Derivaten war der mit den Fettsäuren ähnlich.Solche Wechselwirkungen zwischen Elastin und den Lipiden können auch in vivo stattfinden, und die Abnahme der Elastizität der Elastin-Fibern, und folglich die Entfaltung der arteriosklerotischen Schädigungen resultieren.

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. - — — 10° - + 50°. , . , . , , .