Ethylene hydroformylation over a nafion-supported rhodium catalyst

Ethylene hydroformylation over a Nafion-supported rhodium catalyst has been studied under atmospheric pressure in the temperature range of 100–135 °C, using the transient response method.

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, , 100–135°C, .

     

Changes in iron oxidation state and surface composition of iron-chromium catalyst reduced by hydrogen

X-ray photoelectron spectroscopic studies of the reduction of iron-chromium catalysts have been carried out to determine changes in the relative surface concentrations of iron(II) and (III) oxides and metallic iron and in its surface composition at 100–500°C.

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(II), (III) 100–500°C. .

     

Kinetics of oxidation of phenanthrene by acidic hexacyanoferrate(III)

Under kinetically controlled conditions, phenanthrene is converted to 9-hydroxyphenanthrene by acid hexacyanoferrate(III) in 90% aqueous acetic acid. The value of –4.0 indicates that the reaction proceeds via the formation of a cation radical intermediate.

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(III) 9- 90%- . =–4,00, -.

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15^*     

51V NMR studies of systems V2O5-KHSO4 and V2O5?K2SO4

Systems V₂O₅–KHSO₄ and V₂O₅–K₂SO₄ have been studied by the⁵¹V NMR method. The first system demonstrates the same states of vanadium as the previously studied V₂O₅–K₂S₂O₇, in this system a compound with an equimolar ratio of components has been found. In V₂O₅–K₂SO₄ the state of vanadium differs from the above systems and the formation of a compound with V/K=4 is observed.

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⁵¹V KHSO₄–V₂O₅ K₂SO₄–V₂O₅. , K₂S₂O₇–V₂O₅, . K₂SO₄–V₂O₅ V/K4.

     

Estimation of nonlinear relaxation of catalytic reactions

Nonlinear relaxation time has been considered as a differential characteristic determined by the reciprocal value of the relative decrease in the deviation rate of the current concentration vector of intermediates from that of their steady-state concentrations. This characteristic is used for the analysis of some model reactions.

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, , .

     

Comparison of activities of cracking catalysts containing ZSM-5 and Y-zeolite

Studies on the catalytic cracking of diesel oil fraction with the boiling range of 493–603 K on H-ZSM-5 and RE, H-Y zeolites has been carried out. The results show that in the presence of H-ZSM-5 zeolite no significant increase in the yield of gasoline is observed. Higher percentage of unsaturated hydrocarbons in the gasoline and gases indicates that the hydrogen transfer activity of H-ZSM-5 containing catalyst is lower than that of RE, H-Y zeolites.

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H-ZSM-5 RE, H-Y , 493–603 . H-ZSM-5 . , , H-ZSM-5 , RE, H-Y .

     

George Martine,M.D., F.R.S. (1700–1741) an early thermal analyst?

A study of the life and work of George Martine, who seems to have been the first to have used the principle of differential thermal analysis, reveals that his stature scientifically (and perhaps medically) has not as yet been fully appreciated. A complete bibliography of his writings is appended.

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Zusammenfassung Durch das Studium von Leben und Werk von George Martine, der augenscheinlich der erste Anwender der Prinzipien der Differentialthermoanalyse war, wird offenkundig, daß sein Wesen bisher wissenschaftlich (und möglicherweise auch medizinisch) nicht gebührend gewürdigt wurde. Eine komplette Bibliographie seiner Schriften ist beigelegt.

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. , , , , , ( ) . .

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The author expresses his sincere gratitude to Mr R. N. Smart of the University of St. Andrews Library, Mr A. J. Clark, Deputy Librarian of the Royal Society, Mrs. J. Currie and Ms. J. Archibald of Edinburgh University Library, Dr. H. MacDonald of the National Library of Scotland, Ms. J. A. Beavan of Aberdeen University Library and all those contacted regarding the existence of a portrait of George Martine for their information and assistance, without which this article could not have been compiled.     

Energetic state of hydrogen on Os-black

Hydrogen adsorption on Os-black has been studied by the TPD method in the range from –85 to 450°C. Energetic inhomogeneity of hydrogen chemisorbed at adsorption temperatures of 150 to 450°C has been elucidated.

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OS (–85)–450°C. , 150 450°C.

     

Valence states and solubility limits in ternary iron-tin-antimony mixed oxide catalysts

The electrical conductivity study of a series of ternary Fe–Sn–Sb mixed oxides with 5 at. % Fe has shown that iron dissolves in the structure of SnO₂ as ferric ions and, consequently creates acceptor centers which compensate the doping effect of Sb⁵⁺ ions simultaneously dissolved, thus increasing the maximum dissolution of pentavalent antimony and shifting thereby the apparition limit of Sb³⁺ ions towards higher Sb contents.

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Fe–Sn–Sb c 5 . %- Fe , SnO₂ , , Sb⁵⁺, . , Sb³⁺ Sb.

     

A rapid method of determination of specific surface areas

An apparatus and a method for the rapid determination of specific surface areas are described. The method is based on low temperature adsorption of nitrogen from the air and requires determination of the adsorbed gas at two relative pressures. The accuracy of the method, as compared with the BET technique, is ±9% for the adsorbents studied.

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. . , BET, ±9% .

     

Thermal analysis of heterocyclic thione donor complexes. Part 1

The thermal decomposition of the Co(II) complexes of 1-methylimidazoline-2(3H)-thione (MImt), general formula Co(MImt)₂X₂ (X=Cl, Br & I), have been studied in air and argon by means of TG and DTG as well as in nitrogen by DTA. Quantitative DTA has been used to derive reaction enthalpies (H _R) from the melting and decomposition endotherms in nitrogen. Decomposition processes have been proposed for the complexes in air and in inert atmospheres. A mean coordinate bond dissociation energy (¯D) has been estimated for the Co-MImt bond in Co(MImt)₂Cl₂.Reaction end products in air have been identified by X-ray powder diffraction.

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Zusammenfassung Die thermische Zersetzung von Kobaltkomplexen des 1-Methylimidazolin-2(3H)-thions (IMmt) der allgemeinen Formel Co(MImt)₂X₂ (X=Cl, Br, J) wurde in Luft und Argon mittels TG und DTG und in Stickstoff mittels DTA untersucht. Reaktionsenthalpien (H_r) wurden durch quantitative DTA aus den in Stickstoffatmosphäre erhaltenen endothermen Schmelz- und Zersetzungspeaks erhalten. Es wurden Mechanismen für die Zersetzungsprozesse der Komplexe in Luft und inerter Atmosphäre vorgeschlagen. Die mittelere Dissoziationsenergie (¯D) der koordinativen Bindung Co—MImt in Co(MImt)₂Cl₂ wurde bestimmt.In Luft erhaltene Reaktionsendprodukte wurden durch Röntgenpulverdiffraktometrie identifiziert.

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1- -2()- () ()₂₂, X=l, I, , . (H _R) . . - ()₂l₂. , , - .

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The author is grateful to Mr. J. R. Creighton, Newcastle upon Tyne Polytechnic, for technical assistance with this work and to Dr. F. Buttler, Teesside Polytechnic for mass spectral data and helpful discussion.     

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.

     

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 , , — , — — . , , . , .

     

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.     

Mechanism of oxidation of molybdovanadophosphoric heteropoly blues by molecular oxygen. Trivanadium heteropoly blue

The oxidation of a heteropoly blue (HPB) of the composition Na_xH_9-xPMo₉V₃O₄₀ with molecular oxygen has been studied by the method of catalytic vanadyl oxidation. It is shown that the reduction of an oxygen molecule requires the addition of a fourth atom of V(IV) in the form of a vanadyl ion to the heteropoly anion.

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: Na_xH_9-xPMo₉V₃O₄₀. , V(IV), .

     

Study of CO oxidation on the (111) face of nickel during Ni?NiO phase transition

CO oxidation on the (111) face of Ni has been studied over a wide temperature range and reactant ratio in CO+O₂ reaction mixtures. A significant nonstationary increase in the reaction rate due to the formation of a two-dimensional surface oxide has been found. Subsequent formation of threedimensional NiO(111) phase sharply decreases the CO oxidation rate.

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CO (111) Ni (CO+O₂). , . , NiO(111) CO.

     

Kinetic studies of Pt/Al2O3 catalyst pellets with nonuniform activity

Catalysts with nonuniform distribution of the catalytically active component (Pt) over their porous support (Al₂O₃) have been studied. A nonuniform activity distribution changes not only the reaction rate but also the kinetics can be different on these catalysts.

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(Pt) (Al₂O₃). , , .

     

Thermodesorption of mixtures. Hydrocarbon, hydrogen sulfide and oxygen from the surface of molybdenum sulfide

The presence of hydrogen sulfide and oxygen in mixtures increases the number of sites for dissociative desorption on the surface of MoS₂ as compared with the adsorption of individual hydrocarbons. This phenomenon can be explained by a change in the coordination state of the active sites (molybdenum ions) upon the adsorption of the gases mentioned.

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, MoS₂ . .

     

Synergetic effect of silver and molybdenum (VI) oxide additives in vanadia catalysts for the selective oxidation of benzene

It has been shown that the selectivity of V₂O₅–MoO₃ catalysts for benzene oxidation to maleic anhydride can be enhanced by small amounts of silver introduced by impregnation with AgNO₃ solution. The effect of Ag₂O additive is synergetic and increases with increasing concentration of MoO₃ up to 28.5 mol %. The best effect was obtained when about 7 Ag atoms were introduced for 1000 (V+Mo) atoms at the surface.

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, V₂O₅–MoO₃ - AgNO₃. Ag₂O MoO₃ 28,5 . %. , 7 Ag 1000 (V+Mo).

     

Phase coexistence and complicated dynamics in open catalytic systems

The simplest catalytic system with surface phase transitions in CSTR has been studied. It is shown that the possible number of steady states is directly determined by that of phase coexistence regions on the phase diagram of the adsorption layer.

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. , , .