State of components in Pd/C catalysts promoted by Ho2O3

Catalysts prepared through the interaction of C₃H₅PdC₅H₅ with the surface of evacuated Ho₂O₃/C after reduction by H₂ at 573 K contain Pd and Ho₂O₃ particles whose size is 30 and 20–40 Å, respectively. XPS and TEM data indicate that Pd particles have a positive charge and their surface is partly covered by Ho oxide.

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, C₃H₅PdC₅H₅ Ho₂O₃/C, H₂ 573 Pd 30 Å Ho₂O₃ 20–40 Å. XPS TEM Pd , Ho.

     

ESR study of the interaction of tribenzyltitanium with diisobutylaluminium chloride

ESR studies of the interaction between⁴⁷Ti enriched tribenzyltitanium and diisobutylaluminium chloride suggest that the observed spectral peculiarities show the formation of the alkylhalide complex of Ti ₂ ⁷⁺ .

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⁴⁷Ti, . Ti ₂ ⁷⁺ .

     

Thermal decomposition of thorium(IV) benzenetricarboxylates prepared in various ways

The thermal decompositions of thorium(IV) trimesinate and trimellitate, prepared under various conditions, have been studied. On heating benzenetricarboxylates of Th(IV) decompose in many stages. First, the hydrated complexes lose crystallization water in one, two or four stages, forming anhydrous comtlexes which decompose to ThO₂ with the intermediate formation of ThOCO₃. The dehydrations of the complexes are associated with strong endothermic effects, and the decompositions of the anhydrous complexes are accompanied by exothermic effects.

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Zusammenfassung Thorium-(IV)-trimesinat und -trimellinat wurden unter verschiedenen Bedingungen gefertigt und ihre thermische Zersetzung untersucht. Beim Erhitzen zersetzen sich Benzyltricarboxylate von Th(IV) in mehreren Stufen. Als erstes geben die hydrierten Komplexe in ein, zwei oder vier Schritten Kristallwasser ab. Die dehydrierten Komplexe zersetzen sich über das Zwischenprodukt ThOCO₃ zu ThO₂. Die Dehydrierung der Komplexe ist mit starken endothermischen Effekten verbunden, während die Zersetzung der dehydrierten Komplexe von exothermen Effekten begleitet wird.

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, . . , , , ThOCO₃. , — .

     

Infrared and mass spectroscopic evidence for hydrocarbon formation on a supported cobalt catalyst

Interrupting the surface carbonyl development at 345 K on an aerosilsupported cobalt oxide catalyst in CO/H₂ atmosphere at maximum surface concentration of linear carbonyl species by heating to 475 K results in the formation of Fischer-Tropsch type products detectable by combined IR and MS measurements.

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345°K , , CO/H₂ , 475° -, .

     

X-ray spectral investigation by synchrotron radiation of supported Re/SiO2 and (Re+Pt)/SiO2 catalysts prepared via triethoxyrhenium

Using synchrotron radiation L_III absorption spectra of rhenium in Re/SiO₂ and (Re+Pt)/SiO₂ catalysts prepared via triethoxyrhenium have been studied. The conclusion has been drawn that reduced catalysts contain lowvalent rhenium ions and their composition is more uniform than that of the previously examined catalysts Re/Al₂O₃ and (Re+Pt)/Al₂O₃ prepared by a conventional impregnation technique.

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L_III- Re/SiO₂ (Re+Pt)/SiO₂, . , , Re/Al₂O₃ (Re+Pt)/Al₂O₃, .

     

Influence of chemical nature and concentration of the catalyst on hydrocarbon pyrolysis

The dependence of pyrolysis rate of hydrocarbons on the concentrations of catalysts of various chemical nature has been studied. Substances active in pyrolysis can be divided into three groups: inhibiting the reaction and enhancing either its homogeneous or heterogeneous components.

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. , : , .

     

Sensitization of the photoadsorption of O2 and NO on SnO2

Photoadsorption activity of SnO₂ with respect to O₂ and NO after CO chemisorption has been revealed to be drastically increased. Photoadsorption is suggested to be sensitized by surface carbonates formed due to CO chemisorption.

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. , .

     

Acid-base properties of Sn?Mo?Ox catalysts

The acidity and basicity of Sn–Mo–O_x catalysts with different Mo/Mo+Sn atomic ratios were measured by determining the adsorption isotherms of pyridine and acetic acid by chromatographic method. It was found that acidity and basicity go through a maximum at a Mo content of 15–20 at.%.

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Sn–Mo–O_x Mo/Mo+Sn, . Mo=15–20 at.%.

     

ESR studies of Mo?Mg oxide catalysts

For 0.1–0.5 wt.% Mo–Mg oxide samples with high concentration of⁹⁵Mo isotopes two types of Mo⁵⁺ have been identified. Their role in the formation of O ₂ ^– anion-radicals in low-temperature oxygen adsorption on reduced samples has been established.

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, ⁹⁵Mo, Mo⁵⁺ Mo–Mg (0,1–0,5 .% Mo) - O ₂ ^– .

     

Ruthenium(VI) catalyzed oxidation of sodium salts of lactic, tartaric and glycolic acid by alkaline hexacyanoferrate(III)

The kinetics of ruthenium(VI) catalyzed oxidation of sodium salts of lactic, tartaric and glycolic acid by hexacyanoferrate(III) in aqueous alkaline medium have been studied at constant ionic strength. The reaction shows first order dependence on ruthenium(VI) and zero order on hexacyanoferrate(III). The rate of reaction increases with increasing substrate concentration and shows Michaelis-Menten type behavior. The rate of reaction decreases with increase in hydroxide ion concentration. Oxidation proceeds via formation of a complex between substrate and ruthenium(VI). A probable mechanism is suggested.

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(VI) , (III) . (VI) (III). -. . (VI). .

     

Le systeme eau-theophylline

The binary system water—theophylline was studied by DTA and radiocrystallography. The slow dehydration of theophylline monohydrate was observed at room temperature at relative humidities lower than 60%, without the formation of any other hydrate. The isochoric phase diagram was established. At 78 °C, a peritectic invariant occurred, owing to decomposition of the monohydrate. The existence of only one binary compound (theophylline H₂O) was confirmed by the.Tammann diagram.

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Zusammenfassung Mittels DTA und Radiokristallographie wurde das binäre System Wasser-Theophyllin untersucht. Bei einer relativen Luftfeuchtigkeit unter 60% wird bei Raumtemperatur eine langsame Dehydratation von Theophyllinemonohydrat ohne Formung anderer Hydrate beobachtet. Es wurde ein isochores Phasendiagramm entwickelt. Wegen der Zersetzung des Monohydrates tritt bei 78 °C eine peritektische Invariantheit auf. Die Existenz nur einer binären Verbindung (Theophyllin, H₂O) wird mittels eines Tammanndiagrammes bekräftigt.

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— . 60% - . . 78° , . -.

     

An inverse DIE method

The inverse of the usual DIE method is presented. The solid or liquid samples are introduced successively into the reagent of high concentration and large volume, and the change in temperature is measured after each sample. In principle the measuring unit need not be opened until the reagent is exhausted. The new technique is rapid and economical.

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Zusammenfassung Ein Inversverfahren der üblichen DIE-Methode wird beschrieben. Die festen oder flüssigen Proben werden der Reihe nach in das hochkonzentrierte Reagenz von großem Volumen eingeführt und die Temperaturänderungen nach jeder Probe gemessen. Im Prinzip muß die Messeinheit bis zur Erschöpfung des Reagenzes nicht geöffnet werden. Das neue Verfahren ist schnell und wirtschaftlich.

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Résumé La publication présente une méthode inverse de celle de DIE utilisée de coutume. On introduit les prélèvements solides ou liquides un à un dans le réactif de forte concentration et de grand volume et on effectue la mesure des variations de température après chaque prélèvement. En principe, il n'est pas nécessaire d'ouvrir l'unité de mesure avant que le réactif ne soit épuisé. La nouvelle technique est rapide et économique.

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, . , . , . .

     

Catalytic oxidation of acrolein to acrylic acid over a molybdenum-vanadium catalyst

By the method of gas chromatography it has been found that the adsorption of acrolein takes place without dissociation whereas acrylic acid is adsorbed dissociatively. The adsorption of water vapor proceeds also dissociatively and results in increasing the number of the Brönsted acid centers. The presence of water vapor has a positive effect on the desorption rate of acrylic acid and a negative effect on the reoxidation rate of the catalyst.

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, , . , . , — .

     

Kinetics and mechanism of oxidation of quinol by alkaline hexacyanoferrate(III)

The reaction between quinol and alkaline hexacyanoferrate(III) at constant ionic strength gives p-benzoquinone. The rate of the reaction was first order in the concentrations of substrate, oxidant and alkali. The slow step of the reaction involves the formation of the p-benzosemiquinone radical, which was detected by esr spectroscopy as a five-line spectrum with peak intensity ratios of 14641.

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(III) -. , . - , , 14641.

     

Recombination of polyatomic ester peroxy radicals in solution

Termination rate constants of peroxy radicals of seven polyatomic esters in benzene and perflouorooctane media have been measured by pulse photolysis. Recombination of peroxy radicals for all esters examined proves to be diffusion controlled. Reactivity of peroxy radicals in the termination reaction grows with increasing number of ester groups.

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. . .

     

Calorimetric studies of adsorptive properties of metallic carbides and nitrides of transition elements. Adsorption of H2, CO and O2 on titanium nitrides

Adsorption heats of hydrogen, oxygen and carbon monoxide on titanium nitrides have been measured calorimetrically in the temperature range from 473 to 673 K. With increasing Me/N ratio, the adsorption heat of oxygen grows.

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, 473–673 . Me/N.

     

Mechanism of methane photooxidation on V/SiO2 catalyst

CH₄ photooxidation on V/SiO₂ catalyst in the presence of gaseous oxygen has been studied by the mass-spectometric method. It has been established that CO₂ forms due to the interaction of CH₄ with surface oxygen anions bonded to vanadium ions. Photodecomposition of V⁴⁺O ₂ ^– species formed in O₂ adsorption on reduced vanadium ions leads to the reoxidation of the latter.

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- CH₄ V/SiO₂ . , CO₂ CH₄ , . V⁴⁺O ₂ ^– O₂ , .