Liquid-phase hydrogenation of cyclohexene by dihydrogen in the presence of dimolybdenum tetraacetate

Catalytic liquid-phase hydrogenation of cyclohexene in DMF by dihydrogen in the presence of dinuclear bridged complex Mo₂(OAc)₄ has been studied. A kinetic equation for the steady-state rate of cyclohexene hydrogenation and the activation parameters are suggested.

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Mo₂(OAc)₄. .

     

Glucose hydrogenation in aqueous isopropanol solutions

Studies of glucose hydrogenation on Raney nickel in aqueous isopropanol solutions indicate a complicated correlation between the solvent composition and the kinetic and potentiometric characteristics of the process.

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. .

     

TPD studies of hydrogen sorption on platinum powder catalysts modified with adsorbed gold

It has been shown that hydrogen determined from the TPD curves of platinum saturated with hydrogen sorbed above room temperature is chiefly absorbed and not adsorbed hydrogen; this absorbed hydrogen has no effect on the charging curve.

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, , , , ; .

     

Activity of tungstate catalysts in the synthesis of metylmercaptane from methanol and hydrogen sulfide

Catalysis obtained by impregnation of Al₂O₃ with solutions of hepta-, dodeca-, meta- and normal alkaline metal tungstates showed approximately the same activity. Most selective towards methylmercaptane were catalysts with an alkaline metal to tungsten atomic ratio equal to 21.

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, Al₂O₃ -, -, -, . , : 21.

     

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⁺ .

     

Inhibiting action of divalent copper compounds on microsomal oxidative demethylation of N,N-dimethylaniline

CuCl₂ is a non-competitive inhibitor whereas CuTyr₂ and CuLys₂ complexes are characterized by mixed-type inhibition. The inhibition action mechanism is discussed.

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CuCl₂ , . .

     

Catalytic oxidation of carbon monoxide by oxygen and nitrogen oxides on a copper-chromium oxide catalyst

The kinetics of CO oxidation by O₂, NO and NO₂ has been studied on a Cu–Cr-oxide catalyst. A comparison with the kinetics of the CO–N₂O interaction has been made. In all cases the reaction rate is described by the equation:r=k p _CO ¹ P _0x ⁰ . The oxidation of CO has been studied in the presence of different oxidants in the reaction mixture.

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CO , . CO . CO . CO .

     

Transition metal phosphomolybdates as catalysts for the gas phase hydration of acetylene to acetaldehyde and acetic acid

Adsorption of electron acceptors with electron affinity from 1.26 to 2.84 eV on two metal oxides have been studied. The limits of electron transfer from the oxide surface to the acceptor in electron affinity are reported.

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1,26 2,84 . .

     

Aminoacid nitrosation kinetics by alkyl nitrites in basic media

A kinetic study of the nitrosation of the aminoacids proline, sarcosine and 4-hydroxyproline using 2-ethoxyethyl nitrite as nitrosating agent has been carried out. The mechanism proposed is considerably different from that found when studying this kind of reactions in acid media.

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(, 4-), 2-- . , .

     

Dependence of the rate of methane oxidation on the surface area of the catalysts

Specific rate of methane conversion into C₂-hydrocarbons and deep oxidation products in its interaction with O₂ or N₂O decreases with growing surface area of catalysts that are metal-like compounds of transition elements. This regularity is interpreted in terms of a heterogeneous-homogeneous mechanism.

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C₂ ( CH₄ O₂ N₂O) - . , - .

     

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 . .

     

Hydrolysis kinetics of the acid and base species of oxacillin in aqueous solution

Using the method of initial rates, a study has been carried out on the different kinetic behavior of the acid and base forms of oxacillin. The acid catalytic constants of both species are determined. The acid form is much more stable with respect to hydrolysis.

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, . . , .

     

Catalytic hydrogenation of carbon monoxide on RuFe/SiO2 catalysts

The H₂+CO reaction on silica supported Ru, Fe and RuFe catalysts prepared from metal carbonyl clusters has been investigated under atmospheric and 20 bar pressure. According to the change of selectivity values with temperature and with pressure, the participation of surface carbon proposed earlier by several authors seems to be confirmed by this work.

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H₂+CO Ru, Fe RuFe, , 20 . , , , .

     

Mass-spectrometric analysis of SO3 in SO2 oxidation over vanadium catalysts

The detailed composition of the reaction mixture and, in particular, SO₃ concentration, in SO₂ oxidation over vanadium catalysts, have been determined experimentally. Both oxidized and reduced catalysts were shown to absorb a considerable amount of SO₃, the desorption rate of SO₃ being lower than that of its adsorption.

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, , . , , SO₃, .

     

Solid state reaction between dichromates and oxalates

The thermal investigation of the reaction taking place between dichromates and oxalates in the solid state has been done taking two systems of potassium dichromate-potassium oxalate and sodium dichromate-sodium oxalate. The techniques employed include thermogravimetry, differential thermal analysis, infrared spectroscopy and X-ray diffraction studies. The results indicate a stoichiometric reaction of dichromate and oxalate in 11 ratio to give the corresponding chromate as the sole product.

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Zusammenfassung Anhand der Systeme Kaliumdichromat-Kaliumoxalat bzw. Natriumdichromat-Natriumoxalat wurde eine thermische Untersuchung der Festkörperreaktion zwischen Dichromaten und Oxalaten durchgeführt. Dazu wurden thermogravimetrische, dififerentialthermoanalytische, IR-spektroskopische und Röntgendiffraktionsverfahren angewendet. Im Ergebnis zeigte sich eine stöchiometrische Reaktion von Dichromat und Oxalat im Verhältnis 11, die das entsprechende Chromat als einziges Produkt liefert.

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, , — — . , 11 .

     

Adsorption properties of microporous silica

The study of CCl₄ adsorption shows that the increase of dispersion potential can increase the specific adsorption in pores up to 3 nm in size.

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CCl₄ , 3 .

     

The dispersity of γ-alumina supported rhenium from hydrogen pulse chemisorption

The applicability of hydrogen chemisorption in a pulse chromatographic system for determining the dispersity of -alumina supported rhenium catalysts (10.4 wt.% and 1.04 wt.%) preheated in hydrogen at 550–800 °C is shown.

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, - (10,4 .% 1,04 .%), 550–800°C.

     

Kinetics of competitive addition of methyldichlorosilane to 1-hexene and to acetone

The competitive addition of methyldichlorosilane (MDChS) to 1-hexene and acetone^** has been studied. The estimated relative constant is effective and depends on acetone concentration and does not obey the Arrhenius temperature equation. A possible explanation is the complexation of methlydichlorosilyl radicals by acetone molecules.

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, 1- , -, . - .

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Initiated by -irradiation of⁶⁰Co.