Investigation of n-heptane conversion over Pt?Al2O3 catalysts under gradientless reforming conditions

The rates of the total and individual directions of n-heptane conversion in reforming over platinum-on-alumina catalysts were shown to be independent of dilution with hydrogen. They can be described by simple equations following from kinetic concepts in ideal adsorbed layers.

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, - , .

     

Effect of the support on the coking of nickel catalysts in hydrocarbon steam reforming

Experiments on the coking rates of variously prepared nickel catalysts on TiO₂, Al₂O₃ and MgO in n-butane steam reforming show that changes in the relative coking rate at a rising steam excess in the gas phase depend mainly on the kind of support. The results obtained are accounted for by changes in the electron density at the site of nickel crystallite contact with the surface of various supports.

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, TiO₂, Al₂O₃ MgO, - , , , , , . .

     

31P-NMR studies on the interaction between Rh(AA)(CO)(PPh3) complexes and free PPh3

Uncoordinated phosphine exchanges with that in Rh(AA)(CO)(PPh₃) (AA—anthranilate and phenylanthranilate ions, respectively) via an S_N2 mechanism.

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Rh (AA) (CO) (PPh₃) (AA — ) S_N2.

     

NO adsorption on tin(IV) oxide

The adsorption of NO on SnO₂ has been studied in the temperature range from 0 to 86°C, at pressures from 0.4 to 3.5 Torr. The adsorption isotherms are described by the Freundlich equation. The rate of adsorption obeys the Roginskii-Zeldovitch equation and decreases with increasing temperature. The reduction of SnO₂ with carbon monoxide results in a drop in the adsorption rate and in the amount of adsorbed NO.

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NO SnO₂ 0°–86°C 0,4–3,5 . . - . SnO₂ NO.

     

Influence of the essential features of the potential energy surface on the temperature dependence of the H+CH3→CH4 reaction

Microcanonical statistical adiabatic channel model calculations show that the temperature dependence of the limiting high pressure rate coefficients of the title reaction becomes less positive (or more negative) when the attractiveness of the radial or the attenuation of anisotropic parts of the potential energy surface increases.

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, ( ) .

     

EPR study of the nature of active sites and the type of their deactivation in CO hydrogenation on (Ni+Ti)/SiO2 catalysts

As shown by EPR, upon supporting Ni(-C₃H₅)₂ on Ti/SiO₂, the Ni complex is coordinated to Ti³⁺ ions. Deactivation of (Ni+Ti)/SiO₂ catalysts so obtained during CO hydrogenation is due to the oxidation of Ti³⁺ ions and metallic nickel particles by reaction products.

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, Ni(-C₃H₅)₂ Ti/SiO₂ Ni Ti³⁺. , (Ni+Ti)/SiO₂ CO Ti³⁺ .

     

Thermogravimetric and kinetic study of a clodronic acid complex formed with sodium

Thermal stability of the clodronic acid complex formed with sodium (Na₂CCl₂(HPO₃)₂ ·4H₂O) was studied using both dynamic and isothermal thermogravimetric analyses as well as mass spectra. The thermal decomposition has two stages: dehydration and loss of two molecules of hydrogen chloride. Using the isothermal TG data the first step was found to be a phase-boundary reaction while the second step obviously cannot be described with just one reaction mechanism. The final residue of the dynamic TG analyses above 810 K was found to be sodium metaphosphate.

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Zusammenfassung Sowohl mittels dynamischer und thermogravimetrischer Untersuchungen als auch and Hand von Massenspektren wurde die thermische Stabilität des mit Natrium gebildeten Säurekomplexes Na₂CCl₂(HPO₃)₂·4H₂O untersucht. Die thermische Zersetzung vollzieht sich in zwei Schritten: Dehydratation und Verlust von zwei Molekülen HCl. Auf Grund der isothermen TG Angaben ist der erste Schritt eine Phasengrenzreaktion, während der zweite Schritt mit einem einzigen Reaktionsmechanismus nicht eindeutig beschrieben werden kann. Das Endprodukt der DTG Analyse oberhalb 810 K erwies sich als Natriummethaphosphat.

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-Na₂CCl₂/HPO_3/2·4H₂O — , - . , , , . , , . 810 .

     

Propagation of vibrational excitation in an adsorbed layer

Using a crystal model with an adsorbed layer, the propagation of vibrational excitation induced by an adsorbed particle is considered. The relaxation times of excitation have been estimated. The role of excitation transfer processes in adsorption-desorption phenomena is discussed.

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, . . - .

     

Dependence of the catalytic properties of cobalt molybdate in propylene oxidation on the surface reduction and oxygen bond energy

The dependences of the tate of partial propylene oxidation and of oxygen bond energy on the degree of cobalt molybdate reduction has been investigated by pulse and caloremetric methods. It has been found that upon reduction, the selectivity to acrolein and the oxygen bond energy increase. The steady state under the conditions examined is characterized by 22% surface reduction and the presence of uniform oxygen with a bond energy of about 85 kcal/mol.

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. , . 22% 85 /.

     

Influence des traitements thermiques sur l'etablissement des equilibres dans le systeme binaire hydroxyde de lithium-hydroxyde de sodium

Résumé L'utilisation systématique de recuits, contrôlés par des examens radiocristallographiques à températures variables, a permis de faire disparaître les équilibres métastables qui se manifestent entre les hydroxydes de lithium et de sodium. Trois composés sont identifiés avec certitude: 2 LiOH · NaOH, LiOH · NaOH et LiOH · 2 NaOH. Le composé équimolaire est dimorphe, la variété haute température étant de symétrie cubique.

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The systematic use of annealing operations controlled by radiocrystallographic examinations at various temperatures permits the elimination of metastable equilibria which occur between lithium and sodium hydroxydes. Three compounds have been characterized with certainty 2 LiOH · NaOH, LiOH · NaOH and LiOH · 2 NaOH. The equimolar compound presents in two crystalline forms: the high-temperature variety crystallizes in the cubic system.

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Zusammenfassung Die systematische Anwendung von Prozessen der Wärmebehandlung, welche durch radiokristallographische Untersuchungen bei verschiedenen Temperaturen kontrolliert wurde, ermöglicht den Abbruch der zwischen dem Lithium- und Natriumhydroxid bestehenden metastabilen Gleichgewichte. Drei Verbindungen konnten mit Sicherheit charakterisiert werden: 2 LiOH · NaOH, LiOH · NaOH und LiOH · 2 NaOH. Die äquimolare Verbindung ist dimorph, wobei die bei höherer Temperatur stabile Art eine kubische Symmetrie besitzt.

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, , , . :2LiOH. NaOH, LiOH. NaOH LiOH. 2 NaOH. , .

     

Correlations between photosorption and photocatalytic activities of alkali metal halides

An analysis of the correlation suggests that the common stages in photosorption, photooxidation and photodecomposition of some simple molecules on alkali metal halides are connected with catalyst photoexcitation.

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, , , .

     

Error analysis of surface area determinations by the chromatographic technique

The systematic and random errors in the determination of the surface area of adsorbents and catalysts by argon thermodesorption chromatography are analyzed.

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.

     

Reactivity of radical complexes Zr(IV) (O2?) in electron transfer reactions

Rate constants of the reactions of the radical complex Zr(IV) (O ₂ ^– ) with Fe(II), Ti(III), resorcinol, guaiacol and ascorbic acid in aqueous solutions have been measured by the ESR flow method. They are similar to the values obtained for the radical complex Ti(IV) (O ₂ ^– ).

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Zr(IV)(O ₂ ^– ) , , , . , Ti(IV)(O ₂ ^– ).

     

Microcalorimetric studies of slag alkaline binders

Calorimetric measurements were carried out on the hydration of slag activated by sodium hydroxide, sodium carbonate and water glass at 60 °C. The results can be correlated with the mechanical properties of the cured cements. The studies confirmed the applicability of calorimetry in the testing of activators used in concrete technology.

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Zusammenfassung Die Hydratation von Schlacke bei 60 °C und Aktivierung mit Natriumhydroxid, Natriumcarbonat oder Wasserglas wurde durch kalorimetrische Messungen verfolgt. Die Ergebnisse lassen sich mit den mechanischen Eigenschaften der erhärteten Zemente korrelieren. Die Untersuchungen bestätigen die Brauchbarkeit der kalorimetrischen Methode zum Testen von Aktivatoren in der Betontechnologie.

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, 60° , . . , - .

     

Structural and thermal analysis of silicon isothiocyanates complexes of Fe(III) and Mn(II)

New complexes of Fe(III) and Mn(II) with R_xSi(NCS)_4–x as ligands have been prepared and characterized. The structure of the new compounds are discussed on the basis of their spectroscopic (IR and UV-Vis), magnetic susceptibility and thermal data.

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Zusammenfassung Es wurden neue Fe(III)- und Mn(II)-Komplexe mit Liganden der Formel R_xSi(NCS)_4–x hergestellt und beschrieben. Bei der Diskussion der Struktur dieser neuen Verbindungen wurden spektroskopische (IR, UV), thermische Daten und Daten über die magnetische Suszeptibilität verwendet.

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R_xSi(NCS)_4–x. ( , - ), .

     

Influence of phosphorus additives on the properties of Fe?Sb?O oxide catalysts

Modification of the surface of Fe–Sb–O oxide catalysts by phosphorus additives increases the yield of acrylonitrile in the oxidative ammonolysis of propylene, which can be attributed to the increase of the surface concentration of weakly acidic aprotic centers, viz. Sb³⁺ ions.

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, --Sb³⁺.

     

Effect of water on hydrogen desorption from the surface of Rh/C catalysts

An increase in the number of titration cycles results in a considerable decrease in H_T and O_T values, which in turn, brings about a decrease in the amount of desorbed hydrogen. This shows that water, being a product of titration reaction, is adsorbed on the oxidized surface of rhodium and represents a kinetic-diffusive barrier for hydrogen titration.

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, H_T O_T, , , . , , , , , - .

     

Oxidation of hydrocarbon mixtures over a complex vanadium catalyst

Vapor-phase oxidation of hydrocarbon mixtures over vanadium oxide (promoted by potassium sulfate)-silica catalyst has been studied. It is shown that the inhibition of the rates of formation of individual products depends on the ability of the added hydrocarbons to similar specific interaction with the catalyst.

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. , , .

     

Isomerization-disproportionation of m-xylene over dealuminated mordenites

The isomerization-disproportionation of m-xylene has been investigated over a series of dealuminated mordenites characterized by Si/Al ratios varying from 5 to 15. Catalytic activity increases with the Si/Al ratio and correspondingly also the products of disproportionation. This behavior is interpreted in terms of increasing acid strength leading to a higher activity and selectivity to disproportionation through a common mechanism which involves both a parallel and a consecutive route.

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- - , Si/Al, 5 15. Si/Al, . , , , , .