Decomposition of alkanethiols to dialkyl sulfides and hydrogen sulfide

Disproportionation of thiol to sulfide and H₂S takes place on catalysts of various composition, the most active being those with paired acid-base centers. On these catalysts at 200–400°C methanethiol is quantitatively converted to dimethyl sulfide. Disproportionation of ethanethiol and particularly of 2-propanethiol is accompanied by the decomposition of sulfides formed and initial thiols to produce olefins and H₂S.

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H₂S , - . 200–400°C . 2- H₂S.

     

Palladium adsorption on MgO surface a theoretical model

The bonding energy of Pd atom with the MgO crystal surface has been calculated using semiempirical atomic potentials. The greatest energy for a perfect surface was found for the Pd atom placed over the Mg²⁺ ion (0.35 eV). The bonding energies for surfaces with Mg²⁺ or O^2- vacancies are 2.7 eV and 4.6 eV, respectively.

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Pd MgO. , Pd Mg⁺² (0,35 ). Pd O^–2 Mg⁺² , , 4,6, 2,7 .

     

Coordination polymers. IX

Poly-(butanediol-1,4-adipate) and poly-(diethyleneglycol-succinate) polyesters and their ionized derivatives, containing Mg²⁺ and Zn²⁺ ions with different stoichiometric ratios to the chain-end COOH groups of the polyesters have been investigated by derivatograph.The thermal decompositions of the metal-containing polyesters differ significantly from those of the unionized polyesters. These differences are connected with the chemical repeating unit of the polyesters and the chemical nature of the metal ions, and proportional to the amount of the latter.An explanation is given of the catalytic effect of metal ions on the process of decomposition of the polyesters.

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Zusammenfassung Poly-(butandiol-1,4-adipat) und Poly-(diethylenglycolsuccinat) polyester und ihre «ionisierten» Derivate — mit Mg²⁺ — und Zn²⁺-Ionengehalt in verschiedenen stöchiometrischen Verhältnissen zu den endständigen COOH-Gruppen der Polyester — wurden im Derivatographen untersucht.Die thermische Zersetzung der metallhaltigen Polyester unterscheidet sich wesentlich von nicht-ionisierten Polyestern. Diese Unterschiede sind mit den sich wiederholenden chemischen Einheiten der Polyester und der chemischen Beschaffenheit der Metallionen verbunden, und proportional dem Anteil derselben.Es wird eine Erklärung des katalytischen Effekts der Metallionen auf den Zersetzungsvorgang der Polyester gegeben.

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-1,4 «» , Mg²⁺ Zn²⁺ . , «» . . .

     

Alumina as a nickel catalysts support for steam reforming of hydrocarbons

The coking resistance of six alumina supported nickel catalysts in n-butane steam reforming mainly depends on the average size of nickel crystallites. Thus, by using suitable preparative methods, it is possible to produce good, coking resistant nickel catalysts even with Al₂O₃ support.

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Al₂O₃ -, , . . ., , - Al₂O₃.

     

Vapor phase oxidation of 2-methylpyridine on vanadyl polyphosphates

Vanadyl -and -polyphosphates in vapor phase oxidation of 2-methylpyridine show comparable activity and selectivity to the formation of pyridine-2-carboxaldehyde as traditional vanadium-molybdeum oxide catalysts. A redox mechanism for the reaction of 2-methylpyridine oxidation on vanadyl polyphosphates is suggested with interaction between 2-methylpyridine and oxygen of the catalyst lattice as the rate-determining step.

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- - 2- -- . - 2- . - 2- .

     

Bromine hydrolysis control and two consecutive oscillatory domains in closed, cerium-catalyzed glyoxylic acid Belousov-Zhabotinsky systems

In closed, cerium-catalyzed glyoxylic acid Belousov-Zhabotinsky systems we found a new dynamic behavior, viz. the observation of two oscillatory regimes separated by a nonoscillatory region. Mechanisms for this intermediate nonoscillatory domain are discussed.

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- , , , . .

     

Doping of CoMo?Al2O3 catalyst with Mg and Zn

Effect of Mg (Zn) addition to CoMo–Al₂O₃ catalyst on its activity in hydrogenation of toluene and HDS of thiophene has been determined. These additives decrease the catalyst activity and modify the mechanism of thiophene HDS.

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Mg (Zn) CoMo/Al₂O₃ () . .

     

Formation of the active component of a vanadium complex catalyst for the oxidation of anthracene to anthraquinone

The phase composition in various stages of preparation of the active material coating the catalyst for the partial oxidation of anthracene to anthraquinone was studied. The presence of an active phase was evidenced in the final active material as well in a precursor.

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, . , .

     

Hydrogenation of xylenes over supported Pt catalysts. Influence of different variables on their catalytic activity

In this work we studied and compared the catalytic activity of various supported Pt systems on the gas-phase hydrogenation of o-, m- and p-xylene. We analyzed the influence of different catalyst preparation variables (solvent, precursor, salt, support and catalyst reduction temperature used) on the catalytic activity and selectivity towards the corresponding cis-and trans-dimethylcyclohexanes.

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- o-, m- -. (, , ) - -.

     

Thermoanalytical characterization of amorphous synthetic silicic acids

Due to the various preparation procedures, silicic acid products display differences in dispersity, morphology and structural characteristics.Simultaneous DTA-TG is well suited for the separate determination of water bound adsorptively and chemically in the form of silanol groups, and also the characterization of aftertreated silicic acids. A classification of the different silicic acid types is possible on the basis of the thermoanalytical results.

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Zusammenfassung Nach unterschiedlichen Verfahren hergestellte Kieselsäuren zeigen verschiedene Dispersitäten, Morphologien und strukturelle Charakteristika. Simultane TG-DTA ist gut geeignet zur Bestimmung von adsorptiv oder chemisch-in Form von Silanolgruppen-gebundenem Wasser sowie zur Charakterisierung nachbehandelter Kieselsäuren. Eine Klassifikation der verschiedenen Kieselsäure-Typen ist auf der Grundlage thermoanalytischer Ergebnisse möglich.

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, , . , . .

     

Influence of lanthanum exchange on the catalytic properties of HY zeolite in cyclohexene transformation

Cyclohexene transformation was used as test reaction to study the effect of lanthanum exchange on the catalytic behavior of HY zeolite cracking catalysts. Lanthanum has an overall positive effect increasing both acitivity and stability of HY zeolite and maximum selectivity towards isomerization products is obtained at higher conversion.

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HY. , , HY. .

     

Iodide-promoted uncatalyzed bromate oscillators

Iodide ions—in a rather narrow concentration range—induce some of the uncatalyzed bromate oscillators to a more pronounced oscillatory activity: the number of oscillations increases considerably and the overall rate of the chemical reaction drops about an order of magnitude. Preliminary suggestion is made on the mechanism of iodide-induced oscillatory reactions.

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— — : . - .

     

Studies of adsorption-desorption processes in SO2 oxidation on the active component of vanadium catalysts

Diffusion and solubility coefficients of O₂, SO₂ and SO₃ in the active component of vanadium catalysts have been determined by a high-speed relaxation method. Processes of their dissolution are shown to be quasi-equilibrium with respect to catalytic reactions.

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O₂, SO₂ SO₃ ,

     

Kinetics of oxidation of glycine by aqueous chlorine

The kinetics of oxidation of glycine with aqueous chlorine has been investigated. The reaction is first order with respect to both molecular chlorine and glycine and inverse first order with respect to H⁺. The effect of various factors on the initial rate has also been studied. The kinetic parameters have been calculated and a possible mechanism is proposed.

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. , H⁺. , . .

     

Inhibition of the adsorption of cyclohexene over a Pd/sepiolite catalyst by acrylamide

Cyclohexene acts as a powerful hydrogen donor over supported Pd catalysts. On the basis of the theory of competitive hydrogenations, this paper aims at accounting for the fact that acrylamide cannot be reduced by hydrogen transfer using cyclohexene as donor, whereas methacrylamide can.

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Pd. , , , .

     

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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, - , .

     

Spectroscopic studies of the state of Cu2+ ions in Cu?Zn?Al oxide catalysts

ESR and electronic spectroscopy have reveled that in low-temperature ZnO the copper ions form Cu–O–Cu type cluster structures with highly covalent bonds and strong exchange interaction between the ions. The nearer environment of the Cu²⁺ ions is an octahedron with distortion towards square planar coordination.

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, ZnO Cu–O–Cu . Cu²⁺- , .

     

On the dissociation mechanism of carbonates and their isomorphous mixture

The thermal decomposition processes of carbonate minerals are analyzed by comparison of the notions on chemical bonds in crystals and modern concepts on solid-phase reactions. It is shown that depending on the mechanism of thermal dissociation, the carbonate minerals most widespread in nature may be divided into two groups: first, CaCO₃, SrCO₃ and BaCO₃, characterized by decomposition temperatures close to the equilibrium values and undergoing recombination on cooling; and second, MgCO₃, MnCO₃, FeCO₃ and ZnCO₃, with dissociation temperatures exceeding the equilibrium values by 250° and recombining only at high partial pressures of CO₂ (above 1000 bar).

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Zusammenfassung Die thermischen Zersetzungsprozesse von Carbonatmineralien wurden auf der Basis der Vorstellungen über die chemischen Bindungen in Kristallen und moderner Konzeptionen über Festphasenreaktionen analysiert. Es wird gezeigt, dass die in der Natur weitverbreitetsten Carbonatmineralien, abhängig vom Mechanismus der thermischen Zersetzung, in zwei Gruppen unterteilt werden können: die erste umfasst CaCO₃, SrCO₃ und BaCO₃ und ist durch Zersetzungstemperaturen nahe den Gleichgewichtswerten und durch Rekombination beim Abkühlen charakterisiert, zur zweiten gehören MgCO₃, MnCO₃, FeCO₃ und ZnCO₃ mit Dissoziationstemperaturen, die die Gleichgewichtswerte um etwa 250° überschreiten, und die nur bei hohen CO₂-Partialdrücken (über 1000 bar) rekombinieren.

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, . , , . CaCO₃, SrCO₃, BaCO₃ , . MgCO₃, MnCO₃, FeCO₃, ZnCO₃ , 250°, ( 1000 .).

     

State of copper ions, bond energy of oxygen and catalytic properties in hydrogen oxidation for a copper-magnesium system

The bond energy of surface oxygen in a copper-magnesium catalyst and its reactivity are shown to be greatly dependent on the structure of the nearer environment of copper ions. For catalysts prepared at low temperatures (773 K) this structure changes from a symmetrical square planar in CuO to an octahedral with various degrees of axial distortion depending on the copper content.

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, . , (773 ), CuO .

     

Selective dehydrogenation of tetralin on zeolites

The dehydrogenation of tetralin on two zeolite catalysts has been studied, the experiments were planned statistically according to the Orthogonal Central Composite Design. In order to determine the influence of coke deposits, the time-on-stream theory of catalyst decay is applied too.

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