Redistribution kinetics of isotope molecules due to reversible bimolecular reactions with several atomic channels

Isotope kinetic equations for reversible bimolecular reactions describe the rearrangement of atoms in activated complexes. It has been established from the model reaction CH₄+HCH₃+H₂ that the isotopic homoexchange of methane via two atomic channels is given by one set of equations with different sets of parameters.

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- . CH₄+HCH₃+H₂ , .

     

On the mechanism of chlorobenzene hydrolysis over Cu promoted lanthanum phosphate

The reaction mechanism of chlorobenzene hydrolysis to produce phenol over Cu promoted lanthanum phosphate has been studied taking into account a parallel reaction through which benzene is formed. There is a competition for the adsorption sites between the reactants and the reaction products.

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, , , . .

     

Reaction of vinyl radicals with propylene in the gas phase

The reaction of vinyl radicals with propylene and propyl radicals was investigated in the gas phase. The radicals were produced by mercury sensitized decomposition of molecular hydrogen followed by addition of hydrogen atoms to propylene and acetylene. Vinyl radical adds to propylene effectively while hydrogen atom abstraction does not occur.

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. , , . , , .

     

Kinetics of oxidative sulfonation of butylamine in the presence of CuCl2

Kinetic regularities of butylamine sulfonation to N, N-dibutylsulfamide in the presence of copper(II) chloride have been studied. Reaction mechanism involves the formation of Cu(II) amine complexes, their subsequent interaction with SO₂ and the redox decomposition of an intermediate to final products.

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N-N- (II). Cu(II), SO₂ - .

     

Diffusion of hydrocarbons in mordenite and molecular-sieve selectivity of mordenite catalysts

The diffusion of n-octane and n-propylbenzene in mordenite and the molecularsieve selectivity in hydrocracking of octane-propylbenzene binary mixtures over a mordenite catalyst have been studied. The hydrocarbon diffusivities and molecular-sieve selectivity change are accounted for by diffusion through mordenite channel mouths poisoned with an easily adsorbable hydrocarbon.

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- , () -. , , .

     

Stability of hyperbolic reactors

For the one-phase tubular reactor, a new mathematical model is suggested, viz. a hyperbolic system of first order partial differential equations instead of the usual second order parabolic ones. This physically better model is investigated from the point of view of stability via the second Lyapunov method.

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. .

     

Hydrocarbon conversion on promoted rhodium/Al2O3 catalysts

In (E+Rh)/Al₂O₃ catalysts (E=Sn, Pb, Mo and W) the catalytic properties of rhodium in benzene hydrogenation, propane hydrogenolysis and n-hexane conversion change drastically. For modified rhodium the decrease in the hydrogenolysis rate of C–C bonds in paraffins leads to an increased yield of the products of non-destructive conversion of n-hexane.

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(E+Rh)/Al₂O₃ (E:Sn, Pb, Mo, W) , , -. C–C -.

     

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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. , , .

     

Enhancement of H2- and retardation of O2-adsorption during O2?H2 titration cycles on Pt?Al2O3 catalyst surfaces

The title effects can be eliminated if the slow bleeding of H₂ from freshly reduced CuO-towers (often used as O₂-getters in purifying N₂ carrier gas) can be avoided, then H₂–O₂ titrations of Pt surfaces give consistent values from almost the first titration. Water injected at 25 °C also hardly affects the titer values.

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H₂ O₂ , H₂ CuO ( O₂ N₂ — -). H₂–O₂ Pt . , 25° C, .

     

Non quasi-stationary state pyrolysis. Induction period of neopentane pyrolysis

The principle of an apparatus using an isothermal continuous flow stirred tank reactor to study homogeneous gas phase reactions at space times of the order of 1 sec is given. With this apparatus, the induction period of neopentane pyrolysis (as an example) has been clearly shown.

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, , 1 . , , .

     

Isomerization of unsaturated compounds on Pd/Al2O3 in the presence of additives

Studies of the effect of zinc chloride and aluminium additives on the activity of a Pd/Al₂O₃ catalyst (5 wt.%Pd) in the isomerization of heptene-1, allylbenzene,p-allylphenol and 4-allyl-2-methoxyphenol (eugenol) indicate that the rate and selectivity of isomerization depend on the sequence of addition of salts and reagent to the catalytic system. The simultaneous addition of ZnCl₂ or AlCl₃ with olefin, produces a 2–3 fold increase in the isomer yield compared to ethanol.

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Pd/Al₂O₃- (5 .% Pd) -1, , -, 4--2- (). , . ZnCl₂ AlCl₃ 2–3 .

     

The role of excited states in the photolysis of n-butyraldehyde, II. Intersystem crossing quantum yields

Singlet triplet intersystem crossing quantum yields were determined for n-butyraldehyde, using the photosensitized cis-trans isomerization of piperylene to monitor the process. At room temperature and 313 nm, 0.58±0.05 and 0.72±0.05 were obtained for the triplet yield in the vapor phase and in isooctane, respectively.

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- - - . 0,58±0,05 0,72±0,05 313 .

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For Part I, see Ref. /1/     

Effect of the medium in hexacyanoferrate (III)-iodide and peroxodisulfate-iodide reaction

The kinetics of the two reactions hexacyanoferrate (III)-iodide and peroxodisulfate-iodide in several isodielectric water-cosolvent mixtures have been studied. The results can be rationalized as a consequence of the cosolventwater interaction.

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(III) -. -.

     

Kinetics of hydroperoxide reduction by copper(I) O,O-dialkyldithiophosphates

The kinetics of hydroperoxide ROOH (R=H, t–Bu, Ph(CH₃)₂C) reduction by copper(I) O,O-dialkyldithiophosphates has been studied using the UV-spectrophotometric method. Rate constants for the redox reactions have been determined and some suggestions concerning their mechanisms have been made.

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, - - O,O- (I). .

     

Catalytic properties of phosphorus-containing rhenium complexes in the hydrogenation of hexene-1

Rhenium (V, VI) complexes with organophosphorus ligands proved to be catalytically active in hexene-1 hydrogenation. The kinetics of this process catalyzed by ReOCl₃(PPh₃)₂ has been examined. The organic ligand in the coordination sphere of rhenium complexes was found to affect selectivity to olefin bonds or nitro groups in the hydrogenation of hydrocarbons.

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(V, VI) -1. , ReOCl₃ (PPh₃)₂. , .

     

La and Zn promotion of Ru Fischer-Tropsch catalysts

An investigation of the use of La- and Zn-promoters for Ru/SiO₂ F-T catalysts has been carried out. It was found that, while the use of a La-promoter did not result in any improvement over the use of a K one, Zn-promotion resulted in much higher yields of olefins. The CH₄ and olefin selectivities of the Zn-promoted Ru/SiO₂ were essentially insensitive to temperature over the range 250–320 °C. The Zn-promoted catalyst was found to have many of the same catalytic properties previously found for Ru/ZnO, but was much more active. Thus, it is possible to achieve certain interesting catalytic properties for Ru by the use of Zn-promotion without having to make use of the low surface area support ZnO.

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La Zn- Ru/SiO₂ F-T. , , La- - , Zn- . CH₄ Zn- Ru/SiO₂ , -, 250–320°C. Zn- , Ru/ZnO, . Ru, Zn- ZnO .