Quantum yields of the mercury photosensitized cis-trans isomerization of 1,3-pentadiene

The quantum yields of thecis trans andtrans cis Hg 6(³P₁) photosensitized isomerizations of 1,3-pentadiene at 100 Torr and 22°C are 0.54±0.02 and 0.42±0.02, respectively. The steady state ratio ([trans]/[cis])_ss is 1.27±0.05 which is almost identical with the ratio of the quantum yields, (ct)/(tc)=1.29±0.10. Thecistrans isomerization is suggested as a useful actinometer for mercury sensitized reactions.

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Hg 6(³P₁) 1,3- 100 22°C 0,54±0,02 0,42±0,02, . ([]/[]) 1,27±0,05, ( )/( )=1,29±0,10. , .

     

Kinetic studies of Pt/Al2O3 catalyst pellets with nonuniform activity

Catalysts with nonuniform distribution of the catalytically active component (Pt) over their porous support (Al₂O₃) have been studied. A nonuniform activity distribution changes not only the reaction rate but also the kinetics can be different on these catalysts.

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(Pt) (Al₂O₃). , , .

     

Decomposition of organic hydroperoxides on cation exchangers, III decomposition mechanism of cumene hydroperoxide

Results referring to the decomposition mechanism of cumene hydroperoxide, using strong acidic cation exhangers as catalyst /1/ are presented. It is assumed that the acetone formed in the decomposition condenses with the hydroperoxide, followed by decomposition of the condensed product (leading to the formation of the mono and possibly the diphenylacetal of acetone).

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, . , , , ( - ).

     

Ab initio investigation of the electron structure in bis-Cu+ acetylene and vinylidene complexes

[Cu(-C₂H₂)₂]⁺, [Cu(-CCH₂)₂]⁺ and [Cu(-C₂H₂) (-CCH₂]⁺ complexes have been studied by the ab initio double-zeta basis set method. It has been established that all calculated compounds are stable to decomposition into two C₂H₂ molecules and Cu⁺ cation and into one C₂H₂ molecules and the respective monocomplex. Calculation results suggest the possibility of intramolecular acetylene-vinylidene rearrangement in the coordination sphere of Cu⁺.

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ab initio : [Cu(-C₂H₂)₂]⁺, [Cu(-CCH₂)₂]⁺, [Cu(-C₂H₂) (-CCH₂)]⁺. C₂H₂ Cu⁺ C₂H₂ . - Cu⁺.

     

On the poisoning effect of deuterium exchange reactions

The self-poisoning effect of deuterium exchange reactions of C₁–C₆ straight chain aliphatic hydrocarbons as well as hydrogenolysis and dehydrocyclization of n-hexane in the presence of deuterium on a nickel powder catalyst has been investigated. The poisoning is enhanced with increasing carbon number. The results can be correlated to the ease of dissociative adsorption, i. e. to the formation of multiply bonded species. A tentative model is proposed to explain the decrease of deuterium exchange in n-hexane when the reaction is shifted towards hydrogenolysis and benzene formation. It is shown that at elevated temperatures the poisoning upon deuterium exchange is caused not only by blocking of the active sites with deposits but also by hindrance of desorption of the starting molecules in the original/exchanged form.

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C₁–C₆ , - . , . , .. . - , . , , / .

     

Interaction of PM12?nVnO40?(3+n) (M=Mo, W) heteropoly complexes with nitrogen oxide

In aqueous solution, PM_12–nV_nO₄₀ ^–(3+n) (M=Mo,W) hetero-polyanions provide a much faster oxidation of NO than mononuclear VO ₂ ⁺ ions, yielding HNO₂, NO ₃ ^– and reduced HPA.

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, PM_12–nV_nO₄₀ ^–(3+n) (M=Mo,W) , VO ₂ ⁺ , NO HNO₂ NO ₃ ^– .

     

Electrochemical model of monooxygenase

The monooxygenation of aniline by hemin, with oxygen activation by direct electron transfer from a cathode to the catalytically active center and direct participation of the reduced oxygen species in the reaction has been carried out.

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.

     

AlPO4 as catalyst in organic reactions. IV. Transesterification of methyl methacrylate

Coke deposition on monometallic Pt, Re, Ir, Ge and Sn catalysts supported on -Al₂O₃, and its influence on activity and selectivity over methylcyclopentene reforming was studied. As a result the effect can be interpreted in terms of metal-support interactions that modify the overall catalytic deactivation rates.

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Pt, Re, Ir, Ge Sn, -Al₂O₃ . , .

     

Steady state kinetic equation for SO2 oxidation on vanadium catalysts

From the analysis of the detailed reaction mechanism and taking into account vanadium complex formation processes, a steady state kinetic equation has been derived to describe experimental data in a wide range of reaction conditions.

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, .

     

Estimation of nonlinear relaxation of catalytic reactions

Nonlinear relaxation time has been considered as a differential characteristic determined by the reciprocal value of the relative decrease in the deviation rate of the current concentration vector of intermediates from that of their steady-state concentrations. This characteristic is used for the analysis of some model reactions.

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, , .

     

Oxidative dehydrogenation of ethylbenzene over a charcoal catalyst

The oxidative dehydrogenation of ethylbenzene over a charcoal catalyst has been studied by the pulse technique. The styrene yields for the oxidation of ethylbenzene by gaseous oxygen and upon the interaction of ethylbenzene with oxygen adsorbed on charcoal are shown to be the same.

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. , , , .

     

Simultaneous adsorption of CO and O2 on Ni(100) plane at low temperatures

LEED, AES and TPD studies of CO adsorption at 170 K on the oxygen-covered surface of Ni(100) have revealed its great amount throughout the range of oxygen coverage. With thermal desorption from a mixed layer the appearance of CO₂ due to the reaction CO_ads+O_ads, indicates that a part of oxygen adsorbed on Ni(100) at T=170 K is reactive.

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, () CO 170 Ni(100). . CO₂ Co+ +O, , Ni(100) T=170 .

     

Structural studies of nickel-based Raney catalysts

Electron microscopy and Mössbauer spectroscopy studies of nickel-based Raney catalysts have revealed that the catalysts are formed through the successive aggregation of their structural elements. Catalyst particles are covered by a thin layer of nickel oxide.

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. , . .

     

m-Xylene conversion over dealuminated Y zeolites studied by the pulse method

m-Xylene conversion was studied over dealuminated Y type zeolites in hydrogen forms, SiO₂ to Al₂O₃ ratios were varied from 4.86 to 12.95.

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- . SiO₂/Al₂O₃ 4,86 12,95.

     

Calorimetric study of the BrO3?/Ce4+/cyclohexanone and BrO3?/Ce4+/cyclopentanone oscillating systems

The heat output (Q) during the induction period of a Belousov-Zhabotinskii oscillating reaction usually evolves at a constant rate /6/; we observe in the BrO ₃ ^– /Ce⁴⁺/Cyclohexanone system a sudden change in the slope of the function Q=f(t), which corresponds to the beginning of the quasistationary phase /3/.

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(Q) - ; BrO ₃ ^– /Ce⁺⁴/ Q=f(t), .

     

Effect of additives upon Raney-Nickel alloy catalysts

Addition of small amounts of copper to Raney Ni increases its activity for hydrogenation of crotonaldehyde and its selectivity for C=O bond hydrogenation. Higher amounts lead to higher selectivity but lower activity. The coordination chemical approach to catalysis was used to explain this result.

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C=O. , . .

     

Hreels studies of Hads effect on NO adsorption on Pt(111)

HREELS studies of NO molecular adsorption on clean and hydrogen covered Pt(111) have revealed that a reversible transition between bridge (₁) and on-top (₂) states of NO_ads is realized in the (NO+H₂)/Pt(111) system. In the presence of H_ads the adsorption of NO in the ₁ state is inhibited and the main state of NO_ads is ₂. Upon heating the layer (₂-NO_ads+H_ads) hydrogen desorption is accompanied by on-top to bridge state conversion.

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NO Pt(III). , (NO+H₂)/Pt(III) (₁) (₂) NO. H NO ₁ , , ₂ NO. (₂-NO+H) NO .

     

Influence of ammonia on propane oxidation over a gallium-antimony oxide catalyst

The influence of ammonia on propane oxidation over a Ga–Sb oxide catalyst has been studied. Acrylonitrile is formed upon the interaction of acrolein with partially dehydrogenated ammonia. Ammonia increases the rates of overall and selective oxidation of propane. This is assumed to be due to the formation of electron-donor sites promoting proton separation from the propane molecule.

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. , . . , , .

     

Investigation of the self-heating phenomenon in the bulk polymerization of acrylonitrile

The temperature of the polymerizing system was measured with a thermistor during the bulk polymerization of acrylonitrile initiated by azoisobutyronitrile. The temperature of self-heating suddenly rises at a conversion of about 2%. This jump of temperature is presumably caused by the formation of a gel structure and, consequently, the outfall of thermal convection within the system.

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, -- . , - . - , .