Photochemical reactions of anthraquinone with hydrocarbons in the presence and absence of oxygen: Trapping of radical intermediates

Radical intermediates formed at 25°C in the presence and absence of oxygen during the photolysis of anthraquinone in aromatic, cyclic and aliphatic hydrocarbon solvents were trapped by 2,6-dichloronitrosobenzene, 2,6-dibromonitrosobenzene and 2,4,6-tribromonitrosobenzene. The resulting nitroxide radicals have been characterized in situ by ESR spectra.

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: 2,6-, 2,6- 2,4,6-— , , 25°C. .

     

Reaction between the OH group of hydroxyproline and diisocyanate catalyzed by an organotin compound

We have studied the kinetics of the reaction of L-hydroxyproline with OCH(CH₂)₆NCO, catalyzed by organotin, avoiding side reactions by protecting the other active hydrogens of the aminoacid, and comparing it with the MeOH/n-BuNCO system.

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L-- -OCN(CH₂)₆NCO, , . . - .

     

ESR spin-trapping study of radicals produced by donor-acceptor interactions

Nitroso compounds, well known as spin traps, have not been applied for scavenging free radicals formed in reactions with the contribution of chloranil, so far. In our studies we show that spin traps such as nitrosodurene (ND), 2,6-dichloronitrosobenzene (Cl₂NB) react with radicals formed in the reaction between chloranil and durene, yielding stable spin adducts.

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, , . , 2,6-, , , , . , , , , .

     

On the catalytic system MgO?Na

Acid-base and radical properties of two sets of MgO–Na catalysts have been studied. The catalysts were prepared (I) by impregnation of MgO with NaOH in aqueous solution, and (II) by evaporation of metallic sodium onto a MgO surface. The catalyst prepared by the second method was much more basic than pure MgO (H_o=35) and showed a high activity in olefin isomerization.

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- MgO–Na. 1) MgO (NaOH) 2) MgO. , , , MgO(H₀=35), .

     

Physico-chemical properties of catalysts: Thermal analysis,infrared spectroscopy,X-ray diffraction and magnetic susceptibility of the vanadates of zinc,manganese and silver

Thermal characteristics of the vanadates of zinc, manganese and silver have been studied by DTA and TG techniques and the different transition products thus obtained have been characterised by IR, X-ray diffraction and magnetic susceptibility data. Chemical analyses indicate the following compositions of these vanadates: (1) Zn₂V₂O₇.5H₂O, (2) Zn₃(VO₄)₂.3H₂O, (3) Mn(VO₃)₂.2H₂O and (4) Ag₃VO₄. The DTA curves indicate that zinc pyrovanadate undergoes endothermic changes at 110–195, 265, 365, 440, 660° and one exothermic change at 485°. This system is diamagnetic which becomes completely paramagnetic after 660°. Zinc orthovanadate exhibits a number of endothermic peaks at 300, 470, 700, 815 and 930° respectively. This system is feebly paramagnetic and retains this property up to 930°. Manganese metavanadate undergoes endothermic changes at 240, 280–590, 830 and 880° respectively. This vanadate is paramagnetic and paramagnetism increases appreciably at 590° and remains constant up 830°. Silver orthovanadate exhibits three endothermic changes at 180, 455 and 640°, respectively.

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Zusammenfassung Die thermischen Charakteristika der Vanadate von Zink, Mangan und Silber wurden durch DTA- und TG-Methoden untersucht und die auf diese Weise erhaltenen verschiedenen Übergangsprodukte durch Daten aus IR-, Röntgen- und magnetischer Susceptibilität charakterisiert. Die chemische Analyse deutet auf folgende Zusammensetzung dieser Vanadate: 1) Zn₂V₂O₇.5H₂O, 2) Zn₃(VO₄)₂.3H₂O, 3) Mn(VO₃)₂.2H₂O und 4) Ag₃VO₄. Die DTA-Kurven zeigen endotherme Veränderungen des Zink-pyrovanadats bei 110–195, 265, 365, 440 und 660° und eine exotherme Veränderung bei 485°. Dieses System ist diamagnetisch und wird nach 660° vollständig paramagnetisch. Zink-orthovanadat zeigt eine Anzahl exothermer Peaks bei 300, 470, 700, 815, bzw. 930°. Dieses System ist schwach paramagnetisch und behält diese Eigenschaft bis zu 930°. Im Manganmetavanadat vollziehen sich endotherme Veränderungen bei 240, 280–590, 830 und 880°. Dieses Vanadat is paramagnetisch, der Pararnagnetismus steigt zusehends bei 590° und bleibt bis zu 830° konstant. Silberorthovanadat zeigt drei endotherme Veränderungen bei 180, 455 bzw. 640°.

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Résumé On a étudié par ATD et TG les caractéristiques thermiques des vanadates de zinc, de manganèse et d'argent. La caractérisation des divers produits de transition ainsi obtenus a été effectuée à partir des données fournies par IR, rayons X et susceptibilité magnétique. Les analyses chimiques indiquent les compositions suivantes de ces vanadates: (1) Zn₂V₂O₇.5H₂O, (2) Zn₃(VO₄)₂.3H₂O, (3) Mn(VO₃)₂.2H₂O et (4) Ag₃VO₄. Les courbes ATD du pyrovanadate de zinc montrent des effets endothermiques à 110–195, 265, 365, 440 et 660° ainsi qu'un phénomène exothermique à 485°. Ce corps est diamagnétique; il devient complètement paramagnétique au-dessus de 660°. L'orthovanadate de zinc donne des pics endothermiques à 300, 470, 700, 815 et 930°. Il est faiblement paramagnétique jusqu'à 930°. Le métavanadate de manganèse est le siège de phénomènes endothermiques à 240, 280–590, 830 et 880°. Il est paramagnétique et son paramagnétisme augmente de manière appréciable à 590° pour rester constant jusqu'à 830°. L'orthovanadate d'argent montre trois effets endothermiques à 180, 455 et 640°.

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, . - , . : Zn₂V₂O₇·5H₂O, Zn₃(VO₄)₂ · 3H₂O, Mn(VO₃)₂· 2H₂O Ag₃VO₄. , 110–195°, 265, 365,440 660° 485°. , 660° . 300, 470, 700, 815 930°. 930°. 240, 280–590, 830 880°. , 590° 830°. 180, 455 640°.

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The authors are grateful to the Physical Research Wing and Catalyst Research and Development Section, F. C. I., Sindri and also the Analytical Physics Division and Catalyst Section, I.I.P., Dehradun (India) for their help in getting TG and X-ray patterns of the catalysts studied.     

The Stevens rearrangement of methylenedimethyloxonium ylide: A quantum chemical study

The conversion of methylenedimethyloxonium ylide to ethyl methyl ether was investigated by the semiempirical MNDO method. An activation energy of 51 kJ/mol suggests that this rearrangement is a possible elementary reaction in the well-known MTG process.

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. 51 /, , .

     

Effect of Rh/Al2O3 on the reduction of ZnO in a mechanical mixture of these components

The effect of reoxidation temperature on TPR of 5% Rh/Al₂O₃ catalyst and its mechanical mixture with ZnO has been investigated. The results suggest bimodal character of supported rhodium and surprisingly high effect of this metal on ZnO reduction in the mixture.

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5% Rh/Al₂O₃ ZnO. , ZnO .

     

Basic properties of alkaline earth metal oxides and their catalytic activity in the decomposition of diacetone alcohol

The effect of CO₂ adsorption on the catalytic activity of alkaline earth metal oxides in the title reaction reveals that the number of active (basic) sites follows the order MgO>CaO>SrO>BaO, and the order of base strength is MgO

CO₂ , () : MgO>CaO>SrO>BaO, : MgO     

Mechanism of isotope exchange of dihydrogen with liquid ammonia catalyzed, by amide ions

The interacting bonds method (IBM) has been used for the analysis of hydrogen bonds in liquid ammonia, including estimates of the resonance components of the H=bonds of ammonia molecules with ammonium and amide ions. According to the E_a estimates for the interaction of a hydrogen molecule with an amide-ammonia solution (AAS) and the data on liquid ammonia structure, a kinetic mechanism for isotope exchange (IE) of hydrogen with liquid ammonia is formulated.

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(MBC) , -, - -. E_a - (AAP). () .

     

Studies of n-octane transformations on zeolites under hydrocracking conditions in a two-reactor flow-circulation system

Transformations of n-octane under hydrocracking conditions in a two-reactor flow-circulation system have been studied. It has been established that at high hydro-dehydrogenation activity of zeolite catalysts the reaction mechanism involves an initial step of paraffin dehydrogenation on a metal component and subsequent steps of cracking, isomerization and disproportionation of intermediate olefins on an acid component. Sodium content in zeolite determines the paraffin hydrocracking selectivity.

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- - . , - , . .

     

Partial kinetic models in the H2?O2 system

Using the concepts of maximum mechanism and non-equilibrium free energy, some partial kinetic models of hydrogen oxidation have been found by means of solving a direct kinetic problem. It is shown that the basic difference in the kinetic models of ignition is the initial period of the process (induction period) while the mechanism of the well-developed process slightly depends on the initial conditions and remains mainly the same for the parameters under study.

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H₂–O₂ ( ) . , ( ), , .

     

Investigation of catalytic purification of gases from aromatic hydrocarbons

1,1- (AH) ([AH]=6,9 /, 50°C). AH W_i/W_{O 3}=0,40±0,16.

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The kinetics and oxidation products of 1,1-diethoxyethane (AH) ozonolysis have been investigated at [AH]=6.9 mol/l and 50 °C. The initiation efficiency of radical oxidation by ozone is W_i/W_{O 3}=0.40±0.16.

     

Developpement de la methode thermique de mesure de la tension superficielle liquide-solide

A thermal method connects the solid-liquid surface tension/s of a substance to its triple point temperature depression. Here a practical process for application of this method is described. A previous determination of the thickness of the condensate layer which does not freeze near the wall of the porous material is no longer necessary. The process is applied to some organic substances and to a metal (indium).

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Zusammenfassung Eine thermische Methode ermöglicht die Oberflächenspannung/s einer Substanz mit der Erniedrigung der Tripelpunkttemperatur in Bezug zu bringen. Eine vorangehende Bestimmung der Dicke der Kondensatschicht, deren Aggregatzustand sich bei Kontakt mit dem porösen Material nicht ändert, ist überflüssig. Die Methode wird auf einige organische Verbindungen und ein Metall (Indium) angewandt.

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, _.,. — . , , . .

     

Formation of allyl radicals in the adsorption of propylene on zinc oxide

It has been found by the ESR technique that the adsorption of propylene on zinc oxide leads to the formation of a -allyl radical. It is suggested that the radical species of the surface allyl compound on this catalyst is responsible for its high selectivity in the dehydroaromatization of propylene to benzene.

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, - . , .

     

Hydrogen exchange in intramolecular cycloalkylation of phenylalkanols

Hydrogen exchange in intramolecular cycloalkylation of 2-methyl-4-phenyl-2-butanol (I) and 2-methyl-5-phenyl-2-pentanol (II) in the presence of 85% D₂SO₄ has been studied. The product 1,1-dimethylindane(III) is shown to contain deuterium in both aromatic ring and polymethylene fragment, whereas 1,1-dimethyltetralin (IV) contains deuterium only in the aromatic ring. A probable mechanism of the reaction is discussed.

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2--4--2- (I) 2--5--2- (II) 85% D₂SO₄. , 1,1- (III) , 1,1- (IV) . .

     

Alumina-supported sulfide catalysts for hydrodesulfurization obtained through metal complexes

Sulfide catalysts (Ni, Mo)/Al₂O₃ and (Co,Mo)/Al₂O₃ obtained through metal complexes using a surface assembling principle, are more active in thiophene hydrogenolysis compared with traditional catalysts prepared through impregnation.

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(Ni,Mo)/Al₂O₃ (Co,Mo)/Al₂O₃, , , .

     

Kinetics of the acid catalyzed hydrolysis of hydroxamic acids

The acid catalyzed hydrolysis of some alkylhydroxamic acids has been studied spectrophotometrically in perchloric, hydrochloric and sulfuric acids. Plots of the first order rate constant, k_obs against H⁺ show maxima, which are caused by protonation of the substrate. The mechanism of hydrolysis is found to be similar to that of amides. The variation of reaction rate with acid concentration can be described by a two-parameter equation.

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, , , . k_obs [H⁺] , . . .

     

Creation of acid sites by La-ions in L zeolite

The creation of strong acid sites in alkaline K-L-zeolites on ion-exchanging with La-ions is reported. Acidity measurements have been carried out by temperature programmed desorption of adsorbed ammonia. Reaction data which confirm the creation of acid sites are also reported.

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- K-L La. - . , .

     

A study of the surface heterogeneity and catalytic activity of catalysts by means of reaction thermodesorption

Reaction thermodesorption is studied. A generalized wiew is offered regarding the routes along which the transformations take place under the conditions of temperature-programmed desorption.

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. , .