A thermal synthesis of a new tin(IV) dithiocarbamate

A new tin dithiocarbamate containing sulphur bridges, di--sulphidobis [bis(N,N-diethyldithiocarbamato)tin(IV)], has been isolated from the thermal decomposition of tetrakis(N,N-diethyldithiocarbamato)tin(IV). A dimeric structure is proposed on the basis of results from mass spectrometry, infrared spectroscopy, thermal analysis and vapour pressure osmometry.

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Zusammenfassung Ein neues, Schwefelbrücken enthaltendes Zinn-Dithiocarbamat, Di--sulfidobis[bis(N,N-diäthyldithiocarbamato)Zinn(IV)], wurde bei der Zersetzung von Tetrakis(N,N-diäthyl-dithiocarbamato)Zinn(IV) isoliert. Aufgrund der Ergebnisse der Massenspektrometrie, der Infrarotspektroskopie, der Thermoanalyse und der Dampfdruck-Osmometrie wird eine Dimerstruktur vorgeschlagen.

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Résumé Un nouveau dithiocarbamate d'étain contenant des ponts de soufre, le di--sulfidobis[bis(N,N-diéthyl-dithiocarbamato)é tain(IV)], a été isolé lors de la décomposition thermique du tétrakis(N,N-diethyl-dithiocarbamato) étain(IV). Une structure dimère est proposéeà partir des résultats obtenus par spectrométrie de masse, spectroscopie infrarouge, analyse thermique et osmométrie sous pression de vapeur.

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—-- [/N,N- (/IV)], [/N,N- (/IV)], , (N,N- ) (IV). - , , .

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The authors gratefully acknowledge the assistance given by Dr. A. G. Wedd with the vacuum sublimation technique. One of us, G. K. B., is grateful for a research scholarship provided by La Trobe University.     

A device for pulse investigation of heterogeneous catalytic reactions

In the present work a simple device is described for the pulse investigation of heterogeneous catalytic reactions and catalysts. Owing to the possibility for separate adjustment of the gas flow rate in the catalytic reactor and in the chromatographic column, it can be used for kinetic measurements too.

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- . , .

     

Acetylene adsorption on a clean iridium surface

The interaction of C₂H₂ with a polycrystalline iridium surface at 140 KT500 K has been studied by AES, XPS and UPS. A model of the bonding between C₂H₂ and Ir by the 1 orbitals of the hydrocarbon is proposed. The more pronounced energy splitting between the orbitals of acetylene during adsorption compared to that in the gas phase is ascribed to deformation of the acetylene molecule.

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C₂H₂ . 140 KT500 K AES, XPS UPS. C₂H₂ Ir 1- . - , , .

     

Ba(OH)2 as catalyst in organic reactions. VIII. Nature of the adsorbed species in Claisen-Schmidt reaction

The nature of the adsorbed species in the synthesis ofo-hydroxychalcones by Claisen-Schmidt reaction catalyzed by C-200 is analyzed by IR. The presence of the adsorbed carbanion fromo-hydroxyacetophenone in the surface of the catalyst is proved. The aldehyde molecule is adsorbed too. The mechanism of the surface reaction is discussed.

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- -, C-200, -. - . . .

     

V2O5/TiO2 oxidation catalysts, IV. Adsorption of acrolein on sodium-containing systems

Adsorption of acrolein on vanadia/titania catalysts fits a polymerization kinetics if Na–V compounds are not present or the vanadium content is lower than that corresponding to formation of a monolayer of vanadia on the titania support.

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, Na–V .

     

Basic condensation of triphenylsilane. II. Kinetics in anhydrous isopropanol and influence of silanol

Condensation of triphenylsilane with isopropanol in presence of isopropoxide has been studied in anhydrous medium and the activation parameters have been measured. Dehydration of the medium has been obtained by means of a pre-reaction of triphenylsilane with the residual water in the solvent. In this medium the reaction is extremely slow, moreover, it is inhibited by silanol whose effect would lower the actual catalyst concentration.

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. . , .

     

Thermal decomposition of the solvent-extracted chloro complexes of vanadium(IV) with trioctylamine and trioctylmethylammonium chloride

The complexes (R₃NHVO(OH)Cl₂)₂ and (R₃RNVO(OH)Cl₂)₂ prepared by drying in vacuo the organic solutions from the extraction into benzene of aqueous vanadyl chloride solution with trioctylamine (TOA, R₃N) and trioctylmethylammonium chloride (TOMAC, R₃RNCl), were studied by thermogravimetry and differential thermal analysis under an atmosphere of nitrogen, and the products of their thermal decomposition, such as volatile matter and residues, by gas chromatography. X-ray diffraction and infrared spectroscopy. It was found that the complexes with TOA and TOMAC thermally decompose to V₂O₃ at 200–300° by cracking of the compounds R₃NHVO(OH)Cl₂ and R₃RNVO(OH)Cl₂ formed via dissociation of the complexes at about 150°.

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Zusammenfassung Die Komplexe (R₃NHVO(OH)Cl₂)₂ und (R₃RNVO(OH)Cl₂)₂ wurden hergestellt, indem benzolische und wässrige Vanadylchlorid-Lösungen mit Trioctylamin (TOA, R₃N) und Trioctylmethylammoniumchlorid (TOMAC, R₃RNCl) extrahiert und die erhaltenen Lösungen im Vakuum eingedampft wurden. Die Komplexen wurden in Stickstoffatmosphäre mittels TG und DTA untersucht und die thermischen Zersetzungsprodukte, und zwar sowohl die flüchtigen Verbindungen als auch die Rückstände, gaschromatographisch bzw. röntgendiffraktometrisch und IR-spektroskopisch bestimmt. Es wurde festgestellt, daß die Komplexe mit TOA und TOMAC bei 150° in die Verbindungen R₃NHVO(OH)Cl₂ und R₃RNVO(OH)Cl₂ dissoziieren, die bei 200–300° thermisch zu V₂O₃ zersetzt werden.

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(R₃NHVO(OH)Cl₂)₂ (R₃RNVO(OH)Cl₂)₂ (R₃,) ( , R₃RNCl). , , . , 200–300° V₂₃ R₃NV()l₂ R₃RNVO(OH)Cl₂, 150°.

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We wish to thank the Koei Chemical Co. Ltd. for samples of TOA and TOMAC.     

Decomposition of dimethyl sulfide in the presence of Al2O3, and catalyst deactivation

The catalytic decomposition of dimethyl sulfide has been studied over the temperature range of 400–500 °C. The main reaction products are methylmercaptane, H₂S and methane. Catalyst deactivation is due to its coking during the reaction. The possibility of oxidative catalyst regeneration at 550 °C has been shown.

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400–500°C. , . , . 550°C.

     

Dependence of excitation energy on the coordination of oxygen atoms in cluster models of MgO surface

Cluster models of the MgO surface have been calculated by a semi empirical method. The energies of transitions between the surface states localized on ions of definite coordination are dependent on their coordination numbers. The lower transition energies correspond to a lower coordination number of oxygen ions.

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, . , , , . .

     

Kinetics of Ag(I) catalyzed oxidation of dioxane by peroxydisulfate

Kinetic results of Ag(I) catalyzed oxidation of dioxane by peroxydisulfate ion, followed iodometrically, are discussed. Glyoxal has been indentified as the major oxidation product. On the basis of kinetic studies and product formed a radical mechanism is proposed.

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, Ag(I), . . .

     

Reactivity of hydrocarbons on Fe?Cr?O catalysts

Generalized experimental data for deep and complete oxidation of hydrocarbons on Fe–Cr–O catalysts are presented with calculated kinetic parameters and reactivity of hydrocarbons.

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. .

     

Adaption of thermal analysis for the study of water vapour adsorption isotherms

Water vapour adsorption processes and equilibria on adsorbents with polar surfaces can be well tested with an adsorption method combined with thermal analysis. The first step involves the comparison of isothermal desorption-adsorption curves and thermal curves; in the second step different equilibrium points of the adsorption isotherms are tested by means of thermal analysis.Some examples of building materials are presented to demonstrate the possibilities of the method. The types of adsorption isotherms for the samples were formally equal in all examples; only the complex method presented was able to reveal that formation of the equilibiria was induced by essentially different processes. Such processes are: physical adsorption depending on the structure of the adsorbent and the activity of the external active centres, chemisorption, chemical reaction in the solid/vapour system and chemical reaction in the water phase condensed in the capillaries.

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Zusammenfassung Prozesse und Gleichgewichte der Wasserdampfadsorption an Adsorbenten mit polarer Oberfläche können gut mit einer mit thermischer Analyse kombinierten Adsorptionsmethode getestet werden. Der erste Schritt der Methode schließt den Vergleich der Desorptions-Adsorptionsisothermen und der thermischen Kurven in sich ein, im zweiten werden Gleichgewichtspunkte der Adsorptionsisothermen durch thermische Analyse getestet.Am Beispiel von einigen Baumaterialien werden die Möglichkeiten dieser Methode demonstriert. Die Adsorptionsisothermen waren formell in allen Fällen vom gleichen Typ und nur die vorgestellte komplexe Methode ergab, daß die Ausbildung des Gleichgewichtes durch grundsätzlich verschiedene Prozesse erfolgt. Solche Prozesse sind: von der Struktur des Adsorbenten und der Aktivität der aktiven Oberflächenzentren abhängige physikalische Adsorption Chemisorption, chemische Reaktion im Festkörper/Dampf-System und in der in Kapillaren kondensierten wässrigen Phase.

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- , . — . — . . , . : , , , — , .

     

Radiolysis of nitrous oxide adsorbed on alumina ionic mechanism of radiolysis of nitrous oxide on alumina with small surface areas

A mechanism is proposed for the radiolysis of adsorbed N₂O describing the experimental dependences of the radiation-chemical yields of O _st ^– and N₂ on N₂O coverages.

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N₂O, - O _st ^– N₂ N₂O.

     

Oxidative dehydrogenation (OXD) of n-butane I. Activity of natural quartz II. Kinetic and catalytic activity of nickel oxides

The oxidative dehydrogenation of n-butane on nickel oxide catalysts and on natural quartz, used as catalysts diluent, were studied. It is assumed that oxygen ions from the oxide lattice participate in the initial step of the reaction.

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- , . , .

     

Catalytic oxidation of monosubstituted phenols by hydrogen peroxide

Studies of kinetic peculiarities in hydroxylation of phenols by H₂O₂ in the presence of ferric sulfate have revealed general regularities of this process. A scheme of this process is suggested accounting for the stepwise conversion of Fe³⁺ into various complex forms. The reaction is suggested to take place in the coordination sphere of Fe³⁺.

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H₂O₂ . . , Fe³⁺ .

     

Kinetics of the vapor-phase oxidation of o-xylene over a vanadium oxide catalyst

(Pt–Sn)/Al₂O₃. , , , , .

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The catalytic and adsorption properties of the (Pt–Sn)/Al₂O₃ system have been studied. The results of benzene hydrogenation, cyclohexane dehydrogenation and temperature-programmed hydrogen desorption show that the introduction of tin into the Pt/Al₂O₃ catalyst significantly changes the dispersity and electronic state of supported platinum.

     

A thermogravimetric study of the solid-state reaction between alumina and strontium carbonate

The kinetics of the solid-state reaction between alumina and strontium carbonate were studied by thermogravimetry. The effects of the structure ( or) and/or doping (with Li⁺ or Cd²⁺) of the alumina on the kinetics of the reaction were examined. The results obtained were correlated with the phase composition and structural changes, followed by a number of physicochemical analyses (DTA, XRA and IRA) throughout the course of the reaction.

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Zusammenfassung Die Kinetik der Festkörperreaktion zwischen Aluminiumoxid und Strontium-carbonat wurde thermogravimetrisch untersucht. Die Effekte der Struktur ( und) und/oder des Dopens des Aluminiumoxids (mit Li⁺ oder Cd²⁺) auf die Kinetik der Reaktion wurde untersucht. Die erhaltenen Ergebnisse wurden mit der Phasenzusammensetzung und mit durch physikalisch-chemische Analysenverfahren (DTA, XRA und IRA) während des Reaktionsverlaufs verfolgten strukturellen Veränderungen in Beziehung gebracht.

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. ( ) Li⁺ Cd²⁺ . , , - .

     

Decomposition of isopropanol on V2O5 of different grain morphology and its relation to o-xylene oxidation catalysts

Decompositon of isopropanol has been studied on V₂O₅ samples of different morphology. It has been shown that the selectivity to acetone increases with the increase in the fraction of (010) plane of V₂O₅ on the sample surface, whereas the selectivity to propene decreases. The results are compared with previous data of o-xylene oxidation on the same samples and discussed in terms of the model of V₂O₅ surface [7].

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V₂O₅ . , (010) V₂O₅ , . - V₂O₅.

     

Oxidation of triethylamine by molecular oxygen catalyzed by Ru(III)-ion

The kinetics of Ru(III) catalyzed oxidation of triethylamine by molecular oxygen has been investigated in the pH range 1.5 to 2.5 at 35°C and I=0.1 M KCl. The reaction is first order with respect to substrate, catalyst and molecular oxygen concentrations. The rate of the reaction increases with the increase of pH from 1.5 to 2.5 and then there is a slight decrease in the rate above pH 2.5. Based on the kinetic data, a mechanism for the catalytic oxidation of triethylamine is proposed. The major products in the oxidation of triethylamine are the N-oxide, diethylamine and acetaldehyde.

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, Ru(III), pH=1,5+2,5 35°C I=0,1M KCl. , . pH 1,5 2,5, pH 2,5. , . N-, .