Kinetic dehydroxylation of nontronite,estimated from isothermal and nonisothermal thermogravimetry

Dehydroxylation of an American nontronite (Manito) was followed via records of isothermal and dynamic thermogravimetry. Analysis of the isothermal weight-change curves (673-753 K). was performed with the procedure suggested by Hancock and Sharp. A fourteen-kinetic equation procedure was employed for analysis of the non-isothermal weight change in the range 623–1023 K. (A second-order decomposition equation seems to fit the dehydroxylation better under these conditions). The activation energies associated with the isothermal and nonisothermal processes are 118.8 and 136.8 kJ/mol^–1, respectively.

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Zusammenfassung Anhand isothermer und herkömmlicher Thermogravimetrie wurde die Dehydroxylierung eines amerikanischen Nontronites (Manito) verfolgt. Die isothermen TG-Kurven (673–753 K) wurden mittels der von Hancock und Sharp (1972). Ein kinetisches Vierzehngleichungsverfahren wurde zur Analyse der nichtisothermen TG-Kurven im Bereich 623–1023 K angestellt. Einer Dehydroxylierung unter diesen Bedingungen scheint eine Zersetzungsgleichung zweiter Ordnung besser zu entsprechen. Die Aktivierungsenefgie für die isothermen bzw. nichtisothermen Prozesse beträgt 118,8 bzw. 136,8 kJ/mol.

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(). (673–753 ) . , 623–1023, . . , , 118,8 136,8 /.

     

Role of the V=O double bond in the selective oxidation of benzene on V2O5 and V2O5?MoO3 catalysts

Infrared spectra of both fresh and reductively activated V₂O₅ and V₂O₅–MoO₃ catalysts were recorded and compared with the results of catalytic measurements. The results indicate that the presence of V=O double bonds in the catalytically active mass is not essential for the selective oxidation of benzene to maleic anhydride.

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, V₂O₅ V₂O₅–MoO₃. . , V=O .

     

Calorimetric studies of aluminosilicate catalysts. Heats and entropy of benzene adsorption on monosubstituted alkaline earth (Mg, Ca, Sr, Ba) metakaolinites at small surface coverages

Differential heats of benzene adsorption at 293 K on Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺ metakaolinites at surface coverages of =0.2 have been measured in a Calvet microcalorimeter. An inverse dependence of benzene and cuene adsorption heats on monocationic metakaolinites has been revealed. The presence of two types of adsorption centers is predicted.

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293 Mg²⁺-, Ca²⁺-, Sr²⁺-, Ba²⁺- 0,2. . .

     

Kinetics of solid polypropylene oxidation inhibited by aromatic nitrons

C-phenylcarbamoyl-N-phenylnitron and C(2,4-di-tert-butyl-3-hydroxyphenylcarbamoyl)-N-(p-di-methylaminophenyl) nitron inhibit the oxidation of solid polypropylene. In this case the nitrons studied demonstrate properties of polyfunctional inhibitors: they interrupt oxidation chains by chains by reactions with alkyl and peroxyl radicals.

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C--N- C-(2,4----3-)-N-(-) . , .

     

Infrared studies of CO2(CO)8 adsorption on zeolites Y

Co₂(CO)₈ sublimed onto the surface of HY, CeY, CoY and two dealuminated forms of NaY zeolite is converted at room temperature to Co₄(CO)₁₂ and other surfacebound cobalt carbonyl species. The reaction proceeds in a different way on each of the above zeolites, depending also on their pretreatment.

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Co₂(CO)₈, HY, CeY, CoY NaY, Co₄(CO)₁₂ - . - .

     

Catalytic hydrogenation of carbon monoxide on RuFe/SiO2 catalysts

The H₂+CO reaction on silica supported Ru, Fe and RuFe catalysts prepared from metal carbonyl clusters has been investigated under atmospheric and 20 bar pressure. According to the change of selectivity values with temperature and with pressure, the participation of surface carbon proposed earlier by several authors seems to be confirmed by this work.

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H₂+CO Ru, Fe RuFe, , 20 . , , , .

     

Kinetic studies of thiolane synthesis from tetrahydrofurane and H2S

Kinetic studies of tetrahydrofuran reaction with H₂S were carried out in a flow-circulation reactor. Presumably, the reaction takes place through dissociative chemisorption of reactants and the interaction of surface structures formed to produce thiolane and water. A kinetic equation that agrees with the suggested mechanism has been derived.

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- H₂S. , . , .

     

Thermal decompositions of some transition metal polyacrylates

Polyacrylales of Fe, Cr, Ni, Co and Mn were synthesized by the reaction of poly(sodium)acrylatc with metal halides. The salts obtained were investigated by thermal analysis. During heating in argon or air, all the salts behaved in a similar way. The initial decomposition temperature of the investigated salts increased in the following sequence: Fe<Cr<Ni<Co<Mn. The solid residues of the decompositions of the salts were also analysed.

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Zusammenfassung Polyacrylate von Fe, Cr, Ni, Co und Mn wurden durch Reaktion von Natriumpolyacrylat mit den entsprechenden Metallhaliden synthetisiert. Die erhaltenen Salze wurden thermoanalytisch untersucht. Beim Aufheizen in Argon und Luft verhalten sich alle Salze ähnlich. Die Temperatur, bei der die Zersetzung einsetzt, steigt in folgender Reihenfolge an: Fe < Cr < Ni < Co < Mn. Die festen Rückstände der Zersetzung der Salze wurden ebenfalls analysiert.

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, , , . , , . Fe<Cr<Ni<Co<Mn. .

     

Marcelin-de Donder kinetics near equilibrium

A linear approximation for the Marcelin-de Donder kinetics (MC) near the point of detailed equilibrium (p.d.e./is studied. In particular it is shown that in the invariant plane the p.d.e. is stable knot.

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- (MD) (...). , , ... — .

     

The reaction between nitrous oxide and carbon monoxide over magnesium oxide

The title reaction was carried out with the help of the transient response method over MgO. It was concluded that no catalyst reduction occurred over this catalyst and the reaction proceeded through the reaction between adsorbed nitrous oxide and adsorbed carbon monoxide without participation of MgO oxygen.

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MgO. , - MgO.