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1.
Decomposition of Mn3Mo2TeO12 during oxidation of toluene to benzaldehyde was observed. Depending on the surface composition of the initial catalyst, the decomposition leads to less active but highly selective MnMoTeO6 or to MnMoO4 which is not selective in toluene oxidation.
Mn3Mo2TeO12 . , MnMoTeO6, MnMoO6.
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2.
In the citric acid-Mn2+–H2SO4–KBrO3 system a hysteresis phenomenon in the switching on and off of the oscillations has been observed. The possible bifurcation diagrams of the system are discussed.
-Mn+2–H2SO4–KBrO3 . .
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3.
Oxidative coupling of thiophene and 2-methylfuran to the corresponding dihetaryls in DMFA medium occurs in the presence of the homogeneous catalytic system Pd(II)-molybdovanodophosphoric heteropolyacid (HPA). The data obtained show that HPA may act as a reversible oxidant in polar aprotic media.
, Pd(II)- 2- . , .
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4.
The influence of preparation of tin-molybdenum catalysts on their phase composition and activity has been elucidated. The mutual dissolution of Sn and Mo oxides leads to a considerable increase in their activities and selectivities in the partial oxidation of propylene to acetone.
. , .
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5.
Modification of the surface of Fe–Sb–O oxide catalysts by phosphorus additives increases the yield of acrylonitrile in the oxidative ammonolysis of propylene, which can be attributed to the increase of the surface concentration of weakly acidic aprotic centers, viz. Sb3+ ions.
, --Sb3+.
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6.
The pyrolysis of cyclohexyl thiol has been studied in a static system at subambient pressures in the temperature range 420–497°C. It is proposed that in the presence of a large excess of cyclohexene the mechanism is a radical non-chain process.
, , 420–497°C. , .
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7.
The influence of neodymium content on the catalytic properties of a HNaY zeolite was investigated using the cracking of n-heptane as model reaction. Neodymium zeolites were found to be more active for cracking and hydrogen transfer reactions than zeolites containing lanthanum, cerium or praseodymium.
HnaY . , , , .
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8.
It has been established that the catalytic activity of rhenium oxohalide complexes with phosphorus- or sulfur-containing ligands in hydroganation of C6–C10 olefins, nitrobenzene and p-nitrotoluene is primarily determined by the original ligand to rhenium ion bond. Chain length of olefins does not affect their hydrogenation rate.
- C6–C10, - - . .
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9.
    
Oxygen adsorption with an exposure of 1.33×103 Pa·s has been established to increase the reliability of metal dispersity measurements on -Al2O3. The rise in the stoichiometry of the interaction of the adsorbate with the supported Pd is due to the increased sorbability of -Al2O3 modified by two-dimensional metal clusters.
1.33×103 Pa·s -Al2O3. , .
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10.
The effect of the activation conditions of Pt/Al2O3 catalysts has been investigated in the hydrogenation of benzene and in the hydrogenolysis of ethane. Whatever the conditions of calcination or reduction, specific activities of all catalysts for benzene hydrogenation remain constant. On the other hand, for identical dispersities, the cacination in a wet argon flow increases the specific activity of platinum for hydrogenolysis of ethane, pointing out the role of wet pretreatment on defect building or on the faceting of supported metallic catalysts.
Pt/Al2O3 . , . , , . .
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11.
The thermal decomposition of ferrous sulphate heptahydrate was carried out in air under dynamic and isothermal conditions. The intermediate phases were identified by chemical analysis and an X-ray technique. Ferrous sulphate heptahydrate is converted to tetrahydrate and monohydrate, but this conversion is accompanied by oxidation. Fe(OH)SO4 and Fe2O(SO4)2 are formed as oxidation products, and the latter decomposes to ferric oxide directly and/or through Fe2(SO4)3.
Zusammenfassung Die thermische Zersetzung von Eisen(II)sulfat Heptahydrat wurde in Luft unter dynamischen und isothermen Bedingungen durchgeführt. Die Intermediärphasen wurden durch chemische Analyse und Röntgentechnik identifiziert. Eisen(II)sulfat Heptahydrat wird in Tetrahydrat und Monohydrat überführt, doch wird diese Umwandlung durch eine Oxidation begleitet. Fe(OH)SO4 und Fe2O(SO4)2 werden als Oxidationsprodukte gebildet und letzteres wird unmittelbar und/oder über Fe2(SO4)3 zu Eisen(III)oxid zersetzt.

Résumé La décomposition thermique dans l'air du sulfate de fer(II) heptahydraté a été étudiée en conditions dynamiques et isothermes. Les phases intermédiaires ont été identifiées par analyse chimique et par rayons X. Le sulfate de fer(II) heptahydraté se transforme en tétrahydrate et en monohydrate mais cette conversion s'accompagne d'une oxydation. Il se forme Fe(OH)SO4 et Fe2O(SO4)2 comme produits d'oxydation et ce dernier se décompose en oxyde de fer(III) directement ou quelquefois avec formation intermédiaire de Fe2(SO4)3.

(II) . . (II) . Fe(OH)SO4 Fe2O(SO4)2. (III) Fe2(SO4)3.


The authors express their grateful thanks to Prof. P. K. Jena, Director, for his keen interest and permission to publish the paper, and to Dr. A. Lakshminarayana for the X-ray measurements. One of us (MSRS) also thanks the Regional Research Laboratory (CSIR) for a fellowship.  相似文献   

12.
Zusammenfassung Die Differentialthermoanalyse eignet sich zur Bestimmung der thermischen Stabilität der in Formmassen angewandten montmorillonitischen Bindestoffe. Mit der DTA-Methode können die bei hohen Temperaturen in diesen Bindestoffen auftretenden strukturellen Änderungen bestimmt werden. Waschöl erhöht die Dehydratisierungs- und Dehydroxylierungstemperatur des montmorillonitischen Bindestoffes. In der Folge steigert also die Suszeptibilität des Obigen zur Hydratation und auch die thermische Stabilität.
The hitherto presented results of researches of DTA of montmorillonite binding agent, applied in the moulding sand for foundry practice. With the aid of this method the temperature of dehydratation and dehydroxylation of binding agent with the addition and without of wash oil have been defined.As a result of our investigations it has been found that the same oil rises the appearance of these effects.With the aid of DTA these has also been defined structural changes occurring in montmorillonite binding agent, subjected to the activity of high temperature.

, . . , . , , .
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13.
Chromium catalysts were prepared on monolith supports, some of them with radioactive Cr-51 in the surface. The dehydrogenation-hydrogenation reaction of cyclohexene was used to compare the catalytic activities of the radioactive and inactive catalysts. Differences were observed in the distribution of the main products at low temperatures and of the byproducts also at high temperatures.
, Cr-51. - . , — , .
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14.
Reaction mechanism for selective oxidation of organic compounds at C–H bonds is discussed. The criteria of selecting catalysts for these reactions have been formulated; 1) fast heterolytic activation of C–H bonds; 2) relatively slow primary activation of oxygen; 3) fast diffusion of oxygen vacancies; 4) fast electron transfer from the adsorbed substrate to catalyst.
C–H . : 1) C–H ; 2) ; 3) ; 4) .
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15.
Hydrogen adsorption on chromia supported Pd, Rh and Pt was studied under various pretreatment conditions. The reduction temperature influences strongly the hydrogen uptake for all these metals. Platinum supported on chromia shows an unusually high hydrogen adsorption stoichiometry.
Pd, Rh Pt, Cr2O3, . , . Cr2O3 .
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16.
The influence of the Na2O/Al2O3 mole ratio in sodium aluminate, the pH and the temperature of precipitation upon physicochemical properties of pseudoboehmite obtained from sodium aluminate has been studied. A mole ratio of 11 and low pH are favorable for the preparation of pure alumina.
Na2O/Al2O3 , pH , . , Na2 O/Al2O3=1 , pH, .
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17.
Platinum-tin/alumina supported catalysts have been studied. The TPR results show an assisted reduction of tin by platinum. The effect of alloying in cyclohexane dehydrogenation, o-xylene hydrogenation and cyclopentane hydrogenolysis is discussed.
- , . . , - .
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18.
General forms of the kinetic equations for the conversion of various hydrocarbons in reforming of multicomponent gasoline fractions on platinum/alumina catalysts have been confirmed experimentally by using a gradientless method.
.
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19.
Hydrogenation of benzene on Rh/nylon produced cyclohexene with a high selectivity. The influence of contact time, pretreatment of catalyst and rhodium salt precursors have been studied. Samples prepared from Rh(III) were found more selective than catalysts obtained from Rh(I). It is suggested that electron deficient metal sites are responsible for cycloolefin formation.
Rh/ . , . , Rh(III) , , Rh(I). , .
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20.
Résumé Les équilibres solide liquide vapeur du système binaire CoCl2-H2O sont étudiés dans le domaine de température 120–720. La pression de la solution saturée est mesurée entre 1 et 60 atm. et le diagramme de phases est établi.Deux composés intermédiaires: CoCl2 · 2H2O et CoCl2 · H2O sont observés; ils subissent une décomposition péritectique à 206 et 335.Un tri et un tétrahydrate n'ont pas été obtenus malgré une étude systématique faisant intervenir des mesures d'analyse thermique, de thermogravimétrie et d'ébulliométrie.L'enthalpie et l'entropie de fusion du chlorure de cobalt sont évaluées à partir de la pente de la courbe de liquidus.Les valeurs calculées de l'enthalpie de déshydration de CoCl2 · 2H2O et CoCl2 · H2O entre 1 et 60 bars sont respectivement de 17 et 16 Kcal. mole–1.
Solid liquid vapor equilibria of the binary system CoCl2-H2O are investigated in the temperature range 120–720. The pressure of saturated solutions is measured between 1 and 60 atm, and the phase-diagram is established.Two intermediate compounds, CoCl2 · 2H2O and CoCl2 · H2O, are observed; they undergo peritectic decomposition at 206 and 335.Tri- and tetrahydrate have not been detected in spite of systematic research involving thermal analysis, thermogravimetry and ebulliometry.The enthalpy and entropy of fusion of cobalt chloride are calculated from the slope of the liquidus curve.The calculated enthalpy of dehydration values of CoCl2 · 2H2O and CoCl2 · H2O between 1 and 60 atm are 17 and 16 Kcal · mole–1, respectively.

Zusammenfassung Die Gleichgewichte Festkörper Flüssigkeit Dampf des binären Systems CoCl2-H2O wurden im Temperaturbereich von 120 bis 720C untersucht. Der Druck der gesättigten Lösung wurde zwischen 1 und 60 Atm. gemessen und das Phasendiagramm aufgenommen.Zwei Intermediärverbindungen: CoCl2 · 2H2O und CoCl2 · H2O wurden beobachtet; diese zersetzen sich bei 206 und 335 peritektisch.Ein Tri- und ein Tetrahydrat wurden trotz systematischer Untersuchungen mittels thermoanalytischer, thermogravimetrischer und ebulliometrischer Messung nicht gefunden.Die Enthalpie und Entropie der Kobaltchloridschmelze wurden aus der Steigung der Liquiduskurve ermittelt.Die errechneten Werte der Dehydratierungsenthalpie betrugen für CoCl2 · 2H 2 O und CoCl2 · H2O zwischen 1 und 60 bar 17 bzw. 16 Kcal2 mol–1.

l2-2 120–720. 1 60 . . CoCl2. 22 l2 · 2, 206 335. , , , . . l2. 22 l2. 2 1 60 ., , 17 16 . –1.
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