IR study of 1-hexene isomerization on HZSM-5 zeolites

In the IR spectra of 1-hexene adsorbed on HZSM-5 zeolites with different Si/Al ratios, a new band at 1510 cm^–1 has been observed. The cis/trans-2-hexene and trans-2-hexene/1-hexene ratios were determined.

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1-, HZSM-5 Si/Al, 1510 cm^–1. /-2- -2-/1-.

     

Reactivity of the carbonaceous surface overlayer on supported platinum catalysts studied by high temperature pyrolysis gas chromatography

The reactivity of the carbonaceous surface overlayer formed on Pt/Al₂O₃ catalysts in n-hexane dehydrocyclization has been studied by high temperature Pyrolysis Gas Chromatography. This method can be used to characterize surface carbon overlayers formed on different catalysts in the course of hydrocarbon reactions.

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, Pt/Al₂O₃ -, . , .

     

Non-catalyzed oscillation reaction in the aniline-KBrO3?H2SO4 system. II. Reaction products and their oscillating behavior

By means of thin-layer and gas chromatography the reaction products have been determined in the oscillation system of aniline, KBrO₃ and H₂SO₄. These products include: 2-bromoaniline, 4-bromoaniline, 2,4-dibromoaniline, 2,4,6-tribromoaniline, 1,4-benzoquinone, 2-bromo-1,4-benzoquinone, 2,6-dibromo-1,4-benzoquinone and a brominated oxidation product. The brominated aniline derivatives do not exhibit an oscillating behavior, and the addition of these substances to an oscillating mixture damps the course of other oscillations.

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, KBrO₃ H₂SO₄. : 2-, 4-, 2,4-, 2,4,6-, 1,4-, 2--1,4-, 2,6--1,4- . , , , .

     

Temperature-programmed desorption of hydrogen from Rh/C catalysts

A strong temperature-activated character of hydrogen adsorption on the surface of Rh/C catalyst has been found, especially in relation to high-temperature form. The unreactivity of this form toward oxygen at room temperature suggests that its source is the carbon surface.

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- Rh/C, . .

     

Differential scanning calorimetry study of reactions of phenyl glycidyl ether with phosphoric acid

The reactions of phenyl glycidyl ether (PGE) with phosphoric acid in three molar ratios have been studied by means of DSC alone. The results obtained from isothermal measurements are as follows:H=–91.0 kJ/mole PGE(1:1 molar ratio);H=–100.5 kj/mole PGE (1:2/3 molar ratio).The DSC curves obtained from dynamic experiments are multipeaked and giveHvalues higher than those obtained from isothermal measurements. These results can be explained by taking into account the acid concentration, the different reactivities of the hydrogens of the phosphoric acid and the possibility that secondary reactions occur.

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Zusammenfassung Die Reaktion von Phenylglycidyläther (PGE) mit Phosphorsäure wurde bei drei verschiedenen molaren Verhältnissen allein mittels DSC untersucht. Isotherme Messungen ergaben folgende Werte:H=–91.0kJ/mol PGE (molares Verhältnis 1:1);H=–100.5 kJ/mol PGE (molares Verhältnis 3:2). Die bei dynamischen Experimenten erhaltenen DSC-Kurven weisen viele Peaks auf und ergebenH-Werte, die größer als die durch isotherme Messungen erhaltenen sind. Diese Ergebnisse können erklärt werden, wenn die Säurekonzentration, die unterschiedliche Reaktivität der Wasserstoffatome der Phosphorsäure und die Möglichkeit des Verlaufs sekundärer Reaktionen in Rechnung gestellt werden.

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() () . 11 12/3, H, –91.0 –100.5 ·^–1. , , H . , , .

     

Shape-selective ester hydrolysis by octadecyl immobilized H-ZSM-5 catalyst in liquid phase

The shape-selective property of octadecyltrichlorosilane treated H-ZSM-5, keeping the original acid strength (–5.6<Ho–3.0) in liquid phase in the hydrolysis of straight chain esters has been observed by comparing the reaction rates with those over octadecyltrichlorosilane treated SiO₂-Al₂O₃. The most pronounced effect was found in the case of ethyl decanoate, viz. ca. 6 times.

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H-ZSM-5, (–5.6<–3.0) , - . SiO₂–Al₂O₃, . , 6.

     

Thermal desorption analysis:

Experiments on water desorption from silicate glass powders of different chemical compositions were carried out by means of DSC. In order to establish the desorption energy distributions, a model of the heterogeneous surface was applied to the thermoanalytical desorption curves, and the results are discussed together with contact angle measurements on flat polished glass samples.The maxima in the desorption curves shift to lower temperature with increasing hydrophobic character; this is caused by divalent cations such as Pb²⁺, Ca²⁺ and Zn²⁺, while alkali metal ions are responsible for an increase in the hydrophilic behaviour.

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Zusammenfassung Wasserdesorptionsexperimente an Silikatglaspulvern unterschiedlicher Zusammensetzung wurden mittels DSC ausgeführt. Für die Berechnung von Desorptionsenergieverteilungen wurde ein Modell der heterogenen Oberfläche genutzt und zusammen mit Randwinkelmessungen an glatten, polierten Glasoberflächen diskutiert. Das Maximum der Desorptionskurven verschiebt sich mit wachsendem hydrophoben Verhalten nach tieferen Temperaturen, wofür divalente Kationen wie Pb²⁺ Ca²⁺ Zn²⁺ verantwortlich sind, während Alkaliionen das hydrophile Verhalten begünstigen.

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. . , , , .

     

Thermal analysis of phenolic resin based pyropolymers

The formation and thermal behaviour of pyropolymers based on novolak resin synthesized under carefully controlled processing conditions have been studied by various thermoanalytical techniques. A suitable reaction scheme has been proposed for the formation of these pyropolymers. Only a small (3–8%) weight loss has been observed up to 800 °C in static air. DTA curves confirmed multistage exothermic processes predominantly due to two different linkages which control their thermo/thermo-oxidative stability. Hot metal filtration (700 °C) in an inert atmosphere exhibited only negligible weight loss.

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Zusammenfassung Mittels verschiedener thermoanalytischer Verfahren wurde Bildung und thermisches Verhalten von Pyropolymeren auf Novolackbasis unter streng geregelten Reaktionsbedingungen untersucht. Zur Bildung dieser Pyropolymere wurde ein geeignetes Reaktionsschema entwickelt. In unbewegter Luftatmosphäre kann bis 800 °C nur ein geringer (3–8%) Gewichtsverluft beobachtet werden. Die DTA-Kurven zeigen einen exothermen Mehrstufenprozeß, der hauptsächlich auf zwei verschiedene Verkettungen zurückzuführen ist, welche die thermische/thermisch-oxidative Stabilität bestimmen.

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. . 800° (3–8%) . , , / - . (700° .

     

ESR studies of benzene interaction with the surface of Mo?Ti oxide catalysts

It has been established that in benzene interaction with Mo–Ti oxide catalysts stabilization of Mo⁵⁺ ions in the form of (MoO)³⁺ takes place due to formation of oxidized form of benzene, which leads to one-electron reduction of surface ions.

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Mo⁵⁺ (MoO)³⁺ Mo–Ti , , .

     

Role of transition metals during p-xylene oxidation in aqueous system

The role of transition metals in the mechanism of p-xylene oxidation has been studied in aqueous systems at 140°C and 1.0 MPa of oxygen. The reaction proceeds according to second-order kinetics in p-xylene concentration for all metals and of <0.5 order with respect to metal concentration. For the metals studied the apparent activation energies are almost the same. The results support our previous assumption that (i) the rate-determining propagation step of p-xylene oxidation in aqueous systems does not involve metal ions, (ii) direct oxidation of p-xylene by higher valent metals does not play any significant role.

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- 140°C 1,0 . - , 0,5 . . , , 1. , - , ; 2. - - .

     

TPD studies of hydrogen sorption on platinum powder catalysts modified with adsorbed gold

It has been shown that hydrogen determined from the TPD curves of platinum saturated with hydrogen sorbed above room temperature is chiefly absorbed and not adsorbed hydrogen; this absorbed hydrogen has no effect on the charging curve.

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, , , , ; .

     

Reaction specificity in catalysts reported to exhibit strong metal-support interactions

The specific activities of a 10% Ni/TiO₂ and a 10% Ni/SiO₂ catalyst for the hydrogenolysis of n-hexane and for the methanation reaction have been investigated. Both catalysts have very similar activities and selectivities for hydrogenolysis. However, the titania-supported catalyst exhibits a considerably greater specific activity for methanation. It is concluded that this enhancement of activity is reaction specific, and we propose a mechanism involving the adsorption of CO onto the surface of titania.

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10% Ni/TiO₂ 10% Ni/SiO₂ - . . , TiO₂ . , . , CO .

     

Characterization of active species in alumina and silica supported CuCl2 catalysts by EPR

In a recent paper [1] we proposed that a Cu²⁺ species interacting with the support was responsible for maintaining the catalytic activity of CuCl₂ catalysts used in the methane oxyhydrochlorination reaction (CH₄+HCl+O₂ chloromethanes). This species was detected on Al₂O₃ and TiO₂ supports but it did not appear on SiO₂. In this paper we report EPR results which provide a direct characterization of this species and correlate well with the observed trends in activity.

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[1] , Cu²⁺, , CuCl₂, (CH₄+HCl+O₂ ). Al₂O₃ TiO₂, SiO₂. , .

     

Thermal decomposition of alkylcyclohexane mixtures

Thermal decomposition of model alkylcyclohexane mixtures with different ratios of components has been investigated. The possibility to estimate the yield of reaction products by calculating the relative activities of a group of hydrocarbons is shown.

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. .

     

The determination of the oral form of 5-chloro-7-iodo-8-hydroxyquinoline (clioquinol)

For the routine assay of tabletted dosage forms of clioquinol, as in quality control, the reproducibility of tablet manufacture makes it possible to omit any weighing procedure. The advantages of enthalpimetry allow assay without separation of the analyte from the matrix and colorants.The method can be easily automated and gives an acceptable level of accuracy and precision.

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Zusammenfassung Für die Routineuntersuchung von Clioquinol in Tabletten, beispielsweise zur Qualitätskontrolle, ist ein Wägeverfahren infolge der Reproduzierbarkeit der Tablettenherstellung überflüssig. Die Vorteile der Enthalpimetrie erlauben ein Verfahren ohne Trennung der zu bestimmenden Verbindung von der Matrix und den farbgebenden Substanzen. Die Methode kann leicht automatisiert werden und ist ausreichend genau.

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, , . . .

     

Exchange kinetics of amino acid anions in solutions of ternary copper(II) complexes with diethylenetriamine

Rate constants for the chemical exchange of some amino acid anions in solutions of copper(II) ternary complexes with diethylenetriamine have been determined by the NMR method. The coordination of amino acid anions in ternary and binary species is different and ligand substitution in the Cu(II) complexes follows an associative mechanism.

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- (II) . - (II).

     

Hydrogenation of ethylene on gadolinium X, Y and L-type zeolites

It is shown that Gd-zeolites have a catalytic activity towards ethylene hydrogenation at 1 atm. This activity decreases with an increase in the SiO₂/Al₂O₃ ratio from 2.2 to 6.1 and 4.1, i.e. upon going from an X type zeolite to Y and L. For these types of zeolite the activity grows with an increase in Gd³⁺ content from 50 to 80%. Oxygen addition to the reaction mixture stabilizes the catalytic activity of zeolites.

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, qv 1 . , SiO₂/Al₂O₃ 2,2 6,1 4,1, .. X Y L. , 50 80%. .

     

Measurement of the rate constant of hydrogen atoms with carbon monoxide in tubular and jet stirred open reactors

The reaction of hydrogen atoms with carbon monoxide has been studied in discharge flow systems with a new method of detection of atoms. The results obtained with tubular and jet stirred open reactors agree with those of other authors working in transient conditions and with more sophisticated techniques.

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. , , , .

     

Influence of the entropy factor on the equilibrium and kinetics of chemisorption

A correction to the model of uniform heterogeneous surface has been introduced. This correction extends the limits of application to processes with entropy changes of the adsorbent. On the basis of the model thus corrected a kinetic equation has been deduced, which takes into account the role of the entropy factor. The presence of a compensation effect in chemisorption kinetics is supported theoretically.

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- , , . , . .

     

Effect of the network structure on the flammability ofcis-1,4-polyisoprene vulcanizates

The combustibilities ofcis-1,4-polyisoprene and its peroxide and sulphur vulcanizates have been investigated by means of the oxygen index method. The temperature distribution in the sample and the molecular weight of the liquid products formed as a result of elastomer destruction in the combustion zone have been measured. It has been found that the combustibility ofcis- 1,4-polyisoprene diminishes as its cross-link density increases. This effect is much stronger for sulphur than for peroxide vulcanizates. The investigations lead to the conclusion that a mechanism of network degradation and volatile sulphur compounds penetrating to the flame are responsible for this difference.

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Zusammenfassung Die Brennbarkeit des unvernetztencis-1,4-Polyisoprens und seiner Peroxid- und Schwefelvulkanisate wurde mit der Sauerstoffindexmethode untersucht. Messungen der Temperaturverteilung im Prüfling wurden ebenfalls ausgeführt und das Molekulargewicht der infolge der Zersetzung der Elastomere in der Verbrennungszone entstehenden flüssigen Produkte mit der Methode der dynamischen Osmometrie bestimmt. Es wurde festgestellt, daß die Brennbarkeit des cis-1,4-Polyisoprens mit zunehmender Vernetzungsdichte abnimmt, und zwar viel ausgeprägter im Falle der Schwefel- als im Falle der Peroxidvulkanisate. Es wurde gefolgert, daß flüchtige, in die Flamme gelangende Schwefelverbindungen als Verbrennungsinhibitoren wirken.

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-1,4- . , . , -1,4- . . , .