Acidity modification by thermal and steam treatment in silica-alumina and its relation with methanol to hydrocarbons reaction

The physical properties as well as the acidity of an amorphous silica-alumina were modified by steam and thermal treatments and a general correlation (including samples modified by other methods) between hydrocarbon formation and surface acidity was obtained.

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, . ( , ) .

     

Structural changes of NaX zeolite during the H2S+O2 reaction

Infrared spectra in the 600, 700, and 1000 cm^–1 regions and X-ray investigations indicate that during H₂S+O₂ reaction in the temperature region of 293–473 K partial dealumination of the NaX zeolite crystal structure occurs. The dealumination increases with reaction temperature.

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- 600, 700 7000 ^–1 , H₂S+O₂ 293–473 NaX. .

     

A rapid method for catalyst activity measurements by combination of pulse reactor, mass spectrometer and process computer

The combination of a pulse reactor attached directly (without a separation column) to a mass spectrometer/process computer system is described. To obtain a conversion/temperature diagram for the dehydration and dehydrogenation of 2-butanol less than one hour is required. Therefore, the method can be used for rapid characterization or comparison of the activities of various samples.

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, ( ) - . / 2- . .

     

Activation of magnesia by hydrogen spillover

Magnesia aerogel activated by hydrogen spillover at 430 °C or at 200 °C becomes a catalyst for the hydrogenation of ethylene. This catalytic activity, observed already at 50 °C, is further enhanced by a treatment in oxygen at 430 °C.

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, 430 200°C, . 50°C 430°C.

     

Discrimination of active sites for ethylene homologation and ethylene metathesis on molybdena silica catalyst

Active sites for ethylene homologation (3C₂H₄2C₃H₆) and ethylene metathesis (C₂H₄–¹²C₂+C₂H₄–¹³C₂2C₂H₄–¹³C₁) were discriminated by adding platinum to a reduced molybdena silica catalyst, and the former was presumed to be composed of several molybdenum species, while the latter was presumed to be composed of one molybdenum species.

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(3C₂H₄2C₃H₆) (C₂H₄–¹²C₂+C₂H₄–¹³C₂2C₂H₄–¹³C₁) . , , .

     

Sintering of supported palladium

Sintering results of Pd supported on carbon black at 723–973 K, in water vapor, in H₂ and under high vacuum are reported. They are compared with sintering data of Pd on other supports. The observed sequences are: SiO₂C>sepioliteAl₂O₃>AlPO₄ and H₂O>high vacuum>H₂.

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Pd 723–973 , , H₂ . Pd . : SiO₂Al₂O₃>AlPO₄ H₂O> >H₂.

     

Comparison of DSC and optical transmission measurements of polymorphic transitions

Using optical measurements on single crystals, the speed of first order transitions (K₂Cr207, KNO₃, AgNO₃) was determined and compared with the strongly smeared DSC signals. Such optical measurements are proposed to select materials which are suitable for the determination of the DSC apparatus function.

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Zusammenfassung Mit Hilfe von optischen Messungen wird die Geschwindigkeit von polymorphen Phasenumwandlungen 1. Ordnung (K₂Cr₂O₇, KNO₃, AgNO₃) bestimmt und mit entsprechenden stark verschmierten DSC-Signalen verglichen. Derartige optische Messungen erscheinen geeignet, um Substanzen zu suchen, welche für die Bestimmung der DSC-Apparatefunktion geeignet sind.

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K₂Cr₂O₇, KNO₃ AgNO₃ $ , $ . , $ .

     

On the dioximine complexes of transition metals

Twelve new complexes NH₄[Co(DH)₂(SO₃)(amine)]·t H₂O (DH ₂=dimethylglyoxime) have been synthesized and characterized. Their i.r. spectra show the SO₃ to be co-ordinated to the Co atom through the S atom. The thermal decompositions of a series of derivatives of this type have been investigated with a derivatograph. The first process is an endothermic dehydration reaction, occurring in a single stage or in two successive ones. The loss of the crystallization water is followed by another endothermic reaction, without a clear stoichiometry, which is referred to as deamination. At higher temperatures, exothermic pyrolysis processes occur. From the TG curves, kinetic parameters have been derived for the dehydration and deamination reactions.

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Zusammenfassung Zwölf neue Komplexe der allgemeinen Formel NH₄[Co(DH)₂(SO₃)(amin)]·t H₂O (DH=Dimethylglyoxim) wurden synthetisiert und charakterisiert. Die IR-Spektren zeigen, daß SO₃ über das S-Atom koordinativ an das Co-Atom gebunden ist. Die thermische Zersetzung einer Reihe von Derivaten dieses Typs wurde mittels eines Derivatographen untersucht. Der erste Prozeß ist die in einem einzigen oder in zwei aufeinander folgenden Schritten verlaufende endotherme Dehydratisierung. Auf die Abgabe des Kristallwassers folgt eine andere endotherme Reaktion unklarer Stöchiometrie, die als Deaminierung bezeichnet wird. Bei höheren Temperaturen verlaufen exotherme Pyrolyseprozesse. Aus den TG-Kurven wurden kinetische Parameter für die Dehydratisierung und die Deaminierung bestimmt.

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NH₄Co(DH)₂(SO₃)(a)]·tH₂O, DH ₂ — . , . . , . «». . .

     

Effect of magnetic order on the conductivity in Co-Zn ferrites

A series of samples in the system Co_1–xZn_xFe₂O₄ (x=0.3, 0.4, 0.6, 0.8 and 1) were prepared by the usual ceramic technique. The D. C. electrical resistivity and thermoelectric power were measured in the temperature range from room temperature up to about 600 K. Transition from the ferrimagnetic region to the paramagnetic region is accompanied by an increase in the activation energy by an amountE, which varies in the range 0.052–0.090 eV. The large values ofE obtained may be due to the fairly strong B-B exchange interaction in Co-Zn ferrites.

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Zusammenfassung Mittels üblicher Keramiktechniken wurden Proben des Systemes Co₁–xZn_xFe₂O₄ unterschiedlicher Zusammensetzung (x=0,3, 0,4, 0,6, 0,8, 1,0) dargestellt. Im Temperaturbereich Raumtemperatur-600 K wurde der elektrische Widerstand gegenüber Gleichstrom sowie die Thermospannung dieser Proben ermittelt. Der Übergang von der ferrimagnetischen zur paramagnetischen Region wird von einem Anwachsen der Aktivierungsenergie um den BetragE=0,052–0,090 eV begleitet. Den so erhaltenen grossen E-Werten liegen wahrscheinlich die ziemlich starken B-B Austausch Wechselwirkungen in Co-Zn Ferriten zu Grunde.

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_1–xZn_xFe₂₄ =0,3;0,4;0,6;0,8 1, 600 . E, 0,052–0,090 . E - - .

     

Study of the adsorption properties of a natural Hungarian mordenite and its ion-exchanged derivatives

The texture and adsorption properties of a natural, Hungarian mordenite were investigated by electron microscopy and BET adsorption measurements. The properties of the ion-exchanged adsorbents were characterized by CO₂ and SO₂ isotherms. The measurements were evaluated on the basis of the pore-filling theory of Dubinin. We have found that at 20°C the H⁺-form of mordenite interacts preferably with CO₂, while on the Na⁺- and Ca²⁺-derivatives stronger adsorption of SO₂ takes place. This fact accounts for their applicability as selective adsorbents.

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, . CO₂ SO₂. . , 20°C H⁺- CO₂, Na⁺- Ca²⁺- SO₂ . .

     

Effect of oxygen on the catalytic reduction of nitric oxides by carbon monoxide over NiO

The catalytic reduction of nitrogen oxides (NO, N₂O and NO₂) by carbon monoxide over NiO has been studied in the temperature range from 200 to 500°C. The reaction of NO₂ with CO is much faster than that of NO with CO. The former reaction in the presence of a 3–4-fold excess of oxygen proceeds at a significant rate. In the temperature range studied, NO₂ decomposes to N₂ and O₂.

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200–500°C (NO, N₂O NO₂) NiO. NO₂ CO NO CO. NO₂ CO 3–4- . NO₂ N₂ O₂.

     

The investigation of thermally treated glasses of controlled porosity by means of differential thermal analysis

Some of the materials used as chromatography packings, adsorbents or catalyst supports are glasses of controlled porosity (CPGs). The chemical structure of these materials can easily be changed by heating the porous glass. Such thermal modification leads to the enrichment of the CPG surface in boron atoms. The long exposure of CPGs to thermal treatment can even cause the formation of borate crystals in the pores of the glasses. This paper considers the application of thermal analysis to the investigation of porous glasses heated for different periods of time.

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Zusammenfassung Einige der als chromatographische Säulenpackungen, Adsorbenten oder Katalysatorträger verwendeten Materialien sind Gläser mit definierter Porosität (CPGs). Die chemische Struktur dieser Materialien kann leicht durch Erhitzen verändert werden. Eine solche thermische Modifizierung führt zu einer Anreicherung von Bor in der Oberflächenschicht. Eine langdauernde Erhitzung der CPGs kann sogar zur Bildung von Boratkristallen in den Poren der Gläser führen. Im vorliegenden Artikel wird die Anwendung der thermischen Analyse zur Untersuchung von porösen Gläsern in Abhängigkeit von der Erhitzungsdauer behandelt.

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, , , . . . . , .

     

Thermal analysis of thermosetting resins

Applications of thermoanalytical methods for the study of the resinification and curing of phenolic resins are reviewed. Examples are given to illustrate the use of DSC for practical industrial systems such as paper impregnants and saturated papers.

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Zusammenfassung Es wird eine Übersicht über die Anwendungen thermoanalytischer Methoden zur Untersuchung der Harzbildung und der Aushrtung von phenolischen Harzen gegeben. Anhand von Beispielen wird die Verwendung der DSC für praktische industrielle Systeme wie Papierfüllstoffe und gefüllte Papiere aufgezeigt.

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, . , .

     

On premelting of theC-form of stearic acid

Some evidence is given for the presence of a solid phase just below the melting point of stearic acid. It is not certain whether the existence of this new phase is due to impurities or not.

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Zusammenfassung Einige Beweise zur Gegenwart einer Festphase knapp unterhalb des Schmelzpunktes der StearinsÄure werden gegeben. Es ist nicht geklÄrt ob das Vorhandensein dieser neuen Phase auf Verunreinigungen zurückzuführen ist oder nicht.

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Résumé On donne plusieurs preuves de la présence d'une phase solide juste au-dessous du point de fusion de l'acide stéarique. Il n'est pas certain que l'existence de cette phase nouvelle soit due à des impuretés ou non.

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. , .

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I wish to express my sincere thanks to the following people: Dr. J. A. Morrison for kindly sending the sample and helpful discussion, Dr. D. Dolphin for making the LKB 8700 calorimeter available to me, Dr. L. G. Harrison for allowing the use of his facilities, and Mr. B. Greene, Mr. J. Edwards and Mr. B. Powell for their excellent technical assistances in modifying the apparatus. The financial support from the University of British Columbia is also acknowledged.     

Non-empirical calculations for the probable coordinative binding of electron donor molecules by [AlO4] tetrahedra

Interaction of H₂O, NH₃ and C₅H₅N molecules with the aluminium atom of [AlO₄] tetrahedra has been calculated by the non-empirical SCF-MO LCAO method using an STO-3G basis set. The effect of Al–O bond lengths and O–Al–O angles on the calculated characteristics of chemisorbed complexes is discussed.

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, TO-3C , [AlO₄]. Al–O O–Al–O .

     

Study of selective dissociation in C6F5H?C6F5D mixtures induced by intense CO2 laser pulses

Irradiation of a C₆F₅H–C₆F₅D mixture at 1 Torr by a tunable CO₂ pulse laser brings about chiefly dissociation of one component depending on the frequency of emission absorbed by the proper molecules. The addition of radical acceptors increases the selectivity by suppressing secondary reactions.

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C₆F₅H C₆F₅D 1 CO₂-, , . .

     

Preparation of catalysts by spray decomposition

Spray decomposition of solutions is an uncommon but very promising technique for the preparation of multicomponent solid systems with welldefined structure. The experimental arrangement is described and a summary of the systems prepared until now is given. These are MgO–ZnO, CaO, CdO, Al₂O₃. Fe₂O₃ solid solutions and CdO. CdSO₄ and Al₂O₃. Al₂(SO₄)₃ systems.

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, , . : MgO·ZnO, CaO·CdO,. Al₂O₃·Fe₂O₃ CdO·CdSO₄ Al₂O₃·Al₂ (SO₄)₃.

     

Thermal effects on glass As2Se3·As2Te3

The DTA trace of the chalcogenide glass As₂Se₃·As₂Te₃ shows a single glass transition at 142 °C, a single crystallization exotherm depending on the heating rate, and two melting endotherms, at 290 °C and 312 °C. The X-ray diffraction for a crystallized sample indicates the presence of two solid solution phases: Te in As₂Se₃ (rich in Se) and Se in As₂Te₃ (rich in Te), confirming that the single crystallization peak of the initially homogeneous phase (singleT _g ) represents two coincident peaks superimposed. The crystallization of the glass phase is also clearly manifested in the time-dependence of the electrical conductivity and microphotography.

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Zusammenfassung Die DTA-Kurve von chalcogenidem Glas As₂Se₃·As₂Te₃ läßt eine Glastransformation bei 142 °C, eine von der Aufheizgeschwindigkeit abhängige exotherme Kristallisation und zwei endotherme Schmelzvorgänge bei 290 und 312 °C erkennen. Röntgendiffraktometrie der kristallisierten Probe zeigt das Vorliegen von zwei Phasen fester Lösungen:Te in As₂Se₃ (reich an Se) und Se in As₂Te₃ (reich an Te). Das steht in Übereinstimmung damit, daß der Kristallisationspeak der ursprünglich homogenen Phase (einT _g -Wert) zwei sich überlagernde Peaks repräsentiert. Die Kristallisation der Glasphase ist klar an der Zeitabhängigkeit der elektrischen Leitfähigkeit und durch Mikrophotographie zu erkennen.

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As₂Se₃·As₂Te₃ 142 °, 290 312 dg. : As₂Se₃ ( ) Se As₂Te₃ ( ), , ( _g ), . .

     

Ethylene oxidation by lithium nitrate in the presence of palladium acetate in acetic acid

Data are reported on variations of the gas phase volume and product accumulation in ethylene oxidation by lithium nitrate in acetic acid solutions, catalyzed by palladium acetate. An assumption is made on the routes of nitrate ion reduction.

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