Formation of oxalates and carbonates in the thermal decompositions of alkali metal formates

The influences of gaseous and solid reactants on the yields of oxalates and carbonates in the thermal decompositions of alkali metal formates have been studied. A mechanism of formation of these products is proposed, which explains the influences of basic and acidic species formed in the medium on the thermal decompositions of the alkali metal formates.

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Zusammenfassung Der einfluß von gasförmigen und festen Reaktanten auf die Ausbeute von oxalaten und Karbonaten bei der thermischen Zersetzung von Alkalimetallformiaten wurde untersucht. Es wurde ein Mechanismus für die Bildung dieser Produkte vorgeschlagen, der den Einfluß der während der thermischen Zersetzung von Alkalimetallformiaten entstehenden Basen und Säuren erklärt.

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, . , , .

     

Calorimetric studies of adsorptive properties of metallic carbides and nitrides of transition elements. Adsorption of H2, CO and O2 on titanium nitrides

Adsorption heats of hydrogen, oxygen and carbon monoxide on titanium nitrides have been measured calorimetrically in the temperature range from 473 to 673 K. With increasing Me/N ratio, the adsorption heat of oxygen grows.

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, 473–673 . Me/N.

     

Precipitation of aluminium hydroxide in the presence of surfactant and its effect on the surface acidity

Surface acidity of aluminas prepared by precipitation from sodium aluminate solutions and nitric acid with and without surfactant were determined by IR spectroscopy. It was found that the amounts of aprotic acidic sites increase with increasing pH of precipitation and with increasing concentration of surfactant used in the course of precipitation and washing of the precipitate.

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, -. , -, .

     

Thermogravimetric and kinetic study of a clodronic acid complex formed with sodium

Thermal stability of the clodronic acid complex formed with sodium (Na₂CCl₂(HPO₃)₂ ·4H₂O) was studied using both dynamic and isothermal thermogravimetric analyses as well as mass spectra. The thermal decomposition has two stages: dehydration and loss of two molecules of hydrogen chloride. Using the isothermal TG data the first step was found to be a phase-boundary reaction while the second step obviously cannot be described with just one reaction mechanism. The final residue of the dynamic TG analyses above 810 K was found to be sodium metaphosphate.

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Zusammenfassung Sowohl mittels dynamischer und thermogravimetrischer Untersuchungen als auch and Hand von Massenspektren wurde die thermische Stabilität des mit Natrium gebildeten Säurekomplexes Na₂CCl₂(HPO₃)₂·4H₂O untersucht. Die thermische Zersetzung vollzieht sich in zwei Schritten: Dehydratation und Verlust von zwei Molekülen HCl. Auf Grund der isothermen TG Angaben ist der erste Schritt eine Phasengrenzreaktion, während der zweite Schritt mit einem einzigen Reaktionsmechanismus nicht eindeutig beschrieben werden kann. Das Endprodukt der DTG Analyse oberhalb 810 K erwies sich als Natriummethaphosphat.

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-Na₂CCl₂/HPO_3/2·4H₂O — , - . , , , . , , . 810 .

     

A new procedure for determination of the acid and base strength distribution of colored catalysts

A new procedure for determining the strength distribution of acid and base centers of colored catalysts by the indicator method has been proposed. The procedure basing on the use of a platinum gauze container for the colored catalyst enables us to eliminate the difficulties in the identification of the color of the indicator.

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. , , , .

     

The use of a continuous-flow helium cryostat in low-temperature calorimetry

For experimental investigation of the temperature-dependences of specific heat and thermal conductivity in the range 4–300 K a continuous-flow helium cryostat has been developed. Its adaptation for low-temperature calorimetry and its use for measurement of the temperature-dependences of the specific heats of bulk samples of metals and insulators are described in this note. The phase transition from the normal to the superconductive state has been measured on NbTi and its critical temperature determined. Two methods of determination of the temperature-dependences of the specific heats of metals and insulators have been developed. The inaccuracy of specific heat determination did not exceed 2 % with metal materials and 5 % with insulating materials.

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Zusammenfassung Ein Heliumkryostat mit kontinuierlichem Strom wurde für Versuchszwecke zur Untersuchung der Temperaturabhängigkeit der spezifischen Wärme und der Wärmeleitfähigkeit im Bereich von 4 bis 300 K entwickelt. Sein Einsatz als Tieftemperaturkalorimeter sowie seine Anwendung zur Messung der Temperaturabhängigkeit der spezifischen Wärme einer Anzahl von Metall- und Isoliermaterialproben werden beschrieben. Der Phasenübergang vom normalen in den Supraleitungszustand wurde an NbTi gemessen und seine kritische Temperatur bestimmt. Zwei Methoden wurden zur Bestimmung der Temperaturabhängigkeit der spezifischen Wärme von Metallen und Isolatoren entwickelt. Die Ungenauigkeit der Bestimmungen der spezifischen Wärme war unterhalb von 2 % bei metallischen und unterhalb von 5 % bei isolierenden Materialien.

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Résumé Un cryostat à circulation continue d'hélium, destiné à la détermination expérimentale de la chaleur spécifique et de la conductivité thermique en fonction de la température entre 4 et 300 K, a été mis au point. Son utilisation comme calorimètre à basses températures est décrite ainsi que son application à la mesure de la chaleur spécifique en fonction de la température d'échantillons massifs de métaux et isolants. La transition de phase de l'état normal à l'état supraconducteur a été étudiée sur un échantillon de NbTi et la température critique a été déterminée. Deux méthodes ont été mises au point pour déterminer la variation de la chaleur spécifique en fonction de la température des métaux et isolants. L'imprécision de la détermination de la chaleur spécifique est inférieure à 2 % pour les métaux et 5 % pour les isolants.

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4–300 . ë . NbTi . . 2%, 5%.

     

Interaction of oxygen with preadsorbed hydrogen on magnesium oxide studied by temperature-Programmed desorption method

The interaction of oxygen with preadsorbed hydrogen on thermally activated magnesium oxide has been studied by temperature-programmed desorption (TPD) method. It was found that oxygen at 450 K reacts with preadsorbed hydrogen and the resulting hydroxylation suppresses the adsorptive capacity of magnesia with respect to oxygen.

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. , 450 K , .

     

TEM and XPS studies of Ni/WS2 catalysts for thiophene hydrogenolysis

Differences in the structure of WS₂ samples with S_BET=7.6 and 75 m²/g are manifested in decreasing lengths of basal faces of some small crystallites in the more dispersed WS₂. This effect increases the relative fraction of lateral faces on the catalyst surface. Ni ions in the Ni/WS₂ catalysts are in an electrondeficient state compared to NiS.

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WS₂ 7,6 ²/qg 75 ²/ WS₂. Ni Ni/WS₂ ( NiS) .

     

Modification of preparation technique for highly dispersed Ni/γ?Al2O3 catalysts

Highly dispersed Ni/–Al₂O₃ catalysts have been prepared by the method of double impregnation. The application of ethylenediaminetetraacetic acid (H₄Y) as a chelating agent for activation of the -Al₂O₃ support enables us to prepare highly dispersed Ni/Al₂O₃ catalysts. The use of this chelating agent according to the described modification of the impregnation technique results in the highest dispersity of the metal component in the catalysts obtained.

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Ni/-Al₂O₃ . (H₄Y) -Al₂O₃ Ni/Al₂O₃ . , .

     

Utilization of the affine transformation of thermoanalytical curves for the determination of kinetic parameters

A method is suggested for the affine transformation of thermoanalytical curves, by means of which their comparison with one another becomes feasible. It is demonstrated that the results obtained by the traditional methods of non-isothermal kinetics depend on the heating rate, whereas the results attained by affine transformation are independent of the heating rate. They are consistent with the results obtained by Merzhanov's dmethod, which is also a non-aprioristic method.

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Zusammenfassung Eine Methode zur Affintransformierung thermoanalytischer Kurven wird vorgeschlagen, wodurch ihr Vergleich miteinandere rmöglicht wird. Es wird gezeigt, daß die durch traditionelle Methoden der nicht-isothermen Kinetik erhaltenen Ergebnisse von der Aufheizgeschwindigkeit abhängig sind, während die durch Affintransformierung erhaltenen von der Aufheizgeschwindigkeit unabhängig sind. Sie sind in Übereinstimmung mit den nach der Methode von Merzhanov erhaltenen Ergebnissen, die ebenfalls eine nicht-aprioristische Methode ist.

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Résumé On propose une méthode pour la transformation affine des courbes d'analyse thermique, qui permet leur comparaison. On montre que les résultats obtenus par les méthodes traditionnelles de cinétique non-isotherme dépendent de la vitesse du chauffage, tandis que les résultats obtenus par la transformation affine n'en dépendent pas. Ils sont en accord avec les résultats de la méthode de Merzhanov.

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, . , , , , , , . , , .

     

Correlation between acid strength (Ho) and ammonia desorption temperature for aluminas and silica-aluminas

Correlation between the temperature at which a base is desorbed and the acid strength (H_o) of the sites set free by it, was looked for. Ammonia was employed as base. A linear correlation of the type H_o=+/T (K) is valid with and constants, dependent on the adsorbate and the adsorbent.

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(H_o) , . H_o=+/T (K), .

     

ESR studies of N2O interaction with photoinduced centers on ZnO and MgO

According to the analysis of the formation of O^– anion radicals stabilized on the surface of oxides, it has been shown that on ZnO, only O _s ^– hole centers are formed, whereas in the presence of N₂O molecules, besidese the above centers, MgO surface contains O _ads ^– electron centers.

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- O^–, . , ZnO O _s ^– , MgO N₂O O _s ^– O ^– .

     

Potentiometric titration of sorbed hydrogen on palladium carrier catalysts

A method of determination of adsorbed and absorbed hydrogen on palladium catalysts with carbon carriers is suggested and verified. The method allows H_ad and H_ab to be determined with an accuracy of about 10% using catalysts containing at least 5% Pd.

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- . . . 10% , , - , 5% Pd.

     

Investigation of surface phenomena on solid catalysts by thermogravimetry

Thermogravimetry was applied to the investigation of the phenomena of adsorption, chemisorption, desorption and surface reactions on solid catalysts. The measurements were carried out with 13 NaX and NaY type zeolites and with silica gels treated with sodium hydroxide, in the presence of cumene and methanol. On the basis of the quantitative results it is possible to give an interpretation of surface phenomena and to establish the existence of various active centres on the surface of the catalysts.

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Zusammenfassung Adsorptions-, Chemisorptions- und Desorptionserscheinungen, sowie Oberflächenreaktionen an festen Katalysatoren wurden thermogravimetrisch untersucht. Die Messungen wurden an Zeoliten der Typen 13 NaX und NaY und an mit Natriumhydroxid behandelten Silikagelen in Gegenwart von Cumol und Methanol durchgeführt. Aufgrund der quantitativen Ergebnisse war es möglich, die Oberflächenerscheinungen zu deuten und das Vorhandensein von verschiedenen aktiven Zentren an der Katalysatoroberfläche nachzuweisen.

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Résumé On a appliqué la méthode thermogravimétrique à l'étude des phénomènes d'adsorption, de chemisorption et de désorption ainsi qu'aux réactions de surface sur des catalyseurs solides. Les mesures ont été effectuées sur zéolites de type 13 NaX et NaY et sur des silicagels traités par la soude en présence de cumène et de méthanol. Des résultats quantitatifs permettent de donner une interprétation des phénomènes de surface et d'établir l'existence de divers centres actifs à la surface des catalyseurs.

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, , , . , , , , . 13 NaX NaY , . .

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The authors express their gratitude to Prof. S. Malinowski for help and discussion and to Mr. W. Dziklinski for his technical help.     

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-(-) . , .

     

Catalytic properties and phase composition of multicomponent catalysts for oxidative ammonolysis of propane

Studies of the phase composition and catalytic properties of several complex oxide catalysts for oxidative ammonolysis of propane indicate that the active phases of these catalysts are antimonates of the respective metals. Phosphorus and tungsten additives to the catalysts promote the formation of such phase compositions, i.e. the formation of antimonates and the binding of excess antimony oxide.

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. , ; , .

     

Ba(OH)2 as catalyst in organic reactions, part XIV. Michael addition catalyzed by barium complex salts in the homogeneous phase

Michael addition to chalcone is catalyzed by barium complex salts in the homogeneous phase under various conditions. The nature of these intermediates is analyzed. These complex salts are described for the first time. The Michael adduct of malonodinitrile to chalcone is described for the first time.

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, , . . . . .

     

Tracing of peroxy radicals in hexane cool flames

Stabilized hexane-air cool flames in a separately heated two-section reactor have been studied at T=480–770 K and P=30–63 kPa. ESR spectra of peroxy radicals were analyzed by the radical freezing technique and sonde sampling. Under these conditions high radical concentrations (>10¹⁴ cm^–3) are observed. With increasing pressure and temperature, the fraction of HO₂ radicals in the overall amount of radicals grows.

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480–770 , 30–63 . . , (>10¹⁴cm^–3). , HO₂ .