Thermal stability of alkali metal bifluorides

The thermal stability and non-isothermal kinetics of the decomposition of alkali metal bifluorides were studied using a derivatograph. The removal of hydrogen fluoride from LiF · HF and NaF · HF takes place before melting and their decomposition occurs in a single stage; however, potassium, rubidium and cesium bifluorides at first undergo polymorphous transformation and melting on heating, and their decomposition proceeds stepwise. The thermal stability of alkali metal bifluorides has been found to increase with increasing ionic radius of the cation, reflecting its correlation with the hydrogen bond strength in these compounds.

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Zusammenfassung Es wurde die thermische Stabilität und die nichtisotherme Kinetik der Zersetzung der Alkalibifluoride thermogravimetrisch untersucht. HF entweicht aus LiF · HF und NaF · HF vor dem Schmelzen in einer Stufe. Bei den entsprechenden Salzen des Kaliums, Rubidiums und Cäsiums erfolgt zuerst eine polymorphe Umwandlung, danach das Schmelzen, wobei die Zersetzung in mehreren Stufen vor sich geht. Die thermische Stabilität der Verbindungen wächst mit zunehmenden Ionenradien, was auf die entsprechende Stärke der Wasserstoffbindung zurückgeführt werden kann.

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Résumé Etude thermogravimétrique de la stabilité thermique de fluorhydrates de métaux alcalins et de la cinétique de leur décomposition en conditions non isothermes. Dans le cas de LiF · HF et de NaF · HF, le départ de l'acide fluorhydrique se produit avant la fusion et la décomposition s'effectue en une seule étape. Par contre, les fluorhydrates de potassium, rubidium et césium subissent une transition cristalline et une fusion avant de se décomposer. On observe que la stabilité thermique des fluorhydrates de métaux alcalins augmente avec le rayon ionique du cation et l'on montre qu'elle peut être reliée à la force de la liaison hydrogène dans ces composés.

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. LiF · HF NaF · HF , , , . , , .

     

NMR studies of complex formation between H2PtCl4 and SnCl2 in organic solvents

Complex formation of H₂PtCl₄ with SnCl₂ in isopropanol and isopropanol-acetone solutions with the molar ratio [Sn]: [Pt]=1.0 has been studied by using¹⁹⁵Pt and¹¹⁹Sn NMR method.

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¹⁹⁵Pt ¹¹⁹Sn H₂PtCl₄ co SnCl₂ - Sn:Pt=1,0.

     

Catalytic ammoxidation of coal

Ammoxidation of coal on oxide catalyts has shown the possibility of hydrocyanic acid formation at sufficiently low temperatures.

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. .

     

Reaction routes for hydrogenation of acetylene-ethylene mixtures using a double labelling method

Hydrogenation of C₂H₂:C₂H₄ mixtures using a double labelling method has been studied. Both in the presence and absence of ethylene the rate of acetylene hydrogenation on its partial pressure proceeds through a maximum and the rate is higher when ethylene is added. Using¹⁴C–C₂H₂ it was demonstrated that at low acetylene partial pressures the main route of acetylene hydrogenation was the formation of ethane and C₄ hydrocarbons. Using¹⁴C–C₂H₄ it was also shown that at certain acetylene partial pressures the formation of ethane from ethylene completely ceased. Different surface species are suggested and a reaction mechanism is proposed.

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C₂H₂:C₂H₄, . , , . C¹⁴–C₂H₂, , C₄. C¹⁴–C₂H₄, , . .

     

Microcalorimetric investigation of the recrystallization behaviour of polycrystalline copper deformed at room-temperature

The recrystallization of 5 N copper samples which had been deformed at roomtemperature by torsion to an average shear of by rolling to 65% r.c.s. was investigated by means of a commercial heatflow calorimeter.During recrystallization, which was also studied by hardness tests and optical microscopy, a stored energy release of the order of 0.145 cal/g was observed. Some problems inherent in the use of microsamples are discussed. By kinetic analysis, based on variation of the linear heating rate, a value of 21.9 kcal mole^–1 was determined for the apparent activation energy of the recrystallization process in torsion samples.

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Zusammenfassung Die Rekristallisation von 5 N Kupferproben, die bei Raumtemperatur durch Torsion bzw. durch Walzen (65%) verformt worden waren, wurde mit einem kommerziellen Wärmeströmungskalorimeter untersucht. Bei der Rekristallisation, die ebenfalls mit Härtemessungen und Gefügeuntersuchungen verfolgt wurde, wird eine Energiefreigabe von etwa 0.145 cal/g beobachtet. Einige bei der Verwendung von Microproben auftretende Probleme werden diskutiert. Eine Analyse der Kinetik, die auf der Variation der linearen Aufheizgeschwindigkeit basiert, ergab für die scheinbare Aktivierungsenergie des Rekristallisationprozesses in Torsionsproben einen Wert von 21.9 Kcal Mol^–1.

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Résumé On a étudié à l'aide d'un calorimètre à flux de chaleur commercial la recristallisation d'échantillons de cuivre 5 N, préalablement déformés à température ambiante par torsion ou par laminage (65%).Lors de la recristallisation, également suivie par mesures de dureté et examens de structure, on observe un dégagement d'énergie d'environ 0,145 cal/g. Les problèmes qui surgissent lors de l'utilisation de prélèvements micro sont discutés. L'énergie d'activation apparente du processus de recristallisation après l'écrouissage par torsion s'élève à 21.9 kcal mol^–1.

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5H , , , 65% . . . , , 0.145 /. , . , , , 21.9 ^–1.

     

Mechanism of RuIV-catalyzed oxidation of alkanes in aqueous solutions

The Ru^IV-catalyzed oxidation of alkanes in aqueous solutions includes activation of the oxidant Ox (Cr^VI, HNO₃, HClO₄, etc.) via Ox–Ru^IV complex formation and is accompanied by H atom abstraction from the alkane by the activated oxidant.

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Ru^IV - Ox (Cr^IV, HNO₃, HClO₄ .) Ox–Ru^IV - .

     

Hydrogen adsorption on chromia-supported iridium catalyst

Effect of thermal pretreatment of chromia-supported iridium catalyst on hydrogen adsorption was studied. It was found that the hydrogen uptake by Ir/Cr₂O₃ was highly dependent on the reduction temperature. The catalyst proved to be resistant to sintering in oxygen atmosphere at temperatures up to 700 °C and it showed symptoms of redispersion even at 650 °C.

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. Ir/Cr₂O₃ . 700°C, , 650°C .

     

Violation of steady state process in CO hydrogenation to alcohols

Studies of the effect of iron supported on the surface of a K₂CO₃-doped zinc-chromium catalyst or entrapped from synthesis gas, have revealed violation of the steady state process in alcohol synthesis. Periodic oscillations in temperature and concentrations of reactants and reaction products are observed.

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, K₂CO₃ - -, , , , .

     

Effect of orbital-rotational coupling on the rate of ion-dipole capture at extremely low temperatures

The rate of the ion-dipole capture at very low temperatures or energies has been examined using the Statistical Adiabatic Channel model.

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- .

     

Iodide-promoted uncatalyzed bromate oscillators

Iodide ions—in a rather narrow concentration range—induce some of the uncatalyzed bromate oscillators to a more pronounced oscillatory activity: the number of oscillations increases considerably and the overall rate of the chemical reaction drops about an order of magnitude. Preliminary suggestion is made on the mechanism of iodide-induced oscillatory reactions.

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— — : . - .

     

Mechanism of catalysis and factors responsible for oxide catalyst activity in deep oxidation reactions

A general scheme for the deep oxidation mechanism on oxide catalysts including stepwise and concerted mechanisms as well as their mutual transformations is suggested. The principal factor responsible for the activity in the concerted mechanism region is the rate of oxygen binding. For the stepwise mechanism the main factor is the rate of catalyst interaction with oxidizable reactant.

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, . , . .

     

Investigation of catalytic purification of gases from aromatic hydrocarbons

1,1- (AH) ([AH]=6,9 /, 50°C). AH W_i/W_{O 3}=0,40±0,16.

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The kinetics and oxidation products of 1,1-diethoxyethane (AH) ozonolysis have been investigated at [AH]=6.9 mol/l and 50 °C. The initiation efficiency of radical oxidation by ozone is W_i/W_{O 3}=0.40±0.16.

     

Catalysis of thiophene hydrogenolysis by bimetallic sulfide catalysts of different compositions

The activity of sulfide catalysts M_I/SiO₂, M_I/WS₂, (M_I,W)/SiO₂ and (Ni,M_II)/SiO₂ (M_I is a first row transition metal, and M_II=Nb, Mo, W or Re) in the thiophene hydrogenolysis reaction has been studied. Activities of mono- and bimetallic catalysts are found to change in the same manner depending upon the nature of M_I. The formation of a sulfide bimetallic species (SBMS) is suggested.

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M_I/SiO₂, M_I/WS₂, (M_I,W)/SiO₂ (Ni, M_II)/SiO₂, M_I — , M_II–Nb, Mo, W, Re. - M_I. .

     

Dependence of the rate of methane oxidation on the surface area of the catalysts

Specific rate of methane conversion into C₂-hydrocarbons and deep oxidation products in its interaction with O₂ or N₂O decreases with growing surface area of catalysts that are metal-like compounds of transition elements. This regularity is interpreted in terms of a heterogeneous-homogeneous mechanism.

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C₂ ( CH₄ O₂ N₂O) - . , - .

     

Studies of decomposition kinetics for ozone complexes with cumene and chlorobenzene

Kinetic regularities in decomposition of complexes of aromatic compounds with O₃ have been studied for ozone complexes with cumene and chlorobenzene. Oxidation effect of these complexes on both aromatic compounds and olefins has been established.

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O₃. .

     

Calculation of the energy spectrum of surface oxygen on CuO by the interacting bonds method

Using the interacting bonds model a calculation has been made for the energy spectrum of oxygen on the CuO surface. Dissociative adsorption of oxygen can be realized in one and two-center forms with 9.2 and 60.4 kcal/mol, respectively. Intermediate values of the adsorption heats are attributed to oxygen adsorption on induced and biographic defects. The theoretically calculated energy spectrum of adsorbed oxygen is in reasonable agreement with that obtained experimentally from the dependence of isosteric heats of oxygen adsorption on the surface coverage.

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CuO. - 9,2 60,4 / . . .

     

Comparative testing of the flammability of upholstery textiles

Flash ignition temperatures of upholstery textiles were measured with a modified derivatograph, and the TG, DTG, DTA and T curves were also recorded. The results obtained with the newly-developed system were compared with those of the ASTM D 1929 test procedure and with the simultaneously recorded thermal analysis curves.

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Zusammenfassung Der Flammpunkt von Upholstery-Textilien wurde mittels eines modifizierten Derivatographen gemessen. TG-, DTG-, DTA- und T-Kurven wurden registriert. Die mit diesem neuentwickelten System erhaltenen Ergebnisse wurden mit den nach dem ASTM D 1929 Testverfahren erhaltenen und mit den simultan registrierten thermoanalytischen Kurven verglichen.

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, -, -, - -. , ASTM 1929 .

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Paper presented at the World Conference on Thermal Analysis, Madeira (Portugal), 1986.     

Structure and reactivity of vanadium(V) complexes formed in the reaction between vanadyl acetylacetonate and alkyl hydroperoxides. To the mechanism of selective epoxidation of olefins

Vanadium(V) complexes formed in the reaction between vanadyl acetylacetonate and alkylhydroperoxides are characterized according to their¹H and⁵¹V NMR spectra and the reactivity of these complexes towards cyclohexene is studied.

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¹H ⁵¹V , .

     

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), .

     

Monooxygenase activity of immobilized iron(III) porphyrins

New silica-immobilized iron(III) porphyrin systems possessing monooxygenase activity in aniline oxidation to p-aminophenol, have been found. The catalytic activity depends on both the porphyrin structure and coordination by an axial ligand. The maximum activity in this reaction is observed for imidazol-coordinated hemin. The hydroxylation in the above system is shown to follow a non-radical mechanism.

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— , -. , , . , . , .

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This term refers to catalysis with the formation of monooxygenated products using dioxygen oxidants