Mechanism of alkyl iodide reduction to alkanes in aqueous solutions of Na2PtCl4?NaI?HClO4

Platinum(II) catalyzes the reduction of alkyl iodides to alkanes according to a mechanism involving oxidative addition of RI to Pt(II), reduction of the product complex RPt(IV) to RPt(II) by iodide ions and protolysis of the latter particle.

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(II) , RI Pt^II, - RPt^IV RPt^II .

     

Effect of composition of the solvent on the selectivity of competitive hydrogenation of 2-methyl-3-butene-2-ol and 1-hexene

The selectivity of competitive hydrogenation of 2-methyl-3-butene-2-ol and 1-hexene on 5% Pt on silica gel catalyst at 20°C and atmospheric pressure was investigated, and the effect of changes in the composition of the solvent on the selectivity of hydrogenation was examined. Three solvent systems have been used: methanol-water, 1-heptanol-cyclohexane and ethanol-cyclohexane mixtures. The causes underlying changes in the selectivity of hydrogenation with changing composition of the solvent are discussed.

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2--3--2- 1- 5% Pt 20°C . . 1- . .

     

Kinetics of methane conversion over microspherically grained nickel-alumina catalysts

Kinetics of methane conversion in a fluidized bed of microspherically grained nickel-alumina catalyst has been studied at pressures from 0.3 to 3.1 MPa. The rate equation shows that the reaction is inhibited by H₂O.

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0,3 3,1 . , .

     

Combination and disproportionation of methyl and 2-propyl radicals with 1,1,2-trimethylallyl radicals

The combinations and disproportionations of the CH₃ and 2-propyl (iP) radicals with the 1,1,2-trimethylallyl (TMA) radical have been studied in the gas phase in the temperature interval of 389–451 K and 490–540 K, respectively. For the ratios of the terminal (t) and non-terminal (n) combinations of the CH₃ and iP radicals with the TMA radical, values of 1.9±0.1 and 2.84±±0.10 were obtained, respectively. The ratios of the tt and tn and nn to tn combinations of the TMA radical were 1.59 and 0.46, respectively. The disproportionation-combination rations were (CH₃ , TMA)=0.022±±0.012 and (iP, TMA)=0.026±0.011.

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CH ₃ 2- (iP) 1,1,2- (TMA) : 389–451 K 490–540 K. (t) (n) TMA 1,9±0,1 2,84±0,10, . tt tn nn tn TMA 1,59 0,46, . (CH ₃ , TMA)=0,022±0,012 (iP, TMA)=0,026±0,011.

     

Evaluation of quantum yields in the presence of an absorbing additive

A method is proposed for the evaluation of quantum yields of photochemical reactions studied in the presence of absorbing additives using cylindrical sample tubes.

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.

     

IR and thermal studies on lithium oxomolybdenum(VI) oxalate

A new molybdenum(VI) complex, Li₂[Mo₂O₆(C₂O₄)] · 2 H₂O (LMO), was prepared and characterized by chemical analysis and IR spectral studies. Its thermal decomposition was studied by using TG and DTA techniques. LMO loses its two moles of water between 75 and 170° to give the anhydrous product, which decomposes in three stages between 240 and 380°. The first two stages occur in the temperature ranges 240–280° and 280–305°, to give intermediates with the tentative compositions Li₆[Mo₆O₁₉(C₂O₄)₂] and Li₆[Mo₆O₂₀(C₂O₄)], respectively. In the third stage, which extends up to 380°, Li₆[Mo₆O₂₀(C₂O₄)] decomposes to give the end-product, Li₂Mo₂O₇.

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Zusammenfassung Ein neuer Molybdän(VI)-Komplex der Formel Li₂[Mo₂O₆(C₂O₄)] · 2 H₂O (LMO) wurde dargestellt und durch chemische Analyse und IR-spektroskopisch charakterisiert. Die thermische Zersetzung dieses Komplexes wurde mittels TG und DTA untersucht. LMO verliert die zwei Wassermoleküle zwischen 75 und 170° unter Bildung des wasserfreien Produktes, das zwischen 240 und 380° in drei Stufen zersetzt wird. Die in den Temperaturbereich von 240–280° und 280–305° verlaufenden ersten zwei Reaktionsschritte ergeben Intermediäre der tentativen Zusammensetzung Li₆[Mo₆O₁₉(C₂O₄)₂] bzw. Li₆[Mo₆O₂₀(C₂O₄)]. In dem sich bis 380° erstreckenden dritten Reaktionsschritt wird Li₆[Mo₆O₂₀(C₂O₄)] unter Bildung des Endproduktes Li₂Mo₂O₇ zersetzt.

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Li₂[MO₂O₆(C₂O₄] · 2 ₂ . . - 70–170° , , 240–380°. 240–280° 280–305° - Li₆[Mo₆O₁₉(C₂O₄)₂] Li₆[Mo₆O₂₀(C₂O₄)]. - 380° Li₂Mo₂O₇.

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The authors are grateful to Prof. S. N. Tandon, Head of the Chemistry Department, for providing the research facilities.     

Steady conduction of heat in prolate spheroidal systems

The steady local temperature distribution has been determined for arbitrary prolate spheroidal systems with various boundary conditions. The temperature was derived for all possible systems, such as when the temperature was kept constant on the hyperbolic surfaces and variable on the prolate spheroidal surfaces, and vice versa. In'the latter case, roots with respect to the degree of the associated Legendre function for arguments larger than unity had to be determined. Some of the presented solutions have been evaluated numerically, and the isothermal surfaces have been presented.

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Zusammenfassung Für beliebig ausgedehnte sphäroide Systeme wurde mit verschiedenen Randbedingungen eine stationäre lokale Temperaturverteilung ermittelt. Die Temperatur wurde für alle möglichen Fälle ermittelt, so auch für den Fall, in dem die Temperatur an der Hyperbeloberfläche konstant gehalten und an den ausgedehnten sphäroiden Flächen veränderlich ist bzw. umgekehrt. Für letzteren Fall mußten für Argumente größer als eins Wurzeln betreffs des Grades der zugehörigen Legendre Funktion ermittelt werden. Einige der dargestellten Lösungen wurden numerisch ermittelt und die isothermen Flächen dargestellt.

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. , . , . .

     

Thermal investigation of the phase composition of poly(ethylene terephthalate). Analysis of different methods of determination of the degree of crystallinity of partially crystalline substances

The literature data on the degree of crystallinity of non-deformed poly(ethylene terephthalate) measured at various temperatures have been subjected to comparative analysis. There is no correlation between the results obtained by the different methods. The reason for this is shown to be the imperfections in the methods of determining the degree of crystallinity, which do not provide the true composition of the crystalline phase. Consideration has been paid to the validity of the main principles involved in the thermal method of determining the degree of crystallinity, so as to eliminate the imperfections in the existing methods and to provide the correct value of the mass of the crystalline phase. The phase composition of PET has been analyzed by the thermal method at different temperatures and conditions of crystallization. A marked difference from the literature data is observed in the range of low temperatures.

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Zusammenfassung Eine vergleichende Analyse der Literaturangaben bezüglich des bei verschiedenen Temperaturen gemessenen Kristallisationsgrades von nicht-deformiertem Poly(äthylen-terephthalat) wurde durchgeführt. Zwischen den mit verschiedenen Methoden erhaltenen Ergebnissen besteht keine Korrelation. Es wurde gezeigt, daß der Grund hierfür in der Unvollkommenheit der Methoden zur Bestimmung des Kristallisationsgrades liegt, da diese nicht die wahre Zusammensetzung der Kristallinen Phase angeben. Die Gültigkeit der wichtigsten Prinzipien, welche die thermische Bestimmung des Kristallisationsgrades unter Ausschaltung der Unvollkommenheit der bestehenden Methoden gewährleisten und den richtigen Wert der Masse der kristallinen Phase angeben, wurden in Erwägung gezogen. Die Analyse der Phasenzusammensetzung von PET wurde durch die thermische Methode bei verschiedenen Temperaturen und Kristallisationsbedingungen durchgeführt. Ein deutlicher Unterschied zu den Literaturangaben kann im Bereich der niedrigen Temperaturen beobachtet werden.

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51V NMR studies of systems V2O5-KHSO4 and V2O5?K2SO4

Systems V₂O₅–KHSO₄ and V₂O₅–K₂SO₄ have been studied by the⁵¹V NMR method. The first system demonstrates the same states of vanadium as the previously studied V₂O₅–K₂S₂O₇, in this system a compound with an equimolar ratio of components has been found. In V₂O₅–K₂SO₄ the state of vanadium differs from the above systems and the formation of a compound with V/K=4 is observed.

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⁵¹V KHSO₄–V₂O₅ K₂SO₄–V₂O₅. , K₂S₂O₇–V₂O₅, . K₂SO₄–V₂O₅ V/K4.

     

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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