Displacement of metal atoms from salts by hydrogen and the role of this reaction in chain processes

The interaction of hydrogen atoms with a variety of alkali metal and alkaline-earth metal salts results not only in the recombination of these atoms but also in the displacement, into the gas phase, of free radicals (CaCl^·(A ¹ P _1/2, B ² S ⁺) and CaF^·(A ² P)) and metal atoms, including their excited species, which are detected spectroscopically. Transmission spectra indicate that the NaCl surface undergoes metallization when treated with a high-frequency discharge and a rarefied hydrogen flame. Combustion is affected by the gas-phase hydrogen atoms involved in the chain reaction and by the varying composition and properties of the surface. The concentration of Na atoms over the NaCl surface at 770 K is 10⁹?10¹¹ cm^?3 in a stream of H atoms at 1 Torr and in the 2H₂ + O₂ flame at 4 Torr. The concentration of sodium atoms in the ² P _3/2 and ² P _1/2 excited states is ～5 × 10⁶?5 × 10⁸ cm^?3. The role of the discovered reactions in combustion, pyrolysis, and plasma chemistry is discussed.     

Spectral-luminescent analysis of sugar cane juice

A spectral-luminescent analysis has been made of the low-, medium-, and high-molecular mass fractions of sugar cane juice. The presence of pigments was detected in all the fractions. The medium-molecular-mass fraction was distinguished by the most considerable and most diverse composition of the pigments, a substantial contribution to which was made by the products of the alkaline decomposition of sugars. The amounts of pigments in all the fractions of the juice depended on the age of the plant. A pronounced dependence on the age of the plant was characteristic for the medium-molecular-mass fraction.B. I. Stepanov Institute of Physics, Belorussian Academy of Sciences, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 456–459, May–June, 1993.     

NMR spectroscopy of metal cyclopentadienyls VIII. Prototropism and dimerisations of silicon cyclopentadienyls

Studies have been made of the slow dynamic processes which occur with the silicon cyclopentadienyls C₅H₅Si(CH₃)Cl₂, such as prototropic rearrangement and dimerisation. The product formed through spontaneous dimerisation has been found to consist almost entirely of the dimer of the main vinylic isomer of C₅H₅Si(CH₃)Cl₂. The dimeric structure has been proved by means of PMR spectra (100 MHz). From kinetic studies values of the rate constants at temperatures of 20,44,55, and 65° have been obtained and an approximate plot of log kvs. (1/T)x10³, has enabled the thermodynamic characteristics of the prototropic rearrangement and of the dimerisation to be calculated. The ability of cyclopentadienyl systems to undergo hydrogen migration is discussed and the reactivity of fluxional systems is shown to be governed by the rate of metallotropic rearrangement.     

Influence of electronegative substituents on the electronic spectra of the porphyrins in the form of dications

The positions of the electronic absorption bands and also the intensities of the Soret bands of the porphyrins with ethoxycarbonyl substituents in the form of dications have been calculated by the LCAO MO method in Huckel's approximation. Comparison with the experimental results shows good agreement.     

Untersuchung der Temperaturabhängigkeit derg ik -Tensoren von Polyäthyleneinkristallen

Zusammenfassung Es wurden die Kristallitgröße und die Änderungen der parakristallinen Gitterstörungen aus den Linienbreiten des Röntgenweitwinkeldiagramms von lösungskristallisiertem linearem Polyäthylen bei den Temperaturen 15°K, 73°K, 173°K und Zimmertemperatur bestimmt. Es wurde eine Zunahme der Gitterstörungen mit fallender Temperatur gefunden.

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Summary The crystallite size and the paracrystalline distortions in polyethylene single crystals were evaluated by the measurement of the linewidth in the X-ray wide angle diagram at four different temperatures (15°K, 73°K, 173°K and 297°K). An increase of the lattice distortions with decreasing temperature was found.

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Mit 3 Abbildungen

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Vorgetragen auf der Arbeitssitzung des Fachausschusses Physik der Hochpolymeren in der Frühjahrstagung 1970 des Regionalverbandes Hessen-Mittelrhein-Saar der Deutschen Physikalischen Gesellschaft in Darmstadt, 10.–13. März 1970.     

Coalescence in three-phase fluid systems

Summary The gravity coalescence of drops at flat fluid/liquid interfaces was studied in three-phase systems. Rest-time distributions were in qualitative agreement with the earlier theory of Charles and Mason for two-phase systems. The probability of coalescence increased inversely with the square of intervening film thickness. Partial coalescence was similar to that previously observed in two-phase systems. The viscosity of the drop affected the mechanism of coalescence more than the viscosities of the other phases.

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Zusammenfassung Es wurde die Koaleszenz von Tropfen an ebenen Flüssigkeits-Flüssigkeitsgrenzfl?chen in Dreiphasensystemen untersucht. Die beobachtete Verteilung der Verweilzeiten ist in qualitativer übereinstimmung mit der Theorie von Charles und Mason für Zweiphasensysteme. Die Wahrscheinlichkeit dafür, da? Koaleszenz auftritt, nimmt umgekehrt proportional mit dem Quadrat der Filmdicke zwischen Tropfen und Phasengrenze zu. Die partielle Koaleszenz war ?hnlich, wie sie früher in Zweiphasensystemen beobachtet worden war. Die Viskosit?t des Tropfens beeinflu?t den Mechanismus der Koaleszenz mehr als die Viskosit?t der anderen Phasen.

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Oxidation of the [Rh(CO)2Cl2] anion in aqueous solution

The reaction of rhodium(I) carbonyl chloride, [Rh(CO)₂Cl]₂, with dichromate, cerium(IV) sulfate, hexachloroplatinic acid or p-benzoquinone in aqueous hydrochloric acid proceeds by consumption of 4 equivalents of oxidizing agent per mole or rhodium(I) in accordance with the equation Rh^I(CO)₂  4e + H₂O → Rh^III(CO) + 2H⁺ + CO₂A “cyclic” oxidation mechanism is suggested.     

1,2-oxazine chemistry—II : The crystal and molecular structure of N-(p-carboxybenzyl)-tetrahydro-1,2-oxazine

The crystal structure of the title compound has been determined from X-ray diffractometer data by direct methods, and refined by full matrix least squares techniques to R = 0·057 for 1231 reflections. The crystals are monoclinic, space group C2/C, cell dimensions a = 1665, b = 987, c = 1443 pm, β = 107·37° and Z = 8. The conformation of the tetrahydro-1,2-oxazine ring is a chair with the N-substituent equatorial. There is evidence of significantly greater torsional angles around the N and O atoms than around the ring C atoms, showing the ring to be more puckered than cyclohexane. The hydrogen bond is between the acid group on one molecule and the ring nitrogen on its neighbour.     

Preparation of isomeric 1,3- and 1,5- (o-phenylene)-hexamethylcyclotetrasiloxanes and investigation of their spectral characteristics

Workup of the mixture of products of pyrolysis of cyclotetrasiloxane (Me₂SiO)₂(MePhSiO)₂ yielded 1,3- (I) and 1,5-(o-phenylene)cyclosiloxane (II), the structures of which were established on the basis of data from their IR, PMR, and mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 24–25, January, 1978.     

Analyse systemati oue d'elements en traces dans l'or metalli oue par activation neutroni oue

Résumé Une méthode d'analyse des impuretés dans l'or métallique par activation neutronique, a été mise au point. Après irradiation de 15 heures dans un flux de 2·10¹⁴ n·cm⁻²·sec⁻¹, l'échantillon d'or est traité en cellule blindée. La matrice est séparée des impuretés à analyser par des méthodes électrolytiques. Les impuretés sont généralement séparées en 3 fractions qui sont mesurées par spectrométrie γ. Le traitement des informations est effectué sur ordinateur IBM 360/91 moyennant un programme écrit au laboratoire. 29 éléments sont détectables par cette méthode.