Liquid-phase noncatalytic butene oxidation with nitrous oxide

The kinetics and mechanism of noncatalytic liquid-phase oxidation of but-1-ene and but-2-ene with nitrous oxide in a benzene solution in the temperature range from 180 to 240°C were studied. Oxidation proceeds via the 1,3-dipolar cycloaddition mechanism to form carbonyl compounds. Both of these reactions occur with close rates and activation energies and have the first orders with respect to the alkene and N₂O. A considerable fraction (39%) of but-1-ene involved in oxidation undergoes cleavage at the double bond yielding propanal and an equivalent amount of methylene, the latter producing ethylcyclopropane and cycloheptatriene. The oxidation of but-2-ene proceeds with a minimum bond cleavage and affords methyl ethyl ketone with 84% selectivity. Regularities of the oxidation of terminal and internal alkenes C₂—C₈ with nitrous oxide were analyzed using the previously published data. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–933, April, 2005.     

Nonvanishing derivatives and normal families

We consider the differential operators Ψ _k , defined by Ψ₁(y) =y and Ψ _k+1(y)=yΨ _k y+d/dz(Ψ _k (y)) fork ∈ ℕ fork∈ ℕ. We show that ifF is meromorphic in ℂ and Ψ _k F has no zeros for somek≥3, and if the residues at the simple poles ofF are not positive integers, thenF has the formF(z)=((k-1)z+a)/(z ²+β z+γ) orF(z)=1/(az+β) where α, β, γ ∈ ℂ. If the residues at the simple poles ofF are bounded away from zero, then this also holds fork=2. We further show that, under suitable additional conditions, a family of meromorphic functionsF is normal if each Ψ _k (F) has no zeros. These conditions are satisfied, in particular, if there exists δ>0 such that Re (Res(F, a)) <−δ for all polea of eachF in the family. Using the fact that Ψ _k (f ^′/f) =f ^(k)/f, we deduce in particular that iff andf ^(k) have no zeros for allf in some familyF of meromorphic functions, wherek≥2, then {f ^′/f :f ∈F} is normal. The first author is supported by the German-Israeli Foundation for Scientific Research and Development G.I.F., G-643-117.6/1999, and INTAS-99-00089. The second author thanks the DAAD for supporting a visit to Kiel in June–July 2002. Both authors thank Günter Frank for helpful discussions.     

Model spectral function and superconductivity in BaxK1−xBiO3 (x=0.5-0.7)

The Eliashberg spectral density function is constructed for the superconducting compound Ba_xK_1−xBiO₃ with x=0.5, 0.6, 0.7. The functions, besides yielding some prominent structures, show widely spreading spectra that inhibit lattice instability by yielding not too large values of λ(<1.32). The resulting spectral functions show similar shape as other results, where available, and also successfully reproduce the observed critical temperature, isotope exponent, gap ratio and several other parameters.     

Tautomeric Equilibrium in Polyfluoroalkylated 5,6,7,8-Tetrahydrofurans by IR Spectroscopy

The tautomeric equilibrium in substituted 5,6,7,8-tetrahydroquinazolines was studied by IR spectroscopy. The effect of various substitutents in the pyrimidine ring and the solvent on the state of the tautomeric equilibrium was evaluated.     

Improvements in Depth Selective Electron Mössbauer Spectroscopy

The conditions for achievement of high resolving power of depth selective conversion electron Mössbauer spectroscopy method at a combined installation ‘electron spectrometer–nuclear gamma-resonance spectrometer’ have been obtained. There has been made a considerable step in development of the method at its realization at a magnetic sector electron spectrometer with double focusing, equipped with electron source (a sample under investigation) of large-area and position-sensitive detector. The paper presents a prospective symmetrical version of a magnetic sector electron spectrometer that allows realizing more completely possibilities of the method. It is noted that the proposed method is particularly valuable for investigations of nanosystems, nanostrutures that contain Mössbauer nuclei.     

What Oxidation State of Iron Determines the Amethyst Colour?

A colourless quartz crystal doped with ⁵⁷Fe³⁺ was obtained by hydrothermal synthesis in an NH₄F solution. The crystal was transformed into violet amethyst by gamma-irradiation. The change in colour was accompanied by changes in the Mössbauer spectrum that can be interpreted as the conversion of trivalent iron into the tetravalent state: Fe³⁺→Fe⁴⁺.

     

Investigations of low- and high-spin states of <Superscript>132</Superscript>La

The fusion evaporation reaction ¹²²Sn(¹⁴N, 4n)¹³²La was used to populate the high-spin states of ¹³²La at the beam energy of 60 MeV. A new band consisting of mostly E2 transitions has been discovered. This band has the interesting links to the ground state 2^- and the isomeric state 6^-. A new transition of energy 351 keV connecting the low-spin states of the positive-parity band based on the πh _11/2 ⊗ νh _11/2 particle configuration, has been found. This has played a very important role in resolving the existing ambiguities and inconsistencies in the spin assignment of the band head. Received: 12 August 2002 / Accepted: 18 March 2003 / Published online: 7 May 2003     

Numerical study of the effects of the rupture process of a secondary diaphragm in expansion tubes

The results of a numerical study are described in which the interactions of a primary shock wave with a secondary diaphragm in expansion tubes are taken into account. The developing wave pattern in the interacting process of the shock with a secondary diaphragm are visualized by many kinds of figures (e.g., the time-distance diagrams of the wave phenomena on the axis, the acoustic impedance contours, and the time histories of the pitot pressure on the axis), and the influences of the shape and rupture process of the diaphragm on the quality of the test gas are explored.