Vacuum Ultraviolet Photolysis of Polyethylene,Polypropylene, and Polystyrene

Using infrared reflection absorption spectroscopy (IRRAS), quartz crystal microbalance (QMB) measurements, and X-ray photoelectron spectroscopy (XPS) in combination with chemical derivatization techniques the VUV photolysis of polyethylene (PE), polypropylene (PP), and polystyrene (PS) was investigated. A mass balance obtained from the quantification of the data was used to suggest reaction path ways. Although PE and PP behave similar, the mass loss is about 8 times higher in the case of PP. These differences originate from the higher disproportionation to recombination ratio for the branched polymer. Both polymers form double bonds and at extended treatment times they tend to crosslink. PS is rather stable due to the possibility of the energy dissipation by fluorescence.     

Zur Theorie des mechanischen und dielektrischen Relaxationsverhaltens von Makromolekülen in verdünnten Lösungen

Zusammenfassung Aufbauend auf den grundlegenden Untersuchungen vonKirkwood, Kirkwood undFuoss, Hammerle undKirkwood sowieErpenbeck undKirkwood werden die allgemeinen Grundgleichungen des mechanischen und dielektrischen Relaxationsverhaltens verdünnter und hochpolymerer L?sungen abgeleitet. Dabei wird unter Vernachl?ssigung von Valenz- und Deformationsschwingungen das ausN Atomen bestehende Makromolekül beliebiger chemischer Struktur und beliebigen Verzweigungsgrades durch ein Modell ersetzt, das ausK≤N Kugeln besteht, wobei die geometrische Struktur des Makromoleküls streng nachgebildet wird. Die zugeh?rigenK Kraftgleichungen werden zun?chst als eine Vektorgleichung im 3K-dimensionlen vollst?ndigen Konfigurationsraum gedeutet und anschlie?end unter Einführung eines geeigneten Koordinatensystems in denF-dimensionalen eigentlichen Konfigurationsraum projiziert, wobeiF die Zahl der Freiheitsgrade des Molekülmodells ist. Unter Verwendung der Kontinuit?tsgleichung gewinnt man daraus die Diffusionsgleichung, durch welche die Wahrscheinlichkeitsdichte im eigentlichen Konfigurationsraum bestimmt ist. Wird diese Differentialgleichung gel?st, so lassen sich die komplexe Viskosit?t und die komplexe Polarisation der hochpolymeren L?sung bestimmen. Im Rahmen der Rechnung wird gezeigt, da? die vonErpenbeck undKirkwood für das zugrundeliegende Koordinatensystem geforderten Orthogonalit?tsbedingungen nicht notwendig sind.     

Einwirkung von Schwefel und Ammoniak auf Propiophenon,n-Butyrophenon und i-Butyrophenon

Zusammenfassung Bei der Einwirkung von Schwefel und Ammoniak auf Propiophenon,n-Butyrophenon undi-Butyrophenon entstehen die entsprechenden Thiazoline-(3), deren saure Hydrolyse zu -Mercaptopropiophenon, -Mercapto-n-butyrophenon bzw. -Mercapto-i-butyrophenon führt. Die Dehydrierung dieser -Mercaptoketone mit Schwefel zu Di- bzw. Trisulfiden wird beschrieben. Die Kondensation der -Mercaptoketone mit Ammoniak und einer Oxokomponente führt zu neuen Thiazolinen-(3), von denen die in 2- und 5-Stellung monosubstituierten Vertreter sich mittels Schwefel zu Thiazolen dehydrieren lassen.

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The interaction of sulfur and ammonia with propiophenone,n-butyrophenone andi-butyrophenone leads to the corresponding thiazolines-(3). On acid hydrolysis of the latter -mercaptopropiophenone, -mercapto-n-butyrophenone and -mercapto-i-butyrophenone respectively are formed. The dehydrogenation of these -mercaptoketones with sulfur to di- and trisulfides respectively is described. The condensation of the -mercaptoketones with ammonia and oxo-components yields new thiazolines-(3) of which the 2- and 5-monosubstituted compounds can be dehydrogenated to thiazols with elementary sulfur.

     

Goldstone mode singularities and equation of state of an isotropic magnet

Static properties of an isotropic magnet are calculated in the whole critical region including the magnetization curve. The method proposed is a resummation of renormalized perturbation theory without use of recursion relations. This is possible because only special diagrams or subdiagrams show infrared divergencies at the magnetization curve due to Goldstone modes. The arguments given are heavily based on Ward identities. The resulting perturbation theory is well behaved in the total critical region and exhibits explicitely the form of the Goldstone mode singularities at the magnetization curve. The equation of state is calculated including two-loop contribution. Resulting effective exponents are then correct in order in the whole critical region. In various limits agreement with known results is found. A one-loop calculation of the correlation functions is also given.     

Density fluctuations from elastic dipoles in glasses at low temperatures

The contribution of the population fluctuations of two-level systems in glasses to the dynamic structure factor is calculated using the concept of elastic dipoles. Describing the two-level systems by the tunneling model, with reasonable assumptions about the distribution of tunneling frequencies an essentially logarithmic decay in time of is obtained.     

Technetium-99 in Fucusand seawater samples in the Finnish coastal area of the Baltic Sea, 1999

Liquid discharges of ⁹⁹Tc from the Sellafield nuclear facilities increased largely in the mid 90"s. These releases are transported to the Nordic sea areas by the ocean currents. Results of the ⁹⁹Tc activities along the Norwegian coastal areas and in the North Sea have been reported but then again, the spreading of ⁹⁹Tc into Baltic Sea has not been studied thoroughly. Fucus vesiculosus and seawater samples were collected in the summer 1999 from the Finnish coastal areas for measuring ⁹⁹Tc in the Baltic Sea area. A modified analytical method for measuring ⁹⁹Tc in the environmental samples was developed at that time. The method based on extraction chromatography and liquid scintillation measurement of ⁹⁹Tc. The ⁹⁹Tc concentration in the Fucus vesiculosus in the Finnish coast of the Baltic Sea varied from 1.6 to 11.6 Bq/kg (dry weight) being highest at the most northern sampling sites. These values were considerable lower than those in the Danish and Norwegian coasts. The variation in the concentrations observed are probably due to biological factors. The ⁹⁹Tc concentration in the Baltic Sea water studied was below 0.2 Bq/m³.     

One-electron versus electron-electron interaction contributions to the spin-spin coupling mechanism in nuclear magnetic resonance spectroscopy: analysis of basic electronic effects

For the first time, the nuclear magnetic resonance (NMR) spin-spin coupling mechanism is decomposed into one-electron and electron-electron interaction contributions to demonstrate that spin-information transport between different orbitals is not exclusively an electron-exchange phenomenon. This is done using coupled perturbed density-functional theory in conjunction with the recently developed J-OC-PSP [=J-OC-OC-PSP: Decomposition of J into orbital contributions using orbital currents and partial spin polarization)] method. One-orbital contributions comprise Ramsey response and self-exchange effects and the two-orbital contributions describe first-order delocalization and steric exchange. The two-orbital effects can be characterized as external orbital, echo, and spin transport contributions. A relationship of these electronic effects to zeroth-order orbital theory is demonstrated and their sign and magnitude predicted using simple models and graphical representations of first order orbitals. In the case of methane the two NMR spin-spin coupling constants result from totally different Fermi contact coupling mechanisms. (1)J(C,H) is the result of the Ramsey response and the self-exchange of the bond orbital diminished by external first-order delocalization external one-orbital effects whereas (2)J(H,H) spin-spin coupling is almost exclusively mitigated by a two-orbital steric exchange effect. From this analysis, a series of prediction can be made how geometrical deformations, electron lone pairs, and substituent effects lead to a change in the values of (1)J(C,H) and (2)J(H,H), respectively, for hydrocarbons.     

Combined electron diffraction,conformational energy and vibrational investigations of cis-1,4-ditertiary butyl-cyclohexane

The structure of cis-1,4-ditertiarybutylcyclohexane(DTBC) was investigated by combined electron diffraction, conformational and vibrational analyses in order to obtain results which are more conclusive than those previously obtained by electron diffraction alone. In this study, first the minimum energy conformations for DTBC were calculated by the Westheimer-Hendrickson procedure using various force fields described in the literature; the same fields and the minimum energy conformations were used in subsequent vibrational analyses to calculate the mean amplitudes of vibration for each minimum energy conformation of DTBC; these mean amplitudes and the corresponding internuclear distances were then used to calculate the theoretical electron diffraction radial distribution curves which were compared to the experimental curves. The results indicate that the conformational energies of all the minimum energy chair and non-chair forms of DTBC are very similar. In excellent agreement with this, the theoretical radial distribution curves of all minimum energy forms have to be mixed for a best fit to the experimental radial distribution curve. A least squares analysis of the mixture under the described conditions yields for 110 °C a composition of approximately one third chair and two thirds non-chair forms. The quality of the empirical conformational force fields has a definite influence on the reliability of these results.     

Die Hydrohalogenierung von Hexaphenyldigerman und die Schwingungsspektren einiger Ge2(C6H5) n X6−n -Verbindungen

The reactions of Ge₂(C₆H₅)₆ with HCl and HBr lead in nearly quantitative yields to the 1,1,2,2-tetrahalo derivatives Cl₂(C₆H₅)GeGe(C₆H₅)Cl₂ (I) and Br₂(C₆H₅)GeGe(C₆H₅)Br₂ (II), resp. The Si?Ge bond of (C₆H₅)₃SiGe(C₆H₅)₃ is cleaved under the conditions of hydrohalogenation. The vibrational spectra of Ge₂Br₆, Ge₂(C₆H₅)₆, I, and II are reported. The influence of vibrational coupling on ν GeGe in these compounds is discussed in detail, including vibrational calculations.