Die chemie der schweren carben-analogen R2M,M = Si,Ge, Sn: IX. Eigenschaften und thermolyse von neuen 7-silabicyclo[2.2.1]heptadienen

Factors governing the ease and mechanism of 7-silabicyclo[2.2.1]heptadienes thermolysis in order to generate free silylenes and the corresponding benzene derivatives are investigated. For this purpose, 29 new compounds of the types VII–X have been prepared. No indications for a polar mechanism or an intermediate biradical could be found. The degradation is exactly of first order in all cases investigated sofar, and is enhanced by phenyl groups at the bridgehead C atoms, if a conformation coplanar with the basic ring is allowed by the neighbouring substituents, but is not enhanced by phenyl groups at the Si. The X-ray structure of two typical derivatives is discussed with this respect. A special mechanism is operating in the easy thermolysis of carbomethoxy-substituted compounds leading to cyclic sila enolether intermediates.     

ICP-AES detection of silicon carbide impurities volatilized in a graphite furnace with the use of carbon tetrachloride vapour

The analytical capability of high-temperature halogenation with carbon tetrachloride vapour in a graphite furnace was investigated for silicon carbide powder with known chemical composition and particle size. Intensity vs heating time curves were determined for analytical lines of Al, B, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Ti, V and Si constituents, volatilized with and without the presence of CCl₄ vapour in the furnace atmosphere. Igniting 10 mg SiC at 2100 °C for 60 s in chlorinating atmosphere, the evaporated fraction of most of the constituents was higher than 90% (for Al about 50%). The line intensity vs sample mass (4–26 mg) relationships were linear for all impurities studied, while the intensity of silicon line showed a relatively small change with the sample mass. BEC (background equivalent concentration) values for this solid sampling technique (10 mg loaded sample) were 2–20 fold lower than those calculated for the conventional solution sample introduction method.     

Coverage‐ and Temperature‐Dependent Metalation and Dehydrogenation of Tetraphenylporphyrin on Cu(111)

Using temperature‐programmed desorption, supported by X‐ray photoelectron spectroscopy and scanning tunneling microscopy, a comprehensive overview of the main reactions of 5,10,15,20‐tetraphenyl‐21H,23H‐porphyrin (2HTPP) on Cu(111) as a function of coverage and temperature is obtained. Three reactions were identified: metalation with Cu substrate atoms, stepwise partial dehydrogenation, and finally complete dehydrogenation. At low coverage the reactions are independent of coverage, but at higher coverage metalation becomes faster and partial dehydrogenation slower. This behavior is explained by a weaker interaction between the iminic nitrogen atoms and the Cu(111) surface in the high‐coverage checkerboard structure, leading to faster metalation, and the stabilizing effect of T‐type interactions in the CuTPP islands formed at high coverage after metalation, leading to slower dehydrogenation. Based on the amount of hydrogen released and the appearance in STM, a structure of the partially dehydrogenated molecule is suggested.     

On Topological Properties of Min-Max Functions

We examine the topological structure of the upper-level set M ^max given by a min-max function φ. It is motivated by recent progress in Generalized Semi-Infinite Programming (GSIP). Generically, M ^max is proven to be the topological closure of the GSIP feasible set (see Guerra-Vázquez et al. 2009; Günzel et al., Cent Eur J Oper Res 15(3):271–280, 2007). We formulate two assumptions (Compactness Condition CC and Sym-MFCQ) which imply that M ^max is a Lipschitz manifold (with boundary). The Compactness Condition is shown to be stable under C ⁰-perturbations of the defining functions of φ. Sym-MFCQ can be seen as a constraint qualification in terms of Clarke’s subdifferential of the min-max function φ. Moreover, Sym-MFCQ is proven to be generic and stable under C ¹-perturbations of the defining functions which fulfill the Compactness Condition. Finally we apply our results to GSIP and conclude that generically the closure of the GSIP feasible set is a Lipschitz manifold (with boundary).     

Comparison of calorimetric and IR-spectroscopic data for alcohols and alcoholic solutions

The heats of solution of alcohols in hexane can be considered as the energy necessary to break hydrogen bonds (H-bond). The amount of non H-bonded OH groups estimated from caloric data, are in good agreement with IR-spectroscopic data. Comparison of calorimetric and IR-spectroscopically determined H-bond energies permit the separation of intermolecular van der Waals effects from H-bond interactions. This separation shows that van der Waals interactions of alcohols or water should not be underestimated.     

Highly resolved fluid flows: "liquid plasmas" at the kinetic level

Fluid flow around an obstacle was observed at the kinetic (individual particle) level using "complex (dusty) plasmas" in their liquid state. These "liquid plasmas" have bulk properties similar to water (e.g., viscosity), and a comparison in terms of similarity parameters suggests that they can provide a unique tool to model classical fluids. This allows us to study "nanofluidics" at the most elementary-the particle-level, including the transition from fluid behavior to purely kinetic transport. In this (first) experimental investigation we describe the kinetic flow topology, discuss our observations in terms of fluid theories, and follow this up with numerical simulations.     

Shear induced phase transition in PbO under high pressure

We have studied the structural behavior of lead monoxide (PbO) as a function of pressure via angular dispersive X-ray diffraction employing two different pressure transmitting media that were quasi-hydrostatic (N₂) and non-hydrostatic (MgO), respectively. Besides litharge (-PbO) and massicot (β-PbO), which are both stable at ambient pressure, there is an orthorhombic γ-PbO phase which appears upon application of pressure to -PbO. We have found that the orthorhombic γ-PbO phase is favored by shear stress under non-hydrostatic conditions. -PbO shows strong anisotropy in compressibility. The a-axis is rather incompressible with a linear stiffness coefficient of K_a0=540(30) GPa whereas the c-axis stiffness is K_c0=25(1) GPa. The bulk modulus of -PbO is K₀=23.1(3) GPa and its derivative .     

Boundary layer solutions for some nonlinear elastic membrane problems

Summary The method of matched asymptotic expansions is used to describe finite axisymmetric deformations of two thin elastic membrane problems: a circular membrane with a small radial traction at the edge, an annular membrane with a small circular hole at the center. In both problems, the surface load is assumed to be an axial pressure. There is a boundary layer at the outer edge in the first problem, and at the hole in the second problem.

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Zusammenfassung Mit Hilfe der in der singulären Störungsrechnung benutzten Methode einer inneren und äußeren asymptotischen Entwicklung werden endliche, axialsymmetrische Deformationen bei zwei Membranproblemen beschrieben: eine dünne elastische Kreismembran mit kleiner radialer Zugspannung am Rande, und eine Kreisringmembran mit einem kleinen konzentrischen Loch. In beiden Problemen wird die Belastung als ein axial gerichteter Oberflächendruck angenommen. Im ersten Problem zeigt die Lösung am äußeren Rand Grenzschichtverhalten, welches im zweiten Problem am Lochrand vorliegt.