Does the HO2 radical react with H2S,CH3SH,and CH3SCH3?

The kinetics of the title reactions were investigated in a discharge flow tube by using laser magnetic resonance detection of HO₂. The upper limits for the bimolecular rate constants for the reactions of HO₂ with H₂S (k₁), CH₃SH (k₂), and CH₃SCH₃ (k₃) are <3 × 10^?15, <4 × 10^?15, and <5 × 10^?15 cm³ molecule^?1 s^?1, respectively, at 298 K. Our upper limit for k₁ is three orders of magnitude lower than the previously reported value. Measurements at higher temperatures also yield similar upper limits. Our results suggest that HO₂ is not an important oxidant for these reduced compounds in the atmosphere. © 1994 John Wiley & Sons, Inc.     

Kinetics and mechanism of the thermal decomposition reaction of acetone cyclic diperoxide in the gas phase

The kinetics of the thermal decomposition reaction of gaseous 3,3,6,6-tetramethyl-1,2,4,5-tetroxane (ACDP) in the presence of n-octane was studied in the 403.2–523.2 K temperature range. This reaction yields acetone as the organic product. Under optimum conditions, first-order kinetics were observed, included when the S/V ratio of the Pyrex reaction vessel was increased by a nearly six-fold factor. In the range 443.2–488.2 K the temperature dependence of the rate constants for the unimolecular reaction in conditioned vessels is given by In k₁/(s^?1) = (31.8 ± 2.5) ? [(39.0 ± 2.5)/RT]. The value of the energy of activation in kcal/mol correspond to one O? O bond homolysis of the ACDP molecule in a stepwise biradical initiated decomposition mechanism. At the lower reaction temperatures as well in preliminary experiments participation of a surface catalyzed ACDP decomposition process could be detected. © 1994 John Wiley & Sons, Inc.     

Temperature-dependent behavior of birefringence and rotation of the optical indicatrix in crystals of deuterated triglycinesulfate

On the basis of a complex null-polarimetric method, the natural birefringence and the rotation of the optical indicatrix in crystals of deuterated triglycinesulfate are measured in the temperature range of 300–340 K. The temperature-dependent behavior of the optical parameters is shown to be close to that observed previously in triglycinesulfate crystals. Changes in them upon the ferroelectric phase transition can be accounted for by the spontaneous quadratic electro-optic effect, with the values of the electro-optic coefficients being larger by a factor of 1.4 than in triglycinesulfate crystals.     

LOCALIZED FAMILIES OF BENDING WAVES IN A THIN MEDIUM-LENGTH CYLINDRICAL SHELL UNDER PRESSURE

The initial-boundary-value problem for the equations describing motion of a thin, medium-length, non-circular cylindrical shell is examined. The shell edges are not necessarily plane curves, with the conditions of a joint support, a rigid clamp or a free edge being considered as the boundary conditions. The shell is supposed to experience normal internal (or external) dynamic pressure which may be non-uniform in the circumferential direction. It is assumed that the initial displacements and velocities of the points at the shell middle surface are functions decreasing rapidly away from some generatrix. Using the complex WKB method the asymptotic solution of the governing equations is constructed by superimposing localized families (wave packets) of bending waves running in the circumferential direction. The dependence of frequencies, group velocities, amplitudes and other dynamic characteristics upon variable pressure and geometrical parameters of the shell are studied. As an example, the wave forms of motion of a circular cylindrical shell with sloping edges under growing dynamic pressure are considered. The effect of localization of bending vibrations near the longest generator as well as the effects of reflection, focusing and increasing amplitude in the running wave packets are revealed.     

LIDAR mapping of ozone-episode dynamics in Paris and intercomparison with spot analyzers Supplementary material available at http://link.springer.de/journals/apb

Continuous mapping of an ozone episode in Paris in June 1999 has been performed using a differential absorption lidar system. The 2D ozone concentration vertical maps recorded over 33 h at the Champ de Mars are compiled in a video clip that gives access to local photochemical dynamics with unprecedented precision. The lidar data are compared over the whole period with point monitors located at 0-, 50-, and 300-m altitudes on the Eiffel Tower. Very good agreement is found when spatial resolution, acquisition time, and required concentration accuracy are optimized. Sensitivity to these parameters for successful intercomparison in urban areas is discussed. Received: 11 February 2002 / Published online: 14 March 2002     

An algebraic multigrid solver for Navier-Stokes problems

An efficient numerical method is presented for solving the equations of motion for viscous fluids. The equations are discretized on the basis of unstructured finite element meshes and then solved by direct iteration. Advective fluxes are temporarily fixed at each iteration to provide a linearized set of coupled equations which are then also solved by iteration using a fully implicit algebraic multigrid (AMG) scheme. A rapid convergence to machine accuracy is achieved that is almost mesh-independent. The scaling of computing time with mesh size is therefore close to the optimum.     

On the magnetic and crystallization behaviour of iron based amorphous alloys determined by nuclei quenched in

The tendency of boron-containing, iron-based glasses to show non monotonic changes of Curie Temperature (T _c ) and room temperature saturation magnetization (SM) was examined by magnetic measurements and Mossbauer spectroscopy. Depending on B/Fe ratio theT _c and SM first increased up to a maximum value and then steadily decreased, probably because of a shortrange ordering, due to the strong chemical interaction between iron and boron atoms, leading iron atoms in vicinity with Fe-atoms rather than another TM-atom. Finally, the phenomenon becomes analogous to the order-disorder phenomenon in crystalline alloys. An observed unusual crystallization behaviour, consisting of heterogeneous nucleation, was also ascribed to this ordering, which leads to the formation of associations, acting as the first nuclei of crystallization.