Kinetics of the bromate–bromide reaction at high bromide concentrations

At bromide concentrations higher than 0.1 M, a second term must be added to the classical rate law of the bromate–bromide reaction that becomes ?d[BrO₃^?]/dt = [BrO₃^?][H⁺]²(k₁[Br^?] + k₂[Br^?]²). In perchloric solutions at 25°C, k₁ = 2.18 dm³ mol^?3 s^?1 and k₂ = 0.65 dm⁴ mol^?4 s^?1 at 1 M ionic strength and k₁ = 2.60 dm³ mol³ s^?1and k₂ = 1.05 dm⁴ mol^?4 s^?1 at 2 M ionic strength. A mechanism explaining this rate law, with Br₂O₂ as key intermediate species, is proposed. Errors that may occur when using the Guggenheim method are discussed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 17–21, 2007     

Elektrische Charakterisierung von Hochfrequenz-Niederdruck-Gasentladungen

In recent years there has emerged significant interest in low pressure radio frequency (rf) glow discharges which are used widely particulary in IC fabrication. Various parameters of the rf glow discharge have been found to be useful for its electrical characterization; however, there is no uniformity and agreement. Extensive experimental investigations on various discharge systems have shown, that the self-bias on the rf driven electrode, the complex conductivity and the breakdown characteristic are preferable parameters of rf discharges. Advantageously the self-bias and the complex conductivity should be presented in dependence on the pressure and the applied rf voltage. The discharge current cannot be measured quite accurately due to currents via leaky capacitors and the deviations from a sinusoidal form of the current due to nonlinearities.     

Investigation of the stability of metal species with respect to liquid chromatographic separations

Summary For accurate speciation analyses it is important to know the stability of the respective species, especially in the case of metal complexes. Factors affecting the chromatographic stability of such metal species are investigated. By using thermodynamic models for complex formation and chromatographic retention equilibria the influence of species concentration, stoichiometry and excess of ligand is calculated and compared with experimental results for iron complexes (lactate, gluconate and citrate species). Iron citrate is the only species, that is chromatographed as 1:2 complex (metal: ligand), while iron lactate and gluconate are transformed to 1:1 species. Problems resulting from the coelution of different species are discussed.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Complex polymer architectures through dimethoxymethyl 1,1‐diphenylethylene derivatives

The reactions of polystyryllithium and potassium on dimethoxymethyl 1,1‐diphenylethylene derivatives were studied in different solvents. In a polar medium, A₃ and A₆ star types were formed according to the stoichiometry, whereas in a nonpolar medium, hyperbranched structures were synthesized. Extensions of an already proposed mechanism in polar and nonpolar media were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3329–3335, 2003     

A Note about the Appearance of Non-Hyperbolic Solutions in a Mechanical Pendulum System

The investigation of the behavior of a nonlinear system consists in theanalysis of different stages of its motion, where the complexity varieswith the proximity of a resonance region. Near this region the stabilitydomain of the system undergoes sudden changes due basically tocompetition and interaction between periodic and saddle solutions insidethe phase portrait, leading to the occurrence of the most differentphenomena. Depending of the domain of the chosen control parameter,these events can reveal interesting geometric features of the system sothat the phase portrait is not capable to express all them, since theprojection of these solutions on the two-dimensional surface can hidesome aspects of these events. In this work we will investigate thenumerical solutions of a particular pendulum system close to a secondaryresonance region, where we vary the control parameter in a restrictdomain in order to draw a preliminary identification about what happenswith this system. This domain includes the appearance of non-hyperbolicsolutions where the basin of attraction in the center of the phaseportrait diminishes considerably, almost disappearing, and afterwardsits size increases with the direction of motion inverted. Thisphenomenon delimits a boundary between low and high frequency of theexternal excitation.     

Grafting of silica during the processing of silica‐filled SBR: Comparison between length and content of the silane

The treatment of nanoscopic silica grafted in the blend during the processing of silica‐filled styrene butadiene rubber was performed with silane, introduced at different concentrations, or at a constant concentration with a given length of alkyl chain. From swelling measurements in water and in solvent, the maximum silane content that can be grafted has been calculated as a function of the length of the silane alkyl chains as well as their efficiency to cover the silica surface. The found values are close to the values found in the literature for grafting in solution. Moreover, a direct correspondence between the length of the silane alkyl chains and their concentration has been deduced. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 143–152, 2006     

The crystal and molecular structure of 12,13-dibromopseurotin.

The crystal structure of 12,13-dibromopseurotin has been determined by single crystal X-ray analysis. The crystals belong to space group P2₁ with a = 16.75, b = 9.63, c = 7.42 Å, β 95.9°, Z = 2. The structure was solved by the heavy atom technique and refined to R = 0.062 with 819 significant reflexions for 299 parameters.     

Structural and electronic comparative analysis of aminopyridazines showing anti-GABA activity. Crystal structure of 2-(carboxy-3′-propyl)-3-amino-6-cyclohexylpyridazinium bromide.Ab initio Mulliken population analysis of the 6-phenyl-substituted analog compared to GABA

The crystal structure of 2-(carboxy-3-propyl)-3-amino-6-cyclohexylpyridazinium bromide has been determined by single-crystal X-ray diffraction techniques and refined by full-matrix least squares. The compound crystallized in the tri-clinic space groupP ¯1 witha=10.275(1),b=11.215(1),c=7.082(1) Å,=91.84(1),=102.21(1), =106.77(1)°, andZ=2. FinalR-factor is 0.045. The main structural results are very similar to the ones observed for the 6-phenyl analog. These two compounds are GABA-A antagonists.Ab initio molecular orbital calculations, with STO-3G and 4-31G basis sets, suggest that the exocyclic nitrogen accurately mimics the nitrogen atom of GABA.