Isothermal catalytic combustion of <Emphasis Type="Italic">n</Emphasis>-pentane/air mixtures on platinum wire

The transient response of the input power necessary to maintain isothermal conditions after a step temperature perturbation applied to a platinum wire immersed in a gaseous fuel/air mixture allows for the measurement of the reaction heat flow rate, directly related to the rate of the catalytic combustion. The S-shaped variation of this rate in time is employed to evaluate the induction period of the catalytic ignition. The effect of mixture composition, total pressure, and catalyst temperature on the induction period for the catalytic ignition of lean to stoichiometric n-pentane/air mixtures on isothermally heated platinum wire is reported and discussed. The mixture composition was varied between 1.40 and 2.56% n-pentane in air, the total pressure between 20 and 101 kPa, and the wire temperature between 470 and 600 K. The reaction rates, turnover frequencies, overall and partial reaction orders, and activation energies were determined from the analysis of the obtained results and compared to other reported data.     

Azulen-1-yl diazenes substituted at C-3 with phenyl-chalcogene moieties: dye synthesis, product characterization and properties

Abstract  

Two synthesis strategies were used for the generation of azulene-1-yl diazenes substituted at C-3 with a phenyl-chalcogenyl moiety, the synthesis of azulenes substituted at C-3 followed by azo-coupling and azulene substitution at C-3 in azulene-azo dyes. The last synthetic route seems to give more satisfactory results for the synthesis of the desired chalcogenic derivatives. Another target of this study was to investigate the changes induced by the phenyl-chalcogenic substitution on the NMR and UV-vis spectra, and also to compare this effect with the one exerted by halogen atoms and by strongly electron donating groups such as AcNH or PhCOO. Whereas the latter groups exhibit a strong influence on the NMR and UV-vis spectra, PhS, PhSe, or PhTe groups as well as halogen atoms produce only a small effect because of the moderate change in electron distribution over the entire molecule.     

A simplified kinetic model for isothermal catalytic ignition

The ignition of catalytic combustion of the stoichiometric propane/air mixture on an isothermally heated platinum wire in different experimental conditions of total pressure and wire temperature is studied and discussed on the basis of a simplified kinetic model. The platinum wire is heated electrically with a specially designed power supply, which ensures a quasi-rectangular profile of its temperature. The ignition process is monitored by measuring the input power required to maintain a constant temperature of the wire during an exothermic catalytic reaction. The difference between the input powers recorded in air and in a fuel/air mixture, for the same wire temperature and gas total pressure, allows the elimination of the heat transferred to surroundings and conversion of the results into the catalytic reaction rate r _R versus time curves of S-shaped form, illustrating the transition from kinetic to diffusion regime. The curve can be used to evaluate the ignition delay, as reported previously and also to fit different models to the data. The quasi-exponential increase of the isothermal reaction rate during the early stages of the process can be rationalized on the basis of a simplified kinetic model implying the multiplication of the adsorbed active intermediates. The adopted hypotheses allow the derivation of an analytical solution for the catalytic reaction rate before and during the ignition process, without diffusion limitations.     

Mechanism of copper underpotential deposition at Pt(<Emphasis Type="Italic">hkl</Emphasis>)-electrodes: Quantum-chemical modelling

Mechanism of copper underpotential deposition at stepped faces of platinum single crystals Pt(hkl) is studied using cyclic voltammetry, scanning probe microscopy, and quantum-chemical modelling. It is shown that the first stage of UPD is one-dimensional decoration of the (100)- or (110)-orientated steps, then copper monolayer forms at (111)-terraces. The final stage is the secondary step decoration. Quantum-chemical modelling, with the using of long-distance potentials of the Cu-Pt and Cu-Cu pair interactions, allows estimating the energy of copper adsorption at different structure elements of the substrate (steps, kinks, terraces) and revealing the succession of the adatom monolayer formation; it also provides additional information for the identifying of the nature of voltametric peaks for different stages of the copper adsorption-desorption.     

求解复杂湍流的非线性涡黏性系数模型和代数应力模型

非线性涡黏性系数模型和代数应力模型联系了线性涡黏性系数湍流模型和完整的微分 雷诺应力模型.随着它们受到日益关注,其形式也越来越多样化.本篇综述的目的是对这些模 型加以总结并比较它们之间的共同点及不同之处,指出它们与完整微分雷诺应力模型之间的 关系,以及相对于线性涡黏性系数模型而言它们在预报流场上所具有的优势.