Kinetic Studies on the Reaction of Sodium Hexa-cyanoferrate(II) Complex with Peroxydisulfate Anion

Introduction In the previous studies on the oxidation reaction,peroxydisulfate was widely used as an oxidizingagent.1-5 One of the advantages of this oxidant lies in itsstability in a wide range of pH values. The reaction be-tween Fe(CN)5L3- (L=N-aromatic heterocyclic li-gands) and S2O8 2- has been proved to proceed throughan outer-sphere electron transfer mechanism.5 For a re-action [(Eq. (1)] to be under an outer-sphere mechanismthe steps involved are the formation of a reactant …     

Hydromagnetic rotating flow of a fourth‐order fluid past a porous plate

The rotating flow in the presence of a magnetic field is a problem belonging to hydromagnetics and deserves to be more widely studied than it has been to date. In the non‐linear regime the literature is scarce. We develop the governing equations for the unsteady hydromagnetic rotating flow of a fourth‐order fluid past a porous plate. The steady flow is governed by a boundary value problem in which the order of differential equations is more than the number of available boundary conditions. It is shown that by augmenting the boundary conditions based on asymptotic structures at infinity it is possible to obtain numerical solutions of the nonlinear hydromagnetic equations. Effects of uniform suction or blowing past the porous plate, exerted magnetic field and rotation on the flow phenomena, especially on the boundary layer structure near the plate, are numerically analysed and discussed. The flow behaviours of the Newtonian fluid and second‐, third‐ and fourth‐order non‐Newtonian fluids are compared for the special flow problem, respectively. Copyright © 2004 John Wiley & Sons, Ltd.     

The long‐time behaviour of the thermoconvective flow in a porous medium

For the Boussinesq approximation of the equations of coupled heat and fluid flow in a porous medium we show that the corresponding system of partial differential equations possesses a global attractor. We give lower and upper bounds of the Hausdorff dimension of the attractor depending on a physical parameter of the system, namely the Rayleigh number of the flow. Numerical experiments confirm the theoretical findings and raise new questions on the structure of the solutions of the system. Copyright © 2004 John Wiley & Sons, Ltd.     

Some non‐standard problems in viscous flow

Energy bounds are derived for Dirichlet type boundary value problems for the Navier–Stokes and Stokes equations when a combination of the solution values initially and at a later time is prescribed. The bounds are obtained by means of a differential inequality and imply uniqueness and continuous data dependence of the solutions for a range of values of the parameter in the non‐standard auxiliary condition. Copyright © 2004 John Wiley & Sons, Ltd.     

TTF-porphyrin dyads as novel photoinduced electron transfer systems

A TTF-linked porphyrin dyad and its zinc complex have been synthesized as novel photosystems with a redox-active pendant. The two chromophores of these dyads are not interactive in the absorption spectra, but the fluorescence of the porphyrin chromophore is dramatically quenched by intramolecular electron transfer from the TTF pendant.     

Electron transfer induced dissociations of 2- and 4-alkyl cyclohexadienones

Several 2- and 4-alkylcyclohexadienones were prepared and shown to accept electrons to produce ketyl radical anions that dissociated rapidly at room temperature to release carbon-centered radicals and an aromatic phenoxide type anion. In the PET process with benzyl-substituted cyclohexadienones, initiated with triethylamine, the benzyl radicals dimerised or abstracted an H-atom from solvent. In electrochemical reductions, and in reductions with alkali metals in liquid ammonia, the benzyl radicals were further reduced to anions.     

工程施工中运输网络优化方案

施工工地运输方案的优化设计可以归结为 :按施工期要求设计运输线路或验证已有线路通行能力 ,计算总线路中影响提高流量的关键路段 ,取得最小费用最大流 .本文运用图论理论这一数学工具把实际问题抽象为有向网络 ,进而建立数学模型 .此方法理论上严密 ,解题步聚直观清晰 ,对水利、公路、水路、铁路等其它运输系统有普遍意义 .     

Electromagnetic energy flow near nanoparticles—I: single spheres

The electromagnetic (EM) energy flow near single spheres is investigated by applying Mie theory. From the patterns of the energy flow, the absorption and the scattering of light can be understood in the microscopic point of view. In the absorption profiles of metallic particles, most absorbed energy is consumed on the surface of the particles, which indicates that the resonance of surface plasmon is different from that of the bulk plasmon. Two mechanisms to enhanced local EM field are also distinguished. One is the surface plasmon resonance, and another one is the intensified energy flow.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

A compact shock-assisted free-piston driver for impulse facilities

A free-piston driver that employs entropy-raising shock processes with diaphragm rupture has been constructed, which promises significant theoretical advantages over isentropic compression. Results from a range of conditions with helium and argon driver gases are reported. Significant performance gains were achieved in some test cases. Heat losses are shown to have a strong effect on driver processes. Measurements compare well with predictions from a quasi-one-dimensional numerical code. Received 7 September 1996 / Accepted 5 October 1996