Reaction path for oxidation of ethylene to acetic acid over Pd/WO3-ZrO2 in the presence of water

Pd-supported on WO3-ZrO2 (W/Zr atomic ratio=0.2) calcined at 1073 K was found to be highly active and selective for gas-phase oxidation of ethylene to acetic acid in the presence of water at 423 K and 0.6 MPa. Contact time dependence demonstrated that acetic acid is formed via acetaldehyde formed by a Wacker-type reaction, not through ethanol by hydration of ethylene.

THEORETICAL-STUDIES ON THE CYCLIZATION PROCESS OF A NEW ORGANOSULFUR REACTION

The cyclization process of a new organosulfur reaction was studied by the MNDO (UHF) method. The first reaction path was assumed to be via the organosulfur radical intermediate, the second via the ionic (cationic and anionic) intermediates. The dehydroxylation process was assumed to occur with the synergistic cyclization. The results obtained indicate that the potential energy barrier of the first reaction path was about 102 kcal mol(-1), and although the formation of the ionic intermediate is comparatively difficult, the potential energy barrier of the second path is comparable to the first. The sequential reaction path via the radical intermediate, i.e. first cyclization, then dehydroxylation, was investigated for comparison. The cyclization reaction was found to be the thermodynamically favored process, while the ensuing dehydroxylation process was found to have a potential energy barrier of about 62 kcal mol(-1).

Preparation of highly active Pt/C cathode electrocatalysts for DMFCs by an improved aqueous impregnation method

An improved aqueous impregnation method was used to prepare 40 wt% Pt/C electrocatalysts. TEM analysis of the samples showed that the Pt particles impregnated for a short time have a very narrow size distribution in the range of 1-4 nm with an average size of 2.6 nm. UV-vis spectroscopy measurements verified that the redox reaction between PtCl62- and formaldehyde took place with a slow rate at ambient temperature via a two-step reaction path, where PtCl42- serves as an intermediate. The use of the short-time-impregnated 40 wt% Pt/C as cathode electrocatalysts in direct methanol fuel cells yields better performance than that of commercial 40 wt% Pt/C electrocatalyst. Experimental evidence provides clues for the fundamental understanding of elementary steps of the redox reactions, which helps in guiding the design and preparation of highly dispersed Pt catalyst for fuel cells.

A density function theory study on the properties and decomposition of CF3OF

The density function theory was used to calculate the potential energy surface for the decomposition of CF3OF. The geometries, vibrational frequencies and energies of all stationary points were obtained. The calculated harmonic frequencies agreed well with the experimental ones. Three decomposition channels of CF3OF were studied. The calculated reaction enthalpy (29.85 kcal/mol) of the elimination reaction CF3OF --> CF2O + F-2 was in good agreement with the experimental value (27.7 kcal/mol). The O-F bond of CF3OF is broken easily by comparing the energies, while the decomposition channel to yield the CF30 and F radicals is the main reaction path. (C) 2002 Published by Elsevier Science B.V.

The Main Path to C, N, O Elements in Big Bang Nucleosynthesis

The production of C, N, O elements in a standard big bang nucleosynthesis scenario is investigated. Using the up-to-date data of nuclear reactions in BBN, in particular the Li-8 (n, gamma) Li-9 which has been measured in China Institute of Atomic Energy, a full nucleosynthesis network calculation of BBN is carried out. Our calculation results show that the abundance of C-12 is increased for an order of magnitude after addition of the reaction chain Li-8(n, gamma) Li-9(alpha, n) B-12(beta) C-12, which was neglected in previous studies. We find that this sequence provides the main channel to convert the light elements into C, N, O in standard BBN.

Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to Alkynes

The B3LYP hybrid density functional method has been carried Out to Study theoretically the mechanisin of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH3)(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH3)2, and in path C of each reaction, the first step is the PH3 dissociation front Pd(PH3)2 to form monophosphine complex Pd(PH3) For both reactions, path B is favored.

DETERMINATION OF PARAMETERS OF FAST CHEMICAL REACTION OF ALIZARIN RED S BY SPECTROELECTROCHEMICAL METHOD WITH LOPTLC

The rate constant of very fast chemical reaction generally can be measured by electrochemical methods, but can not by the thin layer electrochemical methods because of the influence of diffusion effect. Long optical path length thin layer cell (LOPTLC) with large ratio of electrode area to solution volume can be used to monitor the fist chemical reaction in situ with high sensitivity and accuracy. It enable the adsorption spectra to be measured without the influence of diffusion effect. In the present paper, a fast chemical reaction of Alizarin Red S (ARS) with its oxidative state has been studied. The reaction equilibrium constant (K) under different potentials can be determined by single step potential-absorption spectra in LOPTLC. An equilibrium constant of 7.94 x 10(5) l.mol(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)'). Rate constant (k) under different potentials can be measured by single step potential-chronoabsorptiometry. A rate constant of 426.6 l.mol(-1).s(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)') with (E - E-1(0)') = 0.

Improved method makes a soft landing of well path

Research and field experience have shown that well-path control is important in many cases, not only to reach the desired coordinates, but also to arrive at the well completion target from the preferred trajectory.

Ni25Al75合金快速凝固过程中的包晶反应与凝固进程

用平面流铸技术制备了Ni25Al75合金条带，利用XRD，TEM和EDS对快速凝固后的显微组织和微区成分进行了分析。研究表明，Ni—A1合金快速凝固过程中的包晶反应受到了很大程度的抑制，从而影响到快速凝固进程，造成最终相组成中出现了平衡条件下不可能出现的α(A1)，并使NiAl3相有效合金浓度和生长速度增加，导致最终相组成中NiAl_3相质量分数增加。

Numerical Simulation of Gaseous Detonation of H_2-O_2 Mixture with Detailed Chemical Reaction Model

采用高精度的ENO格式和基于基元化学反应的真实化学反应模型求解氢氧混合气体一维爆轰波的精细结构。采用直接起爆方法得到稳定传播的爆轰波,计算的爆轰波阵面参数和实验相当符合。对爆轰波反应区化学反应的研究表明,参与反应的不同组分具有不同类型的变化特征。网格尺寸影响的研究表明,计算结果的精度随着网格尺寸的增加而增加,并能保持较好的收敛性。移动网格研究结果表明,网格运动速度和爆轰速度接近时,两者的相互作用对计算结果产生一定影响。

A geometry model for tortuosity of flow path in porous media

A simple geometry model for tortuosity of flow path in porous media is proposed based on the assumption that some particles in a porous medium are unrestrictedly overlapped and the others are not. The proposed model is expressed as a function of porosity and there is no empirical constant in this model. The model predictions are compared with those from available correlations obtained numerically and experimentally, both of which are in agreement with each other. The present model can also give the tortuosity with a good approximation near the percolation threshold. The validity of the present tortuosity model is thus verified.

On crack path stability in a layered material

Crack paths in an elastic layer on top of a substrate are considered. Crack growth is initiated from an edge crack in the layer. The plane of the initially straight crack forms an angle to the free surface. The load consists of a pair of forces applied at the crack mouth and parallel to the interface. Crack paths are calculated using a boundary element method. Crack growth is assumed to proceed along a path for which the mode II stress intensity factor vanishes. The inclination and the length of the initial crack are varied. The effect of two different substrates on the crack path evolution is demonstrated. A crack path initially leading perpendicularly to the interface is shown to be directionally unstable for a rigid substrate. Irrespective of its initial angle, the crack does not reach the interface, but reaches the free surface if the layer is infinitely long. At finite layer length the crack reaches the upper free surface if the initial crack inclination to the surface is small enough. For an inextendable flexible substrate, on the other hand, the crack reaches the interface if its initial inclination is large enough. For the flexible substrate an unstable path parallel with the sides of an infinitely long layer is identified. The results are compared with experimental results and discussed in view of characterisation of directionally unstable crack paths. The energy release rate for an inclined edge crack is determined analytically.

Microscopic theory of chemical-reaction rate

In this paper we deduce the formulae for rate-constant of microreaction with high resolving power of energy from the time-dependent Schrdinger equation for the general case when there is a depression on the reaetional potential surface (when the depression is zero in depth, the case is reduced to that of Eyring). Based on the assumption that Bolzmann distribution is appropriate to the description of reactants, the formula for the constant of macrorate in a form similar to Eyring's is deduced and the expression for the coefficient of transmission is given. When there is no depression on the reactional potential surface and the coefficient of transmission does not seriously depend upon temperature, it is reduced to Eyring's. Thus Eyring's is a special case of the present work.

Path Planner for Intelligent Laser Surface Modification

An optimal algorithm of manufacturing path planner for intelligent laser surface modification is presented. Elements included in the optimal objective have been analyzed. A 6-D manufacture trace that satisfies the requirements of special craft and 5-axis laser processing robot system has been generated from the path planner by method of parallel section in which combinations of modification spots size with curvature of processing surfaces and modification craft parameters are considered. Related experiments have been successfully carried out with the computer integrated multifunctional laser manufacturing system.

Electron quantum path tuning and isolated attosecond pulse emission driven by a waveform-controlled multi-cycle laser field

We investigate high-order harmonic emission and isolated attosecond pulse (IAP) generation in atoms driven by a two-colour multi-cycle laser field consisting of an 800 nm pulse and an infrared laser pulse at an arbitrary wavelength. With moderate laser intensity, an IAP of similar to 220 as can be generated in helium atoms by using two-colour laser pulses of 35 fs/800 nm and 46 fs/1150 nm. The discussion based on the three-step semiclassical model, and time-frequency analysis shows a clear picture of the high-order harmonic generation in the waveform-controlled laser field which is of benefit to the generation of XUV IAP and attosecond electron pulses. When the propagation effect is included, the duration of the IAP can be shorter than 200 as, when the driving laser pulses are focused 1 mm before the gas medium with a length between 1.5 mm and 2 mm.