OH+HCl→Cl+H_(2)O反应中的反应物转动激发效应

本文在最近构建的F12a势能面上,对OH+HCl→Cl+H_(2)O的一系列反应物转动激发态进行了势能平均的五维含时波包计算,得到了初始态选择的反应几率和速率常数。研究发现,除了很低碰撞能量,单独激发反应物HCl到j_(1)=2或者OH到j_(2)=1得到了总反应几率的最大值.在低能区域,随着OH转动激发的增加,反应几率的共振增强迅速减小,导致250K以下的速率常数迅速下降HCl和OH同时转动激发的速率常数不是单独激发结果的简单叠加。最后,通过对(5,5)态以下初始转动态的速率常数进行玻尔兹曼平均,得到了反应的热速率常数,与实验结果基本吻合。

基于广义逆理论的转角信息重构近似算法

针对结构识别中转角信息难以测量的问题,完善了一种基于广义逆理论的转角信息重构问题近似算法.该算法从静力凝聚的基本方程出发,求解广义逆矩阵,由结构的位移测量信息计算结构的转角信息.通过理论分析给出了广义逆理论近似算法的适用条件和广义逆解答是精确解答的条件.数值算例表明:该近似算法的范数误差一般较小,而绝对量较小的分量误差较大.

动静转换装置的结构与应用

我公司有相同的三条冶金生产线,为了提高反应效率和反应速度,该生产线合成工艺采用中压转动反应釜进行合成反应,本文介绍了中压转动反应釜最重要的附属设备--动静转换装置的作用、主要结构和使用效果。

Kinetic Model and Simulation Analysis for Toluene Disproportionation and C9-Aromatics Transalkylation

A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation is developed based on the reported reaction scheme.A time based catalyst deactivation function taking weight hourly space velocity(WHSV)into account is incorporated into the model,which reasonably accounts for the loss in activity because of coke deposition on the surface of catalyst during long-term operation.The kinetic parameters are benchmarked with several sets of balanced plant data and estimated by the differential variable metric optimiza- tion method.Sets of plant data at different operating conditions are applied to make sure validation of the model and the results show a good agreement between the model predictions and plant observations.The simulation analysis of key variables such as temperature and WHSV affecting process performance is discussed in detail,giv- ing the guidance to select suitable operating conditions.

Stereodynamics of O（^3P）＋H2 at Scattering Energies of 0.5, 0.75, and 1.0 eV

Quasiclassical trajectory calculation of the title reaction O（^3P）＋H2→OH＋H at three different scattering energies of 0.5, 0.75, and 1.0 eV on the lowest electronic potential energy surface 1^3A＂ has been done. Distribution P（θr） of polar angles between the relative velocityk of the reactant and rotational angular momentum vector j＇ of the product, distribution P（φr） of the azimuthal as well as dihedral angles correlating k-k＇-j＇, 3-dimensional distri-bution, and polarization-dependent differential cross sections （PDDCSs）dependent upon the scattering angle of the product molecule OH between the relative velocity k of the reactant and k＇ of the product at different scattering energies of 0.5, 0.75, and 1.0 eV are presented and discussed.

Kinetics of celestite conversion to acidic strontium oxalate hydrate in aqueous solution of oxalic acid

Conversion of SrSO4 to acidic strontium oxalate hydrate(H[Sr(C2O4)1.5(H2O)]) in aqueous H2C2O4 solutions proceeds as a consecutive reaction. In the first step of the consecutive reaction, SrSO4 reacts with H2C2O4 and pseudomorphic conversion to SrC2 O4·H2O occurs. In the second step, SrC2 O4·H2O reacts with H2C2O4 to form H[Sr(C2 O4)1.5(H2O)]. Sr(HC2 O4)(C2 O4)0.5·H2 O crystallizes during cooling of the reaction mixture to room temperature if the solution reaches the saturation concentration of (H[Sr(C2O4)1.5(H2O)]. The aims of this study are the derivation of reaction rate equations and the determination of the kinetic parameters such as pre-exponential factor, apparent activation energy and order of H2C2O4 concentration for each reaction step.Fractional conversions of SrSO4 were calculated using the quantitative amounts of dissolved S and Sr. It was determined that the reaction rate increased at the initial time of reaction by increasing the temperature using solutions with approximately same H2C2O4 concentrations. The reaction extends very slowly after a certain time in solutions with low H2C2O4 concentration and ends by the formation of a protective layer of SrC2O4-H2O around the surfaces of solid particles. Fractional conversion of SrSO4 is increased by increasing concentration of H2C2O4 at constant temperature. Kinetic model equations were derived using shrinking core model for each step.

Proton-gradient-transfer acid complexes and their catalytic performance for the synthesis of geranyl acetate

Special proton-gradient-transfer acid complexes （PGTACs） in which the bonded protons are not equivalent and have gradients in transfer ability, acidity, and reactivity were reported. The acidity gradient of the protons gave the PGTACs excellent catalytic activity and selectivity in the esterifica- tion of terpenols. These PGTACs are ＂reaction-induced self-separation catalysts＂ and can be easily reused. The kinetics with PGTACs as catalyst in the esterification of geraniol were also studied for use in engineering design.

Siderite pyrolysis in suspension roasting:An in-situ study on kinetics,phase transformation,and product properties

Siderite,as an abundant iron ore,has not been effectively utilized,with a low utilization rate.In this study,the in-situ kinetics and mechanism of siderite during suspension magnetization roasting(SMR)were investigated to improve the selective conversion of siderite to magnetite and CO,enriching the theoretical system of green SMR using siderite as a reductant.According to the gas products analyses,the peak value of the reaction rate increased with increasing temperature,and its curves presented the feature of an early peak and long tail.The mechanism function of the siderite pyrolysis was the contraction sphere model(R_(3)):f(α)=3(1−α)2/3;E_(α)was 46.4653 kJ/mol;A was 0.5938 s^(−1);the kinetics equation was k=0.5938exp[−46.4653/(RT)].The in-situ HT-XRD results indicated that siderite was converted into magnetite and wüstite that exhibited a good crystallinity in SMR under a N_(2) atmosphere.At 620℃,the saturation magnetization(M_(s)),remanence magnetization(Mr),and coercivity(Hc)of the product peaked at 53.63×10^(-3)A·m^(2)/g,10.23×10^(-3)A·m^(2)/g,and 12.40×10^(3)A/m,respectively.Meanwhile,the initial particles with a smooth surface were transformed into particles with a porous and loose structure in the roasting process,which would contribute to reducing the grinding cost.

CATALYSIS OF POLYSTYRENE N-HYDROXYL SULFONAMIDE FOR ESTERIFICATION OF BUTANOL WITH ACETIC ANHYDRIDE

Polystyrene N-hydroxyl sulfonamide resin 1 was prepared and used to catalyze the esterification of n-butanol and acetic anhydride. The mechanism of catalytic esterification proved by IR spectra of the resins was found that O-H and N-H of the N-hydroxyl sulfonamide resin reacted with the acetic anhydride respectively to form the active intermediate polystyrene N,O-diacetyl sulfonamate which was cleaved by n-butanol to produce butyl acetate. The catalytic esterification by resin 1 was in good agreement with the kinetic model of 揵i-bi-ping-pong?mechanism.

Role of Acetylated p53 in Regulating the Expression of map2 in Retinoic Acid-induced P19 Cells

Objective To investigate the regulatory mechanisms of acetylated p53 in the expression of microtubule-associated protein-2(MAP2) in neuronal differentiation of P19 cells induced by all-trans retinoic acid(RA).Methods Neuronal differentiation of P19 cells was initiated with 4-day RA treatment.Immunofluorescence,real-time reverse transcription-polymerase chain reaction(RT-PCR) assay,and map2 promoter driven luciferase assay were performed to detect the expression and relative promoter activity of MAP2 in those RA-treated cells.Real-time PCR-based chromatin immunoprecipitation assay(ChIP) was carried out to reveal the specific recruitment of acetylated p53 onto its binding sites on map2 promoter.Results The expression of MAP2 was markedly increased in RA-induced P19 cells.The map2 mRNA increased 34-fold after 4 days of RA treatment and 730-fold 2 days after the treatment,compared with the cells without RA treatment(control).p53 was recruited to the promoter of map2 gene in acetylated form and thereby enhanced its promoter activity.p300/CBP associated factor(PCAF) was found induced in RA-treated cells and enriched in the nucleus,which might contribute to the acetylation of p53 in the regulation of map2 gene.Conclusions Acetylated p53 may participate in regulating the expression of map2 in RA-induced differentiation of P19 cells.PCAF is possibly involved in this process by mediating the acetylation of p53.

Quasi-classical Trajectory Study of F-I-H20→HF-I-OH Reaction： Influence of Barrier Height, Reactant Rotational Excitation, and Isotopic Substitution

The reaction dynamics of the F＋H20/D20→HF/DF＋OH/OD are investigated on an accurate potential energy surface （PES） using a quasi-classical trajectory method. For both isotopomers, the hydrogen/deuterium abstraction reaction is dominated by a direct rebound mechanism over a very low ＂reactant-like＂ barrier, which leads to a vibrationally hot HF/DF product with an internally cold OH/OD companion. It is shown that the lowered reaction barrier on this PES, as suggested by high-level ab initio calculations, leads to a much better agreement with the experimental reaction cross section, but has little impact on the product state distributions and mode selectivity. Our results further indicate that rotational excitation of the H20 reactant leads to significant enhancement of the reactivity, suggesting a strong coupling with the reaction coordinate.

Sulfur poisoning mechanism of three way catalytic converter and its grey relational analysis

Combining a detailed catalytic surface reaction mechanism with noble metal and promoter elementary reactions, a new three-way catalytic converter(TWC) reaction mechanism is established. Based on the new mechanism, steady condition numerical simulation is carried out, and the change of light-off temperatures and conversion efficiency with various SO2 contents is obtained. By grey relational analysis(GRA), the relational grade between conversion efficiency and SO2 content is obtained. And, the result shows that SO2 content has the most important influence on C3H6 and NOX conversion efficiency. This provides an important reference to the improvement of activity design of TWC, and may provide guidance for the condition design and optimization of TWC.

Operational mode transition in a rotating detonation engine

The relationship between the number of detonation waves and the evolution process of the flow field in a rotating detonation engine was investigated through a numerical analysis.The simulations were based on the Euler equation and a detailed chemical reaction model.In the given engine model,the flow-field evolution became unstable when a single detonation wave was released.New detonation waves formed spontaneously,changing the operational mode from single-wave to four-wave.However,when two or three detonation waves were released,the flow field evolved in a quasi-steady manner.Further study revealed that the newly formed detonation wave resulted from an accelerated chemical reaction on the contact surface between the detonation products and the reactive mixture.To satisfy the stable propagation requirements of detonation waves,we proposed a parameter called NL,which can be compared with the number of detonation waves in the combustor to predict the evolution(quasi-stable or unstable)of the flow field.Finally,we verified the effectiveness of NL in a redesigned engine.This study may assist the operational mode control in rotating detonation engine experiments.

Modeling Chemically Reactive Flow of Sutterby Nanofluid by a Rotating Disk in Presence of Heat Generation/Absorption

In this article we investigate the flow of Sutterby liquid due to rotating stretchable disk. Mass and heat transport are analyzed through Brownian diffusion and thermophoresis. Further the effects of magnetic field, chemical reaction and heat source are also accounted. We employ transformation procedure to obtain a system of nonlinear ODE's. This system is numerically solved by Built-in-Shooting method. Impacts of different involved parameter on velocity, temperature and concentration are described. Velocity, concentration and temperature gradients are numerically computed. Obtained results show that velocity is reduced through material parameter. Temperature and concentration are enhanced with thermophoresis parameter.

A Numerical Investigation of 3D MHD Rotating Flow with Binary Chemical Reaction,Activation Energy and Non-Fourier Heat Flux

In this investigation we analyze the rotating three-dimensional magnetohydrodynamic flow of Maxwell fluid in attendance of binary chemical reaction with activation energy. Furthermore, effects of non-Fourier heat flux are taken into account. Formulation is done in the presence of heat and mass convective boundary conditions. Self-similar forms from boundary layer equations are obtained using apposite transformations. Numerical solution is obtained via built-in bvp-4c function in MATLAB for the system of differential equations. Effects of ensuing parameters on flow distributions are portrayed graphically. It is witnessed that increasing values of rotational parameter lowers the velocity profile and both Biot numbers have escalating effect on temperature and concentration distributions. A comparative study to a previously done investigation is also included to corroborate our results.

Investigations on control algorithm of steady-state cornering and control strategy for dynamical correction in a steer-by-wire system

To improve the handling performance of a steer-by-wire (SBW) vehicle, a series of control logics are proposed. Firstly, an algorithm for enhancing the maneuvering in steady-state cornering is presented. On this basis, two categories of control strategies are used to dynamically correct and compensate the transient state steering responses and vehicle behaviors. Simulator tests including subjective evaluations and virtual field tests are both conducted to make comprehensive investigations on the series of control logics. The subjective evaluations demonstrate that the SBW vehicle with a specifically selected value of steering sensitivity tends to be more desirable for driving than a conventional one in which a fixed steering ratio exists. The virtual field tests indicate that the control strategies for dynamical correction and compensation could effectively improve the handling per-formances of an SBW vehicle by reducing the work load of drivers, enhancing the track-holding performance, and improving steering response properties.

In-situ tracking of phase conversion reaction induced metal/metal oxides for efficient oxygen evolution

Due to the unique interface and electronic structure,metal/metal oxide composite electrocatalysts have been designed and exploited for electrocatalytic oxygen evolution reaction(OER)in alkaline solution.However,how to fabricate metal/metal oxides with abundant interfaces and well-dispersed metal phases is a challenge,and the synergistic effect between metal and metal oxides on boosting the electrocatalytic activities is still ambiguous.Herein,by controlling the lithium-induced conversion reaction of metal oxides,metal/metal oxide composites with plentiful interfaces and excellent electrical interconnection are fabricated,which can enhance the active sites,and accelerate the mass transfer during the electrocatalytic reaction.As a result,the electrocatalytic oxygen evolution activities of the as-fabricated metal/metal oxide composite catalysts including NiCo/NiCo2O4,NiMn/NiMn2O4 and CoMn/CoMn2O4 are greatly improved.The catalytic mechanism is also explored using the in-situ X-ray and Raman spectroscopic tracking to uncover the real active centers and the synergistic effect between the metal and metal oxides during water oxidation.Density functional theory plus U(DFT+U)calculation confirms the metal in the composite can optimize the catalytic reaction path and reduce the reaction barrier,thus boosting the electrocatalytic kinetics.

Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides

Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.