A theoretical study of solvent effects on Kolbe-Schmitt reaction kinetics

A theoretical DFT study was employed to confirm the Kolbe-Schmitt reaction mechanism and investigate solvent effects on this reaction. The use of a solvent in the Kolbe-Schmitt reaction is desirable to facilitate a homogeneous reaction mixture and potentially improve the reaction rate. The candidate solvents were designed using computer aided molecular design (CAMD) and tested using DFT solvation calculations. The results from the quantum mechanical calculations were then used to determine the rate constants for each elementary step, the overall reaction yields and the corresponding residence time. The methodology was tested on the reaction without solvent, with solvents reported in the literature, and with the designed solvents. The study revealed that in the presence of solvents with high dielectric constant the reaction becomes reversible, leading to low product yields.     

基于变速积分PID的恒温控制系统的应用研究

在多个领域都会用到恒温控制系统,设计一种基于变速积分PID的恒温控制系统,系统以STM32为核心处理器。该文讲述了系统的构成,分析了变速积分PID算法,并在恒温控制系统中得到运用。经过长时间的调试,得到合适的PID系数,使得系统的控制精度达到＆#177;0.01℃/30min。系统具有性能稳定,可靠性高的优点。     

Rate of adsorption to and desorption from a langmuir surface: The case of zero activation barrier to adsorption without dissociation

Many rate constants of elementary steps on single crystals have been measured. Their pre-exponential factors can now be compared to those calculated by transition state theory. Such a calculation is presented in this Letter with due attention to microscopic reversibility, standard states, and configurational entropy.     

Measurement of AC conductivity and dielectric properties of flexible conductive styrene–butadiene rubber‐carbon black composites

Flexible conductive polymer composites were prepared using styrene–butadiene rubber (SBR) as a matrix and conductive carbon black as filler. The filler loading was varied from 10 to 60 phr. The effect of frequency, filler loading, temperature, and applied pressure on the AC conductivity, permittivity, and loss factor of the composites was studied. The AC conductivity of low and high loaded composites was found to be frequency dependent and independent respectively. The permittivity and the loss factor were continuously decreasing with increasing frequency. The increase in filler loading increased the AC conductivity, dielectric constant, and loss factor of the composites. Increase in temperature imposed increase in conductivity and permittivity of the composites. With increasing applied pressure the properties showed exponential increase. The effect of time under a constant compressive stress was studied and dielectric relaxation times were evaluated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 986–995, 2007     

Oil absorbents based on styrene–butadiene rubber

Four oil absorbents based on styrene–butadiene (SBR)—pure SBR (PS), 4‐tert‐butylstyrene–SBR (PBS), EPDM–SBR network (PES), and 4‐tert‐butylstyrene‐EPDM‐SBR (PBES)—were produced from crosslinking polymerization of uncured styrene–butadiene rubber (SBR), 4‐tert‐butylstyrene (tBS), and ethylene–propylene–diene terpolymer (EPDM). The reaction took place in toluene using benzoyl peroxide (BPO) as an initiator. Uncured SBR was used as both a prepolymer and a crosslink agent in this work, and the crosslinked polymer was identified by IR spectroscopy. The oil absorbency of the crosslinked polymer was evaluated with ASTM method F726‐81. The order of maximum oil absorbency was PBES > PBS > PES > PS. The maximum values of oil absorbency of PBES and PBS were 74.0 and 69.5 g/g, respectively. Gel fractions and swelling kinetic constants, however, had opposite sequences. The swelling kinetic constant of PS evaluated by an experimental equation was 49.97 × 10^?2 h^?1. The gel strength parameter, S, the relaxation exponent, n, and the fractal dimension, d_f, of the crosslinked polymer at the pseudo‐critical gel state were determined from oscillatory shear measurements by a dynamic rheometer. The morphologies and light resistance properties of the crosslinked polymers were observed, respectively, with a scanning electron microscope (SEM) and a color difference meter.     

大气湍流中光传播的数值模拟

大气分子等粒子的存在对光的空间传播通常会产生光束的扩展、漂移等的影响.文中在随机媒质中光的传播理论的基础上,分析了构造大气湍流随机相位屏所需要的条件,采用McGlamery算法和Huygens-Fresnel原理,数值模拟给出了Kolmogorov谱下的大气湍流随机相位屏.分析了光波从发射机经湍流大气传播到达接收机平面时的光场变化特征.模拟分析表明:大气分子等粒子的存在,对光的振幅及能量的空间分布均造成很大的影响.     

Dy_2O_3掺杂对钛酸锶钡陶瓷结构性能的影响

采用草酸盐沉淀法,以硝酸锶、硝酸钡、钛酸丁酯和草酸为原料,Dy2O3为掺杂剂,制得了Ba0.6Sr0.4TiO3粉体,并于1250℃将其烧结成Ba0.6Sr0.4TiO3系电介质陶瓷。利用扫描电镜、X射线衍射及TH2818自动元件分析仪对Dy2O3掺杂量为0.2%~2%的Ba0.6Sr0.4TiO3陶瓷的微观结构和介电性能进行研究。结果表明,Dy2O3的掺杂没有影响到BST陶瓷的主晶相钙钛矿结构,且一定量的Dy3+进入到BST晶格中。BST陶瓷的介电损耗随着掺杂量的增加而逐渐减小,介电常数随着掺杂量的增加呈现先增大后减小的趋势,当掺杂量为0.5%时,介电常数最大,为4 474.48。     

Stieltjes常数的弱有界及其衍生Euler常数的数学表示

为了探讨Euler常数γ的数学表示式,通过对Stieltjes常数γk=nl→im∞S(Nk)=∑Nn=1lnknn-1k+1lnk+1(N+1)(k=0,1,2,…)的一个弱有界进行了进一步的优化估计,然后从该估计出发,把Euler常数γ的一个数学表达式γ=limx→0+{∑∞n=11n1+x-1x}的右边函数展成关于x的幂级数,并对其一致收敛性进行了详细地讨论.最后通过构造一个函数g(x)∑∞n=1(-1)n-1n1+x,(∞1,x∈R)而得到Euler常数γ的一个新的数学表达式.     

一类差分方程的渐近概周期序列解的存在性

利用渐近概周期函数以及序列的定义和基本性质,得出下面离散系统存在正渐近概周期序列解唯一性的充分条件.     

光谱法研究Ni[S2P（OCH2CH2Ph）2]2与α,α＇-联吡啶加合反应

利用紫外光谱法研究了Ni[S2P（OCH2CH2Ph）2]2与α,α-联吡啶的加合反应。研究发现Ni[S2P（OCH2CH2Ph）2]2与α,α-联吡啶形成1∶1型加合物,在25℃的苯溶剂中,加合物的离解度α=0.07,稳定常数K稳^θ=2.1×10^6。