Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds

The replacement of oxygen within a chloroformate ester (ROCOCl) by sulfur can lead to a chlorothioformate (RSCOCl), a chlorothionoformate (ROCSCl), or a chlorodithioformate (RSCSCl). Phenyl chloroformate (PhOCOCl) reacts over the full range of solvents usually included in Grunwald-Winstein equation studies of solvolysis by an addition-elimination (A-E) pathway. At the other extreme, phenyl chlorodithioformate (PhSCSCl) reacts across the range by an ionization pathway. The phenyl chlorothioformate (PhSCOCl) and phenyl chlorothionoformate (PhOCSCl) react at remarkably similar rates in a given solvent and there is a dichotomy of behavior with the A-E pathway favored in solvents such as ethanol-water and the ionization mechanism favored in aqueous solvents rich in fluoroalcohol. Alkyl esters behave similarly but with increased tendency to ionization as the alkyl group goes from 1° to 2° to 3°. N,N-Disubstituted carbamoyl halides favor the ionization pathway as do also the considerably faster reacting thiocarbamoyl chlorides. The tendency towards ionization increases as, within the three contributing structures of the resonance hybrid for the formed cation, the atoms carrying positive charge (other than the central carbon) change from oxygen to sulfur to nitrogen, consistent with the relative stabilities of species with positive charge on these atoms.     

戊二醛与链霉素反应动力学的光谱学研究

根据朗伯比尔定律,建立戊二醛与链霉素标准曲线,用紫外分光光度法测定不同温度、浓度和反应时间下反应物的吸光度,计算单位时间内反应物浓度变化,进而得到该反应的动力学方程。结果表明,戊二醛与链霉素的反应较容易进行,属于四级反应,反应速率与各自浓度的二次方成正比,反应速率方程为ν=K[C戊二醛]2[C链霉素]2,反应的表观活化能为21.06 k J/mol。     

田下凝灰岩应力松弛特性及数值模拟研究

岩石应力松弛特性是预测地下工程长期稳定性的重要基础。首先,对峰前、峰值和峰后区域应变水平下田下凝灰岩进行分别加载应力松弛试验,研究松弛过程中应力变化规律,并分析了应力松弛水平随应变水平的变化规律;其次;对田下凝灰岩进行分级加载应力松弛试验,研究分级加载条件下应力的变化规律,试验结果表明,分级加载和分别加载应力松弛具有相同的规律,且峰值处、峰值后的应力松弛特与峰值前的基本相似;最后,利用基于弹簧模型的可变模量本构方程对田下凝灰岩应力松弛试验进行数值模拟,试验结果与计算结果一致性很好,表明该本构方程可以较好的描述田下凝灰岩的应力松弛特性,可以预测工程流变破坏寿命。     

The conditional mean spectra by disaggregating the eta spectral shape indicator

Conditional spectra are a recent development in this field, which utilizes the advantages of spectral shape indicators, for example, epsilon and eta. The application of an eta indicator in conditional spectra calculations depends mainly on calculating the peak ground velocity epsilon, data about which are not readily available in the current literature. This issue has been solved by linear regression between the conventional epsilon and the peak ground velocity epsilon. However, not enough attention has been paid in the literature to the disaggregation of the eta indicator. For this reason, the disaggregation of seismic hazard based on the use of an eta indicator has been investigated in this paper, based on a simplified linear seismic source. The obtained results were compared with the available approach in the literature, which shows that this refinement has a meaningful effect on the conditional spectra specifically in the short period range. Furthermore, eta‐based conditional spectra are used at different hazard levels to select ground‐motion records. A three‐storeyed building is then analysed, and the corresponding annual probability of failure is calculated based on the full dataset as well as on the records, which were selected based on conditional spectra.     

装配式建筑项目投资风险评价

推行装配式建筑是建筑产业化的必然趋势。与传统建筑相比,装配式建筑不仅在施工和技术等方面有所不同,在投资风险管理,以及投资风险评价指标的选用上也存在差异。从政策、市场、技术、经济及管理 5 个层面进行投资风险影响剖析,据此建立装配式建筑项目投资风险评价体系。通过问卷调研以及 SEM 结构方程模型拟合,得出相应的评价指标权重,并结合案例,实现对装配式项目投资风险的定量评价,为装配式项目的投资风险评价提供了参考依据。     

基于刀具位姿的多轴数控机床运动链构建

现有数控机床(CNC)运动链构建方法多只适用于二、三轴等简单数控机床,且缺乏高效的理论分析基础和工具,针对此问题,文中选用几何分析方法,通过分析刀具在工件表面上的运动轨迹,并结合刀轴矢量规划方法,有效地解析了刀具的位姿关系;通过齐次坐标变换,有效地将数控机床运动链在工件和刀具之间的运动传递功能函数化;构建并求解刀具位姿矩阵方程组,获得一种适用于含有复杂曲面且多轴的数控机床运动链的构建方法。     

高精密3-PPR并联平台的对位精度分析与试验研究

为了获得3-PPR并联平台的最佳对位精度,针对平台的结构布局与工作影响因素对其对位精度的影响,采用理论误差分析与实验验证的方法对平台进行对位精度研究,得出平台误差数学模型并确定在速度为7.5 mm/s、加速度为100 mm/s~2时平台的对位精度最好,上述分析结果为进一步改善与开发平台性能提供了必要的理论依据,可用于各种高精密对位场合,具有一定的实际应用价值。     

常用旋转薄壳通用计算模式

本文是根据弹性薄壳理论,对部分应用非常广泛的旋转壳,通过它们内在的联系导出以超几何函数作为统一计算模式,使复杂的壳体分析(多种函数表达)规范化,便于掌握和运用.文中较多地涉及超几何方程在极限状态时的新方程解,故从应用角度称它们为“退化超几何方程”及“退化超几何函数”解.     

A model for the frequency of extreme river levels based on river dynamics

A new model for predicting the frequency of extreme river levels is proposed which encapsulates physical knowledge about river dynamics. The central idea is the use of continuous time stochastic processes that use hydrological equations and ergodic theory to model extreme events, rather than relying on statistical fits of classical models to local maximum data. A simple example shows how changes in discharge characteristics change the extreme river level frequencies. Solutions are provided for special cases, and directions for more general techniques are provided.