Über den Einfluß von Isotopieeffekten auf die Verbreitung der Isotope in der Natur

Die Isotopenzusammensetzung der chemischen Elemente in ihren natürlichen Vorkommen wird von kernphysikalischen Vorgängen, vom Einfall extraterrestrischer Materie und, namentlich bei den leichten Elementen (etwa bis zum Chlor), von kinetischen und thermodynamischen Isotopieeffekten beeinfluβt. Deshalb ist die Kenntnis der in der Natur wirkenden Isotopieeffekte eine entscheidende Voraussetzung für das Verständnis der Gesetzmäβigkeiten der Verbreitung der Isotope in der Natur und für die Anwendung dieser Gesetzmäβigkeiten als Mittel der geo- und kosmoswissenschaftlichen Forschung und der Umweltforschung [1].     

REACTION OF LITHIUM DERIVATIVE OF DIETHYL PHENYLMETHANE-PHOSPHONATE WITH KETONES

Abstract

The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time.     

A new method for the determination of the 34S/32S ratio of water-soluble sulphur in soil

A new method for the determination of the ³⁴S/³²S ratio of water-extractable sulphate in soil is described. Soils are extracted directly with deionized water, which is evaporated down. The remaining residue is then rehydrated and transferred to tin cups containing an adsorbent and mixed with an oxygen donor (V₂O₅). Samples are then analysed using a continuous flow isotope ratio mass spectrometer. The new method requires around 10?g soil per determination, compared to much larger amounts (up to kilograms) of soil required for the previous methods. Sample preparation and subsequent analysis is quick and efficient. The method is demonstrated using a number of soils collected from around the world to provide a range of determined δ³⁴S values. The δ³⁴S values of water-extractable sulphur were broadly similar to those of the soil total sulphur.     

A numerical investigation of the influence of the aspect ratio in three‐dimensional separated flows

The influence of aspect ratio in three‐dimensional, numerical experiments of separated flows is studied in the case of the backward‐facing step at Reynolds numbers 600, 800, and 950. The computational domain is designed as an actual laboratory experiment. The governing equations are the steady state, isothermal, and incompressible Navier–Stokes equations. The expansion ratio of the computational domain is 1:2. The aspect ratio varies from 1:10 to 1:40. The results of the computations focus on the spanwise variations of the length and the strength of the two eddies along the lower and upper wall. It is concluded that both numerical and laboratory experiments should be designed with an aspect ratio of at least 1:20, if only the accuracy of the position of the detachment and the re‐attachment points matters. If the accuracy of the shear‐stress distributions is also taken into account, then an aspect ratio of at least 1:30 should be chosen. Finally, if the magnitudes of the vortex centers are also considered, then only the aspect ratio of 1:40 qualifies for a realization of two‐dimensional flow conditions in the plane of symmetry. This is contrary to the common practice in the field, at least from the side of laboratory experiments, where an aspect ratio of 1:10 is still considered adequate for this purpose. Copyright © 2011 John Wiley & Sons, Ltd.     

复杂应力构件弹性失效疲劳失效新判据——动态静态八面体应力强度理论

本文,在研究现代和经典强度理论的基础之上,提出了一个在复杂应力下弹性失效与疲劳失效的总准则,即动态静态八面体应力强度理论,同时建立了并分析了一个独立的比较完整的理论体系,给出了36种材料广义失效系数,和一点复杂应力的11个状态的计算理论,导出了广义允许强度算子方程.给出了总准则能应用到静态、动态的计算方法,通过8个工程实例的计算,表明该方法有很高的精度,因而笔者建议广泛地应用到工程.     

异方差回归中的广义方差比检验

在同方差假设之下,线性模型在回归分析的理论与应用方面起着突出的作用,很受许多研究工作者的青睐.然而,回归模型中同方差性这一标准假设不一定总是成立的.因此我们考虑了用一类基于似残差的方法来检验异方差情形下线性模型拟合观测数据的情况.本文既给出了大量的模拟,又给出了实际数据作为应用的例子.效果都很好.     

关于最优存贮策略的两点注记

本文统一论述了确定性静态存贮系统的最优存贮策略 ,并将具有数量折扣的经典 EOQ公式推广到了一般的确定性静态存贮系统 ;用机会损失 (后悔值 )概念对随机存贮系统的各种临界比公式进行了统一处理 .     

随机变量的截尾与一类强偏差定理

通过极限相对对数似然比，利用随机变量截尾的方法并结合鞅这一工具研究相依连续型和离散型随机变量序列的性质，得到一类用不等式表示的强偏差定理．     

在非线性回归模型中误差为AR(2)的相关性检验

本文讨论了在非线性回归模型中误差为AR(2)的相关性检验，得到了误差相关性检验的似然比检验统计量、Score检验统计量．对感兴趣参数和多余参数，利用Cox and Reid(1987)提出的正交化方法，给出了修正的似然比检验统计量和Score检验统计量．推广了胡跃清，韦博成(1994)讨论的在非线性回归模型中误差为AR(1)相关性检验的结果．     

工件有到达时间的两机器自由作业稠密时间表

对于两机器自由作业加工总长问题，工件带有到达时间，我们证明了稠密时间表的性能比为1.5。