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1.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
2.
It is long known that the Fokker-Planck equation with prescribed constant coefficients of diffusion and linear friction describes
the ensemble average of the stochastic evolutions in velocity space of a Brownian test particle immersed in a heat bath of
fixed temperature. Apparently, it is not so well known that the same partial differential equation, but now with constant
coefficients which are functionals of the solution itself rather than being prescribed, describes the kinetic evolution (in
the N→∞ limit) of an
isolated
N-particle system with certain stochastic interactions. Here we discuss in detail this recently discovered interpretation.
An erratum to this article can be found at 相似文献
3.
A simple method of determining ultra-trace Au in natural water was presented by using graphite furnace atomic absorption spectrophotometry (GFAAS) after in situ enrichment with thiol cotton fiber (TCF). The sample solution was adjusted to pH 1.5-2.0 with HCl, then the water sample was passed through a column packed with 0.10-0.20 g TCF and the flow rate was controlled at 20-40 ml min−1. The effects of interferences, such as complexing and oxidizing agents and other elements adsorbed on TCF were overcome by chemical treatments prior to the desorption of Au. The adsorbed Au was adsorbed with 2.0 ml hot acid, then it was extracted with 1.00 ml methyl isobutylketone (MIBK). For a 5 l water sample, the detection limit of Au is 0.02 ng l−1. The relative standard deviation (R.S.D.) for the determination of 1.44 ng l−1 Au was 9.4%.The method was applied to determine ultra-trace Au both in suspended phase and soluble phase in natural water, the concentrations of total Au in natural water samples range from 0.51 to 67.82 ng l−1. The recovery of added 0.50-6.00 ng l−1 Au was 80-95%. The method is useful in prospecting for Au deposits by means of hydrogeochemical methods. The enrichment is carried out in the field, and then the determination of Au is completed later in the laboratory. 相似文献
4.
苯并噻唑重氮氨基偶氮苯与汞(Ⅱ)的显色反应及其应用 总被引:26,自引:2,他引:24
报道了新试剂苯并噻唑重氮氨基偶氮苯的合成及其与汞(Ⅱ)的显色反应,在TritonX-100存在下弱碱性介质中,试剂与汞形成2:1的橙红色络合物,最大吸收波长位于520nm处,表观摩尔吸光系数为1.51×10^5L.mol^-1.cm^-1。汞量在0~1.2mg/L范围内遵守比尔定律,直接应用于废水中微量汞的测定,结果满意。 相似文献
5.
本文简述了乳浓聚合动力学研究的进展,着重于澳大利亚Sydney大学Gilbert等在乳液聚合阶段Ⅱ动力学方面的研究概况。介绍了不同水溶性单体的小尺寸种子乳液体系的SmithEwart递推方程的求解方法及其解析解形式和乳液聚合动力学数据的处理。同时讨论了该研究的局限性。 相似文献
6.
饮食中微量元素砷的分布规律与人体健康关系 总被引:3,自引:1,他引:2
采用催化动力学光度法测定了六大类(共三十种)样品中的总砷含量,探讨了砷在食品中的分布规律,建立了砷在人体中的安全系效和积累系效的效学评价公式,用于评价砷与人体健康的关系,这对人们选择食物有一定的指导意义。 相似文献
7.
Massimo Camarda Antonino La Magna Francesco La Via 《Journal of computational physics》2007,227(2):1075-1093
A modified Kinetic Lattice Monte Carlo model has been developed to predict growth rate regimes and defect formation in the case of the homo-epitaxial growth of close packed crystalline structures. The model is an improvement over standard Monte Carlo algorithms, which usually retain fixed atom positions and bond partners indicative of perfect crystal lattices. Indeed, we extend the concepts of Monte Carlo growth simulations on super-lattices containing additional sites (defect sites) with respect to those of the reference material. This extension implies a reconsideration of the energetic mapping, which is extensively presented, and allows to describe a complex phenomenology that is out of accessibility of standard stochastic approaches. Results obtained using the Kawasaki and the Bond-Counting rules for the transition probability of the Monte Carlo event are discussed in details. These results demonstrate how the defect types (local or extended), the formation mechanisms and the defect generation regimes can be characterized using our approach. 相似文献
8.
本文研究了新席夫碱吡哆醛缩邻氨基酚的合成及其分析应用,提出了钒(V)的分光光度测定法,该法简便,灵敏,选择性好。 相似文献
9.
After describing simplified equations exspressing the temparature dependency of the viscosity of carrier gases (helium, nitrogen and hydrogen ) relative to a base value, absolute relationships based on the kinetic theory of gases are discussed. Comparative data obtained using various calculation methods are given and are compared to measured values. Based on the kinetic relationshipsm, of viscosity. Finally, the influence of pressure on the viscosity is also briefly discussed. As a supplement, Viscosity data are tabulated for the three gases in the range of 0°C to 400°C in increments of 2 K, calculated using the kinetic relationships. 相似文献
10.
Carlo Cercignani 《Journal of statistical physics》1990,58(5-6):817-823
The problem of finding the summational collision invariants for the Boltzmann equation is tackled with the aim of proving that the most general solution of the problem is not different from the standard one even when the equation defining a collision invariant is only satisfied almost everywhere inR
3×R
3×S
2. The collision invariant is assumed to be in the Hilbert spaceH
of the functions which are square integrable with respect to a Maxwellian weight. 相似文献