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901.
Kenneth W. Bullins Thomas T. S. Huang Scott J. Kirkby 《International journal of quantum chemistry》2009,109(6):1322-1327
The formation of the tropylium ion, C7H7+, in the mass spectrum of toluene is a chemical process that has been extensively studied. There is, however, still debate as to the structure of the moieties and the reaction pathways involved. This work presents the first computationally complete reaction schemes for the formation of tropylium from toluene to be reported. The calculations were performed at the HF/6‐31G(d, p) and the DFT/B3LYP/6‐311++G(2d) levels of theory using Gaussian 03W. The previously unreported optimized structures and energies for a transition state and an intermediate in one scheme and a transition state in the other have been determined. These results are consistent with the previously reported literature and the available experimental data. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 相似文献
902.
Yuanlin Ren Bowen Cheng Jinshu Zhang Weimin Kang Zhenhuan Li Xupin Zhuang 《Frontiers of Chemistry in China》2009,4(2):136-141
The thermal decomposition kinetics of the N,N′-bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) ethylenediamine (DPTDEDA) in air were studied by TGDTG techniques. The
kinetic parameters of the decomposition process for the title compound in the two main thermal decomposition steps were calculated
through the Friedman and Flynn-Wall-Ozawsa (FWO) methods and the thermal decomposition mechanism of DPTDEDA was also studied
with the Coats-Redfern and Achar methods. The results show that the activation energies for the two main thermal decomposition
steps are 128.03 and 92.59 kJ·mol−1 with the Friedman method, and 138.75 and 106.78 kJ·mol−1 with the FWO method, respectively. Although there are two main thermal decomposition steps for DPTDEDA in air, the thermal
decomposition mechanism of DPTDEDA in the two steps are the same, i.e. f(α) = 3/2(1 − α)4/3[(1 − α)−1/3 − 1]−1.
__________
Translated from Acta Chimica Sinica, 2008, 66(9) (in Chinese) 相似文献
903.
904.
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906.
Mohamed Rafat Mahmoud Maher Mohamed Ahmed Hamed Ali Mohamed Shaker 《Journal of solution chemistry》1986,15(9):765-776
Kinetics of base hydrolysis of new heterocyclic azomethines derived from active methyl quaternary salts and aromatic nitroso compounds were investigated in the presence of 70% (wt/wt) water-methanol. The base hydrolysis of these compounds is strictly first-order with respect to OH– and azomethine. The rate determining step is suggested to be the attack of the hydroxide ion on the free base. Effects of water content and nature of organic hydroxylic solvent have been studied. It is concluded that specific solute-solvent interactions through dispersion forces play a major role in the base hydrolysis rate of the azomethines investigated. The effect of pH (2.98 – 12.24) on hydrolysis rates of compounds having a diethylamino substituent in the presence of 30% methanol has been studied. In acidic media, the rate determining step is probably the water attack on the protonated substrate. 相似文献
907.
Using cyclic voltammetric techniques the electrochemical behaviour of gallium in alkali media has been investigated. Three
anodic peaks, one cathodic peak, and a secondary anodic peak—an observation hitherto unreported—are obtained. Detailed analyses
of these various stages of oxidation and reduction based on their peak potential and peak current characteristics have revealed
the nature of the underlying electrochemical reactions. 相似文献
908.
Johannes Smid 《Journal of polymer science. Part A, Polymer chemistry》2002,40(13):2101-2107
A brief overview of the role that Dr. Michael Szwarc has played in unraveling the mechanism of living anionic polymerization is presented. Emphasis is placed on the different ionic species that control the propagation reaction in ether-type solvents. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2101–2107, 2002 相似文献
909.
首先对微晶粒尺寸增长速率的表征进行总结.从微晶核和粒—高分子链组网络结构特点(高分子链组是微晶核和微晶粒同连接链段的复合体)同增长速率间的三个相关性的特征: ①晶核和晶粒加大同连接链段缩短的并存性; ②微晶核和粒表面上连接链段的缩短机制存有简并性; ③微晶粒内和粒表面上stem的反顺式构象共存性出发.建议了一种评估和计算微晶粒尺寸增长速率的新方法和原则,基于该种计算方法和原则用统计力学和动力学相结合法推导出了高分子熔体内几种不同结晶生长机制(近邻折叠、近邻伸直分凝和近邻折叠同近邻伸直分凝并存等生长方式)下微晶粒—高分子链组中微晶粒数增长速率和微晶粒尺寸增长速率动力学方程. 相似文献
910.