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201.
Luis A.?León Rafael?Notario Jairo?QuijanoEmail author Ederley?Vélez Claudia?Sánchez J. Camilo?Quijano Nouria?Al-Awadi 《Theoretical chemistry accounts》2003,110(6):387-394
Theoretical studies on the thermolysis in the gas phase of 4-arylideneimino-1,2,4-triazol-3(2H)-ones and 4-arylideneimino-1,2,4-triazol-3(2H)-thiones were carried out using density functional theory methods, at the B3LYP/6-31G(d) and B3LYP/6-311+G(2d,p) levels of theory. The proposed reaction mechanism occurs in one step, leading to the formation of 3-hydroxy-(2H)-1,2,4-triazole or 3-mercapto-(2H)-1,2,4-triazole and a 4-substituted benzonitrile, via a six-membered cyclic transition state. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous, in the case of triazolones, and show a higher asynchronicity in the case of triazolthiones. The bond-breaking processes are slightly more advanced than the bond-forming ones, indicating a small bond deficiency in the transition states. Kinetic and activation parameters for the reactions studied have been calculated and compared with available experimental data.From the Proceedings of the 28th Congreso deQuímicos Teóricos de Expresión Latina (QUITEL 2002) 相似文献
202.
203.
Leonid M. Blumberg 《Journal of separation science》1993,16(1):31-38
In linear chromatography (i.e. chromatography performed in the absence of sample overloading), when the plate height of a column is roughly uniform along its length, variations in the velocities of solutes are the only possible causes of erosion of efficiency. The sources of these variations (variations in capacity ratio and in the density of the mobile phase, etc.) play no direct role in the erosion of efficiency except through their effect on solute velocities. In other words, what eventually causes the erosion of efficiency is merely variation in the time required for solutes to traverse equally small segments of a column. Significant erosion can only arise from abrupt and deep deceleration of solutes in one or several relatively small segments of a column. If erosion of efficiency caused by pressure gradients in linear SFC is to be large, the depth and the sharpness of the deceleration of a solute must go beyond that hitherto confirmed experimentally. Many relevant examples are analyzed graphically. 相似文献
204.
Quan HAN Hong Tao YAN* Zhen Jie QIAN Department of Chemistry Northwest University Xi抋n 《中国化学快报》2002,13(12)
Thermal lens spectrometry (TLS) is an excellent tool for trace analysis1. TLS allows the detection of absorbances of 10-7~10-8, concentration of ≈ 10-11 mol稬-1 and the analysis of 10-15 L volumes with ≈10-2 absorbing molecules2. Kinetic analysis is playing an increasingly important part in modern analytical chemistry. Therefore, TLS shows much promise in combination with kinetic analysis. However, there are few data on TLS applications in kinetic analysis method so far3~4. A ne… 相似文献
205.
The acylation of 2-methoxynaphthalene with acetic anhydride was carried out over zeolite beta catalysts having various Si/Al
ratios. It was found that the reaction performance is strongly dependent on the Si/Al ratio of the catalyst. The catalytic
reaction features were elucidated in terms of the acidic properties of the catalysts.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
206.
本文综述了利用多种不同的天然生物分子如蛋白质(包括酶和氨基酸)、糖类、核酸、多巴胺和柠檬汁等为模板合成导电聚苯胺的研究进展。本文首先介绍了这些天然生物分子对产物聚苯胺的手性、导电率、形态以及其它方面性质的影响,归纳了利用天然生物分子合成导电聚苯胺的研究进展,然后分析了导电聚苯胺合成过程中面临的问题并对该领域的未来发展进行了展望,以期为制备性质优良和环境友好的新型导电聚苯胺材料提供有益的参考。 相似文献
207.
Summary The solubility of the system Tl2O3-SeO3-H2O was studied at 100°C. The compounds obtained were subjected to X-ray and thermal analysis. The symmetry and the crystallographic constants of some of the compounds were determined. 相似文献
208.
针对点阵夹层结构主动热防护问题,建立了夹层结构面板和芯体导热与冷却剂对流耦合的非稳态传热理论模型,利用有限体积法离散控制方程并在MATLAB中进行了迭代求解.模型首次考虑了面板与夹芯杆之间的收缩热阻,并利用分离变量法得到了收缩热阻的近似解析解.基于单胞模型和周期性边界条件,模拟得到了模型所需的表面对流传热系数h_(b)和h_(fin).最后,选取多单胞计算工况进行数值模拟和理论模型对比,并讨论了收缩热阻对模型预测精度的影响.结果表明:理论模型能够准确预测夹层结构及内部流体的温度变化,理论与仿真之间的最大误差不超过1%;随着外加热流密度不断增大,忽略收缩热阻使得计算结果造成的误差不断增大;与数值模拟相比,理论模型可显著地减少计算时间并节省计算资源,尤其适用于非均匀、非稳态复杂热载荷下点阵夹层结构的温度响应计算. 相似文献
209.
We make a high-precision Monte Carlo study of two- and three-dimensional self-avoiding walks (SAWs) of length up to 80,000 steps, using the pivot algorithm and the Karp-Luby algorithm. We study the critical exponentsv and 2
4 – as well as several universal amplitude ratios; in particular, we make an extremely sensitive test of the hyperscaling relationdv = 2
4 –. In two dimensions, we confirm the predicted exponentv=3/4 and the hyperscaling relation; we estimate the universal ratios <R
g
2
>/<R
e
2
>=0.14026±0.00007, <R
m
2
>/<R
e
2
>=0.43961±0.00034, and *=0.66296±0.00043 (68% confidence limits). In three dimensions, we estimatev=0.5877±0.0006 with a correctionto-scaling exponent
1=0.56±0.03 (subjective 68% confidence limits). This value forv agrees excellently with the field-theoretic renormalization-group prediction, but there is some discrepancy for
1. Earlier Monte Carlo estimates ofv, which were 0.592, are now seen to be biased by corrections to scaling. We estimate the universal ratios <R
g
2
>/<R
e
2
>=0.1599±0.0002 and *=0.2471±0.0003; since *>0, hyperscaling holds. The approach to * is from above, contrary to the prediction of the two-parameter renormalization-group theory. We critically reexamine this theory, and explain where the error lies. In an appendix, we prove rigorously (modulo some standard scaling assumptions) the hyperscaling relationdv = 2
4 – for two-dimensional SAWs. 相似文献
210.
The distribution of the likelihood ratio for mixtures of densities from the one-parameter exponential family 总被引:2,自引:0,他引:2
Dankmar Böhning Ekkehart Dietz Rainer Schaub Peter Schlattmann Bruce G. Lindsay 《Annals of the Institute of Statistical Mathematics》1994,46(2):373-388
We here consider testing the hypothesis ofhomogeneity against the alternative of a two-component mixture of densities. The paper focuses on the asymptotic null distribution of 2 log
n
, where
n
is the likelihood ratio statistic. The main result, obtained by simulation, is that its limiting distribution appears pivotal (in the sense of constant percentiles over the unknown parameter), but model specific (differs if the model is changed from Poisson to normal, say), and is not at all well approximated by the conventional
(2)
2
-distribution obtained by counting parameters. In Section 3, the binomial with sample size parameter 2 is considered. Via a simple geometric characterization the case for which the likelihood ratio is 1 can easily be identified and the corresponding probability is found. Closed form expressions for the likelihood ratio
n
are possible and the asymptotic distribution of 2 log
n
is shown to be the mixture giving equal weights to the one point distribution with all its mass equal to zero and the 2-distribution with 1 degree of freedom. A similar result is reached in Section 4 for the Poisson with a small parameter value (0.1), although the geometric characterization is different. In Section 5 we consider the Poisson case in full generality. There is still a positive asymptotic probability that the likelihood ratio is 1. The upper precentiles of the null distribution of 2 log
n
are found by simulation for various populations and shown to be nearly independent of the population parameter, and approximately equal to the (1–2)100 percentiles of
(1)
2
. In Sections 6 and 7, we close with a study of two continuous densities, theexponential and thenormal with known variance. In these models the asymptotic distribution of 2 log
n
is pivotal. Selected (1–) 100 percentiles are presented and shown to differ between the two models. 相似文献