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91.
以差示扫描量热法对热致液晶聚酯酰亚胺的结晶过程和液晶化过程的非等温相转变动力学行为进行了初步研究,根据Jeziorny方法处理数据得到了表征聚合物非等温相转变动力参数Zc,Gc并对其进行了讨论,结果表明,在所研究的条件下聚合物的相转变过程基本上符事Jeziorny结论,但两种相转变的成核与生长方式是不同的。 相似文献
92.
Xinbo Zhang Danzi Sun Wenya Yin Yujun Chai Minshou Zhao 《Journal of Solid State Electrochemistry》2006,10(4):236-242
This paper presents results concerning structure and electrochemical characteristics of the La0.67Mg0.33 (Ni0.8Co0.1Mn0.1)
x
(x=2.5–5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously
with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5–3.5 is LaMg2Ni9 phase with a PuNi3-type rhombohedral structure, but the main phase of the alloys with x=4.0–5.0 is LaNi5phase with a CaCu5-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg2Ni9phase and the LaNi5 phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g
(x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I
0) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability
of the alloy electrodes. 相似文献
93.
V. Ramamoorthy A. Ramasubbu S. Muthusubramanian S. Sivasubramanian 《Journal of inclusion phenomena and macrocyclic chemistry》1999,33(1):69-80
The nitrone is found to be included in the -cyclodextrin cavity in two different stoichiometries viz., 1G : 1H and 1G : 2H – the existence of which is proved by physical methods. The 1G : 2H complex of the nitrone serves as a good potent dipolarophile in the 1,3-dipolar cycloaddition reactions with olefins resulting in rate acceleration and regioselection. 相似文献
94.
Melt or cold crystallization kinetics has a strong bearing on morphology and the extent of crystallization, which significantly affects the physical properties of polymeric materials. Nonisothermal crystallization kinetics are often analyzed by the classical Johnson–Mehl–Avrami–Kolmogorov (JMAK) model or one of its variants, even though they are based on an isothermal assumption. As a result, during the nonisothermal (e.g. constant heating or cooling rate) crystallization of polymeric material, different sets of model parameters are required to describe crystallization at different rates, thereby increasing the total number of model parameters. In addition, due to the uncorrelated nature of these model parameters with the cooling or heating rate, accurate modeling at any intermediate condition is not possible. In the present work, these two limitations of the conventional approach have been eliminated by exhibiting the existence of a functional relationship between cooling or heating rate and effective activation energy during nonisothermal melt or cold crystallization in three linear aromatic polyesters. Furthermore, it has been shown that when the JMAK model is used in conjunction with this functional relationship, it is possible to precisely predict the experimental nonisothermal melt or cold crystallization kinetics at any linear cooling or heating rate with a single set of model parameters. 相似文献
95.
根据Fe(Ⅲ)、Mo(Ⅵ)对H2O2氧化邻氨基酚的催化反应速率不同,结合流动注射停留技术,建立了同时测定Fe(Ⅲ)、Mo(Ⅵ)的速差动力学分光光度法.测定铁和钼的线性范围分别为0.1~2.5μg/mL和0.5~15μg/mL.除W(Ⅵ)的允许量较小外,其它离子不干扰测定.用本法测定了合成样液中铁和钼含量,结果满意. 相似文献
96.
T. P. Elango V. Ramakrishnan S. Vancheesan J. C. Kuriacose 《Journal of Chemical Sciences》1984,93(1):47-52
Rate constants for the reaction of carbonate radical with aniline and some parasubstituted anilines have been determined by
the flash photolysis technique. Using σ+ para values the rate constants at pH 8.5 correlate very well with the Hammett equation yielding ρ= − 1. The carbonate radical oxidises aniline giving the anilino radical. The products so formed have been identified through
studies under conditions of continuous irradiation. 相似文献
97.
Ryan Simon 《Analytica chimica acta》2005,542(1):104-110
The dependence of enantio-selective chromatographic performance on particle size, as measured by separation factor, was investigated for one-monomer molecularly imprinted polymers (OMNiMIPs) compared to traditionally formed EGDMA/MAA molecularly imprinted polymers (MIPs). Five particle size ranges were compared (<20 μm, 20-25 μm, 25-38 μm, 38-45 μm, and 45-63 μm), revealing that the particle sizes above 25 μm provided the highest separation factor, and thus the best enantiomer separation, for both imprinted polymers. Other chromatographic parameters such as the number of theoretical plates and resolution exhibited only minor changes for the OMNiMIPs as the particle size changed, except for particles 20 μm and below. However, the number of theoretical plates and resolution for EGDMA/MAA are higher for particles in the 20-25 μm range. Thus, chromatographic factors for the EGDMA/MAA polymers are better in this range, despite better enantioselectivity for particle sizes above 25 μm. In contrast, OMNiMIPs generally show the most favorable performance for particle sizes in the 38-45 μm range. It was also found that decreasing flow rate resulted in improved enantioselectivity for both MIPs for all particle sizes. 相似文献
98.
The hydrogen abstraction reaction of O(^3P) with Si2H6 has been studied theoretially. Two transition states of ^3A″ and ^3A′ symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 leve with 6-311G (d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200-3000K using canonical variational transition-state sheory (CVT) with small curvature tunneling effect(SCT). The calculated CVT/SCT rate constants match well with the experimental value. 相似文献
99.
John E. Nicholas Andrew I. Spiers Nicholas A. Martin 《Plasma Chemistry and Plasma Processing》1986,6(1):39-51
Studies of time-resolved absorption spectra of transient species in the decomposition of NH3 by an r.f. pulse discharge together with product analysis showed that the major radical formed was NH at concentrations of the order of 10–6 mol dm–3 (105 molec. cm–3). Possible mechanisms for the formation of the radical during the discharge and its decay following pulse cut-off were tested by computer simulation of the kinetic data. Following zero-order formation with rate coefficient 0.19±0.03 mol dm–3 s–1, the decay was second order in NH with rate coefficient 2.1±0.5×109 mol–1 dm3 s–1 both for pure NH3 and where NH3/rare gas mixtures were investigated. The kinetic data are consistent with NH removal in a nonassociative radical-radical reaction proceeding via a short-lived collision complex, probably 2NH N2H2 N2 + H2. 相似文献
100.
在束-气条件下,通过检测产物的化学发光,研究了亚稳电子激发态He(23S)原子与CH3Cl、CH3I传能反应.采用参比反应的方法,测得了由上述反应产生的主要碎片CH(A2△)、CH(B2∑-)、CH(C2∑+)和H*形成速率常数.通过对测得的CH(A2△-X2∏r)和CH(B2∑--X2∏r)色散谱进行计算机模拟,获得了初生态的CH(A2△,v=0-2)和CH(B2∑-,v=0态)的振动-转动布居,实验结果表明,CH(A2△,v=0)态的转动布居是呈双Boltzman分布的,并且反应的可资用能大部分将转变成产物的平动能.根据实验结果和反应阈能的分析,本文对He(23S)与CH3Cl/CH3I传能反应机理进行了探讨。 相似文献