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91.
J. A. Poulis C. H. Massen E. Robens G. Reichenauer 《Journal of Thermal Analysis and Calorimetry》2004,76(2):583-592
On the basis of a molecular model for adsorption kinetics Jäntti introduced a method to calculate equilibriums shortly after a change of the pressure of the sorptive gas. In the present paper we show that this method is useful in many more situations than those intended originally. 相似文献
92.
H. Stutz J. Mertes K. Neubecker 《Journal of polymer science. Part A, Polymer chemistry》1993,31(7):1879-1886
A theoretical approach to thermoset cure kinetics based on Arrhenius kinetics and mobility was developed by considering the activation of the reacting group and chain mobility as elementary steps for reaction. This extended kinetic equation was successfully applied to the curing of an epoxy by an amine, the trimerization of a cyanate, and to the polymerization of methyl methacrylate. Full agreement between theory and experimental data was obtained in all cases. The activation energies for chain mobility were exceptionally low (0.3–1 kJ/mol for bisphenol-A-based epoxy and cyanate) which indicates that the structural units must undergo only small-angle rotational oscillations to allow a reaction. A theoretical time–temperature–transformation (TTT) diagram is also presented. © 1993 John Wiley & Sons, Inc. 相似文献
93.
94.
95.
Modeling Studies of the Formation and Destruction of NO in Pulsed Barrier Discharges in Nitrogen and Air 总被引:1,自引:0,他引:1
This paper presents the results of modeling studies on the formation and destruction of NO in pulsed barrier discharges in nitrogen and air. The goals of this work are to identify the major processes involved in the formation and destruction of NO in air discharges, to distinguish between oxidative and reductive paths for NO destruction, to explore the potential importance of excited state reactions, to evaluate the role of water in such systems, and to identify the final products in the absence of heterogeneous processes. In all cases, the systems were modeled with 100×10–4% (100 ppm) of added NO, with and without 3% added water. The focus in all of this work is chemistry in the post-pulse regime. 相似文献
96.
A new technique, called modulated thermogravimetry, is introduced as a tool for obtaining continuous kinetic information for
decomposition and volatilization reactions. The approach makes use of an oscillatory temperature program to obtain kinetic
parameters during a mass loss. MTGA™ may be used under quasi-isothermal conditions to observe a single mass loss or may be
combined with linear heating rate or Hi-Res™ controlled rate thermogravimetry to scan from one mass loss region to another.
Results obtained are in agreement with those obtained by other kinetic methods.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
97.
98.
Characteristic features of the kinetics of solid-state cage reactions with distributed parameters of the relaxing matrix were
considered. Depending on the ratio of the constants of the reaction rate and relaxation of environment, the kinetics of chemical
conversions can be either exponential or nonexponential. Plausible reasons for the unsteady-state character of the kinetics
of the processes of two types,viz., the reactions of alkyl radicals in amorphous alcohol matrices and conversions in biological systems, were discussed. The
main reason for the unsteady-state character of the reactions of the first type is a dispersion of the equilibrium distances
between the reagents. Kinetics of the reactions of the second type, such as rebinding of the ligands in the heme-containing
proteins (e.g., in myoglobin), is determined by the distances in the pairs of reagents and the relaxation transitions.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 469–476, March, 1997. 相似文献
99.
Summary Kinetics of dehydration of equilibrium swollen poly(acrylic acid) hydrogel was investigated using methods of non-isothermal
thermal analysis. Methods of Kissinger, Coats-Redfern, Van Krevelen and Horowitz-Metzger were applied for determination the
kinetics parameters: activation energy (E), pre-exponent (lnA) as well as the kinetics model ƒ(69) for the process of hydrogel dehydration under different heating rates. An existence
of good agreement between determined values of kinetic parameters (Eand A), which were obtained applying different methods under the same heating rate. Functional relationship between changes of
kinetic parameters of dehydration and changes of heating rate was established. An existence of compensation effect is accepted
and explanation of compensation effect appearance during the hydrogel dehydration is suggested. 相似文献
100.
表面能与晶体生长/溶解动力学研究的新动向 总被引:3,自引:0,他引:3
界面现象使物质在结晶过程中出现了临界现象.但最近的研究指出在物质溶解过程中,在表面能量的控制下也存在着临界现象以及尺寸效应.实验发现,当晶体自身小到一 定的程度时(通常在纳米尺度上并和临界蚀坑的大小相近),在溶解过程中其速度会自发降 低,反应被抑制乃至停止.尽管在热力学上表面能的因素可以赋予小颗粒晶体较大的溶解度 ,但表面能却也能通过对临界条件的控制而使这些微粒在动力学上不被溶解.这个发现不仅 解决了纳米颗粒在水溶液中稳定性的问题,而且还从动力学的角度解释了生物矿物选择纳米 尺度作为其基本构成单元的原因.由于表面能和晶体生长/溶解的动力学有着密切的关系, 我们可以通过对表面能的调节来修改它们的动力学速度和晶体的形貌.反过来,也可以用动力学的方法来测定表面能及表面吸附/脱附常数等.相对于常规的界面研究手段,通过生 长和溶解动力学途径所得的数据有着很好的可靠性及重复性.我们认为,晶体生长和溶解的 动力学和表面能的研究相结合,不仅为界面研究提供了新的思路和方法,而且也会推动晶体生长和材料科学的发展. 相似文献