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121.
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
122.
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
123.
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
124.
D. Choudhury R. C. Borah R. L. Goswamee H. P. Sharmah P. G. Rao 《Journal of Thermal Analysis and Calorimetry》2007,89(3):965-970
Pyrolysis of petroleum refinery sludge has received global acclamation as a clean conversion technique for providing solution
of sludge disposal as well as efficient resource utilization. This communication reports the kinetics study of pyrolysis of
petroleum refinery sludge. Experiments were carried out by means of thermogravimetric analysis at different heating rates
of 5, 10 and 20°C min−1. The pyrolytic reaction is significant in the temperature range of 200–350°C and analysis and evaluation of kinetic parameters
is done in the 100–500°C region of non-isothermal TG curves obtained in nitrogen atmosphere.
The activation energy is calculated by iso-conversional method, then other kinetic parameters are determined by considering
single reaction and two reaction global kinetic model. Two-reaction model is found to fit satisfactorily the experimental
results. 相似文献
125.
Fearon P. K. Bigger S. W. Billingham N. C. 《Journal of Thermal Analysis and Calorimetry》2004,76(1):75-83
The oxidation of (Ti,W)C ceramics have been studied as a part of the program to investigate of properties of powder materials.
Thermogravimetry, derivative thermogravimetry (TG-DTG), and differential thermal analysis DSC have been used in the non-isothermal
study of powder oxidation (Ti,W)C in dry air atmosphere. The powder of crystalline carbide cermets with a ratio of W:Ti equals
0.3 was used in this study. The diagrams were recorded on a sample mass 3.42 mg on the Setaram apparatus in temperatures ranging
from 25 to 1000°C. Seven different heating rates were used. The analytical techniques SEM, WDX, EDX and XRD were used in the
research. The kinetics of the oxidation process was followed by the integral method by applying the Coats-Redfern's approximation.
The kinetic models of particular stages of (Ti,W)C oxidation were evaluated from the dynamic mass losses data. The values
of apparent activation energy E and the pre-exponential factor A of each stage of the oxidation were calculated.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
126.
Slow pyrolysis of walnut shell which is a cheap and abundantly available solid waste was carried out using thermogravimetric
analysis. The effects of raw material heating rate on the pyrolysis properties and kinetic parameters were investigated. A
two-step consecutive reaction model were used to simulate the pyrolysis process. The kinetic parameters were established by
using the pattern search method. Comparison between experimental data and the model prediction indicated that the two-step
consecutive reaction model can better describe the slow pyrolysis of walnut shell as the formation of an intermediate during
the pyrolysis process was taken into account. 相似文献
127.
采用水热法成功地合成了一种含有亚微米级孔洞的微孔磷酸盐晶体材料(记为HAP-TAP),其形貌特征是:六棱柱形的晶体表面分布着大量0.4~0.8μm的亚微米级孔洞,孔洞内长有片层状晶体.在样品晶化的过程中,通过控制合成时间,获得了纯六棱柱形晶体的大单晶(记为HAP).使用扫描电子显微镜(SEM)、粉末X射线衍射(XRD)、红外光谱和电子能谱(EDX)对HAP-TAP独特形貌的形成机理进行了研究和揭示.HAP的单晶XRD数据表明,HAP是一种具有二维空旷骨架结构的新型微孔磷酸铝晶体,其分子式为Al5(OH)2(PO4)7(C2N2H10)3.0.5H2O.EDX分析结果表明,生长于六棱柱形晶体孔洞内的片层状晶体为磷酸钛铝材料. 相似文献
128.
Xilin Ren Chingkuang Tu Deepa Bhatt J. Jefferson P. Perry John A. Tainer Diane E. Cabelli David N. Silverman 《Journal of Molecular Structure》2006,790(1-3):168-173
Incorporation of 3-fluorotyrosine and site-specific mutagenesis have been used with stopped-flow spectrophotometry and pulse radiolysis to investigate the catalytic properties of human manganese superoxide dismutase (MnSOD). All of the nine tyrosine residues in each of the four subunits of the homotetramer of human MnSOD were replaced with 3-fluorotyrosine. Previous studies showed that the crystal structures of the unfluorinated and fluorinated human MnSOD are nearly superimposable with the root-mean-square deviation for 198 -carbon atoms at 0.3 Å. However, the catalytic activity kcat/Km of the fluorinated MnSOD at 30 μM−1 s−1 was less than unfluorinated wild type at 800 μM−1 s−1. Comparison of the values of kcat/Km for fluorinated and unfluorinated wild-type andY34F MnSOD showed that this decrease for the fluorinated enzyme was in significant part due to 3-fluorotyrosine residues distant (>7 Å) from the active-site metal, not to 3-fluorotyrosine at position 34 close (5 Å) to the metal. Although many rate constants for the catalysis are decreased by this fluorination, the rate of dissociation of the product-inhibited complex appears unchanged by the presence of fluorinated tyrosines. These results suggest that Tyr34 is not a proton donor in the release of the product-inhibited complex, which involves protonation of a peroxo complex of the metal with release of hydrogen peroxide. 相似文献
129.
L. F. Kosyanchuk N. V. Kozak O. I. Antonenko G. Ya. Menzheres Yu. S. Lipatov 《Theoretical and Experimental Chemistry》2006,42(6):357-363
For semi-interpenetrating polymer networks (semi-IPNs) based on an incompatible polyurethane network/linear polymethylmethacrylate
pair formed in situ in the presence of 3d metal chelates, we have studied the effect of the system composition on the kinetics
of formation of the components and the nature of complex formation between the metal compound and the polymer matrix. The
ratio of the system components has been shown to have an effect on the selection of the macroligand in formation of complexes
of the metal chelate with the polar groups of the semi-IPN, where the general character of the kinetic behavior for the formation
of the network and the linear polymer is preserved.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 351–356, November–December, 2006. 相似文献
130.
用结晶动力学方法对不同摩尔比的 Mg O/B2 O3在摩尔分数为 1 8% Mg Cl2 -H2 O中的过饱和溶液在2 0℃的结晶动力学过程进行了研究 .n(Mg O) /n(B2 O3) =1 /1和 1 /1 .5时分别结晶析出 2 Mg O· 2 B2 O3·Mg Cl2 · 1 4H2 O和 2 Mg O· 3 B2 O3· 1 5 H2 O(多水硼镁石 ) .n(Mg O) /n(B2 O3) =1 /2时依次结晶析出 Mg O·3 B2 O3· 7.5 H2 O,Mg O· 2 B2 O3· 9H2 O和 2 Mg O· 3 B2 O3· 1 5 H2 O(多水硼镁石 ) 3种固相 .n(Mg O) /n(B2 O3)=1 /3时结晶析出不同结晶水的六硼酸镁 Mg O· 3 B2 O3· 7H2 O和 Mg O· 3 B2 O3· 7.5 H2 O.析出固相采用X射线粉末衍射、红外光谱和热分析进行物相鉴定 .拟合并给出结晶动力学方程 ,同时对水合镁硼酸盐的结晶反应机理进行了探讨 相似文献