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首页> 外文期刊>Thermochimica Acta: An International Journal Concerned with the Broader Aspects of Thermochemistry and Its Applications to Chemical Problems >COMPENSATION BEHAVIOUR RECOGNIZED IN LITERATURE REPORTS OF SELECTED HETEROGENEOUS CATALYTIC REACTIONS - ASPECTS OF THE COMPARATIVE ANALYSES AND SIGNIFICANCE OF PUBLISHED KINETIC DATA
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COMPENSATION BEHAVIOUR RECOGNIZED IN LITERATURE REPORTS OF SELECTED HETEROGENEOUS CATALYTIC REACTIONS - ASPECTS OF THE COMPARATIVE ANALYSES AND SIGNIFICANCE OF PUBLISHED KINETIC DATA

机译：选定的非均相催化反应的文献报告中的补偿行为-对比分析的观点和发表的动力学数据的意义

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A comparative analysis of selected examples of compensation behaviour, reported in the literature or identified here in published rate studies for heterogeneous catalytic reactions, showed that the isokinetic temperature often occurs within the interval of the kinetic measurements. (At the isokinetic temperature the rate constants for all reactions of the set are equal). Detailed comparisons of data for a diverse group of nickel metal catalyzed cracking-type processes showed significant variations of the magnitudes of the activation energies reported for ethane hydrogenolysis, though levels of reactivity were similar to other chemical changes in the set. It is also concluded that the factors determining the magnitude of Arrhenius parameters for many surface processes are insufficiently well understood to warrant the formulation of detailed mechanisms of the contributory surface reactions. It is also concluded here that the similarity of reactivities over a range of reaction temperatures, for a set of rate processes, is demonstrated by the existence of compensation behaviour. This observation may be useful in providing insights into the identity of common factors controlling reactivities within each group of isokinetically related reactions. A similar level of reactivity characterizes the compensation set. A theoretical explanation of the magnitudes of Arrhenius parameters for many surface processes is not at present practicable because we have insufficient knowledge of the conditions and controls prevailing. Mechanistic proposals are often based on presumed extensions of the theory accepted for homogeneous rate processes. (C) 1997 Elsevier Science B.V. [References: 29]
机译：对文献报道的或在已发表的有关多相催化反应的速率研究中确定的补偿行为示例的比较分析表明，等动力学温度通常发生在动力学测量的间隔内。 （在等速温度下，该组所有反应的速率常数相等）。各种镍金属催化裂化类型工艺数据的详细比较表明，乙烷氢解反应所报告的活化能大小存在显着变化，尽管反应性水平与该组反应中的其他化学变化相似。还得出结论，对于许多表面过程，确定Arrhenius参数大小的因素还没有得到足够的了解，以致无法制定出有助于表面作用的详细机理。在此还得出结论，对于一组速率过程，反应温度在一定反应温度范围内的相似性由补偿行为的存在证明。该观察结果可能有助于洞悉控制等速动力学相关反应的各组反应性的共同因素。相似的反应性是补偿集的特征。目前尚无法对许多表面过程的Arrhenius参数的大小进行理论解释，因为我们对当时的条件和控制方法知之甚少。机械建议通常基于均质速率过程所接受的理论的假定扩展。 （C）1997 Elsevier Science B.V. [参考：29]

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