An extended mechanism for chemical activation systems
An extended mechanism for chemical activation systems
复制标题
化学活化系统的扩展机制
DOI：
10.1002/kin.550230909
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发表时间：
1991
影响因子：
1.5
通讯作者：
K. Scherzer
中科院分区：
文献类型：
--
作者：
M. Olzmann;J. Gebhardt;K. Scherzer
化学活化单分子反应的经典机制被扩展以解释烯烃/氢原子系统中的实验结果。在后者大量过量的情况下，必须考虑通过与氢原子重组产生化学活化的烷烃分子来对主要形成的自由基进行第二次化学活化。自由基以及烷烃分子都可能分解，并且开发了一种基于两个稳态主方程耦合的方法来评估两个反应路径中的任何一个对比率分解到稳定的贡献。所提出的处理方法以顺式丁-2-烯/过量热氢原子为例子，在分子氢作为浴气的情况下在 298 K 下进行了论证。事实证明，在这些条件下，通过活化丁烷的步骤是不可忽略的。
The classical mechanism of chemically activated unimolecular reactions is extended to interpret experimental results in systems olefin/hydrogen atoms. In the case of a large excess of the latter, one has to take into consideration a second chemical activation of the primarily formed radicals by their recombination with H-atoms to yield chemically activated alkane molecules. The radicals as well as the alkane molecules may decompose, and a method based on the coupling of two steady-state master equations is developed to evaluate the contribution of either of the two reaction paths to the ratio decomposition to stabilization. The treatment proposed is demonstrated for the example cis but-2-ene/excess of thermal hydrogen atoms in the presence of molecular hydrogen as a bath gas at 298 K. It turns out that the step via activated butane is not negligible under these conditions.