Shock wave study of the thermal dissociations of C3F6 and c-C3F6. II. dissociation of hexafluorocyclopropane and dimerization of CF2.
Shock wave study of the thermal dissociations of C3F6 and c-C3F6. II. dissociation of hexafluorocyclopropane and dimerization of CF2.
复制标题
C3F6 和 c-C3F6 热解离的冲击波研究。
DOI：
10.1021/jp501577k
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
J. Troe
中科院分区：
文献类型：
--
作者：
C. Cobos;L. Sölter;E. Tellbach;J. Troe
在监测CF2紫外吸收的620-1030K的冲击波中，研究了c-C3F6的热解离。该反应的研究接近其高压极限，但考虑到了一些高温衰减。量子化学和动力学模型使实验数据更加合理。该反应涉及1，3-双自由基CF2CF2CF2中间体。由c-C3F6二聚体解离形成的CF2生成C2F4。该反应的测量速率也被发现与衰减范围相对应。给出了2CF2-→-C2F4的速率常数随温度和浴气浓度[Ar]的变化关系，并与文献值符合较低温度下的高压速率常数和较高温度下衰减区的离解速率常数。分析了在中温条件下的衰减量开始。
The thermal dissociation of c-C3F6 has been studied in shock waves over the range 620-1030 K monitoring the UV absorption of CF2. The reaction was studied close to its high-pressure limit, but some high-temperature falloff was accounted for. Quantum-chemical and kinetic modeling rationalized the experimental data. The reaction is suggested to involve the 1,3 biradical CF2CF2CF2 intermediate. CF2 formed by the dissociation of c-C3F6 dimerizes to C2F4. The measured rate of this reaction is also found to correspond to the falloff range. Rate constants for 2CF2 → C2F4 as a function of temperature and bath gas concentration [Ar] are given and shown to be consistent with literature values for the high-pressure rate constants from experiments at lower temperatures and dissociation rate constants obtained in the falloff range at higher temperatures. The onset of falloff at intermediate temperatures is analyzed.