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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Shock Wave Study of the Thermal Dissociations of C_3F_6 and c-C_3F_6. I. Dissociation of Hexafluoropropene
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Shock Wave Study of the Thermal Dissociations of C_3F_6 and c-C_3F_6. I. Dissociation of Hexafluoropropene

机译：C_3F_6和c-C_3F_6热解离的冲击波研究。 I.六氟丙烯的离解

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摘要

The thermal dissociation of C_3F_6 was studied between 1330 and 2210 K in shock waves monitoring the UV absorption of CF_2. CF_2 yields of about 2.6 per parent C_3F_6 were obtained at reactant concentrations of 500-1000 ppm in the bath gas Ar. These yields dropped to about 1.8 when reactant concentrations were lowered to 60 ppm. The increase of the CF_2 yield with increasing concentration was attributed to bimolecular reactions between primary and secondary dissociation products. Quantum-chemical and kinetic modeling calculations helped to estimate the contributions from the various primary dissociation steps. It was shown that the measurements correspond to unimolecular reactions in their falloff range. Falloff representations of the rate constants are given, leading to an overall high pressure rate constant k_∞ = 2.0 × 10~(17)(-104 kcal mol~(-1)/RT) s~(-1) and a relative rate of about 2/3:1/3 for the reactions C_3F_6 → CF_3CF + CF_2 versus C_3F_6 → C_2F_3 + CF_3.
机译：在监测CF_2的紫外线吸收的冲击波中，在1330和2210 K之间研究了C_3F_6的热解离。在浴气体Ar中的反应物浓度为500-1000ppm时，每母体C_3F_6的CF_2收率约为2.6。当反应物浓度降低至60ppm时，这些产率降低至约1.8。 CF_2产量随浓度增加而增加，这归因于初级和次级解离产物之间的双分子反应。量子化学和动力学建模计算有助于估算各种主要离解步骤的贡献。结果表明，测量值对应于其衰减范围内的单分子反应。给出了速率常数的衰减表示，从而得出总体高压速率常数k_∞= 2.0×10〜（17）（-104 kcal mol〜（-1）/ RT）s〜（-1）和相对速率对于反应C_3F_6→CF_3CF + CF_2相对于C_3F_6→C_2F_3 + CF_3约为2/3：1/3。

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