C-$_2$（{ \it a} $^3Pi_u$）与选定饱和烷烃的反应：温度依赖性研究
Reactions of C$_2$({\it a}$^3Pi_u$) with selected saturated alkanes: A temperature dependence study
摘要：
采用脉冲激光光解/激光诱导荧光技术研究了C-$_2$（{ \it a} $^3Pi_u$）自由基与一系列饱和烷烃（C-$_2$ H-$_6$，C-$_3$ H-$_8$，n-C-$_4$ H $_10$，i-C-$_4$ H $_10$，n-C-$_6$ H $_14$）的气相反应.在298 ~ 673 K范围内得到了这些反应的双分子速率常数。对于n-C $_4$ H $_10$、i-C $_4$ H $_10$和n-C $_6$ H $_14$观察到明显的负温度效应，并解释为反应性较低的CH $_3$基团对反应性较高的仲或叔C-H键的空间位阻。我们的实验结果的详细分析定量揭示了这些饱和烷烃中的初级，二级和三级C-H键的反应性的温度依赖性，并进一步支持氢提取的机制。
英文摘要：
We present a temperature dependence study on the gas phase reactions of the C$_2$({\it a}$^3Pi_u$) radical with a selected series of saturated alkanes (C$_2$H$_6$, C$_3$H$_8$, n-C$_4$H$_10$, i-C$_4$H$_10$, and n-C$_6$H$_14$) by means of pulsed laser photolysis/laser-induced fluorescence technique. The bimolecular rate constants for these reactions were obtained between 298 and 673 K. A pronounced negative temperature effect was observed for n-C$_4$H$_10$, i-C$_4$H$_10$, and n-C$_6$H$_14$ and interpreted in terms of steric hindrance of the more reactive secondary or tertiary C-H bonds by less reactive CH$_3$ groups. Detailed analysis of our experimental results reveals quantitatively the temperature dependence of reactivities for the primary, secondary, and tertiary C-H bonds in these saturated alkanes and further lends support to a mechanism of hydrogen abstraction.
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