Reactions of C2_2({\it a}3Piu^3Pi_u) with selected saturated alkanes: A temperature dependence study

preprint2010arXivOpen access

Abstract

We present a temperature dependence study on the gas phase reactions of the C2_2({\it a}3Piu^3Pi_u) radical with a selected series of saturated alkanes (C2_2H6_6, C3_3H8_8, n-C4_4H10_10, i-C4_4H10_10, and n-C6_6H14_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-C4_4H10_10, i-C4_4H10_10, and n-C6_6H14_14 and interpreted in terms of steric hindrance of the more reactive secondary or tertiary C-H bonds by less reactive CH3_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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