Abstract
The thermal decomposition and isomerization processes of C3−C4 alkyl radicals, 1-C5H11, and 1-C6H13 have been investigated by using a shock-tube apparatus coupled with atomic resonance absorption spectrometry (ARAS). Isomeric alkyl radicals were generated by the thermal decomposition of respective alkyl iodides. Branching fractions for the competitive pathways (C−C bond cleavage, C−H bond cleavage, and isomerization) have been determined by following the hydrogen-atom concentration by ARAS. In the investigated temperature range (900−1400 K), for all alkyl radicals, the energetically favored C−C bond cleavage was found to dominate over the C−H bond cleavage. The 1,2 or 1,3 isomerization reaction was found to be minor in C3 and C4 alkyl radicals. On the other hand, the results for 1-C5H11 and 1-C6H13 radicals clearly show the occurrence of 1,4 and 1,5 isomerization reactions. From an RRKM analysis of the present result and the previous lower temperature data, with consideration of the tunneling effect, the ...
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