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Self-inhibition or the lack of it in the pyrolyses of neopentane and n-hexane

✍ Scribed by Roger M. Marshall

Publisher: John Wiley and Sons
Year: 1987
Tongue: English
Weight: 455 KB
Volume: 19
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550190707

No coin nor oath required. For personal study only.

✦ Synopsis

Published data show that in its early stages (up to 3% decomposition), the pyrolysis of n-hexane in the ranges 723-823 K and 10-100 Torr is not inhibited by the olefin products, in contrast with neopentane pyrolysis which is very strongly inhibited in similar conditions. Detailed consideration of the chain mechanisms for the two pyrolyses shows that the reactivity of the chain terminating radical towards hydrogen abstraction from an allylic C-H bond in product olefin is the factor which determines whether or not observable self-inhibition occurs. Thus, n-hexane pyrolysis, whose chain decomposition is terminated by recombination and disproportionation of ethyl, is not significantly self-inhibited, whereas that of neopentane which is terminated by recombination of methyl is very strongly inhibited because methyl is 14x more reactive than ethyl. The implications for other alkanes are briefly discussed.

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