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Influence of butadiene-1,3 on ethanal pyrolysis at 495°C

✍ Scribed by Claude Richard; René Martin

Publisher: John Wiley and Sons
Year: 1980
Tongue: English
Weight: 350 KB
Volume: 12
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550121211

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✦ Synopsis

Abstract

At 495°C and a low extent of reaction, ethanal pyrolysis is slightly inhibited by the addition of small quantities of butadiene‐1,3, whereas it is accelerated by more important quantities. The inhibiting effect is interpreted in terms of a free‐radical chain mechanism in which the main chain carriers of ethanal pyrolysis (CH~3~.free radicals) reversibly add to butadiene‐1,3 and yield penten‐2‐yl (R.) free radicals. These free radicals either react in a metathetical step:
equation image
or in terminating steps. But butadiene‐1,3 also gives rise to new initiation steps:
equation image
which account for the accelerating effect. Process (i~3~) seems to be more important than process (i~2~) in the experimental conditions, but its nature could not be identified. The results are consistent with literature data and the following value of k~6~:
(4.57__T__ in cal/mol).

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