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H2S-promoted thermal isomerization of butene-2 CIS to butene-1 or butene-2 trans around 500°C

✍ Scribed by C. Richard; A. Boiveaut; R. Martin

Publisher
John Wiley and Sons
Year
1980
Tongue
English
Weight
470 KB
Volume
12
Category
Article
ISSN
0538-8066

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✦ Synopsis

H2S increases the thermal isomerization of butene-2 cis (B,) to butene-1 (B1) and butene-2 trans (Bt) around 500°C. This effect is interpreted on the basis of a free radical mechanism in which buten-2-yl and thiyl free radicals are the main chain carriers. B1 formation is essentially explained by the metathetical steps:

(2)

( 3 ) C4H7 + B, + B1+ C4H7 C4H7 + H2S -B1+ HS the latter being in agreement with values given in a previous work. Lastly, the activation energy of the addition process:

(4) HS + B, -CdHsSH is shown to be Ed N 3.5 f 2 kcal/mol, of the same order as the activation energy of the corresponding metathetical step.

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H,S accelerates the thermal isomerization of cis-2-pentene (P2c) to 1-pentene (P1) and trans-2-pentene (P2t) to around 800 K. This effect is interpreted on the basis of a free radical mechanism in which 2-pentenyl and thiyl radicals are the main chain carriers. P1 formation is essentially explained