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H2S-promoted thermal isomerization of cis-2-pentene to 1-pentene and trans-2-pentene around 800 K

✍ Scribed by D. Perrin; C. Richard; R. Martin

Publisher: John Wiley and Sons
Year: 1988
Tongue: English
Weight: 457 KB
Volume: 20
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550200804

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✦ Synopsis

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 by the competing processes: i 10) CH;CHCHC,H, + H,S -+ PI + HS (2) C H ~C H CHC,H, CH,. + I , ~-C * H , P2t formation is due to addition-elimination processes: (113(-11)(123 the importance of which has been evaluated against process ( -4 ~) : HS. + P2c F=? C5HIoSH. -P2t + HS. 14p) i -4p) CHXH CHC,H, + H,S e p2C + HS. The following ratios of rate constants have been measured and are discussed: klO/& 10-2 19-2.1 exp(31,200 ? 800/RT) mol cm3 k,,/k-a, = 10 R9+ 49 exp(2100 * 1700/RT) IRT in cal mol-'1.

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