Thermal reaction of azoisopropane in the presence of (E)-CH3CH = CHCH3: Reactions of the radical 2-Ċ3H7

László Seres, Ronald Fischer, Klaus Scherzer, Miklós Görgényi

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The azoisopropane-initiated thermal reaction of (E)-CH3CH=CHCH3 has been studied in the temperature range 489.5-542.0 K. For the reactions (CH3)2CHN=NCH(CH3)2 → 2 2-Ċ3H7 + N2 (1), 2-Ċ3H7 + (E)-CH3CH=CHCH3 → C3H8 + (E)-Ċ4H7 (4), → (CH3)2CHCH(CH3)ĊH(CH3) (5), 2 2-Ċ3H7 → (CH3)2 CHCH(CH3)2 (2) the following Arrhenius parameters were determined: log(k1/s- 1) = (16.42 ± 0.30) - (201.9 ± 3.0) kJ mol- 1/θ, log[(k4/k21/2)/dm3/2 mol- 1/2 s-1/2] = (3.64 ± 0.40) - (46.9 ± 2.1) kJ mol-1/θ, log[(k5/k21/2)/dm3/2 mol- 1/2 s-1/2] = (2.53 ± 0.60) - (39.5 ± 2.4) kJ mol-1/θ where θ = RT In 10. For the cross-combination ratios of the radicals 2-Ċ3H7 and (Z)-Ċ4H7, φ[2-Ċ3H7, (Z)-Ċ4H7]t = 2.12 ± 0.10 was obtained, where the subscript t refers to the terminal combination. Formation of certain characteristic products was observed in various addition/isomerization/dissociation processes. 2-Ċ3H7 addition to (E)-CH3CH=CHCH3 is suggested as the rate-determining step, followed by 1,4- and 1,5-H-atom shifts.

Original languageEnglish
Pages (from-to)1303-1312
Number of pages10
JournalJournal of the Chemical Society, Faraday Transactions
Volume91
Issue number9
DOIs
Publication statusPublished - Dec 1 1995

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Thermal reaction of azoisopropane in the presence of (E)-CH<sub>3</sub>CH = CHCH<sub>3</sub>: Reactions of the radical 2-Ċ<sub>3</sub>H<sub>7</sub>'. Together they form a unique fingerprint.

  • Cite this