A kinetic study of the reaction between ĊH3 radicals and azoisopropane; reactions of the radicals ĊH3, (CH3)2 ĊN = NCH(CH3)2 and (CH3)2CH ṄN(CH3)CH(CH3)2

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Abstract

The reaction of ĊH3 generated from di-tert-butyl peroxide with azoisopropane (AIP) in the temperature range 395-450 K was investigated by product analysis. The regioselectivity of ĊH3 with the carbon and nitrogen radical centres of (CH3)2 ĊN=NCH(CH3)2 was determined: ĊH3 + (CH3)2ĊN=NCH(CH3)2 → (CH3)3CN=NCH(CH3)2 (18) → (CH3)2C=NN(CH3)CH(CH3)2 (19) k18/k19 = 1.95 ± 0.24. The Arrhenius parameters of the H-abstraction and decomposition reactions ĊH3 + AIP → CH4 + (CH3)2ĊN=NCH(CH3)2 (3) (CH3)2CHṄN(CH3)CH(CH3)2 → 2- ĊH7 + (CH3)2CHN=NCH3 (23) relative to the combinations 2 ĊH3 → C2H6 (13) 2 (CH3)2CHṄN(CH3)CH(CH3)2 → (CH3)2CHN(CH3)N(CH(CH3)2)N(CH(CH3)2)N(CH3)CH(CH3)2 (26) were determined: log[(k3/, k13/(1/2)) / mol(-1/2) dm(3/2)s(-1/2)] = (3.1 ± 0.3) - (30.6 ± 2.4) kJ mol-1/θ log[k23 (φ k26/(1/2))- 1/mol(1/2)dm(-3/2)s(-1/2)] = (8.8 ± 0.5) - (110.0 ± 6.5) kJ mol-1/θ where θ = RT In 10 and φ is the cross-combination ratio of ĊH3 and (CH3)2CHṄN(CH3)CH(CH3)2.

Original languageEnglish
Pages (from-to)591-609
Number of pages19
JournalJournal de Chimie Physique et de Physico-Chimie Biologique
Volume96
Issue number4
DOIs
Publication statusPublished - jan. 1 1999

ASJC Scopus subject areas

  • Biochemistry

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