Free radical addition to olefins. Part 5. - Addition of difluorobromomethyl radicals to trifluoroethylene and ethylene

J. M. Tedder*, J. C. Walton

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)

Abstract

The photochemical reaction of CF2Br2 with CHF=CF 2 and CH2=CH2 has been examined in a series of gas-phase experiments. A mechanism for the radical chain addition which takes place is proposed. The variation in the rate of formation of the termination products, CF2BrCF2Br and CF2BrCHFCF 2CF2Br, with reactant concentration is explained if five important termination reactions are taken into account and a long-lived excited state of the CF2Br2 is accepted. Arrhenius parameters for the addition of CF2Br· radicals to the olefins have been derived: CF2Br·+ E→CF2BrE· (2) CF 2Br·+CF2Br·→ CF2BrCF 2Br (4) k2/k41/2 (addition to=CHF)=(1.2±0.3)×102 exp (-3300±200/RT), k 2/k41/2 (addition to=CF2)=(2. 0±0.3)×102 exp (-4400±200/RT), k 2/k41/2 (addition to=CH2)=(2. 5±0.5) exp (-1000/RT). A factors are in 1.1/2 mol -1/2 s-1/2; activation energies in kcal/mol; R=1.99 cal deg.-1 mol-1; 1 cal=4.184 J.

Original languageEnglish
Pages (from-to)1135-1144
Number of pages10
JournalTransactions of the Faraday Society
Volume66
DOIs
Publication statusPublished - 1 Jan 1970

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