Free radical addition to olefins. Part 1. - Addition of bromotrichloromethane to ethylene

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

The light-induced addition of bromotrichloromethane to ethylene has been studied in a series of gas-phase experiments in which relative concentration, temperature and light intensity have been varied. The reaction is shown to involve the following process. CCl3+hv→CCl3· +Br· (1) CCl3·+E→CCl3E· (2) CCl3E·+CCl3Br→CC3EBr+CCl 3· (3) CCl3·+CCl3·→ C2Cl6 (4) Br·+E→EBr· (5) CCl 3·+CCl3·→(CCl3E) 2. (7) When bromotrichloromethane is in excess, reaction (4) is the predominant chain-termination process, and using literature data for k 4, the value k2 = 4.17×105 exp (-3240/RT)l. mole-1 sec-1 was determined. With ethylene in large excess, reaction (7) becomes the main chain termination process, and assuming A7≈108 and E7≈0, the value k3≈105 exp (-3400/RT)l. mole-1 sec -1 was determined.

Original languageEnglish
Pages (from-to)1769-1774
Number of pages6
JournalTransactions of the Faraday Society
Volume60
DOIs
Publication statusPublished - 1 Jan 1964

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