TY - JOUR
T1 - Free radical addition to olefins. Part 1. - Addition of bromotrichloromethane to ethylene
AU - Tedder, J. M.
AU - Walton, J. C.
PY - 1964/1/1
Y1 - 1964/1/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=2542614878&partnerID=8YFLogxK
U2 - 10.1039/TF9646001769
DO - 10.1039/TF9646001769
M3 - Article
AN - SCOPUS:2542614878
SN - 0014-7672
VL - 60
SP - 1769
EP - 1774
JO - Transactions of the Faraday Society
JF - Transactions of the Faraday Society
ER -