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Substituent effects on the disproportionation‐combination rate constant ratios for gas‐phase halocarbon radicals. Part III: Reactions of CF 3 + CF 3 CH 2 CHCF 3 and CF 3 CH 2 CHCF 3 + CF 3 CH 2 CHCF 3
Author(s) -
McDowell Derek R.,
Holmes Bert E.
Publication year - 1996
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1996)28:2<109::aid-kin6>3.0.co;2-z
Subject(s) - chemistry , disproportionation , radical , substituent , reaction rate constant , halocarbon , gas phase , radical disproportionation , photochemistry , medicinal chemistry , computational chemistry , organic chemistry , kinetics , catalysis , physics , quantum mechanics
Disproportionation/combination rate constant ratios, k d /k c , for the reactive collision between CF 3 CH 2 CHX + CF 3 radicals and between CF 3 CH 2 CHX + CF 3 CH 2 CHX radicals have been measured for X = CF 3 . The k d /k c = 0.066 ± 0.013 when H is transferred to the CF 3 radical and 0.125 ± 0.025 for H transfer to the CF 3 CH 2 CHCF 3 radical. Comparison of these results with previous work shows that X = CF 3 increases the k c /k c ' s relative to X = Cl or H. The effect of the CF 3 substituent on the disproportionation rate is discussed. © 1996 John Wiley & Sons, Inc.