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“Surprising kinetics” or the major role of trace quantities in radical chain mechanisms
Author(s) -
Olbregts Jean
Publication year - 1993
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/kin.550250208
Subject(s) - chemistry , radical , chlorine , chain reaction , kinetics , hydrogen atom abstraction , photochemistry , chain termination , torr , chlorine atom , medicinal chemistry , organic chemistry , thermodynamics , radical polymerization , physics , quantum mechanics , polymer , copolymer
Abstract Although hydrogen abstraction from 1,1,1,2‐tetrachloroethane should produce only one kind of radical, CCl 3 CHCl, the presence of small amounts of trichloroethene, as impurity as well as product of reaction, induces the formation of the a priori unexpected CHCl 2 CCl 2 radicals. The importance of this radical in the reaction pathways of the chlorination and the chlorine induced dehydrochlorination of CCl 3 CH 2 Cl, under different experimental conditions, is computed and discussed. For example, at 380 K, and for small partial pressures of chlorine (2 torr), the CHCl 2 CCl 2 radicals account for more than 70% of the formation of the reaction products after only 2% reaction. The major role of trace quantities in long chain radical reactions is emphasized. © 1993 John Wiley & Sons, Inc.