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'Surprising kinetics' or the major role of trace quantities in radical chain mechanisms

par Olbregts, Jean
Référence International journal of chemical kinetics, 25, 2, page (125-135)
Publication Publié, 1993-02

Article révisé par les pairs

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Résumé :

Although hydrogen abstraction from 1,1,1,2-tetrachloroethane should produce only one kind of radical, CCl3CHCl, the presence of small amounts of trichloroethene, as impurity as well as product of reaction, induces the formation of the a priori unexpected CHCl2CCl2 radicals. The importance of this radical in the reaction pathways of the chlorination and the chlorine induced dehydrochlorination of CCl3CH2Cl, under different experimental conditions, is computed and discussed. For example, at 380 K, and for small partial pressures of chlorine (2 torr), the CHCl2CCl2 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.