Kinetic analysis radical halogenations

A simplified reaction scheme for the kinetic analysis of radical chain halogenations can be formulated as follows ... 

The kinetic parameter for the radical dissociation of a carbon—halogen terminal was obtained with the use of an isolated polystyrene with a terminal C—Br bond in the presence of a copper catalyst and a conventional radical initiator with a long half-life.282-283 The result was compared with that of low molecular weight compounds of similar carbon-halogen bonds.163 The second-order rate constant of the model compound 1-13 (X = Br), an effective initiator for styrene, is comparable to that of the polymer terminal. Alternatively, rate constants can be obtained by using a combination of nitroxide-exchange reactions and HPLC analysis.242... 

The next chapter reviews the reactions of free atoms and radicals which play an important role in the modeling of complex processes occurring in the polluted atmosphere and in combustion chemistry. J. Jodkowski discusses the computational models of the reaction rate theory most frequently used in the theoretical analysis of gas-phase reaction kinetics and presents examples of the reactions of reactive components of the polluted atmosphere, such as 02, NOx, OH, NH2, alkyl radicals, and halogen atoms. Kinetic parameters of the reactions under investigation are provided in an analytical form convenient for kinetic modeling studies. The presented expressions allow for a successful description of the kinetics of the reaction systems in a wide temperature range and could be used in kinetic studies of related species. 

---