Abstract
The reactions of Cl with hydrocarbons have been the subjects of study since the early days of experimental chemical kinetics. The reactions of Cl atoms with alkanes are prototypical atom abstractions; the reactions with alkenes and alkynes display a richer chemistry because of the possibility of addition to form a chlorinated hydrocarbon radical. This review discusses recent infrared absorption investigations of the reactions of Cl with unsaturated hydrocarbons, with an emphasis on deconvolution of the addition and metathesis (i.e. abstraction or addition-elimination) pathways. These experiments are described in relation to other Cl+ hydrocarbon reactions, and several examples illustrate the sensitivity of the kinetic and mechanistic behaviour of the Cl+ alkene reactions to the thermochemistry of the individual systems. In the Cl+C2H4 reaction, where metathesis is endothermic, addition dominates except at elevated temperatures or low pressures, but the exothermic metatheses of Cl with C3 unsaturated speci...
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