Thermal gas-phase decomposition of chloroethylenes. II. Vinyl chloride

The thermal gas-phase decomposition of vinyl chloride has been studied behind shock waves over the temperature range of 1350-1900°K and the density range of 7 × 10^?7-1.5 × 10^?3 mol/cm³ (at 1600°K) in mixtures of C₂H₃Cl highly diluted with argon. The ultraviolet absorption of C₂H₃C was recorded at 230 nm as a function of time. The decomposition proceeds via molecular elimination of HCl. The unimolecular dissociation rate is pressure dependent at all but the highest pressures applied. Application of modified HKRR theory results in the rate expression for the limiting high pressure rate constant, and in a collision efficiency of derived from the limiting low-pressure rate constant.