Kinetic and Product Distribution Analysis of the Reaction of Atomic Hydrogen with Vinyl Chloride

Article abstract of DOI:10.1021/j100185a021

An elementary reaction mechanism has been developed to model the experimentally observed loss of vinyl chloride by reaction with atomic hydrogen, as well as the observed products.At the low-pressure, room temperature experimental conditions, the consumption of C2H3Cl by reaction with H occurs primarily by nonipso attack by H on the =CH2 group to form (CH3C.HCl)^<*>.This energized complex then undergoes an H shift to form (C.H2CH2Cl)^<*>, which decomposes to form Cl + CH2=CH2.Collisional stabilization of the original adduct is alo important.Abstraction of Cl by H is negligible at these conditions.Our mechanism is based on quantum Rice-Ramsperger-Kassel (QRRK) analysis of the reactions of the energized adducts from the separately considered ipso and nonipso additions.We also utilized transition-state theory for the isomerization reactions, evaluated with literature rate constants and barriers.We extend the QRRK calculations to higher pressures and temperatures for use by the modeling community.A mechanistic pathway is presented to explain the formation of the various reaction products observed.