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 also important. Abstraction of Cl by H is negligible at these conditions. Our mechanism is based on quantum Rice-Ramsperger-Kasse (QRRK) analyse of the reactions of the energized adducts from the separately considered ipso and nonipso additions. We also utilized transition-state theory of 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.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry