Kinetic and product distribution analysis of the reaction of atomic hydrogen with vinyl chloride

Journal Article · Thu Mar 19 04:00:00 EST 1992 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100185a021· OSTI ID:263241

Barat, R B; Bozzelli, J W ^[1]

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1. New Jersey Inst. of Technology, Newark, NJ (United States)

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 C{sub 2}H{sub 3}Cl by reaction with H occurs primarily by nonipso attack by H on the =CH{sub 2} group to form (CH{sub 3}C{center_dot}HCl){sup {double_dagger}}. This energized complex then undergoes an H shift to form (C{center_dot}H{sub 2}CH{sub 2}Cl){sup {double_dagger}}, which decomposes to form Cl + CH{sub 2}=CH{sub 2}. Collisional stabilization of the original adduct is also important. Abstraction of Cl by H is negligible in these conditions. The authors` 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. The authors also utilized transition-state theory for the isomerization reaction, evaluated with literature rate constants and barriers. The authors 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. 26 refs., 13 figs., 7 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 263241
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 6 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CHEMICAL REACTION KINETICS
HYDROGEN
MATHEMATICAL MODELS
VINYL CHLORIDE