Reaction of OH Radical with C2H3Cl: Rate Constant and Reaction Pathway Analysis

Document Type

Article

Publication Date

9-30-1999

Abstract

There are two different carbon sites in C2H3Cl where OH addition or abstraction reactions can occur, α and β to the Cl atom, with several dissociation and isomerization products of each addition adduct. Thirteen elementary reactions and 18 species are included in the analysis of this reaction system. Thermochemical kinetic parameters are developed for each elementary reaction process. Chemical activation kinetic analysis with multifrequency QRRK theory for k(E) and master equation for falloff are used to estimate overall rate constants as functions of temperature and pressure. Thermodynamic parameters, including Δ;H°f 298, S°298, and Cp°(T) (300 ≤ T/K ≤ 1500), of stable species are from the literature when available or estimated by the group additivity method. Values for CHC1OHCH2 are determined by density functional calculation and isodesmic reactions. Results are compared with the experimental data. Rate constants (300∼2000 K, in cm3 mol-1 s-1, Ea in cal/mol) for the important addition and abstraction channels at 760 Torr are as follows: k = 1.22 × l084T-25.5 exp(-15000/RT) for C2H3C1 + OH → CHC1OHCH2; k = 1.77 × l040T-9.08 exp(-7240/ RT) for C2H3C1 + OH → CHC1CH2OH; k = 9.72 × 106T2 exp(-3800/RT) for C2H3Cl + OH→ CH2=CCl + H2O; k = 1.69 × 107T2 exp(-4390/RT) for C2H3C1 + OH → CH=CHCl + H2O.

Identifier

0000567009 (Scopus)

Publication Title

Journal of Physical Chemistry A

External Full Text Location

https://doi.org/10.1021/jp9904015

ISSN

10895639

First Page

7800

Last Page

7810

Issue

39

Volume

103

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