Reaction of OH radical with C{sub 2}H{sub 3}Cl: Rate constant and reaction pathway analysis

Journal Article · Thu Sep 30 04:00:00 EDT 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp9904015· OSTI ID:20001128

Zhu, L; Bozzelli, J W; Ho, W P

There are two different carbon sites in C{sub 2}H{sub 3}Cl where OH addition or abstraction reactions can occur, {alpha} and {beta} 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 {Delta}H{degree}{sub f}{sub 298}, S{degree}{sub 298}, and C{degree}{sub p}(T) (300 {le} T{vert{underscore}bar}K {le} 1,500), of stable species are from the literature when available or estimated by the group additivity method. Values for CHClOHCH{sub 2} are determined by density functional calculation and isodesmic reactions. Results are compared with the experimental data. Rate constants (300{approximately}2000 K, in cm{sup 3}mol{sup {minus}1}s{sup {minus}1}, E{sub a} in cal/mol) for the important addition and abstraction channels at 760 Torr are as follows: k = 1.22 x 10{sup 84}T{sup {minus}25.5} exp({minus}15,000/RT) for C{sub 2}H{sub 3}Cl + OH {r{underscore}arrow} CHClOHCH{sub 2}; k = 1.77 x 10{sup 40}T{sup {minus}9.08}exp({minus}7,240/RT) for C{sub 2}H{sub 3}Cl + OH {r{underscore}arrow} CHClCH{sub 2}OH; k = 9.72 x 10{sup 6}T{sup 2} exp({minus}3,800/RT) for C{sub 2}H{sub 3}Cl + OH {r{underscore}arrow} CH{sub 2}={dot C}CI + H{sub 2}O; k = 1.69 x 10{sup 7}T{sup 2} exp({minus}4,390/RT) for C{sub 2}H{sub 3}Cl + OH {r{underscore}arrow} {dot C}H=CHCl + H{sub 2}O.

• Research Organization: New Jersey Inst. of Tech., Newark, NJ (US)
• OSTI ID: 20001128
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 39 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

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