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Atmospheric reactions of chloroethenes with the OH radical
Author(s) -
Tuazon Ernesto C.,
Atkinson Roger,
Aschmann Sara M.,
Goodman Mark A.,
Winer Arthur M.
Publication year - 1988
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550200305
Subject(s) - chemistry , scavenger , chlorine atom , chlorine , vinyl chloride , propene , reaction rate constant , medicinal chemistry , radical , photochemistry , kinetics , organic chemistry , catalysis , physics , quantum mechanics , copolymer , polymer
The kinetics and products of the homogeneous gas‐phase reactions of the OH radical with the chloroethenes were investigated at 298 ± 2 K and atmospheric pressure. Using a relative rate technique and ethane as a scavenger for the chlorine atoms produced in these OH radical reactions, rate constants (in units of 10 −12 cm 3 molecule −1 s −1 ) of 8.11 ± 0.24, 2.38 ± 0.14, and 1.80 ± 0.03 were obtained for 1,1‐dichloroethene, cis ‐1, 2‐dichloroethene and trans ‐1,2‐dichloroethene, respectively. Under these conditions, the major products observed by long pathlength FT‐IR absorption spectroscopy were HCHO and HC(O)Cl from vinyl chloride; HC(O)Cl from cis ‐ and trans ‐1,2‐dichloroethene; HCHO and COCl 2 from 1,1‐dichloroethene; HC(O)Cl and COCl 2 from trichloroethene; and COCl 2 from tetrachloroethene. In the absence of a Cl atom scavenger, significant yields of the chloroacetyl chlorides, CH x Cl 3− x C(O)Cl, were observed from 1,1‐dichloro‐, trichloro‐ and tetrachloroethene, indicating that these products resulted from reactions involving chlorine atoms. The yields of all of these products are reported and the mechanisms of these gas‐phase reactions discussed. In addition, OH radical reaction rate constants were redetermined, in the presence of a Cl atom scavenger, for cis ‐ and trans ‐1,3‐dichloropropene and 3‐chloro‐2‐chloromethyl‐1‐propene, being (in units of 10 −12 cm 3 molecule −1 s −1 ) 8.45 ± 0.41, 14.4 ± 0.8, and 33.5 ± 3.0, respectively.