Atmospheric chemistry of tetrachloroethene (Cl{sub 2}C{double{underscore}bond}CCl{sub 2}): Products of chlorine atom initiated oxidation

Journal Article · Thu Oct 28 04:00:00 EDT 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp991929c· OSTI ID:20003222

Thuener, L P; Barnes, I; Becker, K H; Wallington, T J; Christensen, L K; Orlando, J J; Ramacher, B

The products following Cl atom initiated oxidation of C{sub 2}Cl{sub 4} at 700--760 Torr of air and 230--299 K in the presence and absence of NO{sub x} were investigated using three different FTIR smog chamber techniques. There was no measurable effect of temperature on the product yields. CCl{sub 3}C(O)Cl and COCl{sub 2} were formed with molar yields of 68 {+-} 6% and 77 {+-} 12% in the presence of NO{sub x} and 0.84 and 0.16 in the absence of NO{sub x}. Contrary to a recent report by Hasson and Smith, variation of the initial C{sub 2}Cl{sub 4} by a factor of 300 over the range (0.016--5.6) x 10{sup 14} molecule cm{sup {minus}3} had no discernible effect ({lt}10%) on the product distributions. The different product distribution observed in the presence of NO{sub x} may reflect the formation and subsequent decomposition of chemically activated C{sub 2}Cl{sub 5}O radicals, formed in the exothermic reaction of C{sub 2}Cl{sub 5}O{sub 2} with NO. The kinetics of the reaction of Cl atoms with C{sub 2}Cl{sub 4} were measured in 2.0--700 Torr of air at 296 K. The results are in good agreement with the previous study by Nicovich et al. The combined data can be described using F{sub c} = 0.6, k{sub o}= (1.8 {+-} 0.3) x 10{sup {minus}28} cm{sup 6} molecule{sup {minus}2}s{sup {minus}1} and k{sub {infinity}} = (4.0 {sup {minus}} 0.4) x 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Results are discussed with respect to the atmospheric chemistry of C{sub 2}Cl{sub 4}.

• Research Organization: Bergische Univ. GH Wuppertal (DE)
• OSTI ID: 20003222
• 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: 43 Vol. 103; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
ATMOSPHERIC CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
NITROGEN OXIDES
ORGANIC SOLVENTS
OXIDATION