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Kinetics of the reactions of CF sub 2 ClO sub 2 radicals with nitrogen dioxide

Journal Article · · Journal of Physical Chemistry; (USA)
DOI:https://doi.org/10.1021/j100367a036· OSTI ID:6663796
;  [1]
  1. Univ. of Minnesota, Minneapolis (USA)

The kinetics of the reaction of CF{sub 2}ClO{sub 2} radicals with NO{sub 2} at 298 K, investigated by flash photolysis with time-resolved mass spectrometry, are reported. The peroxy radical, CF{sub 2}ClO{sub 2}, was formed in broadband flash photolysis of CF{sub 2}ClBr in the presence of O{sub 2} and detected mass spectrometrically via the fragment ion, CF{sub 2}O{sub 2}{sup +}. With NO{sub 2} present, peroxy radical decay occurs by pseudo-first-order kinetics. The decay rates are also first order in NO{sub 2}. The second-order rate coefficients are pressure dependent over the 1-10 Torr experimental range. The pressure-dependent rate coefficients were fitted by the Troe expression for termolecular reactions. Numerical simulation of the peroxy radical decay rates, using a mechanism consisting of known reactions that also occur in this system, were done to investigate the influence of secondary reactions on the measured rates.

OSTI ID:
6663796
Journal Information:
Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:4; ISSN 0022-3654; ISSN JPCHA
Country of Publication:
United States
Language:
English