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Thermochemistry and Kinetics of the Cl+O2 Association ReactionLaser flash photolysis of Cl2/O2 mixtures has been employed in conjunction with Cl((sup 2)P(sub 3/2)) detection by time-resolved fluorescence spectroscopy to investigate equilibration kinetics for the reactions Cl + O2 + O is in equilibrium with ClOO + O2 at temperatures of 181-200 K and O2 pressures of 15-40 Torr. The third-order rate coefficient for the association reaction at 186.5 +/- 5.5 K is (8.9 +/- 2.9) x 10(exp -33) cm(exp 6) molecule(exp -2) s(exp -1) and the equilibrium constant (K(p)) at 185.4 K is 18.9 atm(exp -1) (factor of 1.7 uncertainty). A third law analysis of our data leads to a value for the Cl-OO bond dissociation energy of 4.76 +/- 0.49 kcal mol(exp -1).
Document ID
Document Type
Reprint (Version printed in journal)
Nicovich, J. M.
(Georgia Tech Research Inst. Atlanta, GA United States)
Kreutter, K. D.
(Georgia Tech Research Inst. Atlanta, GA United States)
Shackelford, C. J.
(Georgia Tech Research Inst. Atlanta, GA United States)
Wine, P. H.
(Georgia Tech Research Inst. Atlanta, GA United States)
Date Acquired
August 17, 2013
Publication Date
April 9, 1997
Publication Information
Publication: Laboratory Investigations of Stratospheric Halogen Chemistry
ISSN: 0009-2614
Subject Category
Inorganic And Physical Chemistry
Funding Number(s)
Distribution Limits
Work of the US Gov. Public Use Permitted.
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