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Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.
Document ID
Acquisition Source
Document Type
Reprint (Version printed in journal)
Wine, P. H.
(Georgia Inst. of Tech. Atlanta, GA United States)
Wells, J. R.
(Georgia Inst. of Tech. Atlanta, GA United States)
Nicovich, J. M.
(Georgia Inst. of Tech. Atlanta, GA United States)
Date Acquired
August 17, 2013
Publication Date
April 9, 1997
Publication Information
Publication: Laboratory Investigations of Stratospheric Halogen Chemistry
Publisher: American Chemical Society
ISSN: 0022-3654
Subject Category
Inorganic And Physical Chemistry
Funding Number(s)
Distribution Limits
Work of the US Gov. Public Use Permitted.
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