Kinetics of the reactions of F(/sup 2/P) and Cl(/sup 2/P) with HNO/sub 3/

Journal Article · Thu Apr 21 00:00:00 EDT 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100319a028· OSTI ID:7004459

Wine, P H; Wells, J R; Nicovich, J M

The kinetics of the reactions of HNO/sub 3/ 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 NO/sub 3/ radicals following 351-nm pulsed laser photolysis of X/sub 2//HNO/sub 3//He mixtures (X = F, Cl). Absolute rate coefficients for the F(/sup 2/P) + HNO/sub 3/ 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/sup -12/ exp((400 +/- 120)/T) cm/sup 3/ molecule/sup -1/ s/sup -1/. Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO/sub 3/ production was observed in the experiments with X = Cl, thus establishing that k/sub 2/(298K) < 2 x 10/sup -16/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The Cl(/sup 2/P) + HNO/sub 3/ 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/sup -16/ cm/sup 3/ molecule/sup -1/ s/sup -1/, are 13 at 298 K and 10 at 400 K.

• Research Organization: Georgia Institute of Technology, Atlanta (USA)
• OSTI ID: 7004459
• Journal Information: J. Phys. Chem.; (United States), Vol. 92:8
• Country of Publication: United States
• Language: English

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37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
CHLORINE
CHEMICAL REACTION KINETICS
PHOTOCHEMICAL REACTIONS
FLUORINE
NITRIC ACID
EXPERIMENTAL DATA
MEDIUM TEMPERATURE
PHOTOLYSIS
PULSE TECHNIQUES
TEMPERATURE DEPENDENCE
CHEMICAL REACTIONS
DATA
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HALOGENS
HYDROGEN COMPOUNDS
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INORGANIC ACIDS
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