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HERO ID
7537113
Reference Type
Journal Article
Title
Atmospheric chemistry of hydrazoic acid (HN3): UV absorption spectrum, HO reaction rate, and reactions of the N3 radical
Author(s)
Orlando, JJ; Tyndall, GS; Betterton, EA; Lowry, J; Stegall, ST
Year
2005
Is Peer Reviewed?
1
Journal
Environmental Science & Technology
ISSN:
0013-936X
EISSN:
1520-5851
Volume
39
Issue
6
Page Numbers
1632-1640
Language
English
PMID
15819219
DOI
10.1021/es048178z
Web of Science Id
WOS:000227636300039
URL
http://
://WOS:000227636300039
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Abstract
Processes related to the tropospheric lifetime and fate of hydrazoic acid, HN3, have been studied. The ultraviolet absorption spectrum of HN3 is shown to possess a maximum near 262 nm with a tail extending to at least 360 nm. The photolysis quantum yield for HN3 is shown to be approximately 1 at 351 nm. Using the measured spectrum and assuming unity quantum yield throughout the actinic region, a diurnally averaged photolysis lifetime near the earth's surface of 2-3 days is estimated. Using a relative rate method, the rate coefficient for reaction of HO with HN3 was found to be (3.9 +/-0.8) x 10(-12) cm3 molecule(-1) s(-1), substantially larger than the only previous measurement. The atmospheric HN3 lifetime with respect to HO oxidation is thus about 2-3 days, assuming a diurnally averaged [HO] of 10(6) molecule cm(-3). Reactions of N3, the product of the reaction of HO with HN3, were studied in an environmental chamber using an FTIR spectrometer for end-product analysis. The N3 radical reacts efficiently with NO, producing N2O with 100% yield. Reaction of N3 with NO2 appears to generate both NO and N2O, although the rate coefficient for this reaction is slower than that for reaction with NO. No evidence for reaction of N3 with CO was observed, in contrast to previous literature data. Reaction of N3 with O2 was found to be extremely slow, k < 6 x 10(-20) cm3 molecule(-1) s(-1), although this upper limit does not necessarily rule out its occurrence in the atmosphere. Finally, the rate coefficient for reaction of Cl with HN3 was measured using a relative rate method, k = (1.0+/-0.2) x 10(-12) cm3 molecule(-1) s(-1).
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