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 ≈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) × 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 106 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 •N 3 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 × 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) × 10-12 cm3 molecule-1 s-1.
ASJC Scopus subject areas
- Environmental Chemistry