Kinetics and mechanism of the reaction of sodium azide with hypochlorite in aqueous solution.

Production of toxic sodium azide (NaN(3)) surged worldwide over the past two decades to meet the demand for automobile air bag inflator propellant. Industrial activity and the return of millions of inflators to automobile recycling facilities are leading to increasing release of NaN(3) to the environment so there is considerable interest in learning more about its environmental fate. Water soluble NaN(3) could conceivably be found in drinking water supplies so here we describe the kinetics and mechanism of the reaction of azide with hypochlorite, which is often used in water treatment plants. The reaction stoichiometry is: HOCl + 2N(3)(-) = 3N(2) + Cl(-) + OH(-), and proceeds by a key intermediate chlorine azide, ClN(3), which subsequently decomposes by reaction with a second azide molecule in the rate determining step: ClN(3) + N(3)(-) --> 3N(2) + Cl(-) (k = 0.52+/-0.04 M(-1) s(-1), 25 degrees C, mu = 0.1 M). We estimate that the half-life of azide would be approximately 15 s at the point of chlorination in a water treatment plant and approximately 24 days at some point downstream where only residual chlorine remains. Hypochlorite is not recommended for treatment of concentrated azide waste due to formation of the toxic chlorine azide intermediate under acidic conditions and the slow kinetics under basic conditions.

Atmospheric chemistry of hydrazoic acid (HN3): UV absorption spectrum, HO reaction rate, and reactions of the N3 radical.

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).