Betterton Eric A, Craig David
a Department of Atmospheric Sciences , University of Arizona , Tucson , Arizona , USA.
J Air Waste Manag Assoc. 1999 Nov;49(11):1347-1354. doi: 10.1080/10473289.1999.10463958.
The stoichiometry of the reaction of aqueous ozone with sodium azide was studied at pH 12 (mainly) where a yellow metastable intermediate is observed. We propose that this is hypoazidite (NO ), analogous to hypobromite, and that it plays a central role in the azide catalyzed decompostion of ozone. The yellow intermediate is unstable in acid, in which it rapidly decomposes, generating N and NO. The rate of reaction was studied at pH 2.0-3.5, with the ionic strength at 0.6 M and temperature at 3-15 ° C. The intrinsic second-order rate constants were found to be k ≤ ≈ 400 Msec and k - = (8.7 ± 0.5) × 10 Msec (3 °C, 0.6 M), both in agreement with the only other previous study. The rate constant at 25 °C was estimated using the following experimentally determined parameters: ln k- (Msec) = (5.73 ± 0.36) × 10/T (K) + (28.34 ± 1.27). The value of k- estimated in this way is (2.5 ± 0.1) × 10 Msec at 25 °C and 0.6 M. The enthalpy of reaction (A H) is -48 ± 3 kJ mol.
在pH值为12（主要是此条件）时研究了臭氧水溶液与叠氮化钠反应的化学计量关系，在此条件下观察到一种黄色亚稳中间体。我们认为这是次叠氮酸盐（NO），类似于次溴酸盐，并且它在叠氮化物催化的臭氧分解中起核心作用。该黄色中间体在酸性条件下不稳定，会迅速分解，生成N和NO。在pH值为2.0 - 3.5、离子强度为0.6 M以及温度为3 - 15°C的条件下研究了反应速率。发现本征二级速率常数为k≤≈400 M⁻¹sec⁻¹和k⁻ = (8.7 ± 0.5) × 10³ M⁻¹sec⁻¹（3°C，0.6 M），这与之前仅有的另一项研究结果一致。使用以下实验测定参数估算了25°C时的速率常数：ln k⁻ (M⁻¹sec⁻¹) = (5.73 ± 0.36) × 10³/T (K) + (28.34 ± 1.27)。通过这种方式估算出25°C和0.6 M时k⁻的值为(2.5 ± 0.1) × 10⁴ M⁻¹sec⁻¹。反应焓（ΔH）为 - 48 ± 3 kJ mol⁻¹。
