Kinetics and mechanism of the reaction of azide with ozone in aqueous solution

被引:18
|
作者
Betterton, EA [1 ]
Craig, D [1 ]
机构
[1] Univ Arizona, Dept Atmospher Sci, Tucson, AZ 85721 USA
来源
关键词
D O I
10.1080/10473289.1999.10463958
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
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 (N3O-), 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-2 and NO2-. 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 degrees C. The intrinsic second-order rate constants were found to be k(HN3) less than or equal to approximate to 400 M(-1)sec(-1) and k(N3)- = (8.7 +/- 0.5) x 10(5) M(-1)sec(-1) (3 degrees C, 0.6 M), both in agreement with the only other previous study. The rate constant at 25 degrees C was estimated using the following experimentally determined parameters: In k(N3)- (M(-1)sec(-1)) = (5.73 +/- 0.36) x 10(3)/T (K) + (28.34 +/- 1.27). The value of k(N3)- estimated in this way is (2.5 +/- 0.1) x 10(6)M(-1)sec(-1) at 25 degrees C and 0.6 M. The enthalpy of reaction (Delta H) is -48 +/- 3 kJ mol(-1).
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页码:1347 / 1354
页数:8
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