Abstract
The rapid reaction of CeIV with hydrazoic acid in perchlorate media has been followed by use of the stopped-flow technique. Oscilloscope traces show a rapid rise in optical density followed by a slower, but still rapid, decay: the rise is ascribed to the formation of CeIV–hydrazoic acid complexes, and the decay to the oxidation of hydrazoic acid. A detailed kinetic study of the latter reaction shows that it is of the first order in [CeIV] and zero order in both [H+] and [HN3]: the consumption ratio Δ[CeIV]/Δ[HN3]= 1·0. These kinetic orders contrast with those found for the oxidation of hydrazoic acid by other cations, and they are discussed in terms of mechanisms involving hydrazido- and azido-complexes. The low value for the activation energy contrasts with the values obtained for the oxidation of hydrazoic acid by other cations.
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