Abstract
The rapid reaction of CoIII with hydrazoic acid has been investigated at high initial ratios [HN3]/[CoIII] using the stopped-flow technique. The rate is proportional to [CoIII][HN3]2 and is independent of acidity in the region 0·5–5·0M-HClO4. This is contrasted with the slower reaction at low initial ratios [HN3]/[CoIII]. This system is compared with other cation–HN3 systems, and it is concluded that intermediate hydrazido-complexes are involved in the reaction. The kinetics of the CoIII+ HN3 reaction and other redox reactions of CoIII are consistent with a hydrolysis equilibrium constant for CoIIIaq of Khca. 10–2–10–3 mole l.–1, and the kinetics of substitution reactions of CoIIIaq are not inconsistent with this value for Kh. The mechanism of the CoIII+ HN3 reaction is discussed in terms of possible dimeric species of CoIIIaq.
Published Version
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