Kinetics of the oxidation of hydrogen azide (hydrazoic acid) by bis(2,2′-bipyridine)manganese(III) ions in aqueous perchlorate media
Abstract
On mixing HN3 with solutions containing [Mn(bipy)2]3+(aq)(bipy = 2,2′-bipyridine) the absorbance at 400 nm first increases before decreasing to zero. The analysis of the absorption coefficient extrapolated to zero time for the rise in absorbance shows that two 1 : 1 complexes are formed between N3– and [Mn(bipy)2]3+. The kinetics of the subsequent decay in absorbance shows that both these complexes, [Mn(bipy)2(N3)]2+ and [Mn(bipy)2(OH)(N3)]+, are involved in the oxidation process producing free radicals N3˙. This oxidation is compared with the kinetics of the oxidation of HN3 by aqua cations and by [Ni(bipy)3]3+.