Redox chemistry of hyponitrite: Part III-oxidation by hexacyanoferrate(III) in aqueous alkaline solution

Abstract

Oxidation of hyponitrite by hexacyanoferrate(III) in alkaline solution occurs by two paths resulting in a stoichiometry of 1.21:1(oxidant:substrate). The final products are N₂O,N₂ and NO<img src='/image/spc_char/3_bar.gif' border=0>, and the intermediates are NO<img src='http://www.niscair.res.in/jinfo/two.gif' border=0> and peroxonitrite. Rate has first order dependence in [Fe(CN)<img src='http://www.niscair.res.in/jinfo/threebysix.gif' border=0>] and [(N₂O<img src='http://www.niscair.res.in/jinfo/twobytwo.gif' border=0>] and no dependence on [OH^-]. The second order rate constant is found to be (0.87 &plusmn; 0.025) dm³ mol^-1 at 35&deg; and <em>1= </em>0.515 mol dm^-3. Rate significantly increases in the presence of alkali metal cations.