Mechanism of the oxidation of hydroxylamine by ferricyanide

Abstract
The kinetics of the oxidation of hydroxylammonium ion by ferricyanide has been investigated at low hydrogen-ion concentrations (pH 4·2–5·7). Reaction occurs by the interaction between ferricyanide and unprotonated hydroxylamine. The radical NH3O·first formed is further oxidised except at low ratios for [Fe(CN)6 3–]0 : [NH3OH+]0 where it dimerises and subsequently gives the product. The rate law has been obtained as –d//dt [Fe(CN)6 3–]=k[Fe(CN)6 3–][NH3OH+][H+]–1 with k= 0·69 × 10–6 l. mole–1 sec.–1 at 25 °C.

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