Acid–base behaviour of the ferricyanide ion in perchloric acid media. Spectrophotometric and kinetic study

A wide study was carried out of the acid–base behaviour of ferricyanide ions in aqueous perchloric acid media in the range 0.1–11.5 M. This study shows that protonation and decomposition of the ferricyanide ions occur simultaneously. The three successive protonation equilibria were found in the acidity ranges 0.1–4.0, 3.5–8.5, and 7.0–11.5 M HClO4, respectively. A kinetic study was also made of the decomposition reaction at 60 °C. The kinetic data are explained by considering a reaction mechanism involving homolytic and heterolytic dissociation steps. The homolytic and heterolytic rate constants corresponding to each of the four protonated species were determined, along with the acid–base protonation constants, pK1 = −6.25 ± 0.10; pK2 = −3.23 ± 0.03; and pK3 = −0.60 ± 0.02. Keywords: acid–base behaviour, protonated species, decomposition, homolytic dissociation, heterolytic dissociation.