Kinetics and mechanism of mercury catalysed ligand exchange reaction between hexacyanoferrate(II) and phenanthroline in aqueous medium

Abstract

Kinetic and mechanistic studies of Hg(II)-catalysed exchange of co-ordinated cyanide in hexacyanoferrate(II) by phenanthroline (Phen) were performed by following the appearance of the coloured complex [Fe(CN)₄ Phen]^3– at 528 nm, temperature = 25 ± 0.10 ⁰C, pH = 3.0 ± 0.02. The effects of pH, [Fe(CN)₆]^4– and [Phen] concentrations on the reaction rate have been studied and explained. The rate shows variable order dependence on [Fe(CN)₆]^4–. The effects of dielectric constant, water content, temperature and ionic strength of the medium on the reaction rates have been used to visualise the formation of a polar activated complex and suggest an interchange dissociative mechanism for the catalysed reaction. The varying catalytic activity of Hg(II) as a function of concentration has also been studied and explained in detail. Activation parameters of both catalysed and uncatalysed reactions has were derived and supported the proposed mechanistic scheme.

Keywords

kinetics and mechanism UV spectroscopy ligand substitution phenanthroline hexacyanoferrate(II)

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