Abstract
The increase in the bimolecular rate constant k0 for the reaction of iron(II) with hydrogen peroxide found with added halide ions is also observed with added sulphate, selenate, trimetaphosphate, and triphosphate ions. k0 increases to a limiting value which is different for each anion. Following the interpretation of the results with halide ions, 1:1 complexes of anions with FeII ions are found. Heats ΔH and entropies ΔS of formation of FeSO4, FeSeO4, FeHSO4+, FeHSeO4+, FeP3O9–, and FeHP3O9 are compared with ΔH and ΔS for the halogenoaquoiron(II) complexes and the hydroxoaquoiron(ii) ion. ΔH and ΔS are related to changes in the solvent structure induced by transferring the anion from bulk solvent to the FeII ion. Comparison is also made with ΔH and ΔS for other cation–ligand systems. Energies E and entropies ΔS* of activation for the reactions of these oxyanion aquoiron(II) complexes with H2O2 are compared with E and ΔS* for the reactions of halogenoaquoiron(II) complexes with H2O2.
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