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Hydrolysis of Ferrous Ions : a Kinetic Method for the Determination of the Fe(II) Species

Abstract

WE have recently shown1 that the increase in the rate of the reaction of Fe(II) with hydrogen peroxide obtained by the addition of anions, Xn, such as Cl−, SO2−4, P3O3−9 and HP3O2−9, is due to the species FeX2–n reacting more rapidly with hydrogen peroxide than the hexa-aquoferrous ion. Following Hardwick's single observation2 in perchlorate media that the rate at [H+] = 5.3 × 10−4 M is slightly greater than at lower pH, we have extended our investigation to higher pHs. We find that the observed bimolecular rate constant k0 in perchlorate media under nitrogen remains constant over a wide range of acidity, and then changes quickly over a narrow pH range to a higher limiting value which remains unchanged when the acidity is decreased further. Such a plot of k0 against [H+3O] is shown in Fig. 1, and resembles curves usually associated with acid-base reactions, for example, a titration curve.

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WELLS, C., SALAM, M. Hydrolysis of Ferrous Ions : a Kinetic Method for the Determination of the Fe(II) Species. Nature 205, 690–692 (1965). https://doi.org/10.1038/205690b0

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