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The solubility of magnetite and the hydrolysis and oxidation of Fe2+ in water to 300°C

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Abstract

The solubility of carefully characterized magnetite, Fe3O4, in dilute aqueous solutions saturated with H2 has been measured at temperatures from 100 to 300°C in a flow apparatus. Solution compositions included either HCl or NaOH molalities of up to 1 and 40 mmole-kg−1, respectively, and H2 molalities of 0.0779, 0.779, and 8.57 mmole-kg−1. The dependence of the equilibrium solubility on the pH and reduction potential were fitted to a scheme of soluble ferrous and ferric species consisting of Fe2+, FeOH+, Fe(OH)2, Fe(OH) −3 , Fe(OH)3, and Fe(OH) −4 . Solubility products from the fit, corresponding to the reactions

$$\tfrac{1}{3}Fe_3 O_4 + (2 - b)H^ + + \tfrac{1}{3}H_2 \rightleftharpoons Fe(OH)_b^{2 - b} + (4/3 - b)H_2 O$$

and

$$\tfrac{1}{3}Fe_3 O_4 + (3 - b)H^ + \rightleftharpoons Fe(OH)_b^{3 - b} + \tfrac{1}{6}H_2 + (4/3 - b)H_2 O$$

were used to derive thermodynamic constants for each species. The extrapolared value for the Gibbs energy of formation of Fe2+ at 25°C is −88.92±2.0 kJ-mole−1, consistent with standard reduction potentials in the range Eo(Fe2+)=−0.47±0.01 V. The temperature coefficient of the equilibrium Fe molality, (∂m(Fe, sat.)/∂T)m(H2).m(NaOH), changes from negative to positive as the NaOH molality is increased to the point where Fe(OH) −3 and Fe(OH) −4 predominate.

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Authors and Affiliations

  1. Research Chemistry Branch, Whiteshell Nuclear Research Establishment, Atomic Energy of Canada Limited, R0E 1L0, Pinawa, Manitoba, Canada, R0E 1L0

    Peter R. Tremaine & Jacques C. LeBlanc

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  1. Peter R. Tremaine
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  2. Jacques C. LeBlanc
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Tremaine, P.R., LeBlanc, J.C. The solubility of magnetite and the hydrolysis and oxidation of Fe2+ in water to 300°C. J Solution Chem 9, 415–442 (1980). https://doi.org/10.1007/BF00645517

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  • DOI: https://doi.org/10.1007/BF00645517

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