The effect of ionic interactions on the oxidation of metals in natural waters

Frank J. Millero

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144 Scopus citations


The effect of ionic interactions of the major components of natural waters on the oxidation of Cu(I) and Fe(II) has been examined. The various ion pairs of these metals have been shown to have different rates of oxidation. For Fe(II), the chloride and sulfate ion pairs are not easily oxidized. The measured decrease in the rate constant at a fixed pH in chloride and sulfate solutions agrees very well with the values predicted. The effect of pH (6 to 8) on the oxidation of Fe(II) in water and seawater have been shown to follow the rate equation -d in [Fe(II)]/dt = k1β1αFe/[H+] + k2β2αFe/[H+]2 where k1 and k2 are the pseudo first order rate constants, β1 and β2 are the hydrolysis constants for Fe(OH)+ and Fe(OH)0. The value of αFE is the fraction of free Fe2+. The value of k1 (2.0 ±0.5 min-1) in water and seawater are similar within experimental error. The value of k2 (1.2 × 105 min-1) in seawater is 28% of its value in water in reasonable agreement with predictions using an ion pairing model. For the oxidation of Cu(I) a rate equation of the form -d ln [Cu(I)]/dt = k0αCu+ k1β1αCu[Cl] was found where k0 (14.1 sec-1) and k1 (3.9 sec-1) are the pseudo first order rate constants for the oxidation of Cu+ and CuCl0, β1 is the formation constant for CuCl0 and αCu is the fraction of free Cu+. Thus, unlike the results for Fe(II), Cu(I) chloride complexes have measurable rates of oxidation.

Original languageEnglish (US)
Pages (from-to)547-553
Number of pages7
JournalGeochimica et Cosmochimica Acta
Issue number2
StatePublished - Feb 1985

ASJC Scopus subject areas

  • Geochemistry and Petrology


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