The effect of pH on the kinetics of spontaneous Fe(II) oxidation by O2 in aqueous solution--basic principles and a simple heuristic description.

The spontaneous chemical oxidation of Fe(II) to Fe(III) by O(2) is a complex process involving meta-stable partially oxidized intermediate species such as green rusts, which ultimately transform into a variety of stable iron oxide end-products such as hematite, magnetite, goethite and lepidocrocite. Although in many practical situations the nature of the end-products is of less interest than the oxidation kinetics, it is difficult to find in the literature a description of all the basic steps and principles governing the kinetics of these reactions. This paper uses basic aquatic-chemistry equilibrium theory as the framework upon which to present a heuristic model of the oxidation kinetics of Fe(II) species to ferric iron by O(2). The oxidation rate can be described by the equation (in units of mol Fe(II)/(l min)): -d[Fe(2+)]/dt = 6 x 10(-5)[Fe(2+)]+1.7[Fe(OH)(+)]+4.3 x 10(5)[Fe(OH)(2)(0)]. This rate equation yields a sigmoid-shaped curve as a function of pH; at pH values below approximately 4, the Fe(2+) concentration dominates and the rate is independent of pH. At pH> approximately 5, [Fe(OH)(2)(0)] determines the rate because it is far more readily oxidized than both Fe(2+) and FeOH(+). Between pH 5 and 8 the Fe(OH)(2)(0) concentration rises steeply with pH and the overall oxidation rate increases accordingly. At pH values> approximately 8 [Fe(OH)(2)(0)] no longer varies with pH and the oxidation rate is again independent of pH. The paper presents a heuristic overview of the pH dependent kinetics of aqueous ferrous oxidation by O(2(aq)) which we believe will be useful to professionals at both research and technical levels.