Coupled diffusion and oxidation of ferrous iron in soils. I. Kinetics of oxygenation of ferrous iron in soil suspension

The kinetics of oxidation of iron in an aqueous suspension of a thoroughly reduced low-humus tropical rice paddy soil were followed by measuring the extractable ferrous iron in the whole suspension and in the solution. Three-quarters of the initial ferrous iron was oxidized rapidly (first-order rate constant = 9.2 × 10^?5 s^?1). The subsequent reaction was slow (first-order rate constant = 9.4 × 10^?7 S^?1) and was not studied in detail. The pH fell from 6.6 to 4.9 over the course of the fast reaction. In further experiments the rate of oxidation was followed at constant pH values in the range 6.5 to 4.5. It was concluded that the oxidation of adsorbed iron was much faster than solution iron, and that the adsorbed iron was oxidized at a rate that was nearly independent of the pH. During the reaction some ferrous iron is adsorbed on the ferric hydroxide formed. The proportion of the remaining ferrous iron adsorbed on ferric hydroxide rather than the original exchange surfaces was high at pH > 6.0 and low at pH < 5.0. The rate of oxidation of the ferrous iron was similar whether it was adsorbed on exchange sites or on the ferric hydroxide formed. Since the rate of oxidation of the iron adsorbed on ferric hydroxide was very much slower than that on ferric hydroxide formed in the absence of soil, it is suggested that the rate in soil may be controlled by diffusion of oxygen to the adsorption sites.