The iron catalyzed oxidation of sulfur(IV) in aqueous solution: Differing effects of organics at high and low pH

Abstract

We have studied the oxidation of sulfur dioxide by dissolved oxygen in highly dilute solutions with a new differential optical absorption technique. We measured the rate of oxidation catalyzed by iron(III) over a wide range of pH, ionic strength, and in the presence of various organic materials. The studies indicate that noncomplexing organic molecules are highly inhibiting at “high” pH values of 5 and above and are not inhibiting at “low” pH values of 3 and below. Furthermore, the order of the reaction with respect to iron is different in the two pH regimes. This suggests that the mechanism of this reaction differs in the two pH regimes and is probably a free radical chain at high pH and a nonradical mechanism at low pH. Some of the mechanisms proposed in the literature are discussed in the light of these new data. None of the proposed mechanisms give completely satisfactory agreement with the data. We propose a modified free radical chain mechanism for the high pH regime, which correctly predicts the organic inhibitions. For the low pH regime, mechanisms proposed by Conklin and Hoffmann (1988) and by Hoffmann and Jacob (1984) give fair agreement with the pH data and correctly predict the self‐inhibition, the sulfate inhibition, and the ionic strength inhibition. In view of the new data we believe that the iron(III) catalyzed reaction in tropospheric clouds can be a major contributor to the rate of sulfate formation, but there will be significant inhibition of this process by formic acid in some situations.