The Oxidation of Ferrous Sulfate Solutions By S(IV) and Dissolved Oxygen

The oxidation of Fe(II) with S(IV) and oxygen can be used advantageously in leaching systems requiring both Fe(III) and sulfuric acid; e.g., heap leaching of sulfide-containing ores or concentrates. The oxidation of Fe(II) with SO2/air is several orders of magnitude faster than with air alone; rates of up to ?20 g/L'h were observed at 25°C. The reaction proceeds via an intermediate orange-red mixed-valence Fe(II)/Fe(III) sulfite complex, which is present at an essentially constant concentration throughout most of the oxidation process. The oxidation rate of Fe(II) is approximated by the formula -d[Fe(II)]/dt = k [S(IV)] [02]0'3. The concentration of the mixed-valence complex, and thus the iron oxidation rate, decreases with increasing acidity. Certain impurities, such as SCN- and thiourea, negatively affect the rate. The oxidation reaction 2Fe2 + SO2 + 02 4 2Fe3+ + S042- is accompanied by the side reaction H20 + SO2 + 1/202 4 H2SO4. The side reaction becomes particularly important at low temperatures and whenever the oxygen mass transfer is insufficient with respect to the rate of addition of S(IV). Thus, effective oxygen mass transfer is essential for achieving high oxidation rates with minimal acid formation. The activation energy was estimated as 141 kJ/mol over the temperature range 10-35°C.