Iron(VI) and iron(V) oxidation of copper(I) cyanide.
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Copper(Il) cyanide (Cu(CN)4(3-)) in the gold mine industry presentsthe biggest concern in cyanide management because it is much more stable than free cyanide. Cu(CN)4(3-) is highlytoxic to aquatic life; therefore, environmentally friendly techniques are required for the removal of Cu(CN)4(3-) from gold mine effluent. The oxidation of Cu(CN)4(3-) by iron-(VI) (FeVIO4(2-), Fe(VI)) and iron(V) (FeVO4(3-), Fe(V)) was studied using stopped-flow and premix pulse radiolysis techniques. The stoichiometry with Fe(VI) was determined to be 5HFeO(4-) + Cu(CN)4(3-) + 8H2O - > 5Fe(OH)3 + Cu2+ + 4CNO- +3/202 + 6OH-. The rate law for the oxidation of Cu(CN)4(3-) by Fe(VI) was found to be first-order with each reactant. The rates decreased with increasing pH and were mostly related to a decrease in concentration of reactive protonated Fe(VI) species, HFeO4-. A mechanism is proposed that agrees with the observed reaction stoichiometry and rate law. The rate constant for the oxidation of Cu(CN)4(3-) by Fe(V) was determined at pH 12.0 as 1.35 +/- 0.02 x 10(7) M(-1) s(-1), which is approximately 3 orders of magnitude larger than Fe(VI). Results indicate that Fe(VI) is highly efficient for removal of cyanides in gold mill effluent.
author list (cited authors)
Sharma, V. K., Burnett, C. R., Yngard, R. A., & Cabelli, D. E.