Mechanism of oxidation of iron(II) chelates by hexavalent chromium and heptavalent manganese in aqueous sulfuric acid and micellar media - a kinetic approach

Summary Oxidation of the Fe^II chelates FeL] (L = phen or bipy) by Cr^VI and Mn^VII in H₂SO₄ medium was found to proceed through the formation of a bimetallic insertion complex which decomposes in the slow step, followed by electron transfer from FeL] to the oxidant. The reactions are catalysed by both anionic and non-ionic micelles SDS and triton-x (Tx), respectively]. A mechanism is suggested involving electrostatic stabilization of the cationic forms of the Fe^II chelates by anionic SDS and the partial anionic character of polyoxyethylene moiety of Tx, respectively. The marginal catalysis of cationic micelles (CTAB) is attributed to co-anion-micellar interactions.