Ca²⁺‐Induced Oxygen Generation by FeO₄²⁻ at pH 9<b>–</b>10

Abstract

Although FeO4(2-) (ferrate(IV)) is a very strong oxidant that readily oxidizes water in acidic medium, at pH 9-10 it is relatively stable (<2 % decomposition after 1 h at 298 K). However, FeO4(2-) is readily activated by Ca(2+) at pH 9-10 to generate O2. The reaction has the following rate law: d[O2]/dt=kCa [Ca(2+) ][FeO4(2-)](2). (18)O-labeling experiments show that both O atoms in O2 come from FeO4(2-). These results together with DFT calculations suggest that the function of Ca(2+) is to facilitate O-O coupling between two FeO4 (2-) ions by bridging them together. Similar activating effects are also observed with Mg(2+) and Sr(2+).