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Ca 2+ ‐Induced Oxygen Generation by FeO 4 2− at pH 9 – 10
Author(s) -
Ma Li,
Lam William W. Y.,
Lo PoKam,
Lau KaiChung,
Lau TaiChu
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201510156
Subject(s) - chemistry , decomposition , oxygen , ion , inorganic chemistry , nuclear chemistry , crystallography , organic chemistry
Although FeO 4 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, FeO 4 2− is readily activated by Ca 2+ at pH 9–10 to generate O 2 . The reaction has the following rate law: d[O 2 ]/d t = k Ca [Ca 2+ ][FeO 4 2− ] 2 . 18 O‐labeling experiments show that both O atoms in O 2 come from FeO 4 2− . These results together with DFT calculations suggest that the function of Ca 2+ is to facilitate O–O coupling between two FeO 4 2‐ ions by bridging them together. Similar activating effects are also observed with Mg 2+ and Sr 2+ .