Unusual Thermal Decomposition of AgIISO4 Yielding AgI2S2O7: Bending Hammond’s Rule

Przemysław Jan Malinowski, Mariana Derzsi, Armand Budzianowski, Piotr J. Leszczyński, Bartłomiej Gaweł, Zoran Mazej and Wojciech Grochala

Issue Chemistry – A European Journal Volume 17, Issue 38, pages 10524–10527,
Chem. Eur. J., 17: 10524–10527. doi: 10.1002/chem.201101952


O2 at low expense from AgIISO4: Silver(II) sulfate provides the first example among metal sulfates of low-temperature “reductive” thermal decomposition, which results in AgI disulfate and molecular dioxygen. Despite the similarity of this reaction to the one known for peroxodisulfates (e.g., K2S2O8), the thermodynamics and kinetics of both processes are markedly different, and when compared they severely disobey Hammond’s rule (see scheme).