Unusual Thermal Decomposition of Ag super(II)SO sub(4) Yielding Ag super(I) sub(2)S sub(2 )O sub(7): Bending Hammond's Rule

O sub(2) at low expense from Ag super(II)SO sub(4): Silver(II) sulfate provides the first example among metal sulfates of low-temperature "reductive" thermal decomposition, which results in Ag super(I) disulfate and molecular dioxygen. Despite the similarity of this reaction to the one known for peroxodisulfates (e.g., K sub(2)S sub(2)O sub(8)), the thermodynamics and kinetics of both processes are markedly different, and when compared they severely disobey Hammond's rule (see scheme).