Three   metathetical (ligand exchange) reactions have been performed: (i) AgF_2(s) + CF₃SO₃H_(l), (ii) AgF₂ + FSO₃H_(l), (iii) Ag(SbF₆)_{2(dissolved in HF)} + K₂SO_{4(dissolved in HF)}. The solid products have been subject to combined thermogravimetric / calorimetric / evolved gas analysis involving infrared spectroscopy of evolved gases using Bruker’s Vertex 80V vacuum FT–IR spectrometer. All products decompose thermally in two distinct steps in the temperature range 80–400 ^oC yielding derivatives of Ag(I) and simultaneously evolving O₂ and/or SO₃, and peroxo dimers: (SO₃F)₂ or (SO₃CF₃)₂ (in equilibrium with their corresponding radicals: SO₃F, SO₃CF₃). Solid products of the metathetical reactions (i-iii) and solid products of their thermal decomposition have been studied with FT mid- and far-IR spectroscopy. Analyses performed indicate that reaction (i) leads to Ag(SO₃CF₃)₂, reaction (ii) to an unidentified oxo- derivative, possibly Ag(SO₃F)₂, while reaction (iii) to either Ag^IISO₄ or its electromeric peroxo form Ag^I₂S₂O₈. Complete thermal decomposition of (i) leads to Ag^I(SO₃CF₃), that of (iii) to an unidentified product different from Ag^I(SO₃F), while that of (iii) to Ag^I₂SO₄.

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