Abstract
The oxidations of the ions Cr/sup 3 +/, CO/sup 2 +/, and VO/sup 2 +/ by the fluoroxysulfate ion, SO/sub 4/F/sup -/, in aqueous solution are catalyzed by Ag/sup +/. The rate-determining step for all three catalyzed reactions is the bimolecular oxidation of Ag/sup +/ by SO/sub 4/F/sup -/, which has a rate constant of (1.3 +- 0.2) x 10/sup 3/ M/sup -1/ s/sup -1/ at 17/sup 0/C. Activation parameters for this reaction are ..delta..H/sup + +/ = 6.1 +- 0.5 kcal/mol and ..delta..S = -23 +- 2 cal/(mol deg). In the absence of Ag/sup +/, Co/sup 2 +/, and VO/sup 2 +/ react very slowly with SO/sub 4/F/sup -/, while Cr/sup 3 +/ does not react at all. Despite its high thermodynamic oxidizing power, the fluoroxysulfate ion acts as a very selective oxidant.
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