Oxidation by aqueous fluoroxysulfate: catalysis by silver(I)

Journal Article · Wed Jul 01 04:00:00 EDT 1981 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50221a035· OSTI ID:6456081

Thompson, R C ^[1]; Appelman, E H

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1. Univ. of Missouri, Columbia

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.

• OSTI ID: 6456081
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 20:7; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ANIONS
CATALYTIC EFFECTS
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPOUNDS
COBALT COMPOUNDS
ELEMENTS
FLUORINE COMPOUNDS
HALOGEN COMPOUNDS
IONS
KINETICS
METALS
OXIDATION
OXYGEN COMPOUNDS
REACTION KINETICS
SILVER
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
VANADIUM COMPOUNDS