Oxidizing radical formed by reaction of e/sub aq//sup -/ and SF/sub 6//sup 1/. [Kinetics]

Journal Article · Sun Aug 01 04:00:00 EDT 1976 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100557a002· OSTI ID:7349390

Bansal, K M; Fessenden, R W

Evidence from optical absorption pulse radiolysis experiments is presented for the existence of an oxidizing radical other than OH produced by the reaction of SF/sub 6/ and e/sup -//sub aq/. This radical is capable of oxidizing phenol and hydroquinone directly to phenoxyl and p-semiquinone ion radicals, respectively, even at neutral pH. From an analysis of the yield and kinetics of formation of the p-semiquinone ion it was found that the intermediate reacts with water with a rate constant of approximately 1.1 x 10/sup 5/ s/sup -1/. The reaction with hydroquinone has a rate constant of 1.7 x 10/sup 9/ M/sup -1/ s/sup -1/. Conductometric pulse radiolysis experiments are in agreement with the optical results. The radical .SF/sub 5/ is the simplest and most probable candidate for the oxidizing species. Sulfur hexafluoride can conveniently be used to introduce a strongly oxidizing radical into various systems where e/sup -//sub aq/ can be scavenged. This approach is demonstrated for methanol solution by the production of Br/sub 2//sup -/ from 10/sup -2/ M KBr.

• Research Organization: Carnegie-Mellon Univ., Pittsburgh
• OSTI ID: 7349390
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 80:6; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400200 -- Inorganic
Organic
& Physical Chemistry
400600* -- Radiation Chemistry
AROMATICS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
ELECTRONS
ELEMENTARY PARTICLES
FERMIONS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROXY COMPOUNDS
IRRADIATION
KINETICS
LEPTONS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDATION
PHENOL
PHENOLS
PULSED IRRADIATION
QUINONES
REACTION KINETICS
SOLVATED ELECTRONS
SULFUR COMPOUNDS
SULFUR FLUORIDES