Kinetics and mechanisms of the reductions of thallium(III) and chromium(III) by uranium(III) in perchlorate media

Journal Article · Sun May 01 04:00:00 EDT 1977 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50171a013· OSTI ID:7312604

Ekstrom, A; McLaren, A B; Smythe, L E

The kinetics and mechanisms of the reaction of U(III) with Tl(III) and Cr(III) have been examined in perchlorate media. The Tl(III) reaction was found to obey the rate law -d(U(III))/ dt = (U/sup 3 +/)(Tl/sup 3 +/) (k/sub -1/K/(H + K)) in which k/sub -1/ has a value of (3.6 +- 0.2) x 10/sup 5/ M/sup -1/ s/sup -1/ at 20/sup 0/C and an ionic strength of 2.0 M, whereas the Cr(III) reaction was found to exhibit a mechanism dominated by a reaction path having an inverse second-order concentration dependence. The rate constants are compared with those obtained for other similar systems; it is suggested, that the acid concentration independent and the inverse acid concentration dependent reaction paths of many electron-transfer reactions involving metal ions exhibit a limiting rate of 10/sup 6/ to 10/sup 7/ M/sup -1/ s/sup -1/. Plausible reasons for this limiting value are discussed.

• Research Organization: Australian Atomic Energy Commission, Sydney
• OSTI ID: 7312604
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 16:5; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPOUNDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPOUNDS
DISPERSIONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
KINETICS
MIXTURES
REACTION KINETICS
SOLUTIONS
THALLIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
URANIUM COMPOUNDS