Kinetics and mechanism of the oxidation of uranium(III) by cobalt(III) in perchlorate media
The kinetics of the oxidation of U(III) by Co(III) was studied in perchlorate media. The rate law of the reaction was found to be given by the expression -d[Co(III)]/dt = k1 [Co(III)][U(III)]. The value of k1 was determined as (1.12 ± 0.1) x 106 M-1 sec-1 at 20°C and ionic strength of 2.00 and was found to be independent of acid concentration at constant ionic strength. The temperature dependence of the reaction was studied in the range 11 to 31°C, and the values of ΔH2+ and ΔS2+ were determined as 2.00 ± 0.25 kcal mole-1 and -25.6 ± 0.8 cal deg-1 mole-1, respectively. In common with many other reactions of Co(III), the rate constant of this reaction is much lower than expected from the very high ΔG0 value and plausible reasons for this observation are discussed.
- Research Organization:
- Australian Atomic Energy Commission, Lucas Heights, Sydney (Australia)
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-33-016699
- OSTI ID:
- 4096107
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 12 Vol. 14; ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
*COBALT COMPOUNDS-- CHEMICAL REACTION KINETICS
*URANIUM COMPOUNDS-- OXIDATION
400702* --Chemistry--Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
MEDIUM TEMPERATURE
N40420* --Chemistry--Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
PERCHLORATES
TEMPERATURE DEPENDENCE
*URANIUM COMPOUNDS-- OXIDATION
400702* --Chemistry--Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
MEDIUM TEMPERATURE
N40420* --Chemistry--Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
PERCHLORATES
TEMPERATURE DEPENDENCE