Kinetics and mechanism of single electron oxidations of the tervalent uranium ion, U3+(aq), by free radicals in aqueous solutions

Daniel Golub; Haim Cohen; Dan Meyerstein

doi:10.1039/DT9850000641

Kinetics and mechanism of single electron oxidations of the tervalent uranium ion, U³⁺(aq), by free radicals in aqueous solutions

Daniel Golub
, Haim Cohen
, Dan Meyerstein

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

The specific rates of oxidation of U³⁺(aq) by OH^., Cl₂^.-, Br₂^.-, I₂^.-, (NCS)₂^.-, ^.CH₂CO₂H, ^.CH(CH₃)CO₂H, ^.CH₂C(CH₃)₂OH, and ^.CH₃ are reported. The results are interpreted as indicating that all these reactions occur via an inner-sphere mechanism with an increase in co-ordination number. This conclusion contradicts earlier suggestions that oxidations of aqua complexes by OH^. radicals proceed via hydrogen-atom abstraction from one of the aqua ligands. The specific rate of the reaction U³⁺(aq) + H₂O₂ is estimated to be 2 × 10⁵ dm³ mol^-1 s^-1.

Original language	English
Pages (from-to)	641-644
Number of pages	4
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	4
DOIs	https://doi.org/10.1039/DT9850000641
State	Published - 1985
Externally published	Yes

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10.1039/DT9850000641

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title = "Kinetics and mechanism of single electron oxidations of the tervalent uranium ion, U3+(aq), by free radicals in aqueous solutions",

abstract = "The specific rates of oxidation of U3+(aq) by OH., Cl2.-, Br2.-, I2.-, (NCS)2.-, .CH2CO2H, .CH(CH3)CO2H, .CH2C(CH3)2OH, and .CH3 are reported. The results are interpreted as indicating that all these reactions occur via an inner-sphere mechanism with an increase in co-ordination number. This conclusion contradicts earlier suggestions that oxidations of aqua complexes by OH. radicals proceed via hydrogen-atom abstraction from one of the aqua ligands. The specific rate of the reaction U3+(aq) + H2O2 is estimated to be 2 {\texttimes} 105 dm3 mol-1 s-1.",

author = "Daniel Golub and Haim Cohen and Dan Meyerstein",

year = "1985",

doi = "10.1039/DT9850000641",

language = "אנגלית",

pages = "641--644",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1472-7773",

number = "4",

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T1 - Kinetics and mechanism of single electron oxidations of the tervalent uranium ion, U3+(aq), by free radicals in aqueous solutions

AU - Golub, Daniel

AU - Cohen, Haim

AU - Meyerstein, Dan

PY - 1985

Y1 - 1985

N2 - The specific rates of oxidation of U3+(aq) by OH., Cl2.-, Br2.-, I2.-, (NCS)2.-, .CH2CO2H, .CH(CH3)CO2H, .CH2C(CH3)2OH, and .CH3 are reported. The results are interpreted as indicating that all these reactions occur via an inner-sphere mechanism with an increase in co-ordination number. This conclusion contradicts earlier suggestions that oxidations of aqua complexes by OH. radicals proceed via hydrogen-atom abstraction from one of the aqua ligands. The specific rate of the reaction U3+(aq) + H2O2 is estimated to be 2 × 105 dm3 mol-1 s-1.

AB - The specific rates of oxidation of U3+(aq) by OH., Cl2.-, Br2.-, I2.-, (NCS)2.-, .CH2CO2H, .CH(CH3)CO2H, .CH2C(CH3)2OH, and .CH3 are reported. The results are interpreted as indicating that all these reactions occur via an inner-sphere mechanism with an increase in co-ordination number. This conclusion contradicts earlier suggestions that oxidations of aqua complexes by OH. radicals proceed via hydrogen-atom abstraction from one of the aqua ligands. The specific rate of the reaction U3+(aq) + H2O2 is estimated to be 2 × 105 dm3 mol-1 s-1.

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SN - 1472-7773

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JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 4

ER -

Kinetics and mechanism of single electron oxidations of the tervalent uranium ion, U³⁺(aq), by free radicals in aqueous solutions

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