TY - JOUR
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 - 1985/12/1
Y1 - 1985/12/1
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.
UR - http://www.scopus.com/inward/record.url?scp=37049097364&partnerID=8YFLogxK
U2 - 10.1039/DT9850000641
DO - 10.1039/DT9850000641
M3 - Article
AN - SCOPUS:37049097364
SN - 1472-7773
SP - 641
EP - 644
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 4
ER -