ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of the reaction have been investigated in H2SO4 medium under different conditions. The observed bimolecular rate constant kobs, has been found to depend on [H+]-0.55 and to increase with the initial concentration ratio of the reactants R0 = [H2O2]0/[U (IV)]0 above 0.49. The activation energy of the overall reaction has been determined as 13.79 and 14.3 kcal/mol at R0 = 1 and 0.35, respectively. Consistent with experimental data, a detailed reaction mechanism has been proposed where the hydrolytic reaction (4) followed by the rate-controlling reaction (10) and subsequent fast reactions of U (V) and OH radicals are involved: A kinetic expression has been derived from which a graphical evaluation of (kK4)-1 and k-1 has been made at R0 = 1 as (12.30 ± 0.09) × 10-3 M min, (6.23 ± 2.19) × 10-4 M min; and at R0 = 0.35 as (12.63 ± 2.13) × 10-3 M min, (8.32 ± 6.62) × 10-4 M min, respectively. Indications of some participation of a chain reactionat R0 = 1 have been obtained without affecting thesecond-order kinetics as observed.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550130405
