To complement earlier studies of the complexation kinetics of Np(V) and U(VI) by oxydiacetic acid and several diphosphonic acids, the rate of complexation of these metal ions by dipicolinic acid (pyridine-2,6-dicarboxylic acid, DPA) has been investigated by stopped-flow spectrophotometry. This ligand is distinguished from the previously studied species by the rigid planar arrangement of the ligand functional groups and the presence of a pyridine nitrogen donor atom. Reactions of DPA with UO22+ at p[H] 1 and NpO2+ at p[H] 1 and 3 adhere to the comparatively simple first-order approach to equilibrium kinetic model used to describe the earlier results. At p[H] 3, the UO22+ reaction is characterized by consecutive pseudo-first order reactions. The first is an apparent approach to equilibrium while the second process demonstrates a saturation effect, indicating the existence of a stable intermediate complex. Relative rates and activation parameters are discussed in comparison with the previous results.
Print ISSN: 0033-8230
Volume: 89, 01/2001
Pages: 035