Effect of the formation of EDTA complexes on the diffusion of metal ions in water

The diffusion coefficients of aquo metal ions (Mz+) and their EDTA complexes (M–EDTA(z−4)+) were compared to understand the effect of EDTA complexation on the diffusion of metal ions by the diffusion cell method for Co2+, Ga3+, Rb+, Sr2+, Ag+, Cd2+, Cs+, Th4+, UO22+, and trivalent lanthanides. Most studies about ionic diffusion in water have dealt with free ion (hydrated ion). In many cases, however, polyvalent ions are dissolved as complexed species in natural waters. Hence, we need to study the diffusion behavior of complexes in order to understand the diffusion phenomenon in natural aquifer and to measure speciation by diffusive gradient in thin films (DGT), which requires the diffusion coefficients of the species examined. For many ions, the diffusion coefficients of M–EDTA(z−4)+ are smaller than those of hydrated ions, but the diffusion coefficients of M–EDTA(z−4)+ are larger than those of hydrated ions for ions with high ionic potentials (Ga3+ and Th4+). As a result, the diffusion coefficients of EDTA complexes are similar among various metal ions. In other words, the diffusion of each ion loses its characteristics by the complexation with EDTA. Although the difference is subtle, it was also found that the diffusion coefficients of EDTA complexes increase as the ionic potential increases, which can be explained by the size of the EDTA complex of each metal ion.