Application of permeation liquid membrane and scanned stripping chronopotentiometry to metal speciation analysis of colloidal complexes

The potential of permeation liquid membrane (PLM) to obtain dynamic metal speciation information for colloidal complexes is evaluated by measurements of lead(II) and copper(II) complexation by carboxyl modified latex nanospheres of different radii (15, 35, 40 and 65 nm). The results are compared with those obtained by a well characterized technique: stripping chronopotentiometry at scanned deposition potential (SSCP). Under the PLM conditions employed, and for large particles or macromolecular ligands, membrane diffusion is the rate-limiting step. That is, the flux is proportional to the free metal ion concentration with only a small contribution from labile complexes. In the absence of ligand aggregation in the PLM channels, good agreement was obtained between the stability constants determined by PLM and SSCP for both metals.

Metal speciation dynamics in colloidal ligand dispersions. Part 3: Lability features of steady-state systems

A lability criterion is developed for dynamic metal binding by colloidal ligands with convective diffusion as the dominant mode of mass transport. Scanned stripping chronopotentiometric measurements of Pb(II) and Cd(II) binding by carboxylated latex core-shell particles were in good agreement with the predicted values. The dynamic features of metal ion binding by these particles illustrate that the conventional approach of assuming a smeared-out homogeneous ligand distribution overestimates the lability of a colloidal ligand system. Due to the nature of the spatial distribution of the binding sites, the change in lability of a metal species with changing ligand concentration depends on whether the ligand concentration is varied via manipulation of the pH (degree of protonation) or via the particle concentration. In the former case the local ligand density varies, whereas in the latter case it is constant. This feature provides a useful diagnostic tool for the presence of geometrically constrained binding sites.

Metal speciation dynamics in colloidal ligand dispersions. Part 2: electrochemical lability

We investigate the dynamic nature of metal speciation in colloidal dispersions using a recently proposed theory [J.P. Pinheiro, M. Minor, H.P. Van Leeuwen, Langmuir, 21 (2005) 8635] for complexing ligands that are situated on the surface of the particles. The new approach effectively modifies the finite rates of association/dissociation of the colloidal metal complexes, thus invoking consideration of the two basic dynamic criteria: the association/dissociation kinetics of the volume complexation reaction (the ‘‘dynamic’’ criterion), and the interfacial flux of free metal to a macroscopic surface due to dissociation of complex species (the ‘‘lability’’ criterion). We demonstrate that the conventional approach for homogeneous systems that assume a smeared-out ligand distribution, overestimates both the dynamics and the lability of metal complexes when applied to colloidal ligands. It is also shown that the increase of lability with increasing particle radius, as expected for a homogeneous solution, is moderated for spherical microelectrodes and practically eliminated for planar electrodes.