Lability and mobility effects on mixtures of ligands under steady-state conditions

Abstract

Analytical solutions for the steady-state flux arriving at an active surface from a mixture (in which one active species reacts with non-active ligands in the medium) can be helpful in a variety of problems: voltammetric techniques, heterogeneous processes in reactors, toxic or nutrient uptake, techniques of diffusive gradients in thin films (DGT), etc. Under any geometry that sustains steady-state, a convenient combination of the reaction–diffusion equations leads to a simpler formulation of the problem for arbitrary diffusivities of the species and arbitrary rate constants of the first-order conversion between the active species and the non-active species. The resulting problem can be characterised in terms of a list of dimensionless parameters involving the kinetic and mobility properties of each species. A lability degree for each 1∶1 complex in terms of the surface concentrations leads to: (i) a lability criterion specific for each complex in the mixture and (ii) the assessment of the relative contribution of each complex to the resulting flux. Semi-infinite spherical diffusion (as in the Gel Integrated MicroElectrode, GIME, biouptake modelling of micro-organisms, etc.) is specifically considered and some consequences of its full analytical solutions are discussed.