Evaluation of Egorov's improved separate solution method for determination of low selectivity coefficients by numerical simulation.

The group of Egorov has recently proposed an elegant method to determine unbiased selectivity coefficients of ion-selective electrodes (Egorov et al. Anal. Chem. 2014, 86, 3693). Once the electrode is exposed to a solution containing only interfering ions, the time-dependent experimental selectivity coefficients are plotted as a function of the inverse fourth root of time and extrapolated to zero. The principal assumption of the approach is the progression of the diffusion layer in the membrane phase with square root of time. This letter critically evaluates the usefulness of this methodology by finite element analysis. The results suggest that the improvement of observed selectivity values are highly significant for an initially uniform distribution of primary ions across the membrane, strongly supporting the methodology. When strong inward ion fluxes of primary ions are present instead, a modification of the method by extrapolation of logarithmic selectivity coefficients appears to give the best results.