Improved detection limits and sensitivities of potentiometric titrations.

Zero-current ion fluxes through polymer membranes of ion-selective electrodes (ISEs) may lead to biased endpoints of potentiometric titrations. The bias is eliminated, and the sensitivity of the end-point detection is improved through reducing transmembrane ion fluxes by an appropriate choice of the inner solution. Surprisingly, ISE membranes that have a significant primary ion flux toward the inner solution show much larger sensitivities than expected by titration theory; however, depending on the experimental conditions, their application may bias the endpoint. With the optimal systems, endpoint detection is now possible with total sample concentrations below 10(-6) M, as demonstrated by the titration of EDTA with a Pb2+ solution.