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The influence of the composition of the internal electrolyte solution on the response of Pb 2+ -and Ca 2+ -selective membrane electrodes is investigated. It is shown that the lower detection limit is improved by generating, in the membrane, ionic gradients that lead to a flux of primary ions toward the inner reference electrolyte solution. If the ion flux is too strong, it may cause analyte depletion at the membrane surface and, as a consequence, apparent super-Nernstian response. Such electrodes are not adequate to measure low analyte activities but can be used to determine unbiased selectivity factors. The results are interpreted in terms of a steady-state model, introduced in the companion paper, that describes the influence of concentration gradients generated by ion-exchange and coextraction processes on both sides of the membrane.

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