Description of the Effects of Non‐ion‐exchange Extraction and Intra‐membrane Interactions on the Ion‐selective Electrodes Response within the Interface Equilibria‐triggered Model

The recently proposed interface equilibria‐triggered dynamic diffusion model of the boundary potential has proven its high predictive efficiency for quantification of the ion exchange and co‐extraction effects at the interface, as well as of the trans‐membrane transfer effect, on the electrode response. It is applicable for both ion exchanger‐based and neutral carrier‐based electrodes. In this communication, the adaptability of this model to more complex cases, when non‐ion‐exchange extraction processes at the interface (partition of organic acids’ and bases’ molecular forms and extraction of ionic associates) are coupled with protolytic equilibria in the aqueous phase and with self‐solvation process in the membrane phase, is demonstrated. By the example of electrodes reversible to ions of highly lipophilic physiologically active bases and acids (amiodarone, verapamil, vinpocetine, salicylic acid), it is shown that the peculiarities of their functioning, such as a very strong pH effect on the potential of cation‐selective electrodes, non‐monotonic pH dependence of the potential and super‐Nernstian response slope in certain pH region for a salicylate‐selective electrode, are well described within the model.