Analytical Sciences

Threshold Ionic Site Concentrations Required for Nernstian Potentiometric Responses of Neutral Ionophore-Incorporated Ion-Selective Liquid Membranes

Koji TOHDA, Takashi HIGUCHI, Diana DRAGOE, and Yoshio UMEZAWA 

Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo, Tokyo 113-0033, Japan

An equation that can describe the concentrations of ionic sites required for a Nernstian potentiometric response slope of neutral ionophore-incorporated ion-selective liquid membranes is presented. This equation is derived from a model based on electrical diffuse layers on both the membrane and the aqueous sides of the interface, in which the phase boundary potential is correlated to the surface charge density as well as the salt concentrations in the bulk membrane and aqueous solution. To experimentally and accurately confirm the validity of this equation, respons e characteristics of field effect transistors covered by neutral ionophore-based liquid membranes with varying concentrations of a derivative of tetraphenylborate as an anionic site but free of ionic impurities were examined. The observed membrane potentials and the response slopes for membranes with various concentrations of anionic sites were in good agreement with the values calculated from the theory presented in this paper with the measured complexation stability constants for the relevant systems. This result indicates that the theoretical prediction based on the proposed equation for the anionic site concentration is accessible for the preparation of neutral ionophore-incorporated ion-selective liquid membranes, which show Nernstian response slopes for the primary ions.

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