By R. P. Buck (auth.), Henry Freiser (eds.)
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Extra resources for Ion-Selective Electrodes in Analytical Chemistry
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W 37 Theory and Principles of Membrane Electrodes coefficients. The chemical potentials bend in relation to the surface region concentrations (center panel) and when the local potential is added to the chemical potentials, the electrochemical potential of each species becomes constant. In Fig. 12b, a hypothetical intrinsic semiconductor electrode in contact with an aqueous redox couple (M 2+/M+) is illustrated. The electrolyte is rich in oxidant M2+ such that the standard chemical potential of holes exceeds the valence band energy by more than the electron energy in M+ is below Ee.
P. Buck x A B I I 5,0 em IFilm ...... -.... C s d I -.... ' I is-"" I I I Membrane I led y I Filmll Bulk Solution Side "0" Bulk Solution Side "d" Fig. 10. Illustration of steady-state diffusion (from left to right) of uncharged species through an inert, unchanged membrane. Although the bathing solutions are stirred, account is taken of exterior surface fi 1m diffusion (external concentration polarization) through the Nernst layer. o, and Cs,d and Cs •d are related by partition equilibria. Diffusion coefficients in the external and internal phases are 0 and D.
Yet there are no ions in this region whose concentration could adjust appropriately to maintain constancy of the electrochemical potential of the particular ions. In addition to water dipole layers, other dipolar materials in water solvent and oil-soluble dipolar molecules in the membrane will become oriented at the two sides of an interface. Precise direction of orientation is a matter of conjecture. One intuitive approach is to assume that polar ends align with their end of sign opposite to the external phase charge nearest the interface.