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Example text

The two first arrangements are those usually taken for characterizing the electrochemistry of solids, whereas the last situation relates directly to batteries and will be only tangentially treated here. 2 General Approach Let us consider the case of a particle of microporous solid deposited on an inert electrode immersed into a suitable electrolyte. It will be assumed that the material is not a metallic conductor but incorporates immobile redox centers so that electron transport and ion transport are allowed through the solid via electron hopping between redox-active centers and ion diffusion across the micropores of the material.

19), lead to a lower De value of 2 × 10 −11 cm2/sec. The discrepancy can be rationalized by considering that short-time experiments reflect the electrochemical response of the more external PY+ ions, whereas 39 Electrochemical Processes Involving Porous Materials long-time experiments yield the response of a population of such ions more extensively distributed within the zeolite framework. Accordingly, the average concentration of PY+ in the more external zeolite boundary should be larger than the average concentration when more depth layers are involved.

If De = 0, the reaction propagates along the particle/electrode interface, whereas if DM = 0, the reaction layer is confined to the lateral sides of the particle. Comparable situations can be obtained when DM >> De or De >> DM. This last condition appears to be the case for proton-assisted electron transfer processes involving organic molecules in contact with aqueous buffers. Here, charge transfer is ensured by proton hopping between immobile redox centers via chemical bond breaking and reforming rather than cation insertion into the organic lattice.

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