Solution systems model structure

The subject matter covered below is divided into sections according to the structure of the redox unit(s). This review is restricted primarily to materials for which well-defined redox behavior has been repiorted, usually involving cyclic voltammetric studies and other electrochemical techniques in solution. Unraveling the electron transfer processes in laiger macromolecules which contain multiple redox sites can be very challenging, thus for some systems model branched oligomers have been studied in detail, and this work will be discussed. Selected synthetic schemes are included to acquaint the reader with the building blocks which are available for the construction of new derivatives, and with the synthetic steps involved. 

The first piezoceramic to be developed commercially was BaTi03, the model ferroelectric discussed earlier (see Section 2.7.3). By the 1950s the solid solution system Pb(Ti,Zr)03 (PZT), which also has the perovskite structure, was found to be ferroelectric and PZT compositions are now the most widely exploited of all piezoelectric ceramics. The following outline description of their properties and fabrication introduces important ideas for the following discussion of the tailoring of piezoceramics, including PZT, for specific applications. It is assumed that the reader has studied Sections 2.3 and 2.7.3. 

Cation, anion, and water transport in ion-exchange membranes have been described by several phenomenological solution-diffusion models and electrokinetic pore-flow theories. Phenomenological models based on irreversible thermodynamics have been applied to cation-exchange membranes, including DuPont s Nafion perfluorosulfonic acid membranes [147, 148]. These models view the membrane as a black box and membrane properties such as ionic fluxes, water transport, and electric potential are related to one another without specifying the membrane structure and molecular-level mechanism for ion and solvent permeation. For a four-component system (one mobile cation, one mobile anion, water, and membrane fixed-charge sites), there are three independent flux equations (for cations, anions, and solvent species) of the form... 

Information about tautomeric systems relies on physical measurements which do not affect the tautomeric equilibria reactions of tautomeric systems give no reliable information about equilibria. In tautomeric studies of hydroxy-, thiol-, and aminopyrimidines, or heterocycles in general, methyl-ation has been used to isolate the various tautomeric forms which were to serve as models for comparison of spectroscopic data (UV, IR, NMR) or values. However, recent NMR techniques allow direct tautomeric determinations in solution. X-ray structure data gives full information in the solid, crystalline state. 

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