By Michael E. G. Lyons (auth.), Michael E. G. Lyons (eds.)
'A complete evaluation of the present kingdom of the theoretical improvement during this very important zone of power software of accomplishing polymers, and is particularly timely...The editor-author is to be congratulated for his marathon efforts and the creation of an important contribution to the literature.' -TRIP This three-part sequence offers undergraduate and graduate scholars in electrochemistry and fabrics technological know-how with a large knowing of electroactive polymers. partially I, popular scientists study the basic rules underlying electrochemical habit of electroactive polymer fabrics. members specialize in the basics of cost percolation and conductivity habit linked to the membrane houses of electroactive polymer movies. half I additionally contains insurance of the phenomenon of heterogeneous redox catalysis at electroactive polymer changed electrodes.
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Additional resources for Electroactive Polymer Electrochemistry: Part 1: Fundamentals
31 or in Eqn. 31a is very small due to the fact that the physical diffusion contribution is very large, typically 10-6 cm2 S-l. In contrast the opposite applies in polymer media. In such systems the observation of a linear increase in the apparent charge transport diffusion coefficient with redox CHARGE PERCOLA TION IN ELECTROACTIVE POL YMERS 19 site concentration has in the context of the Dahms-Ruff approach been employed as a test for the presence of significant electron hopping. Sharp, Lindholm, and Lind(40) have recently examined the process of charge propagation through Nafion films loaded with Os(bpYH+/3+ centers using potential step chronocoulometry and complex impedance spectroscopy.
In this case the Nernst equation is valid, and we can write In (~) = -(0 - ( 0 ) (65) where 00 is the normalized potential when a = b = c~/2. Differentiating Eqn. 65 and using the result obtained in Eqn. 62, we obtain ( ab)(aO) = _ ab c~ ax ax (66) If we substitute this expression into the equation for the total flux given in Eqn. 65, we note that the net flux is zero, as indeed it should be. We can now use the result obtained in Eqn. 66 to express Eqn. 62 in the following form: . _ D (ab) a[O + In (b/a)] E c~ ax (67) J~ As previously noted by Albery,(62) this form of the flux expression emphasizes the coupled nature of the bimolecular exchange process.
Alternative approaches to quantifying the relationship between the diffusion coefficient and redox site concentration have been proposed; for instance the work of He and Chen(41) is of interest. These researchers based their analysis on nafion films loaded with either Ru(bpy)~+/3+ or Os(bpy)~+/3+ redox centers. (40) Redox sites may have to diffuse physically toward each other so that the electrons hop. Typically the physical diffusion coefficient for the M(bpy)~+/3+ species is ca. (42) Hence if the diffusion process is slower than the self-exchange reaction, then the observed bimolecular rate constant kl; is given by kl; = kexkD/(kex + k D) (32) where k ex and kD denote the exchange and diffusional rate constants, respectively.