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9) anF k^f We assume that neither the preexponential factor of the conditional electrode reaction rate constant nor the charge transfer coefficient changes markedly in a series of substituted derivatives and that the diffusion coefficients are approximately equal In view of (5252) and (5253), (5910) where AAHl is the difference between the activation energies of the electrode reactions of substance i and of the reference substance R W Brockman and D E Pearson, S Koide and R Motoyama and P Zuman applied the Hammett equation, originally deduced for chemical reactions, to electrode processes In this concept the activation energy or standard Gibbs energy of a reaction where members of a homologous series participate is given by the relationship AAHl = 0:0/, (5 9 11) where py and p) characterize the type of the reaction and ok the substituent.

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The values of ok which are the same for all reaction types have been listed by L Hammett Thus, for the series of half-wave potentials of the same electrode reaction type we have (5912).

In an experiment on main-chain versus side-chain azopolymers, the polarization behavior of photodeformation was opposite (Keum et al, 2003) This may be explained by postulating that the main-chain polymer contracts upon isomerization, whereas the side-chain polymer architecture leads to net expansion Similarly, the opposite phase behavior in amorphous and LC systems may be due to the fact that the former photoexpand and the latter photocontract (Bublitz et al, 2000) Lastly, many large surface structures were observed in an azo-dye-doped elastomer lm irradiated at high power (4 W/cm2) (Ciuchi et al, 2003) The formation of structures both parallel and perpendicular.

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390 where p" characterizes the electrode reaction type (reduction of the nitro, aldehydic, chlorine, etc., group) and ok the substituent (mainly in the para or meta position on the benzene ring).

2 1.8 1.6 TX100 bound/polymer (g/g) 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 0.2 0.4 0.6 TX100 free (g/L) (a) 0.8 1

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Baizer, M. and H. Lund (Eds), Organic Electrochemistry, M. Dekker, New York, 1983. Fleischmann, M., and D. Pletcher, Organic electrosynthesis, Roy. Inst. Chem. Rev., 2, 87 (1969). Fry, A. J., Synthetic Organic Electrochemistry, John Wiley & Sons, Chichester, 1989. Fry, A. J., and W. E. Britton (Eds), Topics in Organic Electrochemistry, Plenum Press, New York, 1986. Kyriacou, D. K., and D. A. Jannakoudakis, Electrocatalysis for Organic Synthesis, Wiley-Interscience, New York, 1986. Lamy, C , see page 368. Peover, M. E., Electrochemistry of aromatic hydrocarbons and related substances, in Electroanalytical Chemistry (Ed. A. J. Bard), Vol. 2, p. 1, M. Dekker, New York, 1967. Shono, T., Electroorganic Chemistry as a New Tool in Organic Synthesis, SpringerVerlag, Berlin, 1984. Torii, S., Electroorganic Syntheses, Methods and Applications, Kodansha, Tokyo, 1985. Weinberg, N. L. (Ed.), Techniques of Electroorganic Synthesis, Wiley-Interscience, New York, Part 1, 1974, Part 2, 1975. Weinberg, N. L., and H. R. Weinberg, Oxidation of organic substances, Chem. Rev., 68,449(1968). Yoshida, K., Electrooxidation in Organic Chemistry, The Role of Cation Radicals as Synthetic Intermediates, John Wiley & Sons, New York, 1984. Zuman, P., Substitution Effects in Organic Polarography, Plenum Press, New York, 1967.

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Photoelectrochemistry studies the effects occurring in electrochemical systems under the influence of light in the visible through ultraviolet region. Light quanta supply an extra energy to the system, hence the electrochemical reactions, which are thermodynamically or kinetically suppressed in the dark, may proceed at a high rate under illumination. (There also exists an opposite effect, where the (dark) electrochemical reactions lead to highly energetic products which are able to emit electromagnetic radiation. This is the principle of 'electrochemically generated luminescence', mentioned in Section 5.5.6.) Two groups of photoelectrochemical effects are traditionally distinguished: photogalvanic and photovoltaic. The photogalvanic effect is based on light absorption by a suitable photoactive redox species (dye) in the electrolyte solution. The photoexcited dye subsequently reacts with an electron donor or acceptor process, taking place in the vicinity of an electrode, is linked to the electrode

Figure 7.7. Association isotherms of micelles (TX 100) or the protein bovine serum albumin on azobenzene-modi ed poly (sodium acrylate) in dilute water solution, as measured from capillary electrophoretic analysis. Closed symbols: dark-adapted samples, open symbols: samples exposed to UV light (365 nm). (a) Polymer, as shown in Fig. 7.1, with n = 5 and x = 7%, (b) n = 12 and x = 3%.

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