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where D+ and D_ are the diffusion coefficients of the cation and anion. The overall material flux of the electrolyte J = = (2.5.39) v + v_ where v+ and v_ are the stoichiometric coefficients of the anion and of the cation in the salt molecule. From Eqs (2.5.37) to (2.5.39) we then obtain Z)+D_(v+ + v_) v_D+ + v + D_ 5

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Fissi A, Pieroni O, Balestreri E, Amato C. 1996. Photoresponsive polypeptides. Photomodu lation of the macromolecular structure in poly(N((phenylazophenyl)sulfonyl) L lysine). Macromolecules 29(13):4680 4685. Fujino T, Tahara T. 2000. Picosecond time resolved raman study of trans azobenzene. J Phys Chem A 104(18):4203 4210. Fujino T, Arzhantsev SY, Tahara T. 2001. Femtosecond time resolved uorescence study of photoisomerization of trans azobenzene. J Phys Chem A 105(35):8123 8129. Fujita T, Iyi N, Klapyta Z. 1998. Preparation of azobenzene mica complex and its photoresponse to ultraviolet irradiation. Mater Res Bull 33(11):1693 1701. Fujita T, Iyi N, Klapyta Z. 2001. Optimum conditions for photoresponse of azobenzene organophilic tetrasilicic mica complexes. Mater Res Bull 36(3 4):557 571. Funke U, Gruetzmacher HF. 1987. Dithiadiaza[n.2]paracyclophenes. Tetrahedron 43(16):3787 3795. Furukawa J, Takamori S, Yamashita S. 1967. Preparation of block copolymers with a macro azo nitrile as an initiator. Angew Makromol Chem 1(1):92 104. Gabor G, Fischer E. 1971. Spectra and cis trans isomerism in highly dipolar derivatives of azobenzene. J Phys Chem 75(4):581 583. Gallot B, Fa otte M, Fissi A, Pieroni O. 1996. Liquid crystalline structure of poly(L lysine) containing azobenzene units in the side chain. Macromol Rapid Commun 17(8):493 501.

Diffusion of a single electrolyte ('salt') is thus characterized by an effective diffusion coefficient

Replacement of the diffusion coefficients by the electrolytic mobilities according to Eq. (2.3.22) yields the Nernst-Hartley equation:

Figure 11.8. Polarized optical micrographs for (a) two gratings (10-mm fringe spacing) inscribed on an ATE lm stretched to 300% extension, with their fringes parallel and perpendicular, respectively, to the strain direction; and (b) the two gratings on the same lm retracted to the half-length. Source: Zhao et al., 2002. Reprinted with permission.

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It could be expected for less dilute solutions that an expression for the effective diffusion coefficient could be derived theoretically from Eq. (2.5.42) by using correction terms for U+ and U_ taken from the Debye-Huckel-Onsager theory of electrolyte conductivities. However, it has been demonstrated experimentally that this approach does not lead to a correct description of the dependence of the diffusion coefficient on the concentration. The mobility of ions in the diffusion process varies far less with changes in the concentration than when charge is transported in an external electric field, and the effect of the concentration on the mobility can be either retarding, zero or accelerating, depending on the type of salt (increasing concentration always reduces ion mobility in an external electric field). This difference between the two transport phenomena is a result of the fact that diffusion is connected with the movement of cations and anions in the same direction, so that faster species are retarded by slower species, and vice versa, whereas during electric current flow, oppositely charged ions move in opposite directions and the two types of ions retard one another. The electrophoretic effect caused by the retardation of the movement of the central ion by the moving ionic atmosphere is thus of a different magnitude in diffusion. The time-of-relaxation effect is completely absent, as the symmetry of the ionic atmosphere is not disturbed during diffusion. As mentioned, the gradient of the diffusion electric potential is suppressed in the case of diffusion of ions present in a low concentration in an excess of indifferent electrolyte ('base electrolyte'). Under these conditions, the simple form of Fick's law (2.3.18) holds for the diffusion of the given ion. The