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The Donnan potentials contain the individual ionic activities and cannot be measured by using a purely thermodynamic procedure. In the concentration range where the Debye-Hiickel limiting law is valid, the ionic activities can be replaced by the mean activities. The membrane potentials are measured by constructing a cell with a semipermeable membrane separating solutions 1 and 2: Ag | AgCl, sat. KC11 solution 1 | solution 2 | sat. KC1, AgCl | Ag (6.1.16) whose EMF is given by the sum of the membrane potential and the two liquid junction potentials, which can usually be neglected. Equations (6.1.3) and (6.1.4) could be derived from the relationships for the liquid junction potential formed by a single salt (Eq. 2.5.31), assuming that the anion mobility in Eq. (6.1.3) and the cation mobility in Eq. (6.1.4) equal zero. The general case, i.e. that the membrane only changes the transport number of the cation and anion, was solved by J. Bernstein at the beginning of this century using a relationship analogous to Eq. (2.5.31), which assumes the following form for a uni-univalent electrolyte: , = (*_-*+) l n - ^ (6.1.17)

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Polarization direction (a) (b)

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where T+ and T_ are the transport numbers of the cation and anion in the membrane, respectively, which are different from the corresponding values in solution. References

1 m

Blank, M. (Ed.), Bioelectrochemistry: Ions, Surfaces, Membranes, American Chemical Society, Washington, 1980. Bioelectrochemistry, CTE, 10 (1985). Butterfield, D. A., Biological and Synthetic Membranes, John Wiley & Sons, New York, 1989.

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Figure 5.13. (a) TEM image of the azo polymer colloidal spheres with an average diameter of 212 nm. (b) SEM image of the colloidal spheres after exposure to a linearly polarized Ar+ laser beam for 10 min.(c) TEM image of the deformed colloids after irradiation with the laser beam for 15 min and released from the surface of the silicon wafer by sonication. Source: From Li et al., 2006b.

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Eisenman, G. (Ed.), Membranes A Series of Advances, M. Dekker, New York, Vol. 1, 1972; Vol. 2, 1973; Vol. 3, 1975. Galvani, L., De Viribus Electricitatis in Motu Musculari, Typographia Instituti Scientiarum, Bologna, 1791, Translation: Green, R. M., Commentary on the Effect of Electricity on Muscular Motion, p. 66, E. Licht, Cambridge, Mass., 1953. Jain, M. K., Introduction to Biological Membranes, John Wiley & Sons, New York, 1988. Keynes, R. D., The generation of electricity by fishes, Endeavour, 15, 215 (1956). Koryta, J., Ions, Electrodes and Membranes, 2nd ed. John Wiley & Sons, Chichester, 1991. Koryta, J., What is bioelectrochemistry , Electrochim. Acta, 29, 1291 (1984). Membrane phenomena, Discussion Faraday Soc, 21, 1956. Milazzo, G., and M. Blank (Eds), Bioelectrochemistry III Charge Separation Across Biomembranes, Plenum, New York, 1988. Overbeck, J. T., The Donnan equilibrium, in Progress in Biophysics and Biophysical Chemistry, Vol. 6, p. 57, Pergamon Press, London, 1965. Schlogl, R., Stofftransport durch Membranen, D. Steinkopff, Darmstadt, 1964. Sollner, K., The early developments of the electrochemistry of polymer membranes, in Charged Gells and Membranes (Ed. E. Selegny), Vol. 1, Reidel, Dordrecht, 1976. Williams, R. J. P., A general approach to bioelectrics, in Charge and Field Effects in Biosystems (Eds M. J. Allen and P. N. R. Usherwood), Abacus Press, London, 1984. Wu, C. H., Electric fish and the discovery of animal electricity, Am. Scientist, 72, 598 (1984).

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