INSTRUMENTATION Some experimental techniques ap plicable to the ITIES are also of a more fundamental nature. Fast scan voltam metry, in particular on microinter faces, can be used for determination of charge-transfer rate constants. Imped ance analysis, which is an extension to ac voltammetry, can be used not only to detect analytes, but also to obtain a better understanding of surface phe nomena (33) and adsorption (34). A special case of impedance analysis is derived from measurement of noise generated by the electrochemical sys tem (35). This is especially useful for work on microinterfaces that have large absolute resistance. The second direction of interest is in application to new or improved analyt ical sensors. These can be potentiometric, voltammetric, or based on other ap propriate techniques. The L-L inter face is actually a component of an ionselective electrode with a liquid ion exchanger. Recent analytical applica tions have resulted in construction and systematic studies of microinterfaces solidified by gels. The advantage of such a modification is ease of handling (36-39). The immobilization can be ex tended further to studies of frozen in
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terfaces, or even to use of solid electro lytes. Significantly, ITIES theory also applies to interfaces that are encoun tered in ion-doped, conductive, poly mer-coated electrodes. This work and the author's research work de scribed herein were supported in part by the Office of Naval Research. I thank Elizabeth A. Burton for review of the draft version.
References (1) Nernst, W. Z. Phys. Chem. 1888,2,61337. (2) Koryta, J.; Vanysek, P.; Bfezina, M. J. Electroanal. Chem. 1976,67, 263-66. (3) Blank, M.; Feig, S. Science 1963, 95, 561-72. (4) Gavach, C. C. R. Acad. Sci. (Paris) 1969, 269,1356-59. (5) Vanysek, P. Electrochemistry on Liq uid/Liquid Interfaces; Springer: Berlin, 1985. (6) Koryta, J.; Vanysek, P.; Bfezina, M. J. Electroanal. Chem. 1977, 75, 211-28. (7) Vanysek, P.; Buck, R. P. J. Electrochem. Soc. 1984,131,1792-96. (8) Sinru, L.; Freiser, H. Anal. Chem. 1987, 59,2834-38. (9) Freiser, H. Abstracts of Papers, 40th Pittsburgh Conference and Exposition, Atlanta, GA; Pittsburgh Conference and Exposition: Pittsburgh, PA, 1989; Ab stract 217. (10) Yoshida, Z.; Freiser, H. J. Electroanal. Chem. 1984,162, 307-19.
(11) Yoshida, Ζ.; Freiser, H. Inorg. Chem. 1984,23,3931-35. (12) Kihara, S.; Yoshida, Z.; Fujinaga, T. BunsekiKagaku 1982,31, E297-E300. (13) Hundhammer, B.; Solomon, T.; Alemu, H. J. Electroanal. Chem. 1983, 149,179-83. (14) Marecek, V.; Samec, Z. Anal. Lett. 1981,14,1241-53. (15) Hung, L. Q. J. Electroanal. Chem. 1980,115,159-74. (16) Melroy, 0 . R.; Buck, R. P. J. Elec troanal. Chem. 1983,143, 23-36. (17) Cosofret, V. V.; Buck, R. P. In Funda mentals and Applications of Drug Sen sors; Schuetzle, D.; Haemmerli, R., Eds.; ACS Symposium Series 309; American Chemical Society: Washington, DC, 1986; pp. 362-72. (18) Koczorowski, Z.; Paleska, I.; Geblewicz, G. J. Electroanal. Chem. 1984, 164, 201-4. (19) Solomon, T.; Alemu, H.; Hundham mer, B. J. Electroanal. Chem. 1984,169, 311-14. (20) Koryta, J. In The Interface Structure and Electrochemical Processes at the Boundary between Two Immiscible Liq uids; Kazarinov, V. E., Ed.; Springer: Ber lin, 1987. (21) Girault, H.H.J.; Schiffrin, D . J . In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1989; Vol. 15. (22) Hofmanovâ, Α.; Hung, L. Q.; Khalil, M. W. J. Electroanal. Chem. 1982, 135, 257-64. (23) Homolka, D.; Hung, L. Q.; Hofmanovâ, Α.; Khalil, M. W.; Koryta, J.; Marecek, V.;
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