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In addition to transmission experiments, it is possible to use more sensitive re¯ectance protocols. In particular, in internal re¯ectance spectroscopy (IRS) the light beam is introduced to the electrode at an angle, and the spectrum is recorded from the re¯ected beam at the solid±solution interface. Prisms are used to allow the radiation enter and leave. In addition to its higher sensitivity, IRS is less prone to solution resistance effects. Infrared spectroelectrochemical methods, particularly those based on Fourier transform infrared (FTIR) spectroscopy can provide structural information that UVvisible absorbance techniques do not.

Extrapolation of the linear portions of these plots to the zero overvoltage gives an intercept that corresponds to log i0 ; the slope can be used to obtain the value of the transfer coef®cient a. 303 RT =anF. For a ˆ 0:5 and n ˆ 1, this corresponds to 118 mV (at 25  C). Equation (1-29) indicates that the application of small potentials (beyond the equilibrium potential) can increase the current by many orders of magnitude. In practice, however, the current could not rise to an in®nite value due to restrictions from the rate at which the reactant reaches the surface.

Dekker, New York, 1996. J. Janata, Principles of Chemical Sensors, Plenum Press, New York, 1989. J. Koryta and J. Dvorak, Principles of Electrochemistry, Wiley, Chichester, 1987. P. Rieger, Electrochemistry, Prentice-Hall, Englewood Cliffs, NJ, 1987. D. Sawyer and J. Roberts, Experimental Electrochemistry for Chemists, Wiley, New York, 1974. M. Smyth and J. Vos, Analytical Voltammetry, Elsevier, Amsterdam, 1992. P. Turner, I. Karube and G. Wilson, Biosensors, Oxford University Press, Oxford, 1987.

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