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The cation radical thus formed rapidly undergoes a dimerization reaction to yield an easily oxidized p-aminodiphenylamine product. Another example (of industrial relevance) is the reductive coupling of activated ole®ns to yield a radical anion, which reacts with the parent ole®n to give a reducible dimer (7). If the chemical step is very fast (in comparison to the electron-transfer process), the system will behave as an EE mechanism (of two successive chargetransfer steps). Table 2-1 summarizes common electrochemical mechanisms involving coupled chemical reactions.

Albery, Electrode Kinetics, Clarendon Press, Oxford, 1975. J. Bard and L. Faulkner, Electrochemical Methods, Wiley, New York, 1980. M. Bockris and A. Reddy, Modern Electrochemistry, Vol. 1,2, Plenum Press, New York, 1970. M. Bond, Modern Polarographic Methods in Analytical Chemistry, Dekker, New York, 1980. 26 FUNDAMENTAL CONCEPTS C. M. Oliveira Brett, Electrochemistry: Principles, Methods and Applications, Oxford University Press, Oxford, 1993. D. Diamond, Chemical and Biological Sensors, Wiley, New York, 1998.

Thin-layer spectroelectrochemistry can be extremely useful for measuring the formal redox potential (E  ) and n values. This is accomplished by spectrally determining the concentration ratio of oxidized to reduced ([O]=[R]) species at each applied potential (from the absorbance ratio at the appropriate wavelengths). Since bulk electrolysis is achieved within a few seconds (under thin-layer conditions), the whole solution rapidly reaches an equilibrium with each applied potential (in accordance to the Nernst equation).

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