By Sidney D. Ross, Manuel Finkelstein and Eric J. Rudd (Eds.)
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Academic Press, New York, 1966. 4. P. " Wiley (Interscience), New York, 1954. 5. O. H. Muller, in "Physical Methods of Organic Chemistry" (A. ), Vol. I, Part IV, p. 3155. Wiley (Interscience), New York, 1960. 6. P. " Macmillan, New York, 1964. 7. C. L. Perrin, Prog. Phys. Org. Chem. 3, 165 (1965). 8. P. Zuman and S. Wawzonek, in "Progress in Polarography" (P. Zuman and I. M. ), Vol. I, p. 303. Wiley (Interscience), New York, 1962. 9. J. E. Page, Quart. , Chem. Soc. 6, 262 (1952). 10. P. J. Elving, Ree.
It is this relationship that has led to the applica tion of chronopotentiometry to analytical chemistry and, particularly, to analysis by an oxidation technique. 6 x 104 coulombs), D is the diffusion coefficient of the reactant (cm2 sec - 1 ), and Cb is the bulk concentration of the reactant (moles cm" 3 ). In order to interpret a chronopotentiogram it is necessary to make a distinction between the reversible and irreversible electrode processes, as is the case in polarography. Then for the reaction O + ze .
B. , the difference between the anodic and cathodic current densities which themselves reflect the rates of the forward and reverse reac tions. There is a contribution from the reverse reaction at all potentials, but ///. Reactions under Activation-Controlled Conditions 37 when the electrode is significantly polarized, the rate of the reverse reaction is very small and therefore negligible. At the reversible electrode potential the system is at equilibrium, and the rates of the forward and reverse reaction are equal, so that the net current density is zero.
Anodic Oxidation by Sidney D. Ross, Manuel Finkelstein and Eric J. Rudd (Eds.)