Cyclic chronocoulemetry: Disproportionation and dimerization reactions coupled to electron transfer

An extension of double-potential-step chronocoulemetry to multiple or cyclic techniques has been developed, and its potential applications in the study of coupled chemical reactions in electrochemistry are discussed. Disproportionation and dimerization mechnisms are considered. Wroking curves have been calculated with the use of the finite difference digital simulation method. It is shown that better resolution for disproportionation and dimerization reactions can be obtained with cyclic chronocoulometry than with double-potential-step chronocoulemetry. The method has been experimentally verified measuring the disproportionation reaction U(V) in 1 mol dm^?3 sodium hydrogen carbonate solutions. A rate coefficient of 15.6 dm³ mol^?1 was calculated for this reaction.