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Electroreduction of some pyridine carboxamides on carbon electrodes in aqueous solutions
Author(s) -
Angulo Matiide,
Montoya Mercedes Ruiz,
Galvin Rafael Marin,
Mellado José Miguel Rodriguez
Publication year - 1997
Publication title -
electroanalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.574
H-Index - 128
eISSN - 1521-4109
pISSN - 1040-0397
DOI - 10.1002/elan.1140090417
Subject(s) - chemistry , electron transfer , aqueous solution , glassy carbon , electrode , isonicotinamide , inorganic chemistry , nicotinamide , dropping mercury electrode , electrochemistry , cyclic voltammetry , protonation , pyridine , ion , photochemistry , organic chemistry , enzyme
The electroreductions of the NAD + model compounds nicotinamide (I), N 1 ‐methyl nicotinamide (II), N ′‐methyl nicotinamide (III) and isonicotinamide (IV) on carbon electrodes have been studied in aqueous media in the pH range 0–12 by linear‐sweep cyclic voltammetry (Scheme 1, I‐IV). Logarithmic analyses of the reduction peaks were performed by computing the convolution of the current with time as a function of the potential. On the basis of the experimental results it was concluded that the irreversibility of the electron transfers increased when a glassy carbon electrode was used, and this irreversibility being more marked when a plastic formed carbon electrode was employed. The reduction processes occurred with more difficulty on carbon electrodes than on mercury electrodes. Both the reduction and the reoxidation (when occurred) processes changed with respect to those observed on mercury electrodes, being irreversible electron transfers the rate‐determining steps in most cases. Thus, for compounds I, II and III at pH < 2 the reductions occurred by the uptake of two electrons and two H + ions, and the rate determining step was found to be the first one‐electron transfer, for I and III, and the irreversible second electron transfer, preceded by the uptake of an H+ ion, for II. At pH>3 the processes consisted of electrodimerization reactions, preceded by the protonation of the heterocyclic nitrogen in cases I and III. The second electron transfer of the electroreduction of IV always appeared irreversible, in contrast with that found for mercury electrodes.