Rotating ring-disk voltammetric investigations on the degradation rate of the nickel(III)-glycylglycyl-L-histidine complex

Alip�zaga, Mar�a V.; Lowinsohn, Denise; Bertotti, Mauro; Coichev, Nina
December 2007
Canadian Journal of Chemistry;Dec2007, Vol. 85 Issue 12, p1064
Academic Journal
The voltammetric behavior of the Ni(II)/glycylglycyl-L-histidine complex and the degradation of the electrogenerated Ni(III) species were investigated by cyclic voltammetry. Results of electrochemical and spectrophotometric experiments indicated some differences in the nature and reactivity of Ni(III) complexes formed by two independent routes, i.e., anodic oxidation of Ni(II) and homogeneous oxidation by an autocatalytic reaction in a medium containing oxygen and S(IV) (H2SO3, HSO[IMG], and SO[IMG]). The Ni(III) species formed electrochemically reacts in a fast chemical process (EC mechanism) and the observed rate constant of the degradation (k = 0.17 s�1) was determined by a rotating ring-disk electrode technique measuring kinetic collection efficiency values as a function of the rotation rate. Key words: nickel, glycylglycyl-L-histidine, sulfite, degradation reaction, rotating ring-disk voltammetry. Faisant appel � des m�thodes de voltamp�rom�trie cyclique, on a �tudi� le comportement voltamp�rom�trique du complexe Ni(II)/glycylgly-L-cylhistidine et la d�gradation des esp�ces Ni(III) �lectro g�n�r�es. Les r�sultats des exp�riences �lectrochimiques et spectrophotom�triques indiquent qu�il existe de l�g�res diff�rences dans la nature et la r�activit� des complexes de Ni(III) qui se forment par deux voies r�actionnelles ind�pendantes, soit l�oxydation anodique du Ni(II) et l�oxydation homog�ne par une r�action autocatalytique dans un milieu contenant de l�oxyg�ne et des esp�ces � base de S(IV), telles H2SO3, HSO[IMG] et SO[IMG]. Les esp�ces de Ni(III) qui se forment d�une fa�on �lectrochimique r�agissent par un processus chimique rapide (m�canisme EC) et on a d�termin� la constante de vitesse observ�e pour la d�gradation (k = 0,17 s�1) par la technique de l��lectrode � disque tournant en mesurant les valeurs de l�efficacit� de la collection cin�tique en fonction de la vitesse de rotation. Mots-cl�s: nickel, glycylglycyl-L-histidine, sulfite, r�action de d�gradation, voltamp�rom�trie � disque tournant. [Traduit par la R�daction]


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