Effects of unequal diffusion coefficients and coupled chemical equilibria on square wave voltammetry at disc and hemispherical microelectrodes

Olmos Martínez, José Manuel; Molina Gómez, María de los Ángeles; Laborda Ochando, Eduardo; Martínez-Ortíz, Francisco Asís

Publication:
Effects of unequal diffusion coefficients and coupled chemical equilibria on square wave voltammetry at disc and hemispherical microelectrodes

dc.contributor.author	Olmos Martínez, José Manuel
dc.contributor.author	Molina Gómez, María de los Ángeles
dc.contributor.author	Laborda Ochando, Eduardo
dc.contributor.author	Martínez-Ortíz, Francisco Asís
dc.contributor.department	Química Analítica
dc.date.accessioned	2024-02-10T18:29:48Z
dc.date.available	2024-02-10T18:29:48Z
dc.date.created	2015
dc.date.issued	2015
dc.description	©<2015>. This manuscript version is made available under the CC-BY-NC 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the, Accepted, version of a Published Work that appeared in final form in Electrochimica Acta. To access the final edited and published work see: https://doi.org/10.1016/j.electacta.2015.07.048
dc.description.abstract	Square wave voltammetry (SWV) at disc and hemispherical microelectrodes is studied when the electroactive species show different diffusivities and/or take part in chemical equilibria in solution, under both transient and steady state conditions. Despite the use of microelectrodes, experiments in pulse techniques such as SWV frequently correspond to transient conditions since the pulse duration are typically very short (<100ms, f>5Hz). As will be shown, under such conditions the case of unequal diffusion coefficients gives rise to a complex behaviour of the SWV peak, the features of which deviate from the theory and criteria already established under the assumption of equal diffusion coefficients. Also, the theoretical treatment is notably more difficult and no analytical solution has been deduced for multipulse techniques.The effects of coupled chemical equilibria and, particularly, of unequal diffusion coefficients on SWV will be described in depth as a function of the electrode size and shape and they will be compared with those observed in differential double pulse voltammetry (DDPV). The main discrepancies in the peak height, width and position with respect to the case of equal diffusion coefficients will be studied. Also, appropriate methodologies and experimental conditions will be discussed for the determination of, formal potentials and equilibrium constants.	es
dc.format	application/pdf	es
dc.format.extent	30	es
dc.identifier.citation	Electrochimica Acta.176, pp. 1044 - 1053. 2015
dc.identifier.doi	https://doi.org/10.1016/j.electacta.2015.07.048
dc.identifier.issn	Print: 0013-4686
dc.identifier.uri	http://hdl.handle.net/10201/139210
dc.language	eng	es
dc.publisher	Elsevier	es
dc.publisher	International Society of Electrochemistry (ISE)
dc.relation	Esta publicación es resultado de 2 proyectos de investigación. El primero de ellos es de ámbito nacional, está financiado por el Ministerio de Economía y Competitividad dentro de la Convocatoria 2012 de Concesión de Ayudas para la Realización de Proyectos de Investigación, Subprograma de Proyectos de Investigación Fundamental no Orientada y tiene por título "Electroquímica dinámica en interfases convencionales, micrométricas y nanométricas" (referencia CTQ2012-36700). El segundo proyecto es de ámbito regional, está financiado por la Fundación Séneca de la Región de Murcia dentro del III Programa PCTRM 2011-2014 y tiene por título "Desarrollo de modelos para la caracterización de nanopartículas mediante técnicas electroquímicas" (referencia 18968/JLI/13)	es
dc.relation.publisherversion	https://www.sciencedirect.com/science/article/pii/S0013468615301158?casa_token=VvYx_bnEAS8AAAAA:fiXCKB_0K-fu9d2aUNA1FOYxycqk2NDgNntSp4qvsYQBQxzaOscR_fJBfMXY2z4xG0VTWa0IFzjB	es
dc.rights	info:eu-repo/semantics/openAccess	es
dc.rights	Attribution-NonCommercial-NoDerivatives 4.0 Internacional	*
dc.rights.uri	http://creativecommons.org/licenses/by-nc-nd/4.0/	*
dc.subject	Square wave voltammetry	es
dc.subject	Microelectrode	es
dc.subject	Unequal diffusion coefficients	es
dc.subject	Coupled chemical equilibria	es
dc.subject	Differential double pulse voltammetry	es
dc.subject.other	CDU::5 - Ciencias puras y naturales	es
dc.title	Effects of unequal diffusion coefficients and coupled chemical equilibria on square wave voltammetry at disc and hemispherical microelectrodes	es
dc.type	info:eu-repo/semantics/article	es
dspace.entity.type	Publication	es