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Transfer of complexed and dissociated ionic species at soft interfaces: voltammetric study of chemical kinetic and diffusional effects

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Transfer of complexed and dissociated ionic species at soft interfaces voltammetric study of chemical kinetic and diffusional effects.pdf(1.22 MB)
Date
2016
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Authors
Laborda Ochando, Eduardo ; Olmos Martínez, José Manuel ; Molina Gómez, María de los Ángeles
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Publisher
Royal Society of Chemistry
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Química Analítica
DOI
https://doi.org/10.1039/C6CP00780E
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info:eu-repo/semantics/article
Description
©<2016>. 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 Physical Chemistry Chemical Physics. To access the final edited and published work see: https://doi.org/10.1039/C6CP00780E
Abstract
A new transfer mechanism is considered in which two different ionic species of the same charge can be transferred across a soft interface while they interconvert with each other in the original phase through a homogeneous chemical reaction: the aqueous complexation-dissociation coupled to transfer (ACDT) mechanism. This can correspond to a free ion in aqueous solution in the presence of a neutral ligand that complexes it leading to a species that can be more or less lipophilic than the free ion. As a result, the transfer to the organic phase can be facilitated or hindered by the aqueous-phase chemical reaction. Rigorous and approximate explicit analytical solutions are derived for the study of the above mechanism via normal pulse voltammetry, derivative voltammetry and chronoamperometry at macrointerfaces. The solutions enable us to examine the process whatever the species’ lipophilicity and diffusivity in each medium and the kinetics and thermodynamics of the chemical reaction in solution. Moreover, when the chemical reaction is at equilibrium, explicit expressions for cyclic voltammetry and square wave voltammetry are obtained. With this set of equations, the influence of the different physicochemical phenomena on the voltammetric response is studied as well as the most suitable strategies to characterization them.
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Ion transfer , Liquid/liquid interface , Chemical reactivity , Mass transport , Voltammetry
Citation
Physical Chemistry Chemical Physics. 18, pp. 10158-10172. 2016
URI
http://hdl.handle.net/10201/139212
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