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On the non-ideal behaviour of polarised liquid-liquid interfaces

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Show simple item record Suárez-Herrera, Marco F. Scanlon, Micheál D. 2020-01-14T16:22:14Z 2019
dc.identifier.issn 0013-4686
dc.description peer-reviewed en_US
dc.description.abstract Interpretation of electrochemical data generated at the interface between two immiscible electrolyte solutions (ITIES), and realisation of the ITIES for technological applications, requires comprehensive knowledge of the origin of the observed currents (i.e., capacitive, ion or electron transfer currents) and the factors influencing the electrical double layer. Upon formation, the ITIES is away from equilibrium and therefore is a close approximation, but not a perfect realisation, of an ideally polarisable interface. Nevertheless, the formalism of equilibrium thermodynamics, e.g., the Nernst equation, are universally applied to interpret electrochemical processes at the ITIES. In this study, electrochemical impedance spectroscopy (EIS), cyclic and AC voltammetry were applied to probe electrochemical processes at an ITIES formed between aqueous and α,α,α-trifluorotoluene electrolyte solutions. A significant contribution from faradaic currents is observed across the whole polarisable potential window and the electrolyte solution is not an ideal resistor (especially at high electric field frequencies). The electrical double-layer at the interface is influenced by the nature of the ions adsorbed. Small inorganic ions, such as sulfate anions and aluminium cations, are shown to absorb at the interface, with methanesulfonic acid absorbing strongly. The nature of ions adsorbed at the interface shifts the potential of zero charge (PZC) at the ITIES, which we propose in turn influences the kinetics of ion transfer en_US
dc.language.iso eng en_US
dc.publisher Elsevier en_US
dc.relation 13/SIRG/2137 en_US
dc.relation.ispartofseries Electrochimica Acta;328, 135110
dc.rights This is the author’s version of a work that was accepted for publication in Electrochimica Acta Changes publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Electrochimica Acta, 328, 135110, en_US
dc.subject electrical double layer en_US
dc.subject electro-adsorption en_US
dc.subject interface between two immiscible electrolyte solutions en_US
dc.subject liquid-liquid interface en_US
dc.subject potential of zero charge en_US
dc.title On the non-ideal behaviour of polarised liquid-liquid interfaces en_US
dc.type info:eu-repo/semantics/article en_US
dc.type.supercollection all_ul_research en_US
dc.type.supercollection ul_published_reviewed en_US 2020-01-10T14:52:01Z
dc.description.version ACCEPTED
dc.identifier.doi 10.1016/j.electacta.2019.135110
dc.contributor.sponsor SFI en_US
dc.contributor.sponsor ERC en_US
dc.relation.projectid 13/SIRG/2137 en_US
dc.relation.projectid 716792 en_US 2021-10-23
dc.embargo.terms 2021-10-23 en_US
dc.rights.accessrights info:eu-repo/semantics/openAccess en_US
dc.internal.rssid 2932397
dc.internal.copyrightchecked Yes
dc.identifier.journaltitle Electrochimica Acta
dc.description.status peer-reviewed

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