Volcano Plots Emerge from a Sea of Nonaqueous Solvents: The Law of Matching Water Affinities Extends to All Solvents

dc.contributor.authorMazzini, Virginia
dc.contributor.authorCraig, Vincent
dc.date.accessioned2020-05-18T04:27:28Z
dc.date.available2020-05-18T04:27:28Z
dc.date.issued2018
dc.date.updated2019-12-19T06:01:04Z
dc.description.abstractThe properties of all electrolyte solutions, whether the solvent is aqueous or nonaqueous, are strongly dependent on the nature of the ions in solution. The consequences of these specific-ion effects are significant and manifest from biochemistry to battery technology. The "law of matching water affinities" (LMWA) has proven to be a powerful concept for understanding and predicting specific-ion effects in a wide range of systems, including the stability of proteins and colloids, solubility, the behavior of lipids, surfactants, and polyelectrolytes, and catalysis in water and ionic liquids. It provides a framework for considering how the ions of an electrolyte interact in manifestations of ion specificity and therefore represents a considerable conceptual advance on the Hofmeister or lyotropic series in understanding specific-ion effects. Underpinning the development of the law of matching water affinities were efforts to interpret the so-called "volcano plots". Volcano plots exhibit a stark inverted "V" shape trend for a range of electrolyte dependent solution properties when plotted against the difference in solvation energies of the ions that constitute the electrolyte. Here we test the hypothesis that volcano plots are also manifest in nonaqueous solvents in order to investigate whether the LMWA can be extended to nonaqueous solvents. First we examine the standard solvation energies of electrolytes in nonaqueous solvents for evidence of volcano trends and then extend this to include the solubility and the activity/osmotic coefficients of electrolytes, in order to explore real electrolyte concentrations. We find that with respect to the solvent volcano trends are universal, which brings into question the role of solvent affinity in the manifestation of specific-ion effects. We also show that the volcano trends are maintained when the ionic radii are used in place of the absolute solvation energies as the abscissa, thus showing that ion sizes, rather than the solvent affinities, fundamentally determine the manifestation of ion specificity. This leads us to propose that specific-ion effects across all solvents including water can be understood by considering the relative sizes of the anion and cation, provided the ions are spherical or tetrahedral. This is an extension of the LMWA to all solvents in which the "water affinity" is replaced with the relative size of the anion and cation.en_AU
dc.description.sponsorshipThe authors recognize the great importance of the fundamental work of Y. Marcus to the data analysis presented here. V.S.J.C. gratefully acknowledges the financial support of the Australian Research Council (FT0991933).en_AU
dc.format.mimetypeapplication/pdfen_AU
dc.identifier.issn2374-7951en_AU
dc.identifier.urihttp://hdl.handle.net/1885/204405
dc.language.isoen_AUen_AU
dc.provenanceThis is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.en_AU
dc.publisherAmerican Chemical Societyen_AU
dc.relationhttp://purl.org/au-research/grants/arc/FT0991933en_AU
dc.rights© 2018 American Chemical Societyen_AU
dc.rights.licenseACS AuthorChoice Licenseen_AU
dc.sourceACS Central Scienceen_AU
dc.titleVolcano Plots Emerge from a Sea of Nonaqueous Solvents: The Law of Matching Water Affinities Extends to All Solventsen_AU
dc.typeJournal articleen_AU
dcterms.accessRightsOpen Accessen_AU
local.bibliographicCitation.issue8en_AU
local.bibliographicCitation.lastpage1064en_AU
local.bibliographicCitation.startpage1056en_AU
local.contributor.affiliationMazzini, Virginia, College of Science, ANUen_AU
local.contributor.affiliationCraig, Vincent, College of Science, ANUen_AU
local.contributor.authoremailu9204140@anu.edu.auen_AU
local.contributor.authoruidMazzini, Virginia, u5329723en_AU
local.contributor.authoruidCraig, Vincent, u9204140en_AU
local.description.notesImported from ARIESen_AU
local.identifier.absfor020405 - Soft Condensed Matteren_AU
local.identifier.absfor030603 - Colloid and Surface Chemistryen_AU
local.identifier.absseo970103 - Expanding Knowledge in the Chemical Sciencesen_AU
local.identifier.absseo970102 - Expanding Knowledge in the Physical Sciencesen_AU
local.identifier.ariespublicationa383154xPUB10608en_AU
local.identifier.citationvolume4en_AU
local.identifier.doi10.1021/acscentsci.8b00348en_AU
local.identifier.scopusID2-s2.0-85051948345
local.identifier.uidSubmittedBya383154en_AU
local.publisher.urlhttps://pubs.acs.org/en_AU
local.type.statusPublished Versionen_AU

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