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Origin of the correlation between the standard Gibbs energy of ion transfer and the solubility of water in organic solvents
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SYSNO ASEP 0574240 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Origin of the correlation between the standard Gibbs energy of ion transfer and the solubility of water in organic solvents Tvůrce(i) Trojánek, Antonín (UFCH-W) RID
Mareček, Vladimír (UFCH-W) RID
Fiedler, Jan (UFCH-W) RID, ORCID
Samec, Zdeněk (UFCH-W) RID, ORCIDČíslo článku 142966 Zdroj.dok. Electrochimica acta. - : Elsevier - ISSN 0013-4686
Roč. 465, OCT 2023 (2023)Poč.str. 10 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova Steady-state voltammetry ; Standard Gibbs energy of ion transfer ; Solubility of water Vědní obor RIV CG - Elektrochemie Obor OECD Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) CEP GA22-32631S GA ČR - Grantová agentura ČR Způsob publikování Omezený přístup Institucionální podpora UFCH-W - RVO:61388955 UT WOS 001059062900001 EID SCOPUS 85167605033 DOI 10.1016/j.electacta.2023.142966 Anotace Standard Gibbs energies ΔwoGi0 of the Cs+ and Li+ ion transfer from water to 1,2-dichlorobenzene, and to an n-octanol + α,α,α-trifluorotoluene mixture were obtained from the steady-state voltammetric measurements. The equilibrium concentrations of water in these solvents were determined by the Karl Fischer method. Analogous data have previously been reported for the transfer of these ions to α,α,α-trifluorotoluene, 1.6-dichlorohexane, 1,4-dichlorobutane, 1,2-dichloroethane, o-nitrophenyl octyl ether, nitrobenzene, and n-octanol. Based on this collection of data, a correlation was established between the experimental values of ΔwoGi0 for the Cs+ or Li+ ion transfer and the reported content of water in the organic solvent characterized by the ratio cW/cS of the molar concentrations of water (cW) and the organic solvent molecules (cS) in the organic solvent S. This correlation exhibits a rapid decay of ΔwoGi0 in the range of the small values of the ratio cW/cS= 0.0025 - 0.02, while towards higher values of cW/cSthe standard Gibbs energy of ion transfer tends to attain a constant value. The relationship was successfully simulated using the equations derived for a Born-type electrostatic model of solvation of the ion, which was combined with a thermodynamic model of the preferential solvation in the mixed solvents. The mechanism of an ion transfer assumes the partial replacement of the water molecules in the first hydration layer of the transferred ion by molecules of the organic solvent. Spectroscopic evidence is presented pointing to the absence of water clusters in pure 1,2-dichloroethane saturated with water, which therefore should not play a role in the ion transfer mechanism. © 2023 Elsevier Ltd. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2024 Elektronická adresa https://hdl.handle.net/11104/0344578
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