A revisit to the non-Bornian theory of the Gibbs energy of ion transfer between two immiscible liquids

Murakami, Wataru; Eda, Kazuo; Yamamoto, Masahiro; Osakai, Toshiyuki

doi:10.1016/j.jelechem.2013.06.009

Cited by 15 publications

(23 citation statements)

References 38 publications

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“…In this comparison, the term

Δ_{D C E}^{normalw} G_{M^{+}}^{o, w \to D C E}

for the back transfer of the alkali metal cation (as an ion‐pair with OH − ) makes the energetic difference that favors the chemical ORR after the enforced transfer of alkali metal ions. The differentiation between the cations is in line with the solvation of those cations according to the non‐Bornian solvation model taking into account the charge, hydration radius, and hydration number of each cation . A similar sequence is reached by looking at the hydration enthalpies (Figure ) and the hydration entropy, which make only a small modification to the trend from the enthalpies (Δ S

_{Li^{+}}

=−142 J mol −1 K −1 , Δ S

_{Na^{+}}

=−103 J mol −1 K −1 , Δ S

_{normalK^{+}}

=−88 J mol −1 K −1 ) .…”

Section: Resultssupporting

confidence: 58%

Catalytic Activity of Alkali Metal Cations for the Chemical Oxygen Reduction Reaction in a Biphasic Liquid System Probed by Scanning Electrochemical Microscopy

Rastgar

Santos

Angelucci

2020

Chemistry A European J

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Chemical reduction of dioxygen in organic solvents for the production of reactive oxygen species or the concomitant oxidation of organic substrates can be enhanced by the separation of products and educts in biphasic liquid systems. Here, the coupled electron and ion transfer processes is studied as well as reagent fluxes across the liquid|liquid interface for the chemical reduction of dioxygen by decamethylferrocene (DMFc) in a dichloroethane‐based organic electrolyte forming an interface with an aqueous electrolyte containing alkali metal ions. This interface is stabilized at the orifice of a pipette, across which a Galvani potential difference is externally applied and precisely adjusted to enforce the transfer of different alkali metal ions from the aqueous to the organic electrolyte. The oxygen reduction is followed by H2O2 detection in the aqueous phase close to the interface by a microelectrode of a scanning electrochemical microscope (SECM). The results prove a strong catalytic effect of hydrated alkali metal ions on the formation rate of H2O2, which varies systematically with the acidity of the transferred alkali metal ions in the organic phase.

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“…In this comparison, the term

Δ_{D C E}^{normalw} G_{M^{+}}^{o, w \to D C E}

_{Li^{+}}

=−142 J mol −1 K −1 , Δ S

_{Na^{+}}

=−103 J mol −1 K −1 , Δ S

_{normalK^{+}}

=−88 J mol −1 K −1 ) .…”

Section: Resultssupporting

confidence: 58%

Catalytic Activity of Alkali Metal Cations for the Chemical Oxygen Reduction Reaction in a Biphasic Liquid System Probed by Scanning Electrochemical Microscopy

Rastgar

Santos

Angelucci

2020

Chemistry A European J

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“…is formulated by considering only short-range interactions of an ion and solvent molecules (which include Coulomb, polarization, and charge-transfer interactions). [7][8][9] For the ions that are spherical or may be assumed as such (i.e., for mainly inorganic ions), the ∆ !" ∘,!→!…”

Section: Introductionmentioning

confidence: 99%

Prediction of the Standard Gibbs Energy of Ion Transfer across the 1,2-Dichloroethane/Water Interface

et al. 2018

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The standard Gibbs energy of ion transfer at the 1,2-dichloroethane/water interface ( ∆ !" ∘,!→! ) was determined for 26 organic cations and 24 anions by means of ion-transfer voltammetry with a micro oil/water interface. Based on the data sets, a theoretical analysis was performed with the non-Bornian solvation model, in which the solvation energy of an organic ion is evaluated from local electric fields on the surface of the ion. The semi-empirical equations thus obtained are available for relatively accurate prediction of ∆ !" ∘,!→! for organic ions. The mean absolute error was 1.9 or 3.1 kJ mol -1 for cations or anions, respectively, corresponding to the error of ~20 or ~30 mV in the standard ion-transfer potential. In this paper, energy decomposition has been performed to discuss different contributions to ∆ !" ∘,!→! from the "hydrated" (strongly charged) and positively and negatively charged "non-hydrated" (moderately charged) surfaces as well as from the hydrophobic interaction (cavity formation energy).

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“…Thus, we could determine the Δ O W ϕ°values for several ions, which are shown in Table 1. As also shown in the table, some relatively hydrophilic anions (e.g., 8,13,23) gave no clear transfer peak in the potential window; their Δ O W ϕ°values have been evaluated as < −0.23 V.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Coextraction of Water into Nitrobenzene with Organic Ions

et al. 2015

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Various organic anions (sulfonates (RSO3(-)), carboxylates (RCO2(-)), and phenolates (RO(-))) and ammonium cations (RNH3(+), R2NH2(+), and R3NH(+)) were distributed in the nitrobenzene (NB)-water system by using Crystal Violet and dipicrylaminate, respectively. The number of water molecules (n) being coextracted into NB with an ion was then determined by the Karl Fischer method. The n values determined and those reported previously showed the variation from 0.51 to 3.4, depending on not only the charged groups but also the noncharged R-groups. In this study, we focused our attention to the strong electric field on the charged group and its facilitation effect for binding water molecules in NB. The local electric field (Ei) on the surface of an organic ion was evaluated by using Gaussian09 program with a subprogram developed in our recent study. It was found that the n values showed a clear dependence on the average value of Ei on oxygen or hydrogen atoms, respectively, of an anionic or cationic group.

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A revisit to the non-Bornian theory of the Gibbs energy of ion transfer between two immiscible liquids

Cited by 15 publications

References 38 publications

Catalytic Activity of Alkali Metal Cations for the Chemical Oxygen Reduction Reaction in a Biphasic Liquid System Probed by Scanning Electrochemical Microscopy

Catalytic Activity of Alkali Metal Cations for the Chemical Oxygen Reduction Reaction in a Biphasic Liquid System Probed by Scanning Electrochemical Microscopy

Prediction of the Standard Gibbs Energy of Ion Transfer across the 1,2-Dichloroethane/Water Interface

Coextraction of Water into Nitrobenzene with Organic Ions

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