Simple Ion Transfer at Liquid|Liquid Interfaces

Vallejo, L. J. Sanchez; Ovejero, Juan Manuel; Fernández, Ricardo Ariel; Dassie, Sergio Alberto

doi:10.1155/2012/462197

Cited by 30 publications

(11 citation statements)

References 573 publications

(325 reference statements)

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“…Meanwhile, although some progress has been made in the field of ionics in ILs, it is still not fully developed. For example, the electrode potential of the redox couple between protons and dihydrogen gas, − acidity, − correlations between acidities in ILs and those in molecular solvents, ,, studies of reference electrodes (wherein negligible liquid junction potential (NLJP) difference is frequently assumed), − interfaces between two immiscible electrolyte solutions (ITIES) for charge-transfer processes, − and three-phase electrodes using droplets were reported. However, almost all of these measurements are formal concentration-based and not activity-based.…”

Section: Introductionmentioning

confidence: 99%

Experimental Insight into the Thermodynamics of the Dissolution of Electrolytes in Room-Temperature Ionic Liquids: From the Mass Action Law to the Absolute Standard Chemical Potential of a Proton

2016

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Room-temperature ionic liquids (ILs) are a class of nonaqueous solvents that have expanded the realm of modern chemistry, drawing increasing interest over the last few decades, not only in terms of their own unique physical chemistry but also in many applications including organic synthesis, electrochemistry, and biological systems, wherein charged solutes (i.e., electrolytes) often play vital roles. However, our fundamental understanding of the dissolution of an electrolyte in an IL is still rather limited. For example, the activity of a charged species has frequently been assumed to be unity without a clear experimental basis. In this study, we have discussed a standard component-based scheme for the dissolution of an electrolyte in an IL, supported by our observation of ideal Nernstian responses for the reduction of silver and ferrocenium salts in a representative IL, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([emim + ][NTf 2 – ] or [emim + ][TFSI – ]). Using this scheme, which was also supported by temperature-dependent measurements with ILs having longer alkyl chains in the imidazolium ring, and the solubility of the IL in water, we established the concept of Gibbs transfer energies of “pseudo-single ions” from the IL to conventional neutral molecular solvents (water, acetonitrile, and methanol). This concept, which bridges component- and constituent-based energetics, utilizes an extrathermodynamic assumption, which itself was justified by experimental observations. These energies enable us to eliminate inner potential differences between the IL and molecular solvents (solvent–solvent interactions), that is, on a practical level, conditional liquid junction potential differences, so that we can discuss ion–solvent interactions independently. Specifically, we have examined the standard electrode potential of the ferrocenium/ferrocene redox couple, Fc + /Fc, and the absolute intrinsic standard chemical potential of a proton in [emim + ][NTf 2 – ], finding that the proton is more acidic in the IL than in water by 6.5 ± 0.6 units on the unified pH scale. These results strengthen the progress on the physical chemistry of ions in IL solvent systems on the basis of their activities, providing a rigorous thermodynamic framework.

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Section: Introductionmentioning

confidence: 99%

Experimental Insight into the Thermodynamics of the Dissolution of Electrolytes in Room-Temperature Ionic Liquids: From the Mass Action Law to the Absolute Standard Chemical Potential of a Proton

2016

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“…While most researchers take advantage of ion transfer at the interface between two immiscible electrolyte solutions (ITIES) to study more complicated biological molecules such as proteins, few have reported studies with simple yet toxic metal ions. 11 Wilke and Wang reported a thermodynamic study of Cd( ii ), Cu( ii ), and Pb( ii ) ion transfer across a water/nitrobenzene interface using ETH1062 as the ionophore with microITIES. 12 Benvidi et al characterized Cd( ii ) transfer across water/1,2-dichloroethane (DCE) using a different microITIES geometry in the presence of 1,10-phenanthroline (phen).…”

Section: Introductionmentioning

confidence: 99%

Electrochemical detection of Cd(ii) ions in complex matrices with nanopipets

et al. 2022

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“…In electrochemistry at liquid/liquid interfaces, such as water/nitrobenzene (w/NB) and w/1,2-dichloroethane (w/DCE) ones, formal potentials ( 0 dep j ′ ) for the transfer of single ions j across the interfaces have been determined [1] [2]. These potentials have been obtained at 298 K from standardized potentials of cations or anions based on the extra-thermodynamic assumption for the distribution of tetraphenylarsonium tetraphenylborate ( 4 4 Ph As BPh + − ) and so on [1] [2] [3] in many cases. In these studies, there are many data for the potentials 0 dep j ′ in the w/NB and w/DCE systems [1] [2] [3] [4], while there are some data [5] [6] for w/o-dichlorobenzene (oDCBz) one.…”

Section: Introductionmentioning

confidence: 99%

“…These potentials have been obtained at 298 K from standardized potentials of cations or anions based on the extra-thermodynamic assumption for the distribution of tetraphenylarsonium tetraphenylborate ( 4 4 Ph As BPh + − ) and so on [1] [2] [3] in many cases. In these studies, there are many data for the potentials 0 dep j ′ in the w/NB and w/DCE systems [1] [2] [3] [4], while there are some data [5] [6] for w/o-dichlorobenzene (oDCBz) one. Especially, the data [6] for the metal ions (M z+ at z = 1) seems to be very few.…”

Section: Introductionmentioning

confidence: 99%

Distribution of Ag(I), Li(I)-Cs(I) Picrates, and Na(I) Tetraphenylborate with Differences in Phase Volume between Water and Diluents

Ikeda¹,

Morioka²,

Kudo³

2020

AJAC

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Ionic strength conditions in distribution experiments with single ions are very important for evaluating their distribution properties. Distribution experiments of picrates (MPic) with M = Ag(I) and Li(I)-Cs(I) into o-dichlorobenzene (oDCBz) were performed at 298 K by changing volume ratios (V org /V) between water and oDCBz phases, where "org" shows an organic phase. Simultaneously, an analytic equation with the V org /V variation was derived in order to analyze such distribution systems. Additionally, the AgPic distribution into nitrobenzene (NB), dichloromethane, and 1,2-dichloroethene (DCE) and the NaB(C 6 H 5 ) 4 (=NaBPh 4 ) one into NB and DCE were studied at 298 K under the conditions of various V org /V values. So, extraction constants (K ex ) for MPic into the org phases, their ion-pair formation constants (K MA,org ) for MA = MPic in the org ones, and standard distribution constants ( S D,M K ) for the M(I) transfers between the water and org bulk phases with M = Ag and Li-Cs were determined at the distribution equilibrium potential (dep) of zero V between the bulk phases and also the K ex (NaA), K NaA,org , and S D,A K values were done at 4 A BPh − − = . Here, the symbols K ex , K MA,org , and S D,M K or S D,A K were defined as [MA] org /[M + ][A − ], [MA] org /[M + ] org [A − ] org , and [M + ] org /[M + ] or [A − ] org /[A − ] at dep = 0, respectively. Especially, the ionic strength dependences of K ex and K MPic,org were examined at M = Li(I)-K(I) and org = oDCBz. From above, the conditional distribution constants, K D,BPh4 and K D,Cs , were classified by checking the experimental conditions of the I, I org , and dep values. BPh − into some diluents. The S D,Ag K values were obtained from NB, DCE, oDCBz, and dichloromethane (DCM) systems with the reported S D,Pic K value [5] [8] [11] of picrate ion (Pic − ), the S D, j K values at j = Li + -Cs + from oDCBz one with that [5] of Pic − , and the S D,BPh4 K values from NB and DCE ones with the S D,Na K value [8] of Na + . In the experiments corresponding to the above systems, volume ratios (=V org /V = r org/w ) of the both phases were changed and accordingly an equation for analyzing such systems was derived; V org and V refer to an experimental volume (L unit) of the org phase and that of the w one, respectively. Also, the K ex , K MA,org , and K D,MA values were obtained at 298 K from the same combinations of M + A − and the diluents. Here, the symbols K ex , K MA,org , and K D,MA were defined as [MA] org /[M + ][A − ], [MA] org /[M + ] org [A − ] org , and [MA] org /[MA], respectively. Moreover, extraction, ion-pair formation, and distribution properties for the above systems were S. Ikeda et al.

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Simple Ion Transfer at Liquid|Liquid Interfaces

Cited by 30 publications

References 573 publications

Experimental Insight into the Thermodynamics of the Dissolution of Electrolytes in Room-Temperature Ionic Liquids: From the Mass Action Law to the Absolute Standard Chemical Potential of a Proton

Experimental Insight into the Thermodynamics of the Dissolution of Electrolytes in Room-Temperature Ionic Liquids: From the Mass Action Law to the Absolute Standard Chemical Potential of a Proton

Electrochemical detection of Cd(ii) ions in complex matrices with nanopipets

Distribution of Ag(I), Li(I)-Cs(I) Picrates, and Na(I) Tetraphenylborate with Differences in Phase Volume between Water and Diluents

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