Gibbs Energies of Transfer of Cations from Water to Mixed Aqueous Organic Solvents

Kalidas, C.; Hefter, Glenn; Marcus, Yizhak

doi:10.1021/cr980144k

Cited by 322 publications

(393 citation statements)

References 164 publications

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“…Apparently, this phenomenon requires further investigation. (Mazzarese & Popovych, 1983) 6400 ± 100 (Kalida et al, 2000) 4210 8590 ± 100 (*) 8330 ± 100 (Mazzarese & Popovych, 1983) 8000 ± 100 (Kalida et al, 2000) 8620 ± 100…”

Section: Standard Thermodynamic Functions Of Transfer Of Salt From Wamentioning

confidence: 99%

Electromotive Force Measurements and Thermodynamic Modelling of Sodium Chloride in Aqueous-Alcohol Solvents

Uspenskaya¹,

Konstantinova²,

Veryaeva³

et al. 2011

Electromotive Force and Measurement in Several Systems

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Section: Standard Thermodynamic Functions Of Transfer Of Salt From Wamentioning

confidence: 99%

Electromotive Force Measurements and Thermodynamic Modelling of Sodium Chloride in Aqueous-Alcohol Solvents

Uspenskaya¹,

Konstantinova²,

Veryaeva³

et al. 2011

Electromotive Force and Measurement in Several Systems

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“…Clearly, the magnitude of ∆ t Y°reflects the differences in the solvation of MX (i.e., of its component ions) in the two solvents s1 and s2, which may be neat or mixed. The choice of "reference" solvent, s1, from which the ions are transferred, is arbitrary but for aqueous-organic mixtures (s2 = w + s) the obvious choice is usually water (s1 = w) [5,7].…”

Section: Transfer Thermodynamicsmentioning

confidence: 99%

“…The various assumptions that have been used for estimating single ion thermodynamic properties have been reviewed on many occasions [1,5,9,10]. All can be objected to on some grounds, since they are assumptions whose ultimate validity cannot be established except by comparison with other assumptions or with reliable theoretical predictions.…”

Section: Ionic Transfer Thermodynamicsmentioning

confidence: 99%

“…On the other hand, the sensitivity to small changes in ∆ sln G makes solubility measurements an excellent method for the determination of such quantities [3][4][5]. Consider, for example, a 1:1 salt with an experimentally determined solubility of say (5.0 ± 0.5) × 10 -3 mol/l.…”

Section: Introductionmentioning

confidence: 99%

“…Of course, accurate determination of solubility is not as straightforward as it may appear [4][5][6]. First, the solubility should be neither too high nor too low.…”

Section: Introductionmentioning

confidence: 99%

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Ion solvation in aqueous–organic mixtures

Hefter

2005

Pure and Applied Chemistry

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Abstract:The importance of ion solvation in determining the properties of electrolyte solutions in aqueous-organic solvent mixtures is discussed. Solubility measurements are shown to be particularly useful for determining the Gibbs energies of transfer of ions between solvents, which reflect differences in the overall solvation of the ions in different solvent mixtures. Solubility measurements can also be used to determine the other thermodynamic parameters of transfer, but such quantities are usually better obtained by more direct methods. The inadequacy of current theories of ion solvation to quantitatively account for the thermodynamics of ion transfer is discussed by reference to measurements on some simple model systems. Although donor/acceptor interactions can explain many of the observed effects between pure solvents, the situation is more complex in aqueous-organic mixtures because selective solvation and even solvent-solvent interactions may become significant. This is illustrated by consideration of ion transfer from water to water + t-butanol solutions, where spectacular effects are observed in the enthalpies and entropies and especially in the heat capacities and volumes.

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Thermodynamics of Complexation of Cadmium(II) by Open-Chain N-Donor Ligands in Dimethyl Sulfoxide Solution

Comuzzi

Grespan

Melchior

et al. 2001

Eur. J. Inorg. Chem.

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Thermodynamic parameters for the complexation of CdII by the amines n‐butylamine (n‐but), ethylenediamine (en), N,N′‐dimethylethylenediamine (dmen), N,N,N′‐trimethylethylenediamine (trmen), N,N,N′,N′‐tetramethylethylenediamine (tmen), diethylenetriamine (dien), N,N′′‐dimethyldiethylenetriamine (dmdien), and N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdien) have been determined in dimethyl sulfoxide (DMSO) solution by potentiometric and calorimetric techniques at 298 K and 0.1 mol dm−3 ionic strength (NEt4ClO4). Only mononuclear complexes are formed, in which the polyamines act predominantly as chelating agents. All the complexes are enthalpy‐stabilized, whereas the entropy changes counteract the complexation. The steric requirements of the donors have a strong influence on the stoichiometry and nature of the CdII complexes formed. Comparisons are made with data reported for some of these systems in water and with available data on silver(I) complexation by the same amines in DMSO, the latter showing that the selectivity of the ligands towards metal ions is also influenced by N‐alkylation.

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Gibbs Energies of Transfer of Cations from Water to Mixed Aqueous Organic Solvents

Cited by 322 publications

References 164 publications

Electromotive Force Measurements and Thermodynamic Modelling of Sodium Chloride in Aqueous-Alcohol Solvents

Electromotive Force Measurements and Thermodynamic Modelling of Sodium Chloride in Aqueous-Alcohol Solvents

Ion solvation in aqueous–organic mixtures

Thermodynamics of Complexation of Cadmium(II) by Open-Chain N-Donor Ligands in Dimethyl Sulfoxide Solution

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