The Solvation of Electrolytes in Dioxane-Water Mixtures, as Deduced from the Effect of Solvent Change on the Standard Partial Molar Free Energy<sup>1</sup>

For the first time, the standard Gibbs energies of the transfer of peptide anions from aqueous solution to nitrobenzene were determined with the help of electrochemical measurements. These systematic studies clearly show that the lipohilicity contributions of single amino acid residues to the overall lipohilicity of a peptide anion strongly depend on the position of the amino acid in the backbone of the peptide. Therefore, additive models to calculate the overall lipophilicity of a peptide cannot provide very precise data. The present study is a plea for the experimental establishment of a data set that takes into account the individual nature of an amino acid residue and its position in a peptide.

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“…All of the estimated values of the standard Gibbs energies of transfer are based on the so-called Grunwald assumption. 42 …”

Section: Methodsmentioning

confidence: 99%

Lipophilicity of Peptide Anions: An Experimental Data Set for Lipophilicity Calculations

Gulaboski

Scholz

2003

J. Phys. Chem. B

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“…Subsequently we have re-examined the properties of hydrogen 14. A further possibility is that methanol is undergoing reduction to methane.…”

Section: Rydrobromic Acidmentioning

confidence: 99%

Studies in Ion Solvation in Mixed Solvents

Feakins¹

1962

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These results ar. disoussed and explained on. the assumption that the. solvation of the ions is dominated by an aoid-base interaction between the ion and the solvent moleoules, rather than by ion-dipole interactions or ion-dieleotrio interaotion,though the latter will play some part.Because of the inductive release of the methyl group, the methanol molecule will be a stronger base than the water molecule and will therefore oolvate cations more * ::* efficiently than water. The reverse will be true for anions, as the methanol molecule is a weaker acid than the water molecule. These assumptions about the basicity and acidity of methanol are not generally accepted, but no method exists whereby these quantities can be determined directly or even estimated with confidence.No clear pattern emerges for the enthalpies and entropies of transfer, and a reason for this is advanced.An account of some preliminary work on dioxan-water mixtures is given in a special section.(iv) Pinal

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“…Most frequently the "TATB assumption" [3,9,29,40,[194][195][196][197][198][199] is made stating that the anion and the cation of tetraphenylarsonium tetraphenylborate have equal standard Gibbs transfer energies. On the basis of this assumption a scale for standard Gibbs transfer energies of ions from one solvent to another can be obtained using standard Gibbs transfer energies of salts calculated from partition coefficients.…”

Section: Representative Experimental Datamentioning

confidence: 99%

Simple Ion Transfer at Liquid|Liquid Interfaces

Vallejo

Ovejero

Fernández

et al. 2012

International Journal of Electrochemistry

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The main aspects related to the charge transfer reactions occurring at the interface between two immiscible electrolyte solutions (ITIES) are described. The particular topics to be discussed involve simple ion transfer. Focus is given on theoretical approaches, numerical simulations, and experimental methodologies. Concerning the theoretical procedures, different computational simulations related to simple ion transfer are reviewed. The main conclusions drawn from the most accepted models are described and analyzed in regard to their relevance for explaining different aspects of ion transfer. We describe numerical simulations implementing different approaches for solving the differential equations associated with the mass transport and charge transfer. These numerical simulations are correlated with selected experimental results; their usefulness in designing new experiments is summarized. Finally, many practical applications can be envisaged regarding the determination of physicochemical properties, electroanalysis, drug lipophilicity, and phase-transfer catalysis.

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The Solvation of Electrolytes in Dioxane-Water Mixtures, as Deduced from the Effect of Solvent Change on the Standard Partial Molar Free Energy¹

Cited by 263 publications

References 10 publications

Lipophilicity of Peptide Anions: An Experimental Data Set for Lipophilicity Calculations

Lipophilicity of Peptide Anions: An Experimental Data Set for Lipophilicity Calculations

Studies in Ion Solvation in Mixed Solvents

Simple Ion Transfer at Liquid|Liquid Interfaces

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The Solvation of Electrolytes in Dioxane-Water Mixtures, as Deduced from the Effect of Solvent Change on the Standard Partial Molar Free Energy1

Cited by 263 publications

References 10 publications

Lipophilicity of Peptide Anions: An Experimental Data Set for Lipophilicity Calculations

Lipophilicity of Peptide Anions: An Experimental Data Set for Lipophilicity Calculations

Studies in Ion Solvation in Mixed Solvents

Simple Ion Transfer at Liquid|Liquid Interfaces

Contact Info

Product

Resources

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The Solvation of Electrolytes in Dioxane-Water Mixtures, as Deduced from the Effect of Solvent Change on the Standard Partial Molar Free Energy¹