Enthalpies and Entropies of Transfer of Electrolytes and Ions from Water to Mixed Aqueous Organic Solvents

Hefter, Glenn; Marcus, Yizhak; Waghorne, W. Earle

doi:10.1021/cr010031s

Cited by 140 publications

(133 citation statements)

References 232 publications

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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%

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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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Section: Transfer Thermodynamicsmentioning

confidence: 99%

“…In practice, however, such parameters are usually better measured by other means. For example, ∆ sln H and ∆ sln C p are best determined by various types of calorimetry [7], whilst ∆ sln V is normally obtained from density or dilatometry measurements [8].…”

Section: Introductionmentioning

confidence: 99%

Ion solvation in aqueous–organic mixtures

Hefter

2005

Pure and Applied Chemistry

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“…Many papers have dealt with the effect of the properties of pure [7,[11][12][13][14][15] and mixed solvents on physical and chemical processes [16,17]. The effects of solvent energetic and structural properties [18][19][20], solvation capabilities [21][22][23][24][25][26][27], and acid-base properties of pure and mixed solvents on chemical changes have been reported [28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

Effect of base–acid properties of the mixtures of water with methanol on the solution enthalpy of selected cyclic ethers in this mixture at 298.15 K

Jóźwiak

Warczakowska

2015

J Therm Anal Calorim

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The enthalpies of solution of cyclic ethers: 1,4-dioxane, 12-crown-4 and 18-crown-6 in the mixture of water and methanol have been measured within the whole mole fraction range at T = 298.15 K. Based on the obtained data, the effect of base-acid properties of watermethanol mixtures on the solution enthalpy of cyclic ethers in these mixtures has been analyzed. The solution enthalpy of cyclic ethers depends on acid properties of watermethanol mixtures in the range of high and medium water contents in the mixture. Based on the analysis performed, it can be assumed that in the mixtures of high methanol contents, cyclic ether molecules are preferentially solvated by water molecules.

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“…Introduction of the so-called "green" solvents (of which supercritical CO 2 [4] and room-temperature ionic liquids [5][6][7] are promising examples) has increased our need to probe solute/solvent interactions at the molecular level. The importance of understanding solvation of organic and inorganic species, as well as solvent effects on chemical phenomena, is shown by the fact that there are several books and review articles devoted to these subjects [8][9][10][11][12][13][14][15][16].…”

Section: Introductionmentioning

confidence: 99%

Solvation in pure and mixed solvents: Some recent developments

Seoud

2007

Pure and Applied Chemistry

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The effect of solvents on the spectra, absorption, or emission of substances is called solvatochromism; it is due to solute/solvent nonspecific and specific interactions, including dipole/dipole, dipole-induced/dipole, dispersion interactions, and hydrogen bonding. Thermo-solvatochromism refers to the effect of temperature on solvatochromism. The molecular structure of certain substances, polarity probes, make them particularly sensitive to these interactions; their solutions in different solvents have distinct and vivid colors. The study of both phenomena sheds light on the relative importance of the solvation mechanisms. This account focuses on recent developments in solvation in pure and binary solvent mixtures. The former has been quantitatively analyzed in terms of a multiparameter equation, modified to include the lipophilicity of the solvent. Solvation in binary solvent mixtures is complex because of the phenomenon of "preferential solvation" of the probe by one component of the mixture. A recently introduced solvent exchange model allows calculation of the composition of the probe solvation shell, relative to that of bulk medium. This model is based on the presence of the organic solvent (S), water (W), and a 1:1 hydrogen-bonded species (S-W). Solvation by the latter is more efficient than by its precursor solvents, due to probe/solvent hydrogen-bonding and hydrophobic interactions. Dimethylsulfoxide (DMSO) is an exception, because the strong DMSO/W interactions probably deactivate the latter species toward solvation. The relevance of the results obtained to kinetics of reactions is briefly discussed by addressing temperature-induced desolvation of the species involved (reactants and activated complexes) and the complex dependence of kinetic data (observed rate constants and activation parameters) in binary solvent mixtures on medium composition.

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Enthalpies and Entropies of Transfer of Electrolytes and Ions from Water to Mixed Aqueous Organic Solvents

Cited by 140 publications

References 232 publications

Ion solvation in aqueous–organic mixtures

Ion solvation in aqueous–organic mixtures

Effect of base–acid properties of the mixtures of water with methanol on the solution enthalpy of selected cyclic ethers in this mixture at 298.15 K

Solvation in pure and mixed solvents: Some recent developments

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