Polarity and hydrogen-bonding ability of some binary aqueous–organic mixtures

Migron, Yoelit; Marcus, Yizhak

doi:10.1039/ft9918701339

Cited by 97 publications

(45 citation statements)

References 11 publications

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“…As revealed by our experimental data, these polarities, expressed in E T or other units, are mostly a function of the solvatochromic dye used together with the solvent system studied and not solely of the solvent system. Similar conclusions can be drawn from the papers of Marcus and Migron 25,26 concerning a variety of solvatochromic indica- Figure 11. Relationship between the position of the longest wavelength absorption maximum (in 1000 cm Ϫ 1 ) and the molar fraction of water, temperature 298·2 K, for (a) merocyanine dye Ij in the acetonitrile-water system, (b) betaine dye II in the pyridine monohydrate-water subsystem.…”

Section: Discussionsupporting

confidence: 80%

Solvatochromism of dyes. Part III. Solvatochromism of merocyanines in some binary mixtures of solvents.SA-SAB-SB, a new model of solvatochromism

Soroka

1997

J. Phys. Org. Chem.

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A quantitative model of solvatochromism in a binary solvent system is presented. Although it is derived for merocyanine and betaine dyes, it explains a majority of known examples of solvatochromism in binary solvents. The model provides an estimation of equilibrium constants between particular types of solvates present therein. UV-VIS absorption spectra of solvated species can be simulated. They perfectly fit the experimental data. The model proposed describes the internal solvent picture from the solute point of view, which differs from other known models and may be useful for studying the structure of liquids.

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Section: Discussionsupporting

confidence: 80%

Solvatochromism of dyes. Part III. Solvatochromism of merocyanines in some binary mixtures of solvents.SA-SAB-SB, a new model of solvatochromism

Soroka

1997

J. Phys. Org. Chem.

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“…The same factor is apparently responsible for the similar shape of the concentration dependence of the proton-donor power a(X 2 ) of the mixed solvent water3DMF [35]. This assumption is confirmed by computer simulation of this mixture at 298.15 K [36], which showed that the integral three-dimensional network of hydrogen bonds in water is broken in separate clusters even at X 2~0 .4.…”

supporting

confidence: 53%

Thermodynamic parameters of intermolecular interaction in strongly associated solvents and their mixtures with dimethylformamide

Zaichikov

Krest’yaninov

2004

Russ J Gen Chem

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The specific and nonspecific constituents of the total energy of intermolecular interasction in ethylene glycol, diethylene glycol, and formamide were determined for the range 288.153323.15 K using a simulation approach. Diethylene glycol, like formamide and ethylene glycol, forms networks of hydrogen bonds. In ethylene glycol and formamide, the hydrogen bonds make a predominant contribution to the total interaction energy. The specific and nonspecific contributions in mixtures of the above solvents with dimethylformamide were calculated, and the results were discussed in combination with the data for aqueous dimethylformamide solutions.Owing to the presence of three-dimensional networks of hydrogen bonds in certain nonaqueous solvents, solvation of atomic and molecular species in them has a number of characteristic features [1]. In ethylene glycol and formamide, both of which contain two proton-acceptor and two proton-donor sites in the molecule, formation of the network structures has been reliably proved [2, 3], whereas with diethylene glycol this is still the matter of discussion [4]. Search for correlations between the structure and properties of strongly associated solvents and thermodynamic characteristics of their nonelectrolyte mixtures reflecting the specific features of intermolecular interaction of the components is an urgent problem of the modern chemistry of solutions [5]. This work is a part of studies of the structural and thermodynamic properties of mixtures of carboxylic acid amides with compounds forming a network of hydrogen bonds. Previously we studied the thermochemical characteristics of mixtures of formamide and ethylene glycol with N,N-disubstituted amides [6,7]. One of the main goals of this work was to estimate the contribution of specific and nonspecific interactions to the intermolecular interaction of strongly associated nonelectrolytes (ethylene glycol, diethylene glycol, formamide) and their binary systems with DMF, a typical aprotic polar solvent capable of formation of hydrogen-bonded heteroassociates. Important information on the structure and properties of nonaqueous solutions with hydrogen bond networks is furnished by computer simulation methods. Formamide and its mixtures with dimethylformamide were studied by this method in [3,8,9]. However, the thermodynamic characteristics of formamide and its mixtures with DMF, calculated by these methods, are poorly consistent with the results of a physicochemical experiment [3,9], which is most probably caused by inadequacy of the existing interaction potentials. Computer simulation of glycols and their solutions is hindered by the lack of data on the intermolecular interaction potentials. Analysis of the excess thermodynamic functions of mixing in nonelectrolyte solutions with hydrogen bonding, usually performed within the framework of associative models [10], is inadequate for these systems, because it is principally impossible to single out the associative formations. Therefore, it seems reasonable to consider nonaqueous solvents an...

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“…The following bulk solvent percentages, when mixed with the corresponding percentage of water, yield hydroorganic solvent mixtures which have partition coefficients for benzene and toluene which bracket the waterto-SDS partition coefficients: 90-100% methanol, 70-80% acetonitrile, 80-100% 2-propanol, and 50-60% tetrahydrofuran. These are all very polar solvent mixtures 162,163 and provide further support for the conclusion that even polar solutes such as benzene and toluene are located in very polar, hydrated environments such as the Stern and palisade layers of the micelles.…”

Section: Resultsmentioning

confidence: 79%

Study of Water−Sodium Dodecyl Sulfate Micellar Solubilization Thermodynamics for Several Solute Homolog Series by Headspace Gas Chromatography

1996

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We employed headspace gas chromatography to measure water-to-sodium dodecyl sulfate (SDS) micellar partition coefficients for homologous series of n-alkylbenzenes, 1-nitroalkanes, 1-alkanols, and 2-ketones. The free energy of transfer per methylene unit is -612 cal/mol for polar solutes and -534 cal/mol for nonpolar solutes. Henry's law was also explored for the n-alkylbenzenes and 2-ketones and found to hold to total solute mole fractions of at least 7 × 10 -3 and 3.4 × 10 -2 in the SDS micellar phase, respectively. Additionally, we compared water-to-SDS partition coefficients to water-to-bulk organic solvent partition coefficients for methylene units and whole solutes. From these comparisons we conclude that short, polar organic solvents such as methanol and nitromethane make the best models of the solutes' micellar environment and that the solutes and their methylene units are located in the relatively polar palisade and/or Stern layers of the SDS micelles.

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Polarity and hydrogen-bonding ability of some binary aqueous–organic mixtures

Cited by 97 publications

References 11 publications

Solvatochromism of dyes. Part III. Solvatochromism of merocyanines in some binary mixtures of solvents.SA-SAB-SB, a new model of solvatochromism

Solvatochromism of dyes. Part III. Solvatochromism of merocyanines in some binary mixtures of solvents.SA-SAB-SB, a new model of solvatochromism

Thermodynamic parameters of intermolecular interaction in strongly associated solvents and their mixtures with dimethylformamide

Study of Water−Sodium Dodecyl Sulfate Micellar Solubilization Thermodynamics for Several Solute Homolog Series by Headspace Gas Chromatography

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