Ionic solvation in water + cosolvent mixtures. Part 10.—Free energies of transfer of single ions from water into water + ethanonitrile mixtures

Groves, Grahame S.; Wells, Cecil F.

doi:10.1039/f19858101985

Cited by 18 publications

(3 citation statements)

References 2 publications

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“…The cosolvents were acetone (AC), acetonitrile (AN), dioxane (Diox), dimethyl ether (DME), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethanol (EtOH), methanol (MeOH), and urea. We obtained ion solvation free energies in each mixture by adding tabulated transfer free energies [77][78][79][80][81][82][83][84][85] to experimental ion solvation free energies in water. 43 Mixture dielectric constants were taken to be experimental values.…”

Section: Predicting Solvation In Mixturesmentioning

confidence: 99%

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

Tabrizi

Goossens

Rahimi

et al. 2017

The Journal of Chemical Physics

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We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics (Gibbs free energies, entropies, and heat capacities) in numerous polar solvents. We are also able to predict ion solvation free energies in water-co-solvent mixtures over available concentration series. The first modification to the classical dielectric Poisson model is a perturbation of the macroscopic dielectric-flux interface condition at the solute-solvent interface: we add a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is including the microscopic interface potential (static potential) in our model. We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water-co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. These and previous tests of the SLIC model indicate that it is a promising dielectric continuum model for accurate predictions in a wide range of conditions. Published by AIP Publishing. [http://dx.

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Section: Predicting Solvation In Mixturesmentioning

confidence: 99%

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

Tabrizi

Goossens

Rahimi

et al. 2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…The co-solvents were acetone (AC), acetonitrile (AN), dioxane (Diox), dimethyl ether (DME), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethanol (EtOH), methanol (MeOH), and urea. We obtained ion solvation free energies in each mixture by adding tabulated transfer free energies [73][74][75][76][77][78][79][80][81] to experimental ion solvation free energies in water 41 . Mixture dielectric constants were taken to be experimental values [82][83][84][85][86][87][88][89] .…”

Section: Predicting Solvation In Mixturesmentioning

confidence: 99%

Predicting Solvation Free Energies and Thermodynamics in Polar Solvents and Mixtures Using a Solvation-Layer Interface Condition

Tabrizi,

Goossens,

Rahimi

et al. 2016

Preprint

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We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics in numerous polar solvents, and ion solvation free energies in water-co-solvent mixtures. The first modification involves perturbing the macroscopic dielectric-flux interface condition at the solute-solvent interface with a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is a simple treatment of the microscopic interface potential (static potential). We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water-co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. The present work, together with previous studies of SLIC illustrating its accuracy for biomolecules in water, indicates it as a promising dielectric continuum model for accurate predictions of molecular solvation in a wide range of conditions.

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“…The free energy of transfer on the mole fraction scale for the total process (a) transfer of 1 mole of H+(H,O), from the standard state in water to that in the mixture, followed by (b) the solvent sorting eqn (2) with the standard states now defined in the mixture, is given by eqn (8) for any particular solvent composition. where d is density, M is molecular weight with M , = 100/((wt % ROH/M,,,) + (wt % H,O/M,)] and [ROH,] is given by eqn ( 9) and ( 10)…”

Section: + +mentioning

confidence: 99%

Ionic solvation in water–Co-solvent mixtures. Part 18.—Free energies of transfer of single ions from water into water–2-methoxyethanol mixtures

Halawani¹,

Wells²

1989

J. Chem. Soc., Faraday Trans. 1

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Ionic solvation in water + cosolvent mixtures. Part 10.—Free energies of transfer of single ions from water into water + ethanonitrile mixtures

Cited by 18 publications

References 2 publications

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

Predicting Solvation Free Energies and Thermodynamics in Polar Solvents and Mixtures Using a Solvation-Layer Interface Condition

Ionic solvation in water–Co-solvent mixtures. Part 18.—Free energies of transfer of single ions from water into water–2-methoxyethanol mixtures

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