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Ions in a binary asymmetric dipolar mixture: Mole fraction dependent Born energy of solvation and partial solvent polarization structure
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10.1063/1.2792953
/content/aip/journal/jcp/127/18/10.1063/1.2792953
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/18/10.1063/1.2792953

Figures

Image of FIG. 1.
FIG. 1.

Born free energy of solvation, (upper panel) and excess Born free of solvation, (lower panel) of a unipositive, rigid ion as a function of mole fraction of second component with higher dipole moment at different solvent-solvent size ratios . The circles, triangles, inverted triangles, and squares are for solvent-solvent size ratios equal to 1.2, 1.0, 0.8, and 0.5, respectively. The line going through the points for each is a guide to the bare eye. The dipole moments of two solvent components ( and ) and diameter of the ion are kept fixed for all the solvent-solvent size ratios (Table I).

Image of FIG. 2.
FIG. 2.

Upper panel. Comparison of Born free energy of solvation for (circles), (triangles), (squares), and (inverted triangles) ions as a function of mole fraction of methanol in methanol-water mixture. Middle panel. Comparison of excess Born free energies of solvation for (circles) and (triangles) ions as a function of mole fraction of methanol in methanol-water mixture. Lower panel. Comparison of excess Born free energy of solvation for (squares) and (inverted triangles) ions as a function of mole fraction of methanol in methanol-water mixture. Other representations remain the same as in the Fig. 1.

Image of FIG. 3.
FIG. 3.

Upper panel: Comparison of Born free energy of solvation for (circles), (triangles), (squares), and (inverted triangles) ions as a function of mole fraction of tertiary butanol in tertiary butanol-water (TBA-water) mixture. Middle panel. Comparison of excess Born free energy of solvation for (circles) and (triangles) ions as a function of mole fraction of TBA in TBA-water mixture. Bottom panel: Comparison of excess Born free energy of solvation for (squares) and (inverted triangles) ions as a function of mole fraction of TBA in TBA-water mixture.

Image of FIG. 4.
FIG. 4.

Comparison of Born free energy of solvation (upper panel) and excess Born free energy of solvation (lower panel) for ion in methanol-water (circles), ethanol-water (triangles), and TBA-water mixture (squares). For further discussion, see text.

Image of FIG. 5.
FIG. 5.

Partial polarization of water and TBA (both scaled by ) around and ions as a function of distance (scaled by water diameter ) from the center of the ion at three different TBA mole fractions. In all the panels calculated data for TBA mole fractions 0.11, 0.30, and 0.50 are represented by solid, dashed, and dotted-dash lines, respectively. For discussion, see text.

Image of FIG. 6.
FIG. 6.

Excess partial polarization of water (upper panel) (peak) and TBA (peak) calculated from the peak values of respective partial polarizations for (circles), (triangles), (squares), and (inverted triangles) ions as a function of mole fraction of TBA in TBA-water mixture. The following expression has been used to calculate (peak) ( or TBA): .

Image of FIG. 7.
FIG. 7.

Comparison between the calculated excess Born free energy of solvation and experimental excess free energy of solvation for (circles), (triangles), (squares), and (inverted triangles) ions in binary mixtures of methanol-water (upper panels), ethanol-water (middle panels), and DMSO-acetonitrile (bottom panel). These excess functions are shown as a function of mole fraction of one of the components in the mixture. The experimental data are represented by the solid symbols, while the predictions from the extended MSA theory are shown by the open symbols.

Image of FIG. 8.
FIG. 8.

Comparison between experiment (left panels) and theory (right panels) for excess free energy of mixing in alcohol-water (upper panels) and DMSO-acetonitrile mixtures (lower panels). The solid line represents the experimental results for methanol-water mixture, dashed line the ethanol-water, and the dot-dashed line the TBA-water results. The line going through the symbols (squares, triangles, and circles) is simply a guide for the eye. Note that no experimental data exist for for DMSO-acetonitrile mixture; only the excess enthalpy of mixing is available. The excess volume of mixing for dimethysulfoxide-acetonitrile mixture is very small compared to that in alcohol-water mixture which are known to posses a large volume contraction (Ref. 66). Under certain approximations, Hildebrand and Wood (Ref. 68) and Scatchard (Ref. 69) showed that .

Tables

Generic image for table
Table I.

Parameters used in the calculation for model binary dipolar mixture. and are dipole moment of solvents 1 and 2, respectively. is packing fraction, , , and are diameters of ion and solvent components 1 and 2, respectively. D stands for Debye.

Generic image for table
Table II.

Solvent parameters used in the calculation for alcohol-water mixtures. Diameters of , , , and ions are taken as 1.24, 1.96, 3.52, and , respectively (Ref. 2).

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/content/aip/journal/jcp/127/18/10.1063/1.2792953
2007-11-08
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Ions in a binary asymmetric dipolar mixture: Mole fraction dependent Born energy of solvation and partial solvent polarization structure
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/18/10.1063/1.2792953
10.1063/1.2792953
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