Ionic radii from scaled particle theory of the salt effect

Masterton, William L.; Bolocofsky, David; Lee, Tei Pei

doi:10.1021/j100687a017

Cited by 104 publications

(72 citation statements)

References 8 publications

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“…, and Cl À ) and divalent (inset) ions (Ca 2þ , Zn 2þ , Cd 2þ , Pb 2þ , and Cu 2þ ) with different effective ionic radius a [38,39] For comparison, we also include the result for the transfer free energy as implied by the simple linear mixing rule for the dielectric constant of the mixture. This mixing rule, together with the simple Born expression for the solvation energy, implies the following expression for the transfer free energy:…”

Section: Fig 1 (Color Online) the Solvation Free Energymentioning

confidence: 99%

Ion Solvation in Liquid Mixtures: Effects of Solvent Reorganization

2012

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Using field-theoretic techniques, we study the solvation of salt ions in liquid mixtures, accounting for the permanent and induced dipole moments, as well as the molecular volume of the species. With no adjustable parameters, we predict solvation energies in both single-component liquids and binary liquid mixtures that are in excellent agreement with experimental data. Our study shows that the solvation energy of an ion is largely determined by the local response of the permanent and induced dipoles, as well as the local solvent composition in the case of mixtures, and does not simply correlate with the bulk dielectric constant. In particular, we show that, in a binary mixture, it is possible for the component with the lower bulk dielectric constant but larger molecular polarizability to be enriched near the ion. DOI: 10.1103/PhysRevLett.109.257802 PACS numbers: 77.84.Nh, 31.15.xr, 31.70.Dk, 78.20.Ci Salt ions are essential in biology, colloidal science, electrochemistry, and many other areas of science and engineering. For example, protein stability and solubility are well known to be significantly affected by the addition of salts [1]. In the energy arena, there is much current interest in lithium salt-doped polymers as new battery materials [2].The effects of salt ions on the properties of soft matter can often be understood in terms of translational entropy and electrostatic screening. However, recently it has been shown that the solvation energy of the salt ions can significantly affect the phase behavior [3,4] and interfacial properties of liquid mixtures [5][6][7][8]. For example, Ref. [4] showed that the dramatic increase in the order-disorder transition temperature of (polyethylene oxide)-b-polystyrene block copolymers upon adding a small amount of lithium salt can be explained on the basis of the preferential solvation energy of the anions. Physically, the tendency of an ion to be preferentially solvated by the more polarizable component in a two-component mixture provides a significant driving force for phase separation [3], as well as differential adsorption between the cation and anion at the interface [5][6][7][8].While a very large body of theoretical literature exists for ion solvation in single-component liquids for comprehensive reviews and Ref. [14] for recent developments of ion force fields for solvation.), we are not aware of any theory that predicts the composition dependence of ion solvation in liquid mixtures. In Refs. [3][4][5][6]8], the solvation energy is modeled phenomenologically at the linear dielectrics level by a crude Born expression: ÁG Born ¼ ½ðzeÞ 2 =ð8 a 0 Þ ð1=" À 1Þ, where e is the elementary charge, a is the radius of the ion, and z is the valency. The local dielectric constant is taken to be given by a simple composition weighted average " ¼ " A A þ " B B . The Born model has the virtue of being simple and intuitive in capturing the essential qualitative physics of solvation. However, quantitatively, the Born expression is known to be a poor description of the solva...

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Section: Fig 1 (Color Online) the Solvation Free Energymentioning

confidence: 99%

Ion Solvation in Liquid Mixtures: Effects of Solvent Reorganization

2012

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“…even if we do not need all these parameters for the present study. Masterton et ill. (10) have also calculated some ionic radii of the R4Nt solutes using the equations of the SPT applied to the salting coefficients of nonpolar gases in aqueous electrolyte solutions; as it will be shown, there is some discrepancy of diameters between the two. 'Using eq.…”

Section: Resultsmentioning

confidence: 99%

“…As the apparent moial volumes of the W4NBr in water appear in these SPT equations, we may assume that most of the soft part of the mixed solvent potential is then taken into account. On the other hand, for the nonpolar soiute, Masterton et al (10) had to estimate some inductive and dispersion terms. These latter calculations may be fairly uncertain especially in the presence of the higher homologs R4NBr where the dispersion forces may play an important role.…”

Section: Diar~zeters Of Watermentioning

confidence: 99%

“…Since then, Lucas and co-kvorkers (6-81, Masterton et cil. (9,10): and Shoos and Gubbins (11) have extended these calculations t o the solubility of gases in aqueous electrolyte solutions. Lucas u et al (12)(13)(14) have also applied the SPT to the heats and entropies of nonpolar gases in some aqueous solutions of t e t r a a l k y l a n~n~o n i~~n~ halides (R4NX) and alcohols.…”

Section: Introductionmentioning

confidence: 99%

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Enthalpies, heat capacities, and volumes of transfer of the tetrabutylammonium ion from water to aqueous mixed solvents from the point of view of the scaled-particle theory

Desrosiers¹,

Desnoyers²

1976

Can. J. Chem.

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NICOLE DESROSIERS and JACQUES E. DESNOYERS. Can. J. Cheni. 54, 3800 (19761. The enthalpies. heat capacities, and volumes of transfer of the tetrabutjlammoniuni ion from water to urea-~+ater, 1ei.t-butyl alcohol -water, and sodium chloride -hater mixtures have been calculated at 25 C ~~s i~i g the scaled-particle theor). In general, the signs, magnitudes. and overall trends in the cosolve~lt concentration dependence of the properties are predicted from the cavit) contributions only. T h e x calculations are found to be very sensitive to the diameters chosen for the various species.For these calculations it was necessary t o liieasure with a dilatometer the coefticients of therlnal expansion of re1.r-butql alcohol-water niixtures as a function of concentration and temperature. NICOLE DESROSIERS et J A C Q U E~ E. D E \~Y E R S .Can. J. Cheni. 54. 3800 (1976). Les enthalpies, capacitis calorificl~~es et volumes de transfert du cation tCtrabutylanimoiiium de I'ea~i aux melanges eau-uree, eau -chlorure de s o d i~u n et eau-r~i.t-b~~ta!ioI ont Cte c a l c~~l e s a 25 ' C B I'aide de la theorie des particules calibrees (scalecl-particle theory). En general, les signes, les ordres de grandeur et les tendances deb dilYerentes propriet6s en fonction tie la concerltration en co\olvant sont predits h partir des tcrmes relatifs 2 la formation de cavitC seulenient. Ces calculs sont trks sensibles a u choix des diametres des dilferentes espkces en solution. Pour ces calculs il a etC nCcessaire de mesurer au moqen d'un dilatomktre les coellicients de dilatation cubiclue des melanges eau-rerr-butanol en fonction de la co~lcentratio~l et de la temperature.

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“…Thus for a spherical bubble of radius r in a liquid, the equation has been advanced, where m refers to the plane surface. Equation [18] is based on thermodynamic arguments which may not be expected to hold for very small r, where the equation obviously breaks down. It has been suggested that the equivalent of eq.…”

Section: Discussionmentioning

confidence: 99%

A surface tension approach to the salting-out of nonpolar nonelectrolytes

Aveyard¹

1982

Can. J. Chem.

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ROBERT AVEYARD. Can. J. Chem. 60, 1317Chem. 60, (1982. A simple approach is developed for the salting-out of nonpolar molecules by strongly solvated salts. The standard free energy of transfer of solute from pure solvent to salt solution, and hence the salting coefficient, k, is calculated in terms of the surface tension increment caused by the addition of salt to the solvent. In its simplest form the method gives k in terms of the molar volumes of solvent and solute, and the osmotic coefficient of the salt solution. It is more successful in the prediction of k than the McDevit and Long theory, and it also has advantages over the more complex scaled particle theory of salt effects. In addition to a range of nonpolar solutes, the salt effects on some alcohols are also considered but application to polar solutes generally requires a knowledge of experimentally determined surface tension increments which are not widely available. The correct order of magnitude for the temperature coefficient of k at room temperature for some alkanes and H, in water is given, although minima ink as a function of temperature, which have sometimes been observed, are not reproduced.ROBERT AVEYARD. Can. J. Chem. 60, 1317Chem. 60, (1982. On a mis au point une methode simple de relargage des mol6cules non polaires par les sels fortement solvatb. On a calcule 1'6nergie libre standard de transfert du solute a partir du solvant pur jusqu'l une solution saline, et par consequent le coefficient de salinite, k, en fonction de I'incrdment de la tension de surface provoque par I'addition de sel au solvant. Dans saforme la plus simple, la mdthode permet d'obtenir k en fonction des volumes molaires de solvant et de solute et du coefficient d'osmose de la solution saline. Elle a plus de succks dans la prevision de k que la theorie de McDevit et Long et elle a certains avantages sur la theorie plus complexe de la particule a l'8chelle des effets de sel. En plus d'une variitk de solutes non polaires, on a igalement considere les effets de sel sur certains alcools; toutefois son application des solutes polaires requiert generalement une connaissance des increments de la tension de surface d6termin6s exp6rimentalement et ces incrdments ne sont generalement pas disponibles. On donne l'ordre de grandeur reel du coefficient de temperature de k a la temperature ambiante pour quelques alcanes et I'hydrogkne dans I'eau bien que les minima observes quelque fois pour k en fonction de la temperature ne soient pas reproduits.[Traduit par le journal]

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Ionic radii from scaled particle theory of the salt effect

Cited by 104 publications

References 8 publications

Ion Solvation in Liquid Mixtures: Effects of Solvent Reorganization

Ion Solvation in Liquid Mixtures: Effects of Solvent Reorganization

Enthalpies, heat capacities, and volumes of transfer of the tetrabutylammonium ion from water to aqueous mixed solvents from the point of view of the scaled-particle theory

A surface tension approach to the salting-out of nonpolar nonelectrolytes

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