Molecular Motion and Structure around the Hydrated Ions Li<sup>+</sup>and Al<sup>3+</sup>

Hertz, H. G.; Tutsch, R.; Versmold, H.

doi:10.1002/bbpc.19710751108

Cited by 86 publications

(23 citation statements)

References 34 publications

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“…We did not discover any anomalies of the properties of aqueous LiCl solutions. To demonstrate this fact we present in Figure just the activity coefficient 13 and the 7 Li spin−lattice relaxation rate for aqueous LiCl solutions as a function of the molal concentration at 298 K …”

Section: Resultsmentioning

confidence: 96%

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

et al. 1999

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Some years ago I. V. Kreitus measured changes in the optical characteristics of pulse radiolytically generated solvated electrons in solutions of LiCl in H2O and D2O over the LiCl concentration range 0−14.06 M (J. Phys. Chem. 1985, 89, 1987). With increasing LiCl concentration he observed a nonuniform blue-shift of the position of the esolv - absorption maximum and a similar discontinuous increase of the half-width of the absorption band. More rapid changes were observed just in those concentration regions which correspond to the stoichiometric mixtures such as LiCl·6H2O and LiCl·4H2O, respectively. Kreitus asserted that this effect is related to the microstructure of the solutions produced by Li+. He concluded finally that the high sensitivity of the esolv - absorption spectrum to slight microstructural changes in the medium could be used in future as a precise method for investigation of the solution structure. These experimental results and especially their interpretation have far reaching consequences. We therefore felt there is a need to repeat at least some of these measurements very carefully. It became all the more necessary as a femtosecond study on the solvation dynamics of electrons in concentrated aqueous LiCl solutions was interpreted according to the results of Kreitus. We report on our experimental results which neither corroborate the experimental data of Kreitus nor support his theoretical conclusions.

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Section: Resultsmentioning

confidence: 96%

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

et al. 1999

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“…Let Li+ serve as an example: In solutions of moderately low solute concentration (c> Ì mol/1) the self-diffusion coefficient D + of this ion has a value of about 10~5cm2s_1 [52]. The favoured model As a result of the above consideration the experimental (0) values are finally treated assuming a comparatively stable shell of dielectrically saturated hydration water molecules around small ions.…”

Section: Results and Treatment Of Datamentioning

confidence: 99%

Dielectric Effects in Aqueous Solutions of 1:1, 2:1, and 3:1 valent Electrolytes: Kinetic Depolarization, Saturation, and Solvent Relaxation

Kaatze¹

1983

Zeitschrift Für Physikalische Chemie

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Static dielectric constant / Dielectric spectroscopy / Electrolyte solutions / Hydration / LiquidsThe complex relative electric permittivity of aqueous solutions of various electrolytes has been measured as a function of frequency between 0.3 and 58 GHz by an interferometric transmission method. Appropriate relaxation functions have been fitted to the measured dielectric spectra. The results of this analysis have been interpreted by assuming that in solutions of small ions both effects, kinetic depolarization and dielectric saturation, are present. Formation of ion pairs is not only indicated by an additional dispersion/absorption region at frequencies below 2 GHz. In these cases the parameters characterizing the solvent water are less influenced by the solute than in solutions of similar but fully dissociated electrolytes.Durch interferometrische Abtastung fortschreitender elektromagnetischer Wellen wurde die komplexe Dielektrizitätszahl wäßriger Lösungen verschiedener Elektrolyte zwischen 0,3 und 58 GHz als Funktion der Frequenz gemessen. An die so erhaltenen dielektrischen Spektren wurden jeweils mehrere geeignete Relaxationsfunktionen angepaßt. Das Ergebnis dieser Analyse der Meßdaten wird bezüglich des Einflusses der kinetischen Depolarisation und der dielektrischen Sättigung diskutiert. Bei einigen Lösungen macht sich auf mehrerlei Weise die Bildung von Ionenpaaren bemerkbar: durch ein zusätzliches Dispersions/Absorptions-Gebiet unterhalb von 2 GHz, aber auch dadurch, daß die das Lösungswasser charakterisierenden Parameter weniger stark beeinflußt sind, als in Lösungen ähnlicher, aber vollständig dissoziierter Elektrolyte.

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“…77,88,124,133,135,137. 150,153,163,[166][167][168][169]172,176,186,199,202,[206][207]235,241,244,254,260,269,278,[308][309]322,327,331,334,336,341,348,357,[364][365]375,379,384,[395][396]405,409,[422][423]432,457,465,469,[489][490]510,[516][517]522,...…”

Section: H O F M E I S T E R Effects: a Notementioning

confidence: 99%

The Hofmeister effect and the behaviour of water at interfaces

Collins

Washabaugh

1985

Quart. Rev. Biophys.

1,534

1,455

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Starting from known properties of non-specific salt effects on the surface tension at an air-water interface, we propose the first general, detailed qualitative molecular mechanism for the origins of ion-specific (Hofmeister) effects on the surface potential difference at an air-water interface; this mechanism suggests a simple model for the behaviour of water at all interfaces (including water-solute interfaces), regardless of whether the non-aqueous component is neutral or charged, polar or non-polar. Specifically, water near an isolated interface is conceptually divided into three layers, each layer being I water-molecule thick. We propose that the solute determines the behaviour of the adjacent first interfacial water layer (I1); that the bulk solution determines the behaviour of the third interfacial water layer (I3), and that both I1 and I3 compete for hydrogen-bonding interactions with the intervening water layer (I2), which can be thought of as a transition layer. The model requires that a polar kosmotrope (polar water-structure maker) interact with I1 more strongly than would bulk water in its place; that a chaotrope (water-structure breaker) interact with I1 somewhat less strongly than would bulk water in its place; and that a non-polar kosmotrope (non-polar water-structure maker) interact with I1 much less strongly than would bulk water in its place. We introduce two simple new postulates to describe the behaviour of I1 water molecules in aqueous solution. The first, the 'relative competition' postulate, states that an I1 water molecule, in maximizing its free energy (--delta G), will favour those of its highly directional polar (hydrogen-bonding) interactions with its immediate neighbours for which the maximum pairwise enthalpy of interaction (--delta H) is greatest; that is, it will favour the strongest interactions. We describe such behaviour as 'compliant', since an I1 water molecule will continually adjust its position to maximize these strong interactions. Its behaviour towards its remaining immediate neighbours, with whom it interacts relatively weakly (but still favourably), we describe as 'recalcitrant', since it will be unable to adjust its position to maximize simultaneously these interactions.(ABSTRACT TRUNCATED AT 400 WORDS)

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Molecular Motion and Structure around the Hydrated Ions Li⁺and Al³⁺

Cited by 86 publications

References 34 publications

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

Dielectric Effects in Aqueous Solutions of 1:1, 2:1, and 3:1 valent Electrolytes: Kinetic Depolarization, Saturation, and Solvent Relaxation

The Hofmeister effect and the behaviour of water at interfaces

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Molecular Motion and Structure around the Hydrated Ions Li+and Al3+

Cited by 86 publications

References 34 publications

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H2O Solutions?

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H2O Solutions?

Dielectric Effects in Aqueous Solutions of 1:1, 2:1, and 3:1 valent Electrolytes: Kinetic Depolarization, Saturation, and Solvent Relaxation

The Hofmeister effect and the behaviour of water at interfaces

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Product

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About

Molecular Motion and Structure around the Hydrated Ions Li⁺and Al³⁺

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?