Structure of the Solvation Shell of Dissolved Particles

Hertz, H. G.

doi:10.1002/anie.197001241

Cited by 49 publications

(10 citation statements)

References 148 publications

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“…45 years ago Hertz & An suggested that water molecules restructure even around inert NPs (Hertz, 1970). The difficulty of discerning the interfacial signal from the bulk solvent prevented its experimental validation for a long time.…”

Section: Solvent Restructuring Around Nanoparticles and Shortrange Ordermentioning

confidence: 99%

Observing structural reorientations at solvent–nanoparticle interfaces by X-ray diffraction – putting water in the spotlight

Zobel

2016

Acta Crystallogr A Found Adv

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Nanoparticles are attractive in a wide range of research genres due to their size-dependent properties, which can be in contrast to those of micrometre-sized colloids or bulk materials. This may be attributed, in part, to their large surface-to-volume ratio and quantum confinement effects. There is a growing awareness that stress and strain at the particle surface contribute to their behaviour and this has been included in the structural models of nanoparticles for some time. One significant oversight in this field, however, has been the fact that the particle surface affects its surroundings in an equally important manner. It should be emphasized here that the surface areas involved are huge and, therefore, a significant proportion of solvent molecules are affected. Experimental evidence of this is emerging, where suitable techniques to probe the structural correlations of liquids at nanoparticle surfaces have only recently been developed. The recent validation of solvation shells around nanoparticles has been a significant milestone in advancing this concept. Restructured ordering of solvent molecules at the surfaces of nanoparticles has an influence on the entire panoply of solvent-particle interactions during, for example, particle formation and growth, adhesion forces in industrial filtration, and activities of nanoparticle-enzyme complexes. This article gives an overview of the advances made in solvent-nanoparticle interface research in recent years: from description of the structure of bulk solids and liquids via macroscopic planar surfaces, to the detection of nanoscopic restructuring effects. Water-nanoparticle interfaces are given specific attention to illustrate and highlight their similarity to biological systems.

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Section: Solvent Restructuring Around Nanoparticles and Shortrange Ordermentioning

confidence: 99%

Observing structural reorientations at solvent–nanoparticle interfaces by X-ray diffraction – putting water in the spotlight

Zobel

2016

Acta Crystallogr A Found Adv

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“…Therefore, comparing Equations 31 and 30, AG,-0 = AGps 0 /n -RT ln [(n + 1 -i)/i] (32) or in the form of equilibrium constants (33) be formulated as the weighted average of the chemical shifts arising from all possible arrangements of solvent around the ion (13). Hence, if the ith species has an intrinsic shift of 6t, the observed shift 6 is given by…”

Section: Thusmentioning

confidence: 98%

“…Adopting the mole fraction scale and introducing standard chemical po- Equation 13 is Equation 4 of the previously given treatment (3) and derived there by an alternative but equivalent method (noting that w° + p° = 55.5 if an aquamolality scale is adopted as henceforth). It is also similar to GBK's Equation 53.…”

Section: Basic Thermodynamic Treatmentmentioning

confidence: 99%

Thermodynamics of Preferential Solvation of Electrolytes in Binary Solvent Mixtures

Covington

Newman

1976

Thermodynamic Behavior of Electrolytes in Mixed Solvents

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The solvation changes of an ion, as the composition of a binary solvent is varied, can be treated on the basis of n successive equilibria where n is the solvation number. From a detailed consideration of the thermodynamics of preferential solvation, it is possible to define a free energy of preferential solvation ∆G ps ө and relate it to the more familiar free energy of trans fer, ∆G ps ө determinable for a neutral combination of ions from emf measurements. The treatment can be modified to include a case of change of solvation number and to non-statis tical distribution of the solvated species. When separate sol vent NMR signals from solvation shells can be detected or mixed solvates isolated, a further development enables a satis factory explanation to be given for the observed distribution of solvated species.

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“…Here r is the capillary radius (cm), u the surface tension h = 2u/dgr (9) (dyn/cm), d the density (g/cm3), g the acceleration due to gravity (980.66 cm/s2), and h the capillary rise (cm). Using the cited sources of u for the standards, the respective values of r computed were 0.05334, 0.05320, 0.05266, 0.05308, 0.05281, and 0.05283 cm.…”

Section: -mentioning

confidence: 99%

Fused organic salts. 8. Properties of molten straight-chain isomers of tetra-n-pentylammonium salts

Gordon¹,

Rao²

1978

J. Am. Chem. Soc.

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A representative selection of the 64 straight-chain isomers of tetra-n-pentylammonium cation (Q+) has been prepared. Twenty-seven halides, perchlorates, and tetraphenylborates of these cations make up a suite of salts in which the cation's shape and the asymmetry of placement of its charge vary widely. Temperatures, heats, and entropies of solid-solid transition and fusion were measured by hot-stage microscopy and differential scanning calorimetry. Phase diagrams for a number of salt-salt and salt-nonelectrolyte systems were studied by hot-stage microscopy, and the permissible limits of structure variation in Q+ for observation of complete miscibility of two solid salts are reported. The effect of Q+ structure on the critical solution temperatures of salt-nonelectrolyte systems are reported for two nonelectrolytes. The molar volume ( V,) and surface tension (a) of 1 1 liquid salts were determined over a 30-40 O C temperature range near the freezing point. As the charge placement in Q+ becomes progressively more asymmetric, the quantity u / V,'I3, taken as a measure of the cohesive energy density, rises to a maximum and then falls abruptly. The rising portion of this curve is predicted by a simple electrostatic model. Possible origins of the descending portion are discussed. A prefreezing anomaly for liquid dimethyldioctylammonium perchlorate is characterized by sharp breaks in the temperature dependence of surface tension and viscosity some 30 and 40 OC above the freezing point. RJ values for chromatography of Q+C104-and Q+Ph4B-on thin silicic acid layers in three solvent systems are reported. The dominant retardation mechanism appears to be nonelectrostatic.The simple R4N+A-salts have been productive tools in electrolyte-solution chemistry,'-1° fused-salt chemistry,' and organic reactivity m a n i p u l a t i~n . l~-~~ Some important aspects of their chemistry remain to be developed, however. Detailed modeling of charge distribution, shielding, and interaction with solvent and counterion largely remain to be worked out.16-20 More simply, the radii of these ions are not accurately fixed. The most commonly used values are equivalent-sphere radii determined from molecular models.21 Both in the crystal22 and in ion pairs in solution23 Br-is known to approach n-Pr4N+ more closely than the equivalent-sphere radius would imply; it penetrates between the alkyl chains of Pr4N+. There is evidence that organic ions bearing the charge on a peripheral atom display effective radii in their electrostatic interactions that are much closer to the van der Waals radii of the charge-bearing atom than to the mean radii of the organic ions as a whole.24 Since the charge in R4N+ is neither peripheral nor perfectly buried, the effective electrostatic radius must depend upon what charged site or sites the ion is interacting with. Can useful effective electrostatic radii for R4N+ be determined? Most of the work done with R4N+ has used the simple symmetrical ions tetramethyl through tetrabutyl. Radii of any description are presently lacki...

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Structure of the Solvation Shell of Dissolved Particles

Cited by 49 publications

References 148 publications

Observing structural reorientations at solvent–nanoparticle interfaces by X-ray diffraction – putting water in the spotlight

Observing structural reorientations at solvent–nanoparticle interfaces by X-ray diffraction – putting water in the spotlight

Thermodynamics of Preferential Solvation of Electrolytes in Binary Solvent Mixtures

Fused organic salts. 8. Properties of molten straight-chain isomers of tetra-n-pentylammonium salts

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