The polarizabilities of species present in ionic solutions

Pyper, N.C.; Pike, C.G.; Edwards, P. P.

doi:10.1080/00268979200101381

Cited by 93 publications

(121 citation statements)

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“…The polarizability of cations generally increases going from the gaseous phase to the crystalline phase, probably due to the stronger shielding of the electrostatic field by the surrounding species in the more condensed phases. 19 However, we note that the cation polarizabilities in the aqueous phase are closer to their gaseous-phase values than to their crystalline-phase values, suggesting that the water molecules surrounding cations only exert a minimal shielding effect on the electric field. The opposite trend is observed for anions in the halogen series, with the ion polarizability decreasing from the gaseous phase to the crystalline phase.…”

Section: Resultsmentioning

confidence: 88%

“…In order to obtain the polarizability of a single ion in water, a reference polarizability value needs to be defined. Earlier work 15,18,19,33 suggested that the polarizabilities of small cations are largely unaffected by the aqueous environment. In addition, the smaller value of the polarizability of smaller cations makes them appropriate choices as references since this will minimize the errors -the errors will be bounded by the value of the polarizability of the reference ion.…”

Section: Resultsmentioning

confidence: 99%

“…Pyper et al obtained what they termed the "total in-solution molar polarizability" by the DE method. 19 However, the apparent salt polarizability generally varies nonlinearly with concentration, with large error bars in the low concentration range. Therefore the DE method introduces significant uncertainties in the value of salt polarizability at infinite dilution (see Figure S1).…”

Section: Resultsmentioning

confidence: 99%

“…We shall refer to this approach as the direct extrapolation (DE) method. 19,27 Such a method, though valid in principle, suffers from two sources of error. First, in the experimentally relevant ranges of salt concentration, the relation between salt polarizability and salt concentration is usually not simply linear.…”

Section: Introductionmentioning

confidence: 99%

“…16 However, ion polarizabilities in the aqueous phase can be significantly different from their corresponding the gas-phase values 17,18 due to the strong interactions between the charge of ions and the permanent or induced dipoles of solvent molecules. 19 Unfortunately, Pauling's theoretical framework cannot be readily extended to calculate polarizabilities of ions to account for these interactions in the aqueous phase.…”

Section: Introductionmentioning

confidence: 99%

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Accurate Determination of Ion Polarizabilities in Aqueous Solutions

Zhuang

et al. 2017

J. Phys. Chem. B

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We present a novel method for obtaining salt polarizabilities in aqueous solutions based on our recent theory for the refractive index of salt solutions, which predicts a linear relationship between the refractive index and the salt concentration at low concentrations, with a slope determined by the intrinsic values of the salt polarizability and the density of the solution. Here we apply this theory to determine the polarizabilities of 32 strong electrolyte salts in aqueous solutions from refractive index and density measurements. Setting Li + as the standard ion, we then determine the polarizabilities of seven cations (Na + , K + , Rb + , Cs + , Ca 2+ , Ba 2+ and Sr 2+ ) and seven anions (F − , Cl − , Br − , I − , ClO − 4 , NO − 3 and SO − 4 ), which can be used as important reference data.We investigate the effect of temperature on salt polarizabilities, which decreases slightly with increasing temperature. The ion polarizability is found to be proportional to the cube of bare ionic radius (r 3 bare ) for univalent ions, but the relationship does not hold for multivalent ions. Contrary to findings of Krishnamurti, we find no significant linear relationship between ion polarizability and the square of the atomic number (N 2 ) for smaller ions.

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Section: Resultsmentioning

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Accurate Determination of Ion Polarizabilities in Aqueous Solutions

Zhuang

et al. 2017

J. Phys. Chem. B

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Optical Response of Porous Titania-Silica Waveguides to Surface Charging in Electrolyte Filled Pores

Šefčı́k

Kroslak

Morbidelli

2002

HCA

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Dedicated to Professor Dieter Seebach on the occasion of his 65th birthdayIn this work, we present a novel method for in situ investigation of surface charging and ion transport inside nanopores of titania-silica waveguide by means of the optical-waveguide-lightmode spectroscopy. Porous oxide waveguides show a strong optical response when exposed to electrolyte solutions, and this response is consistent with oxide surface charging due to changes in ionic strength and pH of the solution in contact with the waveguide. The optical response to pH or electrolyte concentration change is stabilized within several minutes when the solution ionic strength is sufficiently high (0.1m), while it takes two orders of magnitude longer to reach stable optical response at very low ionic strengths (< 0.1mm). The relaxation times at the high ionic strength are still by several orders of magnitude slower than expected from bulk diffusion coefficients of electrolytes in water. Our results indicate that diffusion of electrolytes is severely hindered (and more so with decreasing ionic strength) in charged pores inside waveguides.1. Introduction. ± Sol-gel-based silica-titania mixed oxides are important materials in catalysis [1] [2] and optical applications [3 ± 5]. Sol-gel synthesis typically involves one or more metal alkoxides undergoing hydrolysis in aqueous solutions and subsequent condensation eventually forming particles or gels [6]. Resulting materials are usually nanoporous with substantial internal surface areas on the order of 100 m 2 / cm 3 and even higher, when pore filling surfactants or molecular templates are used. Water can be removed from wet gels by supercritical drying to produce low-density aerogels or at ambient pressure with various heating protocols. Ambient-pressure drying causes further condensation and collapse of nanopores due to capillary pressure, resulting in densification and internal surface loss. Heat treatment promotes phase changes such as nucleation and growth of crystalline phases, and phase separation, also leading to densification and decreased porosity. Microstructure of mixed oxides is thus influenced in early stages, when small metal-oxide oligomers have a chance for heterocondensation to achieve molecular-scale homogeneity in the wet gel, as well as in later stages, when porosity and homogeneity can be severely modified during drying.Planar optical waveguides can be prepared by coating silica-titania sols on appropriate substrates to obtain wet gel films, into which diffraction gratings are embossed, followed by further heat treatment in order to achieve required film hardness and stability [7] [8]. The final waveguide thickness is on the order of few hundred nanometers. Depending on temperature and duration of drying, the film porosity can be as high as 20%. For standard drying procedures (few hours at 5008) typical porosity was found to be around 15% [9]. With temperatures as high as 9008, the porosity of silica-titania films can be reduced below 1% [10].

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Functional Zwitterionic Polymers on Surface: Structures and Applications

Zhuang

2020

Chemistry An Asian Journal

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Zwitterionic polymers are important in a wide range of industrial, biological and medical fields. Their chemical structures include an equal amount of anion and cation groups, and such structures give rise to many unique functionalities, such as temperature response, anti-polyelectrolyte effect, and strong hydration properties. In this review, we focus on the structures and applications of functional zwitterionic polymers on surfaces. We review three areas of applications according to the architecture of the polymeric systems: surface coating, complex solutions, and hydrogel. We review the simulation and theory work, and highlight some outlooks for further development.

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The polarizabilities of species present in ionic solutions

Cited by 93 publications

References 56 publications

Accurate Determination of Ion Polarizabilities in Aqueous Solutions

Accurate Determination of Ion Polarizabilities in Aqueous Solutions

Optical Response of Porous Titania-Silica Waveguides to Surface Charging in Electrolyte Filled Pores

Functional Zwitterionic Polymers on Surface: Structures and Applications

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