Hydration Properties Of Ions Research Articles

Ultraviolet Resonant Raman Scattering of Electrolyte Solutions.

Saltwater stands as the most prevalent liquid on Earth. Consequently, substantial interest has been directed toward its characterization, both as an independent system and as a solvent for complex structures such as biomacromolecules. In the last few decades, special emphasis was placed on the investigation of the hydration properties of ions for the fundamental role they play in numerous chemical processes. In this study, we employed multi-wavelength Raman spectroscopy to examine the hydration shell surrounding bromide ions in solutions of simple electrolytes, specifically lithium bromide, potassium bromide, and cesium bromide, at two different concentrations. Cation-induced differences among electrolytes were observed in connection to their tendency to form ion pairs. An increased sensitivity to reveal the structure of the first hydration shell was evidenced when employing ultraviolet excitation in the 228-266 nm range, under resonance conditions with the charge transfer transition to the solvent peaked at about 200 nm. Other than a significant increase in the Raman cross-section for the OH stretching band when shifting from pure water to the solution, a larger enhancement for the Raman signal of the H-O-H bending mode over the stretching vibration was observed. Thus, the bending band plays a crucial role in monitoring the H-bond structure of water around the anions related to the charge distribution within the first hydration shell of anions, being an effective probe of hydration phenomena.

Structural and charge transfer properties of ion intercalated 2D and bulk ice.

Ion trapping at the nanoscale within low-dimensional and bulk ice and their corresponding hydration properties are studied using ab initio techniques. We study the structural and charge transfer properties of ion intercalated two-dimensional (2D) and bulk ice and the corresponding ion hydration properties. We found that (i) the nanochannel size and ionic radius are two important factors that control the spatial distribution of hydrated ions, (ii) the alkali metal and halide ions are located in the center of the graphene-made nanochannel of size ≃6.5 Å, whereas in the nanochannel with size ≃9 Å, large (K+, Rb+, Cl-, Br-, and I-) and small (Li+, Na+, and F-) ions are located in different positions, (iii) the binding energy decreases with increase in the ionic radius, (iv) the hydration of ions decreases for large ions within 2D ice, giving a reduction in coordination number and allowing dehydration of large ions, and (v) the charge transfer mechanism is found to be different for large and small ions.

Accurate Modeling of Bromide and Iodide Hydration with Data-Driven Many-Body Potentials.

Ion-water interactions play a central role in determining the properties of aqueous systems in a wide range of environments. However, a quantitative understanding of how the hydration properties of ions evolve from small aqueous clusters to bulk solutions and interfaces remains elusive. Here, we introduce the second generation of data-driven many-body energy (MB-nrg) potential energy functions (PEFs) representing bromide-water and iodide-water interactions. The MB-nrg PEFs use permutationally invariant polynomials to reproduce two-body and three-body energies calculated at the coupled cluster level of theory, and implicitly represent all higher-body energies using classical many-body polarization. A systematic analysis of the hydration structure of small Br-(H2O)n and I-(H2O)n clusters demonstrates that the MB-nrg PEFs predict interaction energies in quantitative agreement with "gold standard" coupled cluster reference values. Importantly, when used in molecular dynamics simulations carried out in the isothermal-isobaric ensemble for single bromide and iodide ions in liquid water, the MB-nrg PEFs predict extended X-ray absorption fine structure (EXAFS) spectra that accurately reproduce the experimental spectra, which thus allows for characterizing the hydration structure of the two ions with a high level of confidence.

Enthalpic and Entropic Selectivity of Water and Small Ions in Polyamide Membranes.

While polyamide reverse osmosis and nanofiltration membranes have been extensively utilized in water purification and desalination processes, the molecular details governing water and solute permeation in these membranes are not fully understood. In this study, we apply transition-state theory for transmembrane permeation to systematically break down the intrinsic permeabilities of water and small ions in loose and tight polyamide nanofiltration membranes into enthalpic and entropic components using an Eyring-type equation. We analyze trends in these components to elucidate molecular phenomena that induce water-salt, monovalent-divalent, and monovalent-monovalent selectivity at different pH values. Our results suggest that in pores that are either too small or contain an electrostatically repelling mouth, the thermal activation of ions in the form of ion dehydration is less likely, promoting entropically driven selectivity with steric exclusion of hydrated ions. Instead, larger uncharged pores enable ion dehydration, inducing enthalpic selectivity that is driven by differences in the ion hydration properties. We also demonstrate that electrostatic interactions between cations and intrapore carboxyl groups hinder salt permeability, increasing the enthalpic barrier of the transport. Last, permeation tests of monovalent cations in the loose and tight polyamide membranes expose opposite rejection trends that further support the phenomenon of ion dehydration in large subnanopores.

Role of cation size on swelling pressure and free energy of mica pores

The ion exchange capacity of clay plays an important role in many industrial applications ranging from radioactive waste disposal to cosmetics. However, swelling or shrinking of clay platelets due to water and ions adsorption in the interstitial zone is also a well-known phenomenon. For their applications, it is crucial to understand the stability of these layered materials, especially after exchange of interstitial ions with surrounding ions having different properties. Here, we probed the role of cation size on swelling pressure and free energy profile. We used molecular simulations to investigate the stability of mica pore, having K+, Rb+, and Cs+ ions. We performed a series of grand canonical Monte Carlo simulations at various pore widths. We probed water adsorption in mica pores from which disjoining pressure, grand potential (swelling free energy), and structural properties of confined water and ions were calculated. While the behavior of these three systems is similar qualitatively because of similar hydration properties of ions, significant differences are observed at the quantitative level due to changes in the hydration structure of cations. The global minimum in swelling free energy is found to be at the smaller pore widths (first minimum) for Rb- and K-mica and at bigger pore widths (second minimum) for Cs-mica pores. We find that ±0.1 Å change in the interstitial cation size leads to a -15 to 5% change in equilibrium loading of adsorbed water and -2 to 35% change in swelling. Our thermodynamic analysis reveals an intricate interplay between enthalpic and entropic contributions caused by the structural change of water in the pores due to the hydration of interstitial cations.

Investigation of ions hydration using molecular modeling

Ion hydration phenomena are of great interest in the fields of physics, chemistry, biology, geochemistry and environment. However, few studies using identical calculation methods to characterize the hydration properties of ions in water and in electrolytic systems are available. Hence, it is difficult to compare the hydration properties of ions when they come from different methods. The objective of this work is, therefore, to use a unique approach to compare the hydration properties of ions in pure water and in presence of counter-ion using a quantum mechanical method, the Density Functional Theory (DFT). For this purpose, a methodology based on the decomposition of the system's energy is described and implemented in this study. In the first part, quantum mechanics calculations are used to determine the hydration properties of ions, without counter-ion, in presence of water molecules. In the second part, the hydration characteristics of solutes in systems containing ions, counter-ions and water molecules are studied. Results show that the presence of an anion (Cl− or SO42−) does not cause structural and energetic changes in the cation first hydration layer (Li+, Na+, K+, Mg2+, Ca2+). Conversely, the anion first hydration layer depends on the cation of the system.

Correlation between Computed Ion Hydration Properties and Experimental Values of Sugar Transfer through Nanofiltration and Ion Exchange Membranes in Presence of Electrolyte

The widespread use of nanofiltration and electrodialysis membrane processes is slowed down by the difficulties in predicting the membrane performances for treating streams of variable ionic compositions. Correlations between ion hydration properties and solute transfer can help to overcome this drawback. This research aims to investigate the correlation between theoretically evaluated hydration properties of major ions in solution and experimental values of neutral organic solute fluxes. In particular, ion hydration energies, coordination and hydration number and the average ion-water distance of Na+, Ca2+, Mg2+, Cl− and SO42− were calculated at a high quantum mechanics level and compared with experimental sugar fluxes previously reported. The properties computed by simple and not computationally expensive models were validated with information from the literature. This work discusses the correlation between the hydration energies of ions and fluxes of three saccharides, measured through nanofiltration and ionic-exchange membranes. In nanofiltration, the sugar flux increases with the presence of ions of increasing hydration energy. Instead, inverse linear correlations were found between the hydration energy and the sugar fluxes through ion exchange membranes. Finally, an empirical model is proposed for a rough evaluation of the variation in sugar fluxes as function of hydration energy for the ion exchange membranes in diffusion experiments.

Hydrated Ion Clusters in Hydrophobic Liquid: Equilibrium Distribution, Kinetics, and Implications.

Hydrophilic ions in oil phase tend to be hydrated in the presence of trace water and form hydrated clusters. The present paper elucidates the equilibrium size distribution of hydrated ion clusters and the microscopic rates of adsorption and desorption of water with the help of molecular dynamics simulations. The size distribution is derived from reversible work of hydration, which is nearly constant over the hydration number except for small clusters. The intrinsic rate constants of adsorption and desorption are evaluated to be in several psec order after correcting the diffusion. The microscopic hydration properties of ions in the oil phase play key roles in chemical reactions involving both hydrophilic and hydrophobic reactants as well as in the transport and reactivity of the ions in oil phase and at the water-oil interface.

Confinement and surface effects of aqueous solutions within charged carbon nanotubes.

We have examined the structure of water and aqueous solutions in carbon nanotubes using molecular dynamics simulations. We find confinement changes the structure of water as well as the interactions between ions and their solvation shells. The density and orientation of water at the nanotube walls are strongly dependent on the surface charge and cations/anions present at the interfaces. Decreasing the nanotube diameter alters the ion hydration properties as well as hydrogen bonding structure and formation dynamics. The results indicate that fluid structure and hydrogen bond characteristics in nano-channels can be tuned through modification of tube charge and with ion selection.

Thermodynamics of small alkali metal halide cluster ions: comparison of classical molecular simulations with experiment and quantum chemistry.

We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali metal halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge nonpolarizable SPC/E, (ii) Drude point charge polarizable SWM4-DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas-phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.

Revisiting a many-body model for water based on a single polarizable site: From gas phase clusters to liquid and air/liquid water systems

We present a revised version of the water many-body model TCPE [M. Masella and J.-P. Flament, J. Chem. Phys. 107, 9105 (1997)], which is based on a static three charge sites and a single polarizable site to model the molecular electrostatic properties of water, and on an anisotropic short range many-body energy term specially designed to accurately model hydrogen bonding in water. The parameters of the revised model, denoted TCPE/2013, are here developed to reproduce the ab initio energetic and geometrical properties of small water clusters (up to hexamers) and the repulsive water interactions occurring in cation first hydration shells. The model parameters have also been refined to reproduce two liquid water properties at ambient conditions, the density and the vaporization enthalpy. Thanks to its computational efficiency, the new model range of applicability was validated by performing simulations of liquid water over a wide range of temperatures and pressures, as well as by investigating water liquid/vapor interfaces over a large range of temperatures. It is shown to reproduce several important water properties at an accurate enough level of precision, such as the existence liquid water density maxima up to a pressure of 1000 atm, the water boiling temperature, the properties of the water critical point (temperature, pressure, and density), and the existence of a "singularity" temperature at about 225 K in the supercooled regime. This model appears thus to be particularly well-suited for characterizing ion hydration properties under different temperature and pressure conditions, as well as in different phases and interfaces.

Differential effects of oligosaccharides on the hydration of simple cations

Changed ion hydration properties near surfaces, proteins, and deoxyribose nucleic acid have been reported before in the literature. In the present work, we extend this work to carbohydrates: We have performed classical-mechanical molecular dynamics simulations to study solvation properties of simple cations of biological relevance (Na(+),K(+),Mg(2+),Ca(2+)) in explicit water, near single and multiple oligosaccharides as glycocalyx models. We find that our oligosaccharides prefer direct contact with K(+) over Na(+), but that the Na(+) contacts are longer lived. These interactions also lead to strong but short-lived changes in oligosaccharide conformations, with oligosaccharides wrapping around K(+) with multiple contacts. These findings may have implications for current hypotheses on glycocalyx functions.

Rotational Mobility of Water around Muscle Proteins by High-Resolution Microwave Dielectric Spectroscopy and a Clue to Molecular Mechanism of Muscle Contraction

A precision microwave dielectric spectroscopic technique has been developed. This technique enables us to analyze hydration properties of ions, proteins, and other biomolecules. φ-scan method gives an image of the information of spatial distribution of dielectric property of water surrounding protein molecules. Fixed φ analysis gives a direct comparison of hydration properties of different proteins. With this technique we analyzed the state change of F-actin hydration upon binding with myosin, and found that hyper-mobile water (HMW) is induced around F-actin and increased upon binding with myosin S1. Thus, we may obtain further information of collective properties of water surrounding proteins and biomolecules.

An empirical method for the determination of single ion hydrogen isotope salt effects in aqueous electrolyte solutions

An empirical method is presented that allows the determination of the individual contributions of anions and cations to the effect of dissolved salts on hydrogen isotope fractionation in aqueous systems (isotope salt effect). The method is solely based on experimental data and does not involve the choice of arbitrary reference values or theoretical assumptions. Plotting experimental liquid–vapor D/H fractionation factors for aqueous solutions of sodium salts vs. O–D stretching frequencies of water molecules in the hydration shells of the anions shows an excellent linear correlation. The distance between this line and the pure water liquid–vapor fractionation data point in the same plot gives the cation contribution to the isotope salt effects. The anion contribution can then simply be derived as the difference between the total salt effect and the cation salt effect. The validity of the concept is demonstrated using precise literature data for the O–D stretching frequencies in the hydration shells of individual ions at 20°C [Bergström, P.A., 1991. Single ion hydration properties in aqueous solution: a quantitative infrared spectroscopic study. PhD Thesis. Uppsala University] and for the liquid–vapor hydrogen isotope fractionation between aqueous solutions and water vapor at the same temperature [Stewart, M.K., Friedman, I., 1975. Deuterium fractionation between aqueous salt solutions and water vapor. Journal of Geophysical Research 80, 3812–3818]. Within the limits of experimental uncertainties, the data set shows internal consistency. Cation salt effects, 1000 ln Γ at 20°C, are (in per mil per mole per liter, using the convention of Horita et al. [Horita, J., Cole, D.R., Wesolowski, D.J., 1993a. The activity–composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: II. Vapor–liquid water equilibration of mixed salt solutions from 50–100°C. Geochimica et Cosmochimica Acta 57, 4703–4711]): Na ++0.7; K ++0.7; Mg 2++6.5; Ca 2++1.8; Al 3++12. The salt effect of H + cannot be determined unequivocally. The combined effect of the fractionation of H + itself plus its salt effect is +4.9. Anion effects are +1.4 for Cl −, +2.7 for Br −, +3.5 for I − and −1.4 for SO 4 2 −. Further single anion salt effects are being predicted as −1.8 for F −, +4.9 for NO 3 −, +6.9 for ClO 4 − and +5.4 for the triflate ion (CF 3SO 3 −).

Affinity of radioactive cesium and strontium for illite and smectite clay in the presence of groundwater ions

Abstract Sorption behaviour of hazardous nuclides such as 137Cs and 90Sr onto illite and smectite clay was studied in the presence of major groundwater ions (Ca2+, Mg2+, K+, Na+ and HCO3 ‐). Illite and smectite clay can selectively sorb small hydrated Cs+ ion in the presence of groundwater cations except K+ ion. In contrast, sorption of larger and stable hydrated Sr2+ ion onto illite and smectite clay is highly competed by background groundwater cations. The sorption characteristics of Cs+ and Sr2+ onto illite and smectite clay are closely related to hydration properties of ions and complex forms of ions (inner‐sphere or outer‐sphere complex) in the siloxane cavity of clay minerals. The mechanism of Cs+ and Sr2+ sorption of illite is ion exchange with an interlayer cation K+, and K+, Ca2+ and Mg2+, respectively. The effect of bicarbonate ion on Sr2+ sorption of illite is due to the change of pH and the precipitation of a solid phase (SrCO3). The zeta potentials of illite and smectite clay as a function of...