Surface tension of electrolytes: hydrophilic and hydrophobic ions near an interface

We calculate the ion distributions around an interface in fluid mixtures of highly polar and less polar fluids (water and oil) for two and three ion species. We take into account the solvation and image interactions between ions and solvent. We show that hydrophilic and hydrophobic ions tend to undergo a microphase separation at an interface, giving rise to an enlarged electric double layer. We also derive a general expression for the surface tension of electrolyte systems, which contains a negative electrostatic contribution proportional to the square root of the bulk salt density. The amplitude of this square-root term is small for hydrophilic ion pairs but is much increased for hydrophilic and hydrophobic ion pairs. For three ion species, including hydrophilic and hydrophobic ions, we calculate the ion distributions to explain those obtained by x-ray reflectivity measurements.     

Aqueous solutions of HEC and hmHEC: effects of molecular mass versus hydrophobic associations on hydrodynamic and thermodynamic parameters

Aqueous solutions of amphiphilic polymers usually comprise of inter- and intramolecular associations of hydrophobic groups often leading to a formation of a rheologically significant reversible network at low concentrations that can be identified using techniques such as static light scattering and rheometry. However, in most studies published till date comparing water soluble polymers with their respective amphiphilic derivatives, it has been very difficult to distinguish between the effects of molecular mass versus hydrophobic associations on hydrodynamic (intrinsic viscosity [η]) and thermodynamic parameters (second virial coefficient A ₂), owing to the differences between their degrees of polymerization. This study focuses on the dilute and semi-dilute solutions of hydroxyethyl cellulose (HEC) and its amphiphilic derivatives (hmHEC) of the same molecular mass, along with other samples having a different molecular mass using capillary viscometry, rheometry and static light scattering. The weight average molecular masses (M _W ) and their distributions for the non-associative HEC were determined using size exclusion chromatography. Various empirical approaches developed by past authors to determine [η] from dilute solution viscometry data have been discussed. hmHEC with a sufficiently high degree of hydrophobic modification was found to be forming a rheologically significant network in dilute solutions at very low concentrations as opposed to the hmHEC with a much lower degree of hydrophobic modification which also enveloped the hydrophobic groups inside the supramolecular cluster as shown by their [η] and A ₂. The ratio A ₂ M _W /[η], which takes into account hydrodynamic as well as thermodynamic parameters, was observed to be less for associative polymers compared to that of the non-associative polymers.     

Molecular dynamics simulation of water near nanostructured hydrophobic surfaces: interfacial energies.

We present results from molecular dynamics simulations of water near structured hydrophobic surfaces. The surface structures reported herein are a planar alkane crystal as a reference and crystals with a hole and a protrusion of approximately 2.5 nm diameter and 0.5 nm depth or height. All indicators show that surface structuring increases the hydrophobicity: The water density is reduced near the structure elements, and the number of residual contacts between water and the surface decreases by about 40 % with respect to the planar surface. Thermodynamic integration shows that the interfacial energy of the structured surfaces is about 7 mJ m(-2) higher for structured surfaces than for the planar surface. The hydrophobicity increases by a similar amount for the hole and the protrusion geometries compared to the planar surface.     

In situ growth of polymer electrolytes on lithium ion electrode surfaces

Polyacrylonitrile (PAN) films were grown on glassy carbon, nickel foam and MnO₂ substrates by cathodic electropolymerisation of acrylonitrile in acetonitrile with tetrabutylammonium perchlorate (TBAP) as the supporting electrolyte. The electronic barrier properties of the films were confirmed by impedance spectroscopy of carbon |PAN| Hg cells while the ionic resistance of the films varied from 200 kΩ cm² in the dry state to 1.4 Ω cm² when plasticised with 1 M LiPF₆ in propylene carbonate. A galvanic cell was prepared by successive electrodepositions of MnO₂ and PAN on a carbon substrate, using liquid lithium amalgam as the top contact. The cell showed a stable open circuit potential and behaved normally under the galvanostatic intermittent titration technique (GITT).     

The inevitable accumulation of large ions and neutral molecules near hydrophobic surfaces and small ions near hydrophilic ones

The present contribution offers a unified explanation to three central phenomena in physical chemistry of interfaces in contact with aqueous solution: (1) Accumulation of large anions at the air/water interface. (2) Accumulation of neutral gas molecules near hydrophobic surfaces and the resulting hydrophobic interaction between two such surfaces, and (3) The Hofmeister effect, namely, the enhanced propensity of small ions to hydrophilic surfaces and large ions to hydrophobic surfaces. The common thread linking these phenomena is the free energy balance between ion or molecule hydration in solution and the cost of localizing these objects at the water-surface interface. Comparing the results of an abstract lattice-gas model to force spectroscopy data collected by AFM we reveal the underlying principles and demonstrate their universality.     

Photodetachment of hydrogen negative ion near inelastic surfaces: Arbitrary laser polarization direction

The photodetachment of hydrogen negative ion near different inelastic surfaces is investigated by the semiclassical closed orbit theory for arbitrary laser polarization direction . A two‐term formula of photodetachment cross section consisting of a smooth background term and an oscillatory term is derived. The oscillatory term contains an extra angular factor that describes the dependence of oscillations in total cross section on the laser polarization direction. It is observed that the amplitude of oscillations in cross section reaches maximum at when laser polarization is parallel to the z‐axis and it approaches zero as the laser polarization direction becomes perpendicular to the z‐axis. It is also observed that as the reflection coefficient , which accounts for the inelastic behavior of the surfaces, increases the amplitude of oscillation also increases. © 2015 Wiley Periodicals, Inc.     

Aqueous GPC of electrolytes and polyelectrolytes

The gel permeation chromatography (GPC) of polyelectrolytes is discussed. The electrostatic exclusion is demonstrated using simple electrolytes with different eluents. The data for aqueous free salt solutions of polyelectrolytes are interpreted. The osmotic coefficient is deduced and its dependence on molecular weight and polymer concentration reported. In salt eluents, the Donnan exclusion is discussed. The universal calibration obtained with different standards in aqueous solution is shown to be valid and identical to that obtained in an organic solvent using polystyrene standards.     

Behavior of mixtures of symmetric and asymmetric electrolytes near discretely charged planar surfaces: a Monte Carlo study

Canonical Monte Carlo (CMC) simulations are employed in this work in order to study the structure of the electrical double layer (EDL) near discretely charged planar surfaces in the presence of symmetric and asymmetric indifferent electrolytes within the framework of a primitive model. The effects of discreteness and strength of surface charge, charge asymmetry, and size asymmetry are specific focuses of this work. The CMC simulation protocol is initially tested against the classical theory, the modified Gouy-Chapman (GC) theory, in order to assess the reliability of the simulation results. The CMC simulation results and the predictions of the classical theory show good agreement for 1:1 electrolytes and low surface charge, at which conditions the GC theory is valid. Simulations with symmetric and asymmetric electrolytes and mixtures of the two demonstrate that size plays an important role in determining the species present in the EDL and how the surface charge is screened. A size-exclusion effect could be consistently detected. Although it is energetically favorable that higher-valence ions screen the surface charge, their larger size prevents them from getting close to the surface. Smaller ions with lower valences perform the screening of the charge, resulting in higher local concentrations of small ions close to the surface. The simulations also showed that the strength of the surface charge enhances the size-exclusion effect. This effect will definitely affect the magnitude of the forces between interacting charged surfaces.     

Quantifying hydrodynamic slip: a comprehensive analysis of dewetting profiles

To characterize nontrivial boundary conditions of a liquid flowing past a solid, the slip length is commonly used as a measure. From the profile of a retracting liquid front (e.g., measured with atomic force microscopy), the slip length can be extracted with the help of a Stokes model for a thin liquid film dewetting from a solid substrate. Specifically, we use a lubrication model derived from the Stokes model for strong slippage and linearize the film profile around the flat, unperturbed film. For small slip lengths, we expand the linearized full Stokes model for small slopes up to third order. Using the respective model, we obtain, in addition to the slip length, the capillary number, from which we can estimate the viscosity of the fluid film. We compare numerical and experimental results, test the consistency and the validity of the models/approximations, and give an easy-to-follow guide of how they can be used to analyze experiments.     

Co-ion and ion competition effects: ion distributions close to a hydrophobic solid surface in mixed electrolyte solutions

We consider within a modified Poisson-Boltzmann theory an electrolyte, with different mixtures of NaCl and NaI, near uncharged and charged solid hydrophobic surfaces. The parametrized potentials of mean force acting on Na+, Cl-, and I- near an uncharged self-assembled monolayer were deduced from molecular simulations with polarizable force fields. We study what happens when the surface presents negative charges. At moderately charged surfaces, we observe strong co-ion adsorption and clear specific ion effects at biological concentrations. At high surface charge densities, the co-ions are pushed away from the interface. We predict that Cl- ions can also be excluded from the surface by increasing the concentration of NaI. This ion competition effect (I- versus Cl-) may be relevant for ion-specific partitioning in multiphase systems where polarizable ions accumulate in phases with large surface areas.     

Equilibrium properties of charged spherical colloidal particles suspended in aqueous electrolytes: finite ion size and effective ion permittivity effects

The adsorption behaviour and mechanism of As(III) and Se(IV) oxyanion uptake using a mixed inorganic adsorbent were studied. The novel adsorbent, based on Fe(III)-Mn(III) hydrous oxides and manganese(II) carbonate, was synthesised using a hydrothermal precipitation approach in the presence of urea. The inorganic ion exchanger exhibited a high selectivity and adsorptive capacity towards As(III) (up to 47.6 mg/g) and Se(IV) (up to 29.0 mg/g), even at low equilibrium concentration. Although pH effects were typical for anionic species (i.e., the adsorption decreased upon pH increase), Se(IV) was more sensitive to pH changes than As(III). The rates of adsorption of both oxyanions were high. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) studies showed that the ion exchange adsorption of both anions took place via OH(-) groups, mainly from Fe(III) but also Mn(III) hydrous oxides. MnCO(3) did not contribute directly to As(III) and Se(IV) removal. A higher adsorptive capacity of the developed material towards As(III) was partly due to partial As(III) oxidation during adsorption.     

Analytical expressions for the electrical potential near planar, cylindrical, and spherical surfaces for symmetric electrolytes

The conjecture of Tuinier (J. Colloid Interface Sci. 258 (2003) 45) for the electrical potentials near a cylindrical surface and near a spherical surface under the conditions of symmetric electrolyte and large scaled radius are derived by solving the corresponding Poisson-Boltzmann equation. The surface charge density-surface potential relations for these surfaces are also derived under the conditions of constant surface potential. We show that the level of surface charge density for planar, cylindrical, and spherical surfaces follows the order spherical surface > cylindrical surface > planar surface.     

Specific ion effects on the surface tension and surface potential of aqueous electrolytes

The phenomena of electrolytes affecting the surface tension of aqueous solutions and producing measurable surface potentials are reviewed in the light of recent studies of them. The factual information presented includes the molar ionic surface tension increments k_i = lim(c_i → 0)(dσ / dc_i) of many ions and the surface potential increments ∆ χ = χ_E − χ_W of electrolytes involving the cations H⁺, Na⁺, K⁺, and NH₄⁺ and various anions. Gaps in the data that invite filling and inconsistencies in reported data are pointed out. Correlations of k_i with several properties of the ions that should be relevant to their specific effects: their sizes, quantities representing their polarizabilities, their effects on the structure of the water and the binding of water molecules by them, are presented. Correlations of the surface potential increment ∆ χ with the electrolyte surface tension increments and with the differences between the cation and anion increments are shown. Models recently proposed for the rationalization of the observed phenomena and relevant theoretical developments are shown and discussed. The paradox of hydrogen ions not promoting significant charge separation at the interface but yielding large surface potentials is emphasized.     

The hydrophobic effect: molecular dynamics simulations of water confined between extended hydrophobic and hydrophilic surfaces

Structural and dynamic properties of water confined between two parallel, extended, either hydrophobic or hydrophilic crystalline surfaces of n-alkane C(36)H(74) or n-alcohol C(35)H(71)OH, are studied by molecular dynamics simulations. Electron density profiles, directly compared with corresponding experimental data from x-ray reflectivity measurements, reveal a uniform weak de-wetting characteristic for the extended hydrophobic surface, while the hydrophilic surface is weakly wetted. These microscopic data are consistent with macroscopic contact angle measurements. Specific water orientation is present at both surfaces. The ordering is characteristically different between the surfaces and of longer range at the hydrophilic surface. Furthermore, the dynamic properties of water are different at the two surfaces and different from the bulk behavior. In particular, at the hydrophobic surface, time-correlation functions reveal that water molecules have characteristic diffusive behavior and orientational ordering due to the lack of hydrogen bonding interactions with the surface. These observations suggest that the altered dynamical properties of water in contact with extended hydrophobic surfaces together with a partial drying of the surfaces are more indicative of the hydrophobic effect than structural ordering, which we suggest to be independent of surface topology.     

Electrophoresis of hydrophilic/hydrophobic rigid colloid with effects of relaxation and ion size

This article deals with a semi‐analytical study on the electrophoresis of charged spherical rigid colloid by considering the effects of relaxation and ion size. The particle surface is taken to be either hydrophilic or hydrophobic in nature. In order to consider the ion size effect we have invoked the Carnahan and Starling model (J. Chem. Phys. 1969, 51, 635‐636). The mathematical model is based on Stokes equation for fluid flow, modified Boltzmann equation for spatial distribution of ionic species and Poisson equation for electric potential. We adopt a linear perturbation technique under a weak electric field assumption. An iterative numerical technique in employed to solve the coupled set of perturbed equations. We have validated the numerically obtained electrophoretic mobility with the corresponding analytical solution derived under low potential limit. Going beyond the widely employed Debye‐Hückel linearization, we have presented the results for a wide range of surface charge density, electrolyte concentration, and slip length to Debye length ratio. We have also identified several interesting features including occurrence of local maxima and minima in the mobility for critical choice of pertinent parameters.     

Pulsed ion beam irradiation effects on surfaces of polymeric materials

Various polymers were irradiated with high energy ( keV) carbon and hydrogen ion beams obtained from a high intensity pulsed power source. Energy deposition was in the range of 0.1–5 J/cm² during each pulse, and ion penetration was limited to a few microns. The rapid energy deposition (<500 ns) corresponded to a dose rate of approximately 10¹² Gy/s and resulted in a considerable temperature rise in the surface material accompanied by the formation of gaseous radiolysis products in amounts as high as the volume of the surface layer in which they were formed. Analysis by scanning electron microscopy revealed that dramatic changes to the polymer surface had occurred in some (but not all) of the materials, which took the form of extensive porosity or roughening. © 1998 John Wiley & Sons, Ltd.     

Simultaneous estimation of zeta potential and slip coefficient in hydrophobic microchannels

Electroosmotic flows through hydrophobic microchannels experience velocity slip at the channel wall, which increases the volumetric flow rate at a given electric potential gradient. The conventional method of zeta potential estimation using the volumetric flow rate may yield quite inaccurate zeta potential unless the velocity slip is appropriately taken care of. In the present investigation we develop a method for simultaneous estimation of zeta potential and velocity slip coefficient in the electroosmotic flow through a hydrophobic microchannel using velocity measurements. The relevant inverse problem is solved through the minimization of a performance function utilizing a conjugate gradient method. The present method is found to estimate the zeta potential and slip coefficient accurately even with noisy velocity measurements.     

Adsorption of trypsin on hydrophilic and hydrophobic surfaces

The adsorption of trypsin onto polystyrene and silica surfaces was investigated by reflectometry, spectroscopic methods, and atomic force microscopy (AFM). The affinity of trypsin for the hydrophobic polystyrene surface was higher than that for the hydrophilic silica surface, but steady-state adsorbed amounts were about the same at both surfaces. The conformational characteristics of trypsin immobilized on silica and polystyrene nanospheres were analyzed in situ by circular dichroism and fluorescence spectroscopy. Upon adsorption the trypsin molecules underwent structural changes at the secondary and tertiary level, although the nature of the structural alterations was different for silica and polystyrene surfaces. AFM imaging of trypsin adsorbed on silica showed clustering of enzyme molecules. Rinsing the silica surface resulted in 20% desorption of the originally adsorbed enzyme molecules. Adsorption of trypsin on the surface of polystyrene was almost irreversible with respect to dilution. After adsorption on silica the enzymatic activity of trypsin was 10 times lower, and adsorbed on polystyrene the activity was completely suppressed. The trypsin molecules that were desorbed from the sorbent surfaces by dilution with buffer regained full enzymatic activity.     

Drop impact characteristics and structure effects of hydrophobic surfaces with micro- and/or nanoscaled structures

We report the drop impact characteristics on four hydrophobic surfaces with different well-scale structures (smooth, nano, micro, and hierarchical micro/nano) and the effects of those structures on the behavior of water drops during impact. The specimens were fabricated using silicon wet etching, black silicon formation, or the combination of these methods. On the surfaces, the microstructures form obstacles to drop spreading and retracting, the nanostructures give extreme water-repellency, and the hierarchical micro/nanostructures facilitate drop fragmentation. The maximum spreading factor (D*(max)) differed among the structures. On the basis of published models of D*(max), we interpret the results of our experiment and suggest reasonable explanations for these differences. Especially, the micro/nanostructures caused instability of the interface between liquid and air at Weber number We > ~80 and impacting drops fragmented at We > ~150.     

Interfacial water at hydrophobic and hydrophilic surfaces: depletion versus adsorption

The structure of the water-solid interface for widely varying surface properties is investigated with Monte Carlo simulations using the SPC/E water model. Of particular interest is the relation between the wetting coefficient as a measure of the hydrophobicity of the substrate and the density depletion close to the solid surface. The substrates are modeled as rigid ordered lattices of sites that interact with water molecules through an orientation-independent Lennard-Jones potential of varying strength. Hydrophilic character is obtained by addition of polar hydroxyl groups on the substrate surface, and the influence of density, spatial distribution, and angular orientation of the polar groups on the interfacial water structure is studied.