Effect of pressure on colloidal behavior in hydrothermal water

The pressure dependence of the colloidal phenomena of nanoparticles in hydrothermal water was investigated by both experiment and theory. Dynamic light scattering experiments show that diamond nanoparticles, which are highly stable in ambient water, easily aggregate in high-temperature and high-pressure water. Although the stability of nanoparticles in ambient pure water does not depend on pressure, it is interestingly found that at constant temperature particles aggregate faster in the hydrothermal regime when the pressure is higher. A theoretical interpretation is proposed to predict the stability of colloids in water as a function of temperature and pressure. Numerical analysis shows that the repulsive interparticle potential barrier, which stabilizes particles in the dispersion, decreases dramatically in high-temperature and high-pressure water. The decrease in the potential barrier arises from the temperature and the pressure dependencies of the dielectric constant (epsilon) and the ion product (p K w) of water. Numerical analysis shows that the pressure dependence of epsilon is negligible in the temperature range of 20-300 degrees C, whereas the pressure dependence of p K w is significant at temperatures of T > 150 degrees C. The theory reveals that the pressure dependence of the rate of size increment in the hydrothermal regime results from the pressure dependence of p K w. An increase in pressure in the hydrothermal water enhances the ionization of water molecules which reduces the surface potential of the particles. This effect lowers the interparticle repulsive potential barrier, which accelerates aggregation of the particles.     

Electrostatic stabilization of colloids in carbon dioxide: electrophoresis and dielectrophoresis

Over the past decade, steric stabilization has been achieved for a variety of inorganic and organic colloids in supercritical fluid carbon dioxide (scCO2). Herein we demonstrate that colloids may also be stabilized in CO2 by electrostatic forces, despite the ultralow dielectric constant of 1.5. Zeta potentials of micrometer-sized water droplets, measured in a microelectrophoresis cell, reached -70 mV corresponding to a few elementary charges per square micrometer of droplet surface. This degree of charge was sufficient to stabilize water/CO2 emulsions for an hour, even with water volume fractions of 5%. Hydrogen ions partition preferentially, relative to bicarbonate ions, from the emulsion droplets to the cores of surfactant micelles in the diffuse double layer surrounding the droplets. The micelles, formed with a low molecular weight branched hydrocarbon surfactant, prevent ion pairing of the hydrogen counterions to the negatively charged emulsion droplets. Dielectrophoresis of the water droplets at a frequency of 60 Hz leads to chains containing a dozen droplets with lengths of 50 mum. The ability to form electrostatically stabilized colloids in carbon dioxide is particularly useful in practical applications, because steric stabilization in CO2 is often limited by the poor solvation of the stabilizers.     

A theoretical study on anomalous temperature dependence of pKw of water

pH, with its well-known value of 7 at ambient condition, is a most basic property of water, with wide implications in chemistry and biology. The pH value is determined by the tendency of autoionization of water molecules into ion pairs, H(+) and OH(-), and is expected to vary extensively with the water condition, which determines the stability of the ion pairs. When temperature rises from the normal to the supercritical region, the pH of water experimentally exhibits complex, nonmonotonic temperature dependence, that is, it first decreases from 7 and then increases rapidly. Accurate theoretical evaluation of pH and microscopic understanding of this anomalous behavior have proven to be a challenging task because the hydration of these ions, especially for OH(-), is very difficult to reproduce. In the present study a molecular simulation is performed to understand this peculiar temperature dependence. The imbalance between the ion-water and the water-water molecular interaction strengths and the concomitant water density enhancement in the hydration shell, observed in the supercritical liquids, serve to put a subtle balance to produce this temperature dependence of the pH value. It is found that the large charge transfers from H(+) and OH(-) to the surrounding water molecules take place. In these transfers, not only water molecules in the neighboring hydration shell but also those in the outer hydration shell play a significant role. The coordination number of water molecules around OH(-) is found to be 4.5 at 300 K, which decreases slowly with temperature, for example, 4 at 800 K, in the present calculation.     

The study of model systems subjected to sub- and supercritical water hydrolysis for the production of fermentable sugars

Bioenergy obtained from lignocellulosic biomass is considered the most efficient way to achieve sustainable development in the future. However, there still are challenges in the cellulose conversion to hexoses, which could be used as raw material for the bioenergy production. Sub- and supercritical water hydrolysis have been researched as emergent technologies to obtain simple sugars from lignocellulosic biomass; however, the reaction pathways and kinetics of the hydrolysis of cellulose into oligomers and monomers, and their degradation under sub- and supercritical conditions, are not completely understood yet. Thus, this review provides an overview of the state-of-the-art on hydrolysis with sub- and supercritical water of model systems, cellulose and starch, in the context of elucidating the reaction pathways and kinetic behavior of the biomass hydrolysis to produce suitable fermentation substrates for the production of second generation bioethanol and other biofuels.     

Temperature dependence of complex formation constants in aqueous solutions of metal acetates

The equilibrium constants of formation of inner- and outer-sphere cation-anion complexes (ion pairs) in aqueous solutions of different metal acetates in a wide temperature range have been calculated by integrating the density function of distribution of ligands around the cation. The standard Gibbs energies, enthalpies, and entropies of formation of 1: 1 complexes have been calculated. It has been shown that, in all solutions under consideration, contact and solvent-separated ion pairs coexist. A conclusion has been drawn that the temperature dependence of ion association constants is mainly determined by the temperature dependence of the water dielectric constant.     

Thermophysical properties of supercritical fluids with special consideration of aqueous systems

Selected thermophysical properties of polar, dense supercritical fluids are discussed. The static dielectric constant of water and the freon R22 (CHClF₂) is shown in some detail. Examples of critical curves for binary systems with water and methanol are given. New experimental data of excess volumes up to 400 °C and 2000 bar are shown for water combined with H₂, CH₄ and benzene. Excess Gibbs energies and activity coefficients for water-benzene are also shown. Results of the solubility of anthracene in ten different high pressure fluids, obtained by UV-spectroscopy, are presented. The PVT-data of concentrated supercritical aqueous NaCl-solutions and the ion product of pure water to 1000 °C are discussed.     

Temperature, pressure, and isotope effects on the structure and properties of liquid water: a lattice approach

We present a lattice model to describe the effect of isotopic replacement, temperature, and pressure changes on the formation of hydrogen bonds in liquid water. The approach builds upon a previously established generalized lattice theory for hydrogen bonded liquids [B. A. Veytsman, J. Phys. Chem. 94, 8499 (1990)], accounts for the binding order of 1/2 in water-water association complexes, and introduces the pressure dependence of the degree of hydrogen bonding (that arises due to differences between the molar volumes of bonded and free water) by considering the number of effective binding sites to be a function of pressure. The predictions are validated using experimental data on the temperature and pressure dependence of the static dielectric constant of liquid water. The model is found to correctly reproduce the experimentally observed decrease of the dielectric constant with increasing temperature without any adjustable parameters and by assuming values for the enthalpy and entropy of hydrogen bond formation as they are determined from the respective experiments. The pressure dependence of the dielectric constant of water is quantitatively predicted up to pressures of 2 kbars and exhibits qualitative agreement at higher pressures. Furthermore, the model suggests a--temperature dependent--decrease of hydrogen bond formation at high pressures. The sensitive dependence of the structure of water on temperature and pressure that is described by the model rationalizes the different solubilization characteristics that have been observed in aqueous systems upon change of temperature and pressure conditions. The simplicity of the presented lattice model might render the approach attractive for designing optimized processing conditions in water-based solutions or the simulation of more complex multicomponent systems.     

Features of ion hydration and ion association in sub- and supercritical aqueous solutions of rubidium bromide

Results of investigations by the integral equation method in the XRISM approximation of features of structure formation in sub- and supercritical 0.5 M aqueous solution of RbBr. As the system passes from the sub- to supercritical state, the tetrahedral network of the solvent is destroyed, which is typical of water and aqueous solutions; thermal dehydration of the cation and anion are also observed. Dehydration is accompanied by contraction of the first hydration sphere of Rb⁺ and extension of the first hydration sphere of Br⁻. Both in sub- and supercritical solutions conditions a minor amount of contact ion pairs is present whose fraction is Higher by 15% compared to that in standard conditions.     

Effects of temperature and salt concentration on the structural stability of human lymphotactin: insights from molecular simulations

Extensive molecular dynamics (MD) simulations ( approximately 70 ns total) with explicit solvent molecules and salt ions are carried out to probe the effects of temperature and salt concentration on the structural stability of the human Lymphotactin (hLtn). The distribution of ions near the protein surface and the stability of various structural motifs are observed to exhibit interesting dependence on the local sequence and structure. Whereas chloride association to the protein is overall enhanced as the temperature increases, the sodium distribution in the C-terminal helical region and, to a smaller degree, the chloride distribution in the same region are found higher at the lower temperature. The similar trend is also observed in nonlinear Poisson-Boltzmann calculations with a temperature-dependent water dielectric constant, once conformational averaging over a series of MD snapshots is done. The unexpected temperature dependence in the ion distribution is explained on the basis of the cancellation of association entropy for ion-side chain pairs of opposite-charge and like-charge characters, which have positive and negative contributions, respectively. The C-terminal helix is observed to partially melt whereas a short beta strand forms at the higher temperature with little salt dependence. The N-terminal region, by contrast, develops partial helical structure at a higher salt concentration. These observed behaviors are consistent with solvent and salt screening playing an important role in stabilizing the canonical chemokine fold of hLtn.     

超临界水的性质及其在化学反应中的应用

介绍了水的热物理性质、结构性质、离子积、扩散系数和粘度等在超临界区域的特殊性，以及超临界水溶液在介电常数、偏摩尔体积、溶解性和极性等方面的特殊性质，并阐述了超临界水的这种特殊性在化学反应和环境治理中的应用。     

Frequency dependence of the dielectric and electro-optic response in suspensions of charged rod-like colloidal particles

We have performed an experimental investigation on the electrokinetic properties of charged rod-like fluorinated latex colloids. Systematic measurements of electrophoretic mobility, dielectric constant and electric birefringence have been performed as a function of the concentration of added nonionic surfactant and salt. In the investigated range of parameters, the zeta potential is a strongly decreasing function of the concentration of nonionic surfactant, while it is basically independent from ionic strength. We have obtained the frequency dependence of dielectric constant and Kerr constant as a function of zeta-potential and ionic strength. We observe the transition from a low frequency behavior, where both the dielectric constant and the Kerr constant are enhanced by the presence of the double layer, to a high frequency behavior, where both quantities take the value expected for unchanged particles in an insulating medium. The shape of the frequency dispersion of the Kerr constant coincides with that of the dielectric constant, but the cut-off frequencies are the same only when the zeta-potential of the particles is low.     

The structure of H-bonded clusters in sub- and supercritical water

The structure of H-bonded complexes in sub- and supercritical water in regions close to and remote from the saturation curve was studied. The Car-Parrinello method was used to calculate water dipole moment distributions in 11 thermodynamic states. The dependence of the mean dipole moment of water molecules on the size of clusters and number of H-bonds was obtained.     

Microwave dielectric properties of aqueous potassium iodide solutions as a function of temperature

The complex dielectric permittivity of aqueous KI solutions was studied for molalities of 0.50–4.01 m and temperatures of 288–323 K in the region of water dielectric permittivity dispersion. The values of high-frequency of dielectric permittivity (ε) and dielectric losses (ε″) were obtained at seven frequencies ranging between 7.5 and 25 GHz. The low-frequency electrical conductivity of the aforementioned solutions was measured for calculating ionic losses. A single relaxation process is observed in these solutions, fitted by the Debye or Cole-Cole equation with small distribution parameters. The static dielectric constant and dielectric relaxation time were studied as functions of temperature and concentration; the activation enthalpy of dielectric relaxation was calculated. The temperature dependence of the static dielectric constant was found to disappear in highly concentrated solutions. The structure-breaking effect on water caused by K⁺ and I⁻ ions was affirmed, this effect disappearing in going to elevated temperatures.     

Reversible activity changes of lipid-coated lipase for enantioselective esterification in supercritical fluoroform

Enzymatic activity of a lipid-coated lipase for enantioselective esterification of (R)-1-phenylethanol in supercritical fluoroform can be reversibly controlled by changing pressure or temperature that reflects changes of dielectric constant.     

Small angle x-ray scattering of a supercritical electrolyte solution: the effect of density fluctuations on the hydration of ions

Synchrotron small angle x-ray scattering measurements on water and zinc bromide ZnBr2 aqueous solutions were carried out from ambient to supercritical conditions. For both systems several isobars (between 285 and 600 bars) were followed beyond the critical isochore. The data were analyzed through an Ornstein-Zernike formalism in terms of correlation length and null angle structure factor. The results for pure water are in agreement with previously published values. Solutions of different electrolyte concentrations were studied. In each case, the values of the correlation length and null angle structure factor are larger than those of pure water. This effect is more pronounced for higher concentrations and/or for pressure closer to the critical point of pure water. This is in agreement with the shift of the critical point determined in the literature for NaCl solutions. Comparing these results to previous x-ray absorption measurements carried out on identical samples we propose the following two step sequence for ionic hydration up to supercritical conditions: (1) from ambient to about 300 degrees C, an increase of ion pairing and formation of multi-ionic complexes which can be correlated to the decrease of the dielectric constant; (2) an enhancement of the local solvation shell of ions due to the onset of the thermal density fluctuations at high temperature, leading to a screening effect between ions and inhibiting the ion pairing processes.     

Re-entrant melting and freezing in a model system of charged colloids

We studied the phase behavior of charged and sterically stabilized colloids using confocal microscopy in a low polarity solvent (dielectric constant 5.4). Upon increasing the colloid volume fraction we found a transition from a fluid to a body centered cubic crystal at 0.0415+/-0.0005, followed by reentrant melting at 0.1165+/-0.0015. A second crystal of different symmetry, random hexagonal close packed, was formed at a volume fraction around 0.5, similar to that of hard spheres. We attribute the intriguing phase behavior to the particle interactions that depend strongly on volume fraction, mainly due to the changes in the colloid charge. In this low polarity system the colloids acquire charge through ion adsorption. The low ionic strength leads to fewer ions per colloid at elevated volume fractions and consequently a density-dependent colloid charge.     

Temperature changes of dielectric permittivity and relaxation in aqueous lithium iodide solutions

The complex permittivity of aqueous LiI solutions is studied over a wide range of concentrations at temperatures of 288–323 K in the water permittivity dispersion region at seven frequencies in the range of 7.5–25 GHz. One relaxation region describable by the Debye or Cole-Cole equation is observed in these solutions. Dielectric relaxation time τ and static permittivity ?_s are studied as dependent on temperature and concentration. The time and enthalpy of activation of dielectric relaxation decrease in going from water to solutions, which corresponds to the distortion of the initial water structure and the increasing mobility of water molecules in hydration shells of ions. In the initial concentration range, the water activity is a linear function of 1/?_s. The negative temperature dependence of ?_s disappears in going to concentrated solutions. At high concentrations, the static dielectric constant increases in response to increasing temperature. The new trends in ?_s and τ at elevated temperatures of 313–323 K are due to the formation of ion pairs and other ion-water groups having high dipole moments.     

Electrostatically stabilized metal oxide particle dispersions in carbon dioxide

We report electrostatic stabilization of micrometer-sized TiO(2) particles at long range (several micrometers) in liquid and supercritical CO(2) despite the ultralow dielectric constant, as low as 1.5. The counterions were solubilized in dry reverse micelles, formed with a low-molecular weight cationic perfluoropolyether trimethylammonium acetate surfactant, to prevent ion pairing with the particle surface. Dynamic light scattering and settling velocities indicate a particle diameter of 620-740 nm. The electrophoretic mobility of -2.3 x 10(-8) m(2)/V s indicated a particle charge on the order of -1.7 x 10(-17) C, or 105 elementary negative charges per particle. The balance of particle compression by an electric field versus electrostatic repulsion generated an amorphous arrangement of particles with 5-9 mum spacing, indicating Debye lengths greater than 1 mum. Scattering patterns also indicate that chains of particles may be achieved in CO(2) by dielectrophoresis with alternating fields. The electrostatic stabilization has been achieved by solubilizing a small concentration of counterions in only a small fraction of the reverse micelles in the double layer. Whereas many low-molecular weight surfactants have been shown to form reverse micelles in CO(2), very few polymers are able to stabilize micrometer-sized colloids sterically. Thus, electrostatic stabilization has the potential to expand markedly the domain of colloid science in apolar supercritical fluids.     

Study of self-association of water in supercritical CO2 by Monte Carlo simulation: Does water have a specific interaction with CO2?

The extent of the self-association of water in supercritical CO₂ has been investigated in a wide range of density and temperature by the test particle insertion technique. The results show that the association constant for water decreases with temperature and weakly depends on CO₂ density. This weak density dependence provides evidence for the lack of a strong specific CO₂–water interaction. Comparing calculated association constants with its gas-phase values shows that the association constant is at most ca. 38% lower than its gas-phase value in the high density–low temperature region. Inspection of the simulated radial distribution functions revealed that forming modest water–CO₂ complexes does not result in substantial interference in H-bonding of water molecules.