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 [g]) and thermodynamic parameters (second virial coefficient A2), 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 (MW) and their distributions for the nonassociative HEC were determined using size exclusion chromatography. Various empirical approaches developed by past authors to determine [g] 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 [g] and A2. The ratio A2MW/[g], 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.

Large Decrease of Fluctuations for Supercooled Water in Hydrophobic Nanoconfinement

Using Monte Carlo simulations we study a coarse­grained model of a water layer confined in a fixed disordered matrix of hydrophobic nanoparticles at different particle concentrations c. For c = 0 we find a 1st order liquid­liquid phase transition (LLPT) ending in one critical point at low pressure P. For c > 0 our simulations are consistent with a LLPT line ending in two critical points at low and high pressure. For c = 25% at high P and low temperature T we find a dramatic decrease of compressibility, thermal expansion coefficient, and specific heat. Surprisingly, the effect is present also for c as low as 2.4%. We conclude that even a small presence of nanoscopic hydrophobes can drastically suppress thermodynamic fluctuations, making the detection of the LLPT more difficult.

Mutual Solubilities of Water and Hydrophobic Ionic Liquids

The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly "neoteric" solvents. One of the main research fields is their exploitation as solvents for liquid-liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length, the number of cation substitutions, the cation family, and the anion identity in these mutual solubilities are analyzed and discussed. The hydrophobicity of the anions increases in the order [C(CN)3] <[PF6] <[Tf2N] while the hydrophobicity of the cations increases from [Cnmim] <[Cnmpy] [Cnmpyr] <[Cnmpip] and with the alkyl chain length increase. From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubilities in water. The COSMO-RS, a predictive method based on unimolecular quantum chemistry calculations, was also evaluated for the description of the water-IL binary systems studied, where it showed to be capable of providing an acceptable qualitative agreement with the experimental data.

Mutual Solubilities of Water and the [Cnmim][Tf2N] Hydrophobic Ionic Liquids

Ionic liquids (ILs) have recently garnered increased attention because of their potential environmental benefits as "green" replacements over conventional volatile organic solvents. While ILs cannot significantly volatilize and contribute to air pollution, even the most hydrophobic ones present some miscibility with water posing environmental risks to the aquatic ecosystems. Thus, the knowledge of ILs toxicity and their water solubility must be assessed before an accurate judgment of their environmental benefits and prior to their industrial applications. In this work, the mutual solubilities for [C2-C8mim][Tf2N] (n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and water between 288.15 and 318.15 K at atmospheric pressure were measured. Although these are among the most hydrophobic ionic liquids known, the solubility of water in these compounds is surprisingly large, ranging from 0.17 to 0.36 in mole fraction, while the solubility of these ILs in water is much lower ranging from 3.2 × 10-5 to 1.1 × 10-3 in mole fraction, in the temperature and pressure conditions studied. From the experimental data, the molar thermodynamic functions of solution and solvation such as Gibbs energy, enthalpy, and entropy at infinite dilution were estimated, showing that the solubility of these ILs in water is entropically driven. The predictive capability of COSMO-RS, a model based on unimolecular quantum chemistry calculations, was evaluated for the description of the binary systems investigated providing an acceptable agreement between the model predictions and the experimental data both with the temperature dependence and with the ILs structural variations.

Liquid marble formation using hydrophobic powders

This work aims to investigate and quantitatively measure “liquid marble” phenomena using hydrophobic powders (granules). The hydrophobic powders based on a copper substrate were prepared by a silver deposition technique of particle sizes 9 µm, 20 µm and 320 µm and of contact angle with water approaching 160°. The hydrophobic powder poly-methylmethacralate (PMMA) particle size 42 µm and contact angle of 120° was also used to determine the effect of powder density on liquid marble stability. The experimental investigations indicated that for successful formation of liquid marbles a number of variables in addition to hydrophobicity need to be considered, namely: powder density; powder particle size; powder shape; liquid marble formation technique. It was found that liquid marbles were formed using all four powders to varying extents, with a low powder particle size forming more stable liquid marbles. In a series of gravimetric tests, adhered powder mass on liquid marbles was found to be directly proportional to the water droplet surface area. A more complete coverage of the water drops were found with PMMA powder than the hydrophobic granules. Moreover, a further procedure was developed to increase the mechanical strength of the liquid marble, by polymerising methylmethacrylate (MMA) on the surface of a PMMA powder – liquid marble, with the aim of maintaining water within a more robust PMMA – liquid marble shell. This technique may prove to be a novel way of encapsulating drug compounds, such as gentamicin sulphate, for PMMA bone cement.

Solvation of 1-butyl-3-methylimidazolium hexafluorophosphate in aqueous ethanol - a green solution for dissolving 'hydrophobic' ionic liquids

The relatively hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate has been found to be totally miscible with aqueous ethanol between 0.5 and 0.9 mol fraction ethanol, whereas the ionic liquid is only partially miscible with either pure water or absolute ethanol; the ability to dissolve 1-butyl-3-methylimidazolium hexafluorophosphate in a 'green' aqueous solvent system has important implications for cleaning, purification, and separations using ionic liquids.

Hydrophobic ionic liquids incorporating N-alkylisoquinolinium cations and their utilization in liquid-liquid separations

The first examples of Room Temperature Ionic Liquids (RTIL) containing fused polycyclic N-alkylisoquinolinium cations ([C(n)isoq](+)) in combination with the bis(perfluoroethylsulfonyl) imide anion ([BETI](-)) have been synthesized, characterized, and utilized in liquid-liquid partitioning from water; these salts have unexpectedly low melting points and give high distribution ratios for aromatic solutes, especially chlorobenzenes, between the RTIL and water.

On the solubilization of water with ethanol in hydrophobic hexafluorophosphate ionic liquids

The solubility of water in the hydrophobic 1-alkyl-3-methylimidazolium hexafluorophosphate (alkyl = butyl, hexyl, and octyl) ionic liquids, can be significantly increased in the presence of ethanol as a co-solute. 1-Hexyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium hexafluorophosphate are completely miscible with ethanol, and immiscible with water, whereas 1-butyl-3-methylimidazolium hexafluorophosphate is totally miscible with aqueous ethanol only between 0.5-0.9 mole fraction ethanol at 25degreesC. At higher and lower mole fraction of ethanol, the aqueous and IL components are only partially miscible and a biphasic system is obtained upon mixing equal volumes of the IL and aqueous ethanol. The observation of a large range of total miscibility between water and the IL in the three-component system has important implications for purifications and separations from IL.