Application of polyamorphism in water to spontaneous crystallization of emulsified LiCl-H2O solution

Aqueous solutions are widely explained by the hydration or the bound waterfree water notion. Amorphous polymorphism (polyamorphism) in pure water, which is presently under vigorous discussion, may provide a different view over the solutions. Here, I changed pressure, P, temperature, T, and concentration, C, of emulsified LiCl-H2O solutions and studied their freezing by detecting its heat evolution. It was experimentally indicated that the homogeneous nucleation of low-density crystalline ice I (phase Ih or Ic), in pure water and in solutions, connects to the polyamorphic transition of high-density amorphous ice (HDA) to low-density amorphous ice (LDA). Thus, the polyamorphism of water relates to the phase behavior of aqueous solution. In accordance with the recent simulation result, the nucleation was thought to occur in two stages: the appearance of the LDA-like state and the crystallization. Usefulness of the polyamorphic point of view about the solutions was seen.     

No fragile-to-strong crossover in LiCl-H2O solution

Dynamics of water, especially in the temperature range of the "no man's land", remain a mystery. We present detailed study of dynamics in aqueous LiCl solution that is often considered as a model for bulk water. We employ broadband dielectric and light scattering spectroscopy in a broad frequency and temperature range. Our analysis reveals no sign of the fragile-to-strong crossover (FSC) neither in structural relaxation nor in translational motions. Our experimental results combined with a large selection of literature data lead to the clear conclusion-there is no FSC in dynamics of aqueous solutions at T ～ 200-230 K. Instead, our analysis reveals appearance of the so-called excess wing at the high frequency tail of the structural relaxation peak. We discuss the localized nature of the relaxation process that contributes to the excess wing.     

Sonic wave separation of invertase from a dilute solution to generated droplets

It has previously been shown that a droplet fractionation process, simulated by shaking a separatory funnel containing a dilute protein solution, can generate droplets richer in protein than present in the original dilute solution. In this article, we describe an alternative method that can increase the amount of protein transferred to the droplets. The new metho uses ultrasonic waves, enhanced by a bubble gas stream to create the droplets. The amount of protein in these droplets increases by about 50%. In this method, the top layer of the dilute protein solution (of the solution-air interface) becomes enriched in protein when air is bubbled into the solution. This concentrating procedure is called bubble fractionation. Once the protein has passed through the initial buildup, this enriched protein layer is transferred into droplets with the aid of a vacuum above the solution at the same time that ultrasonic waves are introduced. The droplets are then carried over to a condenser and coalesced. We found that this new method provides an easier way to remove the protein-enriched top layer of the dilute solution and generates more droplet within a shorter period than the separatory funnel droplet generation method. The added air creates the bubbles and carries the droplets, and the vacuum helps remove the effluent airstream from the condenser. The maximum partition coefficient, the ratio of the protein concentration in the droplets to that in the residual solution (approx 8.5), occurred at pH 5.0.     

Problems related to the optimum separation conditions in liquid adsorption chromatography

Summary Relationships derived from the thermodynamic formulation of TLC with a binary mobile phase are discussed. The adsorption equilibrium constant is determined from the linear form of a basic equation considering the adsorption process. This linear relationship is examined with help of TLC data obtained by using six different chromatographic systems. The adsorption equilibrium constant obtained from the TLC data is compared to the equilibrium constant determined from adsorption measurements. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Infrared and Raman line shapes of dilute HOD in liquid H2O and D2O from 10 to 90 degrees C

A combined electronic structure/molecular dynamics approach was used to calculate infrared and isotropic Raman spectra for the OH or OD stretches of dilute HOD in D2O or H2O, respectively. The quantities needed to compute the infrared and Raman spectra were obtained from density functional theory calculations performed on clusters, generated from liquid-state configurations, containing an HOD molecule along with 4-9 solvent water molecules. The frequency, transition dipole, and isotropic transition polarizability were each empirically related to the electric field due to the solvent along the OH (or OD) bond, calculated on the H (or D) atom of interest. The frequency and transition dipole moment of the OH (or OD) stretch of the HOD molecule were found to be very sensitive to its instantaneous solvent environment, as opposed to the isotropic transition polarizability, which was found to be relatively insensitive to environment. Infrared and isotropic Raman spectra were computed within a molecular dynamics simulation by using the empirical relationships and semiclassical expressions for the line shapes. The line shapes agree well with experiment over a temperature range from 10 to 90 degrees C.     

Phase separation of aqueous solution of methylcellulose

 As we determined visually by the temperature cloud point method, the coexistence phase curve of methylcellulose in aqueous solution belongs to the LCST (low critical solution temperature) type. Rheological dynamic measurements reveal the existence of three gel domains. The gel (I) localized in the homogeneous phase at low concentration and low temperature, is a very weak gel, where the cross-links are attributed to pairwise hydrophobic interactions between the most hydrophobic zones of the backbone: the trimethyl blocks. The second gel (II) was revealed in the high concentration regime and below the LCST, it may be attributed to the formation of crystallites which play the role of cross-linking points. The third gel was concomitant to the micro-phase separation. In these turbid gels, syneresis develops slowly with time: the higher the temperature and the lower the concentration, the faster the syneresis. Near the three sol–gel transitions, a power law frequency dependence of the loss and storage moduli was observed and the viscoelastic exponent Δ(G′∼G″∼ω^Δ) was found to be 0.76 and 0.8 and to reach 1 at high concentration. Received: 18 July 1996 Accepted: 17 February 1997     

Phase separation of poly(γ-benzyl L-glutamate) to liquid crystal and isotropic solution in various helicogenic solvents

Solvent effects on the phase separation of poly(-benzyl L-glutamate) to liquid crystal and isotropic solution have been observed in various helicogenic solvents. The temperature-composition phase diagrams have been determined for each solution. The critical concentrations, ₂ ^* , at which the phase separation occours have been compared in various solvents. In dimethylformamide in which the polymer is molecularly dispersed, the observed ₂ ^* value has agreed with that calculated by Flory's theory. In some solvents in which the polymer aggregates in a head-to-tail mode such as chloroform, the observed ₂ ^* values have been considerably small. It is assumed that the polymer aggregates behave as longer particles than the original particles. In dioxane in which the polymer aggregates highly both in a head-to-tail and a side-by-side modes, the ₂ ^* value has been a little larger than that in chloroform. In this case the relationship between the aggregation and the liquid crystal formation is so complicated that further investigation is necessary. In aromatic solvents such asm-cresol that dissolves the polymer almost molecularly, the ₂ ^* is smaller than that in dimethylformamide. Therefore, the intermolecular interactions between the phenyl groups in the side groups of the polymer and those in solvent molecules must be considered.The author is grateful to Mr. K. Sano and Mr. M. Watanabe for their observation of the liquid crystal formation.     

Mutual diffusion coefficients of Nal-H2O and LiCl-H2O at 25°C from Rayleigh interferometry

Volume-fixed mutual diffusion coefficients of aqueous NaI have been measured from low concentrations to 10.8 mol-(kg H₂O)^–1 (7.6 mol-dm^–3), and those of LiCl up to 1.6 mol-(kg H₂O)^–1 (1.55 mol-dm^–3), at 25°C using free-diffusion Rayleigh interferometry. The accuracy of these diffusion coefficients is 0.1–0.2%. LiCl-H₂O has some of the lowest diffusion coefficients for alkali halides, whereas NaI-H₂O has some of the highest. The significance of these differences is briefly discussed.Work performed under the auspices of Office of Basic Energy Science (Geosciences) of the U.S. Department of Energy by the Lawrence Livermore National Laboratory under contract number W-7405-ENG-48.     

Speciation of Eu(III) in an anion exchange separation system with LiCl-H2O/alcohol mixed media studied by time-resolved

Coordination states of Eu(III) in anion exchange resin (AG 1X8) systems with LiCl-H₂O/alcohol mixed media were determined from the luminescence lifetimes and the emission spectra of Eu(III). The sorption equilibrium of Eu(III) was discussed on the basis of the correlation between the distribution coefficients and the coordination states in the solution and resin phases. The sorption of Eu(III) was mainly caused by the formation of an anionic Eu(III)-chloro complex in the resin phase, which was enhanced by the decrease of 'free' water activity due to the addition of alcohol. The effect of ethanol added was larger than that of methanol.     

Phase separation in dilute polymer solutions at high‐rate extension

In this article the demixing instability and phase segregation in unentangled polymer solutions of semiflexible chains at high‐rate uniaxial extension above the coil to stretched coil transition was studied. Orientation of the stretched chains was described in terms of an effective potential field. Based on the free energy analysis it was shown that the flow‐induced orientation of polymer segments could drastically reduce the energy of their steric repulsion. As a result attraction between the chains gain more importance, and this effect lead to the demixing process and eventual segregation of polymer from the solvent if the strain rate exceeds some critical value. A mean‐field theory was developed to study this flow‐induced phase separation effect. The phase diagrams of the system showing the spinodal and binodal transitions at different extension rates were calculated and discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1066–1073     

Vibrational relaxation of the H2O bending mode in liquid water

We have studied the vibrational relaxation of the H(2)O bending mode in an H(2)O:HDO:D(2)O isotopic mixture using infrared pump-probe spectroscopy. The transient spectrum and its delay dependence reveal an anharmonic shift of 55+/-10 cm(-1) for the H(2)O bending mode, and a value of 400+/-30 fs for its vibrational lifetime.     

Gibbs energy calculations for the distillation of a dilute solution in a multistep separation cascade

Calculations of a decrease in Gibbs energy in the distillation of an ideal dilute solution at cascade steps are presented. A thermodynamic interpretation of the total useful work of the separation of binary mixture components is suggested.     

Conformation and hydration of sugars and related compounds in dilute aqueous solution

The effect of hydroxyl substitution on the nature of the hydration of an alkane chain has been studied by calorimetric techniques. Static permittivities (₀) of a range of monosaccharides and related compounds in aqueous solution have also been determined. The (₀) data, suitably processed, have provided information about the solute dipole moments. In conjunction with earlier results from volumetric, compressibility, and relaxation studies, the specific hydration model is further developed and the relationships between solute molecular conformations and solute-water interactions are discussed.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.     

Phase separation and gelation of polymer-dispersed liquid crystals

Polymerization-induced phase separation in polymer-dispersed liquid crystal is studied by computer simulations in two dimensions. The domain morphology resulting from phase separation is investigated by solving the coupled set of equations for the local volume fraction and the nematic order parameter, taking into account the viscoelastic effects and gelation due to polymerization. Comparing the morphology of phase separation by temperature quench, it is shown that the viscoelastic effects and gelation enable the polymer-rich phase to form a stable interconnected domain even when the polymer component is minority. The experimental evidence consistent with this characteristic feature is also given.     

Phase equilibria and solid solution relationships in the La2O3-TiO2-ZrO2 system

In the ternary La₂O₃-TiO₂-ZrO₂ system the subsolidus phase relations at 1350 °C were determined using X-ray diffraction, scanning electron microscopy end energy dispersive X-ray analysis. The collected results are presented in the form of a phase diagram. In the equilibrium state there are 7 ternary and 5 binary compatible subsystems. In the system TiO₂ss, ZrO₂ss, ZrTiO₄ss, La₂Zr₂O₇ss and La₂O₃ss solid solutions were confirmed and La₄Ti₉O₂ss and La₂Ti₂O₇ss solid solutions were identified. The addition of ZrO₂ does not stabilize the La_2/3TiO₃ perovskite compound, nor the addition of TiO₂ a highly temperature stable compound La_2/3ZrO₃.     

Phase separation kinetics in mixtures of polymers and liquid crystals

Light scattering has been used to study phase separation kinetics in mixtures containing liquid crystals and epoxy resins. In the samples studied, phase separation was induced by the polymerization of the resins with an appropriate curing agent. Experiments were carried out at different compositions and at different temperatures. The results show that the kinetic mechanism of phase separation is composition dependent. For high liquid crystal content the data are in qualitative agreement with existing theories describing spinodal decomposition; at lower concentrations the mechanism is different. The physical properties of the resulting materials are independent of the decomposition mechanism. The data have also been analysed considering the scaling behaviour expected for late stages of phase separation in polyinduced meric mixtures. Samples obtained in a narrow concentration range, where the two kinetic mechanisms overlap, exhibit peculiar physical properties.     

Phase separation in mixtures of ionic liquids and water

The phase separation of ionic liquids (ILs) in water is studied by laser light scattering (LLS). For the ILs with longer alkyl chains, such as [C(8)mim]BF(4) and [C(6)mim]BF(4) (mim = methylimidazolium), macroscopic phase separation occurs in the mixture with water. LLS also reveals the coexistence of the mesoscopic phase, the size of which is in the order of 100-800 nm. In aqueous mixtures of ILs with shorter alkyl chains, such as [C(4)mim]BF(4), only the mesoscopic phase exists. The mesoscopic phase can be effectively removed by filtration through a 0.22 μm filter. However, it reforms with time and can be enhanced by lowering the temperature, thus indicating that it is controlled by thermodynamics. The degree of mesoscopic phase separation can be used to evaluate the miscibility of ILs with water. This study helps to optimize the applications of ILs in related fields, as well as the recycling of ILs in the presence of water.     

From the dilute solution to the pure compound: Extraction strategy based on a multi-stage process of phase separation

It is very rare that a one-step process of extraction leads to the pure compound with a high degree of purity specified by an industrial application. The various stages of a synthesis process and possible secondary reactions may lead to the synthesis of more or less complex and highly diluted solutions. In this work, the rationale and strategy for extraction and purification of a high added value compound are discussed. All the thinking is based on the knowledge and the exploitation of phase diagrams and then developed for different unit operations of the process. The most significant research tools are the experimental data and the modelling of phase equilibrium to estimate the yield of each step of extraction. The significant example chosen involves all the basic methods of phase separation, starting with liquid-vapour equilibrium: stripping of high volatility components and then more or less complex distillation are classically employed. The theoretical plateau number can be deduced from the equilibrium equation curves. The second step is based on the study of the liquid-liquid equilibrium and is an intermediate step for enrichment of the solution when distillation is not possible. A final step based on solid-liquid equilibrium consists of the selective crystallization of the pure product at low temperature, in order to satisfy the requirements of purity and safety imposed by industrial use. The conclusion includes all isolation operations in the form of a general extraction and purification scheme.