Volume properties and structure of aqueous solutions of urea at 263–348 K

The apparent molar volume of urea ? in aqueous solution in the range T = 273–323 K and m = 1–10 (molality) depends linearly on m ^1/2. An equation for ?(m, T) was derived. The partial molar characteristics of urea ? ₂ and water ? ₁ (volume, dilatability, and temperature coefficients of volumes) were calculated. The ?(T) dependences have characteristic points (extrema, inflection points), shifted to the region of lower temperatures for dilute solutions. The ? ₁(T) dependences for 2m and 4m of the urea solution retain the characteristics of the Y ₁(T) of pure water. In these solutions, the proper structure of water is preserved.     

Effect of a magnetic field on the rheological properties of the systems hydroxypropyl cellulose–ethanol and hydroxypropyl cellulose–dimethyl sulfoxide

With the use of viscometry, the cloud-point method, polarization microscopy, the turbidity-spectrum method, and a polarization photoelectric apparatus, the relaxation pattern of the rheological behaviors, phase transitions, and structures of the systems hydroxypropyl cellulose–ethanol and hydroxypropyl cellulose–dimethyl sulfoxide are studied. The regions of existence of isotropic and anisotropic phases and the concentration dependence of the sizes of supramolecular particles are determined. It is found that a magnetic field increases the viscosities of solutions. The concentration dependences of viscosity and particle size are described by curves with maxima.     

Volumetric, rheological, and optical properties of Na-alkylsulfonates aqueous solutions at 29°C

Present paper reports density, relative viscosity and refractive index of sodium salt of 1-heptanesulfonic acid and 1-octanesulfonic acid at 29°C. Density data has been fitted to Masson empirical relation and limiting apparent molar volumes were evaluated. Viscosity A and B coefficients characterizing ion-ion and ion-solvent interactions have been evaluated by fitting viscosity data in Jone-Doles equation. Experimental and calculated properties support the strong ion-solvent interactions in solution.     

Concentration dependences of the physicochemical properties of a water–acetone system

Concentration dependences of the UV spectrum, refractive index, specific electrical conductivity, boiling point, pH, surface tension, and heats of dissolution of a water–acetone system on the amount of acetone in the water are studied. It is found that the reversible protolytic interaction of the components occurs in all such solutions, resulting in the formation of hydroxyl and acetonium ions. It is shown that shifts of the equilibrium between the molecules and ions in the solution leads to extreme changes in their electrical properties. It is concluded that the formation of acetone solutions of water is accompanied by heat absorption, while the formation of aqueous solutions of acetone is accompanied by heat release.     

Heterogeneous interaction between zwitterions of amino acids and glycerol in aqueous solutions at 298.15 K

The enthalpies of mixing of six kinds of amino acid (glycine, L-alanine, L-valine, L-serine, L-threonine, and L-proline) with glycerol in aqueous solutions and the enthalpies of diluting of amino acid and glycerol aqueous solutions have been determined by flow microcalorimetry at 298.15 K. Employing McMillan–Mayer theory, the enthalpies of mixing and diluting have been used to calculate heterogeneous enthalpic pairwise interaction coefficients (h _xy ) between amino acids and glycerol in aqueous solutions. Combining h _xy values of amino acids with glycol in the previous study, the variations of the h _xy values between amino acids and glycerol have been interpreted from the point of view of solute–solute interactions.     

Carbon materials as electrodes for electrosorption of NaCl in aqueous solutions

Different porous carbons (MWCNT, a carbon aerogel, an activated carbon cloth and a chemically activated carbon) were evaluated as electrode material for the electrosorption of NaCl. The results obtained from the chronoamperometric experiments were correlated to the surface area and the size of the pores present in each carbon. These results indicate that all the surfaces are equivalent for the electrosorption process, demonstrating that both, mesopores and micropores, are equally effective. Nevertheless, the kinetics of the process is influenced by the pore size distribution of the carbon, although it is rather fast for all the carbons studied. The chemically activated carbon seems to be the most suitable carbon material for electrosorption of NaCl due to the combination of a high surface area and an appropriate pore size distribution.     

Micellar properties of tetradecyltrimethylammonium nitrate in aqueous solutions at various temperatures and in water-benzyl alcohol mixtures at 25 °C

The micellar properties of tetradecyltrimethylammonium nitrate (C14TANO₃) in aqueous solutions in the temperature range of 10 to 35 °C and in aqueous solutions of benzyl alcohol (BzOH) at 25 °C were studied conductometrically. The specific conductivity data served for the evaluation of critical micelle concentration, cmc, and the degree of ionization of the micelles, , of the surfactant. From the temperature dependence of the cmc the thermodynamic parameters for micellization of C14TANO₃ were calculated by applying Mullers modified equation. BzOH was found to affect strongly the cmc and values of the surfactant. The plot of the cmc/cmc_o ratio (where cmc_o is for pure water) as a function of BzOH molality, exhibits a characteristic break, which was attributed to the commencement of self-association of BzOH in aqueous solution at a molality of ca. 0.05. By applying the theoretical treatment suggested by Motomura for binary surfactant systems, the molar fraction of BzOH in the micelles at cmc, was estimated as a function of molality of the alcohol. C14TANO₃ appears to be slightly more hydrophobic compared to the corresponding bromide.     

Polymer–surfactant interaction for controlling the rheological properties of aqueous surfactant solutions

Controlling viscosity of aqueous surfactant solutions is very important for practical formulations. This can be done by having polymers interact with surfactants, thereby forming interconnected physical networks, where main ways of interaction are electrostatic and hydrophobic forces. Polymer–surfactant interactions are long established for viscosity control, but there are many ongoing activities. They are driven by wanting more biocompatible systems, which depend intricately on the choice of surfactant and polymer, and general predictions are not simple for such systems. Surfactants form spherical or wormlike micelles or vesicles. By choice of (co)polymers one can construct systems responsive to external parameters, like temperature or pH, for having tailored rheological properties. Here we describe recent developments with a focus on systems of low concentration, being interesting for applications. In summary, rheological control of polymer–surfactant systems is a versatile topic and a field of colloid science with high relevance for practical formulations.     

Physico-chemical studies on some saccharides in aqueous cellulose solutions at different temperatures – Acoustical and FTIR analysis

The ultrasonic velocity (u), density (ρ) and viscosity (η) of Fructose, Lactose and Sucrose in 0.4 M of Hydroxy Propyl Methyl Cellulose (HPMC) solutions have been investigated at 303, 313 and 323 K, respectively. The acoustical parameters such as adiabatic compressibility (β), intermolecular free length (L_f), internal pressure (π_i), Rao’s constant (R_a), relaxation time (τ), acoustical impedance (Z_a), absorption coefficient (α/f²), free volume (V_f), cohesive energy (CE) and solvation number (S_n) have been computed. The non linear variations of acoustical parameters with concentration and temperature indicated the existence of strong molecular interaction in the systems studied. The FTIR spectroscopic analysis revealed the possibility of intermolecular hydrogen bonding in various saccharides.     

In‐situ monitoring of a film preparation process for hydroxypropyl cellulose cast from isotropic aqueous solution using microdielectrometry

Solid cast films with polydomain textures were prepared on a glass substrate with transparent interdigitated electrodes from an isotropic aqueous solution of hydroxypropyl cellulose via its liquid crystalline phase under the sinusoidal electric field with small amplitude and frequency of 0.05 V µm^?1 and 10⁵ Hz, respectively. The process was monitored using microdielectrometry as well as polarised optical microscopy. The apparent dielectric constant ε_r′ and loss factor ε_r″ sensitively changed with time depending on the process conditions. On the other hand, the logarithmic relation between ε_r″ and ε_r′ showed a single curve, when they were normalised by an effective portion of the electrostatic energy density estimated using each solid‐film thickness. The conversion to the solid film was estimated during the process based on the concentration dependences of ε_r′ and ε_r″. Characteristic times were reported for the onset of the biphasic phase, fully developed cholesteric phase and termination of the process.     

Debye–Einstein model and anomalies of heat capacity temperature dependences of solid solutions at low temperatures

An approach is proposed for analysing the deviations of the heat capacity C_p(T) of solid solutions from the Kopp–Neumann rule (KNR) ΔC(T)?=?C_p(T)???C_KNR(T). Temperature dependences of the heat capacity C_p(T) of selected compositions of systems (InP)_x (InAs)_1?x and (GaAs)_x (InAs)_1?x at temperatures of 5–300 K are analysed in the Debye–Einstein approximation. It was established that in the case of substitution of atoms in the cation subsystem (Ga³⁺???In³⁺) with the same subsystem of anions (As^3?), the positive values of ΔC(T) at T?<?100 K are due to the appearance of the low-frequency Einstein mode, whereas the negative values of ΔC(T) at T?>?100 K are the result of a decrease in the fraction of the Debye contribution without changing the upper limit of the oscillation frequency. In the case of substitution in the cation subsystem (P^3????As^3?) with the invariant cation subsystem (In³⁺) to the low-temperature positive contribution of the additional low-frequency Einstein mode, a positive part is added from the modified Debye mode having the characteristic temperature θ_D below the additive value θ_DKNR. The adequacy of this model is confirmed by Raman scattering data.

     

Characteristic and mechanism of Cr(Ⅵ) adsorption by ammonium sulfamate-bacterial cellulose in aqueous solutions

A new adsorbent, ammonium sulfamate-bacterial cellulose (ASBC), was prepared through chemical modifications of bacterial cellulose. The process of adsorbing Cr(Ⅵ) including its isotherm and kinetics, was measured and studied. The results showed that pH value was a very important parameter to the adsorbing efficiency. The adsorption kinetics can be described by a pseudo-second rate model and a particle diffusion equation. Both physical and chemical adsorptions existed in the adsorption process, but chemical adsorption was more dominatant. And particles internal diffusion was not the only rate controlling step. The adsorption equilibrium can be described by the Langmuir type, which indicated that a typical single-molecule layer adsorption of Cr(Ⅵ) by ASBC could be described. And the rate of adsorption followed the Slips model well, which indicated that ASBC had some multiphase and asymmetry. The coordination adsorption and ion exchange effect were the main mechanisms of chemical adsorption. The absorbed Cr(Ⅵ) can be desorbed effectively by 0.5 mol/L EDTA or HCl from the adsorbent, which could make it be reusable.     

Ion-solvent and ion-ion interactions of NaCl aqueous and aqueous maltose solutions at 298–323 K on viscosity data

Viscosities of sodium chloride in concentration range 1 × 10^?2 to 9 × 10^?2 ± 0.001 mol dm^?3, have been determined in aqueous and aqueous maltose systems (1.0 to 9.0 wt %) at different temperatures (298 to 323 K). The viscosity data have been analyzed by using Jones-Dole equation and the derived parameters A and B coefficients were also calculated. The data obtained from viscometric studies has been used to investigate the ion-solvent interaction and ion-ion interaction. Thermal effects on the ionic interactions were also examined under the light of transition state theory.     

Excess enthalpies of dilute aqueous solutions of model peptides and urea at 25°C

Excess enthalpies of four dilute aqueous solutions each containing urea and a model peptide (N-acetyl-N-methylamides of either glycine or L-alanine, N-acetylamides of either L-valine or L-proline) have been determined by calorimetry. These results are compared with the excess enthalpies of aqueous solutions of amides and other uncharged peptides. The second enthalpic virial coefficients are discussed on the basis of McMillan-Mayer theory and additivity of group interactions. The results confirm the preliminary conclusions of previous works in this series, i.e., that peptideurea interactions are water assisted, and an extra contribution appears when more than one peptidic or amidic group is present on the same molecule.     

Thermodynamics of aqueous L-proline solutions at 273–323 K

Enthalpies of dissolution of L-proline in water were measured calorimetrically at 283–313 K. The experimental temperature of dissolution of proline in water at the studied temperatures was shown to be almost independent of its concentration over the range 0.01–0.11 mol/kg. Standard enthalpies of dissolution and standard heat capacities of dissolution were calculated over this temperature range. The heat capacity of dissolution was ascertained to increase in the row glycine, proline, and alanine. The partial molar heat capacity of proline in water was determined and compared with the values obtained by extrapolation of the apparent heat capacities. The changes in entropy and reduced enthalpy and the Gibbs energy over the temperature range from 273 to 323 K were determined using familiar thermodynamic relations. The data for glycine and alanine were compared.     

Thermodynamic assessment of phase diagram and concentration–temperature dependences of properties of solid solutions of the GaS–GaSe system

Journal of Thermal Analysis and Calorimetry - Before 100,000&nbsp;years ago, during the Middle Stone Age (MSA) of South Africa, silica varieties of minerals and rocks were sometimes heated...     

Solvation of magnesium chloride and sulfate in aqueous solutions at 278.15–323.15 K

Isoentropy compressibilities of aqueous magnesium chloride and sulfate were determined based on precision measurements of ultrasound velocity, density, and isobaric heat capacity at low to high concentrations at 278.15–323.15 K. The hydration numbers h and the molar parameters of volume and compressibility were calculated based on thermodynamically correct equations for hydration complexes (V _h , β _h V _h ), water in the hydration shell (V _1h , β_1h V _1h ), and the void containing a stoichiometric mixture of ions (V _2h , β_2h V _2h ). The h and β _h V _h values were found to be independent of temperature; the molar compressibility of the hydration sphere (β_1h V _1h ) and the stoichiometric mixture of ions without a hydration shell (β_2h V _2h ) were independent of the concentration under the stated conditions. The effect of the electrostatic field of ions on the temperature dependence of the molar volume of water in the hydration sphere was more significant than the effect of pressure on the temperature dependence of the molar volume of bulk water. This is attributed to changes in the dielectric constant of water in the vicinity of the electrolyte ions.