Structure of liquid mixtures studied by positron annihilation and sound velocity: Water+tert-butanol

Aqueous solutions of tert-butyl alcohol (2-methyl-2-propanol) were investigated using sound velocity and positron annihilation methods. The results are interpreted in terms of changing structure of solution, especially formation of clathrate-like hydrates. The annihilation method was found to be applicable for investigating the structure of aqueous solutions of non-electrolytes. Resolution of annihilation spectrum into three components (instead of two) yield non-physical parameters, suggesting that the short-lived mechanisms of annihilation of positrons are too close to be separated.     

Enthalpies of solution in sodium octanoate + water + alcohol mixtures

Enthalpies of solution of sodium octanoate in water, 1-propanol and aqueous mixtures of 1-propanol, 1-butanol, 1-pentanol and 1-hexanol, and of the alcohols in aqueous solutions of sodium octanoate at various concentrations were determined calorimetrically at 35 °C. MostH(soln) values are exothermic and strongly dependent on the solute concentration. The main energetic factor governing the process of dissolution of the surfactant is associated with changes in the water structure caused by the presence of alcohol. That governing the process of the alcohol dissolution in surfactant solutions is due to the effect alcohols have on the CMC of the octanoate. There is no indication of the alcohol being either solubilized in the interior of the aqueous micelle, or becoming part of the micellar film.The solubility at 35 °C of sodium octanoate in water, 1-propanol and their mixtures has also been determined.     

Ion association of persulphates in water and water+acetone mixtures

Conductometric studies have been made for the persulphates of sodium, potassium, and ammonium in water and water+acetone (X_acetone=0.016, 0.033, 0.072, 0.117 and 0.171) mixtures at 298.15, 303.15, 308.15 and 313.15 K, using Shedlovsky and Fuoss–Kraus extrapolation techniques. The limiting molar conductance (Λ_o), association constant (K_A), Walden product (Λ_oη_o) and the thermodynamic functions for the process of ion-pair formation have been evaluated and discussed.     

Dielectric dispersion in water + 2-hydroxypyridine solid mixtures

The complex electric permittivity was measured in water + 2-hydroxypyridine (2HP) solid mixtures as a function of concentration, temperature and frequency. Just after freezing of diluted mixtures, (mole fraction of 2HP < 0.2) pronounced dielectric dispersion in the MHz region was observed. The dispersion disappears on cooling between -30 and -40 degrees C in a first-order phase transition. The dispersion was explained in terms of the movement of a guest molecule (2HP) in a clathratelike structure of ice.     

Adsorption of thiourea on mercury in water + methanol mixtures

The adsorption of thiourea on mercury has been investigated by capacitance measurements in three water + methanol mixtures, having various mole fractions of methanol.The back integration method was employed to obtain the curves of surface charge densities at the mercury surface for different concentrations of thiourea in the solution.As a test of specific adsorption in the systems studied the Esin-Markov plots were used.     

水＋甲酰胺＋环己烷＋二乙二醇丁醚拟三元系的三临界现象

用改进的体积法研究了拟三元体系水＋甲酰胺＋环己烷＋二乙二醇丁醚的三临界现象. 以水+甲酰胺作为拟“纯组分”，通过控制甲酰胺在拟“纯组分”中的质量分数w，逐渐向三临界点逼近，当w从0增加到0.206时，三相区范围ΔT从1.500 ℃减小到0.228 ℃. 由实验数据得到体系的临界质量分数w=0.286±0.003，临界温度为（54.8±0.7） ℃. 实验发现平均温度下三相区三角形的水-油边与三角坐标中的水-油边几乎平行，而且三相区三角形水-油边的边长及其对应的高与ΔT的指数关系符合三临界的经典理论.     

Picosecond dynamics and microheterogenity of water+dioxane mixtures

Dielectric spectra from 200 MHz up to 3 THz were determined to study the fast dynamics of dilute water+1,4-dioxane. epsilon(nu) could be fitted by a collision induced oscillator at high frequencies plus two Debye relaxations in the microwave region. Isotope substitution was used to assign water and dioxane modes. The presence of the cooperative hydrogen-bond network relaxation down to a water mole fraction of 0.005 suggests a microheterogeneous structure of the mixtures even at low water content. The collision mode of dioxane at approximately 2 THz grows upon water addition, revealing the presence of H2O molecules in dioxane-rich domains.     

The relative permittivity of 1,2-ethanediol+2-methoxyethanol+water ternary mixtures

The relative permittivities for the ternary 1,2-ethanediol (component 1) + 2-methoxyethanol (2) + water (3) solvent system have been measured for 66 mixtures covering the whole mole fraction composition 0X₁/X₂/X₃ 1 range at –10, –5 and 0 °C. The experimental data were used to test some empirical relations stating the dependence of = (X₁, X₂, X₃). A comparison between the calculated and experimental data show that these equations can be usefully employed to predict values in correspondence of the experimental data gaps.     

Mass transport characteristics of alkyl amines in a water/n-decane system

Rhenium (Re) nanoparticles have been synthesized by pulsed-laser decomposition of ammonium perrhenate (NH(4)ReO(4)) or dirhenium decacarbonyl (Re(2)(CO)(10)) in the presence of 3-mercaptopropionic acid (MPA) as capping agent, in both aqueous and organic media. Preliminary studies showed that the MPA-capped Re nanoparticles are capable of catalyzing the isomerization of 10-undecen-1-ol to internal alkenols via long chain migration of the C=C double bond at ca. 200°C. A one-pot synthesis of graphite-coated Re nanoparticles has also been achieved by pulsed-laser decomposition of Re(2)(CO)(10), due to photo-induced catalytic graphitization of the phenyl groups of PPh(3) on the surface of rhenium nanoparticles.     

Measurements and predictions of density and carbon dioxide solubility in binary mixtures of ethanol and n-decane

The solubility of carbon dioxide (CO₂) in binary mixtures of ethanol and n-decane has been measured using an in-house developed pressure-volume-temperature (PVT) apparatus at pressures up to 6 MPa and two different temperatures (303.2 and 323.2 K). Three different binary mixtures of ethanol and n-decane were prepared, and the densities of the prepared mixtures were measured over the studied pressure and temperature ranges. The experimental data of CO₂ solubility in the prepared mixtures and their saturated liquid densities were then reported at each temperature and pressure. The solubility data indicated that the gas solubility reduced as the ethanol mole fraction in the liquid mixture increased. The dissolution of CO₂ in the liquid mixtures resulted in the increase in the saturated liquid densities. The impact of gas dissolution on the saturated liquid densities was more pronounced at the lower temperature and lower ethanol compositions. The experimental solubility and density data were compared with the results of two cubic equations of state (EOSs), Soave–Redlich–Kwong (SRK) and Peng–Robinson (PR). The modeling results demonstrated that both EOSs could predict the solubility data well, while the saturated liquid densities calculated with the PR EOS were much better than those predicted with the SRK EOS.     

Dew points of binary carbon dioxide + water and ternary carbon dioxide + water + methanol mixtures: Measurement and modelling

Dew points for four carbon dioxide + water mixtures between 1.2×10⁵ and 41.1×10⁵ Pa in the temperature range from 251.9 to 288.2 K, and eight carbon dioxide + water + methanol mixtures between 1.2×10⁵ and 43.5×10⁵ Pa and temperatures from 246.0 to 289.0 K were experimentally determined. The experimental results obtained on the binary and ternary systems were analysed in terms of a predictive excess function–equation of state (EF–EOS) method, which reproduced the experimental dew point temperature data with absolute average deviation (AAD) between 0.8 and 1.8 K for the systems with water, and from 0.0 to 2.7 K for the systems with water and methanol. The experimental results obtained for carbon dioxide + water mixtures, with molar fraction of water lower than 0.00174, at pressure values higher than 5×10⁵ Pa were also compared to a predictive equation of state model. It reproduced experimental dew point temperature data with AAD between 0.2 and 0.6 K.     

Structuring effects and hydration phenomena in poly(ethylene glycol)/water mixtures investigated by brillouin scattering

Aqueous solutions of poly(ethylene glycol) (PEG) of mean molecular mass of 600 g/mol (PEG600) are investigated by Brillouin scattering technique. At high PEG content, a relaxation phenomenon is observed, which is related to a local rearrangement of the polymer structure where the interaction, via hydrogen bonding, with the solvent molecules plays a role. The obtained values of the relaxation times match the literature data very well for a fast relaxation time revealed by dielectric relaxation measurements in very similar mixtures. The calculated concentration behaviors of the excess adiabatic compressibility turns out in good agreement with the previous findings from ultrasonic measurements at 3 MHz. The observed minimum in the adiabatic compressibility is interpreted as the result of the interaction between water and the EO units of the PEG chain, which results in a structure tighter then that typical of bulk water and of pure PEG600. Such a hypothesis is supported by the observation that volume fraction value of about 0.3 coincides with the concentration value at which full hydration of EO units takes place. The observation that at the same concentration, the polymer coils start to overlap each other further supports the idea that the adiabatic compressibility behavior is monitoring the structural evolution of the mixture. However, similar results are obtained for largely different binary mixture which suggests caution in taking this conclusion too literally. In particular, the hypothesis that the occurrence of an extreme in the excess adiabatic compressibility could be simply originated by statistical effects and that further work is required for disentangling entropic contribution from effects of hetero-association and self-aggregation of one or both the components.     

Influence of temperature on ultrasonic velocity measurements of ethanol+water+1-propanol mixtures

The ultrasonic velocity of the ternary mixtures ethanol+water+1-propanol at the range 288.15–323.15 K and atmospheric pressure, has been measured over the whole concentration range. The corresponding change of isentropic compressibility was computed from the experimental data. The results were fitted by means of a temperature dependent equation, such parameters being gathered. The obtained experimental values indicate varying extent of interstitial accommodation among unlike molecules as a function of steric hindrance attending to 1-propanol composition as key component and as a function of hydrogen bond and temperature attending to ethanol composition as key component.     

Solubility of sildenafil citrate in propylene glycol + water mixtures at various temperatures

The solubility of sildenafil citrate (SC) in aqueous mixtures of propylene glycol (PG) was investigated. This study was carried out at different mass fractions of PG ranging from 0.1 to 0.9 at T = 293.2–313.2 K. The solubility of SC in the mixed solutions increased with increasing temperature and PG mass fraction.

The solubility values were correlated by two co-solvency models (Jouyban–Acree model and van’t Hoff–Jouyban–Acree model). The mean relative deviations (MRD) were 5.7% and 5.5%, respectively. Density of the SC-saturated solutions over the entire solvent composition and temperature range was also measured and the results correlated with the Jouyban–Acree model. Furthermore, the apparent thermodynamic properties, dissolution enthalpy, dissolution entropy and Gibbs free energy change of dissolution process of SC in all the mixed solvents were calculated according to van’t Hoff and Gibbs equations. Dissolution of SC in these mixed solvents is an endothermic process.     

Experimental determination and modeling of structure II hydrates in mixtures of methane+water+1,4-dioxane

Hydrate phase equilibrium conditions were measured with a Cailletet apparatus in the pressure range 2<14 MPa. The investigated 1,4-dioxane concentrations were 1, 2, 5, 7, 10, 20 and 30 mol% relative to water. The results show that adding 1,4-dioxane up to concentrations of 6 mol%, about the stoichiometric ratio of large sII cages to water (1/17), reduced the equilibrium pressure of hydrate formation. Adding 1,4-dioxane beyond 6 mol% caused a slow increase of the equilibrium pressures. The hydrate phase equilibria data were modeled as equilibrium between a liquid phase of water and 1,4-dioxane, with a small amount of methane, and a sII hydrate of 1,4-dioxane and methane. The chemical potential of the hydrate phase was described using the van der Waals and Platteeuw theory. Activity coefficients of the liquid phase were calculated by a van Laar relation, based on literature 1,4-dioxane+water VLE data. The predicted equilibrium pressures calculated were within 5% of the data up to a concentration of 20 mol% 1,4-dioxane relative to water.     

Supercooling phenomena in binary mixtures of acetamide and inorganic salts

Liquid—solid equilibrium temperatures are measured in binary mixtures of acetamide and inorganic salts [NaClO₄, LiCNS, LiNO₃, CH₃COOLi, Ca(NO₃)₂, (CH₃)₄ NCl, (C₂H ₅)₄ NBr]. In some ranges of concentration all these systems (with the exception of CH₃COOLi, R₄NX) exhibit supercooling phenomena and crystallization occurs only through vigorous agitation and in the presence of crystalline nuclei, or does not occur at all, according to the type of salt. A probable explanation is presented on the basis of the trend of ΔT/νmK vs. m.     

Excess molar volume of dimethyl carbonate +p-xylene + n-decane at 288.15 and 298.15 k

Densities for dimethyl carbonate + p-xylene + n-decane ternary system, at 288.15 and 298.15 K and at atmospheric pressure, were measured. The corresponding excess molar volumes were calculated from the experimental data and were fitted by means of Cibulka equation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of intermolecular interactions and microstructure of supercritical mixtures water +n-heptane and water +n-hexane based onPVT x measurements

The partial molar volumes of n-heptane and n-hexane in super- and nearly critical water are determined based on the PVT_x mesurements of the binary mixtures water + n-heptane and water + n-hexane near the critical point (CP) of the pure solvent (water). The partial molar volumes of n-heptane and n-hexane show nonclassical (scaling) behavior ( ) as the system asymptotically approaches (x → 0) the CP of pure water along the critical isobar-isotherm (T_c, P_c). The microstructure of the supercritical mixture is studied based on our experimental (PVT_x, ) data and Kirkwood-Buff’s fluctuation theory of dilute solutions; the dependence of the cluster size (N ₁ ^∞ ) on thermodynamic conditions (T, P) is established. With minor variations of temperature and pressure near the CP of pure water, the cluster size changes anomalously abruptly. The parameters of the equation of state of the SPHCT model are determined based on the PVT_x measurements, and direct solvent-solute correlation integrals C ₁₂ ^∞ (of water + n-heptane and water + n-hexane) are calculated. The Krichevskii parameter (∂P / ∂x) _VT ^C , adequately defining the behavior and structure of an infinitely dilute mixture near the CP of the pure solvent, is calculated. The effects of interactions between the solvent and solute molecules on the structure of a supercritical fluid are examined. Institute of Geothermal Problems, Dagestan Scientific Center, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 1, pp. 74–85, January–February, 1998. This work was supported by RFFR grant No. 96-02-16005.