Thermodynamics of mixed electrolyte solutions. X. An isopiestic study of the quaternary system NaCl−KCl−MgCl2−H2O at 25°C

Activity coefficients in the aqueous quaternary system sodium chloridepotassium chloride-magnesium chloride were derived from isopiestic measurements at 25°C. The isopiestic data were treated by the various procedures of Scatchard, Friedman, and Reilly, Wood, and Robinson, and results obtained agreed fairly well with those obtained by pseudoternary transforms. Interaction parameters obtained indicated the preponderance of pairwise interactions. Excess Gibbs free energies of mixing were calculated.     

Excess enthalpies of mixing tetrahydrofuran and tetrahydropyran with some chloroalkanes at 26.9°C

Excess enthalpies of mixing H _m ^E of tetrahydrofuran and tetrahydropyran with trichloromethane, tetrachloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane have been determined at 26.9°C and are found to be negative over the entire composition range for both sets of the ether mixtures. H _m ^E decreases in the sequence; dichloroethane > tetrachloromethane > trichloroethane > trichloromethane > tetrachloroethane. The results are explained on the basis of strong O...H-C and weak Cl...O specific interactions. Flory's theory has been used to correlate the experimental data with good agreement found between the theoretical and experimental values of H _m ^E .     

Some selected problems of nonaqueous microemulsions — phase diagrams and variation of the composition in the quaternary and ternary systems

A variety of quaternary and ternary systems of the type of dodecane/aliphatic alcohols/Na-dodecyl sulphate/water or a water-replacing component (formamide, ethylene glycol, propylene glycol, propylene carbonate, dimethylsulfoxide, acetonitrile) were subjected to a comparative analysis of microemulsification. The compositions of the systems of the type of oil/surfactant/cosurfactant/water or nonaqueous liquid were changed with respect to surfactant (Na-dodecyl sulfate and triton X 114) concentration, cosurfactant (homologous aliphatic alcohols) concentration and mixing ratio of water and water-replacing component. The appertaining phase diagrams were plotted and compared with those of aqueous systems.The experimental results suggest that the phase regions, which are designated as nonaqueous microemulsions, probably represent, not only microemulsions in the usual sense, but a separate kind of mixed phase whose microstructure is examined by special studies. Analogously to aqueous microemulsion systems, transparency and spontaneous formation of homogeneous multicomponent systems cannot serve as the sole criteria for waterless microemulsion formation. But they are important guiding properties of microemulsion formation in multicomponent systems.The variety of components involved in the chemical composition and the current insufficient knowledge do not permit to generally decide whether nonaqueous systems can be assigned to microemulsions or to molecular solutions. For clarifying this problem a detailed examination of the miscibility behavior, especially that of binary systems as a function of temperature, and the role that surfactant and cosurfactant play in the formation of homogeneous systems will be necessary.     

Increasing the solubility characteristics of fenofibrate with cyclodextrin

The incidence of genetic lipoprotein disorders, or hyperlipoproteinaemia, is currently increasing. Examinations were carried out on the hyperlipoproteinaemic drug fenofibrate and various cyclodextrin derivatives were applied to increase the solubility of this drug. Numerous products with several compositions (drug: CD mole ratio=2:1, 1:1, 1:2 or 1:3) were studied and three preparation methods (powder mixing, kneading and precipitation) were used. In vitro drug liberation and membrane diffusion examinations revealed compositions suitable for the preparation of a capsule dosage form (1:2 and 1:3 physical mixtures).Dedicated to Dr. Béla Selmeczi, university professor, with the best wishes for his 65th birthday.     

Prediction of critical temperature of n-alkanes and n-alkenes from surface tension vs. temperature data

 The surface tension versus temperature data of homologous series of n-alkanes and n-alkenes is analyzed. Critical temperatures are shown to be predicted from these data, with a very high precision, after some corrections are made. The corrections are shown to arise from the effect of the critical pressure on the extrapolated data to surface tension approaching zero. Received: 29 October 1996 Accepted: 13 December 1996     

Thermodynamic investigation of the state of water adsorbed by carbonaceous adsorbents

The state of water adsorbed on active carbons and canal soot was studied using the “chemical potential—entropy—temperature” diagram. In the range of the relative pressures from 0.174 to 1, the state of adsorbed water is similar to the state of a stretched liquid. The molar volume, heat of evaporation, and surface tension of stretched water were calculated at different relative pressures. Near the spinodal, the molar volume of stretched water is 25% higher, and the surface tension is considerably lower compared to water. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 464–468, March, 1997.     

Conductance Study of Binding of Some Rb+ and Cs+ Ions by Macrocyclic Polyethers in Acetonitrile Solution

A conductance study of the interaction between Rb+ and Cs+ ions and18-crown-6 (18C6), dicyclohexyl-18-crown-6 (DC18C6), dibenzo-18-crown-6 (DB18C6),dibenzo-24-crown-8 (DB24C8), and dibenzo-30-crown-10 (DB30C10) inacetonitrile solution has been carried out at various temperatures. The formationconstants of the resulting 1:1 complexes were determined from the molarconductance-mole ratio data and found to vary in the orderDC18C6 > 18C6 > DB30C10 > DB18C6 DB24C8for Rb+ ion andDC18C6 > 18C6 > DB30C10 DB24C8 > DB18C6for Cs+ ion. The enthalpy and entropy of complexation were determined fromthe temperature dependence of the formation constants. The complexes with the18-crowns are both enthalpy and entropy stabilized while, in the case of largecrown ethers, the corresponding complexes are enthalpy stabilized but entropydestabilized.     

An Empirical Approach for Estimating the Density of Multicomponent Aqueous Solutions Obeying the Linear Isopiestic Relation

An empirical approach is presented for the density of aqueous multicomponentsolutions conforming to the linear isopiestic relation. This approach can be usedto estimate the densities of multicomponent systems from data on the constituentbinary subsystems at the same water activity. Predicted and measured densitiesfor 22 mixtures have been compared, using the simple Young's rule, theisopycnotic mixing rule of Teng and Lenzi, and the present method. The present methodand Young's rule give the most accurate predictions for strong electrolyte mixtureswithout common ions and for the mixtures with strong ion complexes, respectively.There is no universal best method for the strong electrolyte mixtures with commonions. An extensive comparison has also been given between apparent molarvolume predictions by Young's rule and by the new method. The two rules arerelatively better for the strong electrolyte mixtures without common ions andmixtures containing the transition metal chlorides, respectively. However, neitheris universally better for mixtures of strong common-ion electrolytes.     

Catalysis of Ruthenium-Metal Oxides Mechanically Mixed with Sulfated Zirconia for Reaction of Butane to Isobutane

A highly active catalyst for the skeletal isomerization of butane to isobutane was obtained by mechanically mixing SO₄/ZrO₂ and Ru/SnO₂; Ru/SO₂ was prepared by impregnating tin hydroxide with a solution of RuCl₃ followed by calcining at 450°C (0.5 wt.% Ru). The catalyst was much more active than Ru-SO₄/ZrO₂ prepared by co-impregnation of zirconia with the Ru and sulfate materials the temperature difference to show the same conversion between both catalysts being 57°C. The effect of mixing of Ru was observed with other metal oxides as supports, Fe₂O₃, Al₂O₃, ZrO₂, TiO₂, and SiO₂; the calcination temperature of the Ru-impregnated hydroxides was 250, 300, and 400°C for the latter three, respectively.