Search

The results of calorimetric investigations of electrolyte solutions in the mixtures of water, methanol, N, N-dimethylformamide, and acetonitrile with numerous organic cosolvents are discussed with regard to the intermolecular interactions that occur in the solution. Particular attention is given to answer the questions how and to what extent the properties of the systems examined are modified by the cosolvent added and how much the properties of the cosolvent are revealed in the mixtures with the solvents mentioned above. To this goal, the analysis of the electrolyte dissolution enthalpies, single ionic transfer enthalpies, and enthalpic pair interaction coefficients as well as the preferential solvation (PS) model are applied. The analysis performed shows that in the case of the dissolution enthalpies of simple inorganic electrolytes in water-organic solvent mixtures, the shape of the dependence of the standard dissolution enthalpy on the mixed solvent composition reflects to a large extent the hydrophobic properties of the organic cosolvent. In the mixtures of methanol with organic cosolvents, the ions are preferentially solvated either by methanol molecules or by molecules of the cosolvent, depending on the properties of the mixed solvent components. The behavior of inorganic salts in the mixtures containing N, N-dimethylformamide is mostly influenced by the DMF which is a relatively strongly ion solvating solvent, whereas in acetonitrile mixtures, the thermochemical behavior of electrolyte solutions is influenced to a large extent by the properties of the cosolvent particularly due to the PS of cation by the cosolvent molecules. [ABSTRACT FROM AUTHOR]

Abstract  Poly(terephthalamide) microcapsules can be reproducibly and easily prepared by interfacial polycondensation around emulsion droplets in water. Oil drops of cyclohexane/chloroform mixture stabilized with poly(vinyl alcohol) containing terephthaloylchloride serve as soft template. The interfacial polycondensation starts immediately after addition of an amine mixture (hexamethylenediamine/diethylenetriamine). Light and scanning electron microscopy prove the formation of capsules with size distribution in the range from a few up to 100 µm depending on particular composition of the reaction mixture. The morphology of the capsule wall is characterized by precipitated particles. If instead of pure organic solvents a reactive oil phase is used as template, the capsules can serve in subsequent reactions as templates for the synthesis of composite particles. In this way, styrene can be radically polymerized inside the capsule leading to composite capsules. The capsule morphology is determined by the partition of all components between all phases. [ABSTRACT FROM AUTHOR]

Abstract  The enthalpies of solution of benzo-15-crown-5 ether in methanol–water mixtures and methanol–water–sodium iodide systems have been measured at 298.15 K. The values of standard enthalpies of solution of benzo-15-crown-5 ether are positive in the mixtures of water and methanol within the whole range of mixture composition. The equilibrium constants of complex formation of benzo-15-crown-5 ether with the sodium cation have been determined by conductivity measurements at 298.15 K. The thermodynamic functions of the formation of these complexes have been calculated. The Gibbs energy of complex formation depends on the base–acid properties of methanol–water mixture. [ABSTRACT FROM AUTHOR]

This paper describes a potentiometric titration method for the determination of stoichiometric autoprotolysis constants (pKs) in binary mixtures of water with methanol, ethanol, 1-propanol, 2-propanol, dioxane, and acetonitrile. A combined pH electrode modified by replacing its aqueous KCl solution with 0.01 M NaCl + 0.09 M NaClO4 saturated with AgCl was used for the first time in aqueous organic solvent mixtures. The potentiometric cell was calibrated before each experiment so that the hydrogen ion concentration rather than the activity was measured. The calibration constants E° and k were determined by titrating a solution of perchloric acid with sodium hydroxide solution for each medium studied at 25 °C and under nitrogen atmosphere. During each titration the concentration of NaClO4 was maintained at 0.1 M and the pKs values were calculated by using this titration data. It is shown that the combined electrode system could be successfully used to determine autoprotolysis constants in water-organic solvent mixtures. Furthermore, the variation of the pKs values with solvent composition is discussed. [ABSTRACT FROM AUTHOR]