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Abstract: Tri-n-butyl phosphate (TBP) is a common solvent used for extracting metal ions from acidic solutions. In this work, the extraction of water and acid by TBP was modelled up to 16molal HCl, which is considerably above the range of existing work. The solubility parameter and thermodynamic equilibrium constant for the formation of each extracted species were determined using both experimental and literature data. The resulting model was able to successfully predict both the water and hydrochloric acid extraction by undiluted TBP or TBP diluted in aliphatic solvent within this concentration range. Water was shown to be extracted as the mono-hydrate at lower water activities and the di-hydrate as activity further increased. HCl was extracted as the tri-solvate at low acid concentrations, with the di-solvate , and mono-solvate forming as acid concentration increased. The present results show that at high acid concentrations, water is rejected from the organic phase as the acid is extracted, with the species formed having a typical composition of . The speciation also depends upon the extent of the dilution of TBP within the organic phase. Thus, tri-solvates are not present in undiluted TBP below 2mol/L HCl, but are present in TBP diluted in aliphatic solvent. [Copyright &y& Elsevier]

Abstract: The electric conductance of solutions of sulfuric, oxalic, benzoic, and salicylic acid (up to 0.02M) in dioxane–water mixed solvents (90% and 93% dioxane by mass) has been studied in the presence and absence of TiO2 and Al2O3 (0.5–5% by mass). TiO2 and Al2O3 enhanced the conductance of solutions of organic acids in aqueous dioxane. The conductance is interpreted in terms of adsorption of acid in molecular form, dissolution of ceramic oxides in form of anionic complexes, and leaching of acidic impurities from ceramic oxides. [Copyright &y& Elsevier]

The enthalpies of solution of ethylacetate (EtOAc) in water, octane and 1-octanol (OctOH) were measured at 298, 308 and 318 K using a precise isoperibol calorimeter. The standard enthalpies and heat capacities of these non-electrolyte solution were computed and compared with the previously obtained Δ H and $\Delta C_{p}^{\circ}$ values in N,N-dimethylformamide (DMF). Partial molal heat capacities of EtOAc in water and in organic solvents were calculated and compared with the available literature values. [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]

Abstract: Clegg–Pitzer–Brimblecombe ion-interaction semi-empirical approach was rarely exploited for modeling electrolyte, particularly, in mixed solvent systems. Indeed, a review of the literature shows that the use of an exact and complete form of this model (PSC) was only limited to the works of two research groups for the investigation of electrolyte in mixed solvent systems. In this work, we have used both Pitzer and PSC ion-interaction theoretical approaches for modeling the non-ideal behavior of HCl in the ternary HCl+methanol+water electrolyte system. The modeling purposes were achieved based on the experimental determination of the mean molal activity coefficients for HCl in this ternary system by using the potentiometric data of a galvanic cell containing a pH glass membrane and Ag/AgCl electrodes. The measurements were performed over the electrolyte molality ranging from 0.01 up to 5.75mol/kg in mixed methanol (x%)+water (100− x%) solvent, with solvent mass fraction percents: x%=10, 20, 30, 40 and 50%, at 298.15±0.05K. [Copyright &y& Elsevier]

Abstract: A LFE (Linear Free Energy) analysis of kinetic data for different organic reactions in various organic aqueous solutions was carried out. The rate constants of these reactions were compared with those for the solvolysis of tert-butyl chloride in the same solvents in terms of the LFE Relationships, and linear plots were observed in a wide range of the co-solvent content. This similarity points to a common nature of the solvent effect in these reactions in variety of water–organic mixtures, regardless of largely different reaction mechanisms. We explain these results by the prevalence of hydrophobic stabilization of the initial state of these reactions in water-rich solvent mixtures. Recently the same conclusion was also made on the basis of investigations into sonication effects in kinetics of organic reactions. A considerable contribution of hydrophobic effects to the Y scale by Grunwald and Winstein was deduced. [Copyright &y& Elsevier]

Abstract: The asymmetric transfer hydrogenation of nonfunctionalized aromatic ketones catalyzed by Ru-TsDPEN was performed successfully in a mixture of poly(ethylene glycol) (PEG) and water. High activity and enantioselectivity were obtained, which were better than or comparable to those obtained in conventional organic solvents. The unmodified catalyst could be easily recovered after extraction of the reduced product with a less polar solvent such as hexane, and was reused at least 14 times without obvious loss in enantioselectivity. These results indicate that the inexpensive and non-toxic aqueous PEG can serve as a new means for the immobilization of Ru-TsDPEN catalyst and related variants without calling for catalyst modification. [Copyright &y& Elsevier]

Abstract: In this work, densities of binary mixtures of {water+formamide (FM), or + N,N-dimethylformamide (DMF), or +dimethylsulfoxide (DMSO), or + N,N-dimethylacetamide (DMA), or +1,4-dioxane}, have been determined under atmospheric pressure as a function of composition and temperature using a vibrating-tube densimeter. The temperatures studied were T =(288.15, 293.15, 298.15, and 303.15) K. The excess molar volumes , calculated from density data, are negative over the whole mole fraction range for the temperature range studied. The values have been fitted to Redlich–Kister polynomial equation and others volumetric properties were calculated. The partial molar volumes at infinite dilution of each component have been determined using three different methods. [Copyright &y& Elsevier]