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  • 1
    ISSN: 1572-8927
    Keywords: Mixed micelles ; surfactants ; alcohols ; thermodynamic transfer functions ; volume ; heat capacity ; hydrophobic solutes ; chemical equilibrium model and distribution constant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In ternary aqueous solutions, hydrophobic solutes such as alcohols tend to aggregate with surfactants to form mixed micelles. These systems can be studied by meas of the functions of transfer of hydrophobic solutes from water to aqueous solutions of surfactant. These thermodynamic functions often go through extrema in the critical micellar concentration (CMC) region of the surfactant. A simple model based on interactions between surfactant and hydrophobic solute monomers, on the distribution of the hydrophobic solute between water and the micelles and on the shift in the CMC induced by the hydrophobic solute, can simulate the magnitude and trends of the transfer functions using parameters which are mostly derived from the binary systems. In order to check the model more quantitatively, volumes and heat capacities of transfer of alcohols from water to aqueous solutions of a nonionic surfactant, octyldimethylamine oxide, were measured. A quantitative agreement was achieved with three adjustable parameters. Good fits are also obtained for the transfers to the ionic surfactants, octylamine hydrobromide and sodium dodecylsulfate. When the equilibrium displacement contribution is small, the distribution constants and the partial molar properties of the alcohols in the micellar phase agree well with the parameters obtained with similar models.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-8927
    Keywords: Mixed micelles ; surfactant ; alcohol-water mixture ; solubilization ; thermodynamic function of transfer ; volume ; enthalpy ; hydrophobic solutes ; heat capacity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Mixed micelles can be formed in water between various pairs of hydrophobic solutes such as surfactants, alcohols and hydrocarbons. These systems can often be studied through the thermodynamic functions of transfer of one of the solutes, usually kept near infinite dilution, from water to an aqueous solution of the other solute. When mixed micelles are formed, these functions change significantly, and often go through extrema, in the region where the binary system micellizes or undergoes some microphase transition.Three main effects are responsible for the observed trends: pair-wise interactions between both solutes in the monomeric form, a distribution of the reference solute between the aqueous and micellar phases and a shift in the monomer-micelle equilibrium in the vicinity of the reference solute. Simple equations can be derived for these three effects which can account for the sign and magnitude of the observed trends using parameters which are derived for the most part from the two binary systems.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 23 (1994), S. 889-900 
    ISSN: 1572-8927
    Keywords: Excess enthalpy ; enthalpy of solution ; infinite dilution ; organic solvents ; aqueous solution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A Picker flow microcalorimeter was employed in conjunction with asymmetric syringe-type pumps to measure heats of mixing of highly dilute aqueous solutions of organic solvents. These data were used in turn to determine limiting partial molar excess enthalpies of the examined solvents in water. The measurements were carried out at 298.15 K for 29 common, oxygen and/or nitrogen containing solvents exhibiting complete miscibility with water. Except for only one compound, formamide, the limiting partial molar excess enthalpies are exothermic indicating that the process of dissolution is energetically favored. Comparison to literature data (in most cases to solution enthalpies at infinite dilution measured by batch calorimetry) proved the technique applied to be sufficiently accurate.
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  • 4
    ISSN: 1572-8927
    Keywords: Apparent molar heat capacities ; apparent molar volumes ; partial molar properties ; infinite dilution ; aqueous solutions ; organic pollutants ; group contribution method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Well-known Picker flow microcalorimeters for the differential measurements of volumetric heat capacities have been employed in conjunction with vibrating tube densimeters to determine the molar heat capacity, volume, and the apparent properties in dilute aqueous solutions for 17 organic solutes of moderate hydrophobicity. The dependence on concentration of the apparent properties allowed the limiting partial molar quantities at infinite dilution to be extrapolated and the limiting partial molar excess quantities to be evaluated. Comparison with available literature data shows good agreement. The application of group contribution rules to the limiting partial properties has been tested using the original method and parameters proposed by Cabani et al. The predicted values of the partial molar volumes are in fair agreement with the present data except for some less common solutes. With partial molar heat capacities, the agreement is less satisfactory. To improve the performance of the method, missing parameters for some types of monofunctional and bifunctional molecules have been evaluated.
    Type of Medium: Electronic Resource
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