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  • heat capacity changes  (3)
  • Cryptand  (1)
  • 1995-1999  (4)
  • 1
    Digitale Medien
    Digitale Medien
    Enthalpies of Dilution of Aqueous Solutions of NaOH, KOH, and CsOH at 300, 325, and 350°C (1998)
    Springer
    Journal of solution chemistry 27 (1998), S. 183-194 
    Details
    ISSN: 1572-8927
    Schlagwort(e): Dilution enthalpies ; activity coefficients ; alkali metal hydroxides ; equilibrium constants ; enthalpy changes ; entropy changes ; heat capacity changes ; high temperature ; aqueous solution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Dilution enthalpies, measured using isothermal flow calorimetry, are reported for aqueous solutions of KOH and CsOH at 300°C and 11.0 MPa, 325°C and 14.8 MPa, and for aqueous solutions of NaOH, KOH, and CsOH at 350°C and 17.6 MPa. Previously collected dilution enthalpies for aqueous solutions of NaOH at 300°C and 9.3 MPa and at 325°C and 12.4 MPa were included when fitting the Pitzer parameters. The concentration range of the hydroxide solutions was 0.5–0.02 molal. Parameters for the Pitzer excess Gibbs ion-interaction equation were determined from the fits of the experimental heat data. Equilibrium constants, enthalpy changes, entropy changes, and heat capacity changes for alkali metal ion association with hydroxide ion were estimated from the heat data. For all systems, the enthalpy changes and entropy changes were positive and had accelerating increases with temperature. The resulting equilibrium constants show significant, but smaller, increases with temperature.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1023/A:1022661424398
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Enthalpies of Dilution of Aqueous Solutions of LiCl, KCl, and CsCl at 300, 325, and 350°C (1997)
    Springer
    Journal of solution chemistry 26 (1997), S. 47-61 
    Details
    ISSN: 1572-8927
    Schlagwort(e): Dilution enthalpies ; activity coefficient ; alkali metal chlorides ; equilibrium constants ; enthalpy changes ; entropy changes ; heat capacity changes ; high temperature ; aqueous solution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Dilution enthalpies, measured using isothermal flow calorimetry, are reported for aqueous solutions of LiCl, KCl, and CsCl at 300°C and 11.0 MPa, 325°C and 14.8 MPa, and 350°C and 17.6 MPa. The concentration range of the chloride solutions was 0.5 to 0.02 m. Parameters for the Pitzer excess Gibbs ion-interaction equation were determined from the fits of the experimental heat data. Equilibrium constants, enthalpy changes, entropy changes, and heat capacity changes for ion association of the chloride salts were estimated from the heat data. For all systems, the enthalpy and entropy changes were positive and had accelerating increases with temperature. The resulting equilibrium constants show significant, but smaller, increases with temperature.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1023/A:1024485028264
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Enthalpies of dilution of aqueous solution of LiCl, KCl, and CsCl at 300, 325, and 350°C (1997)
    Springer
    Journal of solution chemistry 26 (1997), S. 47-61 
    Details
    ISSN: 1572-8927
    Schlagwort(e): Dilution enthalpies ; activity coefficient ; alkali metal chlorides ; equilibrium constants ; enthalpy changes ; entropy changes ; heat capacity changes ; high temperature ; aqueous solution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Dilution enthalpies, measured using isothermal flow calorimetry, are reported for aqueous solutions of LiCl, KCl, and CsCl at 300°C and 11.0 MPa, 325°C and 14.8 MPa, and 350°C and 17.6 MPa. The concentration range of the chloride solutions was 0.5 to 0.02m. Parameters for the Pitzer excess Gibbs ion-interaction equation were determined from the fits of the experimental heat data. Equilibrium constants, enthalpy changes, entropy changes, and heat capacity changes for ion association of the chloride salts were estimated from the heat data. For all systems, the enthalpy and entropy changes were positive and had accelerating increases with temperature. The resulting equilibrium constants show significant, but smaller, increases with temperature.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF02439443
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    New 2-methylenepropylene-bridged cryptands with high sodium ion selectivity: A thermodynamic study of complexation (1995)
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 23 (1995), S. 223-231 
    Details
    ISSN: 1573-1111
    Schlagwort(e): Cryptand ; alkali metal ion selectivities ; equilibrium constant ; enthalpy change ; entropy change
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Thermodynamic quantities for the interactions of mono- and tri(2-methylenepropylene)-bridged cryptands, cryptand [3.3.1], cryptand [2.2.2], and 18-crown-6-with Na+, K+, Rb+, and Cs+ have been determined by calorimetric titration in an 80:20 (v/v) methanol: water solution at 25°C. Incorporation of the 2-methylenepropylene (−CH2C(=CH2)CH2−) bridge(s) into cryptand [2.2.2] results in a large change in the ligand-cation binding properties. Tri(2-methylenepropylene)-bridged cryptand [2.2.2] (2) shows high selectivity factors for Na+ over K+ and other alkali cations, while 2-methylenepropylene-bridged cryptand [2.2.2.] (1) selects K+ over Na+, as does cryptand [2.2.2]. The K+/Na+ selectivity is reversed with increasing number of 2-methylenepropylene bridges. This observation indicates that increasing the number of 2-methylenepropylene bridges on cryptand [2.2.2] favors complexation of a small cation over a large one. The logK values for the formation of 1 and 2 complexes (except 1-Cs+ and 2-Na+) decrease as compared with those for the corresponding [2.2.2] complexes. Formation of six-membered chelate ring(s) by the propyleneoxy unit(s) of 1 and 2 with a cation stabilizes the cryptate complexes of the small Na+ and destabilizes the complexes of large alkali metal cations. Thermodynamic data indicate that the stabilities of the cryptate complexes studied are dominated mostly by the enthalpy change. In most cases, both stabilization of Na+ complexes and destabilization of the complexes of large alkali metal cations by six-membered chelate ring(s) also result from an enthalpic effect. Cryptand [3.3.1] shows a selectivity for K+ over Cs+, despite its two long CH2(CH2OCH2)3CH2 bridges. The [3.1] macroring portion of [3.3.1]may be too small to effectively bind the Cs+, resulting in the low stability of the Cs+ complex.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00709580
    Standort Signatur Erwartet Verfügbarkeit
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