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  • 1
    Electronic Resource
    Electronic Resource
    A conductance investigation of HCl in aqueous solutions of tetrahydrofuran, dimethoxyethane and dioxane (1990)
    Springer
    Journal of solution chemistry 19 (1990), S. 1211-1224 
    Details
    ISSN: 1572-8927
    Keywords: Hydrochloric acid ; water-tetrahydrofuran ; water-dioxane ; water-dimethoxyethane ; conductance ; association constants ; proton mobility ; Gurney cosphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Conductance of dilute solutions of HCl in water-tetrahydrofuran (THF), water-dioxane and water-dimethoxyethane (DME) were measured and the data processed using the Justice-Ebeling equation to evaluate the limiting conductance ΛO, the association constant KA and the apparent distance of closest approach a'. The Friedman-Rasaiah Gurney cosphere overlap term d+−/kT was calculated from a' values and illustrates the different solvation pattern of dioxane compared to that found for THF and DME. It would appear that dioxane can solvate cations more strongly due to its ability to form a boat configuration around a cation. The association constants are reasonably reproduced by the Bjerrum equation using realistic molecular dimensions of the ions involved for the distance of closest approach. The limiting conductance in the mixtures illustrates clearly the different mechanism for proton conductance compared to that for the cesium ion. The dielectric constants, viscosities and densities of the solvent mixtures were measured and are reported. The lowest dielectric constant for each type of solvent mixture was about 10.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00652546
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  • 2
    Electronic Resource
    Electronic Resource
    Ionic interactions in solutions. I. The association concepts and the McMillan-Mayer theory (1976)
    Springer
    Journal of solution chemistry 5 (1976), S. 543-561 
    Details
    ISSN: 1572-8927
    Keywords: Activity coefficients ; ionic association ; McMillan-Mayer theory ; compressibility equation ; Bjerrum's concept of association ; Hamiltonian models ; short-range ionic interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A review is given of the most common models of ionic-pair association used by Bjerrum, Fuoss, and Eigen to supplement the breakdown of the Debye-Hückel law for the mean activity coefficient of symmetrical electrolytes in lower-dielectric-constant solvents. The compressibility and pressure equations of Rasaiah and Friedman and the virial equation are used to rederive the activity coefficients from the distribution functions of Meeron and of Debye and Hückel. The results are compared to the well-known results of Debye and Hückel and that of Bjerrum. In each case the anion-cation pair association concept of Bjerrum is verified. Finally, a discussion is included on the best evaluation of the critical distance which distinguishes between free and associated ions. The activity equation is easily generalized to any short-range Hamiltonian model.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00647377
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Ionic interactions in solutions. II. The theoretical basis of the equilibrium between free and pairwise associated ions (1977)
    Springer
    Journal of solution chemistry 6 (1977), S. 819-826 
    Details
    ISSN: 1572-8927
    Keywords: Activity coefficients ; ionic association ; mass-action law ; McMillan-Mayer theory ; compressibility equation ; Rasaiah-Friedman Hamiltonian models ; short-range ionic interactions ; Bjerrum association concept ; multistep association
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is shown from recent results based on the statistical mechanics treatment of ionic solutions that the notion of an equilibrium between free ions and paired ions which wasa priori introduced in the chemical model of Bjerrum is essentially correct. The mass-action law which is deduced from such a model is indeed derivable from the more exact treatments of Mayer, Rasaiah, and Friedman starting directly from Hamiltonian models and without any assumptions as to the chemical structure of the ionic solute in the solution. The transformation relation from a primitive-model result to any short-range Hamiltonian model equation is given. It allows a simple mathematical treatment of experimental data for dilute solutions, the derivation of useful information on the Gurney solvation effects, and an interpretation of the multistep association concept.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00648071
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    Paper (German National Licenses)
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  • 4
    Electronic Resource
    Electronic Resource
    A comparison of ion-solvent interactions evaluated from both emf and conductance data for HCl in aqueous solvent mixtures (1994)
    Springer
    Journal of solution chemistry 23 (1994), S. 703-709 
    Details
    ISSN: 1572-8927
    Keywords: Hydrochloric acid ; water-dioxane ; water-tetrahydrofuran ; water-dimethoxyethane ; conductance ; EMF ; association constants ; short range non-coulombic interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Available emf data for HCl in water-dioxane, water-tetrahydrofuran, and water-dimethoxyethane at 25°C have been analyzed using models based on similar levels of approximation as was used previously for conductance data. The emf data were evaluated in terms of standard cell potentials, apparent distances of closest approach, association constants and a Gibbs energy term attributed to non-coulombic ion-solvent interaction. Although emf and conductance data give essentially the same results it is clear that the conductance method, with its much greater precision, is superior for this type of analysis.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00972716
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    Paper (German National Licenses)
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