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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of the solvolysis of the cis-chloroazidobis-(1,2-diaminoethane)cobalt(III) ion in water+t-butanol mixtures (1985)
    Springer
    Transition metal chemistry 10 (1985), S. 223-226 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Rate constants for the solvolysis of the complex ioncis-[Coen2N3Cl]+ have been determined for a range of temperatures in mixtures of water witht-butanol ranging up to 50% v/v of the latter. Linear plots of log (rate constant) against the reciprocal of the absolute temperature are obtained at all concentrations oft-butanol and the variations of the enthalpy and entropy of activation with solvent composition show extrema at compositions where extrema occur in the physical properties of the mixture which are influenced by solvent structure. The importance of solvent structure is shown by the curved plot found for log (rate constant) against reciprocal of dielectric constant at constant temperature. The application of a free energy cycle to the free energies of activation in water and in the mixture and the free energies of transfer of individual ionic species between water and the mixtures shows that the effect of changes in solvent structure on the reacting cation in the transition state dominates over that in the initial state.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00692633
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics of the solvolysis of the trans-chloroazidobis(diaminoethane)cobalt (III) ion in water + t-Butyl Alcohol Mixtures (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 215-226 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the solvolysis of the ion trans-[Coen2N3Cl]+ have been investigated at several temperatures in mixtures of water with t-butyl alcohol with concentrations of the latter ranging up to 50 vol% or a mol fraction of 0.16. Values for the enthalpy and entropy of activation show sharp changes with changing solvent composition which can be correlated with extrema in the physical properties of the mixture concerned with sharp changes in solvent structure. Plots of log(rate constant) against the reciprocal of the dielectric constant and against the Grunwald-Winstein Y factor are both curved. The application of a free energy cycle shows that the effect of changes in solvent structure on the solvolysis dominates on the cobalt(III) cation in the transition state over that on the cation in the initial state.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180207
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    Paper (German National Licenses)
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