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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and experimental chemistry 24 (1989), S. 435-440 
    ISSN: 1573-935X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the oxidation of copper(I) perchlorate with thiuram disulfide (tds) in acetonitrile and its mixtures with benzene or ethyl bromide have been investigated. It has been shown that the rate of the reaction is limited by the inner-sphere transfer of an electron from the copper(I) ion to tds in a complex of the type [CuI(tds)]+. The subsequent dissociation of the anionradical tds —proceeds rapidly and leads to the formation of copper(II) dithiocarbamate which is recorded in the absorption spectra and by EPR. The rate constant of electron transfer has been determined (3·10−4sec−1) and it was found that it is practically independent of the polarity of the medium. The absence of such a correlation is attributed to the negligible energies of reorganization of the solvent in the inner-sphere electron transfer.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 13-29 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of electron transfer between stable verdazyl radicals via bridge Mn(II), Co(II), Ni(II), Cu(I), and Zn ions have been studied in the range 280-330 K using the stopped-flow technique. It was found that the kinetic features of the reactions could be described in terms of the Marcus theory. The reorganization energy of the inner coordination sphere (ICS) of intermediate complexes was estimated from the reported data on the energy of release of various ligands from the ICS of similar complexes. The rest of the kinetic parameters (solvent reorganization energy, transmission coefficients, enthalpy, and entropy of activation) were determined from Marcus equations and from plots of rate constant versus temperature, “standard” free energy, and polarity of the medium. It was also found that the reactions under consideration are nonadiabatic and the transmission coefficient value depends on the mean lifetimes of ligands in the ICS.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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