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  • 1
    Electronic Resource
    Electronic Resource
    Solvent effects on substitution reactions at complexes of the [Fe(CN)5L]3- type in binary aqueous mixtures (1991)
    Springer
    Transition metal chemistry 16 (1991), S. 165-168 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The kinetics of replacement of 4,4′-bipyridine, (4,4′-bipy), and 4-cyanopyridine, (4-CNpy), by cyanide in [Fe(CN)5-(4,4′-bipy)]3-. at 298 K have been studied in binary aqueous mixtures containing different amounts of t-butanol, methanol, glycerol, ethyleneglycol and sucrose. The plots of logarithms of the limiting rate constantsversus the mole fraction of water are linear over the entire composition range studied, showing the importance of solvation phenomena. A different straight line of log (kL/s−1)versus XH2O is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of δΔG exp ≠ with A (acidity vector), B (basicity vector) and GE is used for both reactions; plots of δΔG calc ≠ versus ΔΔG exp ≠ are linear with slopes of near unity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01032825
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  • 2
    Electronic Resource
    Electronic Resource
    Salt effects in the reaction between IrCl 6 2− and MnEDTA2− (1992)
    Springer
    Reaction kinetics and catalysis letters 46 (1992), S. 131-138 
    Details
    ISSN: 1588-2837
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Abstract Окисление MnEDTA2− (EDTA=этилендиаминтетрауксусная кислота) гексахлориридатом(IV) исследовали в концентрированных растворах электролита. Определяя коэффициенты активности частиц на основе теории гидратации Стокса-Робинсона, было найдено, что солевые эффекты вызваны повышенной дестабилизацией исходного состояния по отношению к переходному с повышенной концентрацией соли.
    Notes: Abstract The oxidation of MnEDTA2−. (EDTA=ethylenediaminetetra-acetate) by hexachloroiridate(IV) has been studied in concentrated electrolyte solutions at 298 K. The estimation of the activity coefficients of the species from the Stokes-Robinson hydration theory indicates that the observed salt effects have their origin in a greater destabilization of the initial state with respect to the transition state when increasing salt concentration.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02096688
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Study of the ligand substitution reaction Fe (CN)5H2O3- + pyrazine in micellar solutions (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 377-384 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ligand substitution reaction Fe(CN)5H2O3- + pyrazine → Fe(CN)5 pyrazine3- + H2O has been studied in sodium dodecyl sulfate SDS, hexadecyltrimethylammonium bromide, CTAB, and salt aqueous solutions at 298.2 K. Kinetics were studied in dilute and concentrated salt solutions and in SDS and CTAB solutions at surfactant concentrations below and above the critical micelle concentration. Experimental results show that salt effects can be explained by considering the interaction between the cations present in the working media which come from the background electrolyte, and the Fe(CN)5H2O3- species in the vicinity of the cyanide ligands. This interaction makes the release of the aqua ligand from the inner-coordination shell of the iron(II) complex to the bulk more difficult resulting in a decrease of the reaction rate when the electrolyte concentration increases. Kinetic data in surfactant solutions show that not only micellized surfactants are operative kinetically, but also nonmicellized surfactants are influencing the reactivity. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 377-384, 1997
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 4
    Electronic Resource
    Electronic Resource
    Salt effects upon reactions of different charge type reactants: Peroxodisulphate Oxidations of Fe(CN)4(bpy)2-, cis-Fe(CN)2(bpy)2 and Fe(bpy)32+ and Iron(II) Oxidation by Co(NH3)5Cl2+ (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 299-307 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Salt effects on the oxidation of the iron(II) complexes Fe(CN)4(bpy)2-, cis-(CN)2(bpy)2 and Fe(bpy)32+ by S2O82- as well as on the reaction Fe2+ + Co(NH3)5Cl2+ have been studied in concentrated electrolyte solutions at 298.2 K. We have gone from anion-anion to cation-cation reaction with the intermediate cases of anion-neutral and cation-anion reactions. Results show that the main cause of the kinetic salt effects observed is the interaction between supporting electrolytes and the solvent. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260208
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    Paper (German National Licenses)
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