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  • 1
    ISSN: 1434-4475
    Keywords: Hydrogen peroxide ; Manganese ; TetradentateSchiff base ; Kinetics ; Decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die teradentatenSchiffschen Basen N,N′-bis-Salicyliden-ethylendiamin (salen), N,N′-bis-Salicyliden-Hexylendiamin (salhex) und N,N′-bis-Salicyliden-o-phenylendiamin (sal-o-phen) werden von Kationenaustauschen (Dowex-50W) mit Mangan(II) als Gegenion unter der Bildung stabiler Komplexe adsorbiert. Die Kinetik der katalytischen Zersetzung von H2O2 in Gegenwart dieser Komplexe wurde in wäßrigem Medium untersucht. Die Zersetzungsreaktion ist erster Ordnung bezüglich H2O2 in den Fällensalen undsal-o-phen und dritter Ordnung im Fall vonsalhex. Die Reaktionsgeschwindigkeit steigt mit der Länge der Methylenkette des Liganden und mit dessen Raumbedarf und wird von der Aktivierungsentropie bestimmt. Ein Reaktionsmechanismus wird vorgeschlagen.
    Notes: Summary The tetradentateSchiff bases N,N′-bis(salicylidene) ethylenediamine (salen), N,N-bis-(salicylidene) hexylenediamine (salhex), and N,N′-bis(salicylidene)-o-phenylenediamine (sal-o-phen) are very strongly adsorbed by cation exchange resins (Dowex-50W) with manganese(II) as a counter ion, forming stable complexes. The kinetics of the catalytic decomposition of H2O2 in presence of these complexes has been studied in aqueous medium. The decomposition reaction is first order with respect to H2O2 in the case ofsalen andsal-o-phen and third order in the case ofsalhex. The greater the ligand methylene chain length or the greater the steric effect of the ligand, the greater will be the rate of reaction. The reaction is governed by the entropy of activation. A reaction mechanism is proposed.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 955-962 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetradentate Schiff-base ligands, N,N′-bis(salicylidene)-ethylenediamine (Salen), N,N′-bis(salicylidene) butylenediamine (Salbut), and N,N′-bis(salicylidene)-o-phenylenediamine, (sal-o-phen) are very strongly sorbed by cation exchange resin (Dowex-50W) with Fe2+ ions as a counter ion, forming stable complexes. The kinetics of the catalytic decomposition of H2O2 using these complexes was studied in ethanolic medium. The reaction was first-order with salen and sal-o-phen and second-order with salbut with respect to [H2O2]. The rate of the H2O2 decomposition increased either from salen to salbut or from salen to sal-o-phen. Also, the k (per g dry resin) values decreased with increasing both the particle size and the degree of resin cross-linkage. The active species formed at the beginning of the reaction, had an inhibiting effect on the reaction rate. The corresponding activation parameters were calculated from a least-squares fit of the temperature dependence of the rate constant. A reaction mechanism is proposed. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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