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  • 11
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between chlorite ion and thiourea has been studied both in a closed (batch) system and in a flow reactor (CSTR). The principal stoichiometry is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ 2{\rm ClO}_{\rm 2} ^{\rm - } + {\rm CS(NH}_{\rm 2} {\rm)}_{\rm 2} + {\rm 2NH}_{\rm 4} ^ + + {\rm CO}_{\rm 2} + 2{\rm Cl}^{\rm - } + {\rm SO}_{\rm 4} ^{{\rm 2 - }} $$\end{document} In batch, the reaction displays an induction period, whose length is proportional to [CS(NH2)2]/[ClO2-] [H+], followed by the rapid buildup and disappearance of a ClO2 intermediate. At [ClO2-]/[CS(NH2)2] ratios between 2.5 and 3.5, a second peak in the ClO2 absorbance is observed. In the CSTR, this iodine-free system displays simple and complex periodic oscillation, bistability, aperiodic oscillation, and birhythmicity.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 12
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the oxidation of S2O32- by ClO2- have been studied in aqueous alkaline solution at 900C using classical titrimetric methods to follow the course of the reaction. The reaction takes place according to the stoichiometry S2O32- + 2ClO2- + 2OH- = 2SO42- + 2Cl- + H2O even in large S2O32- excess. There is some indication of a complex reaction pattern, but 70% of the ClO2- disappearance can be best described by the autocatalytic rate equation -d[ClO2-]/dt = k[S2O32-] [ClO2-] [H+] with k = (1.3 ± 0.2) ×108 M-2 sec-1. The mechanism is explained by postulating nucleophilic attack of S2O32- on HClO2 to form a chlorine-containing intermediate.
    Additional Material: 6 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 345-354 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calculations are performed to model several phenomena observed when a photosensitive oscillating chemical reaction, the Briggs-Rauscher (BR) reaction, is subject to irradiation in a continuous-flow stirred-tank reactor. The BR mechanism proposed earlier by De Kepper and Epstein is supplemented by additional steps involving the photogeneration and subsequent reaction of iodine atoms. The calculations show qualitative agreement with the following experimentally observed phenomena: (a) change in the period and amplitude of oscillation as a function of the intensity of constant illumination, (b) synchronization between periodically varying illumination and the period of chemical oscillation, (c) phase shifts induced by single light pulses, and (d) dark steady states which are excitable by single light pulses and become oscillatory at appropriate levels of constant illumination.
    Additional Material: 5 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 26 (1987), S. 287-293 
    ISSN: 0570-0833
    Keywords: Charge transfer ; Conducting materials ; Electron transport ; Materials science ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Through replacement of cations with neutral molecules of similar shape and polarizability in a highly conducting “metal-like” change-transfer organic conductor, the deliberate control of the electronic structure from a quarter to a half-filled band is possible. This goal has been achieved with the N-methylphenazinium (NMP) salt of the tetracyanoquinodimethane (TCNQ) anion by partial replacement of the cation with phenazine. A detailed study of the optical, electrical, and magnetic properties of these conducting molecular solids has lead to the evolution of a broad understanding of the physics of one-dimensional organic conductors and a reinterpretation of the mechanism of electron transport in such solids. Phenomena such as switching from a low coulomb repulsion two-chain conductor to a high coulomb repulsion one-chain conductor as well as soliton-assisted electron transport are observed.
    Additional Material: 10 Ill.
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