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  • Cathodic dimerization  (1)
  • Industrial Chemistry and Chemical Engineering  (1)
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  • 1
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Manganese mixed oxide composite layers of about 1 μm thickness on titanium sheet as substrate were fabricated by firing of the corresponding nitrates at a typical temperature of 400°C in air. The activity of these anodes was evaluated by cyclic voltammetry (10 mV/s) and the stability was determined by chronopotentiometry (2.5 mA/cm2) in 1M H2SO4. The oxidation of 2-propanol was examined as a simple electroorganic model reaction. The quality of a first category of mixed oxides with general composition MnMe2O4 decresed in the order Me = Co, Ni, Fe. In a second group with the general formula MeMn2O4 a decrease in the order Me = Co, Cu, Fe, Ni, Ti, Zn, Cd, Ca, Mg, (Zn, Ge), Li was observed. The corresponding candidates of the second group were superior to those of the first. The anode service life τ of the optimum spinel anode CoMn2O4/Ti is dependent on the current density, according to jλ τ = const. (λ = 1.7). Thus high current densities are precluded. The mechanism has been discussed in terms of a heterogeneous redox catalysis: surface Mn(VII) states are formed in a slow electrochemical step. In a subsequent fast chemical oxidation of the organic molecule the original reduced state is regenerated. This also explains the comparatively good service life of these anodes.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 760-781 
    ISSN: 0570-0833
    Keywords: Cathodic dimerization ; Dimerization ; Electrochemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The technical, electrochemical, and preparative aspects of cathodic dimerization, which leads to bifunctional compounds, are reviewed. With the hydrodimerization of acrylonitrile as an example, the effects of the reaction parameters and the mechanism are discussed in detail. In addition to the hydrodimerization of activated compounds, the coupling can also proceed via elimination of halide or via the discharge of cations. Processes of special preparative interest are those in which two different molecules are coupled, which can yield e.g. esters, alcohols, or ketones with cyano groups, as well as asymmetric diols. The reductive dimerizations of acrylonitrile, β-chloropropionitrile, acetone, acetylpyridine, nitrobenzene (→ benzidine), and pyridinium salts have already found industrial use.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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