Linear free energy relationships in heterogeneous catalysis. XIII. The dehydration of aliphatic alcohols over silica-alumina.
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概要
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In order to survey the applicability of linear free-energy relationships to the catalytic dehydration of aliphatic alcohols, isopropyl alcohol and <I>n</I>-, <I>s</I>-, and <I>t</I>-butyl alcohols were dehydrated over silica–alumina at 54–166 °C. The dehydration was zero order in alcohol over the pressure range of 0.01 to 0.1 atm. The true activation energies were 32.0, 35.3, 31.7, and 29.9 kcal/mol for isopropyl alcohol and <I>n</I>-, <I>s</I>, and <I>t</I>-butyl alcohols, respectively. The zero-order rate constants were exclusively affected by the activation energy. A linear relationship was found between the true activation energy, as well as the logarithm of the zero-order rate constant, and the heterolytic bond dissociation energy for the C–O bond in alcohols, <I>D</I>(R<SUP>+</SUP>OH<SUP>−</SUP>). The activation energy increased and the rate constant decreased with an increase in the <I>D</I>(R<SUP>+</SUP>OH<SUP>−</SUP>). These correlations were explained in terms of the heterolytic fission of the C–O bond in the rate-determining step.
- 公益社団法人 日本化学会の論文
著者
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Yoneda Yukio
Department Of Molecular Pharmacology Kanazawa University Faculty Of Pharmaceutical Sciences
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Take Jun-ichiro
Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo
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Matsumoto Tadayuki
Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo
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