Polymer effects under pressure. III. Hydrolysis of normal alkyl acetate catalyzed by dodecyl hydrogensulfate micelle.
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概要
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Measurements of the rates of hydrolysis of methyl, ethyl, propyl, and butyl acetates have been made to 2 kbar in water catalyzed by dodecyl hydrogensulfate (DSA) micelle at 40 °C. The rate of hydrolysis decreases with compression up to approximately 1 kbar and then increases above 1 kbar; methyl acetate differs in these respects. The inversion phenomenon under pressure has been explained by the incorporation of both the H<SUB>3</SUB>O<SUP>+</SUP> ion and ester molecules into the micellar phase. The observed value of the over all activation volume at 1 atm Δ<I>V</I><SUP>*</SUP> is −5.3±1 cm<SUP>3</SUP>/mol for methyl, 0.40±1 cm<SUP>3</SUP>/mol for ethyl, 9.7±1 cm<SUP>3</SUP>/mol for propyl, and 20±1 cm<SUP>3</SUP>/mol for butyl acetate, respectively. From the activation volumes of HCl and DSA micellar catalysts, the volume change accompanying the incorporation of the esters into the micellar phase ΔΔ<I>V</I><SUB>micelle</SUB>, has been estimated to be 4.0±1 cm<SUP>3</SUP>/mol for methyl, 9.8±1 cm<SUP>3</SUP>/mol for ethyl, 18.7±1 cm<SUP>3</SUP>/mol for propyl, and 27.9±1 cm<SUP>3</SUP>/mol for butyl acetate, respectively. The values above have been explained in terms of the contribution to the hydrophobic interaction between the ester molecule and the micelle.
- 公益社団法人 日本化学会の論文
著者
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Suzuki Keizo
Department Of Chemistry Faculty Of Science And Engineering Ritumeikan University
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Taniguchi Yoshihiro
Department Of Applied Chemistry Faculty Of Science And Engineering Ritsumeikan University
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Inoue Osamu
Department Of Clinical And Laboratory Medicine Faculty Of Medicine University Of Yamanashi
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Inoue Osamu
Department of Chemistry, Faculty of Science, Toyama University
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Suzuki Keizo
Department of Chemistry, Faculty of Science and Engineering, Ritsumeikan University
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