The effect of the pressure on proton jumps in ethanol-water mixtures at 25.DEG.C.
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概要
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The limiting molar conductances of hydrochloric acid in 0, 5, 10, 20, 30, and 80 mol% ethanol–water mixtures, and those of potassium chloride in 80 mol% of ethanol, were determined at 25 °C as a function of the pressure up to 2000 kgf cm<SUP>−2</SUP> (1 kgf cm<SUP>−2</SUP>=0.9807×10<SUP>5</SUP> Pa) from the conductances measured in a dilute concentration range. In each solvent except for 80 mol% of ethanol, the limiting molar conductances of the proton, λ<SUP>°</SUP>(H<SUP>+</SUP>), are about four to six times larger than those of the potassium ion, λ<SUP>°</SUP>(K<SUP>+</SUP>), at all the pressures studied; in 80 mol% of ethanol, the value of λ<SUP>°</SUP>(H<SUP>+</SUP>) is very close to that of λ<SUP>°</SUP>(K<SUP>+</SUP>) at atmospheric pressure. The results suggest that the proton-jump mechanism acts in the water-rich region, but not in the ethanol-rich region. The excess proton conductances at an infinite dilution, λ<SUP>°</SUP><SUB>E</SUB>, as estimated by [λ<SUP>°</SUP><SUB>E</SUB>=λ<SUP>°</SUP>(H<SUP>+</SUP>)−λ<SUP>°</SUP>(K<SUP>+</SUP>)], were found to increase with an increase in the pressure. The pressure dependence of the excess proton conductances normalized to their values at 1 atm, λ<SUP>°</SUP><SUB>E</SUB><SUP>(<I>P</I>)</SUP>⁄λ<SUP>°</SUP><SUB>E</SUB><SUP>(1)</SUP>, is most prominent in 5 mol% of ethanol; its magnitude decreases in this order; 5>0>10>>20>>30 mol% of ethanol. These results are discussed in relation to the effect of ethanol molecules on the water structure in the mixtures; a small addition of ethanol to water stabilizes the three-dimensional networks of water, while a further addition of ethanol makes it difficult to form them.
- 公益社団法人 日本化学会の論文
著者
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Shimizu Kiyoshi
Deparment of Applied Chemistry, Faculty of Engineering, Doshisha University
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Ueno Masakatsu
Department of Applied Chemistry, Faculty of Engineering, Doshisha University
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Tsuchihashi Noriaki
Department of Applied Chemistry, Faculty of Engineering, Doshisha University
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Ito Kazunori
Department of Applied Chemistry, Faculty of Engineering, Doshisha University
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