Pressure effect on proton jumps in t-butyl alcohol-water mixtures at 25.DEG.C..
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概要
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The limiting molar conductances, <I>Λ</I>°, of hydrochloric acid and potassium chloride in 2,3,5,7,10, and 25 mol% <I>t</I>-butyl alcohol (TBA)–water mixtures 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 within a dilute concentration range. In each solvent mixture the value of <I>Λ</I>° (HCl) was about three- to five-times larger than that of <I>Λ</I>° (KCl) The anomalous excess proton conductance, λ°<SUB>E</SUB>, as estimated by the equation [λ°<SUB>E</SUB>=<I>Λ</I>° (HCl)−<I>Λ</I>°(KCl)], was found to increase with increasing pressure in 2,3,5,and 7 mol% TBA–water mixtures, but to decrease in 10 and 25 mol% TBA-water mixtures. The rate of increase with pressure of the excess proton conductance normalized to the molar concentration of water in the mixture was largest in a 2 mol% TBA mixture, and its magnitude decreased in the order: 2>3>0>5>>7>>10>>25 mol% of TBA. These results are compared with those obtained in ethanol–water mixtures and are discussed in relation to the effect of alcohol molecules on the water structure in the mixtures: the three-dimensional network of water in TBA–water mixtures is more stable at a lower mol% of alcohol, and collapses more rapidly with increasing alcohol content than in ethanol–water mixtures.
- 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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Matsukawa Kazuhito
Department of Applied Chemistry, Faculty of Engineering, Doshisha University
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