Pressure and temperature effects on the excess deuteron and proton conductance |
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| Authors: | Yuichiro Tada Masakatsu Ueno Noriaki Tsuchihashi Kiyoshi Shimizu |
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| Affiliation: | (1) Department of Applied Chemistry, Faculty of Engineering, Doshisha University, Kamigyo-ku, 602 Kyoto, Japan |
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| Abstract: | The limiting molar conductances  ° of deuterium chloride DCl in D2O were determined as a function of pressure and temperature in order to examine the proton-jump mechanism in detail. The excess deuteron conductances  °E(D+), as estimated by the equation [°E(D+) = °(DCl/D2O) – °(KCl/D2O)], increases with an increase in the pressure and temperature as well as the excess proton conductance [°E(H+) = °(HCl/H2O) – °(KCl/H2O)]. The isotope effect on the excess conductances, however, depends on the pressure and temperature contrary to the model proposed by Conway et al.: °E(H+)/°E(D+) decreases with increasing pressure and temperature. The magnitude of the decrease with pressure becomes more prominent at lower temperature. These results are discussed in terms of the pre-rotation of adjacent water molecules, the bending of hydrogen bonds with pressure, and the difference in strength of hydrogen bonds between D2O and H2O. |
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| Keywords: | Deuterium chloride heavy water proton jump excess conductance pressure and temperature effect isotope effect |
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