高圧下におけるハロゲン化物イオンの水中での電気伝導度に対する溶媒同位体効果(<小特集>高圧力小特集)

概要

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For the purpose of disclosing the mechanism of conductivity for halide ions, the limiting molar conductivities of Br^- and I^- ions in heavy and light water have been determined at 25℃ as a function of pressure up to 196.1 MPa (2000 kgf cm^<-2>). The residual friction coefficients (Δζ_<obs>) of the halide ions were compared with the dielectric friction coefficients (Δζ_<HO>) obtained from the Hubbard-Onsager dielectric friction theory. The continuum theory showed a serious limitation : (1) Contrary to the theoretical prediction, Δζ_<obs> was negative at each pressure in both D_2O and H_2O, and was smaller in D_2O than in H_2O. These discrepancies between the theory and the experiment became larger with an increase in ion size. (2) With increasing pressure, Δζ_<ohs> (Cl^-) and Δζ_<ohs> (Br^-) decreased, while Δζ_<obs> (I^-) showed a reverse tendency. These results were discussed in terms of the passing through cavities mechanism and the specific interaction between halide ions and water molecules.
社団法人日本材料学会の論文
1992-03-15