Polarographic Studies of Some Metal Ions in Fused LiCl-KCl and NaF-KF-LiF Eutectics by Using Improved Molybdenum Microelectrode of Dipping Type

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In the first place, polarographic Studies of various metallic ions in fused LiCl-KCl eutectic at 450℃ were carried out by using improved molybdenum microelectrode of dipping type. By using a spiral molybdenum wire or a chlorine reference electrode as anode, effects of temperature, concentration of reducible species, microelectrode area and gas bubbling rate over the microelectrode surface were examined with Zn(II) as an example. The limiting current was independent of the gas bubbling rate from 0.5 to 3.5 sec/bubble and directly proportional to the microelectrode area and to the concentration of Zn(II). From the result of the temperature dependence of limiting current, the activation energy of the electrode process at the voltage showing limiting current was determined as 4.6 kcal/mole of Zn(II). This value may show that the limiting current obtained by this electrode is diffusion-controlled. From the polarographic behavior of Zn(II), it was concluded that this electrode reaction should be completely irreversible, because the relationship of log(i_d-i)/i vs. E was linear, the slope being 150 mV at 450℃. Following the above fundamental studies, polarographic behaviors of T1(I), Cu(II), Cd(II), Al(III) and U(IV) were examined mainly on the relation between i〜E curves and half-wave potentials. In the second place, polarographic studies of lead(II) ion in fused KF-NaF-LiF eutectic at 650℃ were carried out by improving the microelectrode mentioned above. The polarogram obtained showed an S-shaped form without a bend, and resembled that in the fused chloride. The relation between applied voltage and log(i_d-i)/i was linear. The half-wave potential was -0.55±0.01 V vs. the molybdenum anode and the limiting current was proportional to the concentration of lead(II) ion ranging from 1.95〜4.60 mmoles per 1000 g fused salt.
東北大学の論文

Polarographic Studies of Some Metal Ions in Fused LiCl-KCl and NaF-KF-LiF Eutectics by Using Improved Molybdenum Microelectrode of Dipping Type

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