Kitaoka K
Radioisotopes. 1981 May;30(5):247-52.
The electrolytic enrichment process of tritium is in current use for the measurement of its content in natural water. The electrolytic separation factor of tritium which can have experimental values ranging from 4 to 30 is affected by the nature of the cathode, by the electric current density, and by the nature of the electrolyte. It was recently shown that the factor took a value within a limited range when an alkaline solution was electrolyzed by the use of a nickel-cathode cell under a current density around 50 mA/cm2. To re-examine the reproducibility of the separation factor of tritium, the electrolytic enrichment experiment was made using nickel-nickel electrode cells, 0.05 N-alkaline solutions, and a current density of 50 mA/cm2. The observed separation factors were within the range previously reported on nickel-cathode cells. The results, after they were corrected for the carry-over of water vapor and spray droplets, were close to the thermodynamic equilibrium constants for the protium-tritium exchange reaction between liquid water and hydrogen gas at several solution temperatures in the cell ranging from 12 degree C to 33 degree C. The equilibrium conditions would be expected to prevail and to make the factor reproducible, so far as the above conditions were used. At the current densities above 50 mA/cm2 up to 100 mA/cm2, on the other hand, the factors obtained in this work were slightly more than that corresponding to equilibrium, and had a tendency to rise with increase of current density. It is considered that slow exchange by rate process are apt to take place partly at the cathode surface under the condition of such high current strength.
目前,氚的电解浓缩过程用于测量天然水中的氚含量。氚的电解分离系数的实验值范围为4至30,它受阴极性质、电流密度和电解质性质的影响。最近有研究表明,当使用镍阴极电解池在电流密度约为50 mA/cm²的条件下电解碱性溶液时,该系数在有限范围内取值。为了重新检验氚分离系数的可重复性,采用镍 - 镍电极电解池、0.05 N碱性溶液以及50 mA/cm²的电流密度进行了电解浓缩实验。观察到的分离系数在先前关于镍阴极电解池报道的范围内。在对水蒸气和喷雾液滴的夹带进行校正后,结果在电解池内从12℃至33℃的几个溶液温度下接近液态水与氢气之间质子 - 氚交换反应的热力学平衡常数。只要使用上述条件,预计平衡条件会占主导地位并使该系数具有可重复性。另一方面,在电流密度高于50 mA/cm²直至100 mA/cm²时,本研究中获得的系数略高于对应平衡时的系数,并且有随电流密度增加而上升的趋势。据认为,在如此高电流强度条件下,部分缓慢的速率过程交换容易在阴极表面发生。