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本文成功地将Darken法,即从三元系的热力学性质计算二元系活度的方法,应用于熔盐体系,克服了因金属与熔盐发生相互作用而造成的困难。作为第一个例子,文中在待测的二元系中加入电位较正和稳定的第三氯化物,利用Ag|AgCl可逆电极测定了Ag在AgCl-CeCl_3-KCl三元系熔体的电动势,从而得出了AgCl-CeCl_3-KCl(N_(CeCl_3):N_(KCl)≈2:1或1:2),AgCl-CeCl_3以及AgCl-KCl体系中AgCl的活度。根据AgCl-CeCl_3-KCl体系的等ΔF~E图和该三元系中CeCl_3的等活度图,用Darken法算得CeCl_3-KCl二元系的活度和热力学性质。所得结果与文献的实测值相近,也显示一定的负偏差。
The Darken method, that is, the method of calculating the activity of the binary system from the thermodynamic properties of the ternary system, is successfully applied to the molten salt system to overcome the difficulties caused by the interaction between the metal and the molten salt. As a first example, the electromotive force of Ag in AgCl-CeCl_3-KCl ternary melt was measured by Ag | AgCl reversible electrode by adding the more stable and stable third chloride to the binary system to be tested. The activity of AgCl in AgCl-CeCl_3-KCl (N_ (CeCl_3): N_ (KCl) ≈2: 1 or 1: 2), AgCl-CeCl_3 and AgCl-KCl systems was obtained. The activity and thermodynamic properties of the CeCl_3-KCl binary system were calculated by the Darken method according to the isoforms ΔF-E of AgCl-CeCl_3-KCl system and the activity diagrams of CeCl_3 in the ternary system. The results obtained and the actual value of the literature similar, but also shows a certain negative bias.