Gadeau's bath, one of the electrolytes of the aluminum refining, is composed of the ternary molten salt mixtures of sodium fluoride, barium fluoride, and aluminum fluoride.
We have experimented the thermal analysis and the X-ray diffraction for the binary sodium fluoride-barium chloride system, which is one side of the above-mentioned ternary system, and discussed these, results applying the treatment of the reciprocal ternary system.
1) At first. we calculated the free energy change of the next reactions.
2NaF+ BaCl
2=2NaCl+ BaF
2ΔG°1000°C=-5kcal/mol (1)
NaF+ BaCl
2=NaCl+ BaFClΔG°1000°C -5kcal/mol (2)
As a result, we think that the displacement reaction (1) has priority to the reaction (2).
2) In the binary barium fluoride-barium chloride system, the composition of BaF
2 45.8% (BaF
2: BaCl
2=1: 1 in mole ratio) shows the maximum melting temperature 1, 005°C, and this is assumed to be the melting point of the compound BaFCl (barium fluochloride) which is formed in this system
This binary system gives two minimum melting temperatures (e. g. 840°C at BaF
2 13.6% and 930°C at BaF
2 70%). The former is the eutectic temperature of BaCl
2-BaFCl system and the latter is that of BaFCl-BaF
2system.
3) As the results of the thermal analysis and X-ray diffraction, we concluded that the square of the Na, Ba/F, Cl reciprocal ternary system is divided into three triangles, i. e. NaF-BaF
2-BaFCl system, NaF-BaFCl-NaCl system and NaCl-BaFCl-BaCl
2system.
And then sodium fluoride-barium chloride system corresponds to the diagonal of the above-mentioned square, i. e. the pseudobinary system extending over three ternary systems.
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