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By Sydney Marks

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It may be assumed that these peaks arise due to the different BÐF and BÐCl valence vibrations in the anions [BF4−n Cln ]− . The substitution of the ßuorine atom by chlorine in the coordination sphere of the BF− 4 4 anion in the molten KFÐKClÐKBF mixtures was thus conÞrmed. However, the type of the mixed anion was determined neither by physico-chemical analysis nor by spectroscopic methods. 11. Excess Gibbs energy of mixing of the system KFÐKClÐKBF4 . Values are in J · mol−1 . 12. Excess molar volume of the system KFÐKClÐKBF4 at 1100 K.

In systems of this type, the deviation from additivity is proportional to the fractional difference in the radii of different anions. Therefore a relatively large deviation from ideality may be expected, which was conÞrmed by all measured physico-chemical properties. An opposite interaction effect takes place in the system KClÐKBF4 where the mixing of − two relatively large and polarizable anions BF− 4 and Cl occurs. As was found by Sangster and Pelton (1987), no important deviations from additivity were found in systems of alkali metal chlorides, bromides, and iodides with a common cation.

7, it follows that in molten LiCl, the BF− 4 anion undergoes exchange − reaction under the formation of BCl4 ions. 34) and gaseous BCl3 escapes from the melt. Consequently, the number of new particles in the melt decreases (kSt < 6) and the remaining melt corresponds to the ternary system LiFÐLiClÐKCl. 33) in this concentration range. 7. LiCl melting point depression in the system LiClÐKBF4 . 1ÐkSt = 2; 4ÐkSt = 5; 5ÐkSt = 6. 8. NaCl melting point depression in the system NaClÐKBF4 . 1ÐkSt = 2; 2ÐkSt = 6.

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