Relative enthalpies for low-and high-temperature modifications of Na3FeF6 and for the Na3FeF6 melt have been measured by drop calorimetry in the temperature range 723–1318 K. Enthalpy of modification transition at 920 K, δtransH(Na3FeF6, 920 K) = (19 ± 3) kJ mol−1 and enthalpy of fusion at the temperature of fusion 1255 K, δfusH(Na3FeF6, 1255 K) = (89 ± 3) kJ mol−1 have been determined from the experimental data. Following heat capacities were obtained for the crystalline phases and for the melt, respectively: C p(Na3FeF6, cr, α) = (294 ± 14) J (mol K)−1, for 723 = T/K ≤ 920, C p(Na3FeF6, cr, β) = (300 ± 11) J (mol K)−1 for 920 ≤ T/K = 1233 and C p(Na3FeF6, melt) = (275 ± 22) J (mol K)−1 for 1258 ≤ T/K ≤ 1318. The obtained enthalpies indicate that melting of Na3FeF6 proceeds through a continuous series of temperature dependent equilibrium states, likely associated with the production of a solid solution. [...]
The relative enthalpies of melts in the system KF - K2NbF7 were measured by drop-calorimetry at the temperatures 1058, 1140 and 1208 K as a function of composition. Heat capacities of melted mixtures and enthalpies of mixing were determined using the experimental data. The molar heat capacity of melts diverges slightly from additivity. The molar enthalpy of mixing of melts shows small negative deviation from ideality which decreases with decreasing temperature. The thermal effect at mixing was assigned predominantly to association reactions producing more complex fluoroniobate anions. [...]
Enthalpy increment measurements on melts in the system KF-K2TaF7 were carried out by drop calorimetry at temperatures between 298 K and 1063, 1103 and 1143 K for selected compositions. Heat capacities of the melted mixtures and enthalpies of mixing have been determined. Careful calorimetric experiments showed small but distinct non-ideality of the melt. The molar heat capacity of melt exhibits small positive divergence from additivity. The molar enthalpy of mixing shows negative deviation from ideality which decreases with increasing temperature. The thermal effect at mixing was assigned predominantly to association reactions producing more complex fluorotantalate anions. The formation of complex anions with lower coordination number of Ta may not be excluded. [...]
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