Iveta Macková

Determination of the enthalpy of fusion of Na3FSO4

The areas of the fusion and crystallization peaks of Na3FeF6 and of four calibration substances (KCl, NaCl, Na2SO4, and K2SO4) were measured using the DSC mode of a high-temperature calorimeter. Using the measured quantities and known values of the enthalpy of fusion of the calibration substances, the enthalpy of fusion of Na3FeF6 was determined. Its value at the temperature of fusion 1224 K was 70 ± 4 kJ mol−1.

K(3)TaF(8) from laboratory X-ray powder data.

The crystal structure of tripotassium octafluoridotantalate, K(3)TaF(8), determined from laboratory powder diffraction data by the simulated annealing method and refined by total energy minimization in the solid state, is built from discrete potassium cations, fluoride anions and monocapped trigonal-prismatic [TaF(7)](2-) ions. All six atoms in the asymmetric unit are in special positions of the P6(3)mc space group: the Ta and one F atom in the 2b (3m) sites, the K and two F atoms in the 6c (m) sites, and one F atom in the 2a (3m) site. The structure consists of face-sharing K(6) octahedra with a fluoride anion at the center of each octahedron, forming chains of composition [FK(3)](2+) running along [001] with isolated [TaF(7)](2-) trigonal prisms in between. The structure of the title compound is different from the reported structure of Na(3)TaF(8) and represents a new structure type.

Phase transitions of K2TaF7 within 680–800°C

Three thermal effects on heating/cooling of K2TaF7 in the temperature interval of 680–800°C were investigated by the DSC method. The values determined for the enthalpy change of the individual processes are: ΔtransIIHm(K2TaF7; 703°C) = 1.7(2) kJ mol−1, ΔtransIHm(K2TaF7; 746°C) = 19(1) kJ mol−1 and ΔtransIIIHm(K2TaF7; 771°C) = 13(1) kJ mol−1. The first thermal effect was attributed to a solid-solid phase transition; the second to the incongruent melting of K2TaF7 and the third to mixing of two liquids. These findings are supported by in situ neutron powder diffraction experiments performed in the temperature interval of 654–794°C.

Density of the systems (NaF/AlF3)—AlPO4 and (NaF/AlF3)—NaVO3

The densities of two systems of molten mixtures (NaF/AlF3)—NaVO3 and (NaF/AlF3)—AlPO4 were measured using an Archimedean method. Each molten mixture contained varying amounts of “impurity” constituents. The measurements were performed at various NaF/AlF3 mole ratios (CR, cryolite ratio), equal to 3, 2.5, 2, and 1.5.

Determination of the enthalpy of fusion of K3TaO2F4 and KTaF6

Areas of fusion and crystallization peaks of K3TaO2F4 and KTaF6 were measured using the DSC mode of a high-temperature calorimeter (SETARAM 1800 K). On the basis of these quantities, considering the temperature dependence of the calorimeter sensitivity, values of the fusion enthalpy of K3TaO2F4 at the fusion temperature of 1181 K of (43 ± 4) kJ mol−1 and of KTaF6 at the fusion temperature of 760 K of (8 ± 1) kJ mol−1 were determined.

Determination of the enthalpy of fusion of K3NbO2F4

Areas of fusion and crystallization peaks of K3NbO2F4 were measured using the DCS mode of a high-temperature calorimeter (SETARAM 1800 K). On the basis of these quantities, considering the temperature dependence of the calorimeter sensitivity, the value of the fusion enthalpy of K3NbO2F4 of (98 ± 6) kJ mol−1 was determined at the fusion temperature of 1257 K.