Abstract
The molar enthalpies of mixing (ΔmixHm) in the liquid cerium(III)−alkali metal bromide mixtures were measured with a Calvet- type high temperature microcalorimeter over the entire composition range at 1073 K. Mixing the two liquid components was achieved by using the “break-off ampule technique”. All the melts are characterized by negative enthalpies of mixing with a minimum value of approximately −5.3 kJ·mol−1, −12.7 kJ·mol−1, −16.1 kJ·mol−1, and −18.4 kJ·mol−1, for M = Na, K, Rb, and Cs, respectively. For all the systems, the minimum of the enthalpy of mixing is shifted toward the alkali bromide-rich compositions and located in the vicinity of x(CeBr3) ∼ 0.4. The composition dependence of the interaction parameter λ, with a broad minimum at x(CeBr3) ∼ 0.2 for the systems with KBr, RbBr, and CsBr is indicative of LnBr63− complexes formation in the melts.
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