Heats of solution/substitution in TlNO3 and CsNO3 crystals and in RbNO3 and CsNO3 crystals from heats of transition: the complete phase diagrams of TlNO3-CsNO3 and RbNO3-CsNO3 systems

From measurements of the decrease in the heat (enthalpy) of transition in the solid phase using differential scanning calorimetry, the apparent molar heats of solution, slope ΔH_t/x, the partial molar heats of solution at infinite dilution, χ, and the heats of solution, ΔH_s^°, of Tl⁺ in CsNO₃ crystal and Cs⁺ in TlNO₃ crystal and Rb⁺ in CsNO₃ crystal and Cs⁺ in RbNO₃ crystal along with their recovered lattice energies, ΔH_L^°, are reported. ΔH_s^° of Tl⁺ and Rb⁺ in CsNO₃ crystal are each found to be negligible or zero representing an ideal solid solution, i.e. ΔH_mix=0. The complete phase diagrams of the TlNO₃-CsNO₃ and RbNO₃-CsNO₃ systems with details of the sub-solidus regions are included. The properties of Tl_(1−x)Cs_xNO₃ and Rb_(1−x)Cs_xNO₃ compositions are discussed in terms of a ‘mixed crystal’ or ‘crystalline solid solution’ in relation to parallel compositions of Tl_(1−x)Rb_xNO₃.