The Tl–I phase diagram revisited and the thermodynamic properties of thallium iodides

Abstract

The Tl–I system has been studied using differential thermal analysis, X-ray diffraction, and emf measurements on TlI concentration cells. A more accurate Tl–I phase diagram is presented, according to which the compounds existing in the Tl–I system are TlI, Tl₂I₃, and TlI₃. Thallium monoiodide melts congruently at 715 K and undergoes a polymorphic transformation at 440 K. The other iodides melt peritectically at 535 and 404 K, respectively. In contrast to what was reported previously, no compound of composition Tl₃I₄ has been obtained. Using experimental emf data, we evaluated relative partial molar thermodynamic functions of the TlI in alloys of the TlI–I system and the standard Gibbs free energy, enthalpy of formation, and standard entropies of TlI₃ (−ΔG₂₉₈⁰= 142.79 ± 0.73 kJ/mol, −ΔH₂₉₈⁰= 135.37 ± 2.85 kJ/mol, and S₂₉₈⁰= 263.3 ± 7.4 J/(mol K)) and Tl₂I₃ (271.39 ± 1.47, 262.40 ± 5.34, and 322.8 ± 13.2).