Orientational and positional disorder of ions and its freezing in the CsNO2-TlNO2 system2

The heat capacities of Cs_0.695Tl_0.305NO₂ (Specimen I) and Cs_0.385Tl_0.615NO₂ (Specimen II) have been measured between 14 and 350 K. Specimen I underwent a phase transition at (197.7 ± 0.1) K, with ΔS = (19.2 ± 1.5) JK^?mol^?, and specimen II at (214.5 ± 0.2) K, with ΔS = (5.4 ± 1.0) JK^?1mol^?1, respectively. Above the phase transition, an exothermic temperature drift due to phase separation was observed. Annealing of the sample at 203 K for 300 hr brought about complete phase separation. The solid solution system annealed at 203 K gave two heat capacity peaks at (203.3 ± 0.1) K, with ΔS = (13.8 ± 0.8) JK^?1 mol^?1, and (242.4 ± 0.2) K, with ΔS = (10.6 ± 1.3) JK^?1 for Specimen I, and at (203.0 ± 0.1) K with ΔS = (6.7 ± 0.5) JK^?1 mol^?1, and (257.5 ± 0.2) K with ΔS = (17.9 ± 1.7) JK^?1 mol^?1 for Specimen II. The phase diagram of the CsNO₂-TlNO₂ binary system was constructed on the basis of DTA, heat capacity and dielectric measurements. In the metastable phase, the existence of a residual entropy due to the freezing of a random distribution of Cs⁺₁ and Tl⁺ cations in addition to the orientational disorder of the NO₂^?1 ion was confirmed by a comparison of entropies of the stable and the metastable phases.