Phase transition and freezing of ionic disorder in CsNO2 and TINO2 crystals2

The heat capacities of CsNO₂ and TlNO₂ have been measured in the temperature region between 13 and 350 K. The phase transitions of CsNO₂ and TlNO₂ were found at (209.16 ± 0.10)K and (282.4 ± 0.1)K. The enthalpy and entropy of the phase transition were (3.45 ± 0.20) kJ mol^?1 and (17.2 ± 1.0) JK^?1 mol^?1 for the former, and (6.44 ± 0.31) kJ mol^?1 and (23.8 ± 1.1) JK^?1 mol^?1 for the latter. The glass transitions were found around 42 K in CsNO₂ and around 60 K for TlNO₂, respectively. The corresponding dielectric relaxations were observed between 58 and 130 K for CsNO₂ in the frequency range between 10² and 10⁵ Hz and between 80 and 180 K for TlNO₂ in the frequency range between 2 × 10² and 10⁵ Hz. The calorimetric and dielectric relaxation times yielded a straight line in the Arrhenius plot over a wide time scale ranging from 10^?6 to 10⁵ sec. The slope gave the activation enthalpy of 13.8 kJ mol^?1 and 19.5 kJ mol^?1 for CsNO₂ and TlNO₂, respectively. The transition entropy supplemented by a residual entropy R ln 3 for CsNO₂ and R ln 2 for TlNO₂ gave (26.3 ± 1.0) JK^?1 mol^?1 and (29.6 ± 1.1) JK^?1 mol^?1 for the orientational entropy of the NO₂^? ion in the high-temperature phase. Based on the packing and symmetry considerations, these entropies were interpreted by the model which included two different sets of orientations of the NO₂^? ions parallel to 110] and 111] in the CsCl type unit cell. The existence of the different sets of orientation was proved by the doublet (Δv ~ 10 cm^?1) of the Raman spectrum of the bending mode of the NO₂^? ion in the cubic phase of the CsNO₂ crystal. The band narrowed to an ordinary singlet with increasing temperature. This observation was accounted for as the motional narrowing in which the NO₂^? ion felt an averaged field of the two different sets owing to the increased rate of jumping as the temperature increased.