Phase transition and freezing of ionic disorder in CsNO2 and TINO2 crystals†

doi:10.1016/0022-3697(83)90134-8

Journal of Physics and Chemistry of Solids

Volume 44, Issue 12, 1983, Pages 1103-1119

https://doi.org/10.1016/0022-3697(83)90134-8 Get rights and content

Abstract

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.

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^☆: †Contribution No. 47 from Chemical Thermodynamics Laboratory.

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Phase transition and freezing of ionic disorder in CsNO2 and TINO2 crystals†☆

Abstract

J. Solid St. Chem.

J. Chem. Thermodyn.

Chem. Phys. Letters

J. Chem. Thermodyn.

J. Phys. Chem. Solids

J. Chem. Thermodyn.

J. Non-Cryst. Solids

Solid St. Commun.

J. Chem. Thermodyn.

Gazz. Chim. Ital.

Gazz. Chim. Ital.

Ber. Dtsch. Chem. Ges.

Can. J. Chem.

Netsusokutei

Bull. Chem. Soc. Japan

J. Phys. Soc. Japan

Bull. Chem. Soc. Japan

Can. J. Chem.

Z. Electrochem.

Phase transition and freezing of ionic disorder in CsNO₂ and TINO₂ crystals†☆