Calorimetric and dielectric studies of a phase transition in thallium dihydrogen phosphate: A nearly critical case

The heat capacity of thallium dihydrogen phosphate was measured from 12 to 300 K. A lambda anomaly with a small first order discontinuity was found at 229.76 K with the integrated enthalpy and entropy changes equal to 370 J mol^-1 and 1.8 J K^-1 mol^-1, respectively. The entropy discontinuity at the first order transition is 0.25 J K^-1 mol^-1. The Landau theory of phase transitions of the second kind reproduces closely the temperature dependence of the anomalous heat capacity. This, together with the small discontinuity in the entropy, implies that the phase transition is close to a classical critical point of higher order. The relative dielectric permittivity ?_r(b) along the b-axis at 1 kHz is anomalously large and strongly temperature dependent, while the ?_r(a¹) and ?_r(c) are not. A broad absorption centered at 1700 cm^-1 was observed in the infrared absorption spectrum, indicating presence of hydrogen bonding of the length ～ 0.25 nm. Occurrence of a phase transition at 127 ± 2 K was suggested by differential thermal analysis of thallium dideuterium phosphate.