Vaporization and caloric studies on lead titanate

• First time complementary gas phase and solid state experiments.
• Experimental determination of the heat of transition for ferro-paraelectric phase change.
• Experimental and empirical determination of the heat of formation and heat of reaction of PbTiO3.
• Determination of polynomial functions of the heat capacity Cp(T)0 of PbTiO3. Clarification of vaporization processes of PbO and PbTiO3.
• Determination of the activity of Pb and PbO in PbTiO3. Revision of the characteristic value for the Anion (TiO32−) in Le Van׳s approach.

Thermodynamic studies of a single crystal lead titanate (PbTiO3) under equilibrium conditions by the method of Knudsen effusion mass spectrometry (KEMS) were conducted in the temperature range 950–1210 K. The vaporization of pure PbO(c) was investigated at temperatures of 810–1040 K. Thermodynamic quantities of sublimation enthalpy, activity, and entropy were derived from the partial pressures of gaseous Pb, PbO, and O2 over the lead titanate and pure lead oxide reference samples. The sublimation enthalpy of Pb from PbTiO3(c) at T=1080 K was ΔsubH1080K0(Pb)=(340±11)kJmol−1 and for PbO was ΔsubH1080K0=(251±12)kJmol−1. Heat capacity measurements under constant pressure (Cp(T)0) by dynamic scanning calorimetry (DSC) in the temperature range 298–1273 K resulted in two polynomial equations. The Cp(T)0 values increased from 106 to 139±0.2J mol−1 K−1 below the ferroelectric–paraelectric phase transition at Tc=763 K, and Cp(T)0≅(112±0.3) J mol−1 K−1 was almost constant above Tc. The low values of entropy, ΔtrsS=(2.1±0.9) J mol−1 K−1 and enthalpy, ΔtrsH=(1.57±0.7) kJ mol−1, and the λ   (lambda)-shape of the ferro-paraelectric phase change in the Cp(T)0 function suggest that the transition can be classified as a first order one with a tendency to a continuous one. The enthalpy and the entropy values were calculated from the Cp(T)0 polynomials and from the vaporization studies. Deduced from empirical and experimental approaches, the heat of reaction was ΔrH2980(PbTiO3(c))=−(26.4±1.8)kJmol−1 and the heat of formation was ΔfH2980(PbTiO3(c))=−(1190.4±3.9)kJmol−1. The thermodynamic activity of Pb and PbO in lead titanate was temperature dependent and their values were a=(8.67±2.9)10−4, and (9.96±3.6)10−3, respectively, at a temperature of 1000 K. Near the ferroelectric–paraelectric phase change at 770 K, PbTiO3(c) has a long-term stability.