Heat capacity and thermodynamic properties of PbS: Optimization based on calorimetric and electrochemical data

Abstract

Heat capacity of PbS (galena) has been measured in the temperature range from 12 to 338 K using adiabatic calorimetry. Results of the measurements are consistent with previous adiabatic calorimetric data measurements but differ notably from those obtained by relaxation calorimetry. Using experimental data on adiabatic heat capacity measurements in the range of 12–338 K (including our data), results of EMF measurements, and literature data on H0(T) – H0(298.15 K) as inputs, we have optimized the thermodynamic properties of lead sulfide (PbS, galena) based on the quasi-harmonic model vibrational spectrum proposed by Kieffer and advanced to consider intrinsic anharmonicity. In this approach, the volume and temperature dependence of vibrational frequencies are considered, and the enthalpy of formation of PbS, ΔfH0(298.15 K), is treated as an optimized model parameter. The thermodynamic properties of PbS are described with a single set of model parameters over the entire range of its stability (0–1374 K) at a pressure of 1 bar. The model can be optimized based on either the reduced (Cp0 and ΔfG0(T)) or full (Cp0, H0(T) – H0(298.15 K), ΔfG0(T)) datasets. The both variants of the optimization predict the similar thermodynamic properties of PbS, in particular, values of the enthalpies of formation differ less than 0.1 kJ mol−1 and are consistent with ΔfH0(298.15 K) obtained experimentally by oxide melt solution calorimetry. The low-temperature adiabatic calorimetry data and high-temperature results of EMF experiments (or other reliable experimental data on ΔfG0(T)) represent a minimal sufficient set of input data providing optimization of thermodynamic properties at ambient pressure by the technique established in present study.