Thermodynamic characterization of Ni3TeO6, Ni2Te3O8 and NiTe2O5

Abstract

Measurement of vapour pressure of TeO2(g) over the biphasic mixture Ni3TeO6 (s) + NiO(s) in the temperature range 1143–1272 K was carried out using transpiration-thermogravimetric technique (TTG). Gibbs energy of formation of Ni3TeO6 was obtained from the temperature dependence of vapour pressure of TeO2 (g) generated by the incongruent vapourisation reaction, Ni3TeO6 (s) → NiO(s) + TeO2 (g) + 12 O2 in the temperature range 1143–1272 K. An isoperibol type drop calorimeter was used to measure the enthalpy increments of Ni3TeO6, Ni2Te3O8 and NiTe2O5. Thermodynamic functions viz., heat capacity, entropy and Gibbs energy functions of these compounds were derived from the experimentally measured enthalpy increment values. Third-law analysis was carried out to ascertain absence of temperature dependent systematic errors in the measurement of vapour pressure of TeO2 (g). A value of −1265.1 ± 1.5 kJ mol−1 was obtained for ΔHf,298Ko (Ni3TeO6) using third-law analysis.