Heat capacity thermodynamic functions of sphalerite: Implication to sulfide solid-state galvanic cell measurementsстатья
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Дата последнего поиска статьи во внешних источниках: 4 декабря 2016 г.
Аннотация:New adiabatic calorimeter measurements of heat capacity of sphalerite from 13.23 to 312.85 K at ambient pressure agree well with previous adiabatic calorimeter results but overestimate PPMS-derived data (Cardona et al., 2010) at T > 150 K. The adiabatic calorimeter low-temperature heat capacity data and drop-calorimetric high-temperature data on H0(Т) − H0(298.15) are rationalized in the framework of the Kieffer-type vibrational spectrum model accounting for dependence of vibrational frequencies on volume and temperature. Thermodynamic properties of sphalerite are calculated by the elaborated model from 0 to 1300 K.
Present calorimetric results conform to those from high-temperature electromotive force (EMF) experiments (Osadchii et al., 2015) using the Cu/Cu2S buffer. The disagreement with data based the Ag/Ag2S buffer is explained by deviation of silver sulfide from stoichiometry in the EMF experiments. A correction to the Gibbs energy of formation obtained in high-temperature EMF experiments using the Ag/Ag2S buffer is suggested.