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Minerals of the stannite group are typical for tin depositions and their synthetic analogues are intensively used as promising functional material first of all in solar cells. Effective geochemical determinations and applied researches can’t be done because of the lack of thermodynamic data. Lately there were several publications where standard enthalpy was determined by ab-initio method (Jackson, Walsh, 2014) however, the discrepancy in the data reaches about 50-100 kJ/mol. In our work we for the first time we determined primary value of standard enthalpy of formation of stannite and kesterite. For stannite ∆rH0298.15 = 238.76 kJ/mol and for kesterite ∆rH0298.15 = 170.9 kJ/mol.