The Cr---Cr 2 O 3 oxygen buffer and the free energy of formation of Cr 2 O 3 from high-temperature electrochemical measurements

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The free energy of formation of Cr 2 O 3 , defined by the reaction 2 Cr + 3/2 O 2 = Cr 2 O 3 has been measured electrochemically using a yttria-doped thoria (YDT) solid electrolyte, in the temperature range from 900 to 1400 K. Fe + "FeO" was used as the reference electrode. The results have been combined with high temperature heat capacity data from the literature, to give, in J · mol -1 O 2 (±170) = -758.585 + 349.718 T -25.5216 T + 0.00935 T 2 (600 K < T < 1800 K) Our results are not in good agreement with the calorimetric data and imply that the currently accepted calorimetric value for the entropy of Cr 2 O 3 at 298.15 K may be too low by 4.6 J/K · mol.

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