RI 8096 Free Energies of Formation of Ferrous and Ferric Fluoride by Electromotive Force Measurements

The Bureau of Mines studied the standard free energies2 of formation of ferrous fluoride (FeF2) and ferric fluoride (FeF3) with high-temperature galvanic cells employing calcium fluoride doped with 1 mole-pet yttrium fluoride as the electrolyte. A free-energy change for the cell reaction Fe (s) + NiF2 (S) = FeF2 (S) + Ni (s) together with the standard free energy of formation of nickel fluoride yields a standard free energy of formation of ferrous fluoride from the elements of ?GF° = -168.74 + 30.63 x 10-3T ± 0.41 kcal/mole (897-1,098 K). (2) Combining the standard free energies of formation of magnesium fluoride, ferric oxide, and magnesium oxide with the free-energy change for the overall cell reaction 3MgO(s) + 2FeF3 (s) = 3MgF2 (S) + Fe2 03 (S) (3) gives a standard free energy of formation of ferric fluoride from the elements as ?Gf° = -281.45 + 90.46 X 10-3T ± 0,67 kcal/mole (880-935 K). (4) Free energies and equilibrium fluorine pressures for the two univariant equilibria of the Fe-F system are tabulated and illustrated.