1972 Volume 58 Issue 8 Pages 1126-1133
The relations between electrode potentials of buffed surface of iron in chromate solutions and pH values of the solutions were studied in relation to the corrosion region (pH<4) in the Pourbaix diagram for the Fe-Cr03-H20 system at 25°C. The results obtained were as follows:
The buffed surface is covered with thin Fe304 films. The electrode potentials vary with the pH values and the presence of anions, Cl- and SO2-4. The surface reactions are estimated from the observed pH- potential relations as follows:
(1) 0<pH<2;
3Fe+6Fe3O4+4CrO2-4aq+26H+=3Fe2++9γ-Fe2O3+4Cr3+aq+13H2O
(2) 2<pH<4;
3Fe+6Fe3O4+4CrO2-4aq+10H+=3Fe2++9γ-Fe2O3+4CrO-2aq+5H2O
The electrode potentials of the Fe304 film depend on the presence of anions, Cl- and SO2-4, and on the structure of chromic ion species, and concerned with the solid state electrolyte reaction, i. e. the dissolution of Fe2+ ion from iron crystal surface into the thin Fe3O4 film.
The Fe3O4 film is rapidly dissolved in the solution by the presence of Cl- or SO2-4, and the surface reactions of pure iron without oxide film are estimated from the observed potentials as follows:
(1) 0<pH<2;
Fe+CrO2-4aq+8H+aq=Fe3+aq+Cr3+aq+4H2O
(2) 2<pH<4;
Fe+CrO2-4aq+3H+aq=FeOH2+aq+CrO-2aq+H2O
The dissolution reactions and their electrode potentials of pure iron in chromate solutions depend on the structures of both chromic ion and ferric ion species.