On the formation of iron(III) hydroxo acetate complexes.

The formation of hydroxo acetate complexes of iron (III) ion has been studied at 25 degrees C in 3 M (Na)ClO4 ionic medium by measuring with a glass electrode the hydrogen ion concentration in Fe(ClO4)3-HClO4-NaAc mixtures (Ac = acetate ion). The acetate/metal ratio ranged from 0 to 6, the metal concentration varied from 0.005 to 0.06 M, whereas [H+] was stepwise decreased from 0.1 M to initial precipitation of hydroxo-acetates. This occurred, depending on the acetate/metal ratio, in the -log[H+] range 1.85-2.7. The potentiometric data are consistent with the presence of Fe3(OH)3Ac3(3+), Fe2(OH)2(4+), Fe3(OH)4(5+), Fe3(OH)5(4+) and, as minor species, of Fe3(OH)2Ac6+, FeAc2+, FeAc2+, FeOH2+ and Fe(OH)2+. Previously published EMF measurements with redox and glass half-cells were recalculated to refine the stability constants of FeAc2+, FeAc2+ and Fe3(OH)2Ac6+. Formation constants beta pqr for pFe(3+)+(q-r)H2O + rHAc reversible Fep(OH)(q-r)(Ac)r3p-q + qH+ (in parenthesis the infinite dilution value): logbeta 111 = -1.85 +/- 0.02 (-0.67 +/- 0.15), logbeta 122 = -3.43 +/- 0.02 (-1.45 +/- 0.15); logbeta 363 = -5.66 +/- 0.03 (-2.85 +/- 0.40), logbeta 386 = -8.016 +/- 0.006 (-4.06 +/- 0.15), logbeta 220 = -2.88 +/- 0.02 (-2.84 +/- 0.05), logbeta 340 = -6.14 +/- 0.18 (-6.9 +/- 0.4), logbeta 350 = -8.44 +/- 0.09 (-7.65 +/- 0.15).