Chemical composition and Gibbs standard free energy of formation of Fe(II)-Fe(III) hydroxysulphate green rust and Fe(II) hydroxide

Abstract

Abstract The redox potential and pH of aerated suspensions of iron(II) hydroxide in sulphate–containing aqueous solutions are measured during the oxidation process. Plateaux corresponding to the equilibrium conditions between Fe(OH) 2(s) and Fe(II)-Fe(III) hydroxysulphate GR2(SO 2- 4 ) (s) on the one hand, and between GR2(SO 2- 4 ) (s) and FeOOH (s) on the other hand, are displayed. Potentiometry, voltammetry, pH-metry and Mössbauer spectroscopy are applied to follow all reactions. The thermodynamic meaning of the measured potential of the first plateau which corresponds to the GR2(SO 2- 4 ) (s) /Fe(OH) 2(s) equilibrium is demonstrated. The chemical composition of GR2(SO 2- 4 ) (s) is found to be Fe II 4 Fe III 2 (OH) 12 SO 4 · n H 2 O all along the oxidation process, implying that this compound must be considered as a pure phase with a well-defined composition. The Gibbs standard free energy of formation or chemical potential μ°[GR2(SO 2- 4 ) (s) ] in ‘anhydrous form’ ( n = 0) is determined at −3790±10 kJ mol -1 . A consistent value of μ°[Fe(OH) 2(s) ] at −490±1 kJ mol -1 is obtained.