Review of the hydrolysis of iron(III) and the crystallization of amorphous iron(III) hydroxide hydrate

Abstract Hydrolysis of ferric solutions leads initially to mono‐ and dinuclear species which interact to produce further species of higher nuclearity. These polynuclear species age eventually to either crystalline compounds or to an amorphous precipitate (amorphous iron(III) hydroxide hydrate). Amorphous iron(III) hydroxide hydrate is thermodynamically unstable and gradually transforms to α‐FeO(OH) and α‐Fe 2 O 3 . These crystalline products form by competing mechanisms and the proportion of each in the final product depends on the relative rates of formation. The master variable governing the rates at which these compounds form is pH. Other important factors are temperature and the presence of additives. Most additives retard the transformation and by suppressing formation of α‐FeO(OH) lead to an increase in the amount of α‐Fe 2 O 3 in the product; some additives also directly promote formation of the latter compound. Metal ions can oftxen replace a proportion of Fe in the α‐FeO(OH) and α‐Fe 2 O 3 lattices. At high enough concentrations they can induce formation of additional phases. Additives may also modify the morphology of the crystalline products.