Dyeing behaviour of iron(III)-gallic acid complexes on wool as function of pH-dependent iron(III)-complex stoichiometry

Iron complexes with polyphenolics e.g. gallotannins and flavonoids have been used since ancient times for coloration of textiles, painting and preparation of inks. The composition of iron gall inks on historical artefacts has been investigated with modern instrumental methods. However the dyeing behaviour of iron-complexes with polyphenols still bases on empirical knowledge. In this study Fe(III)-complexes with gallic acid were used as model system to elucidate their pH dependent sorption and dyeing behaviour on wool. At dyebath pH 3 high sorption of Fe(III)-gallic acid complexes was observed, however darker dyeings were obtained at dyebath pH 4. Model calculations for the complex species present in the dyebath indicated the presence of the binary complex [Fe(III)(GA 2− )] + as main species at pH 3, while at pH 4 the ternary species [Fe(III)(GA 2− ) 2 ] - prevails. The dye sorption bases on Van-der-Waals forces, while ionic interactions between Fe(III)-complex and keratin are of minor relevance. The elaborated theoretical model also explains the influence of dyebath pH in dyeing with gallotannins, polyphenols and flavonoids in presence of iron salts and thus is of particular relevance for improved utilisation of these natural colorants. • Iron(III)-gallic acid complexes exhibit pH dependent colour depth in wool dyeing. • Model calculations indicate presence of different complex species at pH 3 and pH 4. • At pH 3 the [Fe(III)(GA 2− )] + is the main species, at pH 4 [Fe(III)(GA 2− ) 2 ] - prevails. • Presence of different iron(III)-complexes explains pH dependent colour depth. • Van-der-Waals forces determine the sorption of iron(III)-gallic acid complexes.