Antimony(V) complexing with O-bearing organic ligands in aqueous solution: an X-ray absorption fine structure spectroscopy and potentiometric study

The stabilityand structure of aqueous complexes formed by pentavalent antimony (SbV) with simple organic ligands (acetic, adipic, oxalic, citric acids, catechol and xylitol) having O-functional groups (carboxyl, alcoholic hydroxyl, aliphatic and aromatic hydroxyl) typical of natural organic matter (NOM), were determined at 25°C from potentiometric and X-ray absorption fine structure spectroscopy (XAFS) measurements. In organic-free aqueous solutions, spectroscopic data are consistent with the dominant formation of SbV hydroxide species, Sb(OH)5 and Sb(OH)6-, at acid and near-neutral to basic pH, respectively. Potentiometric measurements demonstrate negligible complexing with mono-functional organic ligands (acetic) or those having non-adjacent carboxylic groups (adipic). In contrast, in the presence of poly-functional carboxylic, hydroxyl carboxylic acids and aliphatic and phenolic hydroxyl, SbV forms stable 1:1 or 1:3 complexes in coordination 6 with the studied organic ligands, over a wide pH range pertinent to natural waters (3 ≤ pH ≤ 9). The XAFS measurements show that in these species the central SbV atom has an octahedral geometry with 6 oxygen atoms from hydroxyl moieties and adjacent functional groups (O = C—OH and/or C—OH) of the ligand, forming bidendate chelate cycles. Stability constants for SbV-oxalate complexes generated from potentiometric experiments were used to model SbV complexing with di-carboxylic functional groups of natural humic acids. Our predictions show that in an aqueous solution of pH between 1 and 4 containing 1 μg/l of Sb and 5 mg/l of dissolved organic carbon (DOC), up to 15% of total dissolved Sb maybe bound to aqueous organic matter via di-carboxylic groups.