Sequestration of Aluminium(III) by different natural and synthetic organic and inorganic ligands in aqueous solution

Abstract

The speciation of Al³⁺ in aqueous solutions containing organic and inorganic ligands important from a biological (citrate (Cit^3-), gluconate (Gluc^-), lactate (Lac^-), silicate (H₂SiO₄^2-), carbonate (CO₃^2-), fluoride (F^-)) and industrial (Gantrez^®; polymethyl-vinyl-ether-co-maleic acids; GTZ S95 and GTZ AN169) point of view is reported. The stability constants of Al³⁺/L^z- complexes (L^z- = ligand with z^- charge) were determined by potentiometry at T = 298.15 K and 0.10 ≤ I/M ≤ 1.00 in NaCl_(aq) (in NaNO_3(aq) only for Al³⁺/GTZ S95 and Al³⁺/Gluc^- acid systems). For Al³⁺/Cit^3-, Al³⁺/Lac^- and Al³⁺/GTZ AN169^4- systems, the investigations were also carried out at 283.15 ≤ T/K ≤ 318.15. The dependence of the thermodynamic parameters on ionic strength and temperature was modelled with a Debye-Hückel type equation. Different speciation schemes of Al³⁺/L^z- systems were obtained, including protonated, simple metal-ligand, polynuclear and hydrolytic mixed species. At I → 0 M and T = 298.15 K the stability trend for the AlL^(3-z) species is: 14.28 ± 0.02, 13.99 ± 0.03, 10.16 ± 0.03, 3.16 ± 0.08, 2.84 ± 0.10 for GTZ S95, GTZ AN169, Cit^3-, Gluc^- and Lac^-, respectively. From the investigations at different temperatures, it results that the entropic contribution is the driving force of the reactions. The sequestering ability of the ligands towards Al³⁺ was investigated determining the pL_0.5 parameter at different experimental conditions, finding the following trend: Cit^3- » Gluc^- > GTZ S95^4- > GTZ AN169^4- > Lac^- for the organic ligands, and pL_0.5: F^- » CO₃^2- > H₂SiO₄^2- for the inorganic ones.

Keywords: Aluminium(III); Inorganic ligands; Low and high molecular weight carboxylic ligands; Sequestration; Speciation.