Forward osmosis for heavy metal removal: Multi-charged metallic complexes as draw solutes

Protonated betaine bis(trifluoromethylsulfonyl)imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium(II) oxide, mercury(II) oxide, nickel(II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese(II) oxide, and silver(I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis(trifluoromethylsulfonyl)imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C (temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis(trifluoromethylsulfonyl)imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

The role of ionized groups in biological systems is determined by their affinity for water [Biophys. J. 72 (1997) 65-76]. The tightly bound water associated with biologically important ions increases their apparent size. We define the apparent dynamic hydration number of an ion here as the number of tightly bound water molecules that must be assigned to the ion to explain its apparent molecular weight on a Sephadex G-10 size exclusion column, and report the first accurate determination of tightly bound water for 23 ions of biological significance, including H(+) and HO(-). We also calculate the radius of the equivalent hydrated sphere (r(h)) for each ion. We find that the ratio of the hydrated volumes of two ions approximates the ratio of the square of the charges of the same two ions. Since the 'ionic strength' of the solution also depends upon the square of the charges on the ions, our results suggest that ionic strength effects may largely arise from local effects related to the hydrated volume of the ion--that is, from space filling, osmotic, water activity, surface tension and hydration shell overlap effects rather than from long-range electric field effects.