Dialkylphosphoric acids as carriers in separation of lanthanides and thorium on supported liquid membranes

Permeation of seven lanthanides (Ln) and thorium through a supported liquid membrane containing di-(n- octyl)phosphoric (DOPA) or di-(n-pentyl)phosphoric (DPPA) acid as a carrier has been studied as a function of the chemical composition of the system. The results have been compared with a previous study in which di-(2-ethylhexyl)phosphoric acid was used. Metal cations were transported from feed solutions of pH 1.1-4.8 (HNO(3)) into strip solutions of 0.015-0.1 mol l(-1) nitric acid. The ionic strength was kept constant at 0.1 mol l(-1) (HNO(3), KNO(3)). The initial lanthanide concentration and carrier concentration in the liquid membrane were varied from 0.5 to 500 mumol l(-1) and from 0.01 to 0.5 mol l(-1) respectively. To describe the mass transfer of metal cations, permeability coefficients have been determined by inductively-coupled plasma atomic emission spectroscopy or by on-line flow-injection analysis of metal concentrations in strip or feed solution. Probably as the result of a higher solubility of the carrier in aqueous media, transport of Ln with DPPA was not observed. By using DOPA, La, Ce, Pr, and Nd permeated through the membrane while transport of heavier Ln was partly or totally suppressed. This enables these four Ln (separation factor alpha = 3.0 for Nd and Sm) to be separated from the others. Furthermore, at a very low acidity gradient, only La (III) is transported over the membrane (alpha >/= 3.4 for La, Ce and next Ln). The seven elements from La to Tb can be separated from Th(IV) because no evidence of its permeation through the membrane was found under the conditions of Ln transport. In contrast to previous studies on Ln transport with dialkylphosphoric acid carrier, the possibility of participation of species other than Ln(AHA)(3) in the transport has been discussed. The decrease of permeability observed at higher Ln concentrations and higher pH of the feed solution has been explained as the result of formation of species, e.g. polymeric ones, that are unable to permeate through the membrane.