Exchanges of uranium(VI) species in amidoxime-functionalized sorbents.
Amidoxime (AO)-functionalized polymer sorbents used in this study were prepared by two different routes involving UV grafting and electron-beam grafting of acrylonitrile (AN) into poly(propylene) fibrous and microporous sheets, and subsequent conversion of AN to AO groups by reacting the precursor sorbent with hydroxylamine. The values of self-diffusion coefficient (D(s)) of UO(2)(2+) in fibrous and sheet AO sorbents were found to be 1.1 x 10(-6) and 2.3 x 10(-10) cm(2) s(-1), respectively. The higher diffusion mobility of UO(2)(2+) in the fibrous AO sorbent was attributed to its higher free volume as observed in scanning electron microscopic studies. The water content was also found to be maximum in AO-fibrous sorbent (165-200 wt %) and minimum in AO-sheet sorbent (70 wt %). In fibrous AO sorbent, the values of D(s) for Na(+) and Sr(2+) were found to be comparable to their self-diffusion coefficients in the aqueous medium. This indicated that the retardation in diffusion mobility of the ions was a minimum in the fibrous AO sorbent. However, D(s) of UO(2)(2+) in the fibrous membrane was found to be significantly lower than that of Sr(2+), which has a self-diffusion coefficient comparable to that of UO(2)(2+) in aqueous medium. This could be attributed to stronger binding of UO(2)(2+) with AO groups as compared to Sr(2+). To understand the parameters affecting the U(VI) sorption from seawater, the U(VI) exchange rates between fibrous AO sorbent (S) and seawater (aq) involving (H(+)/Na(+))(S) right harpoon over left harpoon ([UO(2)(CO(3))(3)](4-))(aq) and (UO(2)(2+))(S) right harpoon over left harpoon ([UO(2)(CO(3))(3)](4-))(aq) systems were experimentally measured. The exchange profiles thus obtained were found to be non-Fickian and much slower than (H(+))(S) right harpoon over left harpoon (UO(2)(2+))(aq) and (UO(2)(2+))(S) right harpoon over left harpoon (UO(2)(2+))(aq) exchanges. This seems to suggest that the reaction kinetics involved in decomplexation of [UO(2)(CO(3))(3)](4-) into UO(2)(2+), which forms a complex with AO groups, is the rate-determining step in sorption of U(VI) from seawater. The kinetics of U(VI) sorption in AO-gel and AO-fibrous sorbents followed the pseudo-second-order rate equation. The density of AO groups in the sorbents and their conditioning were found to influence the U(VI) sorption from seawater.
Radiochemistry Division, BARC, Mumbai 400 085, India.
Sadananda
S
Das
Ashok K
AK
Pandey
Anjali A
AA
Athawale
Vijay K
VK
Manchanda