Kinetics and Mechanism of Ce(IV) Phase Transfer by the Neutral Extractants Tributyl Phosphate and N,N-Di(2-ethylhexyl)isobutyramide

Abstract

Tributyl phosphate and N,N-di(2-ethylhexyl)isobutyramide (DEHiBA) are uranium-selective extractants that could be used to recover low-enriched uranium from commercial used nuclear fuel. The economic viability of liquid–liquid extraction processes for chemical separations depends on both thermodynamic and kinetic considerations. We used microfluidic droplet extraction to measure interfacial phase transfer rate constants for the extraction and stripping of Ce(IV), a nonradioactive actinide surrogate. The Damköhler numbers for each system were calculated and the phase transfer processes were determined to be diffusion-limited under all conditions, contrary to prior studies using constant interface stirred cells and single drop methods. A well-extracted 2:1 DEHiBA/Ce(IV) complex in the organic phase was determined from batch distribution studies, suggesting a different extraction mechanism for Ce(IV) compared with poorly extracted Pu(IV). Finally, phase disengagement rates were found to be rapid in both systems, in agreement with other studies.