Selective Extraction of Light Lanthanides(III) by N,N-Di(2-ethylhexyl)-diglycolamic Acid: A Comparative Study with...

The complexation and selectivity of N,N-di(2-ethylhexyl)-diglycolamic acid (HDEHDGA/kerosene, HA) toward the light lanthanides, La(III), Ce(III), Pr(III), and Nd(III), are presented for the extraction from chloride media. In the low pH region (pH 1.8-2.8), the obtained data reveal that the extraction of Ln(III) is governed by cation-exchange mechanism and is driven by the negative change in enthalpy. The results from the slope analysis method suggest the formation of LnA₃·(HA)_1or2 in the extraction process. As major extracted species with a core of LnA₃ in the first coordination sphere, LnA₃ might connect with one or two additional HA molecules in the second coordination sphere by hydrogen bonding. The LnA₃ core might share similar coordination geometry to those of 1:3 Ln(III) complexes (LnA'₃) with water-soluble N,N-dimethyl-diglycolamic acid (HDMDGA, HA') formed in aqueous solutions or in solid-state compounds. The correlation between the extraction with HDEHDGA (HA) as an extractant and the complexation with HDMDGA (HA') as a chelator has been explored by interpreting the separation factors for HA with the difference in the stability constants for HA'. Consequently, the ratios of the stability constants of the corresponding 1:3 complexes (LnA'₃) with HDMDGA could be reasonably translated to the separation factors (SFs) with HDEHDGA, providing a valuable approach for understanding the origin of the extraction/separation mechanism. By comparing the extraction selectivity of HDEHDGA with that of the currently deployed extractants in the industry such as P204, P507, and Cyanex 272, HDEHDGA offers outstanding selectivity with considerable SFs (SF_Ce/La = 6.68, SF_Pr/Ce = 2.79, and SF_Nd/Pr = 2.65) for light Ln(III) pairs under conditions of low acid concentrations.