6,6′‐Bis(5,5,8,8‐tetramethyl‐5,6,7,8‐tetrahydro‐benzo[1,2,4]triazin‐3‐yl) [2,2′]bipyridine, an Effective Extracting Agent for the Separation of Americium(III) and Curium(III) from the Lanthanides

Abstract

The extraction of americium(III), curium(III), and the lanthanides(III) from nitric acid by 6,6′‐bis(5,5,8,8‐tetramethyl‐5,6,7,8‐tetrahydro‐benzo[1,2,4]triazin‐3‐yl)‐[2,2′]bipyridine (CyMe₄‐BTBP) has been studied. Since the extraction kinetics were slow, N,N′‐dimethyl‐N,N′‐dioctyl‐2‐(2‐hexyloxy‐ethyl)malonamide (DMDOHEMA) was added as a phase transfer reagent. With a mixture of 0.01 M CyMe₄‐BTBP+0.25 M DMDOHEMA in n‐octanol, extraction equilibrium was reached within 5 min of mixing. At a nitric acid concentration of 1 M, an americium(III) distribution ratio of approx. 10 was achieved. Americium(III)/lanthanide(III) separation factors between 50 (dysprosium) and 1500 (lanthanum) were obtained. Whereas americium(III) and curium(III) were extracted as disolvates, the stoichiometries of the lanthanide(III) complexes were not identified unambiguously, owing to the presence of DMDOHEMA. In the absence of DMDOHEMA, both americium(III) and europium(III) were extracted as disolvates. Back‐extraction with 0.1 M nitric acid was thermodynamically possible but rather slow. Using a buffered glycolate solution of pH=4, an americium(III) distribution ratio of 0.01 was obtained within 5 min of mixing. There was no evidence of degradation of the extractant, for example, the extraction performance of CyMe₄‐BTBP during hydrolylsis with 1 M nitric acid did not change over a two month contact.