The partitioning of minor trivalent actinides (An) from lanthanides (Ln) is one of the challenges in the chemical treatment of nuclear waste. The optimal ligand to carry out the separation of An(III) and Ln(III) using solvent extraction has to meet several important criteria: high selectivity towards the solute, chemical and radiolytic stability, stripping possibilities and recycling of the organic phase, high separation factors and good distribution ratio, to name just a few of them. A chronological line can be drawn along the development of each extraction ligand family and some milestones are emphasized in this overview.Further developments in organic synthesis of extracting ligands are expected.

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Solvents intended for the separation of trivalent actinides from trivalent lanthanides in spent nuclear fuel have been irradiated with gamma-radiation. The solvents initially contained 0.005 M C5-BTBP dissolved in either hexanol or cyclohexanone and they were exposed to doses up to 20 kGy. Identification of degradation products was done using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). Structures were suggested for a number of degradation products and the relative intensity of the peaks in the MS spectra was estimated. It was clear that the content of the original molecule, C5-BTBP, decreased with dose, while the content of the various degradation products increased. It was also shown that both the choice of diluent and the dose rate (Gy/h) affect the amount of degradation products formed. A degradation scheme was proposed for the radiolytic degradation of C5-BTBP.

The extraction of Am(III), Th(IV), Np(V), and U(VI) from nitric acid by 6,6 0 -bis(5,6-dialkyl-[1,2,4]-triazin-3-yl)-[2,2 0 ]-bipyridines (C2-, C4-, C5-, and CyMe 4 -BTBP) was studied. Since only americium and neptunium extraction was dependent on the BTBP concentration, computational chemistry was used to explain this behavior. It has been shown that the coordination of the metal played an important role in forming an extractable complex into the organic phase, thus making it possible to extract pentavalent and trivalent elements from tetravalent and hexavalent elements. This is very important, especially because it shows other possible utilizations of a group of molecules meant

Hydrochemical separation processes are one of the methods used for the treatment of spent nuclear fuel. Solvent extraction is also used in many other non-nuclear applications like the mining industry. In the nuclear case, hydrochemical separation processes are already employed in the world today for the recovery of uranium and plutonium. The method is however also considered for future separation systems for use in combination with the transmutation of the minor actinides. In a hydrochemical separation process the two phases are the pregnant (usually) aqueous feed and the organic phase comprising a diluent together with one or more extractants. One such class of extractants developed for partitioning and transmutation purposes is the bis(triazine)−bipyridine-type (BTBP) molecules. When assessing the feasibility and loading properties of such an extraction system, the solubility of the ligands is of the outmost importance. The understanding of whether the dissolution is enthalpically or entropically driven will also help the understanding of the differences in extraction observed between various diluents and temperatures. In this paper the enthalpy and entropy of dissolution of the BTBP-class ligands have been determined for different diluents. It has also been shown that it is possible to predict the extraction behavior of these molecules in the selected diluent once the solubility is known.

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Low doses of gamma radiation were given to four different solvents containing C5-BTBP and CyMeThe results were unexpected. The presence of a cyclic molecule as both a side group or diluent seems to keep the extraction of europium almost unaffected by radiolysis, while americium behaves differently from solvent to solvent. The diluent alone does not protect the extracting molecule. In some of the studied systems there is a distinct change in the extraction behaviour of Am between the irradiated and reference solutions, an effect that is however only present at the beginning of the experimental series. At later times the difference in distribution ratios between the irradiated and reference solution is constant. This phenomenon is found only when the side group and diluent are structurally dissimilar.