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Abstract Technetium-99 is a high yield (~6% fission yield) fission product and long-lived (2.13×105 year half-life) component of nuclear waste that will be disposed of in a geological repository. Some 99Tc has been released into the environment due to nuclear fuel and weapon production activities at sites such as Hanford, WA. Strongly complexing ligands such as ethylenediamine-N,N,N′,N′-tetraacetic acid (EDTA) are known to increase Tc(IV) solubility and mobility in environmental systems and an accurate quantification of the complexation of Tc(IV) with EDTA is important for predicting its behavior in a geological repository. A liquid–liquid extraction system utilizing 0.2 M TOPO in dodecane was used to measure the stability constants of Tc(IV)-EDTA in 0.50 m NaNO3 at variable temperatures (14.0±0.1, 25.0±0.1, and 32.0±0.1°C). The acid dependence of the apparent stability constants in the pCH range of 2.00–2.70 indicated the formation of TcO(EDTA)2− (logβ101=17.9±0.3, 25.0±0.1°C) and a protonated complex TcO(H)(EDTA)− (logβ111=20.5±0.1, 25.0±0.1°C). The associated thermodynamic parameters ΔrG101=−101.7±0.4 kJ·mol−1, ΔrH101=−47±9 kJ·mol−1, ΔrS101=179±36 J·mol−1·K−1, ΔrG111=−117.2±0.3 kJ·mol−1, ΔrH111=−23±5 kJ·mol−1, and ΔrS111=315±63 J·mol−1·K−1 (0.50 m NaNO3, 25.0±0.1°C) were determined by van’t Hoff analysis. The formation of each Tc(IV)–EDTA complex is exothermic and present favorable entropy terms.

Appropriate management of fission products in the reprocessing of spent nuclear fuel (SNF) is crucial in developing advanced reprocessing schemes. The addition of aqueous phase complexing agents can prevent the co-extraction of these fission products. A solvent extraction technique was used to study the complexation of Hf(IV) – an analog to fission product Zr(IV) – with oxalate at 15, 25, and 35°C in 1 M HClO