DOE OSTI2016
The pyrochemical recycling of actinides is a promising option for closing the nuclear fuel cycle. The technology is particularly attractive for recycle of metallic and molten salt fuels. The Republic of Korea is also taking a serious look at the application of pyrochemical treatment of used oxide fuel from Pressurized Water Reactors (PWR). The science behind pyrochemical recycling is being actively studied at the various national labs and universities. The Rare Earth Drawdown process is proposed to be included in a commercial pyrochemical recycling facility in order to minimize the amount of waste generated from the processing that will require permanent disposal in a geological repository. This process involves selective extraction of rare earth elements from electro-refiner salt. The salt can then be further processed to selectively remove Group I-II active metals and eventually be recycled back to the electro-refiner. The preferred method of separation of the rare earths from the salt is using electrolysis due to its inherent selectivity and ease of operation. The purpose of this study is to evaluate the effects of the presence of cesium (Group I) on the electrochemical behavior of neodymium in a molten eutectic LiCl-KCl salt. The activity and by extension the activity coefficient of a species determines many of the key electrochemical properties such as apparent reduction potential. In this study, we have undertaken a series of experiments to experimentally determine the activity coefficient of the dissolved neodymium(III) ions as a function of concentration, both in the presence and absence of cesium. This was done using a first of its kind electrochemical cell. Previously, activity of dissolved species has been determined using electrochemical cells in which equilibrium potentials are measured for the Nd/Nd(III) versus a Ag/AgCl reference electrode. There are several issues associated with such an approach. These electrodes are associated with several sources of errors; indeterminate values of Standard Reduction Potentials of (E{sup θ}) for Ag and Nd in molten salts, unknown liquid junction potentials and potential drifts. These uncertainties contribute errors to the experimental measurements. For this study, we employed a Nd/LiCl-KCl-NdCl{sub 3(Saturatedelectrode)}. There are several advantages with using such an electrode. If the expanded Nernst Equation is written for the aforementioned electrochemical cell, all of the terms cancel out except the activity term. This enables us to directly experimentally measure the activity of the species in solution. When we use a saturated NdCl{sub 3} reference electrode, the activity that is measured is defined as the activity versus a 'Saturated Solid State'. To determine the activity coefficients, we need to determine the activity versus the 'Liquid Standard Sate'. To convert the activity from solid standard state to liquid standard state, we correct for it using the hypothetical Gibbs free energy of fusion for neodymium chloride. (authors)
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗