Print Email Facebook Twitter Coupled structural-thermodynamic modelling of the molten salt system NaCl-UCl3 Title Coupled structural-thermodynamic modelling of the molten salt system NaCl-UCl3 Author van Oudenaren, G. I.L. (Student TU Delft) Ocadiz flores, J.A. (TU Delft RST/Reactor Physics and Nuclear Materials) Smith, A.L. (TU Delft RST/Reactor Physics and Nuclear Materials) Date 2021 Abstract Molten chloride salts are ionic liquids in which the anions and cations exhibit network formation. An attractive salt system for use in molten salt reactors is NaCl-UCl3, an ionic liquid with complex non-ideal thermodynamic behaviour due to the formation of short-range order. The relationship between local structure and thermodynamic properties is investigated in this work, in which molecular dynamics simulations using the Polarizable Ion Model (PIM) and thermodynamic modelling by means of the CALPHAD method are combined. The system is simulated for a wide range of temperatures and compositions and various properties are derived derived from molecular dynamics data: density/molar volume, thermal expansion, heat capacity and excess properties including excess molar volume, mixing enthalpy and excess heat capacity. Generally, there is good agreement with previously published experimental data. An in depth analysis of the local structure of the liquid is performed for multiple temperatures. This analysis demonstrates the transition from a molecular liquid consisting of primarily Na+, Cl−, UCl63-/UCl74- at low UCl3 content to a polymeric liquid at high UCl3 content, manifesting itself in the formation of species like U2Cl126-, U3Cl178-, U4Cl2210- etc. Exceeding 40% UCl3, the liquid consists of a three-dimensional network of corner or edge-sharing uranium polyhedra. The output of the MD simulations and experimental data are incorporated into a coupled structural-thermodynamic model for the NaCl-UCl3 system based on the quasi-chemical formalism in the quadruplet approximation, that provides a physical description of the melt and reproduces (in addition to the thermodynamic data) the chemical speciation of uranium polymeric species predicted from the simulations. Subject CALPHADChloride saltsMolecular dynamicsMolten salt reactorsPolarizable ion model To reference this document use: http://resolver.tudelft.nl/uuid:539614d6-383e-4b82-8303-4271c9ce8e1e DOI https://doi.org/10.1016/j.molliq.2021.117470 ISSN 0167-7322 Source Journal of Molecular Liquids, 342 Part of collection Institutional Repository Document type journal article Rights © 2021 G. I.L. van Oudenaren, J.A. Ocadiz flores, A.L. Smith Files PDF 1_s2.0_S0167732221021942_main.pdf 1.18 MB Close viewer /islandora/object/uuid:539614d6-383e-4b82-8303-4271c9ce8e1e/datastream/OBJ/view