Heterogeneous Structure, Mechanisms of Counterion Exchange, and the Spacer Salt Effect in Complex Molten Salt Mixtures Including LaCl3.

Complex molten chloride salt mixtures of uranium, magnesium, and sodium are top candidates for promising nuclear energy technologies to produce electricity based on molten salt reactors. From a local structural perspective, LaCl3 is similar to UCl3 and hence a good proxy to study these complex salt mixtures. As fission products, lanthanide salts and their mixtures are also very important in their own right. This article describes from an experimental and theory perspective how very different the structural roles of MgCl2 and NaCl are in mixtures with LaCl3. We find that, whereas MgCl2 becomes an integral part of multivalent ionic networks, NaCl separates them. In a recent article (J. Am. Chem. Soc. 2022, 144, 21751-21762) we have called the disruptive behavior of NaCl "the spacer salt effect". Because of the heterogeneous nature of these salt mixtures, there are multiple structural motifs in the melt, each with its particular free energetics. Our work identifies and quantifies these; it also elucidates the mechanisms through which Cl- ions exchange between Mg2+-rich and La3+-rich environments.

Do Ionic Liquids Slow Down in Stages?

High impact recent articles have reported on the existence of a liquid-liquid (L-L) phase transition as a function of both pressure and temperature in ionic liquids (ILs) containing the popular trihexyltetradecylphosphonium cation (P666,14+), sometimes referred to as the "universal liquifier". The work presented here reports on the structural-dynamic pathway from liquid to glass of the most well-studied IL comprising the P666,14+ cation. We present experimental and computational evidence that, on cooling, the path from the room-temperature liquid to the glass state is one of separate structural-dynamic changes. The first stage involves the slowdown of the charge network, while the apolar subcomponent is fully mobile. A second, separate stage entails the slowdown of the apolar domain. Whereas it is possible that these processes may be related to the liquid-liquid and glass transitions, more research is needed to establish this conclusively.

Structural Origins of Viscosity in Imidazolium and Pyrrolidinium Ionic Liquids Coupled with the NTf2- Anion.

Ionic liquid viscosity is one of the most important properties to consider for practical applications. Yet, the connection between local structure and viscosity remains an open question. This article explores the structural origin of differences in the viscosity and viscoelastic relaxation across several ionic liquids, including cations with alkyl, ether, and thioether tails, of the imidazolium and pyrrolidinium families coupled with the NTf2- anion. In all cases, for the systems studied here, we find that pyrrolidinium-based ions are "harder" than their imidazolium-based counterparts. We make a connection between the chemical concept of hardness vs softness and specific structural and structural dynamic quantities that can be derived from scattering experiments and simulations.

Complete Description of the LaCl3-NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity.

Lanthanides are important fission products in molten salt reactors, and understanding their structure and that of their mixtures is relevant to many scientific and technological problems including the recovery and separation of rare earth elements using molten salt electrolysis. The literature on molten salts and specifically on LaCl3 and LaCl3-NaCl mixtures is often fragmented, with different experiments and simulations coinciding in their explanation for certain structural results but contradicting or questioning for others. Given the very practical importance that actinide and lanthanide salts have for energy applications, it is imperative to arrive at a clear unified picture of their local and intermediate-range structure in the neat molten state and when mixed with other salts. This article aims to unequivocally answer a set of specific questions: is it correct to think of long-lived octahedral coordination structures for La3+? What is the nature as a function of temperature of networks and intermediate-range order particularly upon dilution of the trivalent ion salt? Is the so-called scattering first sharp diffraction peak (FSDP) for neat LaCl3 truly indicative of intermediate-range order? If so, why is there a new lower-q peak when mixed with NaCl? Are X-ray scattering and Raman spectroscopy results fully consistent and easily described by simulation results? We will show that answers to these questions require that we abandon the idea of a most prominent coordination state for M3+ ions and instead think of multiple competing coordination states in exchange due to significant thermal energy in the molten state.

SEM-Drude Model for the Accurate and Efficient Simulation of MgCl2-KCl Mixtures in the Condensed Phase.

There is a long history of models that to different extents reproduce structural and dynamical properties of high-temperature molten salts. Whereas rigid ion models can work fairly well for some of the monovalent salts, polarizability is fundamentally important when small divalent or multivalent cations are combined with significantly polarizable anions such as Cl- to form networked liquids that display a first sharp diffraction peak. There are excellent polarizable ion models (PIMs) for these systems, but there has been little success with the less expensive Core-Shell type models, which are often described as unwieldy or difficult to fit. In this article, we present the Sharma-Emerson-Margulis (SEM)-Drude model for MgCl2/KCl mixtures that with the same ingredients used in the latest and most accurate PIM models overcome the aforementioned obstacles at significantly less computational cost; structural and dynamical properties are for all practical purposes very similar to what we obtain from the PIM but typical simulations can be more than 30 times faster. This has allowed us not only to expand our recent studies on the temperature and composition dependence of intermediate range order in MgCl2/KCl mixtures but also to access transport properties that were simply too costly to properly sample in our recently published studies.