Ab-Initio Simulation Studies of Cr Solvation in Fluoride Molten Salts

Winner, Nicholas; Williams, Haley; Scarlat, Raluca; Asta, Mark

doi:10.1016/j.molliq.2021.116351

Ab-Initio Simulation Studies of Cr Solvation in Fluoride Molten Salts

Journal Article · Tue May 04 00:00:00 EDT 2021 · Journal of Molecular Liquids

DOI:https://doi.org/10.1016/j.molliq.2021.116351· OSTI ID:1813415

Winner, Nicholas ^[1]; Williams, Haley ^[2]; Scarlat, Raluca ^[2]; Asta, Mark ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)

Understanding molten salt chemistry is essential in ongoing research of the molten salt nuclear reactor (MSR). In this context, detailed understanding of the mechanisms underlying selective oxidation of metal species, such as Cr, is required to guide the design of effective corrosion mitigation strategies in molten salts. An important starting point for such mechanistic understanding is knowledge of the solvation structure and its role in controlling metal speciation. In this work, we use ab initio molecular dynamics simulations to study the short-range (on the scale of the nearest-neighbor bond lengths) and medium-range (over length scales of several neighbor spacings) structure in three different fluoride melts with and without Cr addition; namely, 2KF-NaF, 2LiF-BeF₂, and 3LiF-AlF3. We find that Cr⁰,Cr²⁺,Cr³⁺ can each be coordinated by different numbers of F-, with the variance in coordination number decreasing as oxidation state increases, and that these coordination geometries are largely independent of solvent. The manner by which Cr changes the medium-range structure, however, is found to be solvent-dependent. While 2KF-NaF melts show short and medium range order that is highly dynamic, 2LiF-BeF₂ and 3LiF-AlF₃ are characterized by molecular associates that are relatively long-lived that organize into oligomer structures on larger length scales. Rather than being solvated by F- ions alone, we find that Cr can incorporate into and be solvated within this oligomer structure. Fluoroacidity, alone, may therefore prove too simple a metric for assessing the corrosivity of molten fluorides. As our work suggests, the ability of Cr to solvate must be understood in the context of the short- and medium-range structure of the solvent.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1813415

Journal Information:: Journal of Molecular Liquids, Journal Name: Journal of Molecular Liquids Vol. 335; ISSN 0167-7322

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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