Impact of iodide ions on the speciation of radiolytic transients in molten LiCl–KCl eutectic salt mixtures

Conrad, Jacy K.; Iwamatsu, Kazuhiro; Woods, Michael E.; Gakhar, Ruchi; Layne, Bobby; Cook, Andrew R.; Horne, Gregory P.

doi:10.1039/d3cp01477k

Impact of iodide ions on the speciation of radiolytic transients in molten LiCl–KCl eutectic salt mixtures

Journal Article · Mon Jun 05 00:00:00 EDT 2023 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d3cp01477k· OSTI ID:1985791

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Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

The fate of fission-product iodine is critical for the deployment of next generation molten salt reactor technologies, owing to its volatility and biological impacts if it were to be released into the environment. To date, little is known on how ionizing radiation fields influence the redox chemistry, speciation, and transport of iodine in high temperature molten salts. Here we employ picosecond electron pulse irradiation techniques to elucidate for the first time the impact of iodide ions (I^–) on the speciation and chemical kinetics of the primary radiation-induced transient radicals generated in molten chloride salt mixtures (e_S^– and Cl₂^˙–) as a function of temperature (400–700 °C). In the presence of I^– ions (≥ 1 wt% KI in LiCl–KCl eutectic), we find that the transient spectrum following the electron pulse is composed of at least three overlapping species: the e_S^– and the Cl₂^˙– and ICl^˙– radical anions, for which a deconvoluted spectrum of the latter is reported here for the first time in molten salts. This new transient spectrum was consistent with gas phase density functional theory calculations. The lifetime of the e_S^– was unaffected by the addition of I^– ions. The newly observed interhalogen radical anion, ICl˙^–, exhibited a lifetime on the order of microseconds over the investigated temperature range. The associated chemical kinetics indicate that the predominate mechanism of ICl˙^– decay is via reaction with the Cl₂˙– radical anion. The iodine containing product of this reaction is expected to be ICl₂^–, which will have implications for the transport of fission-product iodine in MSR technologies.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: SC0012704; AC07-05ID14517

OSTI ID:: 1985791

Alternate ID(s):: OSTI ID: 2203449
OSTI ID: 1983711

Report Number(s):: BNL--224523-2023-JAAM

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 23 Vol. 25; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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