Chlorine Gas and Anion Radical Reactivity in Molten Salts and the Link to Chlorobasicity

Hung N. Nguyen; Luke Douglas Gibson; Matthew S. Emerson; Bichitra Borah; Santanu Roy; Vyacheslav Bryantsev; Claudio Javier Margulis

doi:10.1039/D4CP03285C

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Chlorine Gas and Anion Radical Reactivity in Molten Salts and the Link to Chlorobasicity

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Chlorine Gas and Anion Radical Reactivity in Molten Salts and the Link to Chlorobasicity

Hung N. Nguyen, Luke Douglas Gibson, Matthew S. Emerson, Bichitra Borah, Santanu Roy, Vyacheslav Bryantsev and Claudio Javier Margulis

Physical chemistry chemical physics : PCCP, Vol.27(8), pp.4290-4297

01/22/2025

DOI: 10.1039/D4CP03285C

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Abstract

Next-generation nuclear power plants may include exciting novel designs in which molten salts are the coolant or a combination of coolant and fuel. Whereas it is straightforward to see why having a low volatility coolant can be advantageous for safety, much is not understood about the production of volatile halogenic gases as a result of radiation and even less is known about the distribution of these species at and away from interfaces. Using first principles molecular dynamics simulations, we investigate the product of the disproportionation reaction between chlorine anion radicals (nominally Cl2• – ) in the bulk and slab configurations. We find that the product depends on the chlorobasicity of the medium. For example, in ZnCl2, Cl2 forms, but in a eutectic mixture of LiCl and KCl, Cl3– is formed as product. We also find that Cl3– prefers to form at the vapor interface and this may have implications for corrosion and reactivity. Furthermore, the mechanism of mobility of Cl2 and Cl3– are radically different, the first one being vehicular and the second Grotthus-like. Chlorobasicity is linked to the electronic structure of the host melt; ZnCl2 forms extended networks along which metal ions and anionic counterions have significant electronic orbital overlap forming long, linear, molecular-like constructs; the opposite is true for the alkali metal eutectic salt.

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Details

Title: Subtitle: Chlorine Gas and Anion Radical Reactivity in Molten Salts and the Link to Chlorobasicity
Creators: Hung N. Nguyen - University of Iowa
Luke Douglas Gibson - Oak Ridge National Laboratory
Matthew S. Emerson - University of Iowa
Bichitra Borah - University of Iowa
Santanu Roy - University of Iowa
Vyacheslav Bryantsev - Oak Ridge National Laboratory
Claudio Javier Margulis - University of Iowa
Resource Type: Journal article
Publication Details: Physical chemistry chemical physics : PCCP, Vol.27(8), pp.4290-4297
Publisher: Royal Society of Chemistry
DOI: 10.1039/D4CP03285C
ISSN: 1463-9076
eISSN: 1463-9084
Language: English
Date published: 01/22/2025
Academic Unit: Chemistry
Record Identifier: 9984781373002771

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