Chlorine Gas as a Lewis Acid–Base Probe for Molten Salts of Divalent Metal Ions

Yang Chen; Matthew S. Emerson; Hung H. Nguyen; Raphael Ogbodo; Vyacheslav S. Bryantsev; James F. Wishart; Claudio J. Margulis

doi:10.1021/acs.jpcb.6c01313

Chlorine Gas as a Lewis Acid–Base Probe for Molten Salts of Divalent Metal Ions

Yang Chen
, Matthew S. Emerson
, Hung H. Nguyen
, Raphael Ogbodo
, Vyacheslav S. Bryantsev
, James F. Wishart
, Claudio J. Margulis

Chemical Separations Group

Research output: Contribution to journal › Article › peer-review

Abstract

In the context of energy applications for salts and, more specifically, in the case of molten salt reactors, the solvation of corrosion species, the nature and behavior of radiation-produced excess electrons, transient radicals, and molecular gas species all depend on the Lewis acid–base behavior of the constituent salt melt. Speciation of dissolved species and their transport properties are also influenced by the ability of the melt to form networks. This article focuses on the structural properties of melts composed of alkaline earth metal ions coupled with the Cl^– anion, and the quantum mechanical behavior of Cl₂, a typical product of the reaction of radiation-produced chlorine radicals in Cl^–-based molten salts. We explore the effect of M²⁺ Lewis acidity on chlorobasicity, seen in this work as the availability of Cl^– ions to chemically react with Cl₂ to produce Cl₃^–.

Original language	English
Pages (from-to)	6376-6382
Number of pages	7
Journal	Journal of Physical Chemistry B
Volume	130
Issue number	25
DOIs	https://doi.org/10.1021/acs.jpcb.6c01313
State	Published - Jun 25 2026

Funding

This work was supported as part of the Molten Salts in Extreme Environments (MSEE) Energy Frontier Research Center, funded by the U.S. Department of Energy (DOE) Office of Science, Office of Basic Energy Sciences. Work at Brookhaven National Laboratory (BNL) and Oak Ridge National Laboratory (ORNL) was supported by DOE contracts DE-SC0012704 and DE-AC05-00OR22725, respectively. Work at the University of Iowa was supported under a subcontract from BNL. This research also used resources of the National Energy Research Scientific Computing Center (NERSC) and the Oak Ridge Leadership Computing Facility at Oak Ridge National Laboratory, which are supported by the Office of Science of the U.S. DOE under Contract Nos. DE-AC02-05CH11231 and DE-AC05-00OR22725, respectively. YC, HHN, RO, and CJM acknowledge the University of Iowa High-Performance Computing Facility.

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10.1021/acs.jpcb.6c01313

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title = "Chlorine Gas as a Lewis Acid–Base Probe for Molten Salts of Divalent Metal Ions",

abstract = "In the context of energy applications for salts and, more specifically, in the case of molten salt reactors, the solvation of corrosion species, the nature and behavior of radiation-produced excess electrons, transient radicals, and molecular gas species all depend on the Lewis acid–base behavior of the constituent salt melt. Speciation of dissolved species and their transport properties are also influenced by the ability of the melt to form networks. This article focuses on the structural properties of melts composed of alkaline earth metal ions coupled with the Cl– anion, and the quantum mechanical behavior of Cl2, a typical product of the reaction of radiation-produced chlorine radicals in Cl–-based molten salts. We explore the effect of M2+ Lewis acidity on chlorobasicity, seen in this work as the availability of Cl– ions to chemically react with Cl2 to produce Cl3–.",

author = "Yang Chen and Emerson, \{Matthew S.\} and Nguyen, \{Hung H.\} and Raphael Ogbodo and Bryantsev, \{Vyacheslav S.\} and Wishart, \{James F.\} and Margulis, \{Claudio J.\}",

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doi = "10.1021/acs.jpcb.6c01313",

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AU - Chen, Yang

AU - Emerson, Matthew S.

AU - Nguyen, Hung H.

AU - Ogbodo, Raphael

AU - Bryantsev, Vyacheslav S.

AU - Wishart, James F.

AU - Margulis, Claudio J.

PY - 2026/6/25

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AB - In the context of energy applications for salts and, more specifically, in the case of molten salt reactors, the solvation of corrosion species, the nature and behavior of radiation-produced excess electrons, transient radicals, and molecular gas species all depend on the Lewis acid–base behavior of the constituent salt melt. Speciation of dissolved species and their transport properties are also influenced by the ability of the melt to form networks. This article focuses on the structural properties of melts composed of alkaline earth metal ions coupled with the Cl– anion, and the quantum mechanical behavior of Cl2, a typical product of the reaction of radiation-produced chlorine radicals in Cl–-based molten salts. We explore the effect of M2+ Lewis acidity on chlorobasicity, seen in this work as the availability of Cl– ions to chemically react with Cl2 to produce Cl3–.

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Chlorine Gas as a Lewis Acid–Base Probe for Molten Salts of Divalent Metal Ions

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