Chemical Kinetics for the Oxidation of Californium(III) Ions with Select Radiation-Induced Inorganic Radicals (Cl2•- and SO4•-)

Brian M. Rotermund; Stephen P. Mezyk; Joseph M. Sperling; Nicholas B. Beck; Hannah Wineinger; Andrew R. Cook; Thomas E. Albrecht-Schönzart; Gregory P. Horne

doi:10.1021/acs.jpca.3c07404

Chemical Kinetics for the Oxidation of Californium(III) Ions with Select Radiation-Induced Inorganic Radicals (Cl₂^•- and SO₄^•-)

Brian M. Rotermund, Stephen P. Mezyk, Joseph M. Sperling, Nicholas B. Beck, Hannah Wineinger, Andrew R. Cook, Thomas E. Albrecht-Schönzart, Gregory P. Horne

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2 Scopus citations

Abstract

Despite the availability of transuranic elements increasing in recent years, our understanding of their most basic and inherent radiation chemistry is limited and yet essential for the accurate interpretation of their physical and chemical properties. Here, we explore the transient interactions between trivalent californium ions (Formula Presented) and select inorganic radicals arising from the radiolytic decomposition of common anions and functional group constituents, specifically the dichlorine (Cl₂^•-) and sulfate (SO₄^•-) radical anions. Chemical kinetics, as measured using integrated electron pulse radiolysis and transient absorption spectroscopy techniques, are presented for the reactions of these two oxidizing radicals with Formula Presented ions. The derived and ionic strength-corrected second-order rate coefficients (k) for these radiation-induced processes are k(Formula Presented + Cl₂^•-) = (8.28 ± 0.61) × 10⁵ M^-1 s^-1 and k(Formula Presented + SO₄^•-) = (9.50 ± 0.43) × 10⁸ M^-1 s^-1 under ambient temperature conditions (22 ± 1 °C).

Original language	English
Pages (from-to)	590-598
Number of pages	9
Journal	Journal of Physical Chemistry A
Volume	128
Issue number	3
Early online date	Jan 12 2024
DOIs	https://doi.org/10.1021/acs.jpca.3c07404
State	Published - Jan 25 2024

INL Publication Number

INL/JOU-23-75233
164027

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10.1021/acs.jpca.3c07404

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title = "Chemical Kinetics for the Oxidation of Californium(III) Ions with Select Radiation-Induced Inorganic Radicals (Cl2•- and SO4•-)",

abstract = "Despite the availability of transuranic elements increasing in recent years, our understanding of their most basic and inherent radiation chemistry is limited and yet essential for the accurate interpretation of their physical and chemical properties. Here, we explore the transient interactions between trivalent californium ions (Formula Presented) and select inorganic radicals arising from the radiolytic decomposition of common anions and functional group constituents, specifically the dichlorine (Cl2•-) and sulfate (SO4•-) radical anions. Chemical kinetics, as measured using integrated electron pulse radiolysis and transient absorption spectroscopy techniques, are presented for the reactions of these two oxidizing radicals with Formula Presented ions. The derived and ionic strength-corrected second-order rate coefficients (k) for these radiation-induced processes are k(Formula Presented + Cl2•-) = (8.28 ± 0.61) × 105 M-1 s-1 and k(Formula Presented + SO4•-) = (9.50 ± 0.43) × 108 M-1 s-1 under ambient temperature conditions (22 ± 1 °C).",

author = "Rotermund, {Brian M.} and Mezyk, {Stephen P.} and Sperling, {Joseph M.} and Beck, {Nicholas B.} and Hannah Wineinger and Cook, {Andrew R.} and Albrecht-Sch{\"o}nzart, {Thomas E.} and Horne, {Gregory P.}",

note = "Funding Information: This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Solar Photochemistry Program, under award DE-SC0024191. Cook and electron pulse irradiation experiments at the Laser-Electron Accelerator Facility of the Brookhaven National Laboratory Accelerator Center for Energy Research were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under contract DE-SC0012704. Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

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T1 - Chemical Kinetics for the Oxidation of Californium(III) Ions with Select Radiation-Induced Inorganic Radicals (Cl2•- and SO4•-)

AU - Rotermund, Brian M.

AU - Mezyk, Stephen P.

AU - Sperling, Joseph M.

AU - Beck, Nicholas B.

AU - Wineinger, Hannah

AU - Cook, Andrew R.

AU - Albrecht-Schönzart, Thomas E.

AU - Horne, Gregory P.

N1 - Funding Information: This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Solar Photochemistry Program, under award DE-SC0024191. Cook and electron pulse irradiation experiments at the Laser-Electron Accelerator Facility of the Brookhaven National Laboratory Accelerator Center for Energy Research were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under contract DE-SC0012704. Publisher Copyright: © 2024 American Chemical Society.

PY - 2024/1/25

Y1 - 2024/1/25

N2 - Despite the availability of transuranic elements increasing in recent years, our understanding of their most basic and inherent radiation chemistry is limited and yet essential for the accurate interpretation of their physical and chemical properties. Here, we explore the transient interactions between trivalent californium ions (Formula Presented) and select inorganic radicals arising from the radiolytic decomposition of common anions and functional group constituents, specifically the dichlorine (Cl2•-) and sulfate (SO4•-) radical anions. Chemical kinetics, as measured using integrated electron pulse radiolysis and transient absorption spectroscopy techniques, are presented for the reactions of these two oxidizing radicals with Formula Presented ions. The derived and ionic strength-corrected second-order rate coefficients (k) for these radiation-induced processes are k(Formula Presented + Cl2•-) = (8.28 ± 0.61) × 105 M-1 s-1 and k(Formula Presented + SO4•-) = (9.50 ± 0.43) × 108 M-1 s-1 under ambient temperature conditions (22 ± 1 °C).

AB - Despite the availability of transuranic elements increasing in recent years, our understanding of their most basic and inherent radiation chemistry is limited and yet essential for the accurate interpretation of their physical and chemical properties. Here, we explore the transient interactions between trivalent californium ions (Formula Presented) and select inorganic radicals arising from the radiolytic decomposition of common anions and functional group constituents, specifically the dichlorine (Cl2•-) and sulfate (SO4•-) radical anions. Chemical kinetics, as measured using integrated electron pulse radiolysis and transient absorption spectroscopy techniques, are presented for the reactions of these two oxidizing radicals with Formula Presented ions. The derived and ionic strength-corrected second-order rate coefficients (k) for these radiation-induced processes are k(Formula Presented + Cl2•-) = (8.28 ± 0.61) × 105 M-1 s-1 and k(Formula Presented + SO4•-) = (9.50 ± 0.43) × 108 M-1 s-1 under ambient temperature conditions (22 ± 1 °C).

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IS - 3

ER -

Chemical Kinetics for the Oxidation of Californium(III) Ions with Select Radiation-Induced Inorganic Radicals (Cl₂^•- and SO₄^•-)

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