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^•-)

J Phys Chem A. 2024 Jan 25;128(3):590-598. doi: 10.1021/acs.jpca.3c07404. Epub 2024 Jan 12.

Authors

Brian M Rotermund^{1

2}, Stephen P Mezyk³, Joseph M Sperling^{1

2}, Nicholas B Beck^{1

2}, Hannah Wineinger^{1

2}, Andrew R Cook⁴, Thomas E Albrecht-Schönzart^{1

2}, Gregory P Horne⁵

Affiliations

¹ Department of Chemistry, Colorado School of Mines, Golden, Colorado 80401, United States.
² Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
³ Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Boulevard, Long Beach, California 90840-9507, United States.
⁴ Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973, United States.
⁵ Center for Radiation Chemistry Research, Idaho National Laboratory, Idaho Falls, P.O. Box 1625, Idaho 83415, United States.

PMID: 38215218
DOI: 10.1021/acs.jpca.3c07404

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 ( ${Cf}^{3 +}$ ) 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 ${Cf}^{3 +}$ ions. The derived and ionic strength-corrected second-order rate coefficients (k) for these radiation-induced processes are k( ${Cf}^{3 +}$ + Cl₂^•-) = (8.28 ± 0.61) × 10⁵ M^-1 s^-1 and k( ${Cf}^{3 +}$ + SO₄^•-) = (9.50 ± 0.43) × 10⁸ M^-1 s^-1 under ambient temperature conditions (22 ± 1 °C).