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

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 (Cf3+Cf3+) and select inorganic radicals arising from the radiolytic decomposition of common anions and functional group constituents, specifically the dichlorine (Cl-2(center dot-)) and sulfate (SO4 center dot-) 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 Cf3+Cf3+ ions. The derived and ionic strength-corrected second-order rate coefficients (k) for these radiation-induced processes are k(Cf3+Cf3+ + Cl-2(center dot-)) = (8.28 +/- 0.61) x 10(5) M-1 s(-1) and k(Cf3+Cf3+ + SO4 center dot-) = (9.50 +/- 0.43) x 10(8) M-1 s(-1) under ambient temperature conditions (22 +/- 1 degrees C).