Electrochemical studies of trivalent californium and selected trivalent lanthanides in aqueous solution

Musikas, C.; Haire, R.G.; Peterson, J.R.

doi:10.1016/0022-1902(81)80646-x

Cited by 18 publications

(6 citation statements)

References 7 publications

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“…37 They suggested the possibility that water reduction leads to the formation of soluble hydroxo complexes. Additionally, Musikas et al 41 observed the same phenomenon with CVs of Gd 3þ in aqueous solution, postulating that the irreversible reduction of Gd 3þ followed the mechanism,…”

Section: ' Results and Discussionmentioning

confidence: 89%

Cathodic Preconcentration of f-Elements on a Mercury Film Carbon Fiber Disk Microelectrode

et al. 2011

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Field detection and quantification of f-elements is an important problem in radioanalytical chemistry requiring small, portable devices. Here, characterization of a 10 μm Hg film carbon fiber disk microelectrode to accumulate f-elements is described. Accumulation was performed by cathodic deposition and evaluated by anodic stripping and subsequent ICPMS analyses. La(3+) was used as the model element, and subsequent studies were conducted on a 17 element mixture (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Th). In the model studies, La(3+) undergoes a sorption phenomenon, and as in other studies and confirmed by ICPMS, a monolayer of atoms on the electrode surface is formed. Dissolved O(2) was found to have no effect on the cathodic accumulation of La(3+). Consideration of electrode reaction conditions is made, and reactions are hypothesized. The limit of detection (LOD) was found to be 10(-7) M with mass detection of 10(9) atoms, approximately 5 orders of magnitude less than at conventionally sized electrodes. To solve a dilution problem in follow-on analyses, a suggestion to use microelectrode chip-based sensors was made.

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Section: ' Results and Discussionmentioning

confidence: 89%

Cathodic Preconcentration of f-Elements on a Mercury Film Carbon Fiber Disk Microelectrode

et al. 2011

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“…9 Although Cf 2+ is not inherently stable in solution, its existence has been established by radiopolarography in acetonitrile 10 and in aqueous solutions. 11 The known solid state and solution chemistry of Cf, specifically the stability of the divalent oxidation state, closely parallels that of Sm. Beyond Cf the An II oxidation state becomes increasingly stable, such that Cf occupies a pivotal point in the series at which divalent chemistry becomes significant.…”

Section: Introductionmentioning

confidence: 93%

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(ii)

et al. 2016

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The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf(II) is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf(II)(CH3SO2)3(-), prepared in the gas phase by reductive elimination of CH3SO2 from Cf(III)(CH3SO2)4(-). Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of Cf(III) and Sm(III), and no evidence for reduction of Cm(III). This reflects the comparative 3+/2+ reduction potentials: Cf(3+) (-1.60 V) ≈ Sm(3+) (-1.55 V) ≫ Cm(3+) (-3.7 V). Association of O2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. The new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf(II) coordination complexes and similar chemistry of Cf and Sm.

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“…However, these periodic trends, especially the standard reduction potentials, are almost exclusively obtained from aqueous media, and some of these data again would not withstand contemporary scrutiny. Finally, even though many of these values are available in compendia that long ago gathered dust, − a careful examination of postcurium data shows that much of it is not actually known and is based on rudimentary extrapolations. , …”

Section: Introductionmentioning

confidence: 99%

Electrochemical Studies of Selected Lanthanide and Californium Cryptates

et al. 2019

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Efforts to quantitatively reduce CfIII → CfII in solution as well as studies of its cyclic voltammetry have been hindered by its scarcity, significant challenges associated with manipulating an unusually intense γ emitter, small reaction scales, the need for nonaqueous solvents, and its radiolytic effects on ligands and solvents. In an effort to overcome these impediments, we report on the stabilization of CfII by encapsulation in 2.2.2-cryptand and comparisons with the readily reducible lanthanides, Sm3+, Eu3+, and Yb3+. Cyclic voltammetry measurements suggest that CfIII/II displays electrochemical behavior with characteristics of both SmIII/II and YbIII/II. The °E 1/2 values of −1.525 and −1.660 V (vs Fc/Fc+ in tetrahydrofuran (THF)) for [Cf(2.2.2-crypt)]3+/2+ and [Sm(2.2.2-crypt)]3+/2+, respectively, are similar. However, the ΔE values upon complexation by 2.2.2-cryptand for CfIII/II more closely parallels YbIII/II with postencapsulation shifts of 705 and 715 mV, respectively, whereas the shift of SmIII/II (520 mV) mirrors that of EuIII/II (524 mV). This suggests more structural similarities between CfII and YbII in solution than with SmII that likely originates from more similar ionic radii and local coordination environments, a supposition that is corroborated by crystallographic and extended X-ray absorption fine structure measurements from other systems. Competitive-ion binding experiments between EuIII/II, SmIII/II, and YbIII/II were also performed and show less favorable binding by YbIII/II. Connectivity structures of [Ln(2.2.2-cryptand)(THF)][BPh4]2 (Ln = EuII, SmII) are reported to show the important role that THF plays in these redox reactions.

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Electrochemical studies of trivalent californium and selected trivalent lanthanides in aqueous solution

Cited by 18 publications

References 7 publications

Cathodic Preconcentration of f-Elements on a Mercury Film Carbon Fiber Disk Microelectrode

Cathodic Preconcentration of f-Elements on a Mercury Film Carbon Fiber Disk Microelectrode

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(ii)

Electrochemical Studies of Selected Lanthanide and Californium Cryptates

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