Oxidation of trivalent plutonium in acid solution by xenon difluoride and by the fluoroxysulfate ion, SO sub 4 F sup minus 1

Journal Article · Wed Aug 23 00:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00316a021· OSTI ID:7166955

Cook, R L; Sullivan, J C; Appelman, E H ^[1]; Woods, M ^[2]

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1. Argonne National Lab., IL (USA)
2. Rosary College, River Forest, IL (USA)

Stopped-flow spectrophotometry was used to study the oxidation of plutonium(III) to plutonium(IV) is 1 M HClO{sub 4} by XeF{sub 2} and by the fluoroxysulfate ion, SO{sub 4}F{sup {minus}}. In both reactions, 2 mol of Pu(III) is oxidized per 1 mol of oxidant consumed, and neither Pu(V) or Pu(VI) appears to be formed either as an intermediate or as an initial product, although an excess of XeF{sub 2} does slowly oxidize the Pu(IV) product to Pu(VI). At 2{degree}C the reactions have respective bimolecular rate constants of 1160 {plus minus} 70 and 120 {plus minus} 9 M{sup {minus}1} s{sup {minus}1}, expressed in terms of -d(Pu(III))/dt. Over the temperature range 2-24{degree}C, the activation parameters for the XeF{sub 2} reaction are {Delta}H{sup {double dagger}} = 39.5 {plus minus} 8.6 kJ/mol and {Delta}S{sup {double dagger}} = {minus}48.3 {plus minus} 29 J/(mol K), while those for the SO{sub 4}F{sup {minus}} reaction are {Delta}H{sub {double dagger}} = 30.8 {plus minus} 2.3 kJ/mol and {Delta}S{sup {double dagger}} = {minus}98.5 {plus minus} 7.8 J/(mol K). Mechanisms are postulated that invoke a sequence of two one-electron-oxidation steps. 24 refs., 2 tabs.

• OSTI ID: 7166955
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:17; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPOUNDS
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
NUMERICAL DATA
OXIDATION
OXYGEN COMPOUNDS
PLUTONIUM COMPOUNDS
RARE GAS COMPOUNDS
REDOX REACTIONS
SULFATES
SULFUR COMPOUNDS
TRANSURANIUM COMPOUNDS
XENON COMPOUNDS
XENON FLUORIDES