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rdf:type
lifeskim:mentions
pubmed:issue
13
pubmed:dateCreated
2002-6-24
pubmed:abstractText
Detailed voltammetric results for five uranyl coordination complexes are presented and analyzed using digital simulations of the voltammetric data to extract thermodynamic (E(1/2)) and heterogeneous electron-transfer kinetic (k(0) and alpha) parameters for the one-electron reduction of UO(2)(2+) to UO(2)(+). The complexes and their corresponding electrochemical parameters are the following: [UO(2)(OH(2))(5)](2+) (E(1/2) = -0.169 V vs Ag/AgCl, k(0) = 9.0 x 10(-3) cm/s, and alpha = 0.50); [UO(2)(OH)(5)](3-) (-0.927 V, 2.8 x 10(-3) cm/s, 0.46); [UO(2)(C(2)H(3)O(2))(3)](-) (-0.396 V, approximately 0.1 cm/s, approximately 0.5); [UO(2)(CO(3))(3)](4-) (-0.820 V, 2.6 x 10(-5) cm/s, 0.41); [UO(2)Cl(4)](2-) (-0.065 V, 9.2 x 10(-3) cm/s, 0.30). Differences in the E(1/2) values are attributable principally to differences in the basicity of the equatorial ligands. Differences in rate constants are considered within the context of Marcus theory of electron transfer, but no specific structural change(s) in the complexes between the two oxidation states can be uniquely identified with the underlying variability in the heterogeneous rate constants and electron-transfer coefficients.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Jul
pubmed:issn
0020-1669
pubmed:author
pubmed:issnType
Print
pubmed:day
1
pubmed:volume
41
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
3542-7
pubmed:dateRevised
2003-11-3
pubmed:year
2002
pubmed:articleTitle
Redox energetics and kinetics of uranyl coordination complexes in aqueous solution.
pubmed:affiliation
Chemistry Division and the G. T. Seaborg Institute for Transactinium Science, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. demorris.lanl.gov
pubmed:publicationType
Journal Article