Disproportionation and polymerization of plutonium(IV) in dilute aqueous solutions

Conference · Sat Dec 31 04:00:00 EST 1983

DOI:https://doi.org/10.1557/PROC-26-867· OSTI ID:59149

Newton, T W; Rundberg, V L

The rates of polymerization and disproportionation of Pu(IV) have been studied using low concentrations: (1.7 - 10) x 10{sup -}M Pu, (0.8 - 12) x 10{sup -}M HCl and 0.0iM ionic strength. Osmium(II) complexes such as the tris-4,4`-2,2`-bipyridine complex were found to react rapidly with Pu(IV) but very slowly, if at all, with Pu(IV) polymer, Pu(III), or Pu(V). Thus, it is possible to determine unreacted Pu(IV) in the presence of rection products by using Os(II) complexes. Disproportionation reaction products, Pu(III) and Pu(V), were determined using their reactions with Ce(IV) sulfate. We find -d[Pu(IV)]/dt = k`[Pu(IV)]{sup 2} at constant pH. Log k` varies from about 4.25 at pH 3 to about 7.0 at pH 4.1 (units for k` are M{sup -1}min{sup -1}). The [H{sup +}] dependence varies from about -2 to -3 over the pH range studied. The measured rate is the sum of those for polymerization and disproportionation; the latter reaction amounts to about 75% of the total at pH 3 and 20% at pH 4. The second-order rate constants for disproportionation are very much larger than expected on the basis of extrapolation from 0.2 to 1.0M HC10{sub 4} solutions. The products of the reaction do not affect the rate, but U(VI), aged Pu(IV) polymer, and CO{sub 2} increase the rate.

• Research Organization: Los Alamos National Lab., NM (United States)
• DOE Contract Number: W-7405-ENG-36
• OSTI ID: 59149
• Report Number(s): LA-UR--83-3295; CONF-831174--29; ON: DE84003799
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
AQUEOUS SOLUTIONS
CERIUM SULFATES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
OSMIUM COMPLEXES
OXIDATION
PH VALUE
PLUTONIUM COMPOUNDS
POLYMERIZATION
REDUCTION
Yucca Mountain Project