Actinide Thermodynamics at Elevated Temperatures

The postclosure chemical environment in the proposed Yucca Mountain repository is expected to experience elevated temperatures. Predicting migration of actinides is possible if sufficient, reliable thermodynamic data on hydrolysis and complexation are available for these temperatures. Data are scarce and scattered for 25 degrees C, and nonexistent for elevated temperatures. This collaborative project between LBNL and PNNL collects thermodynamic data at elevated temperatures on actinide complexes with inorganic ligands that may be present in Yucca Mountain. The ligands include hydroxide, fluoride, sulfate, phosphate and carbonate. Thermodynamic parameters of complexation, including stability constants, enthalpy, entropy and heat capacity of complexation, are measured with a variety of techniques including solvent extraction, potentiometry, spectrophotometry and calorimetr

WOSMIP II- Workshop on Signatures of Medical and Industrial Isotope Production

Medical and industrial fadioisotopes are fundamental tools used in science, medicine and industry with an ever expanding usage in medical practice where their availability is vital. Very sensitive environmental radionuclide monitoring networks have been developed for nuclear-security-related monitoring [particularly Comprehensive Test-Ban-Treaty (CTBT) compliance verification] and are now operational

Thermodynamics of neptunium(V) fluoride and sulfate at elevated temperatures

Complexation of neptunium(V) with fluoride and sulfate at elevated temperatures was studied by microcalorimetry. Thermodynamic parameters, including the equilibrium constants and enthalpy of protonation of fluoride and sulfate, and the enthalpy of complexation between Np(V) and fluoride and sulfate at 25 - 70 C were determined. Results show that the complexation of Np(V) with fluoride and sulfate is endothermic and that the complexation is enhanced by the increase in temperature - a three-fold increase in the stability constants of NpO{sub 2}F(aq) and NpO{sub 2}SO{sub 4}{sup -} as the temperature is increased from 25 to 70 C

Complexation of Neptunium(V) with Fluoride at Elevated Temperatures

Complexation of neptunium(V) with fluoride at elevated temperatures was studied by spectrophotometry and microcalorimetry. Two successive complexes, NpO{sub 2}F(aq) and NpO{sub 2}F{sub 2}{sup -}, were identified by spectrophotometry in the temperature range of 10-70 C. Thermodynamic parameters, including the equilibrium constants and enthalpy of complexation between Np(V) and fluoride at 10-70 C were determined. Results show that the complexation of Np(V) with fluoride is endothermic and that the complexation is enhanced by the increase in temperature - a two-fold increase in the stability constants of NpO{sub 2}F(aq) and more than five-fold increase in the stability constants of NpO{sub 2}F{sub 2}{sup -} as the temperature is increased from 10 to 70 C

Spectrophotometric and Calorimetric Studies of Np(V) Complexation with Sulfate at 10-70oC

Sulfate, one of the inorganic constituents in the groundwater of nuclear waste repository, could affect the migration of radioactive materials by forming complexes. Spectrophotometric and microcalorimetric titrations were performed to identify the Np(V)/sulfate complex and determine the equilibrium constants and enthalpy of complexation at 10-70 C. Results show that the complexation of Np(V) with sulfate is weak but slightly enhanced by the increase in temperature. The complexation is endothermic and becomes more endothermic with the increase in temperature. The enhanced complexation at elevated temperatures is due to the increasingly larger entropy of complexation that exceeds the increase in enthalpy, suggesting that the complexation of Np(V) with sulfate is entropy-driven

Actinide Thermodynamics at Elevated Temperatures

The postclosure chemical environment in the proposed Yucca Mountain repository is expected to experience elevated temperatures. Predicting migration of actinides is possible if sufficient, reliable thermodynamic data on hydrolysis and complexation are available for these temperatures. Data are scarce and scattered for 25 degrees C, and nonexistent for elevated temperatures. This collaborative project between LBNL and PNNL collects thermodynamic data at elevated temperatures on actinide complexes with inorganic ligands that may be present in Yucca Mountain. The ligands include hydroxide, fluoride, sulfate, phosphate and carbonate. Thermodynamic parameters of complexation, including stability constants, enthalpy, entropy and heat capacity of complexation, are measured with a variety of techniques including solvent extraction, potentiometry, spectrophotometry and calorimetr

Complexation of Plutonium (IV) with Fluoride at Variable Tempeartures

Complexation of Pu(IV) with fluoride was studied by solvent extraction at 25, 40 and 55 C in 2.2 mol {center_dot} kg{sup -1} HClO{sub 4}. The distribution ratio of Pu(IV) between the organic and aqueous phases decreased as the concentration of fluoride was increased due to the formation of Pu(IV)-F complexes in the aqueous phase. Two complexes, PuF{sup 3+} and PuF{sub 2}{sup 2+}, were identified under the conditions in this work and their stability constants at 25, 40 and 55 C and I = 2.2 mol {center_dot} kg{sup -1} HClO{sub 4} were determined from the distribution data. The Specific Ion Interaction approach (SIT) was used to extrapolate the constants to the state of infinite dilution. Data from this work indicate that the complexation of Pu(IV) with fluoride is endothermic and entropy-driven. The complexation becomes stronger at higher temperatures