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Abstract  

Capillary electrophoresis (CE) is a useful method for rapid separations of metal cations. Under ideal conditions, CE can provide complete separation of the trivalent lanthanides in less than 10 min. Simple organic ligands must be included in the electrolyte matrix to achieve good resolution between the cations. In this paper, we demonstrate how to use complexation constants from the literature to design separation protocols for the trivalent f-elements.

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Summary  

A solvent extraction method was used to determine the stability constants of Np(V) complexes with fluoride and sulfate in 1.0M NaClO4 from 25 to 60 °C. The distribution ratio of Np(V) between the organic and aqueous phases was found to decrease as the concentrations of fluoride and sulfate were increased. Stability constants of the 1 : 1 Np(V)-fluoride complexes and the 1 : 1 Np(V)-sulfate and 1 : 2 Np(V)-sulfate complexes, dominant in the aqueous phase under the experimental conditions, were calculated from the effect of [F-] and [SO4 2-] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different temperatures by using the Van't Hoff equation.

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Abstract  

Complexation of neptunium(V) with fluoride in aqueous solutions at elevated temperatures was studied by spectrophotometry and microcalorimetry. Two successive complexes, NpO2F(aq) and NpO2F2 , 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 NpO2F(aq) and more than five-fold increase in the stability constants of NpO2F2 as the temperature is increased from 10 to 70°C.

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Abstract  

The complexation of plutonium(IV) with sulfate at variable temperatures has been investigated by solvent extraction method. A NaBrO3 solution was used as holding oxidant to maintain the plutonium(IV) oxidation state throughout the experiments. The distribution ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased. Stability constants of the 1:1 and 1:2 Pu(IV)-HSO4 complexes, dominant in the aqueous phase, were calculated from the effect of [HSO4 ] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different temperatures using the Van’t Hoff equation.

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Abstract  

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, indicating that the complexation of Np(V) with sulfate is entropy-driven.

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Abstract  

The complexation of Np(V) with phosphate at elevated temperatures was studied by a synergistic extraction method. A mixed buffer solution of TRIS and MES was used to maintain an appropriate pH value during the distribution experiments. The distribution ratio of Np(V) between the organic and aqueous phases was found to decrease as the concentrations of phosphate were increased. Stability constants of the 1:1 and 1:2 Np(V)-HPO4 2− complexes, dominant in the aqueous phase under the experimental conditions, were calculated from the effect of [HPO4 2−] on the distribution ratio. The thermodynamic parameters including enthalpy and entropy of complexation between Np(V) and HPO4 2− at 25 °C–55 °C were calculated by the temperature coefficient method.

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Journal of Radioanalytical and Nuclear Chemistry
Authors: P. Bachelor, J. Friese, C. Aalseth, J. McIntyre, H. Miley, R. Perkins, and G. Warren

Abstract  

In anticipation of a nuclear detonation, techniques to quickly assess the radiation exposure of evacuees should be developed. Based on experience relating neutron radiation exposures to activation products, measurement of activation products can be performed in a few minutes. Personal items exposed to significant levels of radiation allows neutron dose assessment via the activation products. This approach allows prompt collection of important data on human exposure following a nuclear attack. Data collected will facilitate triage decisions for emergency medical treatment to ameliorate the radiation effects on exposed individuals. Activation experiments with everyday items exposed to a neutron source are presented.

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Journal of Radioanalytical and Nuclear Chemistry
Authors: M. Douglas, J. Friese, G. Warren, P. Bachelor, O. Farmer, A. Choiniere, S. Schulte, and C. Aalseth

Abstract  

A project has been undertaken at Pacific Northwest National Laboratory (PNNL) to tailor a series of efficient chemical separations to allow the rapid quantification of gamma-ray emitting isotopes in mixed fission product (MFP) samples. In support of that goal, modeling of singles and coincident gamma-ray spectra that would result from various chemical separation strategies has been performed. These simulated spectra have identified likely instances of spectral interference and have provided an estimate of the time window available for the detection of radionuclides following various chemical separation schemes. A description of results to date is presented here, demonstrating the utility of this approach for improved processing and analysis of fission product samples.

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Abstract  

Lanthanides are common fission products and the ability to separate and quantify these elements is critical to rapid radiochemistry applications. Published lanthanide separations using Eichrom Ln Spec resin utilize an HCl gradient. Here it is shown that the efficacy and resolution of the separation is improved when a nitric acid gradient is used instead. The described method allows parallel processing of many samples in 1.5 h followed by 60 min counting for quantification of 9 radioisotopes of 7 lanthanide elements.

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Journal of Radioanalytical and Nuclear Chemistry
Authors: Rosara Payne, J. Drader, J. Friese, L. Greenwood, C. Hines, L. Metz, J. Kephart, M. King, B. Pierson, J. Smith, and D. Wall

Abstract  

Washington State University’s 1 MW TRIGA reactor has a long history of utilization for neutron activation analysis (NAA). TRIGA reactors have the ability to pulse, reach supercritical (k > 1) for short bursts of time (~50 ms). At this high power and fast time the energy spectrum and neutron fluence are largely uncharacterized. The pulse neutron energy spectrum and fluence were determined by the activation of Cu, Au, Co, Fe, and Ti. These analyses were completed with and without Cd shielding to determine reproducibility between pulses. The applications and implications of the neutron energy and fluence reproducibility to the use of pulsed NAA will be discussed.

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