To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO 3 ) 3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25 °C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of the Ln(NO 3 ) 3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO 3 ) 3 activity coefficients in the solutions with ionic strength up to 12 mol kg −1 can be estimated by both Pitzer and singleparameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg −1 ). On the other hand, for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO 3 ) 3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ∼ 95 % and ∼ 90 % for all solutions with the ionic strength up to 12 mol kg −1 and 20 mol kg −1 , respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.
This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+ ), sodium (Na + ), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22 Na and 13 C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+ , Na + , lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logK Nd and logK Na extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2 ] x ;(with x > 1). By substituting lanthanum (La 3+ ) for Nd 3+ in this system, NMR scoping experiments using 23 Na, 31 P nuclei and 13 C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of iv potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength.Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+ ) and 8hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+ ) and 8-hydroxyquinoline speciation.Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water.Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explo...
A significantly improved calibration of the High Purity Germanium detectors used by the Idaho National Laboratory Noble Gas Laboratory was performed during the annual NIST calibration. New sample spacers provide reproducible and secure support of samples at distances of 4, 12, 24, 50 and 100 cm. Bean, 15mL and 50mL Schlenk tube geometries were calibrated. Also included in this year's calibration was a correlation of detector dead-time with sample activity that can be used to predict the schedule of counting the samples at each distance for each geometry. This schedule prediction will help staff members set calendar reminders so that collection of calibration data at each geometry will not be missed. This report also correlates the counting efficiencies between detectors, so that if the counting efficiency on one detector is not known, it can be estimated from the same geometry on another detector.
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