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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Experimental Study on the Thermodynamics of the CaO-SiO{sub 2}-Ce{sub 2}O{sub 3} System at 1873 K

The phase relations in the CaO-SiO{sub 2}-Ce{sub 2}O{sub 3} system under the reducing atmosphere at 1873 K were determined by the conventional equilibrium and quenching method combined with scanning electron microscopy-electron probe microanalysis (SEM-EPMA) and X-ray diffraction (XRD) measurements on the quenched samples. Based on these analyses, a large part of the isothermal phase diagram was constructed. Furthermore, the thermodynamic activities of Ce{sub 2}O{sub 3} in the melts at 1873 K were measured by the chemical equilibrium method. Using the measured activity data, an empirical formula to estimate the activity coefficient of Ce{sub 2}O{sub 3} was proposed based on the regular solution model. It was found that, for the melts with the same Ce{sub 2}O{sub 3} contents, the thermodynamic activities of Ce{sub 2}O{sub 3} increase gradually with the rise of basicity (the ratio of CaO to SiO{sub 2}) of the melts. This implies that, from the thermodynamic point of view, the increase of basicity is favorable to the enrichment and precipitation of Ce-containing mineral phases.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Magnesian calcite solid solution thermodynamics inferred from authigenic deep-sea carbonate

Magnesian calcite is perhaps the most well studied solid solution in the geosciences due to the widespread use of marine carbonates to reconstruct paleoenvironment. Despite decades of research, the low temperature thermodynamic properties of magnesian calcite in seawater are poorly constrained, largely because very slow reaction kinetics prevent the direct measurement of equilibrium distribution coefficients ($K_d^{Mg}$) for anhydrous Mg-bearing minerals. In this study, we use the Mg content of authigenic calcite formed in deep-sea marine carbonate sediments to determine the dependence of $K_d^{Mg}$ on temperature and aqueous Mg/Ca between ~2 and 25 °C. We find that the solid activity coefficient of magnesite in Mg-calcite is strongly temperature dependent in this range, leading to predicted exsolution of Mg at low temperatures. At the temperatures typical of ocean bottom water, equilibrium Mg distribution coefficients are at least an order of magnitude lower than values inferred from inorganic calcite growth experiments. Moreover, the equilibrium temperature dependence of $K_d^{Mg}$ agrees well with field-based paleotemperature calibrations determined for low-Mg benthic and planktonic foraminifera at temperatures <20 °C. Partitioning of Mg in foraminiferal tests is expected to be highly dependent on the Mg/Ca ratio in the calcifying fluid, so ignoring secular variations in seawater Mg/Ca can lead to significant underestimation of paleotemperatures.

58 GEOSCIENCES↗
DOE OSTI2018

Magnesium Loss in Nd:YAG Pulsed Laser Welding of Aluminum Alloys

In the current investigation, the loss of magnesium (Mg) in Nd:YAG pulsed laser welding of a number of aluminum (Al) alloys was studied both experimentally and numerically. The experimental results showed that at a fixed average laser power, with the increasing pulse frequency, Mg concentration of the weld metals decreased. A numerical model was developed for the calculation of Mg evaporation from the weld pool. The model predicted a trend in the changes of Mg concentration of the weld pool, working best for alloys containing the higher levels of Mg. The calculations showed that with the increasing pulse frequency from 15 to 40 Hz, due to a decrease in the average temperature of the weld pool, Mg loss in terms of mass per unit area of the weld spot actually decreased from 230 × 10{sup −5} to 120 × 10{sup −5} kg/m{sup 2}. However, due to a decrease in the weld penetration/volume, the effective Mg loss of the weld metal in terms of concentration increased from 110 × 10{sup −1} to 260 × 10{sup −1} kg/m{sup 3}. It was shown that due to interactions between Mg and other main alloying elements, the activity coefficient of Mg had to be modified for the model to accurately predict Mg evaporation of the weld pool.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Recycling of Lead Pastes from Spent Lead–Acid Batteries: Thermodynamic Constraints for Desulphurization

Lead–acid batteries are important to modern society because of their wide usage and low cost. The primary source for production of new lead–acid batteries is from recycling spent lead–acid batteries. In spent lead–acid batteries, lead is primarily present as lead pastes. In lead pastes, the dominant component is lead sulfate (PbSO 4 , mineral name anglesite) and lead oxide sulfate (PbO•PbSO 4 , mineral name lanarkite), which accounts for more than 60% of lead pastes. In the recycling process for lead–acid batteries, the desulphurization of lead sulfate is the key part to the overall process. In this work, the thermodynamic constraints for desulphurization via the hydrometallurgical route for recycling lead pastes are presented. The thermodynamic constraints are established according to the thermodynamic model that is applicable and important to recycling of lead pastes via hydrometallurgical routes in high ionic strength solutions that are expected to be in industrial processes. The thermodynamic database is based on the Pitzer equations for calculations of activity coefficients of aqueous species. The desulphurization of lead sulfates represented by PbSO 4 can be achieved through the following routes. (1) conversion to lead oxalate in oxalate-bearing solutions; (2) conversion to lead monoxide in alkaline solutions; and (3) conversion to lead carbonate in carbonate solutions. Among the above three routes, the conversion to lead oxalate is environmentally friendly and has a strong thermodynamic driving force. Oxalate-bearing solutions such as oxalic acid and potassium oxalate solutions will provide high activities of oxalate that are many orders of magnitude higher than those required for conversion of anglesite or lanarkite to lead oxalate, in accordance with the thermodynamic model established for the oxalate system. An additional advantage of the oxalate conversion route is that no additional reductant is needed to reduce lead dioxide to lead oxide or lead sulfate, as there is a strong thermodynamic force to convert lead dioxide directly to lead oxalate. As lanarkite is an important sulfate-bearing phase in lead pastes, this study evaluates the solubility constant for lanarkite regarding the following reaction, based on the solubility data, PbO•PbSO 4 + 2H + ⇌ 2Pb 2+ + SO 4 2– + H 2 O(l).

25 ENERGY STORAGE↗
DOE OSTI2018

Distribution of P{sub 2}O{sub 5} and Na{sub 2}O Between Solid Solution and Liquid Phase in the CaO-SiO{sub 2}-Fe{sub 2}O{sub 3}-P{sub 2}O{sub 5}-Na{sub 2}O Slag System with High P{sub 2}O{sub 5} Content

The phosphorus content in hot metal will increase in future, because iron ores are steadily deteriorating in quality. Na{sub 2}O addition to slag is considered an effective method for increasing the efficiency of dephosphorization. In addition, Na{sub 2}O modification also facilitates phosphorus recovery from dephosphorization slag with high P{sub 2}O{sub 5} content by selective leaching. Therefore, it is necessary to investigate the distribution ratios of P{sub 2}O{sub 5} and Na{sub 2}O between solid solution and liquid phase in the CaO-SiO{sub 2}-Fe{sub 2}O{sub 3}-P{sub 2}O{sub 5}-Na{sub 2}O slag system. A linear relationship was found between the distribution ratio of P{sub 2}O{sub 5} and the Na{sub 2}O content in slag, and was independent of P{sub 2}O{sub 5} content. When the Na{sub 2}O content was high, the Na{sub 2}O content in the solid solution approached saturation and a new 2CaO·SiO{sub 2}-2CaO·Na{sub 2}O·P{sub 2}O{sub 5} solid solution formed. The addition of Na{sub 2}O decreased the P{sub 2}O{sub 5} content in solid solution, while it increased the mass fraction of solid solution in slag. The distribution ratio of P{sub 2}O{sub 5} increased with increase in the Fe{sub 2}O{sub 3} content and basicity of slag. An increase in P{sub 2}O{sub 5} content in slag results in an increase in the activity coefficient of P{sub 2}O{sub 5} both in the liquid phase and in the solid solution.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Evaluation of Experimental Studies in the U-Rich Region of the U-Pu Phase Diagram

Upon the re-examination of two experimental studies, additional thermophysical data pertaining to the uranium-rich portion of the uranium-plutonium binary phase diagram have been elucidated. The first study involved the analysis of solidification cooling curves following the processing of U-Pu alloys. Two phase transitions (liquidus and bcc) were evaluated and the results agreed very well with the established boundaries. The second study was actually performed over sixty years ago but still warrants recognition due to the paucity of thermodynamic data on the U-Pu system to date. From the investigation, the activity coefficients of plutonium in liquid uranium from 1813 K to 2042 K were derived assuming Henry’s law from which the partial molar excess Gibbs energy change of plutonium was obtained: Δ G-bar {sup ex}=R∗T∗ln γ{sub Pu}{sup o}=− 76694+39.2∗T(J/mol).

36 MATERIALS SCIENCE↗
DOE OSTI2019

Investigation of the Amide Proton Solvent Exchange Properties of Glycosaminoglycan Oligosaccharides

One-dimensional 1 H NMR experiments were conducted for aqueous solutions of glycosaminoglycan oligosaccharides to measure the amide proton temperature coefficients, activation energy barriers for solvent exchange, and evaluate the effect of pH on the solvent exchange properties. A library of mono- and oligosaccharides was prepared by enzymatic depolymerization of amide-containing polysaccharides and by chemical modification of heparin and heparan sulfate saccharides including members that contain a 3- O -sulfated glucosamine residue. The systematic evaluation of this saccharide library facilitated assessment of the effects of structural characteristics, such as size, sulfation number and site, and glycosidic linkage, on amide proton solvent exchange rates. Charge repulsion by neighboring negatively charged sulfate and carboxylate groups was found to have a significant impact on the catalysis of amide proton solvent exchange by hydroxide. Furthermore, this observation leads to the conclusion that solvent exchange rates must be interpreted within the context of a given chemical environment. On their own, slow exchange rates do not conclusively establish the involvement of a labile proton in a hydrogen bond and additional supporting experimental evidence such as reduced temperature coefficients is required.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

The Ionization Constants of DCO{sub 3}{sup -} and DPO{sub 4}{sup 2-} under Candu Reactor Primary Coolant Conditions by Raman Spectroscopy

The ionization constants of bicarbonate and hydrogen phosphate have been measured in light and heavy water up to 325 deg. C using Raman spectroscopy. Ionization constants in heavy water at temperatures above 100 deg. C have been measured for very few acids and bases. Together with other results, this work will be used to develop and verify models of the deuterium isotope effect on oxide solubilities in Candu reactor primary coolant. A custom-built titanium/sapphire flow cell was paired with a Horiba Jobin Yvon HR800 LabRAM system to collect Raman spectra of aqueous solutions under Candu primary coolant temperatures. The temperature-controlled cell is made of materials that are relatively inert under the extreme experimental conditions required for hydrothermal studies. Raman spectra were collected with detector polarizations parallel and perpendicular to the laser polarization. These were subtracted and corrected to obtain the reduced isotropic spectrum, which contains only symmetric vibrations, has a flat baseline, and has peak areas proportional to species concentration. Vibrational modes involving deuterium are shifted to lower wavenumbers in heavy water due to the increased mass of deuterium over hydrogen. The speciation between the two solvents is also measurably different. The relative concentration of the acidic species in solution increases with temperature, making its peaks easier to fit at high temperatures. The Raman band positions shift to lower wavenumbers with increasing temperature because the hydrogen bonding in bulk water begins to break down, which strengthens hydrogen bonding to the ions. The basic equilibrium constants were determined from the concentration of each species in solution combined with an activity coefficient model. A simplified form of the 'density' model was then fitted to the data. These fit results were combined with literature values of pK{sub w} in light and heavy water to determine the pK{sub a} values at saturation vapor pressure. The experimental results show excellent agreement with known literature values in light water where they exist at lower temperatures. These equilibrium constants are the first to be reported for both chemical systems in heavy water above 25 deg. C. This work extends the equilibrium constants in H{sub 2}O: - For HCO{sub 3}{sup -} from 250 deg. C to 325 deg. C; - For HPO{sub 4}{sup 2-} from 50 deg. C to 300 deg. C. These are the first ever ionization constants in D{sub 2}O for DPO{sub 4}{sup 2-} and the first values above 25 deg. C for DCO{sub 3}{sup -}. These results will be used to develop predictive models for the deuterium isotope effect on activated corrosion product transport under Candu nuclear reactor primary coolant conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Element Distribution in the Silicomanganese Production Process

A pilot scale, silicomanganese alloy production campaign was performed in a 440 kVA, single phase electric furnace in order to establish an overview of the minor- and trace element contents in process input raw materials and their distribution in the resulting primary and secondary products. Samples of the in-going raw materials (manganese ore, coke, quartzite, and high carbon ferromanganese slag) and the out-going products (silicomanganese alloy, silicomanganese slag, and dust) were analyzed by inductively coupled plasma mass spectrometry. The distribution of 51 elements between the product phases was discussed in terms of their boiling temperatures, Gibbs energies of oxidation and activity coefficients of elements in the metal. A thermochemical simulation using the thermochemical software FactSage 7.1 was also carried out in order to model element phase distribution between the alloy, slag, and dust/gas. The correlation between the model and experimental element concentrations in the silicomanganese slag and dust is fair for most elements. However, in the metal phase, fewer elements show good correlation between modeled results and measured experimental concentrations. The discrepancy could be explained by a lack of accurate thermodynamic descriptions for several minor species in the database.

36 MATERIALS SCIENCE↗
DOE OSTI2018

CFD Modeling of Boron Removal from Liquid Silicon with Cold Gases and Plasma

The present study focuses on a specific step of the metallurgical path of purification to provide solar-grade silicon: the removal of boron through the injection of H{sub 2}O(g)-H{sub 2}(g)-Ar(g) (cold gas process) or of Ar-H{sub 2}-O{sub 2} plasma (plasma process) on stirred liquid silicon. We propose a way to predict silicon and boron flows from the liquid silicon surface by using a CFD model (©Ansys Fluent) combined with some results on one-dimensional diffusive-reactive models to consider the formation of silica aerosols in a layer above the liquid silicon. The comparison of the model with experimental results on cold gas processes provided satisfying results for cases with low and high concentrations of oxidants. This confirms that the choices of thermodynamic data of HBO(g) and the activity coefficient of boron in liquid silicon are suitable and that the hypotheses regarding similar diffusion mechanisms at the surface for HBO(g) and SiO(g) are appropriate. The reasons for similar diffusion mechanisms need further enquiry. We also studied the effect of pressure and geometric variations in the cold gas process. For some cases with high injection flows, the model slightly overestimates the boron extraction rate, and the overestimation increases with increasing injection flow. A single plasma experiment from SIMaP (France) was modeled, and the model results fit the experimental data on purification if we suppose that aerosols form, but it is not enough to draw conclusions about the formation of aerosols for plasma experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Understanding the Applicability of Gas/Particle Partitioning Theory to SOA using Novel Chemically-Speciated Partitioning Measurements (Final Report)

The main objective of this research grant project was to investigate the physical-chemical processes and properties of particles and partitioning gases that influence gas/particle (G/P) partitioning and timescales for equilibration, to directly determine the conditions under which equilibrium G/P partitioning theory can be applied to secondary organic aerosol (SOA). SOA constitutes a major component of submicron particles in the atmosphere, which have important implications for air quality, human and ecosystem health, radiation balance, and climate; however SOA formation, evolution and losses are not well understood. Use of novel on-line measurements of chemically-speciated partitioning measurements of both gas-phase and particle-phase components was a central component to advancing these scientific goals. The key approach was to conduct environmental chamber studies with systems of increasing complexity to determine G/P partitioning rates and equilibrium states for chemically-speciated SOA components. The project builds on our previous work on gas-wall partitioning that must be understood in order to study G/P partitioning in chambers, and to help extrapolate the results to be atmospherically relevant. The goal was to employ measurements and modeling to systematically determine when G/P partitioning theory accurately describes the distribution of oxidized organic compounds in the gas and aerosol phases, and when and why it does not (e.g., aerosol phase-state kinetic limitations, non-ideal mixing, phase separation, oligomer formation,), for chemical and physical conditions typically found throughout the continental boundary layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2008

How Deep and Hot was Earth's Magma Ocean? Combined Experimental Datasets for the Metal-silicate Partitioning of 11 Siderophile Elements - Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd

Since approximately 1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients (D) for siderophile (iron-loving) elements are much different than those measured at low PT conditions. The high PT data have been used to argue for a magma ocean during growth of the early Earth. Initial conclusions were based on experiments and calculations for a small number of elements such as Ni and Co. However, for many elements only a limited number of experimental data were available then, and they only hinted at values of metal-silicate D's at high PT conditions. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements. At the same time several different models have been advanced to explain the siderophile elements in the earth's mantle: a) intermediate depth magma ocean; 25-30 GPa, b) deep magma ocean; up to 50 GPa, and c) early reduced and later oxidized magma ocean. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to update the predictive expressions outlined by Righter et al. (1997) with new experimental data from the last decade, test the predictive ability of these expressions against independent datasets (there are more data now to do this properly), and to apply the resulting expressions to the siderophile element patterns in Earth's upper mantle. The predictive expressions have the form: lnD = alnfO2 + b/T + cP/T + d(1Xs) + e(1Xc) + SigmafiXi + g These expressions are guided by the thermodynamics of simple metal-oxide equilibria that control each element, include terms that mimic the activity coefficients of each element in the metal and silicate, and quantify the effect of variable oxygen fugacity. Preliminary results confirm that D(Ni) and D(Co) converge at pressures near 25-30 GPa and approximately 2200 K, and show that D(Pd) and D(Cu) become too low at the PT conditions of the deepest models. Furthermore, models which force fit V and Cr mantle concentrations by metal-silicate equilibrium overlook the fact that at early Earth mantle fO2, these elements will be more compatible in Mg-perovskite and (Fe,Mg)O than in metal. Thus an intermediate depth magma ocean, at 25-30 GPa, 2200 K, and at IW-2, can explain more mantle siderophile element concentrations than other models.

Righter, Kevin↗
DOE OSTI2022

Linear relationships for modeling CO 2 absorption in aqueous alkanolamine solutions in a thermodynamically consistent way

A thermodynamically consistent model for the carbon dioxide (CO 2 ) absorption in aqueous alkanolamine system is of great importance in the research and development of a CO 2 capture process. To facilitate the development of thermodynamic models, linear Gibbs free energy, enthalpy, and heat capacity relationships using well-known amines as reference are used to correlate the standard reference state properties of ionic species with those of molecular species in the electrolyte system, which has been approved to provide a reliable and consistent way to estimate required parameters when there is minimal or no appropriate experimental data available. Here, the proposed relationships have been applied to the development of an electrolyte nonrandom two liquid (NRTL) activity coefficient model for CO 2 absorption in aqueous 1-amino-2-propanol (A2P) solution, as an example to demonstration the methodology. With limited vapor–liquid equilibrium data and other thermodynamic properties, the parameters in the electrolyte NRTL model are identified with good accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Influence of Hydronium Ions in Zeolites on Sorption

Abstract In the presence of sufficient concentrations of water, stable, hydrated hydronium ions are formed in the pores and at the surface of solid acids such as zeolites. For a medium‐pore zeolite, such as zeolite MFI, hydrated hydronium ions consist of eight water molecules and have an effective volume of 0.24 nm 3 . In their presence, larger organic molecules can only adsorb in the portions of the pore that are not occupied by hydronium ions. As a consequence, the available pore volume decreases proportionally to the concentration of the hydronium ions. The higher charge density (the increasing ionic strength) that accompanies an increasing concentration of hydronium ions leads to an increase in the activity coefficients of the adsorbed substrates, thus, weakening the interactions between the organic part of the molecules and the zeolite and favoring the interactions with polar groups. The quantitative understanding of these interactions makes it possible to link a collective property such as hydrophilicity and hydrophobicity of zeolites to specific interactions on molecular level.

Eckstein, Sebastian↗
DOE OSTI2023

A Thermodynamic Model for Nd(III)–Sulfate Interaction at High Ionic Strengths and Elevated Temperatures: Applications to Rare Earth Element Extraction

Neodymium (Nd), a rare earth element (REE), is critical to numerous industries. Neodymium can be extracted from ore concentrates, waste materials, or recycled materials such as recycled Nd-Fe-B permanent magnets. In a standard process, concentrated sulfuric acid (H 2 SO 4 ) is used as an extraction/leaching agent. Therefore, knowledge of Nd(III)–sulfate interaction at high ionic strengths is important for optimization of the extraction process. In addition, sulfate is also a major species in natural surface waters and present in nuclear waste streams. Nd(III) has been used a chemical analog to trivalent actinides in nuclear waste research and development. Consequently, knowledge of Nd(III)-sulfate interactions is also impactful to the field of nuclear waste management. Here, in this study, we have developed a thermodynamic model that can describe the interaction of Nd(III) with sulfate to ionic strengths up to ~ 16.5 mol·kg –1 and to temperatures up to 100 °C. The model adopts the Pitzer formulation to describe activity coefficients of aqueous species. This model can be used to design and optimize a chemical process for REE recovery from ore concentrates, recycled materials, and acid mine drainage (AMD) and to understand the mobility of REEs and actinides in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Influence of Oxygen on Cu Distribution Behavior Between Molten Iron and FeS-Based Flux

Cu distribution behavior between molten iron and a sulfide flux was investigated under different oxygen contents in the sulfide flux to clarify the effect of oxygen content in FeS-based flux on Cu removal. The activity coefficient of CuS{sub 0.5} could be experimentally estimated according to the oxygen content. Based on the present result, the possibility of Cu removal by sulfide flux containing a certain amount of oxide was discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermodynamic properties of the Nd-Bi system via emf measurements, $\mathrm{DFT}$ calculations, machine learning, and $\mathrm{CALPHAD}$ modeling

Thermodynamic properties of the Nd-Bi system were investigated using a combination of experimental measurements, first-principles calculations based on density functional theory (DFT), data mining and machine learning (DM + ML) predictions, and calculation of phase diagrams (CALPHAD) modeling. The electromotive force (emf) of Nd-Bi alloys in molten LiCl-KCl-NdCl 3 at 773–973 K was measured via coulometric titration of Nd into Bi for the determination of thermochemical properties such as activity coefficients and solubilities of Nd in Bi. A new peritectic reaction of [liquid + NdBi 2 = Nd 3 Bi 7 ] at 774 K was confirmed using differential scanning calorimetry, structural (X-ray diffraction), and microstructural (scanning electron microscopy) analyses. The unknown crystal structure of NdBi2 was suggested to be a mixture of the anti-La 2 Sb configuration and the La 2 Te-type configuration based on ML predictions for over 26,000 data-mined AB 2 -type configurations together with DFT-based verifications. Using the newly acquired experimental data and DFT-based calculations, the thermodynamic description of the Nd-Bi system was remodeled, and a more complete Nd-Bi phase diagram was calculated, including the Nd 3 Bi 7 compound, invariant transition reactions, and liquidus temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Experimental and modeling studies of PR and ND oxalate solubility to high ionic strengths: Insight into actinide(III) oxalates

Actinide oxalates are chemical compounds important to nuclear industry, ranging from actinide separation in waste reprocessing, to production of specialty actinides, and to disposal of high level nuclear waste (HLW) and spent nuclear fuel (SNF). In this study, the solubility constants for Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O by performing solubility experiments in HNO 3 and mixtures of HNO 3 and H 2 C 2 O 4 at 23.0 ± 0.2 °C have been determined. The targeted starting materials, Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O, were successfully synthesized at room temperature using PrCl 3 , NdCl 3 and oxalic acid as the source metrials. Then, we utilized the targeted solubility-controlling phases to conduct solubility measurements. There was no phase change over the entire periods of experiments, demonstrating that Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O were the solubility-controlling phases in our respective experiments. Based on our experimental data, we have developed a thermodynamic model for Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O in the mixtures of HNO 3 and H 2 C 2 O 4 to high ionic strengths. The model for Pr 2 (C 2 O 4 ) 3 •10H 2 O reproduces well the reported experimental data for Pu 2 (C 2 O 4 ) 3 •10H 2 O, which are not utilized for the model development, demonstrating that Pr(III) is an excellent analog for Pu(III). Similarly, the model for Nd 2 (C 2 O 4 ) 3 •10H 2 O reproduces the solubility of Am 2 (C 2 O 4 ) 3 •10H 2 O and Cm 2 (C 2 O 4 ) 3 •10H 2 O. The Pitzer model was used for the calculation of activity coefficients. Based on the published, well established model for dissociation constants for oxalic acid and stability constants for actinide-oxalate complexes [i.e., AmC 2 O 4 + , and Am(C 2 O 4 ) 2 - ] to high ionic strengths, we have obtained the solubility constants (log 10 K 0 ) for the following reactions at 25 °C, Pr 2 (C 2 O 4 ) 3 •10H 2 O ⇌ 2Pr 3+ + 3C 2 O 4 2- + 10H 2 O(l). Nd 2 (C 2 O 4 ) 3 •10H 2 O ⇌ 2Nd 3+ + 3C 2 O 4 2- + 10H 2 O(l). to be -30.82 ± 0.30 (2σ), and - 31.14 ± 0.35 (2σ), respectively. These values for can be directly applied to Pu 2 (C 2 O 4 ) 3 •10H 2 O, Am 2 (C 2 O 4 ) 3 •10H 2 O and Cm 2 (C 2 O 4 ) 3 •10H 2 O. The model established for actinide oxalates by this study provides the needed knowledge with regard to solubilities of actinide/REE oxalates at various ionic strengths, and is expected to find applications in many fields, including the geological disposal of nuclear waste and the mobility of REE under the surface conditions, as Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O can be regarded as the pure Pr and Nd end-members of deveroite, a recently discovered natural REE oxalate with the following stoichiometry, (Ce 1.01 Nd 0.33 La 0.32 Pr 0.11 Y 0.11 Sm 0.01 Pb 0.04 U 0.03 Th 0.01 Ca 0.04 ) 2.01 (C 2 O 4 ) 2.99 •9.99H 2 O. Regarding its importance in the geological disposal of nuclear waste, Am 2 (C 2 O 4 ) 3 •10H 2 O/Pu 2 (C 2 O 4 ) 3 •10H 2 O/Cm 2 (C 2 O 4 ) 3 •10H 2 O can be the source-term phase for actinides, as demonstrated by the instance in the disposal in clay/shale formations. This is exemplified by the stability of Am 2 (C 2 O 4 ) 3 •10H 2 O in comparison with Am(OH) 3 (am), Am(OH) 3 (s) and AmCO 3 (OH)(s) under the relevant geological repository conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗