The aqueous chemistry of radium

Available literature data on the aqueous chemistry of radium are compiled. There are limited available experimental data and a significant portion of the data has been estimated using electrostatic techniques, typically based on the corresponding data of barium. The available data are compared with the corresponding data of barium (and strontium) and a methodology for estimating additional radium thermochemical data is described

Disordered Crystal Structure and Anomalously High Solubility of Radium Carbonate

XRD measurements of RaCO3 revealedthat it isnot isostructural with witherite, and direct-space ab initio modeling showed that the carbonate oxygens are highly disordered.It was found that the solubility of RaCO3 is unexpectedlyhigher than the solubility of witherite (log(10) K (sp) (0) = -7.5 and -8.56,respectively), supporting the disordered nature of RaCO3. EXAFS data revealed an ionic radius of Ra2+ of 1.55 & ANGS;. Radium is the only alkaline-earth metal which forms disorderedcrystals in its carbonate phase.Radium-226 carbonate was synthesized from radium-bariumsulfate ((Ra0.76Ba0.24SO4)-Ra-226) at room temperature and characterized by X-ray powder diffraction(XRPD) and extended X-ray absorption fine structure (EXAFS) techniques.XRPD revealed that fractional crystallization occurred and that twophases were formed the major Ra-rich phase, Ra(Ba)CO3, and a minor Ba-rich phase, Ba(Ra)CO3, crystallizingin the orthorhombic space group Pnma (no. 62) thatis isostructural with witherite (BaCO3) but with slightlylarger unit cell dimensions. Direct-space ab initio modeling shows that the carbonate oxygens in the major Ra(Ba)CO3 phase are highly disordered. The solubility of the synthesizedmajor Ra(Ba)CO3 phase was studied from under- and oversaturationat 25.1 & DEG;C as a function of ionic strength using NaCl as thesupporting electrolyte. It was found that the decimal logarithm ofthe solubility product of Ra(Ba)CO3 at zero ionic strength(log(10) K (sp) (0)) is-7.5(1) (2 & sigma;) (s = 0.05 g & BULL;L-1). This is significantly higher than the log(10) K (sp) (0) of witheriteof -8.56 (s = 0.01 g & BULL;L-1), supporting the disordered nature of the major Ra(Ba)CO3 phase. The limited co-precipitation of Ra2+ within witherite,the significantly higher solubility of pure RaCO3 comparedto witherite, and thermodynamic modeling show that the results obtainedin this work for the major Ra(Ba)CO3 phase are also applicableto pure RaCO3. The refinement of the EXAFS data revealsthat radium is coordinated by nine oxygens in a broad bond distancedistribution with a mean Ra-O bond distance of 2.885(3) & ANGS;(1 & sigma;). The Ra-O bond distance gives an ionic radius ofRa(2+) in a 9-fold coordination of 1.545(6) & ANGS; (1 & sigma;)

Disordered Crystal Structure and Anomalously High Solubility of Radium Carbonate

Radium-226 carbonate was synthesized from radium-barium sulfate (226Ra0.76Ba0.24SO4) at room temperature and characterized by X-ray powder diffraction (XRPD) and extended X-ray absorption fine structure (EXAFS) techniques. XRPD revealed that fractional crystallization occurred and that two phases were formed─the major Ra-rich phase, Ra(Ba)CO3, and a minor Ba-rich phase, Ba(Ra)CO3, crystallizing in the orthorhombic space group Pnma (no. 62) that is isostructural with witherite (BaCO3) but with slightly larger unit cell dimensions. Direct-space ab initio modeling shows that the carbonate oxygens in the major Ra(Ba)CO3 phase are highly disordered. The solubility of the synthesized major Ra(Ba)CO3 phase was studied from under- and oversaturation at 25.1 \ub0C as a function of ionic strength using NaCl as the supporting electrolyte. It was found that the decimal logarithm of the solubility product of Ra(Ba)CO3 at zero ionic strength (log10 Ksp0) is −7.5(1) (2σ) (s = 0.05 g\ub7L-1). This is significantly higher than the log10 Ksp0 of witherite of −8.56 (s = 0.01 g\ub7L-1), supporting the disordered nature of the major Ra(Ba)CO3 phase. The limited co-precipitation of Ra2+ within witherite, the significantly higher solubility of pure RaCO3 compared to witherite, and thermodynamic modeling show that the results obtained in this work for the major Ra(Ba)CO3 phase are also applicable to pure RaCO3. The refinement of the EXAFS data reveals that radium is coordinated by nine oxygens in a broad bond distance distribution with a mean Ra-O bond distance of 2.885(3) \uc5 (1σ). The Ra-O bond distance gives an ionic radius of Ra2+ in a 9-fold coordination of 1.545(6) \uc5 (1σ)

On the solubility of radium sulfate and carbonate

Radium is one of the most toxic elements and its concentration in different human activities and migration from man-made wastes provokes a strong interest in environmental science. To be able to model the migration process, reliable experimental thermodynamic data of radium compounds are needed.In this work details of the safe radium source disassembly which were previously used in brachytherapy are described and different methods for conversion of RaSO4 into aqueous solution are reviewed. The method of choice included three cycles of RaSO4 heating in 1.5 M Na2CO3 up to 85 \ubaC, cooling and subsequent removal of supernatant. X-ray diffraction studies showed that the method allows the synthesis of amorphous RaCO3, which can be dissolved in mineral acid. Gamma spectrometric measurements showed that most of the initial RaSO4 was converted into solution and that 7 \ub1 1 % of the initial 210Pb was co-precipitated with RaCO3. Synthesized RaCO3 was dissolved in HCl to prepare a radium stock solution. The radium stock solution was used to determine the solubility of pure RaSO4 and RaCO3 from oversaturation using Na2SO4 and Na2CO3 as a source of sulfate and carbonate ions. The solubility was determined at 25.1 \ubaC as a function of ionic strength using NaCl media. The concentration of radium was measured by gamma spectrometry after separation of the aqueous phase from the solid phase using ultracentrifugation. The extended specific ion interaction theory was used to extrapolate solubility product constants to zero ionic strength (log10 Ksp\ub0 = -10.16 \ub1 0.05 for RaSO4 and log10 Ksp\ub0 = -7.73 \ub1 0.56 for RaCO3) and to calculate ion interaction coefficients.A comparison of the shapes of the radium solubility curves for both anions with the shapes of corresponding barium solubility curves demonstrates the similarity of the behaviour of radium and barium salts in saline solutions. It can be supposed that due to the similarity of the radium and barium effective ionic radii, and the same charge, these ions undergo similar specific ion interactions in NaCl media

Weak barium and radium hydrolysis using an ion exchange method and its uncertainty assessment

The hydrolysis of Ba2+and Ra2+was studied at 25 \ub0C in aqueous mixtures of NaOH and NaClO4using an ion exchange method and radiotracer and batch techniques. The distribution of133Ba and226Ra between solid (ion exchange resin) and aqueous (mixture of NaOH and NaClO4) phases was measured via gamma spectrometry and liquid scintillation counting. The total ionic strength was kept constant and the concentration of NaOH in the aqueous phase was varied from 0 (pure NaClO4) to pure NaOH from sample to sample. It was shown that an increase of the Ba2+or Ra2+concentration in the aqueous phase with an increase of the NaOH concentration cannot be explained solely by Ba2+or Ra2+activity coefficient differences in the NaOH and NaClO4media (salting out) and that weak BaOH+and RaOH+ion pairing occurs in the systems studied. A model for weak ion association was developed and apparent BaOH+and RaOH+stability constants were derived assuming the formation of weak aqueous NaOH(aq) ion pairs via non-linear curve fitting. It was demonstrated that systematic uncertainties have a much greater contribution to the NaOH(aq), BaOH+and RaOH+stability constant uncertainty budget compared to stochastic uncertainties and a method for estimation of the systematic uncertainties was proposed. The method combines fitting, restricted primitive model computations with surveyed literature data that resulted in a stability constant for NaOH(aq) that ranged from 0 to 1 at ionic strengths below 5 mol\ub7kg−1(i.e. KNaOH= 0.5 \ub1 0.5, where the uncertainty is a systematic 95% confidence interval). The variation of KNaOHallowed the estimation of the systematic 95% confidence interval in the apparent stability constants of BaOH+and RaOH+. The specific ion interaction theory was used to extrapolate the derived logarithms of the BaOH+and RaOH+apparent stability constants to zero ionic strength (log10K = 0.7 \ub1 0.2 for both ion pairs) and obtain the relevant ion interaction parameters. It was shown that both the Ba2+and Ra2+ions have similar activity coefficients and undergo similar short-range interactions in aqueous NaOH-NaClO4media

On the solubility of radium and other alkaline earth sulfate and carbonate phases at elevated temperature

Solubility constant data for alkaline earth sulfate and carbonate phases were collated. Thermodynamic data for these phases were determined by assuming that the solubility (log K-s) of each phase is a function of the inverse of absolute temperature with a constant, but non-zero, heat capacity change. The solubility for all phases, both sulfate and carbonate, exhibits a maximum at a particular temperature, with the temperature at which the maximum solubility occurs increasing as the alkaline earth metals become heavier (for both sulfate and carbonate phases). The heat capacity change was found to be a quadratic function of the square root of the ionic radius. The enthalpy of reaction, at 25 degrees C, is related to the temperature at which the maximum solubility occurs. Combination of these behaviours allows the solubility of the alkaline earth sulfate and carbonate phases to be determined across a temperature range of 0 to 300 degrees C. These relationships allow solubility data to be determined for the same temperature range for radium sulfate and carbonate for which very few literature data are available, particularly for radium carbonate

Effect of diluent on the extraction of europium(iii) and americium(iii) with N,N,N \u27,N \u27-tetraoctyl diglycolamide (TODGA)

Solvent extraction of Eu3+ and Am(3+)via N,N,N \u27,N\u27-tetraoctyl diglycolamide (TODGA) dissolved in different molecular diluents was studied. The diluent types used in this work were primary and secondary alcohols, secondary ketones and alkanes. Effects of concentration of extracting agent, temperature, diluent type and its carbon chain length on the extractions were determined. Distribution ratios of Eu3+ and Am3+ showed high dependence on the diluent type as well as the carbon chain length within the same type of diluent. The highest distribution ratios for both Eu3+ and Am3+ as well as the separation factors of Eu3+ over Am3+ were observed in the alkane diluents. Unexpectedly high distribution ratios for Eu3+ and Am3+ were observed in polar diluents with 5 carbon atoms in the chain, clearly standing out against the general trends. It was found that Eu3+ and Am3+ extraction via TODGA is enthalpy driven in all the studied diluents and that extraction is more exothermic in alkane diluents. Analysis of the stoichiometry of the extracted complexes shows that the average ligand number of TODGA molecules in the extracted complex is lower for Am3+ compared to Eu3+ except for with alkane diluents

Barium and Radium Complexation with Ethylenediaminetetraacetic Acid in Aqueous Alkaline Sodium Chloride Media

The speciation of Ra 2+ and Ba 2+ with EDTA was investigated at 25 \ub0C in aqueous alkaline NaCl media as a function of ionic strength (0.2–2.5 mol\ub7L −1 ) in two pH regions where the EDTA 4− and HEDTA 3− species dominate. The stability constants for the formation of the [BaEDTA] 2− and [RaEDTA] 2− complexes were determined using an ion exchange method. Barium-133 and radium-226 were used as radiotracers and their concentrations in the aqueous phase were measured using liquid scintillation counting and gamma spectrometry, respectively. The specific ion interaction theory (SIT) was used to account for [NaEDTA] 3− and [NaHEDTA] 2− complex formation, and used to extrapolate the logarithms of the apparent stability constants (log 10 K) to zero ionic strength (BaEDTA 2− : 9.86 \ub1 0.09; RaEDTA 2− : 9.13 \ub1 0.07) and obtain the Ba 2+ and Ra 2+ ion interaction parameters: [ε(Na + , BaEDTA 2− ) = − (0.03 \ub1 0.11); ε(Na + , RaEDTA 2− ) = − (0.10 \ub1 0.11)]. It was found that in the pH region where HEDTA 3− dominates, the reaction of Ba 2+ or Ra 2+ with the HEDTA 3− ligand also results in the formation of the BaEDTA 2− and RaEDTA 2− complexes (as it does in the region where the EDTA 4− ligand dominates) with the release of a proton. Comparison of the ion interaction parameters of Ba 2+ and Ra 2+ strongly indicates that both metal ions and their EDTA complexes have similar activity coefficients and undergo similar short-range interactions in aqueous NaCl media

Feasibility study for production of 99mTc by neutron irradiation of MoO3 in a 250\ua0kW TRIGA Mark II reactor

The subject of this paper is to explore the possibility to obtain 99mTc from activation of 98Mo, using the TRIGA Mark II low flux research reactor (Vienna, Austria). Irradiation of both natural and enriched in 98Mo molybdenum oxides was compared. Aims of this work included the determination of neutron fluxes and 98Mo(n, γ)99Mo reaction effective cross section in the TRIGA Mark II reactor irradiation channels, calculation of 99Mo specific activities, determination of optimal irradiation conditions for the subsequent 99mTc separation from MoO3 targets using concentrating technologies. \ua9 2012 Akad\ue9miai Kiad\uf3, Budapest, Hungary

Crystal structure of radium sulfate: An X-ray powder diffraction and density functional theory study

Radium-barium sulfate (Ra0.76Ba0.24SO4) powder was examined using X-ray Diffraction (XRD) technique and its crystal structure was optimized using Density Functional Theory (DFT). XRD data show that radium and barium sulfate form a solid solution and that Ra0.76Ba0.24SO4 is orthorhombic and isostructural with pure RaSO4, barite (BaSO4), celestite (SrSO4) and anglesite (PbSO4), crystallizing in the space group Pmna (No. 62). The unit cell parameters of the Ra0.76Ba0.24SO4 crystal have been determined using Rietveld refinement and were extrapolated to unit cell parameters of the pure RaSO4 phase using Vegard's law: a=9.129(8), b=5.538(3), c=7.313(5) Å. DFT geometry optimization was used to derive atomic coordinates and interatomic distances in both Ra0.76Ba0.24SO4 and pure RaSO4. The experimental and DFT geometry optimization results obtained in this work are in good agreement with each other, and furthermore with literature data