Recrystallization of 223Ra with barium sulfate

In this work, the kinetics of barium sulfate recrystallization has been studied in acidic 0.01 mol dm^?3 sodium sulfate solution using ²²³Ra and ¹³³Ba tracers at very low total radium concentration, i.e. less than 10^?13 mol dm^?3. It was found that the system follows the homogeneous recrystallization model and that recrystallization rates, inferred by the decrease of ²²³Ra and ¹³³Ba in the aqueous solution, are fast. Therefore, even at very low concentrations, below the solubility limit, radium will be retained by barium sulfate—a mineral present in the deep underground repository.     

Nuclear quadrupole interaction at133Cs in some barium compounds

Nuclear quadrupole interaction frequencies at¹³³Cs following the electron-capture decay of¹³³Ba for BaSO₄, Ba/BrO₃/2 and Ba/NO₃/2 were obtained by measuring the perturbation of 356–81 keV cascade of¹³³Ba. Nuclear quadrupole interaction frequencies for BaSO₄ and Ba/BrO₃/2 are 17.2 Mrad sec^–1 and 14.6 Mrad sec^–1, respectively, while no perturbation of 356–81 keV cascade was observed in case of Ba/NO₃/2. Further the possibility of any after-effects of electron-capture decay is ruled out through the measurement of 276–161 keV gamma-gamma directional correlation.     

Structure investigations by P.A.C.

The perturbed angular correlation /P.A.C./ technique is employed to investigate the structures of barium ferrite and barium hexaferrite using radioactive¹³³Ba /10.7 Y/ as a probe. The quadrupole interaction frequencies /W_Q'S/ are found to be 9.68 and 12.02 Mrad sec^–1 for barium ferrite and barium hexaferrite, respectively, showing a drift from usual cubic structure.     

Application of the sum peak method to determine electric field gradient in different environments of133Cs nucleus

The sum peak method based on the phenomenon of perturbed angular correlation has been applied to study the nuclear quadrupole interaction frequencies at¹³³Cs which is followed by electron-capture decay of¹³³Ba. These values are used to determine the z-component, which is the largest one of the electric field gradient. The electric field gradient /EFG/ is found to vary with different compounds of barium. The method is found to be useful in describing the chemical influences on the attenuation of angular correlations and hence in the study of EFG.     

Separation of Ba and Pb from aqueous solutions of Sr with commercially available “precipitated active manganese dioxide”

Ba and Pb radionuclides can be removed from Sr in aqueous solution in both sodium acetate and acetic acid, containing 20 mg Sr carrier, by stirring with small (0.1–0.5 g) amounts of solid manganese dioxide. In tracer experiments⁸⁵Sr was separated with only small losses from¹³³Ba and²¹⁰Pb by separation factors of 87 and 135, respectively. The separation factor is defined here as the % of the initial⁸⁵Sr activity/ % of the initial¹³³Ba or²¹⁰Pb activity remaining in the aqueous phase after MnO₂ contact. The applicability of this technique for removing Ba and Pb radionuclides in the analysis of⁹⁰Sr in environmental samples (especially milk) is discussed.     

Determination of perturbed angular correlation parameters in some compounds of133Ba using the sum peak method

The sum peak intensity relative to its single peak was determined in various compounds of¹³³Ba by the technique of gamma-ramma-ray sum peaks observed in a single HPGe detector. The change in intensity ratio was used to determine the time integral perturbed angular correlation coefficients for BaCl₂, Ba(NO₃)₂, BaSO₄, Ba-EDTA, Ba-MES and Ba-BSA compounds.     

Rapid determination of molar ratios in binary systems by 14 MeV neutron activation analysis

The magnetic characteristics of barium ferrite, a compound widely used for magnetic materials, depend on the molar ratio of iron(III) oxide to barium oxide. On account of this fact, activation analysis using 14 MeV neutrons was applied for the rapid and non-destructive determination of the molar ratio of iron(III) oxide to barium oxide in barium ferrite. Iron was detected as⁵⁶Mn produced from the⁵⁶Fe(n, p)⁵⁶Mn reaction, and barium as^137mBa originating from the¹³⁸Ba(n, 2n)^137mBa reaction. A linear relation was obtained between the ratio of counts of⁵⁶Mn and^137mBa and the molar ratio of iron(III) oxide to barium oxide; the corrected gradient of the experimental calibration curve, obtained with^137mBa internal standard, agreed well with the calculated value. The molar ratios of iron(III) oxide to barium oxide obtained by activation analysis and by chemical analysis were in good agreement.     

Chemical states of iodine produced by the spontaneous fission of252Cf

The distributions of the chemical states of¹³¹I,¹³²I,¹³³I,¹³⁴I and¹³⁵I produced by the spontaneous fission of²⁵²Cf were investigated by the method of fractional precipitation separation in 6M NH₄OH solution followed by measurement of the X-ray spectrum of the samples with a Ge(Li) detector. The iodine fission fragments were separately collected in the matrices of NaNO₃, NaCl, dehydrated sodium sulfate, CH₃COONa·3H₂O, Na₃H₂IO₆, KI and NaIO₃ crystals. The results showed that the distribution of the chemical states was the function of the collection time, the nature of matrix materials and the type of iodine isotopes. The relative amount of the reduced states of¹³⁴I decreased with the increase of collection time in the matrix of NaNO₃. The ratio of the amount of reduced states to the total amount of the¹³⁴I was the highest (50.4%) in NaCl matrix and the lowest (9.4%) in Na₃H₂IO₆ matrix. The relative quantities of reduced states of¹³⁵I were the highest (58.5% and 97.7%) and that of¹³⁴I were the lowest (16.9% and 63.1%) in matrices of NaNO₃ and NaCl, respectively.     

Sorption and distribution of226Ra in an electrolytic manganese dioxide column in the presence of other ions

Distribution of²²⁶Ra within a segmented electrolytic manganese dioxide (EMD) column was investigated under varying flow rates. Tests show uniform distribution of²²⁶Ra within the EMD column at higher flow rates, as compared to a lower flow rate whereby an apparent two stage sorption process is contributing to the sorption amount. The sorption of²²⁶Ra on EMD decreases from 57% to 14.2% over a short range of Ba²⁺ concentration (5–30 mg Ba²⁺ per 750.0 g solution) using flow rates of 200–300 ml min^–1. The sorption of²²⁶Ra on EMD decreases (58–15%) a consistent higher sorption of²²⁶Ra compared to¹³³Ba under all Ra:Ba ratios indicating the preference for Ra²⁺ ions.     

Use of inorganic adsorbers in radium analysis

Two new simple methods were studied for the analysis of radium in fresh waters by concentration and purification. Both methods are based on the use of an inorganic selective adsorber, namely basic lead rhodizonate, LERHO, and partially reduced tin dioxide (PRTD). The procedures were checked by using filtered fresh waters spiked with 0.1 Bq of²²⁶Ra, and in the presence of few μg/l of barium. In each experiment¹³³Ba radioisotope was added to water samples to measure the yield of the overall procedure by γ-counting. Barium and radium were adsorbed from basic solutions on LERHO packed chromatographic column in the first procedure, while batch experiments were preferred for the adsorption on PRTD. After separation,²²⁶Ra and barium were eluted from the exchangers and co-precipitated onto small filters as thin film, supported on an inactive barium sulphate substrate, to be submitted to alpha-and gamma-spectrometry. Both methods gave promising results.     

Sulfation and Desulfation Mechanisms on Pt–BaO/Al2O3 NOx Storage-Reduction (NSR) Catalysts

NO_x storage-reduction (NSR) catalyst is regarded as the promising solution to effectively remove NO_x emitted from lean-burn engines. However, sulfur poisoning remains the big obstacle for NSR technology to overcome. Here fundamental studies on NSR catalyst, especially focusing on the various characteristics of sulfur poisoning and regeneration mechanism, were reviewed. Various aspects of sulfation mechanism such as the roles of Pt and Ba, and the types of sulfate species were investigated. It was found that the desulfation of barium sulfate with H₂ resulted in the transformation into barium oxide (BaO) or barium sulfide (BaS) depending on the amount of barium loading and the sulfur loading, based on the combined temperature programmed reaction with hydrogen, Sulfur K-edge X-ray absorption near-edge spectroscopy and time-resolved X-ray diffraction results. H₂O played a critical role in converting BaS into BaO, thus promoting the desulfation by producing the additional H₂S. The overall sulfation and desulfation scheme was proposed by integrating the results obtained in this study.     

Influence of Ba on the electrodeposition of226Ra

A detailed study of the influence of barium on the electrodeposition of²²⁶Ra was made using two different procedures. High yields (80–90%) were attained when the amounts of barium were not very significant. However, the²²⁶Ra yields fell drastically for amounts slightly greater than 0.10–0.15 mg of Ba, according to the electrodeposition procedure. Samples containing trace amounts of barium less than 100–150 g can thus be treated with no barium-radium separation being required.²¹⁰Po was also deposited, although practically no influence of barium on the Po plating was observed. The²²⁵Ra resolution rose uniformly (25 to 55 keV) as the amount of barium rose up to 1 mg. These resolutions allow one to make a direct accurate determination of²²⁶Ra as well as an indirect determination of²²⁴Ra and²²³Ra via measurement of their daughter products.     

[Cp3Ba]−: The First Structurally Characterized Barate Complex

A [Cp ₃ Ba] _∞ coordination polymer with a chain structure is present in the compound [Cp₃Ba]⁻[Bu₄P]⁺. The barium center is tetrahedrally coordinated by four η⁵-Cp rings (a section of the chain is shown on the right). The Bu₄P cations bridge neighboring [Cp₃Ba]_∞ chains through short hydrogen bonds, and the cocrystallized THF molecules do not coordinate to the barium centers but are instead involved in short CH⋅⋅⋅O hydrogen bonds with the Bu₄P cations.     

Cumulative yields of short-lived isotopes of barium in the spontaneous fission of252Cf

Cumulative yields of short-lived/barium isotopes^{139, 141, 142}Ba have been determined in the spontaneous fission of²⁵²Cf, using fast radiochemical separation and gamma-ray spectrometry.¹⁴²Ba yield is reported for the first time. The measured cumulative yields are converted to chain yields, assuming normal charge distribution systematics for comparision with the literature data.     

Determination of228Ra in drinking water

A procedure for the analysis of²²⁸Ra in drinking water has been developed. The procedure involves separation of radium by an initial coprecipitation with lead sulfate. The isolated Pb(Ra)SO₄ is then dissolved in sodium diethylenetriamine pentaacetate (DTPA). Radium-228 is co-precipitated from this solution with barium sulfate while the DTPA supernate which contains pre-existing²²⁸Ac is discarded. The purified Ba(Ra)SO₄ precipitate is then allowed to ingrow, generating²²⁸Ac, which is then dissolved in DTPA, isolating both²²⁶Ra and²²⁸Ra in the precipitate while²²⁸ Ac remains in the aqueous supernate. The supernate is partitioned against di-(2-ethylhexyl phosphoric acid), HDEHP, dissolved in n-heptane, which retains the²²⁸Ac. Actinium-228 is then stripped from the organic phase by partitioning against 1M HNO₃. Finally, the²²⁸Ac is coprecipitated onto cerium oxalate. The precipitate is collected on a filter and counted in a low-background beta counter. Radium-228 standards with concentrations ranging from 0.044 to 1.6 Bq were used to establish the detector counting efficiency for²²⁸Ac in cerium oxalate samples, as well as monitoring the chemical yield and absorption factors. The resultant average value of 30.3±2.1 cpm/Bq (uncertainty given at 95% level of confidence) was obtained. Various²²⁸Ra cross checks from U. S. Environmental Protection Agency (EPA) with concentrations of 0.063–0.52 Bq/l were analyzed in order to assess the performance of the procedure. The minimum detectable concentration (MDC) of²²⁸Ra in water with this procedure is 0.015 Bq/l. This is based on a one liter aliquot of sample, a 100 min couting period, and a 3 hour decay interval between the end of²²⁸Ac ingrowth and midpoint of counting. Decontamination factor studies were performed to determine the extent of the carry-over of²³⁸U,²²⁶Ra,²¹⁰Po, and⁹⁰Sr into the final fraction.     

Energetic Salts Based on Monoanions of N,N‐Bis(1H‐tetrazol‐5‐yl)amine and 5,5′‐Bis(tetrazole)

High‐density energetic salts that contain nitrogen‐rich cations and the 5‐(tetrazol‐5‐ylamino)tetrazolate (HBTA^?) or the 5‐(tetrazol‐5‐yl)tetrazolate (HBT^?) anion were readily synthesized by the metathesis reactions of sulfate salts with barium compounds, such as bis[5‐(tetrazol‐5‐ylamino)tetrazolate] (Ba(HBTA)₂), barium iminobis(5‐tetrazolate) (BaBTA), or barium 5,5′‐bis(tetrazolate) (BaBT) in aqueous solution. All salts were fully characterized by IR spectroscopy, multinuclear (¹H, ¹³C, ¹⁵N) NMR spectroscopy, elemental analyses, density, differential scanning calorimetry (DSC), and impact sensitivity. Ba(HBTA)₂ ? 4 H₂O crystallizes in the triclinic space group P$\bar 1$ , as determined by single‐crystal X‐ray diffraction, with a density of 2.177 g cm^?3. The densities of the other organic energetic salts range between 1.55 and 1.75 g cm^?3 as measured by a gas pycnometer. The detonation pressure (P) values calculated for these salts range from 19.4 to 33.6 GPa, and the detonation velocities (ν_D) range from 7677 to 9487 m s^?1, which make them competitive energetic materials. Solid‐state ¹³C NMR spectroscopy was used as an effective technique to determine the structure of the products that were obtained from the metathesis reactions of biguanidinium sulfate with barium iminobis(5‐tetrazolate) (BaBTA). Thus, the structure was determined as an HBTA salt by the comparison of its solid‐state ¹³C NMR spectroscopy with those of ammonium 5‐(tetrazol‐5‐ylamino)tetrazolate (AHBTA) and diammonium iminobis(5‐tetrazolate) (A₂BTA).     

A Molecular Barium Hydrido Complex Stabilized by a Super‐Bulky Hydrotris(pyrazolyl)borate Ligand

Hydrogenolysis of the scorpionate‐supported barium alkyl complex (Tp^Ad,iPr)Ba[CH(SiMe₃)₂](THF) (Tp^Ad,iPr=hydrotris(3‐adamantyl‐5‐isopropyl‐pyrazolyl)borate) afforded the dinuclear barium hydrido complex [(Tp^Ad,iPr)Ba(μ‐H)]₂ ( 2 ), which was characterized by NMR spectroscopy and single‐crystal X‐ray analysis. Exposure of 2 with 1 atm of CO resulted in a reductive coupling process to form the cis‐ethendiolate dianion ( 3 ). Reaction of 2 with one equivalent of PhC≡C−C≡CPh gave barium 1,4‐diphenyl‐2‐butyne‐1,4‐diyl complex {[(Tp^Ad,iPr)Ba]₂(PhCH−C≡C−CHPh) ( 4 ).     

Calibration of a 2D-CDB spectrometer using a reference 133Ba source

A procedure for calibrating a FAST-ComTec 2D-CDB spectrometer using a ¹³³Ba source is presented. The energy calibration consisted of acquiring two-dimensional (2D) spectra by measuring simultaneously with two HPGe detectors the 356 and 511 keV peaks. As the ¹³³Ba source only emits one photon per decay, the Ba contribution to the 2D spectra was built up by taking two successive and uncorrelated events, i.e. one from each detector (pseudo-coincidence technique). The FWHM of the spectrometer was estimated from the E₁=E₂ diagonal of the spectra.     

Uranium ore processing: Kinetics of the growth and dissolution of a potential host solid from a model surface

As part of an investigation concerning the fate of²²⁶Ra during uranium ore milling and long-term tailings storage, we have investigated the growth of potential host solids-barium sulfate and lead sulfate-on mica, a model surface. The kinetics of dissolution of barium sulfate-and of a barium sulfate solid containing²²⁸Ra as a trace component into 10^–3M sulfuric acid were subsequently investigated using a flow-cell and radiotracer techniques. It was found that ther dissolution of both the barium sulfate host and the²²⁸Ra trace component was congruent. The dissolution reaction appears to be surface controlled.     

133Xe gas release during irradiation of uranium metal in the presence of air

Uranium metal samples of large surface to volume ratios were irradiated in the presence of 1 cm³ of air. It was found that 1.708±0.015% of¹³³Xe was released during irradiation. It was proved that this amount of¹³³Xe is due to the decay of¹³³I originally released. The release of¹³³Xe was attributed to the knock-out mechanism.