Accelerating <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>

Combining the powers of a fast pneumatic transport system and the Automatic Activation Analyzer (AAA) of the Atominstitut in Vienna with the newest version of the IAEA k ₀-Software, the application of the k ₀-method to the determination of short-lived radionuclides becomes easily possible. By calculating Asp-values with the IAEA software, the often expensive and time-consuming measurement of Asp-values using certified reference materials is reduced to quality control checks. Measurements clearly show that the two approaches are equivalent, especially since both take self-absorption and neutron self-shielding into account. In this way it is possible to expand the library of the AAA with many hitherto unobtainable Asp-values. At the same time, using highly accurate Asp-values already measured for many short-lived radionuclides, k ₀-values for those can be produced with a simple procedure.     

Determination of <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-values for some elements in neutron capture gamma-ray for prompt gamma activation analysis

Exploration and modification of data for k ₀-PGAA (prompt γ-ray activation analysis) values used as standards for k ₀ standardization are needed. An integrated system has been installed and calibrated in Hot Laboratories Center for PGAA, using ²⁵²Cf isotopic neutron source with neutron flux of 6.16E8 n/cm² s. The prompt k ₀-factors of about 12 elements were determined versus the 1951.1 keV γ-ray of the ³⁵Cl, as well as analyzing crude oil and oil product samples. The concentrations of the elements in crude oil H, B, Mg, Al, Na, Si, P, S, Cl, V and Cd were 1.18E5, 0.084, 5.48E2, 8.45E2 4.88E2, 1.62E2, 3.72E2, 8.2, 144.3, 393 and 209.2 ppm while in oil product samples were 1.32E5, 5.87, 4.56E2, 4.22E2, 7.16E3, 699, 157, 8.74, 492.3, 61 and 198.2 ppm. Validation of the k ₀-PGAA was applied in analyzing standard IAEA reference material (soil-7) which give good agreement with the literature data. The ²⁵²Cf neutron beam in radiation position was characterized by the cadmium-ratio method, and found that the cadmium ratio (f), was 160.     

Development and implementation of <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-INAA standardization at PINSTECH

The k ₀ method has been introduced at the 30 kW miniaturized neutron source reactor (MNSR) at the Pakistan Institute of Nuclear Science & Technology (PINSTECH). It involved the full energy peak efficiency calibration of the HPGe detector for different counting geometries and the characterization of the neutron flux at four inner irradiation channels. The latter involved the determination of the thermal to the epithermal flux ratio, epithermal flux shape factor, the modified spectral index, Westcott’s g-factor, the Maxwellian neutron temperature and the fast flux. The method was validated by analyzing IAEA-SL1 (Lake Sediment) and NIST-SRM-1572 (Citrus Leaves) reference materials. All calculations were performed in Excel, including the optimization step. The results revealed that most of the elements were estimated with less than 10% relative deviation from the certified value.     

Implementation of the <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-NAA method by using <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-IAEA software and the NAA#3 irradiation hole at the HANARO research reactor

This study intended to demonstrate the use of k ₀-IAEA software with the NAA#3 irradiation hole in the HANARO research reactor and the gamma-ray spectrometers at the NAA laboratory in the Korea Atomic Energy Research Institute (KAERI). NIST SRM 2586-Soil was chosen as a sample to validate the analytical protocol by using the k ₀-IAEA software. Twenty four elements were determined and the resultant deviations between the experimental results and the certified values were all within 10% except for Dy. In addition, an analysis of three types of synthetic multielement standards (SMELS) prepared by the Institute for Reference Materials and Measurements (IRMM) and Institute of Nuclear Science (INW) in Belgium was executed. The analytical results agreed well with the assigned values and the U-scores for most of the elements were lower than 2.     

Application of the <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-NAA method at the HANARO research reactor

The k ₀-standardization method (k ₀-NAA) is known as one of the most remarkable progresses of the NAA with its many advantages. For the application of k ₀-NAA method at the NAA #1 irradiation position where the neutrons are well thermalized in the HANARO research reactor, KAERI, Korea, the determination of the reactor neutron spectrum parameters such as α and f have been carried out. The measured values of α and f using the “Cd-ratio” triple monitor method were 0.127±0.022 and 1010±70, respectively. To evaluate the applicability of k ₀-NAA in our analytical system, the analysis of three kinds of SRMs was executed. The analytical results showed that the relative error of most of the elements was less than 10% and the U-scores were within 2. It is turned out that the procedure of the k ₀-NAA in the HANARO research reactor is available for a practical application in the environmental fields.     

Chromium(III) complexes with lutidinic acid: kinetic studies in HClO<Subscript>4</Subscript> and NaOH solutions

Chromium(III)-lutidinato complexes of general formula [Cr(lutH) _n (H₂O)_6−2n ]³⁻ⁿ (where lutH⁻ is N,O-bonded lutidinic acid anion) were obtained and characterized in solution. Acid-catalysed aquation of [Cr(lutH)₃]⁰ leads to only one ligand dissociation, whereas base hydrolysis produces chromates(III) as a result of subsequent ligand liberation steps. The kinetics of the first ligand dissociation were studied spectrophotometrically, within the 0.1–1.0 M HClO₄ and 0.4–1.0 M NaOH range. In acidic media, two reaction stages, the chelate-ring opening and the ligand dissociation, were characterized. The dependencies of pseudo-first-order rate constants on [H⁺] are as follows: k _obs1 = k ₁ + k ₋₁/K ₁[H⁺] and k _obs2 = k ₂ K ₂[H⁺]/(1 + K ₂[H⁺]), where k ₁ and k ₂ are the rate constants for the chelate-ring opening and the ligand dissociation, respectively, k ₋₁ is the rate constant for the chelate-ring closure, and K ₁ and K ₂ are the protonation constants of the pyridine nitrogen atom and coordinated 2-carboxylate group in the one-end bonded intermediate, respectively. In alkaline media, the rate constant for the first ligand dissociation depends on [OH⁻]: k _obs1 = k _OH(1) + k _O[OH⁻], where k _OH(1) and k _O are rate constants of the first ligand liberation from the hydroxo- and oxo-forms of the intermediate, respectively, and K ₂ is an equilibrium constant between these two protolytic forms. Kinetic parameters were determined and a mechanism for the first ligand dissociation is proposed. The kinetics of the ligand liberation from [Cr(lut)(OH)₄]³⁻ were also studied and the values of the pseudo-first-order rate constants are [OH⁻] independent.     

Half-life of <Superscript>97</Superscript>Zr,re-measured

Summary The half-life of ⁹⁷Zr, used for the calculation of thermal/epithermal neutron flux ratio in k₀-NAA, is re-determined using three measurement systems with different pulse processing principles. The result of 16.755±0.013 hours clarifies the discrepancy between two widely used literature values, 16.744±0.011 and 16.90±0.05 hours. Different dead-time correction methods used on various measurement systems are evaluated. Factors influencing precise measurement of relative peak counting rates are discussed in time-series measurements over a dynamic range of 1000-fold radioactive intensities (10 half-lives).     

Electrochemical performance of LiFePO<Subscript>4</Subscript>/C doped with F synthesized by carbothermal reduction method using NH<Subscript>4</Subscript>F as dopant

The effect of fluorine doping on the electrochemical performance of LiFePO₄/C cathode material is investigated. The stoichiometric proportion of LiFe(PO₄)_1−x F_3x /C (x = 0.01, 0.05, 0.1, 0.2) materials was synthesized by a solid-state carbothermal reduction route at 650 °C using NH₄F as dopant. X-ray diffraction, scanning electron microscope, energy-dispersive X-ray, and X-ray photoelectron spectroscopy analyses demonstrate that fluorine can be incorporated into LiFePO₄/C without altering the olivine structure, but slightly changing the lattice parameters and having little effect on the particle sizes. However, heavy fluorine doping can bring in impurities. Fluorine doping in LiFePO₄/C results in good reversible capacity and rate capability. LiFe(PO₄)_0.95 F_0.15/C exhibits highest initial capacity and best rate performance. Its discharge capacities at 0.1 and 5 C rates are 156.1 and 119.1 mAh g⁻¹, respectively. LiFe(PO₄)_0.95 F_0.15/C also presents an obviously better cycle life than the other samples. We attribute the improvement of the electrochemical performance to the smaller charge transfer resistance (R _ct) and influence of fluorine on the PO₄³⁻ polyanion in LiFePO₄/C.     

Synthesis and characterization of the [Ru<Subscript>3</Subscript>O(CH<Subscript>3</Subscript>COO)<Subscript>6</Subscript>(py)<Subscript>2</Subscript>(BPE)Ru(bpy)<Subscript>2</Subscript>Cl](PF<Subscript>6</Subscript>)<Subscript>2</Subscript> dimer

The polymetallic [Ru₃O(CH₃COO)₆(py)₂(BPE)Ru(bpy)₂Cl](PF₆)₂ complex (bpy = 2,2′-bipyridine, BPE = trans-1,2-bis(4-pyridil)ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru₃O] moiety with a [Ru(bpy)₂(BPE)Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry. The [Ru₃O(CH₃COO)₆(py)₂(BPE)Ru(bpy)₂Cl]²⁺ doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)₂(BPE)] charge-transfer bands and to the [Ru₃O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at −1.07 V, 0.13 V, 1.17 V, 2.91 V and −1.29 V (vs SHE) assigned to the [Ru₃O]^{−1/0/+1/+2/+3} and to the bpy^0/−1 redox processes; also a wave is observed at 0.96 V, assigned to the Ru^+2/+3 pair. Despite the conjugated BPE bridge, the electrochemical and spectroelectrochemical results indicate only a weak coupling through the π-system, and preliminary photophysical essays showed the compound decomposes under visible light irradiation.     

Oxidation of Diethyl Sulfide in Aqueous Solutions by Peroxynitrite and the H<Subscript>2</Subscript>O<Subscript>2</Subscript>-NO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> System

It was found that nitrite anions are effective activators of hydrogen peroxide in the reaction with diethyl sulfide. The observed kinetics are consistent with the proposed intermediate formation of peroxynitrous acid (ONOOH). The rate constants for the reaction of diethyl sulfide Et₂S with the acid ONOOH (k₀ = 1.8⋅10³ L/mol⋅s) and with the anion ONOO⁻ (k₋ = 6⋅10⁻² L/mol⋅s) are respectively 10⁵ and three times higher than with hydrogen peroxide. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 5, pp. 290–295, September–October, 2005.     

Thermochemical properties of MnNb<Subscript>2</Subscript>O<Subscript>6</Subscript>

Homogeneous manganocolumbite (MnNb₂O₆) was synthesized from Nb₂O₅ and MnO oxides. Powder sample was orthorhombic with unit cell parameters: α = 0.5766 nm, b = 1.4439 nm, c = 0.5085 nm and V = 0.4234 nm³. Heat capacity over the temperature range of 313–1253 K was measured in an inert atmosphere with combined thermogravimetry and calorimetry using NETZSCH STA 449C Jupiter thermoanalyzer. Melting point was 1767 ± 3 K, enthalpy of melting was 144 ± 4 kJ mol⁻¹. Experimental heat capacity of MnNb₂O₆ is fitted to polynomial C _pm = 221.46 + 3.03 · 10⁻³ T + −39.79 · 10⁵ T ⁻² + 40.59 · 10⁻⁶ T ².     

Computational study on the reaction of CH<Subscript>3</Subscript>SCH<Subscript>2</Subscript>CH<Subscript>3</Subscript> with OH radical: mechanism and enthalpy of formation

The reaction mechanism of CH₃SCH₂CH₃ with OH radical is studied at the CCSD(T)/6-311+G(3df,p)//MP2/6-31+G(2d,p) level of theory. Three hydrogen abstraction channels, one substitution process and five addition–elimination channels are identified in the title reaction. The result shows hydrogen abstraction is dominant. Substitution process and addition–elimination reactions may be negligible because of the high barrier heights. Enthalpies of formation [ \Updelta_f H_{(298.15\textK)}^o \Updelta_{f} H_{(298.15{\text{K}})}^{o} ] of the reactants and products are evaluated at the CBS-QB3, G3 and G3MP2 levels of theory, respectively. It is found that the calculated enthalpies of formation by the aforementioned three methods are in consistent with the available experimental data. Rate constants and branching ratios are estimated by means of the conventional transition state theory with the Wigner tunneling correction over the temperature range of 200–900 K. The calculation shows that the formations of P1 (CH₂SCH₂CH₃ + H₂O) and P2 (CH₃SCHCH₃ + H₂O) are major products during 200–900 K. The three-parameter expressions for the total rate constant is fitted to be k_\texttotal = 1.45 ×10 ^{- 21} T^3.24 exp( - 1384.54/T) k_{\text{total}} = 1.45 \times 10^{ - 21} T^{3.24} \exp ( - 1384.54/T) cm³ molecule⁻¹ s⁻¹ from 200 to 900 K.     

Mixed chromium(III) complexes with pyridinedicarboxylato and oxalato ligands: kinetic studies in HClO<Subscript>4</Subscript> solutions

Three chromium(III) complexes of general formula [Cr(ox)₂(pdaH)]²⁻ (where ox = C₂O₄ ²⁻ and pdaH⁻ is N,O-bonded 2,3-, 2,4- or 2,5-pyridinedicarboxylic acid anion) were obtained and characterized in solution. Acid-catalysed aquation of [Cr(ox)₂(pdaH)]²⁻ gave two products: [Cr(ox)(pdaH)(H₂O)₂]⁰ (P₁) and cis-[Cr(ox)₂(H₂O)₂]²⁻ (P₂). The kinetics of these reactions were studied spectrophotometrically, within the 0.1–1.0 M HClO₄ range, and the pseudo-first-order rate constants for the oxalato (k _obs1) and pdaH⁻ (k _obs2) ligands dissociation were calculated based on the determined pseudo-first-order rate constants (k _obs) and P₁:P₂ molar ratio. The dependencies of the pseudo-first-order rate constants on [H⁺] are as follows: k _obs1 = b ₁[H⁺] and k _obs2 = b ₂[H⁺], where b ₁ and b ₂ are the second-order rate constants for the oxalato and pdaH⁻ ligands dissociation, respectively. Kinetic parameters were determined and the mechanism of the pdaH⁻ ligand dissociation is proposed.     

Solubility of Eu<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>3</Subscript> and sorption of Eu(III) onto TiO<Subscript>2</Subscript> in the presence of Se(IV)

Metal ions sorption can be significantly affected by the presence of other sorbates, especially of complexing ligands. In this study, the effect of Se(IV) on Eu(III) sorption onto TiO₂ at different pH and Eu(III) concentration was investigated. Se(IV) was found to enhance Eu(III) sorption as a function of Se(IV) concentration. Constant capacitance model was successfully used to interpret the sorption experimental data. The solubility product of Eu₂(SeO₃)₃ at ambient temperature was investigated to highlight the sorption mechanism of ternary sorption system. The pK _sp value of Eu₂(SeO₃)₃ was found to be 31.51 ± 0.95.     

Thermochemistry of 2-Aminopyridine (C<Subscript>5</Subscript>H<Subscript>6</Subscript>N<Subscript>2</Subscript>)(s)

The molar enthalpies of solution of 2-aminopyridine at various molalities were measured at T=298.15 K in double-distilled water by means of an isoperibol solution-reaction calorimeter. According to Pitzer’s theory, the molar enthalpy of solution of the title compound at infinite dilution was calculated to be D_solH_m^￥ = 14.34 kJ·mol^-1\Delta_{\mathrm{sol}}H_{\mathrm{m}}^{\infty} = 14.34~\mbox{kJ}\cdot\mbox{mol}^{-1}, and Pitzer’s ion interaction parameters b_MX^(0)L, b_MX^(1)L\beta_{\mathrm{MX}}^{(0)L}, \beta_{\mathrm{MX}}^{(1)L}, and C_MX^fLC_{\mathrm{MX}}^{\phi L} were obtained. Values of the relative apparent molar enthalpies ( ^φ L) and relative partial molar enthalpies of the compound ([`(L)]₂)\bar{L}_{2}) were derived from the experimental enthalpies of solution of the compound. The standard molar enthalpy of formation of the cation C₅H₇N₂ ⁺\mathrm{C}_{5}\mathrm{H}_{7}\mathrm{N}_{2}^{ +} in aqueous solution was calculated to be D_fH_m^o(C₅H₇N₂⁺,aq)=-(2.096±0.801) kJ·mol^-1\Delta_{\mathrm{f}}H_{\mathrm{m}}^{\mathrm{o}}(\mathrm{C}_{5}\mathrm{H}_{7}\mathrm{N}_{2}^{+},\mbox{aq})=-(2.096\pm 0.801)~\mbox{kJ}\cdot\mbox{mol}^{-1}.     

Glass transition and crystallization study of chalcogenide Se<Subscript>70</Subscript>Te<Subscript>15</Subscript>In<Subscript>15</Subscript> glass

Differential scanning calorimetry data at different heating rates (5, 10, 15 and 20 °C min⁻¹) of Se₇₀Te₁₅In₁₅ chalcogenide glass is reported and discussed. The crystallization mechanism is explained in terms of recent analyses developed for use under non-isothermal conditions. The value of Avrami exponent (n) indicates that the glassy Se₇₀Te₁₅In₁₅ alloy has three-dimensional growth. The average values of the activation energy for glass transition, E _g, and crystallization process, E _c, are (154.16 ± 4.1) kJ mol⁻¹ and (98.81 ± 18.1) kJ mol⁻¹, respectively. The ease of glass formation has also been studied. The reduced glass transition temperature (T _rg), Hruby’ parameter (K _gl) and fragility index (F _i) indicate that the prepared glass is obtained from a strong glass forming liquid.     

Advances in <Superscript>79</Superscript>Se analyses on Savannah river site radioactive waste matrices

Waste cleanup efforts underway at the United States Department of Energy’s (DOE) Savannah River Site (SRS) in South Carolina, as well as other DOE nuclear sites, have created a need to characterize ⁷⁹Se in radioactive waste inventories. Successful analysis of ⁷⁹Se in high activity waste matrices is challenging for a variety of reasons. As a result of these unique challenges, the successful quantification of ⁷⁹Se in the types of matrices present at SRS requires an extremely efficient and selective separation of ⁷⁹Se from high levels of interfering radionuclides. A robust ⁷⁹Se radiochemical separation method has been developed at the Savannah River National Laboratory (SRNL) which is routinely capable of successfully purifying ⁷⁹Se from a wide range of interfering radioactive species. In addition to dramatic improvements in the K_d, ease, and reproducibility of the analysis, the laboratory time has been reduced from several days to only 6 h.     

Preparation and electrical properties of Nd and Mn co-doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Ferroelectric thin films of Nd and Mn co-doped bismuth titanate, Bi_3.15Nd_0.85Ti_3−x Mn _x O₁₂ (BNTM) (x = 0–0.1), were fabricated on Pt/TiO₂/SiO₂/Si(100) substrates by a sol–gel technique. The BNTM films had a polycrystalline perovskite structure and uniform and dense surface morphologies. A lattice distortion was observed in the BNTM films due to Mn ion doping. The ferroelectric measurement of the films indicated that the values of coercive field (E _c ) decreased gradually with the increase of the Mn content (x), however, the remanent polarization (P _r ) increase firstly and then decrease with the increase of x. The sample with x = 0.05 had optimum electrical properties and a maximum 2P _r value. The 2P _r and 2E _c values of the film at a maximum applied electric field of 400 kV/cm were 38.3 μC/cm² and 180 kV/cm, respectively. Moreover, this BNTM capacitors did not show fatigue behaviors after 1.0 × 10¹⁰ switching cycles at a frequency of 1 MHz, suggesting a fatigue-free character. The main reason for the increase of the 2P _r and the decrease of the 2E _c might be attributed to the lattice distortion in BNTM films due to Mn ion doping.     

Is there something wrong in the barium determination by k<Subscript>0</Subscript>-INAA?

There was a confusion around the Q ₀- and k ₀-values for the reaction ¹³⁰Ba(n,γ)¹³¹Ba. The problem was clarified in this work by re-determination of the k ₀-values and critical evaluation of the Q ₀-values. The new ¹³¹Ba k ₀-values were found to be about 16% lower than the recommended ones compiled in 1989 and about 10% lower than those recommended in 2003. The Q ₀-value was verified to be 24.3. These new values were successfully applied in k ₀-INAA of Ba in various references samples. Possible error sources in Ba determination were investigated which might compensate the negative bias in Ba results from using the inaccurate k ₀-values, consequently masking the problem of these old k ₀-factors so far. In this context, a few cases were studied and presented.     

Cyclic neutron activation analysis for determination of selenium in food samples using <Superscript>77m</Superscript>Se

Cyclic neutron activation analysis method was conducted for determination of Se in food samples. High accuracy and good precision were proved by analyzing certified reference materials (CRMs) of chicken (GBW10018), rice (GBW10010) and cabbage (GBW10014). The detection limits for the three CRMs reached 0.16, 0.66 and 1.2 ng after 6 cycles at the 161.9 keV γ-peak from ^77mSe, under a neutron flux of 9.0 × 10¹¹ n cm⁻² s⁻¹ and the conditions of 30 s irradiation, 2 s decay, 30 s counting and 2 s waiting, significantly lower than those of conventional neutron activation analysis without any cycles, which were 0.94, 3.6 and 4.3 ng, respectively.