• Title/Summary/Keyword: lanthanides

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Sequential separation of 90Sr, 241Am, 239,240Pu and 238Pu by radioanalytical techniques (방사능 분석기술을 이용한 90Sr, 239,240Pu, 238Pu, 241Am 축차분리)

  • Lee, Myung Ho;Park, Kyoung Kyun;Kim, Jong-Yun;Park, Yeong Jae;Kim, Won Ho
    • Analytical Science and Technology
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    • v.18 no.6
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    • pp.469-474
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    • 2005
  • This paper presents a quantitative method of sequential separation of $^{90}Sr$, $^{241}Am$ and Pu radionuclides with an anion exchange resin and a Sr-Spec resin. The Pu isotopes were purified with an anion exchange resin. The americium and strontium fractions were separated from the matrix elements with an oxalate co-precipitation method. Americium fraction was separated from the strontium fraction with iron co-precipitation method and purified from lanthanides with anion exchange resin. Strontium-90 was purified from other hindrance elements with the Sr-Spec resin after oxalate co-precipitation. The measurement of Pu and Am isotopes was carried out by an ${\alpha}$-spectrometer. Strontium-90 was measured by a liquid scintillation counter. The radiochemical procedure of $^{90}Sr$, $^{241}Am$ and Pu radionuclides investigated in this study has been validated by application to IAEA-Reference soils.

Reprocessing of simulated voloxidized uranium-oxide SNF in the CARBEX process

  • Boyarintsev, Alexander V.;Stepanov, Sergei I.;Kostikova, Galina V.;Zhilov, Valeriy I.;Chekmarev, Alexander M.;Tsivadze, Aslan Yu.
    • Nuclear Engineering and Technology
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    • v.51 no.7
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    • pp.1799-1804
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    • 2019
  • The concept of a new method, the CARBEX (CARBonate EXtraction) process, was proposed for reprocessing of spent uranium oxide fuel. The proposed process is based on use of water solutions of $Na_2CO_3$ or $(NH_4)_2CO_3$ and solvent extraction (SE) by the quaternary ammonium compounds for selective recovery and purification of U from the fission products (FPs). Applying of SE allows to reach high degree of purification of U from FPs. Carrying out the processes in poorly aggressive alkaline carbonate media leads to increasing safety of SNF's reprocessing and better selectivity of separation of lanthanides and actinides. Moreover carbonate reprocessing media allows to carry out a recycling and regeneration of reagents. We have been done laboratory scale experiments on the extraction components of simulated voloxidated spent fuel in the solutions of NaOH or $Na_2CO_3-H_2O_2$ and recovery of U from carbonate solutions by SE method using carbonate of methyltrioctylammonium in toluene. It was shown that the purification factors of U from impurities of simulated FPs reached values $10^3-10^5$. The received results support our opinion that CARBEX after the further development can become more safe, simple and profitable method of spent fuel reprocessing.

Studies on the Spectrophotometric Determination, Electrochemical Behavior of Heavy Lanthanide ions in Nonaqueous System and Heavy Chelates Complexes with Bidendate Ligands (Ⅱ) Electrochemical Behavior of Heavy Lanthanide Ions in Acetonitrile (무거운 란탄이온의 분광학적 정량, 비수용액에서의 전기화학적 거동 및 중금속이온과 두자리 리간드 착물에 관한 연구 (제 2 보))

  • Kang Sam-Woo;Park Chong-Min;Kim Il-Kwang;Do Lee-Mi;Lee Jong-Min
    • Journal of the Korean Chemical Society
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    • v.37 no.5
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    • pp.483-490
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    • 1993
  • Voltammetric behavior of heavy lanthanide ions has been investigated by the DC, DPP and CV in acetonitrile solution. The reduction of $Gd^{3+}, Tb^{3+}, Dy^{3+}, Ho^{3+}, Er^{3+}, Tm^{3+} 및 Lu^{3+} proceed by three-electron change to the metallic state with totally irreversibility in 0.1M tetraethylammonium perchlorate. However, the reduction of Yb(Ⅲ) proceeds in two steps $(Yb^{3+} + e^- \Leftrightarrow Yb^{2+} and Yb^{2+} + 2e^- → Yb^0)$. The first reduction of Yb(Ⅲ) showed quasi reversible behavior, but the second reduction was irreversible in cyclic voltammetry. The cathodic peak current showed adsorptive properties in high concentration with lower sweep rate. The electroreduction of heavy lanthanides in water-acetonitrile mixture has been studied. In water-acetonitrile mixture, the negative shift of the peak potential and the decrease peak current were observed increasing water concentration. Also the Yb(Ⅲ) reduction to Yb(Ⅲ) has been deviated from quasi-reversible character with increase water amount. These results drive from the high solvation abilities of water which has high donor number.

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Chemical Equilibria of Lanthanides{Ln(Ⅲ)=Pr, Sm, Gd, Dy}-Macrocyclic Complexes with Auxiliary Ligands in $CH_3OH$(PartⅡ):Study of the Coordination of Oxygen-Containing Bases. ($CH_3OH$ 용매에서 란탄족 원소{Ln(Ⅲ)=Pr, Sm, Gd, Dy}-거대고리 착물과 보조 리간드 간의 화학평형 (제2보): 주게원자가 산소인 염기를 중심으로 고찰.)

  • Byun, Jong Chul;Park, Yu Chul;Han, Chung Hun
    • Journal of the Korean Chemical Society
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    • v.43 no.6
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    • pp.628-635
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    • 1999
  • Direct preparative method of 2,6-diformyl-p-cresol and 2-hydroxy-3-hydroxy-5-methylbenzaldehyde from 2,6-bis(hydroxymethyl)-4-methylphenol using activated $Mn(IV)O_2$ was described. Hexadentate compartmental Iigands, $H_4L[A]\;and\; H_4L[B]$ were prepared by condensation reactions of 2-hydroxy-3-hydroxy methyl-5-methylbenzaldehyde with ethylenediamine and 1,3-diaminopropane respectively. By the reaction of macrocycle($H_4[20]DOTA$) with Ln(III) nitrate {Ln(III)=Pr, Sm, Cd, Dy }, discrete mononuclear Ln(III) complexes of the type $[Ln(H_2[20]DOTA)(ClO_4)(H_2O)]\;{\cdot}\;3H_2O$ were synthesized in the solid state. $[Ln([20]DOTA)(NO_3)(H_2O)](NO_3)_2\;{\cdot}\;xH_2O$ was placed in methanol for 2 days, and $[Ln([20]DOTA)(NO_3)(CH_3OH)]^{2+}$ was formed. The equilibrium constants(K) for the substitution of coordinated $CH_3OH$ in the Ln-[20]DOTA complexes by various auxiliary ligand, $L_a$(=salicylic acid, p-chlorobenzoic acid, benzoic acid, acetic acid, 4-bromophenol) were determined spectroscopically at 25$^{\circ}C$ and 0.1M $NaClO_4$. The K values calculated were in the order of salicylic acid > p-chlorobenzoic acid > benzoic acid > acetic acid > 4-bromophenol, while pKa of auxiliary ligands was in the opposite trend.

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Separation of Actinides and Lanthanides by DEHPA Extractant(II) (DEHPA 추출제에 의한 악티늄족원소와 란탄족원소의 상호분리연구(II))

  • Yang, H.B.;Lee, E.H.;Lim, J.K.;Yoo, J.H.;Park, H.S.
    • Applied Chemistry for Engineering
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    • v.7 no.1
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    • pp.153-161
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    • 1996
  • Several main nuclides($^{241}Am$, $^{152}Eu$ and $^{237}Np$) in radioactive waste solution were selected and examined to mutual separation with di-(2-ethylhexyl) phosphoric acid by solvent extraction technique. $^{237}Np$ was extracted more than 99.9% adding the $H_2O_2$ that was a good reductant for the oxidation state control of $^{237}Np$. $^{241}Am$, $^{152}Eu$ and $^{237}Np$ could be fairly well separated one another during the different sequence stripping stages, but about 7~9.6% of the other nuclides were still remained for the $^{241}Am$ stripping solution. This result shows that the product of $^{152}Eu$ and $^{237}Np$ was good, but $^{241}Am$ may be needed to further purification process. It was also discussed on the cause of the third phase formation phenomenon that was found in the solvent regeneration.

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FISSION PRODUCT AND ACTINIDE RELEASE FROM THE DEBRIS BED TEST PHEBUS FPT4: SYNTHESIS OF THE POST TEST ANALYSES AND OF THE REVAPORISATION TESTING OF THE PLENUM SAMPLES

  • Bottomley P.D.W.;Gregoire A.C.;Carbol P.;Glatz J.P.;Knoche D.;Papaioannou D.;Solatie D.;Van Winckel S.;Gregoire G.;Jacquemain D.
    • Nuclear Engineering and Technology
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    • v.38 no.2
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    • pp.163-174
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    • 2006
  • The $Ph{\acute{e}}bus$ FP project is an international reactor safety project. Its main objective is to study the release, transport and retention of fission products in a severe accident of a light water reactor (LWR). The FPT4 test was performed with a fuel debris bed geometry, to look at late phase core degradation and the releases of low volatile fission products and actinides. Post Test Analyses results indicate that releases of noble gases (Xe, Kr) and high-volatile fission products (Cs, I) were nearly complete and comparable to those obtained during $Ph{\acute{e}}bus$ tests performed with a fuel bundle geometry (FPT1, FPT2). Volatile fission products such as Mo, Te, Rb, Sb were released significantly as in previous tests. Ba integral release was greater than that observed during FPT1. Release of Ru was comparable to that observed during FPT1 and FPT2. As in other $Ph{\acute{e}}bus$ tests, the Ru distribution suggests Ru volatilization followed by fast redeposition in the fuelled section. The similar release fraction for all lanthanides and fuel elements suggests the released fuel particles deposited onto the plenum surfaces. A blockage by molten material induced a steam by-pass which may explain some of the low releases. The revaporisation testing under different atmospheres (pure steam, $H_2/N_2$ and steam /$H_2$) and up to $1000^{\circ}C$ was performed on samples from the first upper plenum. These showed high releases of Cs for all the atmospheres tested. However, different kinetics of revaporisation were observed depending on the gas composition and temperature. Besides Cs, significant revaporisations of other elements were observed: e.g. Ag under reducing conditions, Cd and Sn in steam-containing atmospheres. Revaporisation of small amounts of fuel was also observed in pure steam atmosphere.

Effects of Dietary Supplementation of Rare Earth and Chlortetracycline on the Performance and Intestinal Microflora in Broiler Chicks (희토와 클로르테트라시이클인이 육계의 생산성 및 장내 미생물에 미치는 영향)

  • Song, T.H.;Park, H.S.
    • Korean Journal of Poultry Science
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    • v.34 no.1
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    • pp.23-29
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    • 2007
  • Rare earth(RE) is a common name indicating 17 of specific elements including 15 of lanthanides, scandium (Sc), and yttrium(Y). This study was conducted to compare the effect of RE to growth stimulating antibiotic products in broiler diet. One of the products commonly used in broiler feeding, Chlorotetracycline(CTC) was used at a level of 200ppm for the antibiotic treatment and replaced by 100ppm RE for the RE treatment. Dietary addition of RE and CTC showed similar effects in improving broiler growth and feed conversion each other, and those were significantly better when compared to those of the control group(P<0.05). Abdominal fats of chicks fed RE were significantly lower than others(P<0.05). Intestinal E. coli and total microbial numbers were reduced by RE addition(P<0.05), but the number of Lactobacillus was not affected. The number of Salmonella was also decreased but it was not significant.

A Chemical Reaction Calculation and a Semi-Empirical Model for the Dynamic Simulation of an Electrolytic Reduction of Spent Oxide Fuels (산화물 사용후핵연료 전해환원 화학 반응 계산 및 동적 모사를 위한 반실험 모델)

  • Park, Byung-Heung;Hur, Jin-Mok;Lee, Han-Soo
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.8 no.1
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    • pp.19-32
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    • 2010
  • Electrolytic reduction technology is essential for the purpose of adopting pyroprocessing into spent oxide fuel as an alternative option in a back-end fuel cycle. Spent fuel consists of various metal oxides, and each metal oxide releases an oxygen element depending on its chemical characteristic during the electrolytic reduction process. In the present work, an electrolytic reduction behavior was estimated for voloxidized spent fuel based on the assumption that each metal-oxygen system is independent and behaves as an ideal solid solution. The electrolytic reduction was considered as a combination of a Li recovery and chemical reactions between the metal oxides such as uranium oxide and the produced Li metal. The calculated result revealed that most of the metal oxides were reduced by the process. It was evaluated that a reduced fraction of lanthanide oxides increased with a decreasing $Li_2O$ concentration. However, most of the lanthanides were expected to be stable in their oxide forms. In addition, a semi-empirical model for describing $U_3O_8$ electrolytic reduction behavior was proposed by considering Li diffusion and a chemical reaction between $U_3O_8$ and Li. Experimental data was used to determine model parameters and, then, the model was applied to calculate the reduction yield with time and to estimate the required time for a 99.9% reduction.

Electrochemical Studies on the Lanthanides (란탄족 원소의 전기화학적 환원에 관한 연구 (제 1 보))

  • Park, Jong Min;Gang, Sam U;Do, Lee Mi;Han, Yang Su;Son, Byeong Chan
    • Journal of the Korean Chemical Society
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    • v.34 no.6
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    • pp.561-568
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    • 1990
  • Voltammetric behavior of some light lanthanide ions (La$^{3+}$, Pr$^{3+}$, Nd$^{3+}$, Sm$^{3+}$, and Eu$^{3+}$) in various supporting electrolytes has been investigated by several electrochemical techniques. The peak potentials and the peak currents, their dependency on the concentration, temperature and pH effects, the reversibility of the electrode reactions are described. The reduction of La$^{3+}$, Pr$^{3+}$ and Nd$^{3+}$ in 0.1 M lithium chloride proceeds by a three-electron change directly to the metallic state (Ln$^{3+}$ + 3e- → Ln$^0$) and charge transfer is totally irreversible. However, the reduction of Sm$^{3+}$ in 0.1 M tetramethylammonium iodide and Eu$^{3+}$ in 0.1 M lithium chloride proceeds in two stages (Ln$^{3+}$ + e- → Ln$^{2+}$ and Ln$^{2+}$ + 2e- → Ln$^0$). At pH values lower than ca.4 the hydrated lanthanide species (Ln(OH)$^{2+}$) reduced before the lanthanide ions (Ln$^{3+}$) due to the catalytic effect of hydrogen ions, and peak current increase with in the order Eu$^{3+}$ < Sm$^{3+}$ < Nd$^{3+}$ < Pr$^{3+}$ < La$^{3+}$ in differential pulse polarography. Some representative plots of $i_{pc}V^{-1/2} (proportional to current function) vs. V show considerable influence of hydrogen ion/lanthanide ion concentration in cyclic voltammetry. It is shown that a reaction of lanthanide ions with proton and/or water and catalytic reaction is enhanced at lower pH and at decreased lanthanide ion concentration.

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Studies on the Effect of Picolines on the Stereochemistry of Lanthanide(III) Nitrate Coordination Compounds of 4[N-Furfural)amino]antipyrine Semicarbazone and Antibacterial Activities (4[N-Furfural)amino]antipyrine Semicarbazone의 질산 란탄(III) 배위화합물의 입체화학에 미치는 Picolines의 영향과 항박테리아 활성)

  • Agarwal, Ram K.;Agarwal, Himanshu;Prasad, Surendra;Kumar, Anil
    • Journal of the Korean Chemical Society
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    • v.55 no.4
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    • pp.594-602
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    • 2011
  • The effect of ${\alpha}$-, ${\beta}$- and ${\gamma}$-picolines on the stereochemistry of the coordination compounds of lanthanide(III) nitrates derived from 4[N-(furfural)amino]antipyrine semicarbazone (FFAAPS) has been studied. The general composition of the present coordination compounds is [Ln(FFAAPS)$(NO_3)_3$Pic] (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy or Ho and Pic=${\alpha}$-, ${\beta}$- or ${\gamma}$-picolines). All these coordination compounds have been characterized by elemental analyses, molecular weight, molar conductance, magnetic susceptibility, infrared and electronic spectra. The infrared studies suggest that the FFAAPS behaves as a neutral tridentate ligand with N, N, O donor while ${\alpha}$-, ${\beta}$- or ${\gamma}$-picoline is coordinated to the lanthanide(III) ions via heterocyclic N-atom. Nitrates are bicovalently bonded in these compounds. From the electronic spectral data, nephelauxetic effect (${\beta}$), covalence factor ($b^{1/2}$), Sinha parameter (${\delta}%$) and the covalence angular overlap parameter (${\eta}$) have been calculated. Thermal stabilities of these complexes have been studied by thermogravimetric analysis. The coordination number of lanthanide(III) ions in the present compound is found to be ten. The antibacterial studies screening of the primary ligand FFAAPS and the complexes showed that the present complexes have moderate antibacterial activities.