• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.143-158
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• 1990

Metal complexes were prepared by reacting uranium (Ⅵ), thorium (Ⅳ) and rare earth metal (Ⅲ) ions including Nd (Ⅲ), Sm (Ⅲ) and Ho (Ⅲ) with macrocyclic ligands including five crown ethers, nine crownands and one cryptand ligands, and subjected to NMR studies in order to examine coordination sites of the ligands and compositions of the complexes formed. Among the marcocyclic ligands, crown ethers and crownand ligands have shown down-field shifts of the methylene protons of the lcigands by forming stable complexes with all the metal ions and the differences of chemical shifts were decreased as increasing of the cavity-size of crown ethers for the same metal ions and decreasing of the atomic number of the rare earth metals for the same ligands. It has been found that crownand 22 gave a stable complex with uranium(Ⅵ) ion by the coordination through both oxygen and nitrogen atoms of the ligand whereas no complex was formed with the rare earth metal(Ⅲ) ions, which on the other hand were found to form stable complexes with cryptand 221. The rest of the crowand ligands have also been found to form stable complexes with uranium(Ⅵ) ion by coordinating through all the oxygen and nitrogen atoms of the ligands whereas no complexes were formed with the rare earth metal(Ⅲ) ions. It has also been shown by 1H-NMR study that uranium(Ⅵ), thorium(Ⅳ) and rare earth metal(Ⅲ) ions formed 1:1 complexes with the macrocyclic ligands except for thorium(Ⅳ) complex of 12C4 in which the mole ratio of metal to ligand is 1:2. More stable metal complexes show larger changes in chemical shifts of the coordinated ligand protons. Finally, the rare earth metal(Ⅲ) complexes of 18C6 have shown ligand exchange reaction with the solvent molecules in acetylacetone solution, which was not observed for the uranium (Ⅵ) complexes.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.232-237
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• 1989

The elution mechanism of rare earth elements in cation exchange resin which was substituted with $NH_4^+,\;Zn^{2+}\;or\;Al^{3+}$ as a retaining ion had been investigated. Rare earths or rare earths-EDTA complex solution was loaded on the top of resin bed and eluted with 0.0269M EDTA solution. When the rare earth-EDTA complex was adsorbed on the $Zn^{2+}\;or\;Al^{3+}$ resin form, retaining ion was complexed with EDTA and liberated rare earths was adsorbed in the resin again. Adsorbed rare earths in resin phase could be eluted by the complexation reaction with EDTA eluent. On $NH_4^+$ resin form, the rare earth-EDTA complex which had negative charge could not adsorbed on the cation exchange resin because the complexation reaction between $NH_4^+$ and EDTA was impossible. So the elution time was much shorter than in $Zn^{2+}\;or\;Al^{3+}$ resin form. When the rare earths solution was loaded on the $Zn^{2+},\;Al^{3+}$ resin form bed, rare earths was adsorbed in the resin and the retaining ion was liberated. Adsorbed rare earths in resin bed was exchanged by EDTA eluent forming rare earths-EDTA complex, and eluted through these processes. On $NH_4^+$ resin form, rare earths loaded was adsorbed by exchange reaction with $NH_4^+$. As the EDTA eluent was added, rare earths was liberated from resin forming negatively charged rare earth-EDTA complex and eluted without any exchange reaction. So the elution time was greatly shortened and there was no metallic ion except rare earths in effluent. When the $Zn^{2+}\;and\;Al^{3+}$ was used as retaining ion, the pH of efflent was decreased seriousely because the $H^+$ liberated from EDTA molecule.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.436-443
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• 2011

The solid complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III) and Gd(III) with 4-hydroxy-3-(1-{2-(2,4-dihydroxy-benzylidene)-amino phenylimino}-ethyl)-6-methyl-pyran-2-one ($H_2$L) derived from o-phenylenediamine, 3-acetyl-6-methyl-(2H)pyran,2,4(3H)-dione (dehydroacetic acid or DHA) and 2, 4-dihydroxy benzaldehyde have been synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-visible, FT-IR, $^1H$-NMR, X-ray diffraction, thermal analysis study, and screened for antimicrobial activity. The FT-IR spectral data suggest that the ligand behaves as a dibasic tetradentate ligand with ONNO donor atoms sequence towards central metal ion. From the microanalytical data, the stoichiometry of the complexes has been found to be 1:1 (metal: ligand). The physico-chemical data suggests distorted octahedral geometry for La(III), Ce(III), Pr(III), Nd(III), Sm(III) and Gd(III) complexes. The X-ray diffraction data suggests monoclinic crystal system for La(III) and Ce(III) and orthorombic crystal system for Pr(III) and Nd(III) complexes. Thermal behavior (TG/DTA) of the complexes was studied and kinetic parameters were determined by Horowitz-Metzger and Coats-Redfern methods. The ligand and its metal complexes were screened for antibacterial activity against Staphylococcus aureus, Escherichia coli, Bacillus Sp. and fungicidal activity against Aspergillus Niger, Trichoderma and Fusarium oxysporum.

• Journal of the Korean Chemical Society
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• v.34 no.3
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• pp.280-287
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• 1990

The electrochemical behavir of trivalent lanthanides [Sm(Ⅲ), Tb(Ⅲ), and Yb(Ⅲ)) complexes were investigated by the use of direct current, differential pulse polarography and cyclic voltammetry in aprotic media. These reduction peak were irreversible one-electron processes at $E_{pc}$ = -0.16 V, -0.35 V, -0.14 V, and -0.03 V of trivalent lanthanide complexes vs. Ag/AgCl electrode and the behavior of heavier lanthanides were decreased Sm > Tb > Ho > Yb order of the stability constant with decreasing atomic number.

• Journal of the Korean Chemical Society
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• v.37 no.10
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• pp.895-902
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• 1993

The chemical behavior of trivalent lanthanide ($Pr^{3+}\;and\;Dy^{3+}$) and organo ligands (phen' and terpy') complexes was investigated by the use of UV/vis-spectrophotometric, magnetization and electrochemical method. The magnitude of crystal field splitting energy, the pairing energy and spin state was obtained from the spectra of complexes. These complexes were founded to be diamagnetics, delocalization and low spin complexes. The electrochemical behavior of complexes was observed by the use of cyclic voltammetry in aprotic media. These reduction peaks were irreversible two step reduction processes by electron transfer.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.233-242
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• 1988

The uranium(VI) complexes with new unsaturated macrocyclic ligands of cryptand types and the neodymium(III) complexes with cryptand 222 and DBC ligands have been investigated polarographically in dimethylsulfoxide solvent. The reduction states, electron numbers involved in the reduction process, effects of the added acid on the polarograms of complexes, and the mechanisms of the reduction electrode reactions have been examined. The stability constants and mole-ratio of new complexes were also obtained by polarographic method. The reaction of ligands was controlled by the diffusion in the reduction with four electrons at a step, whereas the redox reaction with six electrons at three steps in $UO_2\;^{2+}$ complexes with macrocyclic ligands and the redox reaction with one electron at a step in $Nd^{3+}$ complexes with cryptand 222 and DBC have been observed. The imine ligands formed stable complexes with uranium(VI) above pH 7.0, and the neodymium(III) complexes with cryptand 222 and DBC ligands were stable above pH 4.0.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.5 no.1
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• pp.1-7
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• 2007

Electrorefining experiments were successfully carried out in LiCl-KCl eutectic molten salt with a graphite cathode. It was found that the formation of Uranium-Graphite intercalation compound(U-GIC) helped the self-scraping mechanism of the uranium dendrite and the efficiency of the electrorefiner increased due to an elimination of the stripping step. The contaminations of the uranium deposit by rare earth elements was negligible while about 300 ppm of carbon was observed. The carbon contamination is believed to be eliminated by further purification by yttrium reaction. The morphology characteristics of the recovered U deposit was compared to that of steel cathode. These are only qualitative preliminary experimental results, but we believe that further research on this type of activity change the direction of the electrorefining research on spent nuclear fuel.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.13 no.4
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• pp.263-269
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• 2015

It is necessary to investigate the electrodeposition behavior of uranium and other elements on the cathode in the electrorefining process to recover the uranium selectively from the reduced metals of the electrolytic reduction process since transuranic elements and rare earth elements is dissolved in the LiCl-KCl eutectic salt. Study on separation factors of U, Ce, Y and Nd based on U and Ce was performed to investigate the deposition behavior of the cathode with respect to the concentration of rare earth elements in LiCl-KCl eutectic salt. After electrorefining with constant current mode by using Ce metal as a sacrifice anode, the contents of U, Ce, Y and Nd in the salt phase and the deposit phase of the cathode were analyzed, and separation factors of the elements were obtained from the analyses. Securing conditions of pure uranium recovery in the elctrorefining process was investigated by considering the separation factors with respect to $UCl_3$ and $CeCl_3/UCl_3$ ratio.

• Journal of the Korean Chemical Society
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• v.38 no.8
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• pp.590-597
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• 1994

The chemical behavior of the trivalent lanthanide$(Pr^{3+}, Eu^{3+}, Gd^{3+} 그리고 Yb^{3+})$complexes with organo-ligand (2,2,6,6-tetramethyl-3,5-heptanedione) has been investigated by the use of UV/Vis-spectrophotometric, magnetics, and electrochemical method. The two or three energy absorption bands are observed by the spectra of these complexes. The magnetitude of crystal field splitting energy, the spin pairing energy and bond stength was obtained from the spectra of the complexes. These are found to be localization, low-spin (or high-spin state, and strong bonding strength. The magnetic dipole moment are found to be diamagnetic complexes (or paramagnetic). The electrochemical behavior of complexes was observed by the use of cyclic voltammetry in aprotic media. These reduction peaks were irreversible two and three step reduction processes by electron transfer.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.304-308
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• 1989

The spectrophotometric determination of $Lu^{3+},\;Eu^{3+}$ and some other rare earths have been investigated using Methyl Thymol Blue(MTB) as spectrophotometric reagent. Rare earth elements form a stable complex with MTB abount pH 6.5 and the ratio of its complex is 1 to 1. MTB has a absorption maxima at 440nm and rare earth MTB complex has absorption maxima 610nm at pH 6.5, respectively. The absorbance of the rare earth MTB complex is stable in 7 hours after color developing and obey the Beer law in the range of $0{\sim}110{\mu}g/50ml$. The ligand such as phosphate, citrate and EDTA decrease the absorbance of its complex considerably, and this method has a poor selectivity of each rare earth element and the molar absorptivity is $1.2{\sim}2.0{\times}10^4mol^{-1}{\cdot}l{\cdot}cm^{-1}$. In methyl alcohol, ethyl alcohol and acetone medium we did not find out any absorption change of the rare earth MTB complex.