• Bulletin of the Korean Chemical Society
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• v.21 no.1
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• pp.65-68
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• 2000

A $\mu-oxo$ diiron(III) complex and two bis( $\mu-alkoxo)$ diiron(III) complexes with biomimetic tripodal ligand containing mixed N/O donor atoms were synthesized using a mononuclear iron(III) complex as starting material. Depending on the amounts and kinds of bases used, we obtained various kinds of diiron (III) complexes. The reaction of $[$Fe^{III}$(Hbbea)Cl_2]Cl$, 1, with an equivalent amount of $KO_2$ or NaOAc produced $[$Fe^{III}$_2O(Hb-bea)_2Cl_2]Cl_2$, 2. An additional equivalent amount of NaOBz or NaOAc converts complex 2 to complex 3 or complex 4 depending on the base used. The addition of two equivalent amounts of NaOBz orNaOAc directly converts complex 1 to $[$Fe^{III}$_2(bbea)_2(OBz)_2]Cl_2$, 3, or $[$Fe^{III}$_2(bbea)_2(OAc)_2]Cl_2$, 4, depending on the base used. Crystal data are as follows: [$Fe^{III}_2O(Hbbea)_2Cl_2]Cl_2$, 2: monoclinic space group $$P2_1/n$$, a = 8.421 (1) $\AA$, b = 18.416 (2) $\AA$, c = 13.736 (1) $\AA$, $\beta$ = 104.870 $(7)^{\circ}$, V = 2058.9 (4) $\AA^3$, Z = 2, R1 = 0.0469 and wR2 = 0.1201 for reflections with I > 2 ${\sigma}$(I).

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.19 no.2
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• pp.161-176
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• 2021

In this study, the electrochemical behavior of Sm on the binary liquid Al-Ga cathode in the LiCl-KCl molten salt system is investigated. First, the co-reduction process of Sm(III)-Al(III), Sm(III)-Ga(III), and Sm(III)-Ga(III)-Al(III) on the W electrode (inert) were studied using cyclic voltammetry (CV), square-wave voltammetry (SWV) and open circuit potential (OCP) methods, respectively. It was identified that Sm(III) can be co-reduced with Al(III) or Ga(III) to form Al_zSm_y or Ga_xSm_y intermetallic compounds. Subsequently, the under-potential deposition of Sm(III) at the Al, Ga, and Al-Ga active cathode was performed to confirm the formation of Sm-based intermetallic compounds. The X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analyses indicated that Ga₃Sm and Ga₆Sm intermetallic compounds were formed on the Mo grid electrode (inert) during the potentiostatic electrolysis in LiCl-KCl-SmCl₃-AlCl₃-GaCl₃ melt, while only Ga₆Sm intermetallic compound was generated on the Al-Ga alloy electrode during the galvanostatic electrolysis in LiCl-KCl-SmCl₃ melt. The electrolysis results revealed that the interaction between Sm and Ga was predominant in the Al-Ga alloy electrode, with Al only acting as an additive to lower the melting point.

• Journal of the Korean Chemical Society
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• v.37 no.7
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• pp.648-654
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• 1993

$[M(cyclam)X_2]Y(M=Co^{3+},\;Fe^{3+},\;Mn^{3+}\;:\;X=Cl-^,\;Br^-,\;NCS^-\;:\;Y=Cl^-,\;Br^-,\;NCS^-),\;[Co(trans-14-diene)X_2]Y(X=Cl^-,\;Br^-\;:\;Y=ClO_4^-)\;and\;[Co(trans-14-diene)](ClO_4)_2$ were able to activate an molecular oxygen under sodium borohydride. 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol reacted with activated molecular oxygen to give 2,4-tert-butyl-1,6-benzoquinone(BQ) and 3,5,3',5'-tetra-tert-butyldiphenoquinone(DPQ). The saturated tetraazamacrocyclic complexes, $[Co(cyclam)X_2]Y$, were more an effective catalyst than $[Co(trans-14-diene)X_2]Y$ the unsaturated complexes in the formation of BQ and DPQ. The mole ratio of $O_2$ vs. catalyst $(O_2/M)$ for $[Co(cyclam)X_2]Y$ and [Co(trans-14-diene)X_2]Y$ was 1/1, while it was 1/2 for $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$. The results suggested that Co(III)-macrocyclic complexes activated molecular oxygen as superoxolike ${O_2}^-$ and $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$ activated that as peroxolike $O_2^{2-}$.

• Resources Recycling
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• v.18 no.1
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• pp.30-37
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• 2009

Distribution diagram of Pt(IV), Pd(II), and Rh(III) in HCl solution was obtained as a function of HCl concentration from 0.001 to 10 M by considering complex formation reaction together with mass balance. When HCl concentration was higher than 0.1 M, most of Pt and Pd in HCl solution exist as $PtCl_6^{2-}$ and $PtCl_4^{2-}$. The concentration of HCl had a feat effect on the speciation of Rh(III). As HCl concentration increases from 0.1 to 10 M, the pedominant species changes from $PhCl_5^{2-}$ to $PhCl_6^{3-}$. Interaction parameters of $PtCl_6^{2-}$ and $PdCl_4^{2-}$ with hydrogen ion were evaluated from the solvent extraction data of Pt and Pd reported in the literature.

• Journal of Korean Society of Environmental Engineers
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• v.37 no.6
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• pp.325-331
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• 2015

The experimental results of the characteristics of aluminum based and ferric based coagulants for the Nakdong River water showed that the main hydrolysis species contained in alum and $FeCl_3$ are monomeric species of 98% and 93.3%, respectively. The PACl of r=1.2 produced by the addition of base contained 31.2% of polymeric Al species and the PACl of r=2.2 contained 85.0% of polymeric Al species, as showing more polymeric Al species with increasing r value. Coagulation tests using Al(III) and Fe(III) salts coagulants for the Nakdong River water showed that the coagulation effectiveness of turbidity and organic matter was high in the order of $FeCl_3$ > PACl (r=2.2) > PACl (r=1.2) > alum. $FeCl_3$ has showed better flocculation efficiency than Al(III) salts coagulants. In addition, in case of Al(III) coagulants, the Al(III) coagulants of higher basicity, which contained more polymeric Al species, resulted in better coagulation efficiency for both turbidity and organic matter removed. The optimum pH range for all of the coagulants investigated was around pH 7.0 under the experimental pH range of 4.0~9.5. Especially, the highest basicity PACl (r=2.2) and $FeCl_3$ were considered as more appropriate coagulants for the removal of turbidity in the case of raw water exhibiting higher pH.

• Journal of the Korean Chemical Society
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• v.39 no.5
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• pp.364-370
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• 1995

The catalytic oxidations of several olefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin (M=Ga(III), In(III), Tl(III)) complexes as catalyst and sodium hypochlorite as terminal oxidant. Porphyrins were $(p-CH_3O)TPP,\;(p-CH_3)TPP,\;TPP,\;(p-F)TPP,\;(p-Cl)TPP\;and\;(F_20)TPP$ (TPP=tetraphenylporphyrin), and olefins were $(p-CH_3O)-,\;(p-CH_3)-,\;(p-H)-,\;(p-F)-,\;(p-Cl)-\;and\;(p-Br)styrene$styrene and cyclopentene and cyclohexene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin and substrate, and the radius effect of non-redox metal ion. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. But the substituent effect of substrate on the conversion yield decreased with increasing the ${\sigma}^+$ values on substrates in the order of p-CH3O > p-CH3 > H > p-Cl > p-Br. For the oxidation of several olefins, the complexes of In(III)- and Tl(III)-porphyrins turned out to be more active catalysts than Ga(III)-porphyrin.

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.18-23
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• 1983

To understand the abnormal absorption behavior of rare earths in cation exchange resins, the absorption for Ce(III), Tb(III) and $Cl^-$ ions in Dowex 50W-X2 have been investigated by spectrophotometry in the concentration range of $1{\sim}12$ M HCI and $HCl-HClO_4$ mixed solutions. The amount of $Cl^-$ ion absorbed shows that the ratio of amount of $Cl^-$ ions to that of rare earths does not exceed 10% in the concentration range of $6{\sim}8M$ HCl and decreased gradually to 3% at 2M HCl and 6% at 12M HCl. The ratio is further decreased with the fraction of $HClO_4$ in $HCl-HClO_4$ mixed solutions and the decrease is presumably due to the weak tendency to form a complex between rare earths and $Cl^-$ ions in a cation exchange resin. The effect of $ClO_4^-$ is expected to play a more important role than that of $Cl^-$ ions in the large absorption of rare earths.

• Analytical Science and Technology
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• v.5 no.4
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• pp.417-423
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• 1992

The effects of metal ions on the arsenic(III) stripping peak were examined by the cathodic stripping voltammetry. The reduction stripping peak potential and current of arsenic(III) value were -0.79V(vs. Ag/AgCl). $0.86{\mu}A$ by using 0.1N-hydrochloric acid solution. When 10 times of Cu(II) was added to the solution, the reduction stripping peak potential of arsenic(III) was the value of -0.84V(vs. Ag/Cl), which showed a good agreement with theoretical value -0.84V(vs. Ag/Cl) by using 0.1N hydrochloric acid solution. Lead(II) and copper(II) increased the stripping peak heigh of arsenic(III), Among them, the copper(II) extremely enhanced it.

• Journal of the Korean Applied Science and Technology
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• v.15 no.2
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• pp.41-48
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• 1998

The catalytic oxidations of several cycloolefins in $CH_2Cl_2$ were been investigated using Mn(III)-, Fe(III)-porphyrin complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)TTP,\;(p-CH_3)TTP,$ TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})TPP$ (TPP = tetraphenylporphyrin), and olefins were cyclopentene, cyclohexene and cycloheptene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. The conversion of cycloalkene followed the order of $C_5\;<\;C_6\;<\;C_7$.

• Journal of the Korean Chemical Society
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• v.38 no.2
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• pp.101-107
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• 1994

Some molybdenum(III) and (IV) complexes have been prepared from the reaction of $MoCl_4$·2MeCN with N, P, O-donating ligands and characterized by elemental analysis, infrared and UV-Visible spectroscopy. 3,5-Lutidine, 1,2-phenylenediamine, 8-hydroxyquinoline, 9,10-phenanthrenequinone, triphenylphosphine and 1,2-bis(diphenylphosphino)ethane were chosen as coordinating ligands. Stretching frequencies $\upsilon$ (Mo-Cl) of Mo(IV) appear at higher frequencies than those of Mo(III) complexes due to the increasing oxidation number of metal. $MoCl_4(L)_2$ exhibit one Mo-Cl stretching frequency, whereas Mo$Cl_4$(L^L) exhibit four Mo-Cl stretching frequencies. The number of Mo-Cl stretching frequency suggestes the former complexes have trans($D_{4h}$) and the latter complexes have cis($C_{2v}$) symmetry. Stretching frequency ${\nu}g(C{\equiv}N)$ of acetonitrile in Mo(III) complexes are shifted to about 30 $cm^{-1}$ higher frequency compared with that of a free ligand (2260 $cm^{-1}$). These spectral data indicates that Mo(III) complexes are in the octahedral geometries with the coordinated acetonitrile. Finally each molybdenum(III) and (IV) complexes showed the following formulation; $[MoCl_4(L)_2]$,[Mo$Cl_4$(L^L)], $[MoCl_3(L)_2MeCN]$ and [Mo$Cl_3$(L^L)MeCN].