• Journal of Environmental Science International
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• v.4 no.2
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• pp.223-232
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• 1995

New two macrocyclic compounds using as carriers of liquid emulsion menbrame, have been synthesized. These reuslts provide evidance for the usefulness of the theory in designing the systems. The efficiency of selective transport for heavy metal ions have been discussed from the membrane systems that make use of $SCN^-$,<>,$I^-$,CN- and $Cl^-$ ion as co-anions in source phase and make use of $S_2O_3^{2-}$ and $P_2O_7^{4-}$ ion as receiving phase, respectively. The transport rate of M(II) was highest when a maximum amount of the M(II) in the source phase was present as$Cd(SCN)_2$$(P[SCN^-]= 0.40M)$, $Hg(SCN)_2([SCN^-]=0.40M)$ and Pd(CN)$([CN^-]= 0.40M)$. The Cd(II) and Pb(II) over each competitive cations were well transprted with 0.3M-S2032- and 0.3M-P2O74-, respectively in the receiving phase. Results of this study indicate that two criteria must be met in order to have effective macrocycle-mediated transport in these emulsion system. First one must effective extraction of the $M^{n+}$ into the toluene systems. The effectiveness of this extraction is the greatest if locK for $M^{n+}$macrocycle interaction is large and if the macrocycle is very insoluble in the aqueous phase. Second, the ratio of the locK values (or Mn+-receiving phase ($S_2O_3^{2-}$- or $P_2O_7^{4-}$) to $M^{n+}$-macrocycle (($L_1$이나 $L_2$) interaction must be large enough to ensure quantitative stripping of Mn+(($Cd^{2+}$,$Pb^{2+}$)at the toluene receiving Phase interface. $L_1$(3.5-benzo-10,13,18,21-tetraoxa-1,7,diazabicyclo(8,5,5) eicosan) forms a stable ($Cd^{2+}$ and >,$Pb^{2+}$ complexes and $L_1$ is very insoluble in water and its $Cd^{2+}$ and >,$Pb^{2+}$ complex is considerably less stable than $Cd^{2+}$-(S2O3)22- and $Pd^{2+}-P_2O_7^{4-}$ complexes. On the other hand, the stability of the $Hg^{2+}$)+-$L_1$( complex exceed that of the $Hg^{2+}$- (S2O3)22- and Hg2+-P2O74-, and the distribution coefficient of $L_2$(5,8,15,18,23,26-hexaoxa-1,12- diazabicyclo-(10,8,8) octacosane) is much smaller than that of $L_1$. Therefore, the partitioning of Lr is favored by the aqueous receiving Phase, and little heavy metal ions transport is seen despite the large logK for $Hg^{2+}$+-$L_1$ and $Mn^+$($Cd^{2+}$+, $Pb^{2+}$+ and $Hg^{2+}$)-$L_2$ interactions. Key Words : macrocycles, transport, heavy metal, co-anion, source phase, receiveing, complex separation, interaction, destribution coefficient.

• Analytical Science and Technology
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• v.8 no.1
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• pp.1-7
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• 1995

Spectrophotometric determination of U(VI) and Th(IV) by Flow injection method is described. Chrome Azurol S forms water soluble complexes with U(VI) and Th(IV) in the presence of cethyltrimethylammonium bromide. The maximum adsorption of U(VI) and Th(IV) complexes are at 600nm with molar absorptivity of $2.3{\times}10^5Lmol^{-1}cm^{-1}$ and 611nm with molar absorptivity of $3.8{\times}10^5Lmol^{-1}cm^{-1}$ in acetate buffer medium having pH 5.0 and 5.5. The calibration curves of U(VI) and Th(IV) are linear over the range of 0.1~0.8ppm and the correlation coefficients are ca. 0.9960 and 0.9930 respectively. The detection limits(S/N) are 20ppb for U(VI) and 15ppb for Th(IV). The relative standard deviation are ${\pm}1.8%$ for U(VI) and ${\pm}2.1%$ for Th(IV). The sample throughput was ca. $50hr^{-1}$.

• Journal of the Korean Chemical Society
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• v.19 no.2
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• pp.92-97
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• 1975

The molecular and electronic structures of $TiCl(OC_6H_5)_3{\cdot}C_6H_5OH\;and\;Ti(OC_6H_5)_4{\cdot}C_6H_5OH$ have been studied by employing cryoscopic and electronic spectroscopic methods. The cryoscopic data have shown that the dimeric tetraphenoxytitanium(Ⅳ) phenolate in solid undergoes complete dissociation into monomer in solution and also the chlorocomplex starts dissociation around the concentration of 8 m mole/l. Therefore, these two Ti-complexes are pentacoordinated in dilute solution and the local symmetry of the titanium ion in these complexes seems to be trigonalbipyramid. The electronic spectra of $TiCl(OC_6H_5)_3{\cdot}C_6H_5OH$ and $Ti(OC_6H_5)_4{\cdot}C_6H_5OH$ each show two band, systems, one vibration-structural band characteristic of the aromatic ring in the near UV and another visible band at 26.8 kK, 29.6 kK, respectively, which are assigned as a ligand to metal charge transfer band corresponding to $^1A_1''{\to}^1E'\;or\;^1E''$ transition.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.384-392
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• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

• Economic and Environmental Geology
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• v.42 no.1
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• pp.1-8
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• 2009

The Haman mineralized area is located within the Cretaceous Gyeongsang Basin along the southeastern part of the Korean peninsula. Almost all occurrences in the Haman area are representative of copper-bearing polymetallic hydrothermal vein-type mineralization. Within the area are a number of fissure-filling hydrothermal veins which contain tourmaline, quartz and carbonates with Fe-oxide, base-metal sulfide and sulfosalt minerals. The Gunbuk, Jeilgunbuk and Haman mines are each located on such veins. The ore and gangue mineral paragenesis can be divided into three distinct stages: Stage I, tourmaline + quartz + Fe-Cu ore mineralization; Stage II, quartz + sulfides + sulfosalts + carbonates; Stage III, barren calcite. Equilibrium thermodynamic data combined with mineral paragenesis indicate that copper minerals precipitated mainly within a temperature range of $350^{\circ}C$ to $250^{\circ}C$. During early mineralization at $350^{\circ}C$, significant amounts of copper ($10^3$ to $10^2\;ppm$) could be dissolved in weakly acid NaCl solutions. For late mineralization at $250^{\circ}C$, about $10^0$ to $10^{-1}\;ppm$ copper could be dissolved. Equilibrium thermodynamic interpretation indicates that the copper in the Haman-Gunbuk systems could have been transported as a chloride complex and the copper precipitation occurred as a result of cooling accompanied by changes in the geochemical environments ($fs_2$, $fo_2$, pH, etc.) resulting in decrease of solubility of copper chloride complexes.

• Korean Journal of Soil Science and Fertilizer
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• v.37 no.5
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• pp.329-335
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• 2004

Acid deposition in forest adjacent to the industrial complexes causes soil acidification resulting in the leaching of cations, decreases of buffering capacity and increases of toxic metal concentrations such as Al, Fe, Mn and Cu in soil solution. Changes of nutrient availability equilibria by acid deposition have been known to retard the growth of pine trees. Objective of this research was to assess the critical ratios of Ca/Al and Mg/Al limiting the growth of Pinus thunbergii in the hydroponic culture. The Ca concentration and Ca/Al ratio in stalks of pine tree were increased as increasing Ca/Al molar ratio in the nutrient solution, but were not changed when the Ca/Al molar ratio was adjusted to greater than 1. Growth of Pinus thunbergii was inhibited at the Ca/Al molar ratio lower than l due to the Ca deficiency. The molar ratios of Ca/Al in the needles of Pinus thunbergii showed the similar tendency with the stalks. This indicated that Ca/Al molar ratio of 1 in the growth media was the critical level limiting the growth of Pinus thunbergii. Concentration of Mg and Mg/Al molar ratios in the stalks of pine tree were increased as increasing Mg/Al molar ratio in nutrient solution. Molar ratios of Mg/Al in the needles were increased as increasing Mg/Al ratios in nutrient solution up to 0.83, which was the critical level limiting the growth of Pinus thunbergii.

• Journal of the Korean Chemical Society
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• v.19 no.5
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• pp.325-330
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• 1975

Complex formation between ferric ion and phosphoric acid has been studied in the wide range of the acid concentration(0${\sim}40{\%}$) by uv-visible spectroscopy and by characterization of the isolated products. The electronic spectra of Fe(III)-containing phosphoric acid solutions exhibit two visible bands at 19.2 and 24.1 kK, which are characteristic of Fe(III)-phosphate complex formation. The measurements of acid concentration dependence of the opical density of the 24.1 kK band indicates the presence of two distinct forms of Fe(Ⅲ)-phosphate complexes possibly $[Fe(H_xPO_4)]^{x+}\;and\;[Fe_2 (H_xPO_4)]^{(3+x)+}$. The 1:1 complex has been isolated for characterization, and the phosphate ion was found to be coordinated to the metal in monobasic state whereas the isolation of the dimeric species was unsuccessful.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.86.2-86.2
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• 2010

In order to improve polymer electrolyte membrane fuel cell (PEMFC) durability, the durability of membrane electrode assemblies (MEA), in which the electrochemical reactions actually occur, is one of the vital issues. Many articles have dealt with catalyst layer degradation of the durability-related factors on MEAs in relation to loss of catalyst surface area caused by agglomeration, dissolution, migration, formation of metal complexes and oxides, and/or instability of the carbon support. Degradation of catalyst layer during long-term operation includes cracking or delamination of the layer which result either from change in the catalyst microstructure or loss of electronic or ionic contact with the active surface, can result in apparent activity loss in the catalyst layer. Membrane degradation of the durability-related factors on MEAs can be caused by mechanical or thermal stress resulting in formation of pinholes and tears and/or by chemical attack of hydrogen peroxide radicals formed during the electrochemical reactions. All of these effects, the mechanical damage of membrane and degradation of catalyst layers are more facilitated by uneven stress or improper MEA fabrication process. In order to improve the PEMFC durability, therefore, it is most important to minimize the uneven stress or improper MEA fabrication process in the course of the fabrication of MEA. We analyzed the effects of the MEA fabrication condition on the PEMFC durability with MEA produced using CCM (catalyst coated membrane) method. This paper also investigated the effects of MEA fabrication condition on the PEMFC durability by adding additional treatment process, hot pressing and pressing, on the MEA produced using CCM method.

• Journal of the Korean Electrochemical Society
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• v.15 no.2
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• pp.83-89
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• 2012

We investigate the electrocatalytic activities for oxygen reduction at nanoporous gold (NPG) surfaces fabricated by selective dissolution of Ag from electrodeposited Ag-Au layers on electrode surfaces. The structure of NPG was controlled by changing the concentration ratios of precursor metal complexes during the electrodeposition of Ag-Au layers and the corresponding surface morphology and surface area was examined. NPG structures with Ag/Au ratio of 2.0 exhibited the highest electrocatalytic activity for oxygen reduction, where the nanoporous structure plays a key role, but the surface area does not affect on the electrocatalytic activity. The mechanism of electroreduction of oxygen was investigated by rotating disk electrode techniques. In acidic media, oxygen was first reduced to hydrogen peroxide followed by further reduction to water through 2-step 4-electron mechanism, whereas the oxygen was reduced directly to water by 4-electron mechanism in basic media.

• Journal of the Korean Chemical Society
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• v.43 no.2
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• pp.161-166
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• 1999

Transfer of lanthanide ions across the liquid/liquid interface facilitated by ionopore ETH4120 has been studied by using cyclic voltammetry (CV) and chronopotentiometry with cyclic linear current-scanning (CPCLCS) under the condition where the concentration of ETH4120 in nitrobenzene was much smaller than the concentration of lanthanide ions in aqueous solution. One cathodic current peak (transfer from aqueous to nitrobenzene phase) and two anodic current waves (transfer from nitrobenzene to aqueous phase) were observed. The cathodic wave was due to the formation of 1:1 (metal:ligand) complex and two anodic waves showed successive formation of 1:2 and 1:3 complexes in nitrobenzene solution. But there was no cathodic wave corresponding to two anodic waves. The ion transfer mechanism has also been discussed.