• Title/Summary/Keyword: metal complex

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X-ray and Spectroscopy Studies of Mercury (II) and Silver (I) Complexes of α-Ketostabilized Phosphorus Ylides (α-케토안정화된 일리드화 인의 수은(II) 및 은(I) 착물에 대한 X-선 및 분광학적 연구)

  • Karami, K.;Buyukgungor, O.;Dalvand, H.
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.38-45
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    • 2011
  • The complexation behavior of the $\alpha$-ketostabilized phosphorus ylides $Ph_3P$=CHC(O) $C_6H_4-X$ (X=Br, Ph) towards the transition metal ions mercury (II) and Silver (I) was investigated. The mercury(II) complex {$HgX_2$ [Y]} 2 ($Y_1$=4-bromo benzoyl methylene triphenyl phosphorane; X=Cl(1), Br(2), I(3), $Y_2$=4-phenyl benzoyl methylene triphenyl phosphorane; X=Cl(4), Br(5), I(6)) have been prepared from the reaction of $Y_1$ and $Y_2$ with $HgX_2$ (X=Cl, Br, I) respectively. Silver complexes [$Ag(Y_2)_2]$ X(X=$BF_4$(7), OTf(8)) of the $\alpha$-keto-stabilized phosphorus ylides ($Y_2$) were obtained by reacting this ylide with AgX (X=$BF_4$, OTf) in $Me_2CO$. The crystal structure of complexes (1) and (4) was discussed. These reactions led to binuclear complexes C-coordination of ylide and trans-like structure of complexes $[Y_1HgCl_2]_2$. $CHCl_3$ (1) and $[Y_2HgCl_2]_2$ (4) is demonstrated by single crystal X-ray analyses. Not only all of complexes have been studied by IR, $^1H$ and $^{31}P$ NMR spectroscopy, but also complexes 1-3 have been characterized by $^{13}$CNMR.

The Effect of Ligand's Spin-Orbit Coupling and the Intermixing of │3d 〉 and │4p 〉 Cu Atomic Orbitals on Zero-Field Splitting in the Tetragonally Distorted Tetrahedral $CuCl_4^{2-}\;Complex^\ast$ (Cu 3d 와 4p 궤도함수의 혼성과 리간드의 Spin-Orbit Coupling 이 Tetragonally 일그러진 $CuCl_4^{2-}$ 착물의 Zero-Field Splitting에 미치는 영향)

  • Lee, Wang No;Choe, U Seong;Baek, U Hyeon;Kim, Dong Hui;Choe, Chang Jin;Lee, Gi Gye
    • Journal of the Korean Chemical Society
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    • v.34 no.1
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    • pp.37-43
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    • 1990
  • An effect of the spin-orbit coupling interaction of ligand orbitals and the intermixing │3d 〉and│4p > transition metal atomic orbitals on the ground state for a 3$d^9$ system in a strong crystal field of tetragonally distorted tetrahedral symmetry that belongs to the $D_{2d}$ point group has been investigated in this work, applying the degenerate perturbation theory. An LCAO-MO analysis in terms of the known energies of the d-d transitions for the tetragonally distorted $CuCl_4^{2-}$ ion in a single crystal of$Cs_2CuCl_4$shows that the covalent mixing of Cu 3d and ligand Cl 3p orbitals decreases dramatically with increasing Cu 4p contribution. The extent of effect on the energy level splitting for the ground state by the spin-orbit coupling interaction of ligand orbitals decreases significantly in orderTEX>$\Gamma_7(E)\;\to\;\Gamma_6(E)\; >\;\Gamma_7(B_2)\;\to\;\Gamma_6(E)\; >\;\Gamma_7(B_2)\;\to\;\Gamma_7(E)$.

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pH, Alkaline Earth Metal Ion Effects and Miscibility with Hexadecanol on the Monolayer of Palmitic Acid at the Air-Water Interface (기-액 계면에서 Palmitic Acid 단분자막에 대한 pH, 알칼리토금속 이온의 영향 및 Hexadecanol 분자와의 섞임성)

  • Jong-Jae Chung;Byung-Il Seo;Hai-Won Lee;Min-Young Ju
    • Journal of the Korean Chemical Society
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    • v.37 no.3
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    • pp.294-301
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    • 1993
  • ${\pi}$-A isotherms of the Palmitic acid(PA) with increasing pH shifted to the low area/molecule due to the dissociation of PA at the air-water interface. More condensation of PA monolayers occurred by the addition of Mg$^{2+}$, Ca$^{2+}$ and Ba$^{2+}$ ion in subphase. This condensing effect was increased with increasing the concentration of these ions. Due to the interaction with each ion, PA were formed Mg, Ca, Ba-Palmitate complex. The binding structure between alkaline earth ion and carboxylate ligand in PA has been identified by IR spectrometry. The order of condensing effect of alkaline earth ions at pH 8 was Ca$^{2+}$ > Ba$^{2+}$+ > Mg$^{2+}$. The condensing effect except for Mg$^{2+}$ decreased with increasing atomic number. Whereas, the condensing effect in pure water system decreased with decreasing atomic number in the sequence: Ba$^{2+}$ > Ca$^{2+}$ > Mg$^{2+}$. The miscibility of binary system of PA and hexadecanol in monolayer showed that the miscibility was good for the pure water system. But, in the buffered pH 8 system, bad miscibility was found.

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Geochemical Environments of Copper-bearing Ore Mineralization in the Haman Mineralized Area (함안지역 함 동 광화작용의 지화학적 환경)

  • Choi, Sang-Hoon
    • 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.

A Study on Co-precipitation of Indium Hydroxide (In(OH)3) for the Recovery and Determination of Trace Heavy Metals (인듐 수산화물(In(OH)3)의 공동침전을 이용한 미량의 중금속 회수 및 분석방법 연구)

  • Kwon, Seul-woo;Son, Seong-Hun;Lee, Man Seung;Nam, Sang-Ho
    • Resources Recycling
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    • v.26 no.4
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    • pp.50-55
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    • 2017
  • Determination of trace elements in a sample including complicated matrix is very difficult due to the interference by the matrix. Therefore, if the trace elements can be separated from the complex sample matrix and determined, the interference effects can be reduced, and it is very helpful for the overall analysis. In this study, the analytes of trace elements were separated from the sample matrix by co-precipitation with trace elements using indium hydroxide ($In(OH)_3$), then detected by inductively coupled plasma-atomic emission spectrometer (ICP-AES). Above all, the optimal conditions for the co-precipitation of elements with indium hydroxide were experimentally established. At last, salt was analyzed by the developed analytical method. No heavy metals were not found in Shinan Jeungdo salt, but trace amounts of several heavy metals except for cadmium were found in Cheonnam Yongkwang salt.

Selective Dimerization and Cyclotrimerization of Phenylacetylene with Rhodium and Iridium Complexes

  • Chin, Chong-Shik;Won, Gyong-Shik;Song, Joong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.961-966
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    • 1994
  • Oligomerization of phenylacetylene is catalyzed by $Rh(ClO_4)(CO)(PPh_3)_2$ (Rh-1), $[Rh(CO)(PPh_3)_3]ClO_4$ (Rh-2), $[Rh(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, Rh-3; $(PPh_3)(PhCN)$, Rh-4; $(PhCN)_2$, Rh-5), $[Rh(C_3H_5)(Cl)(CO)(SbPh_3)_2]ClO_4$ (Rh-6), $[Ir(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, $Ir-1; (PPh_3)(PhCN)$, $Ir-2; (PhCN)_2$, Ir-3; (AsPh_3)(PhCN)$, $Ir-4; Ph_2PCH_2CH_2PPh_2$, Ir-5; COD, Ir-6 and 2,2'-dipyridyl, Ir-7), $Ir(ClO_4)(CO)(PPh_3)_2$, $Ir-8, [Ir(PhCN)(CO)(PPh_3)_2]ClO_4$, Ir-9 to produce dimerization products, 1,3-diphenylbut-1-yn-3-ene, 1, (E)-1,4-diphenylbut-1-yn-3-ene, 2 and (Z)-1,4-diphenylbut-1-yn-3-ene, 3, and cyclotrimerization products, 1,3,5-triphenylbenzene, 4 and 1,2,4-triphenylbenzene, 5. Product distribution of the oligomers varies depending on various factors such as the nature of catalysts, reaction temperature, counter anions and excess ligand present in the reaction mixtures. Increasing reaction temperature in general increases the yield of the cyclotrimerization products. Exclusive production of dimer 1 and trimer 4 can be obtained with Ir-1 at 0 $^{\circ}$C and with Ir-2 in the presence of excess PhCN (or $CH_3CN$) at 50 $^{\circ}$C, respectively. Dimer 2 (up to 81%) and trimer 5 (up to 98%) are selectively produced with Rh-1 at 50 and 100 $^{\circ}$C respectively. Production of 3 is selectively increased up to 85% by using $PF_6$- salt of $[Ir(COD)(PPh_3)_2]$+ at 25 $^{\circ}$C. Addition of $CH_3I$ to Rh-1 produces $CH_3PPh_3^+I-$ and increases the rate of oligomerization(disappearance of phenylacetylene). Among the metal compounds investigated in this study, Ir-1 catalyzes most rapidly the oligomerization where the catalytically active species seems to contain lr(PPh3)2 moiety. The stoichiometric reaction of phenylacetylene wth Ir-9 at 25 $^{\circ}$C quantitatively produces hydridophenyl-ethynyl iridium(III) complex, $[lr(H)(C{\equiv}CPh)(PhCN)(CO)(PPh_3)_2]ClO_4$ (Ir-11), which seems to be an intermediate for the oligomerization.

Feasibility Study of Different Biochars as Adsorbent for Cadmium and Lead

  • Kim, In Ja;Kim, Rog-Young;Kim, Ji In;Kim, Hyoung Seop;Noh, Hoe-Jung;Kim, Tae Seung;Yoon, Jeong-Ki;Park, Gyoung-Hun;Ok, Yong Sik;Jung, Hyun-Sung
    • Korean Journal of Soil Science and Fertilizer
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    • v.48 no.5
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    • pp.332-339
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    • 2015
  • The objective of this study was to evaluate the effectiveness of different biochars on the removal of heavy metals from aqueous media. The experiment was carried out in aqueous solutions containing $200mg\;CdL^{-1}$ or $200mg\;PbL^{-1}$ using two different biochars derived from soybean stover and orange peel (20 mg Cd or $Pbg^{-1}$ biochar). After shaking for 24 hours, biochars were filtered out, and Cd and Pb in the filtrate were analyzed by flame atomic absorption spectrophotometer (FAAS). In order to provide information regarding metal binding strength on biochars, sequential extraction was performed by modified SM&T (formerly BCR). The results showed that 70~100% of initially added Cd and Pb was adsorbed on biochars and removed from aqueous solution. The removal rate of Pb (95%, 100%) was higher than that of Cd (70%, 91%). In the case of Cd, orange peel derived biochar (91%) showed higher adsorption rate than soybean stover derived biochar (70%). Cd was adsorbed on the biochar mainly in exchangeable and carbonates fraction (1st phase). In contrast, Pb was adsorbed on it mainly in the form of Fe-Mn oxides and residual fraction (2nd and 4th phase). The existence of Cd and Pb as a form of surface-precipitated complex was also observed on the surfaces of biochars detected by field emission scanning electron microscope (FESEM) and energy dispersive X-ray spectrometer (EDAX).

Leaching Behavior of Heavy Metals from an Ore Containing High Concentration as Utilizing Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans (Acidithiobacillus ferrooxidans와 Acidithiobacillus thiooxidans를 활용한 고농도 비소 함유 광석 내 중금속 용출 거동 연구)

  • Kim, Gahee;Kim, Rina;Kim, Kwanho;You, Kwang-suk
    • Resources Recycling
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    • v.30 no.2
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    • pp.14-23
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    • 2021
  • To investigate the potential for leaching of heavy metals by bacteria from ores stacked on actual mining sites, leaching tests of a complex metallic ore (Pb-Zn-As ore) were conducted over 60 days using acidophile bacteria Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans under initial acidic conditions. Initially, a small amount of heavy metals was leached due to the initial acidic conditions. After 20 days, when A. thiooxidans in the reactor was adapted to the ore, the amount of leached heavy metals rapidly increased; the concentrations of leached arsenic, iron, and zinc reached a maximum of 2800, 3700, and 2500 mg/L, respectively. On the other hand, in the presence of A. ferrooxidans or in the control test without bacteria, heavy metals, except zinc, were barely detected in leaching. Through this study, it was confirmed that (i) bacteria could leach heavy metals at mining sites under acidic conditions and (ii) leaching of heavy metals from a high arsenic-containing ore by A. thiooxidans was more significant than that by A. ferrooxidans.

Effect of Temperature on Growth of Tin Oxide Nanostructures (산화주석 나노구조물의 성장에서 기판 온도의 효과)

  • Kim, Mee-Ree;Kim, Ki-Chul
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.20 no.4
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    • pp.497-502
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    • 2019
  • Metal oxide nanostructures are promising materials for advanced applications, such as high sensitive gas sensors, and high capacitance lithium-ion batteries. In this study, tin oxide (SnO) nanostructures were grown on a Si wafer substrate using a two-zone horizontal furnace system for a various substrate temperatures. The raw material of tin dioxide ($SnO_2$) powder was vaporized at $1070^{\circ}C$ in an alumina crucible. High purity Ar gas, as a carrier gas, was flown with a flow rate of 1000 standard cubic centimeters per minute. The SnO nanostructures were grown on a Si substrate at $350{\sim}450^{\circ}C$ under 545 Pa for 30 minutes. The surface morphology of the as-grown SnO nanostructures on Si substrate was characterized by field-emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Raman spectroscopy was used to confirm the phase of the as-grown SnO nanostructures. As the results, the as-grown tin oxide nanostructures exhibited a pure tin monoxide phase. As the substrate temperature was increased from $350^{\circ}C$ to $424^{\circ}C$, the thickness and grain size of the SnO nanostructures were increased. The SnO nanostructures grown at $450^{\circ}C$ exhibited complex polycrystalline structures, whereas the SnO nanostructures grown at $350^{\circ}C$ to $424^{\circ}C$ exhibited simple grain structures parallel to the substrate.

Public Cognition and Information Acquisition Route for Heavy Metals and Organic Solvents in General Population of Korea (한국인의 중금속과 유기용제에 대한 인식도와 정보취득 경로)

  • Lee, Chae Kwan
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.31 no.1
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    • pp.73-82
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    • 2021
  • Objectives: This study aimed to investigate the public cognition and information acquisition route for heavy metals and organic solvents in the general population in order to provide information for the development of public relations materials. Methods: The study was carried out by questionnaire from January to March 2011 by an interview with trained surveyors. There were 700 participants, divided by gender and age. A questionnaire was issued consisting of subjective and objective cognition evaluation items and questions about information acquisition route and preferred information acquisition route for six heavy metals and five organic solvents. Data were expressed as a percentage using the SPSS 23.0 software package. Result: For heavy metals, subjective and objective cognition degrees were higher in the order of lead, mercury, cadmium, and arsenic. They were higher among males than females, and in adults compared to school-age subjects. For organic solvents, both cognition degrees were high in the order of acetone, benzene, and formaldehyde. However, cognition degree by gender and age showed a complex pattern. As a response to information acquisition route, broadcast media had the highest in all ages and genders, followed by word of mouth from neighbors in elementary school children, school education or expert lectures in middle and high school students up to people in their 30s, and print media among those in their 40s to over 60s. There was no difference in the order by gender. As a response to preference for information acquisition route, broadcast media also proved the highest in all ages and genders, followed by school education or professional lectures among those in elementary school and over their 60s, and the internet in other age groups. Females preferred school education or expert lectures and word of mouth from neighbors, while males preferred the internet. In the case of the internet, the ranking was higher for preferred information acquisition route compared with the ranking for information acquisition route. Conclusions: This data on cognition degree, information acquisition route, and preferred information acquisition route according to gender and age can provide basic data for the development of educational and promotional materials for heavy metals and organic solvents exposure management.