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Stable isotope, Fluid Inclusion and Mineralogical Studies of the Samkwang Gold-Silver Deposits, Republic of Korea (삼광 금-은광상의 산출광물, 유체포유물 및 안정동위원소 연구)

  • 유봉철;이현구;최선규
    • Economic and Environmental Geology
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    • v.35 no.4
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    • pp.299-316
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    • 2002
  • The Samkwang gold-silver deposits consist of gold-silver-bearing hydrothermal massive quartz veins which filled the fractures along fault shear (NE, NW) zones within Precambrian banded or granitic gneiss of Gyeonggi massif. Ore mineralization of this deposits occurred within a single stage of quartz vein which was formed by multiple episodes of fracturing and healing. Based on vein mineralogy and paragenesis, massive quartz veins are divided into two main paragenetic stages which are separated by a major faulting event. Main ore mineralization occurred at stage I. Wall-rock alteration from this deposits occur as mainly sericitization, chloritization, silicification and minor amounts of pyritization, carbonitization, propylitization and argillitization. Ore minerals are composed mainly of arsenopyrite (29.21-32.24 As atomic %), pyrite, sphalerite (6.45-13.82 FeS mole %), chalcopyrite, galena with minor amounts of pyrrhotite, marcasite, electmm (39.98-66.82 Au atomic %) and argentite. Systematic studies of fluid inclusions in early quartz veins and microcracks indicate two contrasting physical-chemical conditions: 1). temperature (215-345$^{\circ}$C) and pressure (1296-2022 bar) event with $H_{2}O-CO_{2}-CH_{4}-NaCl$fluids (0.8-6.3 wt. %) related to the early sulfide deposition, 2). temperature (203-441$^{\circ}$C) and pressure (320 bar) event with $H2_{O}$-NaCI $\pm$ $CO_{2}$ fluids (5.7-8.8 wt. %) related to the late sulfide and electrum assemblage. The H20-NaCI $\pm$ $CO_{2}$ fluids represent fluids evolved through fluid unmixing of an $H_{2}O-CO_{2}-CH_{4}-NaCl$fluids due to decreases in fluid pressure and influenced of deepcirculated meteoric waters possibly related to uplift and unloading of the mineralizing suites. Calculated sulfur isotope compositions (${\delta}^{34}S_{fluid}$) of hydrothermal fluids (1.8-4.9$\textperthousand$) indicate that ore sulfur was derived from an igneous source. Measured and calculated oxygen and hydrogen isotope compositions (${\delta}^{18}O_{I120}$, ${\delta}D$) of ore fluids (-5.9~10.9$\textperthousand$, -102~-87$\textperthousand$) indicate that mesothermal auriferous fluids at Samkwang gold-silver deposits were likely mixtures of $H_{2}O$-rich, isotopically less evolved meteoric water and magmatic fluids.

Synthesis and structure analysis of the bis(dicyclohexylammonium) chromate dihydrate complex, [(C6H11)2NH2]2[CrO4]·2H2O

  • Kim, Chong-Hyeak;Moon, Hyoung-Sil;Lee, Sueg-Geun
    • Analytical Science and Technology
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    • v.20 no.5
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    • pp.448-451
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    • 2007
  • A new bis(dicyclohexylammonium) chromate dihydrate complex, $[(C_6H_{11})_2NH_2]_2[CrO_4]{\cdot}2H_2O$, (I), has been synthesized and its structure analyzed by FT-IR, EDS, elemental analysis, ICP-AES, and single crystal X-ray diffraction methods. The Cr(VI) complex (I) is tetragonal system, I${\bar{4}}$2d space group with a = 12.5196(1), b = 12.5196(1), c = $17.3796(3){\AA}$, a = ${\beta}$ = ${\gamma}$ = $90^{\circ}$, V = $2724.09(6){\AA}^3$, Z = 4. The crystal structure of complex (I) consists of tetrahedral chromate $[CrO_4]^{2-}$ anion, two organic dicyclohexylammonium $[(C_6H_{11})_2NH_2]^+$ cations and two lattice water molecules. The chromate anion and protonated dicyclohexylammonium cation is mainly constructed through the ionic bond. The cyclohexylammonium rings of the dicyclohexylammonium cation take the chair form and vertical configuration with each other. The N-H${\cdot}$O and O-H${\cdot}$O hydrogen bond networks between the $N_{dicyclohexylammonium}$, $O_{water}$ and $O_{chromate}$ atom lead to self-assembled molecular conformation and stabilize the crystal structure.

Stable Isotope and Fluid Inclusion Studies of the Daebong Gold-silver Deposit, Republic of Korea (대봉 금-은광상에 대한 유체포유물 및 안정동위원소 연구)

  • 유봉철;이현구;김상중
    • Economic and Environmental Geology
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    • v.36 no.6
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    • pp.391-405
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    • 2003
  • The Daebong gold-silver deposit consists of mesothermal massive quartz veins thar are filling the fractures along fault shear (NE, NW) Bones within banded or granitic gneiss of Precambrian Gyeonggi massif. Based on vein mineralogy, ore textures and paragenesis, ore mineralization of this deposits is composed of massive white quartz vein(stage I) which was formed in the same stage by multiple episodes of fracturing and healing, and transparent quartz vein(stage II) which is separated by a major faulting event. Stage I is divided into the 3 substages. Ore minerals of each substages are as follows: 1) early stage I=magnetite, pyrrhotite, arsenopyrite, pyrite, sphalerite, chalcopyrite, 2) middle stage I=pyrrhotite, arsenopyrite, pyrite, marcasite, sphalerite, chalcopyrite, galena, electrum and 3) late stage I=pyrite, sphalerite, chalcopyrite, galena, electrum, argentite, respectively. Ore minerals of the stage II are composed of pyrite, sphalerite, chalcopyrite, galena and electrum. Systematic studies (petrography and microthermometry) of fluid inclusions in stage I and II quartz veins show fluids from contrasting physical-chemical conditions: 1) $H_2O-CO_2-CH_4-NaCl{\pm}N-2$ fluid(early stage I=homogenization temperature: 203∼3$88^{\circ}C$, pressure: 1082∼2092 bar, salinity: 0.6∼13.4 wt.%, middle stage I=homogenization temperature: 215∼28$0^{\circ}C$, salinity: 0.2∼2.8 wt.%) related to the stage I sulfide deposition, 2) $H_2O-NaCl{\pm}CO_2$ fluid (late stage I=homogenization temperature: 205∼2$88^{\circ}C$, pressure: 670 bar, salinity: 4.5∼6.7 wt.%, stage II=homogenization temperature: 201-3$58^{\circ}C$, salinity: 0.4-4.2 wt.%) related to the late stage I and II sulfide deposition. $H_2O-CO_2-CH_4-NaCl{\pm}N_2$ fluid of early stage I is evolved to $H_2O-NaCl{\pm}CO_2$ fluid represented by the $CO_2$ unmixing due to decrease in fluid pressure and is diluted and cooled by the mixing of deep circulated meteoric waters ($H_2O$-NaCl fluid) possibly related to uplift and unloading of the mineralizing suites. $H_2O-NaCl{\pm}CO_2$ fluid of stage II was hotter than that of late stage I and occurred partly unmixing, mainly dilution and cooling for sulfide deposition. Calculated sulfur isotope compositions ({\gamma}^{34}S_{H2S}$) of hydrothermal fluids (3.5∼7.9%o) indicate that ore sulfur was derived from mainly an igneous source and partly sulfur of host rock. Measured and calculated oxygen and hydrogen isotope compositions ({\gamma}^{18}O_{H_2O}$, {\gamma}$D) of ore fluids (stage I: 1.1∼9.0$\textperthousand$, -92∼-86{\textperthansand}$, stage II: 0.3{\textperthansand}$, -93{\textperthansand}$) and ribbon-banded structure (graphitic lamination) indicate that mesothermal auriferous fluids of Daebong deposit were two different origin and their evolution. 1) Fluids of this deposit were likely mixtures of $H_2O$-rich, isotopically less evolved meteoric water and magmatic fluids and 2) were likely mixtures of $H_2O$-rich. isotopically heavier $\delta$D meteoric water and magmaticmetamorphic fluids.

Theoretical Studies on the Gas-Phase Wittig-Oxy-Cope Rearrangement of Deprotonated Diallyl Ether

  • Kim, Chang-Kon;Lee, Ik-Choon;Lee, Hai-Whang;Lee, Bon-Su
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.678-681
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    • 1991
  • The Wittig-oxy-Cope rearrangements of deprotonated diallyl ether, I, $CH_2={\bar{C}}H-CH-O-CH_2-CH=CH_2$, have been investigated theoretically by the AM1 method. A two step mechanism forming a Wittig product ion, II, $(CH_2=CH)$ $(CH_2=CH-CH_2)$ $CHO^-$, through a radical-pair intermediate was found to provide the most favored reaction pathway in the Wittig rearrangement. The subsequent oxy-Cope rearrangement from species II also involves a two step mechanism through a biradicaloid intermediate. The intramolecular proton transfer in I (to form $CH_2=CH-CH_2-O-{\bar{C}}H-CH=CH_2$) is a higher activation energy barrier process compared to the Wittig and oxy-Cope rearrangements and is considered to be insignificant. These results are in good agreement with the condensed-phase as well as gas-phase experimental results.

Spinnability and Rheological Properties of Sols Derived from Si(OC2H5)4 and Zr(O-nC3H7)4 Solutions

  • HAN, SANG-MOK
    • Journal of Industrial Technology
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    • v.20 no.A
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    • pp.29-36
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    • 2000
  • The shape of the polymers in the mixed alkoxide solutions of Si(OC2H5)4 and Zr(n-OC3H7)4 with various water contents (1, 2, 4, and 8 in molar ratio to alkoxide, r) and catalysts was examined by rheological measurements, and its relation with fiber drawing behavior of the solutions was described. It was found that fibers could be drawn in the viscosity range 1~100 P from the acid-catalyzed solutions with lower water contents of the molar ratio H2O/alkoxide, $r{\leq}2$. On the other hand, no fiber could be drawn from the acid-catalyzed solutions including a large amount of water($r{\geq}4$) and the base-catalyzed solutions. The relation between the intrinsic viscosity [${\eta}$] and number average molecular weight ${\bar{M}}n$, namely $[{\eta}]=K{\bar{M}}n{\alpha}$, has shown that the acid-catalyzed spinnable solution (r = 1 and 2) had linear polymers where the exponent a's were about 0.56 and 0.81, whereas non-spinnable solutions (r = 4 and 8) had three dimensional network polymers or spherical particles where the exponent a's were 0.41-0.51 and 0.35.

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Application of Microwave Digestion Pretreatment Techniques for ICP-AES Analysis of Used Monolithic Automobile Catalysts Having Platinum Group-Metals and Silicates (백금족 금속과 규산염을 포함하는 모노리스형 자동차 폐촉매의 ICP-AES 분석을 위한 극초단파 분해 전처리 기법의 응용)

  • Kim, Choong-Hyon;Woo, Seong Ihl;Jeon, Sung Hwan
    • Applied Chemistry for Engineering
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    • v.10 no.4
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    • pp.568-575
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    • 1999
  • Two different digestion procedures for the simultaneous determination of major and platinum-group element(PGE) in spent automobile catalysts containing PGE and silicates by inductively coupled plasma atomic emission spectrometry(ICP-AES) are compared. Combinations of mixed aids using HF, $HNO_3$, HCl, $HClO_4$, $H_2O_2$, and $H_3BO_3$ are utilized for the hot plate dissolution method and the closed-vessel microwave digestion method, The latter method has been shown to be relatively superior in terms of recovery, analysis time, and amount of aqua regia (3 parts HCl + part $HNO_3$ required to dissolve PGE in comparison with conventional open vessel hot-plate dissolution. The best results were drawn from the following conditions: In closed Teflon PFA vessels under microwave heating with temperature/pressure regulation, a 0.25 g portion of sample was digested in 2 mL of HF, 2 mL of $HNO_3$ and 6mL of HCl under the pressure of 200 psi(13.79 bar) at $180^{\circ}C$ for 1hr, followed by a second digestion stage with 16 mL of 5%(w/v) boric acid under the pressure of 20 psi(1.38 bar) at $100^{\circ}C$ for 10 min. After the microwave heating, the sample was post-treated with 10 mL of aqua regia twice by hot-plate heating. This condition gives the PGE recovery within 85~110% and the relative standard deviations within 2%. The method developed can therefore be regarded as an alternative method for routine analysis of spent automobile catalysts.

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Characteristics of Extraction of Daidzein and Genistein in Soybean Using Sub/Supercritical Fluids (아임계/초임계 유체를 이용한 콩에 포함된 Daidzein과 Genistein의 추출특성)

  • Choi, Du Young;Zheng, Jinzhu;Row, Kyung Ho
    • Applied Chemistry for Engineering
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    • v.16 no.5
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    • pp.609-613
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    • 2005
  • Daidzein and genistein were extracted from Korean soybean by supercritical $CO_2$ and sub/supercritical water. The extracted sample was analyzed by reversed-phase high performance liquid chromatography (RP-HPLC). The retention time, retention factor, column efficiency, column selectivity and resolution of aglycons were compared with the change in the temperature and pressure of supercritical fluid and ethanol concentration. The characteristics of extraction of daidzein and genistein were more affected by ethanol concentration using supercritical $CO_2$. The most desirable extraction yield was obtained by supercritical $H_2O$ with $400^{\circ}C$ and 250 bar. Generally, the extraction yield of aglycons increased over 10 times using supercritical $CO_2$ than sub/supercritical $H_2O$.

Preparation of Microporous Silica Membrane from TEOS-$H_2O$ System and Separation Of $H_2$-$N_2$ Gas Mixture (TEOS-$H_2O$계로부터 다공성 실리카 막의 제조 및 수소-질소 혼합기체의 분리)

  • 강태범;이현경;이용택
    • Membrane Journal
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    • v.10 no.2
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    • pp.55-65
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    • 2000
  • The porous silica membrane was prepared from Si(${OC}_2H_5)_4-H_2O$ system by sol-gel method. To investigate the characteristics of gels and porous silica membrane, we examined gels and porous silica membrane using TG-DTA, X-ray diffractometer, IR spectrophotometer, BET, SEM and TEM. The optimum mole ratio of Si(OC$_2$H$_{5}$)$_4$ : $H_2O$ $C_2$H$_{5}$OH for porous silica membrane was 1 : 4.5 : 4. The porous silica membrane was obtained by heat treatment of the gel above 700 $^{\circ}C$. The specific surface area of sintered gel was 3.8 $m^2$/g to 902.3 $m^2$/g at 100 $^{\circ}C$ to 1100 $^{\circ}C$ The pore size of sintered gel was in the range 20 $\AA$~ 50$\AA$. The particle size of sintered gel was 15 nm to 30 nm at 30$0^{\circ}C$ to 700$^{\circ}C$. The performance of the porous silica membrane was investigated for the separation of $H_2$/$N_2$ gas mixture. Gas separation through porous silica membrane depends upon Knudsen flow and surface flow. The veal separation factor($\alpha$) of $H_2$/$N_2$ was 5.17 at 155.15 cmHg and $25^{\circ}C$. The real separation factor($\alpha$), head separation factor($\beta$), and tail separation factor( $\bar{B}$) increased as the pressure of permeation cell Increased.sed.

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Crystal Structure of Hexapotassium Undecahydrogen Tetratungsto Hexaantimonate(Ⅴ) Tetrahydrate (Hexapotassium Undecahydrogen Tetratungsto Hexaantimonate(Ⅴ) Tetraphydrate의 결정 구조)

  • Park, Gi Min;Yoshiki Ozawa;Lee, Uk;Lee, Uk
    • Journal of the Korean Chemical Society
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    • v.38 no.5
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    • pp.359-365
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    • 1994
  • The crystal stucture of hexapotassium undecahydrogen tetratungsto hexaantimonate(V) tetrahydrate has been determined from single crystal X-ray diffraction data. Crystal data are as follows: $K_6H_{12}[Sb_6W_4O_{36}]{\cdot}4H_2O$, Fw = 2360.62, tetragonal, I$4_1$/a, a = 10.799(1) ${\AA}$, c = 35.244(5) ${\AA}$, V = 4110.1(7) ${\AA}^3$, Z = 4, $D_x$ = 3.82 g$cm^{-3}$, $\mu(MoK\alpha)$ = 160.15 $cm^{-1}$, T = 293 K, final R = 0.0356 for 2400($F_0 > 3\sigma(F_0))$ independent reflections. The $[H_{12}Sb_6W_4O_{36}]^{-6}$ polyanion independently consists of one tungsten, two antimony, and nine oxygen atoms and belongs to the $\bar4(S_4)$ point group. This polyanion is formed by two open octahedra five membered ring of Sb(3)$O_6-W(1)O_6-Sb(2)O_6-W(1)O_6-Sb(3)O_6$ which is connected at right angle. The Sb-W, Sb-O, and W-O bond distances range from 3.2304(9) to 3.2403(5) $\AA$, 1.745(8) to 2.334(6) $\AA$, and 1.914(7) to 2.039(7) $\AA$, respectively.

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Thermodynamic Properties for the Chemical Reactions of [Cu(dl-trans-[14]-diene)]$^{2+}$ with S$_2O_3^{2-},\;SCN^-,\;I^-\;and\;NO_2^-$ ([Cu(dl-trans-[14]-diene)]$^{2+}$ 착이온과 음이온 (S$_2O_3^{2-},\;SCN^-,\;I^-$ 및 NO$_2^-$)간의 화학반응에 대한 열역학적 성질 (${\Delta}G;\;{\Delta}H;\;{\Delta}V$))

  • Yu Chul Park;Jong Chul Byun
    • Journal of the Korean Chemical Society
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    • v.29 no.3
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    • pp.239-246
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    • 1985
  • The equilibria of chemical reaction between [Cu(dl-trans-[14]-diene)]$^{2+}$ and L$^{n-}$(S$_2$O$_3^{2-}$, SCN$^-$, I$^-$, NO$_2^-$) ions were studied by the spectrophotometric method in the range of 15 to 35$^{\circ}C$ and 1 to 1500bar. The equilibrium constants(K) for L$^{n-}$ = S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at 25$^{\circ}C$ and 1500bar were 3.0, 1.9, 0.6 and 0.5, respectively. The values of K decreased with increasing pressure and temperature. From the temperature effect on equlibrium constant, the thermodynamic parameters(${\Delta}G^{\circ}$, ${\Delta}H^{\circ}$, ${\Delta}S^{\circ}$) of reaction were evaluated and the reactions of [Cu(dl-trans-[14]-diene)]2+ ion with S$_2$O$_3^{2-}$, SCN$^-$ and I$^-$ except NO$_2^-$ ion were exothermic. The volume changes of reaction(${\Delta}$V) had positive values for all the used anions. The values of ${\Delta}$V in cm$^3$/mole for S$_2$O$_3^{2-}$ ion at 1,500, 1,000 and 1,500bar were 26, 22, 19 and 16, and those for S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at atmospheric pressure 26, 30, 64 and 45, respectively. Bonding character between Cu(Ⅱ)-complex ion and L$^{n-}$ was discussed by comparing both the equlibrium constants experimentally determined and those calculated according to Fuoss's ion-pair equation in case of S$_2$O$_3^{2-}$ ion.

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