• Title/Summary/Keyword: Pb^{2+} ion

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Impedance Spectroscopy of (Pb0.92La0.08)(Zr0.95Ti0.05)O3 Ceramics above Room Temperatures

  • Jong-Ho Park
    • Korean Journal of Materials Research
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    • v.34 no.5
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    • pp.242-246
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    • 2024
  • La modified lead zirconate titanate ceramics (Pb0.92La0.08)(Zr0.95Ti0.05)O3 = PLZT-8/95/5 were prepared using the conventional solid state reaction method in order to investigate the complex impedance characteristics of the PLZT-8/95/5 ceramic according to temperature. The complex impedance in the PLZT-8/95/5 ceramic was measured over a temperature range of 30~550 ℃ at several frequencies. The complex dielectric constant anomaly of the phase transition was observed near TU1 = 179 ℃ and TU2 = 230 ℃. A remarkable diffuse dielectric constant anomalous behaviour of the complex dielectric constant was found between 100 ℃ and 550 ℃. The complex impedance spectra below and above TU1 and TU2 were fitted by the superposition of two Cole-Cole types of impedance relaxations. The fast component in the higher frequency region may be due to ion migration in the bulk, and the slow component in the lower frequency region is interpreted to be the formation and migration of ions at the grain boundary or electrode/crystal interfacial polarization.

이온현미분석기를 사용한 남서부 경기육괴 변성암류의 U-Pb 저어콘 연대: 남중국지괴와의 대비 가능성

  • 조문섭
    • Proceedings of the Mineralogical Society of Korea Conference
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    • 2001.06a
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    • pp.141-142
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    • 2001
  • 남서부 경기육괴의 편마암류로부터 분리된 저어콘(zircon) 입자를 대상으로, 이온현미분석기(ion microprobe)를 사용한 U-Pb 연대를 구하였다. 그 결과는 후기 원생대(약 820 Ma) 뿐만 아니라 오르도비스기에 상당한 화성활동이 한반도에 있었음을 지시한다. 우리 나라 후기 원생대의 화성-변성 활동에 대해 알려져 있는 바는 극히 제한적이어서 후속연구가 필수적이며, 이러한 연구는 한반도의 지체구조적 변천사를 로디니아 초대륙(Rodinia supercontinent)의 생성-분리와 관련해 재조명할 수 있는 기회를 제공할 것이다. 또한 오르도비스기의 화성작용은 그동안 논란이 되어 왔던 소위 “칼레도니아(Caledonian)” 변동 (cf. 조문섭, 2000)에 대한 또 다른 증거를 제공해준다. 저어콘의 연대측정은 서호주의 커튼공업대학교에 설치되어 있는 SHRIMP-II(Sensitive High-Resolution Ion Microprobe-II; 고감도-고분해능 이온현미분석기)를 사용하였으며, 시료 준비 및 분석방법은 기존에 보고된 바와 같다 (e.g., Kinny et al., 1999). 분석된 3개의 암석 시료(1006-5, 8, 9)는 경기육괴의 남서부에 위치한 홍성 지역의 정편마암들이다. 1006-8 시료는 Turek and Kim (1996)이 전통적인 방법을 사용해 687$\pm$5 Ma의 U-Pb 저어콘 연대를 보고한 바 있는 화강암질 편마암 (시료번호, KJ43)에 해당된다. 두 개의 다른 시료는 1006-8 주변에서 산출하는 전형적인 경기육괴의 편마암류로서 화강암질 정편마암이다. 이들 시료로부터 분리된 저어콘 입자들은 대부분 화성기원의 누대구조와 자형의 결정형태를 보여준다. 과성장띠(overgrouth rims)는 1006-5 시료에서 흔하게, 그리고 1006-9 시료에서 매우 드물게 관찰된다. 음극선발광(cathodoluminescence) 영상의 해석을 통해 저어콘 결정의 성장사를 유추하였으며, 이를 바탕으로 이온현미분석 점(spot)을 정하였다. U-Pb-Th 자료는 퍼스(Perth) 저어콘 스탠다드 (CZ3, 564 Ma, $^{206}$Pb/$^{238}$U=0.0914)를 사용하였다. 아래에 기술하는 연대는 모두 $^{206}$Pb/$^{238}$U 연대에 해당된다. 두 개의 화강암질 편마암 시료로부터 구한 U-Pb 저어콘 연대는 각각 812 $\pm$ 14 Ma(1006-8)와 822 $\pm$ 17 Ma(1006-9)로 분석오차 내에서 서로 일치한다. 이 결과는 춘천 및 전곡 지역의 석류석 각섬암에서 보고된 Sm-Nd 전암연대(852 $\pm$ 24 Ma 및 824 $\pm$ 143 Ma; Lee and Cho, 1995; Ree et al., 1996)와 잘 부합한다. 따라서 후기 원생대 기간 중 화성활동이 한반도에서 광범위하게 일어났음을 시사한다. 한편, 1006-9 시료에서는 예외적으로 한 개의 저어콘 입자 주변부(rim)에서 매우 얇은 과성장띠가 관찰되었으며, 두 개의 점 분석으로부터 구한 U-Pb 저어콘 연대는 약 235 Ma이다. 이 띠는 또한 변성기원의 저어콘에서 흔히 관찰되는 작은 W (<0.05) 비를 보인다. 1006-5 시료는 위 두 시료로부터 수 km 떨어진 지점에서 채집하였으나, 저어콘 연대는 상이한 기록을 보여준다. 즉 매우 작은 Th/U (<0.01) 값을 갖는 저어콘의 주변부에서 223 $\pm$ 5 Ma의 연대가 잘 정의되며, 이는 1006-9 시료에서 관찰된 결과와 함께 트라이아스기의 고온변성작용이 백립암상에 가까운, 매우 높은 온도에 달하였음을 지시한다. 한편 저어콘의 중심부는 335-473 Ma의 비교적 넓은 연대 분포를 보인다. 이는 저어콘이 실제 성장한 연대를 지시하기보다는 트라이아스기의 변성작용에 따른 납손실(Pb loss) 그리고 누대 규모보다 더 큰 빔 크기(beam size, 약 30 $\mu\textrm{m}$)의 영향일 것으로 해석된다. 또한 저어콘이 다양한 외래물질로부터 기원했다는 증거가 관찰되지 않으므로, 이 정편마암의 모암은 오르도비스기(약 430-470 Ma)에 관입하였을 것으로 생각된다. 따라서 그동안 논란이 되어 왔던 소위 “칼레도니아” 변동이 한반도 내에 실존하였을 가능성을 시사한다. 이상의 결과를 종합하여 볼 때, 경기육괴의 변성암류는 후기 원생대 이후 다양한 저어콘의 성장사를 기록하고 있음을 알 수 있다: 즉 (1) 후기원생대(약 820 Ma)의 화성작용; (2) 오르도비스기(약 450 Ma)의 화성작용: 그리고 (3) 트라이아스기 (약 223 Ma)의 부분용융을 수반한 고온 변성작용으로 대표된다. 이러한 지질연대는, 옥천변성대에서 얻어진 756 Ma의 저어콘 연대(Lee et al., 1998)와 더불어, 친링-다비-수루(Qinling-Dabie-Sulu) 대륙 충돌대와 양쯔 지괴에서 보고된 지질연대 결과와 잘 부합한다. 따라서 지구연대학적으로 경기육괴가 북중국보다는 대륙충돌대를 포함하는 남중국지괴에 속할 것으로 결론지을 수 있다.

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SHRIMP Zircon U-Pb Geochronology, Geochemistry and Sr-Nd Isotopic Study of the Cheongju granitoid rocks (청주 화강암의 SHRIMP 저어콘 U-Pb 연대, 지구화학 및 Sr-Nd 동위원소 연구)

  • Cheong, Won-Seok;Kim, Yoon-Sup;Na, Ki-Chang
    • The Journal of the Petrological Society of Korea
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    • v.20 no.4
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    • pp.191-206
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    • 2011
  • The emplacement ages, whole-rock geochemistry and Sr-Nd isotopic compositions of granitoid rocks from Cheongju area, South Korea, were investigated for delineating their petrogenetic link to the Jurassic Daebo granitoid rocks. Zircon crystals were collected from the diorite, biotite granite and acidic dyke samples in a single outcrop. Cross-cutting relationships show that the emplacement of diorite was postdated by the intrusion of biotite granite. Both rocks have been subsequently intruded by acidic dyke. The U-Pb isotopic compositions of zircon from the diorite, biotite granite, and acidic dyke were measured using a SHRIMP-II ion microprobe, yielding the crystallization ages of $174{\pm}2Ma$, $170{\pm}2Ma$, and $170{\pm}5Ma$, respectively, with 95% confidence limits ($t{\sigma}$). The emplacement ages are consistent with those determined from the above relative ages. The major and trace element patterns of the rocks are consistent with those of the Jurassic Daebo granitoid rocks, possibly suggesting a subduction-related I-type granite. The geochemical signature is, however, betrayed by the Sr and Nd isotopic compositions of these rocks. The isotopic signatures suggest that the rocks were produced either by the partial melting of lower-crust or by the mantle-derived magma contaminated by the basement rocks during its ascent and/or emplacement. In addition, the inherited ages of zircons of the rocks (ca. 2.1, 1.8, 0.8 and 0.4 Ga) suggest a possible assimilation with crustal rocks from the Gyeonggi massif and Ogcheon metamorphic belt.

Organopalladium(II) Complexes as Ionophores for Thiocyanate Ion-Selective Electrodes

  • Kim, Dong-Wan;Lee, So-Hyun;Kim, Jung-Hwan;Kim, Jin-Eun;Park, Jong-Keun;Kim, Jae-Sang
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2303-2308
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    • 2009
  • A thiocyanate poly(vinyl chloride) (PVC) membrane electrode based on [1,2-bis(diphenylphosphino)ethane]dihalopalladium( II), [(dppe)$PdX_2$, X = Cl ($L^1$), X = I ($L^2$)] as active sensor has been developed. The diiodopalladium complex, [(dppe)$PdI_2](L^2$) displays an anti-Hofmeister selectivity sequence: $SCN^-\;>\;I^-\;>\;{ClO_4}^-\;>\;Sal^-\;>\;Br^-\;>\;{NO_2}^-\;>\;{HPO_4}^-\;>\;AcO^-\;>\;{NO_3}^-\;>\;{H_2PO_4}^-\;>\;{CO_3}^{2-}$. The electrode exhibits a Nernstian response (-59.8 mV/decade) over a wide linear concentration range of thiocyanate ($(1.0\;{\times}\;10^{-1}\;to\;5.0\;{\times}\;10^{-6}$ M), low detection limit ($(1.1\;{\times}\;10^{-6}$ M), fast response $(t_{90%}$ = 24 s), and applicability over a wide pH range (3.5∼11). Addition of anionic sites, potassium tetrakis[p-chlorophenyl] borate (KTpClPB) is shown to improve potentiometric anion selectivity, suggesting that the palladium complex may operate as a partially charged carrier-type ionophore within the polymer membrane phase. The reaction mechanism is discussed with respect to UV-Vis and IR spectroscopy. Application of the electrode to the potentiometric titration of thiocyanate ion with silver nitrate is reported.

Flotation-Spectrophotometric Determination of Ag(I) at the 10-7 mol L-1 Level Using Iodide and Ferroin as an Ion-associate

  • Hosseini, Mohammad Saeid;Hashemi-Moghaddam, Hamid
    • Bulletin of the Korean Chemical Society
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    • v.26 no.10
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    • pp.1529-1532
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    • 2005
  • A simple and cost effective method for separation and preconcentration of Ag(I) at the $10^{-7}\;mol\;L^{-1}$ level in the environmental and mineral samples is present. The method is based on the flotation of Ag(I)-iodide complex as an ion-associate with ferroin in pH of 4 from a large volume of an aqueous solution (500 mL) using nheptane. The floated layer was then dissolved in dimethylsulfoxide (DMSO) for the subsequent spectrophotometric determination. Beer's law was obeyed over a range of 2.0 ${\times}$ $10^{-7}$-4.0 ${\times}$ $10^{-6}$ mol $L^{-1}$ with the apparent molar absorptivity of 2.67 ${\times}$ $10^5$ L $mol^{-1}\;cm^{-1}$. The detection limit (n = 5) was 4 ${\times}$ $10^{-8}$ mol $L^{-1}$, and RSD (n = 5) obtained for 2.0 ${\times}$ $10^{-6}$ mol $L^{-1}$ of Ag(I) was 2.2%. The interference effects of a number of elements was studied and found that only $Hg^{2+}$ at low concentration, and $Pb^{2+}$, $Cd^{2+}$, $Cu^{2+}$, and $Fe^{3+}$ ions at moderately high concentrations were interfered. To overcome on these interference effects, the solution was treated with EDTA at a buffering pH of 4 and passed through a column containing Amberlite IR-120 ionexchanger resin, just before the flotation process. The proposed method was applied to determine of Ag(I) in a synthetic waste water, a photographic washing sample and a geological sample and the results was compared with those obtained from the flame atomic absorption spectrometry. The results were satisfactorily comparable with together, so that the applicability of the proposed method was confirmed in encountering with the real samples.

Lipophilic Crown-4 Derivatives as Lithium Ionophores for Lithium Ion Selective Liquid Membrane Electrodes

  • Jae Sang Kim;Sung Ouk Jung;Shim Sung Lee;Si-Joong Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.1
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    • pp.123-127
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    • 1993
  • New lipophilic Crown-4 compounds of 16-membered rings containing furan (neutral carrier,I), tetrahydrofuran (neutral carrier,II) and lithium complex of the latter (neutral carrier,III) have been synthesized and tested as the active sensors for lithium ion in poly(vinyl chloride) (PVC) membrane electrode, in the presence and absence of an anion excluder, tetrakis(4-chloro-phenyl)borate (KTClPB), 2-nitrophenyl phenyl ether (NPPE), tris(2-ethylhexyl)phosphate (TEHP), o-nitrophenyl octyl ether (NPOE), dioctyl adipate (DOA), bis(2-ethylhexyl)adipate (BEHA), di-n-octylphenyl phosphonate (DOPP) were used as plasticizing solvent mediators. The electrode response function had a nearly Nernstian slope of 54-61 mV per decade (25$^{\circ}$C) within the concentration range of $10^{-1}-10^{-4}$ M LiCl and the detection limits for all electrodes were ca. $5{\times}10^{-4}$ M. The response time of the electrode was faster at the higher lithium concentration and the response of the electrode was stable for longer than 6 months. The sensor membranes exhibit improved response times and increased lifetimes as compared to the system described earlier.

Treatment Characteristics of Acid Mine Drainage by Porous Ceramics using Wood Flour as Pore-forming Agent (목분 기포제를 이용한 산업부산물 소재 다공성 세라믹에 의한 산성광산배수의 처리특성 연구)

  • Lee, Yeong-Nam;Yim, Soo-Bin
    • Journal of Environmental Science International
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    • v.27 no.2
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    • pp.109-122
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    • 2018
  • This study was conducted to investigate the removal characteristics of heavy metals and sulfate ion from acid mine drainage by porous zeolite-slag ceramics (ZS ceramics) that was prepared by adding wood flour as pore-foaming agent while calcining the mixtures of natural zeolite and converter slag. The batch test showed that the removal efficiency of heavy metals by pellet-type porous ZS ceramics increased as the particle size of wood flour was decreased and as the weight mixing ratio of wood flour to ZS ceramics was increased. The optimal particle size and weight mixing ratio of wood flour were measured to be $75{\mu}m$ and 7~10%, respectively. The removal test with the porous ZS ceramics prepared in these optimal condition showed very high removal efficiencies: more than 98.4% for all heavy metals and 73.9% for sulfate ion. Relative to nonporous ZS ceramics, the increment of removal efficiency of heavy metals by porous ZS ceramics with $75{\mu}m$ and 10% wood flour was 5.8%, 60.5%, 36.9%, 87.7%, 10.3%, and 57.4% for Al, Cd, Cu, Mn, Pb, and Zn, respectively. The mechanism analysis of removal by the porous ZS ceramics suggested that the heavy metals and sulfate ion from acid mine drainage are eliminated by multiple reactions such as adsorption and/or ion exchange as well as precipitation and/or co-precipitation.

Lead Ion Selective Solid Contact Electrode based on Tetramethylthiuram monosulfide ionophore (Tetramethylthiuram monosulfide를 ionophore로 이용한 납 이온 선택성 poly(aniline) 고체 접촉 전극)

  • Han, Won-Sik;Park, Woon-Suk;Kwon, Hye-Yeong;Lee, Young-Hoon;Hong, Tae-Kee
    • Journal of the Korean Applied Science and Technology
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    • v.30 no.2
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    • pp.356-361
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    • 2013
  • Lead (II) ion selective poly(aniline) solid contact electrode based on Tetramethylthiuram monosulfide ionophore as a sulfur containing sensing material is successfully developed. The electrode exhibits good linear response of 25.6 mV / decade (at $20{\pm}0.2^{\circ}C$, r2=0.995) within the concentration range of $1.0{\times}10^{-1}{\sim}4.0{\times}10^{-7}$ M Pb (II). The composition of this electrode was Ionophore : PVC : dioctylphthalate : potassiumtetrakis(4-chlorophenyl)borate : Oleic acid = 5.0 : 20.0 : 25.0 : 4.0 : 5.0. When we consider the results of using different composition electrodes based on only one potassiumtetrakis(4-chlorophenyl)borate or Oleic acid liphophlic additive, poly(aniline) solid contact electrode based on Tetramethylthiuram monosulfide ionophore with potassiumtetrakis(4-chlorophenyl)borate and Oleic acid liphophlic additive had the best result in response characteristics. The electrode shows good selectivity for lead (II) ion in comparison with alkali, alkaline earth, transition and heavy metal ions. This electrode is suitable for use with aqueous solutions of pH 3.0 ~ 7.0 and their standard deviation in the measured emf differences was ${\pm}2.94$ mV at Tris buffered lead sample solution of $1.0{\times}10^{-2}$ M and ${\pm}2.82$ mV at Tris buffered lead sample solution of $1.0{\times}10^{-3}$ M. Their stabilization time was less than 710 s. and response time was less than 16 s.

Characterization of Cation Exchange and Cesium Selectivity of Synthetic Beta-Dicalcium Silicate Hydrate

  • El-Korashy, S.A.
    • Journal of the Korean Chemical Society
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    • v.46 no.6
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    • pp.515-522
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    • 2002
  • Solid beta-dicalcium silicate hydrate $(\beta-C_2SH)$ synthesized under hydrothermal conditions at $240^{\circ}C$ and Ca/Si=2 molar ratio shows cation exchange properties towards divalent metal cations such as Fe, Cu, Zn, Cd, or Pb. The ability of metal cation uptake by the solid was found to be in the order: $Fe^{2+}$$Cu^{2+}$$Zn^{2+}$$Cd^{2+}$ = $Pb^{2+}$. Cesium selectivity of the solid was demonstrated in the presence of univalent cation such as $Li^+$, $Na^+$ and $K^+$ and divalent cations such as $Ca^{2+}$, $Mg^{2+}$ and $Ba^{2+}$, which are one hundred times more concentrated than the $Cs^+$. The uptake of $Cs^+$ is maximum in the presence of $Mg^{2+}$ whereas it is minimum in the presence of $K^+$. The different affinities of ${\beta}-C_2SH$ towards divalent metal cations can be used for the separation of those ions. Due to its selectivity for cesium it can be used in partitioning of radioactive Cs+ from nuclear wastes containing numerous cations. The mechanism of the metal cation exchange and cesium selectivity reactions by the solid is studied.

The Cation Exchange Separation of Metal-Trien Mixed Complexes (금속-Trien 혼합착물의 양이온 교환수지상에서의 분리)

  • Yung-Kyu Park;Chul- Heui Lee;Mu-Kang Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.2
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    • pp.129-138
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    • 1980
  • The formation constants of the mixed-ligand complexes in the Cd(II), Cu(II) and Pb(II)-Trien-OH system were studied by polarograph. The formation constant $(log{\beta}_{ij})$ was determined at $25^{\circ}C$ in the ionic strength of 0.1. It was also confirmed that the mixed ligand complexes in this system were formed above pH 10.2, 10.5 and 9.0 for Cu(II), Cd(II) and Pb(II) by the calculation of the distribution for complexes at the various pH. Masking of Cd(II) by conversion to anionic EDTA-complexes has been used to separate Cu(II) from Cd(II) through passage of a combined Trien-EDTA solution on an cationic resin column. The optimal condition for the separation of Cu(II) from Cd(II) is confirmed at the pH range above 9.0, not only by considering the theoretical equation of the conditional-exchange-constant of metal on the cation exchange resin,but also by calculating the distribution of the mixed ligand complexes in the resin at the various pH with computer. By analyzing the synthetic sample of Cu(II) and Cd(II) with a EDTA masking at pH 9.5, it is found that the results of the experiment are satisfied with the theoretical value.

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