• Title/Summary/Keyword: 환원반응성

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Polarograms of Uranium(VI) and Rare Earth(III) Metal Complexes with Macrocyclic Ligands in Dimethylsulfoxide Solvent (디메틸술폭시드 용매중에서 거대고리리간드를 포함한 우라늄(VI)과 희토류(III) 금속 착물의 폴라로그램)

  • Hak Jin Jung;Oh Jin Jung;Chilnam Choi
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.233-242
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    • 1988
  • The uranium(VI) complexes with new unsaturated macrocyclic ligands of cryptand types and the neodymium(III) complexes with cryptand 222 and DBC ligands have been investigated polarographically in dimethylsulfoxide solvent. The reduction states, electron numbers involved in the reduction process, effects of the added acid on the polarograms of complexes, and the mechanisms of the reduction electrode reactions have been examined. The stability constants and mole-ratio of new complexes were also obtained by polarographic method. The reaction of ligands was controlled by the diffusion in the reduction with four electrons at a step, whereas the redox reaction with six electrons at three steps in $UO_2\;^{2+}$ complexes with macrocyclic ligands and the redox reaction with one electron at a step in $Nd^{3+}$ complexes with cryptand 222 and DBC have been observed. The imine ligands formed stable complexes with uranium(VI) above pH 7.0, and the neodymium(III) complexes with cryptand 222 and DBC ligands were stable above pH 4.0.

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Review of Microbially Mediated Smectite-illite Reaction (생지화학적 스멕타이트-일라이트 반응에 관한 고찰)

  • Kim, Jin-Wook
    • Economic and Environmental Geology
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    • v.42 no.5
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    • pp.395-401
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    • 2009
  • The smectite-illite (SI) reaction is a ubiquitous process in siliciclastic sedimentary environments. For the last 4 decades the importance of smectite to illite (S-I) reaction was described in research papers and reports, as the degree of the (S-I) reaction, termed "smectite illitization", is linked to the exploration of hydrocarbons, and geochemical/petrophysical indicators. The S-I transformation has been thought that the reaction, explained either by layer-by-layer mechanism in the solid state or dissolution/reprecipitation process, was entirely abiotic and to require burial, heat, and time to proceed, however few studies have taken into account the bacterial activity. Recent laboratory studies showed evidence suggesting that the structural ferric iron (Fe(III)) in clay minerals can be reduced by microbial activity and the role of microorganisms is to link organic matter oxidation to metal reduction, resulting in the S-I transformation. In abiotic systems, elevated temperatures are typically used in laboratory experiments to accelerate the smectite to illite reaction in order to compensate for a long geological time in nature. However, in biotic systems, bacteria may catalyze the reaction and elevated temperature or prolonged time may not be necessary. Despite the important role of microbe in S-I reaction, factors that control the reaction mechanism are not clearly addressed yet. This paper, therefore, overviews the current status of microbially mediated smectite-to-illite reaction studies and characterization techniques.

Sulfate Reduction in the Marine Environments: Its Controlling Factors and Relative Significance in Mineralization of Organic Matter (해양환경의 황산염 환원율 조절요인 및 유기물 분해에 있어 황산염 환원의 중요성)

  • 현정호;이홍금;권개경
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.8 no.2
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    • pp.210-224
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    • 2003
  • Sulfate reduction is a microbiological process which occurs ubiquitously in anaerobic marine environment. Sulfate reducing bacteria play a significant role in anaerobic decomposition of organic matter and regeneration of inorganic nutrients which supports the primary production in the water column (i.e., benthic-pelagic coupling) and, in special case, could be responsible for the harmful algal bloom in the coastal marine environment. Summary of the sulfate reduction rates reported in various marine sedimentary environments revealed that supply of organic substrates and presence of various electron acceptors (i.e., $O_2$, NO$_{3}$$^{[-10]}$ , Fe(III) and Mn(IV), etc.) for other aerobic and anaerobic respiration directly affect the sulfate reduction rate and relative significance of sulfate reduction in organic matter mineralization. Significance of temperature, macrophytes and bioturbation is discussed as factors controlling supply of organic substrates and distribution of electron acceptors. Finally, we suggest studies on the anaerobic microbiological processes associated with biogeochemical element cycles in the coastal environments of Korea where massive operation of organic enriched fish cage farm, frequent occurrence of toxic algal bloom and hypoxia and conservation of tidal flat are of major environmental issues.

Effect of Sulfate and Heavy Metals on Methanogenic Activation of in the Anaerobic Digestion of Tannery Wastes (피혁폐수의 혐기성 소화시 황산염과 중금속이 메탄균 활성에 미치는 영향)

  • Shin, Hang Sik;Oh, Sae Eun
    • Journal of the Korea Organic Resources Recycling Association
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    • v.4 no.1
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    • pp.13-21
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    • 1996
  • For treating tannery wastewater containing high sulfate and heavy metals, test was performed to assess their performance, competition between SRB (sulfate reducing bacteria) and MPB (methane producing bacteria), and the activity of MPB according to change of chromium concentrations. COD removal efficiency was above 70% at VLR (volumetric loading rate) of 2.0 gCOD/I.day and HRT (hydraulic retention time) of 18hrs at $35^{\circ}C$. In the competition between SRB and MPB, about 15% of the removed COD was utilized by SRB in the begining, but it became 43% at the end. It indicated that MPB was strongly suppressed by the occurrence of significant sulfate reduction since a large electron flow was uptaken by SRB. For the entire experiment, removal efficiencies of chromium concentration were more than 90%. Despite high removal efficiencies of chromium concentration, performance of reactor did not change significantly during the experimental periods. Expecially, chromium (III) is tannery wastewater is less toxic than chromium (VI).

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Electrochemical Behaviors of N'-phenyl-N-(2-chloroethyl)-N-nitrosourea Analogous and Synthesis of N-aminourea (N'-phenyl-N-(2-chloroethyl)-N-nitrosourea 유사체의 전기화학적 거동 및 N-aminourea의 합성)

  • Won, Mi-Sook;Kim, Jeong-Gyun;Sim, Yoon-Bo
    • Journal of the Korean Chemical Society
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    • v.35 no.6
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    • pp.707-712
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    • 1991
  • N'-phenyl-N-(2-chloroethyl)-N-aminourea has been prepared from N'-phenyl-N-(2-chloroethyl)-N-nitrosourea by means of the electrochemical reduction with the mercury pool electrolytic cell. In order to find out the optimum condition of the reaction, the voltammetric behaviors for N'-aryl-N-(2-chloroethyl)-N-nitrosourea derivatives have been investigated by the cyclic voltammetry and polarography. The peak potentials was shifted to the negative direction as the pH value of the solution decrease. The substituent effects of phenyl ring on the peak potential were not observed in this case. (5:3) EtOH/4 N-HCl mixed solution was employed for the electrolysis. The applied potential was -0.7 V vs. Ag/AgCl/4 N-HCl electrode. The number of electrons participated to the reduction process was 4, respectively. The product was identified by FT-IR, NMR, mass and/or elemental analysis data.

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Electrochemical Reduction of Uranyl Ion in Aqueous Basic Solutions (염기성 수용액에서 우라닐이온의 전기화학적 환원)

  • Chong Min Pak
    • Journal of the Korean Chemical Society
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    • v.29 no.2
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    • pp.121-128
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    • 1985
  • The electrochemical reduction of uranyl ion in aqueous basic media has been examined by d. c. polarography, differential pulsed polarography and cyclic voltammetry. From voltammograms obtained in uranyl solutions containing 0.1M sodium bicarbonate, either with or without the same amounts of sodium tripolyphosphate it is concluded that the first wave corresponds to the reduction of $UO_2^{2+}$ to $UO_2^+$. It is assumed that the uranyl ion undergoes appreciable hydrolysis in these media. The hydrolysis product $UO_2OH^+$ from $UO_2^{2+}$ is not reduced at the first wave, but is reduced at the second wave together with $UO_2^+$. The diffusion current was found proportional to the uranyl concentration in a range between $7.5 {\times} 10^{-4}$ and $3.75 {\times}10^{-3}$M.

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Electrochemical Reduction of 0,0-Dimethyl-0-(3-Methyl-4-Nitrophenyl)-phosphorothioate(Sumithion®) in Acetonitrile Solution (Acetonitrile 용액중(溶液中)에서 0,0-Dimethyl-0-(3-Methyl-4-Nitrophenyl)-phosphorothioate(Sumithion®)의 전기화학적(電氣化學的) 환원반응(還元反應))

  • Park, Seung Heui;Sung, Nack Do
    • Korean Journal of Agricultural Science
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    • v.11 no.2
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    • pp.315-321
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    • 1984
  • The electrochemical reduction of 0,0-dimethyl-0-(3-methyl-4 -nitrophenyl)-phosphorothioate ($Sumithion^{(R)}$) in acetonitrile solution has been studied by direct current (DC), differential pulse (DP) polarography and cyclic voltammetry methods. The irreversible electron-transfer chemical reaction (EC) mechanism of Sumithion proceeds by six electron-transfer to form radical and reduction of three-step which undergoes single bond of the phosphorus atom & phenoxy group by electron-transfer and protonation cleaved to give p-hydroxyamino-m-cresol and dimethylthiophosphonate as major product.

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Decomposition of CO2 with Reduced ferrite by CH4 (CH4로 환원된 페라이트를 이용한 CO2 분해)

  • 신현창;정광덕;주오심;한성환;김종원;최승철
    • Journal of the Korean Ceramic Society
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    • v.39 no.7
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    • pp.657-662
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    • 2002
  • The reduced ferrites, reduced NiF $e_2$ $O_4$ and CuF $e_2$ $O_4$, by C $H_4$ were applied to $CO_2$ decomposition to avoid the greenhouse effects. At the reduction reaction above $700^{\circ}C$, $H_2$ and CO were generated by partial oxidation of C $H_4$ After the reduction reaction up to 80$0^{\circ}C$, the spinel structure ferrites changed to mixture of the oxygen deficient iron oxide (Fe $O_{(1-{\delta})}$(0$\leq$$\delta$$\leq$1)) and the metallic Ni or Cu. The rate and quantity of $CO_2$ decomposition with reduced CuF $e_2$ $O_4$ were larger than those with reduced NiFe $O_4$. The $CO_2$ gas was decomposed by oxidation of the oxygen deficient iron oxide. The metallic Cu and Ni were not oxidized and remained in a metallic state up to 80$0^{\circ}C$. The $CO_2$ decomposition reaction with the reduced ferrite by C $H_4$ gas is excellent process preparing useful gas such as $H_2$and CO and decomposing $CO_2$ gas.

Trichloroethylene Treatment by Zero-Valent Iron and Ferrous Iron with Iron-Reducing Bacteria - Model Development (영가철 및 철환원균을 이용한 2가 산화철 매질에 의한 TCE 제거 연구 - 모델수립)

  • Bae, Yeun-Ook;Kim, Doo-Il;Park, Jae-Woo
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.11
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    • pp.1146-1153
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    • 2008
  • Numerical simulation was carried out to study the trichloroethylene (TCE) degradation by permeable reactive barrier (PRB), and revealed the effect of concentration of TCE, iron medium mass, and concentration of iron-reducing bacteria (IRB). Newly developed model was based on axial dispersion reactor model with chemical and biological reaction terms and was implemented using MATLAB ver R2006A for the numerical solutions of dispersion, convection, and reactions over column length and elapsed time. The reaction terms include reactions of TCE degradation by zero-valent iron (ZVI, Fe$^0$) and ferrous iron (Fe$^{2+}$). TCE concentration in the column inlet was maintained as 10 mg/L. Equation for Fe$^0$ degradation includes only TCE reaction term, while one for Fe$^{2+}$ has chemical and biological reaction terms with TCE and IRB, respectively. Two coupled equations eventually modeled the change of TCE concentration in a column. At Fe$^0$ column, TCE degradation rate was found to be more than 99% from 60 hours to 235 hours, and declined to less than 1% in 1,365 hours. At the Fe$^{2+}$ and IRB mixed column, TCE degradation rate was equilibrated at 85.3% after 210 hours and kept it constant. These results imply that the ferrous iron produced by IRB has lowered the TCE degradation efficiency than ZVI but it can have higher longevity.http://kci.go.kr/kciportal/ci/contents/ciConnReprerSearchPopup.kci#

A Study for Reductive Degradation and Surface Characteristics of Hexachloroethane by Iron Sulfide ($FeS,\;FeS_{2}$) (황화철($FeS,\;FeS_{2}$)을 이용한 헥사클로로에탄의 환원적 분해반응과 표면특성에 관한 연구)

  • Park Sang-Won;Kim Sung-Kuk;Heo Jae-Eun
    • Journal of Soil and Groundwater Environment
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    • v.11 no.5
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    • pp.35-42
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    • 2006
  • The following results were obtained in the reductive degradation of hexachloroethane (HCA), and surface characteristics by using iron sulfide ($FeS,\;FeS_{2}$) mediators. HCA was degraded to pentachloroethane (PCA), tetrachloroethylene(PCE), trichloroethylene(TCE) and cis-l,2-dichloroethylene (cis-1,2-DCE) by complicated pathways such as hydrogenolysis, dehaloelimination and dehydrohalogenation. FeS had more rapid degradation rates of organic solvent than $FeS_{2}$. In liquidsolid reaction, the reaction rates of organic solvents were investigated to explain surface characteristics of FeS and $FeS_{2}$.. To determine surface characteristics of FeS and $FeS_{2}$, the specific surface area and surface potential of each mineral was determined and the hydrophilic site ($N_{s}$) was calculated. The specific surface area ($107.0470m^{2}/g\;and\;92.6374m^{2}/g$) and the $pH_{ZPC}$ of minerals ($FeS\;PH_{ZPC}=7.42,\;FeS_{2},\;PH_{ZPC}=7.80$) were measured. The results showed that the Ns of FeS and $FeS_{2}$ were $0.053\;site/mm^{2}\;and\;0.205\;site/mm^{2}$, respectively. $FeS_{2}$ had more hydrophilic surface than FeS. In other words, FeS have more hydrophobic surface site than $FeS_{2}$.