• 제목/요약/키워드: As(III) oxidation

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유기물분해에 따른 유류${\cdot}$중금속 복합오염토양내 비소화학종 변화의 기초연구 (Preliminary Study on Arsenic Speciation Changes Induced by Biodegradation of Organic Pollutants in the Soil Contaminated with Mixed Wastes)

  • 이상훈;천찬란;심지애
    • 자원환경지질
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    • 제36권5호
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    • pp.349-356
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    • 2003
  • 최근 산업활동의 종류가 점차 복잡해지면서 오염물질의 종류도 많아지고 있으며 오염물질의 성상도 점차 복합화하고 있다. 이런 경향은 과거 단일 물질에 의한 오염에서 점차 유기물과 중금속이 동시에 오염되는 것과 같은 혼합 오염형태가 증가하고 있는데서 인지된다. 본 연구는 유류와 중금속이 동시에 오염된 지역에서 유류분해에 따른 혐기성 환경전환이 비소의 농도와 화학종에 어떤 영향을 미치며 그 결과가 위해성과 정화작용에 어떤 영향을 미치는지를 확인하고자 하였다. 충적대수층에서 채취한 사질토양을 tetradecane으로 오염시킨 후 As(III)과 As(V)를 각각 1:1, As(III)로만 그리고 As(V)로만 등으로 혼합비율을 달리하여 오염시킨 후 마이크로코즘을 제작하여 혐기성 반응기안에 방치, 60일간 운전하였다. 매 10일마다 마이크로코즘을 개방하여 유기물, As(III) 및 As(V)의 농도 그리고 Fe, Mn의 농도변화를 측정하였다. 전체 As 농도에 대한 As(III)의 비율, As(III) 자체의 농도 변화 그리고 유기물 분해경향 등을 바탕으로 유기물분해에 따라 As(III)의 증가에 영향을 미치는 것이 확인되었다. Fe, Mn의 환원에 따른 As의 산화와 유기물 분해에 따른 환원이 서로 상충할 수 있으며 실제 분해 단계에 따라 어느 한쪽의 작용이 우세해지는 것으로 판단된다. 즉, Fe, Mn의 환원은 유기물의 분해에 의해 억제되었으며 유기물 분해가 상당히 진행 된 이후 Fe, Mn의 혐기성 용출이 일어나는 것으로 생각된다. 본 연구 결과는 혼합오염지역의 경우 유기물분해는 비소종의 화학형태에 영향을 미칠 것으로 예상되며 만약 As(III)의 비율이 증가할 경우 비소종의 위해성은 증가하게 될 것으로 판단되며 점차 증가하고 있는 혼합오염물 지역에 대한 정량적 위해성 평가가 요구된다.

Metalloporphyrin-Catalyzed Chemoselective Oxidation of Sulfides with Polyvinylpyrrolidone-Supported Hydrogen Peroxide: Simple Catalytic System for Selective Oxidation of Sulfides to Sulfoxides

  • Zakavi, Saeed;Abasi, Azam;Pourali, Ali Reza;Talebzadeh, Sadegh
    • Bulletin of the Korean Chemical Society
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    • 제33권1호
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    • pp.35-38
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    • 2012
  • Room temperature oxidation of organic sulfides with polyvinylpyrrolidone-supported hydrogen peroxide (PVP-$H_2O_2$) in the presence of Mn(III) complexes of meso-tetraphenylporphyrin, Mn(TPP)X (X = OCN, SCN, OAc, Cl) and imidazole (ImH) leads to the highly chemoselective (ca. 90%) oxidation of sulfides to the corresponding sulfoxide. The efficiency of reaction has been shown to be influenced by different reaction parameters such as the nature of counterion (X) and solvent as well as the molar ratio of reactants. Using Mn(TPP)OCN and ImH in 1:15 molar ratio and acetone as the solvent leads to the efficient oxidation of different sulfides.

Effects of Fe(III) and Cu(II) Ions on the Autoxidation of L-Ascorbic Acid

  • Kim, Mi-Ok
    • Preventive Nutrition and Food Science
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    • 제6권2호
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    • pp.83-86
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    • 2001
  • The autoxidation reaction of L-ascorbic acid(AsA), and, particularly, the oxidation rates of AsA in the presence of Fe(III) or Cu(II) ions were determined in water and methanol. UV spectral measurement (at 265 nm) and HPLC were used to determine the remaining amounts of AsA in water and methanol, respectively. It was found that, in the presence of metal ions, the autoxidation rate of AsA was significantly affected by the kinds of solvents used, and also by the kinds of metal ions present. Moreover, the first-order rate constants for the oxidation of non-dissociated AsA compared with dissociated-AsA were investigated. It was confirmed that the oxidation of AsA was more accelerated in the dissociated form of AsA than in the non-dissociated form of AsA in either with Fe(III) or Cu(II). It was also found that the Cu(II) at a concentration of 0.1 $\mu$M had a more significant effect on the first-order rate constants for the autoxidation of AsA than Fe(III) at 5 $\mu$M.

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철 및 망간 산화물로 코팅된 입자활성탄을 이용한 수용액 중 As(III) 및 As(V)의 제거 (Removal of As(III) and As(V) in Aqueous Phases by Fe and Mn Oxides Coated Granular Activated Carbon)

  • 이희용;양중석;최재영;이승목
    • 대한환경공학회지
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    • 제31권8호
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    • pp.619-626
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    • 2009
  • 본 연구에서는 수용액상의 비소를 산화 및 흡착기작을 이용하여 제거하기 위해서 철과 망간 산화물로 코팅된 입자 활성탄 (FMOCG)을 제조하고, 이의 표면특성 및 회분식 실험을 통하여 비소제거 특성을 규명하였다. 회분식 실험에서는 네 가지 코팅매질의 비소 산화 및 흡착 동역학, pH 영향, 등온흡착실험을 실시하였다. 코팅매질의 철과 망간 함량은 FMOCG-1(178.12 Fe mg/g, 11.25 Mn mg/g)가 비교적 많은 것으로 나타났다. 비소흡착 동역학을 통하여 As(III)의 경우 산화 및 흡착을 통하여 제거됨을 확인하였다. pH 영향실험 결과 pH가 낮을수록 비소의 제거율이 높아지는 것으로 나타났다. 등온흡착실험 결과는 Langmuir isotherm에 잘 적용되었으며 As(III)보다 As(V)의 흡착량이 약간 높았으며, 최대 흡착량은 1.38~8.44 mg As(III)/g과 2.91~9.63 mg As(V)/g이었다.

Co(III)/Co(II) 및 Fe(III)/Fe(II) 산화환원계에 의한 고분자량 폴리에텔렌글리콜류의 매개전해산화 (Mediated Electrochemical Oxidation of High Molecular Weight PEGs by Co(III)/Co(II) and Fe(III)/Fe(II) Redox Systems)

  • 박승조;김익성
    • 공업화학
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    • 제16권2호
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    • pp.206-211
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    • 2005
  • 백금과 티탄늄-이리듐전극으로 0.5 M의 철(II)과 코발트(II) 이온을 함유한 8.0 M의 질산용액 중에서 분자량이 1000, 4000, 20000인 폴리에틸렌글리콜류의 매개전해산화를 하였다. Fe(III)/Fe(II)와 Co(III)/Co(II) 산화환원계를 이용하여 전류밀도, 전극종, 전해질농도, 제거효율 등을 검토하였다. 백금전극 상에서 $0.67A/cm^2$의 전류밀도로 180~210 min 간 Fe(III)/Fe(II)와 Co(III)/Co(II) 전해환원계에서 매개전해산화에 의하여 폴리에틸렌글리콜류는 탄산가스로 분해되었다. 매개전해산화시 폴리에틸렌글리콜류의 제거효율은 Fe(III)/Fe(II) 산화환원계보다 Co(III)/Co(II) 산화환원계가 우수하였고 분자량이 1000, 4000, 20000인 폴리에틸렌글리콜류의 매개전해산화 제거효율은 100%이었다.

Mn(III)-porphyrin에 의한 Styrene 유도체의 산화반응 메카니즘 연구 (Kinetic Investigation of Styrene Derivatives Oxidation Mechanism by Mn(III)-porphyrin)

  • 나훈길
    • 한국응용과학기술학회지
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    • 제19권3호
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    • pp.206-212
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    • 2002
  • The catalytic activities of several metalloporphyrin, wherein the porphyrins are TPP(5,lO,l5,20-Tetraphenyl-21H,23H-porphyrin) and (p-X)TPP (X =$CH_{3}O$, $CH_{3}$, F, Cl), are reported for the oxidation of styrene and it's derivatives. The electronic effects of substrates and porphyrins on the catalytic activity of metalloporphyrin containing the transition metal ion such as Mn(III) was discussed. Investigating the correlation between the Michaelis-Menten's rate parameters and the substituent constants, we are going to analyze the influences on the changes of catalytic activity or rate determining step during the processes of the formation and the dissociation of the M-oxo-olefin.

비소용출에 대한 토양의 물리화학적 특성 영향 (Effect of the Physicochemical Properties of Soil on the Arsenic Bioaccessibility)

  • 양재규;장윤영
    • 대한환경공학회지
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    • 제28권7호
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    • pp.731-737
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    • 2006
  • 미국 Oak Ridge 연구소 관리지역에서 Inceptisol(Inc) 및 Utisol(Ult)이 지배적으로 분포된 토양층의 A- 및 B-층으로부터 채취한 물리화학적 특성이 잘 규명된 4종의 토양시료에 As(III) 및 As(V)를 흡착시킨 후 토양시료에 대한 추출용액의 비 1:100 조건에서 pH를 1.5로 고정시킨 생리학적 추출용액을 이용한 추출시험을 통하여 초기 노화조건에서의 비소의 생접근도(bioaccessibility) 및 As(III) 산화정도와 6개월간의 노화시간 경과에 따른 비소의 생접근도를 조사하였다. 토양시료에 As(C)를 주입시킨 후 48시간이 경과되었을 때 모든 토양시료에서, 특히 Ult-B, 빠르고도 강한 As(V)의 고정화(sequestration) 현상이 일어났다. 그렇지만 3개월이 지난 후에는 As(V)의 고정화에 큰 변화가 없었다. 동일한 토양시료에 As(III)를 인위적으로 오염시킨 후 48시간이 경과되었을 때 Inc-A 및 Ult-A 토양시료에서는 상당 분율의 As(III)가 As(V)로 산화되었다. 이러한 As(III)의 산화정도는 토양시료내의 망간 함량과 비례관계가 있는 것으로 나타났다. As(III)를 오염시킨 Inc-B 및 Ult-B 토양시료에서의 노화시간 경과에 따른 총비소의 생접근도 감소는 Inc-A 및 Ult-A 토양시료에서 얻어진 값보다 더 크게 나타났다. 이러한 경향은 철 함량이 풍부한 Inc-B 및 Ult-B 토양들이 As(III)로부터 산화된 As(V)를 지속적으로 고착화시킴에 따른 것으로 여겨지며 As(V)로 오염시킨 토양시료에서 얻어진 As(V) 고착화 정도와 유사한 경향을 나타내었다.

High Selective Oxidation of Alcohols Based on Trivalent Ion (Cr3+ and Co3+) Complexes Anchored on MCM-41 as Heterogeneous Catalysts

  • Shojaei, Abdollah Fallah;Rafie, Mahboubeh Delavar;Loghmani, Mohammad Hassan
    • Bulletin of the Korean Chemical Society
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    • 제33권8호
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    • pp.2748-2752
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    • 2012
  • Cr(III) and Co(III) complexes with acetylacetonate were anchored onto a mesoporous MCM-41 through Schiff condensation. The materials were characterized by XRD, FT-IR, BET, CHN and ICP techniques. Elemental analysis of samples revealed that one C=N bond was formed through Schiff condensation on MCM-41 surface. The catalysts were tested for the alcohol oxidations using t-butyl hydroperoxide (TBHP) and $H_2O_2$ as oxidant. The catalytic experiments were carried out at both room temperature and reflux condition. Various solvents such as dichloromethane, acetonitrile and water were examined in the oxidation of alcohols. Among the different solvents, catalytic activity is found more in acetonitrile. Further, the catalysts were recycled three times in the oxidation of alcohols and no major change in the conversion and selectivity is observed, which shows that the immobilized metal-acetylacetonate complexes are stable under the present reaction conditions.

Protection by Carnosine and Homocarnosine against L-DOPA-Fe(III)-Mediated DNA Cleavage

  • Kang, Jung-Hoon
    • Bulletin of the Korean Chemical Society
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    • 제26권8호
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    • pp.1251-1254
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    • 2005
  • It has been proposed that oxidation of L-3,4-dihydroxyphenylalanine (DOPA) may contribute to the pathogenesis of neurodegenerative disease. In this study, L-DOPA-Fe(III)-mediated DNA cleavage and the protection by carnosine and homocarnosine against this reaction were investigated. When plasmid DNA was incubated with L-DOPA in the presence of Fe(III), DNA strand was cleaved. Radical scavengers and catalase significantly inhibited the DNA breakage. These results suggest that $H_2O_2$ may be generated from the oxidation of DOPA and then $Fe^{3+}$ likely participates in a Fenton’s type reaction to produce hydroxyl radicals, which may cause DNA cleavage. Carnosine and homocarnosine have been proposed to act as anti-oxidants in vivo. The protective effects of carnosine and homocarnosine against L-DOPA-Fe(III)-mediated DNA cleavage have been studied. Carnosine and homocarnosine significantly inhibited DNA cleavage. These compounds also inhibited the production of hydroxyl radicals in L-DOPA/$Fe^{3+}$ system. The results suggest that carnosine and homocarnosine act as hydroxyl radical scavenger to protect DNA cleavage. It is proposed that carnosine and homocarnosine might be explored as potential therapeutic agents for pathologies that involve damage of DNA by oxidation of DOPA.

Surface Preparation of III-V Semiconductors

  • 임상우
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2015년도 제49회 하계 정기학술대회 초록집
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    • pp.86.1-86.1
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    • 2015
  • As the feature size of Si-based semiconductor shrinks to nanometer scale, we are facing to the problems such as short channel effect and leakage current. One of the solutions to cope with those issues is to bring III-V compound semiconductors to the semiconductor structures, because III-V compound semiconductors have much higher carrier mobility than Si. However, introduction of III-V semiconductors to the current Si-based manufacturing process requires great challenge in the development of process integration, since they exhibit totally different physical and chemical properties from Si. For example, epitaxial growth, surface preparation and wet etching of III-V semiconductors have to be optimized for production. In addition, oxidation mechanisms of III-V semiconductors should be elucidated and re-growth of native oxide should be controlled. In this study, surface preparation methods of various III-V compound semiconductors such as GaAs, InAs, and GaSb are introduced in terms of i) how their surfaces are modified after different chemical treatments, ii) how they will be re-oxidized after chemical treatments, and iii) is there any effect of surface orientation on the surface preparation and re-growth of oxide. Surface termination and behaviors on those semiconductors were observed by MIR-FTIR, XPS, ellipsometer, and contact angle measurements. In addition, photoresist stripping process on III-V semiconductor is also studied, because there is a chance that a conventional photoresist stripping process can attack III-V semiconductor surfaces. Based on the Hansen theory various organic solvents such as 1-methyl-2-pyrrolydone, dimethyl sulfoxide, benzyl alcohol, and propylene carbonate, were selected to remove photoresists with and without ion implantation. Although SPM and DIO3 caused etching and/or surface roughening of III-V semiconductor surface, organic solvents could remove I-line photoresist without attack of III-V semiconductor surface. The behavior of photoresist removal depends on the solvent temperature and ion implantation dose.

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