• Title/Summary/Keyword: 라디칼 생성율

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염류 용액에서의 액체 플라즈마 방전과 히드록실라디칼에 관한 연구

  • Choe, Eun-Jin;Seo, Jeong-Hyeon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2015.08a
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    • pp.134-134
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    • 2015
  • 최근 액체 플라즈마에 대한 주된 이슈는 방전에 의해 발생하는 히드록실라디칼(OH-)과 버블이다. 액체 플라즈마를 이용한 다양한 응용분야에서는 히드록실라디칼에 주목하고 있다. 액체 플라즈마는 그래핀 파생물의 용액 친화도 향상을 위해 이용될 수 있다. 흑연이 포함된 과산화수소(H2O2) 용액에서 전기적인 방전으로 만들어진 히드록실라디칼로 그래핀 파생물의 용액 친화도를 향상시킨다. 이는 잠재적인 프린팅(printing) 기술 발전에 기대된다. 그리고 이 라디칼은 폐수에서 발암성의 트라이클로로아세트산(CCl3COOH)을 탈 염소하고 분해하는 역할을 하여 액체 플라즈마가 새로운 수처리 기술로 부상되고 있다. 또한 인체에서는 살균 작용을 하는 것 뿐만 아니라 단백질 고리를 끊는 역할을 하여 전립선 수술과 같은 인체수술에 적용될 수 있다. 최근 액체 플라즈마를 이용한 돼지 각막 임상수술에서 레이저와 필적할 정도로 매우 정밀하게 수술된 연구결과가 발표되어 인체 각막수술 적용에 기대된다. 이처럼 액체 플라즈마를 이용한 대부분의 응용분야에서 히드록실라디칼의 역할이 중요하다. 액체 플라즈마의 또 다른 이슈인 버블은 2가지의 역할을 한다. 첫 번째로 방전소스의 역할이다. 액체 속에 담긴 얇은 전극에 전압을 인가하면 전극 주변에서 강한 전기장의 발생으로 줄열(joule heating)에 의해 버블이 생성된다. 전극에서 버블이 생성되었을 때, 서로 다른 유전율을 가진 두 물질로 나누어진다. (버블 안은 공기로 상대 유전율 ${\varepsilon}r{\fallingdotseq}=1$, 용액은 ${\varepsilon}r{\fallingdotseq}=80$이다.) 시스템에 인가된 전압이 항복 전압(breakdown voltage)을 넘어서면 유전율이 상대적으로 낮은 버블내부에 강한 전기장이 걸리게 되어 방전이 일어난다. 만약 버블이 존재하지 않는다면 방전을 위해서 매우 높은 전압이 필요하다. 따라서 버블은 플라즈마 방전의 소스역할을 한다. 두번째로 버블은 전극의 부식을 방지하는 역할을 한다. 전극 부식은 주로 전기분해로 인한 산화반응에 의해 발생하는데 버블을 전극에 오래 머무르게 하면 부식을 방지할 수 있다. 이처럼 액체 플라즈마 시스템에서 버블의 역할들은 상당히 중요하다. 일반적으로 버블은 시스템에 인가하는 전원, 전극 극성 그리고 전압크기에 따라 거동이 달라진다. 시스템에 AC파워를 인가하면 버블은 주파수가 높을수록 전극에서 떨어지는 속도가 빨라지는 특성을 보인다. 핀 전극 극성이 음극일 때는 양극일 때보다 버블이 더 잘 생성된다. 또한 인가전압크기에 따라 거동이 달라지며 시스템에 같은 전압을 인가하여도 크기가 항상 같지 않고, 거동도 일관성을 보이지 않은 랜덤적인 모습을 보인다. 본 연구에서는 이 랜덤적인 버블의 거동을 정리하고 응용분야에서 중요하게 여기는 히드록실라디칼 생성에 대해 공부하기 위해 염류 용액(saline solution)에 핀(pin)-면(plane) 전극 구조를 설치하여 10Hz 주파수(1% duty cycle)를 가진 0-600V 구형펄스로 실험하였다. 실험을 통한 결과로서 랜덤적인 버블의 거동을 전극에서 버블이 떨어지는 속도와 플라즈마 특성에 따라 슈팅모드(shooting mode)와 유지모드(keeping mode) 2가지 모드로 분류하였다. 슈팅모드에서는 버블이 핀 전극에서 성장하지 못하고 빠른 속도로 떨어지는 모드로 플라즈마 방전이 잘 이루어지지 않는다. 반면 유지모드에서는 버블이 핀 전극에서 떨어지지 않고 지속적으로 성장한다. 이 모드에서는 펄스 시간 동안 하나의 버블로 연속적인 방전이 가능하다. 방전이 일어날 때 발생하는 히드록실라디칼의 생성은 버블 내부의 쉬스와 관련이 있다. 이 라디칼을 만들기 위해서는 높은 에너지가 요구되기 때문에 버블 내부의 쉬스(sheath)에서 만들어진다. 펄스 동안 쉬스는 주로 핀 전극 주변에서 유지되며 히드록실라디칼은 이곳에서 주로 만들어진다. 따라서 버블과 함께 쉬스도 성장하는 버블유지모드에서 슈팅모드보다 히드록실라디칼이 더 많이 생성된다.

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Numerical Study on Soot Formation in Opposed-flow Nonpremixed Flame by Mixing Toluene (톨루엔 혼합에 따른 대향류 확산화염 내 매연 생성에 대한 수치적 연구)

  • Choi, Jae-Hyuk;Yoon, Seok-Hun;Yoon, Doo-Ho
    • Journal of the Korean Society of Marine Environment & Safety
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    • v.18 no.2
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    • pp.139-144
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    • 2012
  • A numerical simulation has been performed to investigate effects of toluene mixing on soot formation in pure ethylene opposed-flow nonpremixed flame. Mixture ratios of toluene were 3%, 5%, 10%, and 20%. Senkin code for 0-D simulation and oppdif code for 1-D simulation based on CHEMKIN III were utilized. 0-D results by senkin showed that concentrations of methyl radicals and benzene were increased with increasing toluene mixture ratio. This implied that the mixing of toluene in pure ethylene diffusion flame produces more PAHs and soot than those of pure ethylene flame. 1-D result of 10 % toluene reaction by oppdif code showed that production rate for H radical was a crucial factor for benzene formation. These results imply that methyl radical, benzene and H radical play a important role on soot formation in diffusion flames.

Degradation of Humic Acids by Ozone/high pH, Ozone/Hydrogen Peroxide and Ozone/Hydrogen Carbonate System ($O_3$/high pH, $O_3/H_2O_2$$O_3/{HCO_3}^-$ 시스템에서의 부식산의 분해 반응 특성)

  • Shin, Hyun Sang;Kim, Kei Woul;Rhee, Dong Seok
    • Analytical Science and Technology
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    • v.13 no.5
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    • pp.652-658
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    • 2000
  • Chemical degradation of aqueous humic acid by ozonation was studied with respect to the direct reactions of ozone and the indirect reactions due to its preliminary decomposition to secondary oxidant, OH radical. This was characterized by analyzing TOC, $UV_{254}$ and ozone consumption measured in different experimental conditions in which ozone reacted in the presence of various concentrations of $H_2O_2$ and $HCO_3{^-}$ concentrations ranging from 20 to 100 mg/L. and different pH (5-9). The results suggest that the TOC removal is mainly dependent on indirect reactions of OH radical whereas $UV_{254}$ reduction is mainly dependent on direct reactions of ozone with humic acid molecules. It has been also found that ozone consumption was most likely to be affected by pH and alkalinity in the solution.

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A Comparison between the Decomposition of Bisphenol A and the Concentration of Hydrogen Peroxide Formed during Ozone/Catalyst Oxidation Process (오존/촉매 산화공정에서 비스페놀 A의 분해와 생성된 과산화수소의 농도 비교)

  • Choi, Jae Won;Lee, Hak Sung
    • Applied Chemistry for Engineering
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    • v.28 no.6
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    • pp.619-625
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    • 2017
  • In this study, the formation of hydroxyl radical and decomposition characteristics of bisphenol A (BPA) was investigated by quantifying hydrogen peroxide formed as a reaction by-product during the formation stage of hydroperoxyl radical. The direct oxidation reaction by ozone only decomposed BPA just like the Criegee mechanism under the condition where radical chain reactions did not occur. Non-selective oxidation reactions occurred under the conditions of pH 6.5 and 9.5 where radical chain reactions do occur, confirming indirectly the formation of hydroxyl radical. The decomposition efficiency of BPA by the added catalysts appeared in the order of $O_3$/PAC ${\geq}$ $O_3/H_2O_2$ > $O_3$/high pH > $O_3$ alone. 0.03~0.08 mM of hydrogen peroxide were continuously measured during the oxidation reactions of ozone/catalyst processes. In the case of $O_3$/high pH process, BPA was completely decomposed in 50 min of the oxidation reaction, but reaction intermediates formed by oxidation reaction were not oxidized sufficiently with 29% of the removal ratio for total organic carbon (TOC, selective oxidation reaction). In the case of $O_3/H_2O_2$ and $O_3$/PAC processes, BPA was completely decomposed in 40 min of the oxidation reaction, and reaction intermediates formed by the oxidation reaction were oxidized with 57% and 66% of removal ratios for TOC, respectively (non-selective oxidation reactions).

Formation of Hydrogen Peroxide by the Ozonation of Aqueous Humic Acid (수중 부식산의 오존처리시 생성되는 과산화수소의 농도 변화에 대한 연구)

  • Kim, Kei Woul;Rhee, Dong Seok
    • Analytical Science and Technology
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    • v.13 no.5
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    • pp.659-665
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    • 2000
  • The changes in $UV_{254}$ and concentrations of $H_2O_2$ formed by ozonation of aqueous humic acid in ozone/high pH, peroxone process and in the presence of radical scavenger, $HCO_3{^-}$ were investigated. This study confirmed that the formation of $H_2O_2$ by ozonation may undergo different reaction pathways compared to those of $UV_{254}$ reduction in the degradation of the humic acid. The concentration of $H_2O_2$ produced by ozonation was found to be increased with decreasing pH of the sample solution due to the higher stability of ozone molecules at acidic conditions. On the while, $UV_{254}$ reduction was found to be higher at alkaline conditions or larger amount of $H_2O_2$ additions as a radical promoter in which the producing of ${\cdot}OH$, ${\cdot}HO_2$ radicals can be more favorable. From the results, it has been suggested that the formation of $H_2O_2$ by ozonation depends mainly on the direct reactions of ozone with humic acid molecules, while $UV_{254}$ reduction is affected by both the indirect reactions of the radicals and direct reactions of ozone with humic acid.

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The Activity of Anti-oxidation of Cinnamomum loureiroi Extract (Cinnamomum loureiroi 추출물의 항산화 활성)

  • Lee, Hea-Jin;Lim, Hyun-Ji;Lim, Mi-Hye
    • Journal of the Korean Applied Science and Technology
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    • v.37 no.6
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    • pp.1583-1590
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    • 2020
  • In this study, activity of anti-oxidation of Cinnamomum loureiroi extract (CLE). In order to measure anti-oxidation effect of CLE, phenol content of CLE, radical scavenging activity of ABTS and DPPH, and decrease of ROS production. Before the experiment, against Raw 264.7 cell, a cytotoxicity was measured and the result showed no toxicity. CLE's total polyphenol amount was 397.7±8.3 mg/g and the total flavonoid amount was 101.899±0.885 mg/g. As a measurement result of ABTS radical scavenging ability and DPPH radical scavenging ability, radical scavenging ability increased depends on the concentration. CLE's effect on the ROS creation was checked and the result showed that CLE suppressed ROS creation by showing a meaningful decrease of ROS generation. From all of the results, CLE is know to have an antioxidant effect. These results will be provided as fundamental data for further development of the new material of functional cosmetics to the results above.

Decomposition of Chlorinated Methane by Thermal Plasma (열플라즈마에 의한 클로로메탄의 분해)

  • Kim, Zhen Shu;Park, Dong Wha
    • Applied Chemistry for Engineering
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    • v.18 no.2
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    • pp.136-141
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    • 2007
  • The decomposition of chlorinated methanes including $CCl_4$, $CCl_3H$, and $CCl_2H_2$ was carried out using a thermal plasma process and the characteristics of the process were investigated. The thermal equilibrium composition was analyzed with temperature by Fcatsage program. The decomposition rates at various process parameters including the concentration of reactants, flow rate of carrier gas, and quenching rate, were evaluated, where sufficiently high conversion over 92% was achieved. The generation of main products was strongly influenced by the reaction atmosphere; carbon, chlorine, and hydrogen chloride at neutral condition; carbon dioxide, chlorine, and hydrogen chloride at oxidative condition. The decomposition mechanism was speculated considering the results from Factsage and the identification of generated radicals and ionic species. The main decomposition pathways were found to be dissociative electron attachment and oxidative by radicals formed in a plasma state.

A Study on Effect of n-heptane Mixing on PAH and Soot Formation in Counterflow Ethylene Diffusion Flames (대향류 에틸렌 확산화염내 PAH 및 매연의 생성에 미치는 n-헵탄 혼합의 영향에 관한 연구)

  • Choi, Jae-Hyuk;Han, Won-Hui
    • Journal of the Korean Society of Marine Environment & Safety
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    • v.18 no.1
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    • pp.55-60
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    • 2012
  • In order to investigate the effect of n-heptane mixing on PAH and soot formation, small amount of n-heptane has been mixed in counterflow ethylene diffusion flame. Laser-induced incandescene and laser-induced fluorescene techniques were employed to measure soot volume fraction and polycyclic aromatic hydrocarbon(PAH) concentration, respectively. Results showed that the mixing of n-heptane in ethylene diffusion flame produces more PAHs and soot than those of pure ethylene flame. However, signals of LIF for 20% n-heptane mixture flame were lower than that of pure ethylene flame. It can be considered that the enhancement of PAH and soot formation by the n-heptane mixing of ethylene can be explained by methyl($CH_3$) radical in the low temperature region. And it can be found that reaction rate of H radical for 10% n-heptane plays a crucial role for benzene formation.

고급산화공정을 이용한 1,4-dioxane분해 연구

  • Park, Won-Seok;Park, Jin-Do;Lee, Hak-Seong
    • Proceedings of the Korean Environmental Sciences Society Conference
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    • 2006.05a
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    • pp.365-369
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    • 2006
  • [ $O_3$ ]/catalyst를 이용한 고급산화공정에서 pH변화에 따른 1,4-dioxane의 화학적 분해 특성을 알아보기 위해 이 실험을 수행하였다. 초기 pH를 6, 8, 10으로 조절하여 변화를 보면 오존의 pH 완충효과에 의해 시간이 지남에 따라 알칼리와 산의 경우 중성 쪽으로 중화되는 것을 확인하였다. 그리고 시간에 따른 1,4-dioxane의 제거율은 pH 10 > pH 8 > pH 6 의 순서로 나타는 것을 보였다. 이는 오존이 산성에서는 안정하지만 알칼리성에서는 불안정함으로 인해 자기분해를 일으켜 OH라디칼의 생성을 촉진시켜 제거율이 높게 나타났다. 초기 pH를 조절한 실험, 초기 pH를 일정하게 유지한 실험에서의 50분 후의 최종 제거율은 비슷하였지만, 초기 pH를 일정하게 유지한 실험에서 제거율이 꾸준히 감소하는 것을 알 수 있었다.

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Antioxidative and Free Radical Scavenging Activity of Water Extract From Dandelion (Taruaxacum officinale) (민들레 물추출물의 항산화 및 자유라디칼 소거활성)

  • 강미정;신승렬;김광수
    • Food Science and Preservation
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    • v.9 no.2
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    • pp.253-259
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    • 2002
  • The antioxidative and free radical scavenging activity of water extracts of dandelion were investigated. Antioxidative and radical scavenging activity were assessed by means of different tests; inhibition of peroxidation on linoleic acid model system, scavenging DPPH radical, scavenging of hydroxyl radical by chemiluminescence assay, scavenging of superoxide anion radical by EPR spectroscopy and scavenging of hydrogen peroxide. The leaf extract showed strong antioxidant activity in linoleic acid system. The antioxidant activity of water extracts of dandelion increased with increasing concentrations of extracts. The scavenging activity of the dandelion extracts, on inhibition of the DPPH radical, was related to the reaction time. Hydroxyl radical were generated by lenten reaction and dandelion extract was found to scavenge OH˙in a concentration-dependent manner. The water extract of leaf had effective scavenging activities on hydrogen peroxide and superoxide anion radical. From the these data, it is evident that water extract of dandelion leaf is an effective scavenger for OH˙, O$_2$¨, DPPH˙, hydrogen peroxide. And, the antioxidative effect observed is believed to be partly due to this radical scavenger activity.