• Bulletin of the Korean Chemical Society
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• 제4권3호
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• pp.120-123
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• 1983

The reaction of hexacyanoferrate (Ⅲ) with nitrotoluenes in aqueous acetic acid containing perchloric acid(1.0 M) at $50^{\circ}C$ gave the corresponding aldehyde as the major product. The order with respect to each of the reactants ― substrate, oxidant and acid ― was found to be unity. The Hammett plot yielded a ${\sigma}^+$ value of -1.30, and the kinetic isotope effect gave a $k_H/k_D$ value of 6.2. The pathway for the conversion of the nitrotoluenes to the products has been mechanistically visualized as proceeding through the benzylic radical intermediate, formed in the rate determining step of the reaction.

• Bulletin of the Korean Chemical Society
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• 제22권8호
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• pp.850-856
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• 2001

This study investigates the ozonation kinetics of 2-chlorophenol in wastewater under acidic condition. Intermediates and by-products generated during the process were rigorously identified and quantified. The major by-products are four carboxylic acids: tartaric acid, oxalic acid, maleic acid, and hydroxymalonic acid. The generation of these organic acids is in agreement with theoretical predictions. But hydroxylated compounds are more favorable to produce than their corresponding non-hydroxylated ones. Based on the information concerning the generation of organic acids and other aromatic intermediates, the complete reaction pathways toward mineralization can be proposed and mathematically modeled. The fitted second-order rate constants are in the same order of magnitude with the results from other studies. Using these oxidation pathways and the corresponding kinetic model, by-products generated in ozonation process can be predicted. This can help in optimizing the design and operation of any subsequent treatment processes.

• Bulletin of the Korean Chemical Society
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• 제14권6호
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• pp.666-668
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• 1993

A microbial BOD sensor using immobilized Hansenula anomala was prepared for the estimation of BOD. The sensor voltage was increased with time and increasing concentration of GGA when it was inserted in a sample solution. A linear relationship was obtained with a correlation coefficient, 0.998 between the concentration of standard GGA solutions and dV/dt by using the initial change of voltage, in which the response time was 20 min. It could be concluded that the oxidation of GGA conformed to a first-order kinetics. Therefore, the good linearities were also observed at various times. This sensor showed the best linearity at 30 min.

• 분석과학
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• 제18권2호
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• pp.120-129
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• 2005

VOC는 대기오염의 주원인으로서 인식되어왔다. 촉매산화는 저온에서 높은 효율을 나타내기 때문에 VOCs 제거를 위한 가장 중요한 처리기술중 하나이다. 이 연구에서는 $TiO_2$ 담체에 Pt, Ir 그리고 Pt-Ir을 담시지켜 촉매를 제조하였다. 금속 분산에 따르면 $H_2O-H_2$ 처리방법이 사용되었고, 반응물로서 Xylene,Toluene 그리고 MEK을 사용하였다. 단일 또는 두 가지 이상의 촉매들은 함침법에 의해 준비하였고, XRD, XPS, TEM 분석을 통하여 특성화하였다. 그 결과 Pt 촉매는 Ir 촉매에 비해 더 높은 전환율을 나타내었고, Pt-Ir 촉매는 가장 높은 전환율을 나타내었다. $H_2O-H_2$ 처리한 촉매들은 처리하지 않은 것보다 VOCs 전환율이 높았다. VOCs 산화에서, Pt-Ir 촉매는 다양한 활성점을 나타내었고 그것은 Pt의 metal 영역을 강화시켰다. 따라서 두 가지 금속으로 이루어진 촉매가 단일 금속으로 이루어진 촉매에 비해 VOCs 전환율이 더 높았다. $H_2O-H_2$ 처리가 Pt 입자의 분산에서 형태에 영향을 미쳤다. 동역학적으로 VOCs 산화는 1차 반응이다. $H_2O-H_2$ 처리한 촉매들의 활성화에너지가 처리하지 않은 것들보다 낮았다. 이 연구에서 Pt에 Ir을 소량첨가함으로써 VOCs 산화반응에 효과적이었다.

• Korean Chemical Engineering Research
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• 제47권3호
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• pp.292-302
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• 2009

페놀 습식산화에 미치는 반응온도($150{\sim}250^{\circ}C$), 산소분압(25.8~75.0 bar) 및 초기 pH(1.0~12.0)의 영향을 10 g/l의 페놀 초기농도를 사용하여 조사하였다. 습식산화속도는 화학적 산소요구량 COD를 이용하여 산출하였으며 반응 중간 생성물들을 고성능액체크로마토그래피를 사용하여 측정하였다. 습식산화 중 페놀 분해속도는 페놀에 대하여 1차 반응차수를 나타냈으며, COD 변화는 lumped 모델로 잘 묘사할 수 있었다. 금속이온($Cu^{2+}$, $Fe^{2+}$, $Zn^{2+}$, $Co^{2+}$, $Ce^{3+}$) 균일촉매의 습식산화 중 페놀 분해속도 및 COD 제거속도에 미치는 영향도 조사하였다. 페놀 분해속도 및 COD 제거속도는 $CuSO_4$를 사용한 촉매습식산화에서 가장 크게 나타났으며 촉매농도를 증가시킴에 따라 증가하였다. 습식산화 중 생성되는 개미산의 분해속도는 반응온도 및 $CuSO_4$ 농도를 증가시킴에 따라 증가하였다. 난분해성 생성물 초산의 최종농도는 반응온도를 증가시킴에 따라 증가하였으나 $CuSO_4$ 농도를 증가시킴에 따라 감소하였다.

• Environmental Engineering Research
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• 제13권3호
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• pp.131-135
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• 2008

In this study, Fe(VI) was employed as a multi-functional agent to treat the simulated industrial wastewater contaminated with Cu(II)-EDTA through oxidation of EDTA, decomplexation of Cu(II)-EDTA and subsequent removal of free copper through precipitation. The decomplexation of $10^{-4}\;M$ Cu(II)-EDTA species was performed as a function of pH at excess concentration of Fe(VI). It was noted that the acidic conditions favor the decomplexation of Cu(II)-EDTA as the decomplxation was almost 100% up to pH 6.5, while it was only 35% at pH 9.9. The enhanced degradation of Cu(II)-EDTA with decreasing the pH could be explained by the different speciation of Fe(VI). $HFeO_4^-$ and $H_2FeO_4$, which are relatively more reactive than the unprotonated species $FeO_4^{2-}$, are predominant species below neutral pH. It was noted that the decomplexation reaction is extremely fast and within 5 to10 min of contact, 100% of Cu(II)-EDTA was decomplexed at pH 4.0. However, at higher pH (i.e., pH 10.0) the decomplexation process was relatively slow and it was observed that even after 180 min of contact, maximum ca 37% of Cu(II)-EDTA was decomplexed. In order to discuss the kinetics of the decomplexation of Cu(II)-EDTA, the data was slightly fitted better for the second order rate reaction than the first order rate reaction in the excess of Fe(VI) concentration. On the other hand, the removal efficiency of free Cu(II) ions was also obtained at pH 4.0 and 10.0. It was probably removed through adsorption/coagulation with the reduced iron i.e., Fe(III). The removal of total Cu(II) was rapid at pH 4.0 whereas, it was slow at pH 10.0. Although the decomplexation was 100% at lower pH, the removal of free Cu(II) was relatively slow. This result may be explicable due to the reason that at lower pH values the adsorption/coagulation capacity of Fe(III) is greatly retarded. On the other hand, at higher pH values the decomplexation of Cu(II)-EDTA was partial, hence, slower Cu(II) removal was occurred.

• 한국자기학회지
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• 제22권3호
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• pp.85-90
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• 2012

$Nd_2Fe_{14}B$ 화합물 결정의 산화 및 미세 $Nd_2Fe_{14}B$ 결정입자의 보자력에 미치는 산화의 영향을 조사하였다. $Nd_2Fe_{14}B$ 화합물 결정의 산화속도는 $Nd_{15}Fe_{77}B_8$ 합금 잉곳 중의 과잉 성장시킨 $Nd_2Fe_{14}B$ 결정립을 이용하여 조사하였다. $Nd_2Fe_{14}B$ 화합물 결정의 산화는 이 결정상의 ${\alpha}$-Fe, $Fe_3B$, 및 Nd 산화물 복합상으로의 분해에 의해 일어 났다. $Nd_2Fe_{14}B$ 화합물 결정의 산화속도는 결정 방위와는 무관하였다. 산화반응 속도 식은 단순한 직선관계로 나타났다. $Nd_2Fe_{14}B$ 화합물 결정의 산화에 대한 활성화에너지는 약 26.8 kJ/mol로 계산되었다. HDDR 처리한 $Nd_{15}Fe_{77}B_8$ 합금을 볼밀링하여 임계단자구 크기에 유사한 미세한 $Nd_2Fe_{14}B$ 결정입자를 제조하고, 이 입자들을 이용하여 보자력에 미치는 산화의 영향을 조사하였다. 임계단자구 크기에 유사한 미세한 $Nd_2Fe_{14}B$ 결정입자(${\fallingdotseq}0.3\;{\mu}m$)는 9 kOe 이상의 높은 보자력을 가졌다. 그러나, 이 보자력은 공기 중에서 온도 상승에 따라 급격하게 저하하였다($200^{\circ}C$에서 2 kOe 이하). 이러한 급격한 보자력의 감소는 산화에 의해 미세 입자의 표면에 형성된 연자성 ${\alpha}$-Fe 및 $Fe_3B$ 상 때문으로 판단되었다.

• 한국지하수토양환경학회지:지하수토양환경
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• 제20권6호
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• pp.117-126
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• 2015

Reductive degradation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by nanoscale zero-valent iron (nZVI) was investigated to evaluate the feasibility of using it for in-situ groundwater remediation. Batch experiments were conducted to quantify the kinetics and efficiency of RDX removal by nZVI, and to determine the effects of pH, dissolved oxygen (DO), and ionic strength on this process. Experimental results showed that the reduction of RDX by nZVI followed pseudo-first order kinetics with the observed rate constant (k_obs) in the range of 0.0056-0.0192 min⁻¹. Column tests were conducted to quantify the removal of RDX by nZVI under real groundwater conditions and evaluate the potential efficacy of nZVI for this purpose in real conditions. In column experiment, RDX removal capacity of nZVI was determined to be 82,500 mg/kg nZVI. pH, oxidation-reduction potential (ORP), and DO concentration varied significantly during the column experiments; the occurrence of these changes suggests that monitoring these quantities may be useful in evaluation of the reactivity of nZVI, because the most critical mechanisms for RDX removal are based on the chemical reduction reactions. These results revealed that nZVI can significantly degrade RDX and that use of nZVI could be an effective method for in-situ remediation of RDX-contaminated groundwater.

• Environmental Engineering Research
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• 제20권1호
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• pp.89-97
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• 2015

Remediation of wastewater contaminated with metal(II)-complexed species (Cu(II)-NTA (NTA: nitrilotriacetic acid), Cu(II)-EDTA (EDTA: ethylenediamine tetraacetic acid) and Cd(II)-EDTA is attempted using the potential applicability of ferrate(VI). Kinetics of pollutant degradation is obtained with the removal of ferrate(VI) studied at wide range of pH (8.0-10.0) and the concentration of metal(II)-complexed species (0.3 to 15.0 mmol/L) employing a constant dose of ferrate(VI) i.e., 1.0 mmol/L. Pseudo-first-order and pseudo-second-order rate constants were obtained in the reduction of ferrate(VI) which was then employed to obtain the overall rate constants of the pollutant degradation. The mineralization of NTA and EDTA was obtained with the change in TOC (total organic carbon) values collected by the ferrate(VI) treated pollutant samples. Decrease in pH and molar pollutant concentrations was greatly favored the percent mineralization of NTA or EDTA by the ferrate(VI) treatment. The treated pollutant samples were filtered and subjected for AAS (atomic absorption spectrophotometric) analysis to assess the simultaneous removal of copper and cadmium from aqueous solutions at the studied pH as well at the elevated pH 12.0. Results show that an enhanced removal of cadmium or copper was achieved at pH 12.0. Overall, ferrate(VI) possesses multifunctional application in wastewater treatment as it oxidizes the degradable impurities and removes metallic impurities by coagulation process.

• Toxicological Research
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• 제15권1호
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• pp.95-101
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• 1999

Cytochrome P450 (CYP) 3A4 metabolizes aflatoxin B1 (AFB1) to AFB1-exo-8,9-epoxide (8,9-epoxidation) and aflatoxin Q1 (AFQ1; 3$\alpha$-hydroxylation) simultaneously. We investigated whether each metabolite was formed via its own binding site of CAP3A4 active site. Kinetics of the formation of the two metabolites were sigmoidal and consistent with the kinetics of substrate activation. The HIll model predicted that two substrate binding wites are involved in the oxidationof AFB1 by CYP3A4. Dehydronifedipine, a metabolite of nifedipine generated by CYP3A4, inhibited the formation of AFQ1 without any inhibition in the formation of AFB1-exo-8,9-epoxidation. Dehydronifedipine was found to act as a reversible competitive inhibitor against 3$\alpha$-hydroxylation of AFB1. Vmax and S0.5 of the 8,9-epoxidation were not changed in the presence of 0, 50, or 100 $\mu\textrm{M}$ dehydronifedipine. S0.5 of 3$\alpha$-hydroxylation was increased from 58$\pm$4 $\mu\textrm{M}$ to 111$\pm$8 $\mu\textrm{M}$ in the presence of 100 $\mu\textrm{M}$ nifedipine whereas Vmax was not changed. These results suggest that there exist two independent binding sites in the active site of CAP3A4 . One binding site is responsible for AFB1-exo-8,9-epoxidation and the other is involved in 3$\alpha$-hydroxylation of AFB1. Dehydronifedipine might selectively bind to the site which is responsible for the formation of AFQ1 in the active site of CYP3A4.