• Journal of Soil and Groundwater Environment
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• v.6 no.1
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• pp.3-12
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• 2001

During ozonation process, the hydroxyl radical generation rates were measured under different experimental conditions (ozone feed rate, nitrobenzene concentration, hydroxyl radical scavenger, pH, HO$_2$O$_2$/O$_3$ etc.) Nitrobenzene could be decomposed by hydroxyl radical rather than ozone only and nitrobenzene decomposition rate was expressed with functions of ozone and nitrobenzene concentration. The rate was decreased as the hydroxyl radical scavenger concentration was increased, and all results were followed pseudo first-order reaction. Using a competitive method, hydroxyl radical generation rate was measured with probe compound and scavenger. It was proportional to ozone concentration, and 0.24mo1 of hydroxyl radical was produced with 1mol of ozone. Under different pH conditions, hydroxyl radical generation rates were measured (pH 10.2 (0.91Ms$^{-1}$ ) > pH 7.3 (0.72Ms$^{-1}$ ) > pH 5.6 (0.67Ms$^{-1}$ ) > pH 3.4 (0.63Ms$^{-1}$ )) showing higher generation rate at high pH values. Addition of hydrogen peroxide promoted the generation rate of hydroxyl radical. Considering the results of pH experiments and addition of hydrogen peroxide experiments, the hydroxyl radical generation rate was 1.6 times higher in hydrogen peroxide solution than in high pH solution, indicating addition of hydrogen peroxide is better promoter to produce the hydroxyl radical in ozonation. These results could be applied to AOPs to remediate the contaminated wastewater and groundwater.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.523-526
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• 2013

In order to purify the waste water containing natural fatty oil, hydroxy radical and/or ozone are used to remove the fatty oil dispersed in the waste water. The fatty oil is decomposed by oxidation reaction through hydroxy radical and ozone, and eliminated as a function of first order reaction. It is clearly confirmed that the fatty oil in waste water can be effectively removed much more in the use of both hydroxy radical and ozone than only hydroxy radical as an oxydant. In addition, the decomposition chemical reaction mechanism of the fatty oil by hydroxy radical and ozone is proposed.

• Journal of the Korean GEO-environmental Society
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• v.13 no.10
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• pp.69-76
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• 2012

This study focuses both on the quantitative measurement of hydroxyl radicals formed by an electron beam (E-beam) process and on the decomposition of pentachlorophenol(PCP) in the presence of $H_2O_2$ and $Fe^{3+}-EDTA$ as additives. To attain this objective, the quantitative measurement of hydroxyl radical was performed with the hydroylation of benzoic acid (BA), producing hydroxybenzoic acid (OHBA). As a result, the concentrations of hydroxyl radical measured were lower than those of hydroxyl radical predicted. Probably, it indicates that the reactive species generated during E-beam irradiation are able to scavenge the hydroxyl radicals. In particular, the degradation of PCP was promoted by the addition of $H_2O_2$ (< 1mM). On the other hand, its degradation as well as the generation of chloride ions as a by-product was inhibited by the addition of $H_2O_2$ (> 1mM), and thus carbon yield(%) of oxalic acid as a by-product was increased. During E-beam irradiation the addition of $Fe^{3+}-EDTA$ effectively decomposed the PCP, thus increasing the G-values. Considering the formation of OHBA and the decomposition of PCP, these results suggest that the addition of $Fe^{3+}-EDTA$ in the E-beam process can produce the further hydroxyl radicals and enhance the efficiency of PCP decomposition at low dose.

• Journal of Korean Society of Environmental Engineers
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• v.36 no.8
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• pp.534-541
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• 2014

This study investigated a method to determine an efficient operating condition for the $UV/H_2O_2$ process. The OH radical scavenging factor is the most important factor to predict the removal efficiency of the target compound and determine the operating condition of the $UV/H_2O_2$ process. To rapidly and simply measure the scavenging factor, Rhodamine B (RhB) was selected as a probe compound. Its reliability was verified by comparing it with a typical probe compound (para-chlorobenzoic acid, pCBA); the difference between RhB and pCBA was only 1.1%. In a prediction test for the removal of Ibuprofen, the RhB method also shows a high reliability with an error rate of about 5% between the experimental result and the model prediction using the measured scavenging factor. In the monitoring result, the scavenging factor in the influent water of the $UV/H_2O_2$ pilot plant was changed up to 200% for about 8 months, suggesting that the required UV dose could be increased about 1.7 times to achieve 90% caffeine removal. These results show the importance of the scavenging factor measurement in the $UV/H_2O_2$ process, and the operating condition could simply be determined from the scavenging factor, absorbance, and information pertaining to the target compound.

• Journal of the Mineralogical Society of Korea
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• v.28 no.3
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• pp.245-253
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• 2015

The performance of $TiO_2$ photo-catalytic oxidation process is significantly dependent on the amount of hydroxyl radicals produced during the process, and it is an essential prerequisite to quantify its production. However, precise and accurate methods for quantification of hydroxyl radicals have not been developed so far. For this reason, this study was initiated to compare existing methods for analysis of hydroxyl radicals produced by $TiO_2$ photo-catalytic oxidation and to propose a new method to overcome the limitation of established methods. To simulate $TiO_2$ photo-catalytic oxidation process, Degussa P25 which has been widely used as a standard $TiO_2$ photo-catalyst was used with the dose of 0.05 g/L. The light source of process was UVC mercury low-pressure lamp (11 W, $2,975mW/cm^2$). The results indicate that both potassium iodide (KI)/UV-vis spectrometer and terephthalic acid (TPA)/fluorescence spectrometer methods could be applied to qualitatively measure hydroxyl radicals via detection of triiodide ion ($I_3{^-}$) and 2-hydroxyterephthalic acid which are produced by reactions of iodine ion ($I^-$) and TPA with hydroxyl radicals, respectively. However, it was possible to quantitatively measure hydroxyl radicals using TPA method coupled with high-performance liquid chromatograph (HPLC). The analytical results using TPA/HPLC method show that hydroxyl radical of 0.013 M was produced after 8 hours operation of photo-catalytic oxidation under specific experimental conditions of this study. The proposed method is expected to contribute to precise the evaluation of the performance of photo-catalytic oxidation process.

• Journal of Forest and Environmental Science
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• v.13 no.1
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• pp.153-165
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• 1997

Hydroxyl radicals were detected and their qualitative yields were estimated by using chemiluminescence method and $\gamma$-irradiation technique in oxygen or chlorine dioxide radicals bleaching conditions. The correlation of hydroxyl radical formation and lignin model(Apocynol) or carbohydrate model($\alpha$-D-glucopyranose and methyl-$\beta$-D-glucopyranoside) degradation was studied in the presence of metal ion or without metal ion. The results showed that the presence of metal ions efficiently affected the formation of hydroxyl radicals in oxygen bleaching process, in the order of $Cu^{2+}$ > $Mn^{2+}$ > $Mg^{2+}$ > $Fe^{2+}$, and these metal gave also rise to the degradation of carbohydrate. But it was found that the addition of $100{\mu}m\;Mg^{2+}$ gave an efficient protection against carbohydrate degradation and suppressed the hydroxyl radical formation under oxygen bleaching conditions. And the presence of $Cu^{2+}$ had a detrimental effect on the stability of carbohydrates, whereas the addition of $3{\mu}m\;Mn^{2+}$ surprisingly had a small protective effect on methyl--$\beta$-D-glucopyranoside. In the $ClO_2$ radical bleaching conditions the hydroxyl radical expected to generate from water or substrates was not detected in the presence of metals.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 2016.10a
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• pp.132-132
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• 2016

• Ecology and Resilient Infrastructure
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• v.2 no.4
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• pp.330-336
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• 2015

Photocatalytic degradation of bisphenol A (BPA) in aqueous solution was investigated using $TiO_2$ nanoparticles (Degussa P25) in this study. After a 3 hr photocatalytic reaction (${\lambda}=365nm$ and $I=3mW\;cm^{-2}$, $[TiO_2]=2.0g\;L^{-1}$), 98% of BPA ($1.0{\times}10^{-5}M$) was degraded and 89% of the total organic carbon was removed. In addition, BPA degradation by photolytic, hydrolytic and adsorption reactions was found to be 2%, 5% and 13%, respectively. The reaction rate of BPA degradation by photocatalysis decreased with increasing concentration of methanol that is used as a hydroxyl radical scavenger. This indicates that the reaction between BPA and hydroxyl radical was the key mechanism of BPA degradation. The pseudo-first-order reaction rate constant for this reaction was determined to be $7.94{\times}10^{-4}min^{-1}$, and the time for 90% BPA removal was found to be 25 min. In addition, acute toxicity testing using Daphnia magna neonates (< 24 h old) was carried out to evaluate the reduction of BPA toxicity. Acute toxicity (48 hr) to D. magna was decreased from 2.93 TU (toxic unit) to non-toxic after photocatalytic degradation of BPA for 3 hr. This suggests that there was no formation of toxic degradation products from BPA photocatalysis.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.168-168
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• 2016

BDD(Boron Doped Diamond) 전극은 전위창이 넓고, 다른 불용성 전극에 비해 산소발생과전압이 높아 물을 전기화학적인 방법으로 처리하는 영역에 있어 매우 효과적일 뿐만 아니라, 전통적인 불용성 전극에 비해 전극 표면에서 수산화 라디칼(-OH)과 오존(O3)의 발생량이 월등히 높아 수처리용 전극으로서의 유용성이 매우 높다. 따라서 BDD 전극을 수처리용 전극에 사용하는 경우 수산화 라디칼(-OH)과 오존(O3), 과산화수소(H2O2) 등과 같은 산화제의 생성은 물론이고, 염소(Cl2)가 포함되어 있는 전해액에서는 차아염소산(HOCl)이나 차아염소산이온(OCl-)과 같은 강력한 산화제가 발생되어 전기화학적 폐수처리, 전기화학적 정수처리, 선박평형수 처리 등의 분야에 널리 활용될 수 있다. 본 연구에서는 상온 및 상압에서 운전이 가능하고 난분해성 오염물질 제거 효과가 뛰어난 전기화학적 고도산화공정(Electrochemical Advanced Oxidation Process, EAOP)에 적합한 대면적의 BDD 전극을 개발하고 자 하였다. 이러한 BDD 전극의 성막 방법으로는 필라멘트 가열 CVD, 마이크로파 플라즈마 CVD, DC 플라즈마 CVD 등이 널리 알려져 있는데 최근에는 설비의 투자비가 비교적 저렴하고, 대면적의 기판처리가 용의한 필라멘트 가열 화학기상증착법(Hot Filament Chemical Vapor Deposition, HFCVD)이 상업적으로 각광을 받고 있다. 따라서 본 연구에서는 HFCVD 방법을 이용하여 반응 가스의 투입비율, BDD 박막의 두께, 기판의 재질 등에 따른 여러 가지 성막 조건들을 검토하여 $100{\times}100mm$ 이상의 대면적 BDD 전극을 개발하였다. Fig. 1은 본 연구를 통하여 얻어진 BDD 전극의 표면 및 단면 SEM이다.

• 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).