• 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.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.705-709
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• 1994

The kinetics of the oxidation reaction of malonic acid by ceric ion in 1 M sulfuric acid solution at $20^{\circ}C$ have been investigated by spectrophotometric method. The reaction rate at a large excess of malonic acid was found to be pseudo-first order. The observed pseudo-first order rate constants, $k_{obs}$, are dependent on the concentration of malonic acid, [MA], of which relationship has been found to be $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$). A mechanism for the reaction has been suggested on the basis of the above rate equation. The rate determining step may be the electron transfer reaction between enolate type malonate anion, which is formed by the acid dissociation reaction of malonic acid, and Ce(IV). The rate depression in the range of high concentration of MA has been explained by the formation of 1 : 2 chelate between Ce(IV) and malonate. According to the mechanism, the pH dependence of the rate, which was studied by Sengupta et al., has also been explained.

• Applied Chemistry for Engineering
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• v.25 no.6
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• pp.648-653
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• 2014

Cr(VI)-heterocyclic complex (2,4'-bipyridinium chlorochromate) was synthesized by the reaction between heterocyclic compound(2,4'-bipyridine) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium chlorochromate in various solvents showed that the reactivity increased with the increase of the dielectric constant (${\varepsilon}$), in the order : N,N-dimet-hylformamide (DMF) > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as hydrochloric acid (HCl solution), 2,4'-bipyridinium chlorochromate oxidized benzyl alcohol (H) and its derivatives (p-$CH_3$, m-Br, m-$NO_2$). Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.67 (303 K). The observed experimental data have been rationalize the proton transfer occurred followed the formation of a chromate ester in the rate-determining step.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.309-314
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• 1989

A kinetic study was carried out for the redox reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in acidic solution by spectrophotometric methods. This redox reaction system have been found to show a third order for overall reaction as the respective first order with respect to reactant cis-$[Co(en)_2(N_3)_2]^+$, Fe(II), and $H^+$ catalyst. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were obtained as 14.2Kcal/mol and -16.7 e.u., respectively. On the basis of the kinetic data, we suggest that the redox reaction system proceeds via inner sphere mechanism. The rate equation derived from the proposed mechanism is in agreement with the observed rate equation.

• Journal of the Korean Chemical Society
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• v.47 no.6
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• pp.585-590
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• 2003

Cobalt oxygen carrier complex N,N'-ethylenebis(3-methoxysalycylideneiminato)cobalt(II), Co(3MeOsalen) was prepared at $25{\circ}C$. UV and visible absorption spectra of the complex and hydrazobenzene were studied in non-aqueous solvent methanol in the range of wavelength 200-600 nm. The oxidation of hydrazobenzene by oxygen in non-aqueous solvent is catalysed by Co(3MeOsalen). In the presence of triphenylphosphine($PPh_3$), the rate decreases in methanol. This is presumably attributable to the coordination of $PPh_3$ to the Co(3MeOsalen), resulting in the catallytically inactive compound. The initial rates of the oxidation of hydrazobenzene with the ligand triphenylphosphine were measured by the theoretical values of the rates, Rate=$k_1+k_2K_1[P]/1+K_1[P]+K_1K_2[P]^2$. This fact would be a poorer σ-donor ligand than methanol.

• Journal of Korean Society of Environmental Engineers
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• v.32 no.2
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• pp.219-226
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• 2010

In order to evaluate a removal characteristic of chloramphenicol, salicylic acid and ketoprofen according to dose of oxidants, $Cl_2$, $O_3$ and $O_3/H_2O_2$ are used as oxidants in this study. In case of that $Cl_2$ is used for oxidizing harmaceuticals, chloramphenicol, salicylic acid and ketoprofen is not removed entirely at $Cl_2$ dose rang of 0.5~5.0 mg/L for 60 min. However, removal tendency of salicylic acid is so obviously at $Cl_2$ dose higher than 1.0 mg/L. In addition, as $Cl_2$ dose and contact time increase, the removal rate of salicylic acid is enhanced. When $O_3$ is used as oxidant, chloramphenicol and ketoprofen is not eliminated at $O_3$ dose range of 0.2~2.0 mg/L. On the contrary, 30~70% of salicylic acid is removed at $O_3$ dose of 1.0~5.0 mg/L. Only 30% removal of salicylic acid is achieved at contact time of 5 min, however, the removal rate is enhanced remarkably at contact time over 10 min. In experiments using $O_3/H_2O_2$ as an oxidant, we can find that $O_3/H_2O_2$ is much more effective than $O_3$ only for removal of 3 pharmaceuticals, and the efficiency is raised according to increase of $H_2O_2$ dose. On reaction rate constant and half-life of 3 pharmaceuticals depending on $Cl_2$, $O_3$ and $O_3/H_2O_2$ dose, experiments using $O_3/H_2O_2$ show that oxidation of pharmaceuticals is less effective as the $H_2O_2/O_3$ ratio increases to above pproximately 1.0 related to reaction rate constant. An oxidation of salicylic acid by $Cl_2$ and $O_3$ particularly has a comparatively high reaction rate constant comparing $O_3/H_2O_2$, and thus salicylic acid is easily eliminated in oxidation processes.

• Prospectives of Industrial Chemistry
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• v.19 no.5
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• pp.1-11
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• 2016

우리나라는 1970년대를 기점으로 하여 급격한 경제성장과 산업기술의 발전이 이루어졌다. 경제성장과 함께 주택의 보급 또한 급격하게 증가하게 되었고, 주택의 보급을 위한 건축자재 및 생활용품의 개발이 급속도로 이루어졌다. 이에 따라 실내에서 사용하는 기구 및 건축재료가 매우 다양해졌으며, 이로 인한 새로운 오염물질의 배출이 급격히 증가하게 되었다. 최근 새로운 기술로 소개되고 있는 촉매 산화법의 경우 제거하려는 대상 실내대기오염물질을 촉매를 이용하여 CO₂나 H₂O 등으로 산화시켜 제거하는 방법이며, 최근 많은 연구가 활발하게 수행되고 있다. 촉매를 이용하는 촉매 산화법은 광촉매 산화법과, 촉매의 성능만을 이용하여 대상물질을 산화하는 촉매산화법으로 구분된다. 광촉매 산화법은 특정 파장에서 반응하는 촉매에 자외선을 조사하여 실내오염물질을 산화제거하는 방법으로, 산화성능이 우수하여 여러 가지 실내오염가스에 적용되고 있으나, 별도의 광원이 필요하며, 포름알데히드 산화 시 CO₂와 H₂O 이외에도 dichloroacetyl chloride (C₂HCl₃O), trichloroethylene (C₂HCl₃), phosgene (COCl₂) 등과 같은 부수적인 2차 유해물질이 발생함에 따라 이를 처리하기 위한 대책이 수반되어야 한다. 반면, 촉매 산화법의 경우 별도의 광원이나 에너지원 없이, 촉매를 이용하여 대기오염물질을 인체에 무해한 물질로 완전 산화시키는 방법으로써, 최근 많은 연구가 수행되어 상온에서 구동 가능한 촉매가 개발되었고, 이의 연구가 활발히 이루어지고 있다. 이에 상온산화촉매기술의 연구동향 및 사례를 확인하고, 향후 상온산화촉매기술이 나아가야 할 방향을 제시하고자 한다. 본 연구는 환경부 환경산업선진화기술개발사업의 지원을 받아 수행되었습니다(2016000140004).

• Journal of Korean Society of Environmental Engineers
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• v.33 no.6
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• pp.396-404
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• 2011

An investigation on the removals of PAH-quinone compounds, which are commonly produced from the biological and/or chemical treatments of PAH-contaminated soils, from the aqueous phase via birnessite (${\delta}-MnO_2$)-mediated oxidative transformation is described. It was demonstrated that acenaphthenequinone (APQ), p-PAH quinone can be removed via birnessite-mediated oxidative-coupling reactions, and anthraquinone (AQ) and 1,4-naphthoquinone (1,4-NPQ), o-PAH quinones were efficiently removed by birnessite-mediated cross-coupling reactions in the presence of catechol (CAT) as a reactive mediator. The removals of PAH-quinone compounds followed pseudo-first-order reactions, and the rate constant (k, $hr^{-1}$) for the removals of 1,4-NPQ under the experiment conditions (1,4-NPQ = 10 mg/L, CAT = 50 mg/L, ${\delta}-MnO_2$ = 1.0 g/L, pH 5, Reaction time = 6~96 hr) was 0.0426, which was about 4 times lower than that of APQ (0.173). With the observed pseudo-first order rate constants with respect to birnessite loadings under the same experimental conditions, the surface-normalized specific rate constant, $K_{surf}$, for 1,4-NPQ was determined to be $8.5{\times}10^{-4}L/m^2{\cdot}hr$. The analysis of the kinetic data with respect to birnessite loading indicated that the cross-coupling reactions of 1,4-NPQ consist of two different reaction steps over time and the results have also been discussed in terms of the reaction mechanisms.

• Journal of Korean Society of Environmental Engineers
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• v.37 no.2
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• pp.73-80
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• 2015

An investigation on the removals of tetracycline (TTC), which is a family of antibiotics widely founded in the environment, from the aqueous solution by birnessite(${\delta}-MnO_2$)-mediated oxidative transformation was described. This study also examined the potential effect of the naturally occurring substances, humic acid (HA) on the oxidative transformation. The experiment was carried out in various conditions (reaction time, Mn oxide loadings, pH) and in the presence of HA as a batch test. The removals of TTC followed pseudo-first order reactions, and rate constants (k, $hr^{-1}$) for the removals of TTC were constantly increased with decreasing pH from 0.98 (pH 9) to 2.97 (pH 3). The rate constants also increased about 1.3 times when the birnessite loading increased from 1 to 2 g/L. Presence of HA (5 mg-C/L, at $pH{\geq}6$) caused some enhancement in the removals of TTC as compared to the control, and also showed the removal efficiencies of TTC in the birnessite mediated systems (TTC=0.25 mM, ${\delta}-MnO_2=2.0g/L$, pH 6) increased with increasing HA concentrations (1~10 mg-C/L). The results obtained from the oxidative transformation of TTC and the effect of HA were discussed in terms of reaction characteristics and mechanism.

• Journal of the Korean Electrochemical Society
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• v.4 no.3
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• pp.104-108
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• 2001

Naphthalene derived mesophase pitch WP) was spun into short fibers by using melt-blown technology. The pitch fibers oxidative stabilization were carried out heating rates of $2^{\circ}C/min,\;5^{\circ}C/min\;and\; 10^{\circ}/min$. The heating rate was a key factor to maximate the capacity of the Li-ion secondary battery through controlling the morphology of the graphitized fiber. The diameters of the melt-blown fibers prepared were in the range of $4{\mu}m\~16{\mu}m$ with functions of air jet speed, air temperature and the temperature of the nozzle. The graphitized fibers of $10{\mu}m$ diameters showed various morphological structure with heating rate of the stabilization. Radial, radial-random and skin-core cross-sectional structure of the fibers were observed at the respective heating rate of $2^{\circ}C/min\;5^{\circ}C/min\;and\;10^{\circ}C/min$. Most crystalline structure of graphite was obtained from the fiber stabilized at heating rate of $10^{\circ}C/min$ exhibiting the best anode performance with 400 mAh/g of capacitance and $96.8\%$ of charge/discharge efficiency.