• 한국환경과학회지
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• 제26권7호
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• pp.859-868
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• 2017

In this study, the reductive dechlorination of triclosan using zero-valent iron (ZVI, $Fe^0$) and modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium-coated iron (Pd/Fe)) was experimentally investigated, and the reduction characteristics were evaluated by analyzing the reaction kinetics. Triclosan could be reductively decomposed using zero-valent iron. The degradation rates of triclosan were about 50% and 67% when $Fe^0$ and Aw/Fe were used as reductants, respectively, after 8 h of reaction. For the Pd/Fe system, the degradation rate was about 57% after 1 h of reaction. Thus, Pd/Fe exhibited remarkable performance in the reductive degradation of triclosan. Several dechlorinated intermediates were predicted by GC-MS spectrum, and 2-phenoxyphenol was detected as the by-product of the decomposition reaction of triclosan, indicating that reductive dechlorination occurred continuously. As the reaction proceeded, the pH of the solution increased steadily; the pH increase for the Pd/Fe system was smaller than that for the $Fe^0$ and Aw/Fe system. Further, zero-order, first-order, and second-order kinetic models were used to analyze the reaction kinetics. The first-order kinetic model was found to be the best with good correlation for the $Fe^0$ and Aw/Fe system. However, for the Pd/Fe system, the experimental data were evaluated to be well fitted to the second-order kinetic model. The reaction rate constants (k) were in the order of Pd/Fe > Aw/Fe > $Fe^0$, with the rate constant of Pd/Fe being much higher than that of the other two reductants.

• Bulletin of the Korean Chemical Society
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• 제34권4호
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• pp.1145-1152
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• 2013

The rate constant of alkaline fading of methyl green ($ME^{2+}$) was measured in the presence of non ionic (TX-100), cationic (DTAB) and anionic (SDS) surfactants. $ME^{2+}$ hydrolyses and fades in neutral water and in this work we search the effects of surfactants on its fading rate. The rate of reaction showed remarkable dependence on the electrical charge of the used surfactants. It was observed that the reaction rate constant decreased in the presence of DTAB and SDS and increased in the presence of TX-100. Binding constants of $ME^{2+}$ to TX-100, DTAB and SDS and the related thermodynamic parameters were obtained by classical (or stoichiometric) model. The results show that binding of $ME^{2+}$ to TX-100 and DTAB are two-region and that of SDS is three-region. Also, the binding constants of $ME^{2+}$ to surfactant molecules in DTAB/TX-100 and SDS/TX-100 mixed solutions and their stoichiometric ratios were obtained.

• KSBB Journal
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• 제6권2호
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• pp.147-156
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• 1991

Diazotized chitin (CHITN) was synthesized reacting with NaN3 and HCl to alkaline hydrolyzed chitin for the support of immobilized enzyme. Immobilized $\beta$-glucosidase on diazotized chitin(CHITN-Gase) was produced reacting with glutaraldehyds as bifunctional reagent. CHITN-Gase activities were determined reacting with p-nitrophenol-$\beta$-D-glucopyranoside in plug flow reactor as a reference. Optimum temperature, optimum pH, reaction constant and deactivation rate were determined with variation of flow rate and H/D. The particle size of immobilized enzyme in the best was, 35 mesh (CHITN35-Gase). The optimum conditions of immobilized enzyme were $70^{\circ}C$ in temperature and 5.0 in pH. Diameter and flow rate of plug flow reactor in the best was 8.5mm in diameter and 0.8ml/min in flow rate. Reaction constant was mainly influenced by electrostatic force. The best glucose hydrolizing activities of CHITN3 5-Gase was 3.34$\times$10-5 M/1. while that of native-$\beta$-glucosidase was 2.44$\times$10-5 M/1.

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.343-347
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• 1990

A thermal decomposition of the tert-butoxy radical has been studied in the gas phase over the pressure range of 1-200 torr at $413_{\circ}K$ using di-tert-butyl peroxide + trimethylsilane mixtures. The relative rate constants were obtained by studying the competitive reactions between tert-butoxy radical decomposition 4(t-BuO·→ CH_3COCH_3 + CH_3·)$ and hydrogen abstraction reaction from trimethylsilane $(t-BuO·+ HSi(CH_3)_3 → t-BuOH + Si(CH_3)_3)·).$ The conventional RRKM calculations were carried out to compare the observed fall-off behavior of the decomposition rate constant $({\kappa}_d)$ with the theoretical predictions using reasonable values of input parameters. In all cases the calculated half-rate pressure $(P_{1/2})$ were significantly higher than those observed. The failure of RRKM to reproduce the fall-off behavior led us to suggest that not all of vibrational modes contribute to excitation (leading to decomposition) on the same time scale.

• 한국식품조리과학회지
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• 제11권4호
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• pp.396-400
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• 1995

The antioxidant effects in soybean oil was investigated by browning reaction mixtures formed by sugar and reaction temperatures above 110$^{\circ}C$. 0.1 M solution of xylose, glucose and sucrose were heated at 110, 120, 130, 140 and 150$^{\circ}C$ for 24 hrs respectively. A reaction rate constant(k), activation energy (Ea) and Q$\sub$10/ value were determined by color intensity that was measured absorbance at 490 nm in each temperature. Soybean oil containing the ethanol extracts taken from the browning reaction mixtures that were heated at 110, 130 and 150$^{\circ}C$ was stored in an incubator kept at 45.0${\pm}$1.0$^{\circ}C$ for 24 days. The results are as follows: 1. When 0.1 M solution of xylose, glucose and sucrose were heated at 110$^{\circ}C$ and 120$^{\circ}C$, the intensity of glucose browning mixtures was the highest, but heated at 150$^{\circ}C$, the color intensity increased in order of xylose > glucose > sucrose after 24 hrs. 2. The reaction rate constant (k) was increased rapidly above 140$^{\circ}C$ and appeared maximum at 150$^{\circ}C$, esp. xylose was the highest. The activation onergy (Ea) of xylose was the highest as 93.28 Joule/mole and the Q$\sub$10/ value of xylose was appeared 1.28. Q$\sub$10/ value was also the highest in xylose. 3. The browning reaction mixtures that were heated at 110$^{\circ}C$ appeared little antioxidant effects. But, in heated at 130$^{\circ}C$ and 150$^{\circ}C$, the antioxidant effects appeared in sucrose browning reaction mixtures. Therefore, in browning reaction mixtures that heated above 110$^{\circ}C$, only sucrose browning reaction mixtures appeared antioxidant effects and xylose, glucose appeared little antioxidant effects. On the contrary xylose and glucose increased peroxide values of soybean oil.

• Bulletin of the Korean Chemical Society
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• 제6권5호
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• pp.291-295
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• 1985

The efficiency of photosensitization of methyl linoleate (ML) oxidation by N-acetyl-L-trypophan(NAT) and 3-methyl indole(scatole) was markedly enhanced by increased concentration of ML in ethanol solution. The fluorescence intensities of sensitizers were observed to be quenched by ML, indicating that ML interacts with the indole excited singlet state. The inhibition of photosensitization by azide demonstrated a possible role of singlet oxygen in the photosensitization. The steady state kinetic treatment of azide inhibition of photosensitization was expected to show linear increase of reciprocal yield of ML oxidation product vs. reciprocal ML concentration at constant azide concentration, but the actual slope was nonlinear. This indicates another competing reaction involved in the photosensitization, As a possible competing reaction, electron transfer from ML to the excited sensitizer was proposed, since the measured fluorescence quenching rate constant closely resembled electron transfer rate constant determined from ML concentration dependence of oxidation product formation.

• 약학회지
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• 제19권2호
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• pp.101-110
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• 1975

p-Chloronitrobenzene(substrate) and p-nitrophenetole (product) were quantitatively analyzed to know the degree of extent of reaction in the process of time. The calibration curve was prepared by the internal satndard method in gaschromatography. 2,6-Dimethyl-naphthalene was used as internal standard. The rate constant(k), the reaction velocity in various concentrations of NaOH altered, and the formation of byproducts(azo-compound and p-nitrophenol) with the amounts of MnO$_{2}$ and NaOH altered, were studied. From the results of these of MnO$_{2}$ and NaOH altered, were studied. From the results of these experiments, this reaction was second order and the rate constant was k=10.3 $\times$ 10$^{-3}$ mole$^{-21$. When p-chloronitrobenaene 1 pt. NaOH 0.56pts. MnO$_{2}$ 0.5pts. and ethanol 25 pts-were reacted about 10 hours, p-nitrophenetole was nearly quantitatively obtained without byproducts.

• 대한화학회지
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• 제18권4호
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• pp.251-258
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• 1974

아세톤, 아세토니트릴, 메탄올, 에탄올 등의 용매에서 치환염 벤조일과 파라니트로아닐린과의 친핵치환반응에 대한 속도상수를 전기 전도도법으로 구하고 활성화 파라미터를 계산하였다. 결과로 반양성자 용매보다는 양성자성 용매에서 반응속도가 빨랐고 같은 성질의 용매에서는 유전상수가 큰 쪽이 반응이 더 빨랐으며 각 용매에 있어서의 Hammett도시는 정의 기울기를 가진 직선을 나타내었으며, 반응은 첨가-제거 메카니즘으로 일어났다.

• Bulletin of the Korean Chemical Society
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• 제8권5호
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• pp.408-414
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• 1987

The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.

• 대한금속재료학회지
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• 제48권5호
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• pp.424-429
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• 2010

In the RH process, it is possible to obtain quicker processing times by enhancing the decarburization rates at a low carbon range of steel melt through Ar gas injection into the vacuum vessel. The RH decarburization reaction was simulated through a dissolved oxygen removal reaction by injecting nitrogen into a 1/8 scale RH water model system. The gas nozzles for the N$_{2}$ injection into the vacuum vessel were located at the lowest level of the vessel's outer wall. The nitrogen bubbling in the vacuum vessel resulted in an increase in the reaction rate constant, which rose in accordance with an increase in the bubbling flow rate and number of nozzles used. However, there was almost no variation in the reaction rate constant, which depended on the horizontal positions of the bubbling nozzles.