• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2017.05a
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• pp.126-126
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• 2017

Using first principles calculations we unveil fundamental mechanism of hydrolysis reactions of two hazardous chemicals $PCl_3$ and $POCl_3$ with molecular water clusters nearby. It is found that the water molecules play a key role as a catalyst significantly lowing the activation barriers by transferring its protons to the reaction intermediates. Interestingly, torsional angles of molecular complexes at transition states are identified as a vital descriptor on the reaction rate. Analysis of charge distribution over the complexes further reinforces the finding with atomic level correlation between the torsional angle and variation of the orbital hybridization state of P in the complex. Electronic charge separation (or polarization) enhances thermodynamic stability of the activated complex at transition state and reduces the activation energy through hydrogen bonding network with water molecules nearby. Calculated potential energy surfaces (PES) for the hydrolysis reactions of $PCl_3$ and $POCl_3$ depict their two contrastingly different profiles of double- and triple-deep wells, respectively. It is ascribed to the unique double-bonding O=P in the $POCl_3$. Our results on the activation free energy show well agreements with previous experimental data within $7kcalmol^{-1}$ deviation.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.149-149
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• 2009

Generally, Nafion ionomer is used in the polymer electrolyte fuel cell (PEFC) electrodes to achieve high power density. At the high temperature operation of PEFC, however, ionic conductivity of Nafion remarkably decreased due to the evaporation of water in Nafion polymer. Recently, many researchers have focused on using the Ionic Liquids(ILs) instead of water in Nafion polymer. ILs have intrinsic properties such as good electrochemical stability, high ionic conductivity, and non-flammability. Especially, ILs play a crucial role in proton conduction by the Grottuss mechanism and act as water in water-free Nafion polymer. However, it was found that the ILs was leached out of the polymer matrix easily. In this study, we prepared membrane electrode assemblies with various contents of ILs. The effect of ILs in the electrode of each designed was investigated by a cyclic voltammetry measurement and the cell performance obtained through a single cell test using H2/Air gases. Electrodes with different contents of ILs in catalyst layer were examined at high temperature and low humidified condition.

• Transactions of the Korean hydrogen and new energy society
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• v.13 no.3
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• pp.214-223
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• 2002

Kinetic and effectiveness factors for methanol steam reforming using commercial copper-containing catalysts in a plug flow reactor were investigated over the temperature ranges of $180-250^{\circ}C$ at atmospheric pressure. The selectivity of $CO_2$/$H_2$ was almost 100%, and CO products were not observed under reaction conditions employed in this work. It was indicated that $CO_2$ was directly produced and CO was formed via the reverse water gas shift reaction after methanol steam reforming. The intrinsic kinetics for such reactions were well described by the Langmuir-Hinshelwood model based on the dual-site mechanism. The six parameters in this model, including the activation energy of 103kJ/mol, were estimated from diffusion-free data. The significant effect of internal diffusion was observed for temperature higher than $230^{\circ}C$ or particle sizes larger than 0.36mm. In the diflusion-limited case, this model combined with internal effectiveness factors was also found to be good agreement with experimental data.

• Macromolecular Research
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• v.17 no.8
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• pp.557-562
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• 2009

The free radical polymerization of styrene was initiated with azobis(isobutyronitrile) in the presence of benzene sulfonyl chloride. Analysis of the terminal structures of the obtained polystyrene with $^1H$ NMR spectroscopy revealed the presence of a phenyl sulfonyl group at the ${\alpha}$-end and a chlorine atom at the ${\omega}$-end of each polystyrene chain. The terminal chlorine atom in the polystyrene chains was further confirmed through atom transfer radical polymerization (ATRP) of styrene and methyl acrylate using the obtained polystyrenes as macroinitiators and CuCl/2,2'-bipyridine as the catalyst system. GPC traces of the products obtained in ATRP at different reaction times were clearly shifted to higher molecular weight direction, indicating that nearly all the macroinitiator chains initiated ATRP of the second monomers. In addition, the number-average molecular weights of the polystyrenes increased directly proportional to the monomer conversions, and agreed well with the theoretical ones.

• Bulletin of the Korean Chemical Society
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• v.8 no.2
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• pp.102-105
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• 1987

2-Methoxy-6-methyl-3,4-dihydro-2H-pyran ($1_a$), 2-ethoxy-3,6-dimethyl-3,4-dihydro-2H-pyran ($1_b$), and 2-ethoxy-3-methyl-6-ethyl-3,4-dihydro-2H-pyran ($1_c$) were prepared by (4 + 2) cycloaddition reaction from the corresponding vinyl ketones and alkyl vinyl ethers. Compounds $1_{a-c}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, copolymer of head-to-tail (H-T) was also prepared by free radical copolymerization of the mixture of the corresponding monomers. The H-H copolymer exhibited some differences in its $^1H$ NMR and IR spectra. However, significant differences were showed between the H-H and H-T copolymers in the $^{13}C$ NMR spectra. Also noteworthy was that$T_g$ value of H-H copolymer was higher than that of the corresponding H-T structure. Decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. All the H-H and H-T copolymers were soluble in common solvents.

• Bulletin of the Korean Chemical Society
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• v.22 no.7
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• pp.669-672
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

• Corrosion Science and Technology
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• v.21 no.6
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• pp.514-524
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• 2022

Carbon emissions from fuel consumption have been pointed by scientists as the cause of global warming. In particular, fossil fuels are known to emit more carbon when burned than other types of fuels. In this regard, International Maritime Organization has announced a regulation plan to reduce carbon dioxide emissions. Therefore, recently, Liquefied Natural Gas propulsion ships are responding to such carbon reduction regulation. However, from a long-term perspective, it is necessary to use carbon-free fuels such as hydrogen and ammonia. Nitrogen oxides might be generated during ammonia combustion. There is a possibility that incompletely burned ammonia is discharged. Therefore, rather than being used as a direct fuel, Ammonia is only used to reduce NO_X such as urea solution in diesel vehicle Selective Catalyst Reduction. Currently, LPG vehicle fuel feed system studies have evaluated the durability of combustion injectors and fuel tanks in ammonia environment. However, few studies have been conducted to apply ammonia as a ship fuel. Therefore, this study aims to evaluate corrosion damage that might occur when ammonia is used as a propulsion fuel on ships.

• Korean Chemical Engineering Research
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• v.47 no.6
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• pp.762-767
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• 2009

In this study, the feasibility of using vegetable oil extracted from tropical crop seed as a biodiesel feedstock was investigated by producing biodiesel and analysing the quality parameters as a transport fuel. In order to produce biodiesel efficiently, two step reaction process(pre-treatment and transesterificaion) was required because the tropical crop oil have a high content of free fatty acids. To determine the suitable acid catalyst for the pre-esterification, three kinds of acid catalysts were tested and sulfuric acid was identified as the best catalyst. After constructing the experimental matrix based on RSM and analysing the statistical data, the optimal pre-treatment conditions were determined to be 26.7% of methanol and 0.982% of sulfuric acid. Trans-esterification experiments of the pre-esterified oil based on RSM were carried out, then discovered 1.24% of KOH catalyst and 22.76% of methanol as the optimal trans-esterification conditions. However, the quantity of KOH was higher than the previously established KOH concentration of our team. So, we carried out supplemental experiment to determine the quantity of catalyst and methanol. As a result, the optimal transesterification conditions were determined to be 0.8% of KOH and 16.13% of methanol. After trans-esterification of tropical crop oil, the produced biodiesel could meet the major quality standard specifications; 100.8% of FAME, 0.45 mgKOH/g of acid value, 0.00% of water, 0.04% of total glycerol, $4.041mm^2/s$ of kinematic viscosity(at $40^{\circ}C$).

• Clean Technology
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• v.30 no.1
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• pp.47-54
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• 2024

Jatropha oil extracted from the seeds of Nepalese Jatropha curcas, a non-edible crop, was used as a raw material and converted to biodiesel through a two-step process consisting of an esterification reaction and a transesterification reaction. Amberlyst-15 catalyst was applied to the esterification reaction between the free fatty acids contained in the Jatropha oil and methanol. The acid value of the Jatropha oil could be lowered from 11.0 to 0.26 mgKOH/g through esterification. Biodiesel was synthesized through a transesterification reaction between Jatropha oil with an acid value of 0.26 mgKOH/g and methanol over NaOH/γ-Al₂O₃ catalysts. As the loading amount of NaOH increased from 3 to 25 wt%, the specific surface area decreased from 129 to 28 m²/g and the pore volume decreased from 0.249 to 0.129 cm³/g. The amount and intensity of base sites over the NaOH/γ-Al₂O₃ catalysts increased simultaneously with the NaOH loading amount. It was confirmed that the optimal NaOH loading amount for the NaOH/γ-Al₂O₃ catalyst was 12 wt%. The optimal temperature for the transesterification reaction of Jatropha oil using the NaOH/γ-Al₂O₃ catalyst was selected to be 65 ℃. In the transesterification reaction of Jatropha oil using the NaOH/γ-Al₂O₃ catalyst, the reaction rate was affected by external diffusion limitation when the stirring speed was below 150 RPM, however the external diffusion limitation was negligible at higher stirring speeds.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.2
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• pp.241-249
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• 2000

In this study, UV-catalyzed $H_2O_2$ oxidation and $H_2O_2$ oxidation to remove contaminants from photo processing chemicals were investigated at various conditions. Photo processing chemicals contains high concentrations of organic compounds and has very low biodegradability. Hydrogen peroxide is subjected to gradual decomposition as metastable substance. In the process, short-lived and highly reactive hydroxyl radicals are formed. The decomposition can be significantly accelerated by use of appropriate catalyst, such as ultraviolet radiation. The experiments were conducted in a UV-free reflecting reactor in batch and a high-pressure mercury lamp was used as UV source. Mixing, cooling and ventilation of the reactor were operated during experiments. In $UV/H_2O_2$ oxidation and $H_2O_2$ oxidation, the removal efficiencies of $COD_{Cr}$, TOC and chromaticity increased with the increase of $H_2O_2$ dosage and were higher in the controlled pH condition of 3 than in original pH condition of 8. In $UV/H_2O_2$ oxidation under the optimum condition of pH 8 and 1.3 stoichiometric $H_2O_2$ dosage, the removal efficiencies of $COD_{Cr}$, TOC and chromaticity were 47.5%, 75.0% and 91.5% respectively and $BOD/COD_{Cr}$ ratio was significantly increased from 0.04 to 0.21.