• Journal of the Korea Academia-Industrial cooperation Society
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• v.12 no.12
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• pp.5990-5996
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• 2011

6-Methylquinolinium dichromate[$(C_{10}H_9NH)_2Cr_2O_7$] was synthesized by the reaction of 6-methylquinoline with chromium trioxide in $H_2O$, and characterized by IR, ICP. The oxidation of benzyl alcohol using 6-methylquinolinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene < chloroform < acetone < N,N- dimethylformamide. In the presence of hydrochloric acid($H_2SO_4$ solution), 6-methylquinolinium dichromate oxidized benzyl alcohol and its derivatives(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$) smoothly in DMF. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.67(303K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

• 한국신재생에너지학회:학술대회논문집
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• 2006.06a
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• pp.33-36
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• 2006

The effective thermal conductivities of $Mm\;(La_{0.6-0.8})\;Ni_{4.0}Co_{0.6}Mn_{0.2}Al_{0.2}$ (TL-492) with hydrogen and helium have been examined. Experiment results show that pressure has great influence on effective thermal conductivity in Low pressure range (below 0.5 MPa). And that influence decreases rapidly with increase of gas pressure. The reason is at low pressure, the mean free path of gas becomes greater than effective thickness of gas film which is important to the heat transfer mechanism in this research. And, carbon fibers have been used to try to enhance the poor thermal conductivity of TL-492. Three types of carbon fibers and three mass fractions have been examined and compared. Naturally, the highest effective thermal conductivity has been reached with carbon fiber which has highest thermal conductivity, and highest mass fraction. This method has acquired 4.33 times higher thermal conductivity than pure metal hydrides with quite low quantity of additives, only 0.99wt% of carbon fiber. This is a good result comparing to other method which can reach higher effect ive thermal conductivity but needs much higher mass fraction of additives too.

• Applied Chemistry for Engineering
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• v.23 no.2
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• pp.241-246
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• 2012

Cr(VI)-heterocyclic complex (2,2'-bipyridinium dichromate) was synthesized by the reaction between of 2,2'-bipyridine and chromium trioxide in $H_2O$, and characterized by IR and ICP. The oxidation of benzyl alcohol using 2,2'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexene < chloroform < acetone < N,N-dimethylformamide. In the presence of DMF solvent with acidic catalyst such as $H_2SO_4$ solution, 2,2'-bipyridinium dichromate oxidized the benzyl alcohol and its derivatives (p-$p-OCH_3$, $m-CH_3$, H, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant was -0.66 (303 K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

• Applied Chemistry for Engineering
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• v.22 no.6
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• pp.718-722
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• 2011

2,4'-Bipyridinium dichromate [$(C_{10}H_8N_2H)_2Cr_2O_7$] was synthesized by the reaction of 2,4'-bipyridinie with chromium trioxide in $H_2O$. The structure was characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase in the order of the dielectric constant (${\varepsilon}$), in the order : cyclohexene < chloroform < acetone < N,N'-dimethylformamide. In the presence of hydrochloric acid, 2,4'-bipyridinium dichromate effectively oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant (${\rho}$) was -0.65 at 303 K. The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

• Korean Chemical Engineering Research
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• v.49 no.5
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• pp.644-651
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• 2011

Storing hydrogen in solid state hydride is one of the best promising methods for the future hydrogen economy. The total performance of such systems depends on the rate at which the amount of mass and heat migration is supplied to solid hydride. Therefore, an accurate modeling of the heat and mass transfer is of prime importance in optimizing the design of such systems. In this work, Hydrogen storage in Pt-CNTs hydrogen reactor has been intensively investigated by solving 2 dimensional mathematical models. Using a CFD computer software, systematic studies have been performed to elucidate the effect of heat and mass transfer during hydrogen charging periods. It was revealed that the optimized design of hydrogen storage vessel can prevent the increase of system temperature and the charging time due to the convective cooling effects inside the vessels at even high charging pressure. Because none has reported the critical issues of heat and mass transfer for CNT based hydrogen storage system, this work can support the first insight of the optimal design for solid state hydrogen storage system based on CNT in the near future.

• Transactions of the Korean hydrogen and new energy society
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• v.5 no.2
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• pp.81-90
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• 1994

The hydrogen fuel tanks having hydrogen storing capacity of about 300g and 1200g are manufactured using $MmNi_{4.7}Al_{0.25}V_{0.05}Fe_{0.001}$ alloy. They are composed of several unit reactor made of Cu-tube(outer diameter = 50.1mm, thickness = 2mm). In order to increase the heat and mass transfer property of the hydride bed, Al-plates are inserted perpendicular to axial direction at intervals of 5mm and three arteries of diameter 8mm are installed symmetrically in each unit reactor. Hydrogen absorption is proceeded about 80% within 30 minute and is completed within 60 minute at the conditions of charging hydrogen pressure of 25atm and temperature of $22^{\circ}C$. On desorbing hydrogen at a constant rate of 30 slm at $20^{\circ}C$, discharging hydrogen pressure is sustained at 3~5atm for 120 minutes. The discharging pressure is increased upto 5~8atm as the increase of the reactor temperature to $30^{\circ}C$. From the experimental results and the brief discussions about the hydrogen absorption and disorption behaviors of the hydrogen storage tank, it is suggested that the behaviors of hydrogen charging and discharging could be controlled by adjusting the operating parameters and the reactor design parameters.

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.3003-3008
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• 2011

Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.

• Bulletin of the Korean Chemical Society
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• v.4 no.1
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• pp.14-17
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• 1983

The effects of trialkylborane on the stereochemistry of ketone reduction with lithium borohydride were studied for the four representative ketones, namely 4-t-butylcyclohexanone, 2-methylcyclohexanone, norcamphor, and camphor. The presence of trialkylborane increased the yields of the less stable alcohols. For example, in the presence of tri-s-butylborane, 42 % yield of cis-4-t-butylcyclohexanol was observed whereas only 8 % yield with lithium borohydride alone in the reduction of 4-t-butylcyclohexanone. The in situ formation of lithium trialkylborohydride, by the hydride transfer from lithium trialkoxyborohydride to trialkylborane, was demonstrated as a possible mechanism for the catalytic effect of trialkylborane.

• Bulletin of the Korean Chemical Society
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• v.15 no.11
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• pp.957-961
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• 1994

Epoxidation of olefins catalyzed by iron-tetraarylporphyrins were studied to see the shape selectivity in the competing reaction between cis-and trans- or internal and external olefins. Cis-olefins were more reactive than trans-olefins in the competing reaction between cis-and trans-olefins. Interestingly, in the epoxidation of $cis-{\beta}-methystyrene$ by ${\alpha}{\beta}{\alpha}{\beta}$ atropisomer of Fe(III)TNPPPCl and iodosylbenzene, 27% of total product was phenylacetone. The unusually large amount of phenylacetone may be produced by hydride rearrangement of carbocationic intermediate. Regioselectivity of the reaction was also studied by using the most sterically hindered Fe(III)TTPPPCl. In the epoxidation of limonene with Fe(III)TTPPPCl, the disubstituted double bond was more reactive than trisubstituted double bond. This is in contrast to the results obtained with other iron-tetraarylporphyrins. Similar trend was also observed in the competing reaction between mono-and di-substituted olefins.

• Bulletin of the Korean Chemical Society
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• v.8 no.6
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• pp.444-449
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• 1987

Solvent effects on gas phase reactions of methoxide ion with substituted ethylenes, $CH_2$ = CHR where R = CN, CHO and $NO_2$, are investigated theoretically using the AM1 method. Results show that the methoxide approaches in-plane in all reactions, but subsequently rotate out-of-plane to form tetrahedral complexes in additon reactions. All reactions of a bare methoxide are found to be exothermic, the exothermicity being the greatest in the ${\beta}$-addition, in which the excess energy is forced to be contained within the ${\beta}$-adduct rendering extreme instability. However a part of the excess energy can be removed by a solvate molecule giving a stable complex prior to the product formation. The hydride transfer processes were found to be unfavorable due to the high activation barriers. The ${\alpha}-H^+$ abstraction process from acrylonitrile becomes endothermic as a result of monosolvation of the methoxide, in agreement with experimental results.