• Title/Summary/Keyword: 고압화학

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Kinetics on the Reaction of 6-Chloroquinoline and p-Substituted Benzoylcholrides under High Pressures (고압하에서의 6-클로로퀴놀린과 p-치환 염화벤조일류의 반응에 관한 속도론적 연구)

  • Kim, Eung-Ryeol;Im, Jong-Wan;Kim, Se-Gyeong;Go, Yeong-Sin
    • Journal of the Korean Chemical Society
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    • v.46 no.3
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    • pp.187-193
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    • 2002
  • The reaction rates of substituted 6-chloroquinoline with p-substituted benzoyichorides $p-CH_3,$ p-H, $p-NO_2$ have been measured by conductometry in acetonitrile, and the constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ${\Delta}V^{\neq}$, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$, ${\Delta}G^{\neq}$) and the pressure dependence of Hammett p values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substiuents in substrate $(p-NO_2)$ with 6-chloroqinoline. When the activation volume and the activation entropy are all negative And the Hammett p values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical $S_N2$ reaction mechanism and "associative $S_N2$" in bond formation favored with increasing pressures.

Photo-Electrochemical Hydrogen Production Over P- and B- Incorporated $TiO_2$ Nanometer Sized Photo-Catalysts (P와 B 이온이 함유된 나노 티타니아 광촉매의 광 전기화학적 수소 제조 성능)

  • Kwak, Byeong-Sub;Choi, Hee-Chan;Woo, Jae-Wook;Lee, Ju-Seung;An, June-Bum;Ryu, Si-Gyeong;Kang, Mi-Sook
    • Clean Technology
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    • v.17 no.1
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    • pp.78-82
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    • 2011
  • For effectively photochemical hydrogen production, P (negative semiconductor) and B (positive semiconductor) ions (0.1, 0.2, 0.5, and 1.0 mol%) incorporated $TiO_2$ (P- and B-$TiO_2$) nanometer sized particles were prepared using a solvothermal method as a photocatalyst. The characteristics of the synthesized P- and B-$TiO_2$ photocatalysts were analyzed by X-ray Diffraction (XRD), Transmission electron microscopy (TEM), W-visible spectroscopy (UV-Vis), and Photoluminescence spectra (PL). The evolution of $H_2$ from methanol/water (1:1) photo-splitting over B-$TiO_2$ photocatalysts was enhanced compared to those over pure $TiO_2$ and P-$TiO_2$ photocatalysts; 0.42 mL of $H_2$ gas was evolved after 10 h when 0.5 g of a 1.0 mol% B-$TiO_2$ catalyst was used.

Effects of an extrusion process on the chemical properties and pigment stability of turmeric (압출성형처리에 의한 강황의 화학적 특성 및 색소 안정성 변화)

  • Sung, Yunkyung;Son, Heejin;Hong, Jungil
    • Korean Journal of Food Science and Technology
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    • v.50 no.5
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    • pp.457-463
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    • 2018
  • Various health benefits of turmeric have been reported. Therefore, an innovative application of turmeric as a functional food was explored. In the current study, effects of an extrusion process on the chemical properties and antioxidant activities of turmeric were investigated. Extrusion of turmeric was performed at $150^{\circ}C$ using screw revolution speeds of 500, 1,000, 1,300, and 1,600 rpm. A significant reduction in turmeric pigments and the formation of browning compounds occurred due to the extrusion. The degradation of pigments was proportional to the increase in screw speed. Infusion yields were significantly increased after the extrusion. The content of proteins and polyphenols, as well as the content of flavonoids in infusions and EtOH extracts were significantly reduced by the extrusion. Scavenging activities of turmeric against DPPH and ABTS radicals were also significantly reduced following the extrusion. These results indicate that the extrusion process caused a significant loss of pigments and decreased the antioxidant activities of turmeric. Therefore, further study related to the development of a proper extrusion process is to be needed.

Experimental Study on the Changes in the Oxygen Concentration and the Pressure at Temperature of 200 ℃ for the Assessment of the Risks of Fire and Explosion of Propylene (프로필렌의 화재 및 폭발 위험성 평가를 위한 온도 200 ℃에서 산소농도와 압력의 변화에 따른 실험적 연구)

  • Choi, Yu-Jung;Choi, Jae-Wook
    • Korean Chemical Engineering Research
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    • v.58 no.3
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    • pp.356-361
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    • 2020
  • Propylene is widely used in petrochemical manufacturing at over 200 ℃. However, since propylene is a flammable gas with fire and explosion risks, inert nitrogen is injected to prevent them. In this study, experiments were conducted using propylene-nitrogen-oxygen upon pressure changes at 200 ℃. At 21% oxygen, as pressure increased from 0.10 MPa to 0.25 MPa, lower explosion limit (LEL) decreased from 2.2% to 1.9% while upper explosion limit (UEL) increased from 14.8% to 17.6%. In addition, minimum oxygen concentration (MOC) decreased from 10.3% to 10.0%, indicating higher risks with the expanded explosive range as pressure increased. With increase of pressure from 0.10 MPa to 0.25 MPa, explosion pressure increased from 1.84 MPa to 6.04 MPa, and the rate of rise of maximum explosion pressure increased drastically from 90 MPa/s to 298 MPa/s. It is hoped that these results can be used as basic data to prevent accidents in factories using propylene.

Kinetics of the Reaction of Benzyl Chlorides with Pyridine in Methanol Solvent under High Pressure (고압하의 메탄올 용매내에서 염화벤질류와 피리딘과의 반응에 대한 반응속도론적 연구)

  • Oh Cheun Kwon;Young Cheul Kim;Jin Burm Kyong;Kee Joon Choi
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.413-418
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    • 1987
  • Rates of the reaction for p-nitro benzyl chloride, benzyl chloride and p-methyl benzyl chloride with pyridine in methanol solvent have been measured by an electric conductivity method at 40$^{\circ}$C and 50$^{\circ}$C under various pressures (1∼2000bar). Pseudo first-order rate constants and second-order rate constants were determined. Rates of these reactions were increased in the order p-NO$_2$ < p-H < p-CH$_3$ and increased with temperature, pressure and concentration of pyridine. From those rate constants, the activation parameters were evaluated. The activation volume and the activation compressibility coefficient are both negative values, but the activation enthalpy is positive and the activation entropy is large negative value. From the evaluation of the ground state and transition state which was resulted from substituents and pressure, it was found that this reaction proceeds through S$_N$2 reaction, and S$_N$2 fashion is slightly disappeared as pressure increases.

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The Effect of Pyrolysis Pressure on Combustion Reactivity of Coal Char (열분해 압력이 석탄 촤의 연소반응성에 미치는 영향)

  • Park Ho Young;Kim Young Ju;Kim Tae Hyung;Seo Sang Il
    • Journal of Energy Engineering
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    • v.14 no.1
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    • pp.1-10
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    • 2005
  • The combustion reactivity of char depending on the pyrolysis pressure was investigated with Pressurized Thermogravimetric Analyser. The amounts of volatiles released at pyrolysis pressure of 1, 8 and 15 atm were, first, measured with Alaska, Adaro and Denisovsky coals. Reactivities of chars produced at var-ious pyrolysis pressure were evaluated at atmospheric pressure and 500℃, and analysed in terms of char crystal structure, surface area, pore characteristics and chemical composition of char. Finally, the combustion reactivities of three chars were examined at pressure of 1 atm, 8 atm and 15 atm. From this study, it was recognized that the amount of volatiles released decreases with increase in pyrolysis pressure, and reaction rate of char produced at higher pyrolysis pressure was lower than that at lower pyrolysis pressure. It might be resulted from the difference in char surface area and pore characteristics rather than char crystal structure and chemical characteristics. At 15 atm, kinetic parameters of Alaska char were obtained with the grain model, and these were 56.8 KJ/mole for activation energy and 222.34 (1/min) for frequency factor.

Shock Metamorphism of Plagioclase-maskelynite in the Lunar Meteorite Mount DeWitt 12007 (달운석 Mount DeWitt 12007의 마스컬리나이트 충격 변성 특성 연구)

  • Kim, Hyun Na;Park, Changkun
    • Journal of the Mineralogical Society of Korea
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    • v.29 no.3
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    • pp.131-139
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    • 2016
  • Detailed knowledge on maskelynite, a glassy phase of plagioclase found in shocked meteorites and impact craters, is essential to understand a shock metamorphism. Here, we explore an inhomogeneous shock metamorphism in the lunar meteorite Mount DeWitt (DEW) 12007 with an aim to understand the formation mechanism of maskelynite. Most plagioclase grains in the DEW 12007 partially amorphized into maskelynite with a unidirectional orientation. Back-scattered electron (BSE) images of maskelynite show a remnant of planar deformation fracture possibly indicating that the maskelynite would be formed by solid-state transformation(i.e., diaplectic glass). Plagioclase with flow texture is also observed along the rim of maskelynite, which would be a result of recrystallization of melted plagioclase. Results of Raman experiments suggest that shock pressure for plagioclase and maskelynite in the DEW 12007 is approximately 5-32 GPa and 26-45 GPa, respectively. The difference in shock pressures between plagioclase and maskelynite can be originated from 1) external factors such as inhomogeneous shock pressure and/or 2) internal factors such as chemical composition and porosity of rock. Unfortunately, Raman spectroscopy has a limitation in revealing the detailed atomic structure of maskelynite such as development of six- or five-coordinated aluminum atom upon various shock pressure. Further studies using nuclear magnetic resonance spectroscopy are necessary to understand the formation mechanism of maskelynite under high pressure.

Conservation Treatment of Sand Stone by Pressurized Impregnation with Acrylic Materials (아크릴계 보존처리제를 이용한 사암의 가압함침 보존처리)

  • Kim, Youn-Cheol;Kim, Sa-Duk;Kim, Hyung-Joong
    • Journal of Conservation Science
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    • v.27 no.4
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    • pp.395-401
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    • 2011
  • After pressurized impregnation treatment, which has been proposed as an effective conservation method for stone cultural property, was executed with methyl metacrylate (MMA), MMA-butyl acrylate (PMB73) mixture and MMA-vinyl trimethoxy silane (PMV5) co-monomer mixture, the physical-chemical properties on the sand stone and the granite impregnated were evaluated. Compared to the case of granite, the impregnation ratios of sand stone showed larger values in the range of 3.2 to 3.7 wt% and these were increased up to 32% when the decompression process was applied to autoclave. The physical properties of sand stone such as anti-moisture property, flexural strength, impact property and ultrasonic velocity were also higher values than those of granite, which can be interpreted by high impregnation ratio resulted in many void within sand stone. The impact failure energy was 1.22 J for PMMA, 1.84 J for PMB73, and 2.8 J for PMV5, respectively. Since the inorganic affinity of treatment agent is more effective than the molecular structure of acrylic agent, PMV5 improved inorganic property indicates the optimum impact property.

A Numerical Modeling of the Temperature Dependence on Electrochemical Properties for Solid Oxide Electrolysis Cell(SOEC) (고체 산화물 수전해 시스템(SOEC)에서 전기화학적 특성의 온도 의존성에 대한 수치 모델링)

  • Han, Kyoung Ho;Jung, Jung Yul;Yoon, Do Young
    • Journal of Energy Engineering
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    • v.29 no.2
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    • pp.1-9
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    • 2020
  • In recent days, fuel cell has received attention from the world as an alternative power source to hydrocarbon used in automobile engines. With the industrial advances of fuel cell, There have been a lot of researches actively conducted to find a way of generating hydrogen. Among many hydrogen production methods, Solid Oxide Electrolysis Cell(SOEC) is not only a basic way but also environment-friendly method to produce hydrogen gas. Solid Oxide Electrolysis Cell has lower electrical energy demands and high thermal efficiency since it is possible to operate under high temperature and high pressure conditions. For these reasons, experimental researches as well as studies on numerical modeling for Solid Oxide Electrolysis Cell have been under way. However, studies on numerical modeling are relatively less enough than experimental accomplishments and have limited performance prediction, which mostly is considered as a result from inadequate effects of electrochemical properties by temperature and pressure. In this study, various experimental studies of commercial Membrane Electrode Assembly (MEA) composed of Ni-YSZ (40wt%, Ni-60 wt% YSZ)/8-YSZ (TOSOH, TZ8Y)/LSM (La0.9Sr0.1MnO3) was utilized for improving effectiveness of SOEC model. After numerically analyzing effects of electrochemical properties according to operating temperature, causing the largest deviation between experiments and simulation are that Charge Transfer Coefficient (CTC), exchange current density, diffusion coefficient, electrical conductivity in SOEC. Analyzing temperature effect on parameter used in overpotential model is conducted for modeling of SOEC. cross-validation method is adopted for application of various MEA and evaluating feasibility of model. As a result, the study confirm that the numerical model of SOEC based on structured process of effectiveness evaluation makes performance prediction better.

Effect of Pressure on Hydration Number of Some Ions (몇 가지 이온의 水和數에 대한 壓力의 效果)

  • Jung-Ui Hwang;Jong-Jae Chung;Hag-Sung Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.791-795
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    • 1992
  • The limiting equivalent conductances of LiCl, NaCl, KCl and KBr have been obtained in water using conductometric method from 1 to 2000 bars at $25^{\circ}C$. From the limiting equivalent ionic conductances (obtained using TATB[Tetraphenyl Arsonium Tetraphenyl Borate]method) of $Li^+$, $Na^+$, $K^+$, $Cl^-$, and $Br^-$ ions and viscosity of water at given pressure, their Stokes radii have been calculated. From the corrected radii caliberated by Nightingale method and the crystallographic radii at a given pressure, the volume of hydration-shell surrounding ion was calculated and hydration numbers of $Li^+$, $Na^+$, $K^+$, $Cl^-$, and $Br^-$ ions were obtained. From the experimental results, it was found that the hydration number of $Li^+$, $Na^+$, $K^+$, $Cl^-$, and $Br^-$ ions slightly decreased with increasing pressure. This trend may be explained by Horne's suggestion[Advances in High Pressure Research]. Comparing results of this study with those of Nakahara's, the hydration numbers of $K^+$ and $Cl^-$ ions were almost twice as large as those of Nakahara's[Rev. Phys. Chem. Japan, 42, 12 (1972)]. By comparing the present results with those of Kollman's [J. Am. Chem. Soc., 113, 2481 (1991)], the hydration number obtained by applying TATB method and Nightingale method may be inferred to be reasonable.

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